EP4323104A1 - Porous polymeric carbon sorbents and methods of making and using same - Google Patents
Porous polymeric carbon sorbents and methods of making and using sameInfo
- Publication number
- EP4323104A1 EP4323104A1 EP21723565.4A EP21723565A EP4323104A1 EP 4323104 A1 EP4323104 A1 EP 4323104A1 EP 21723565 A EP21723565 A EP 21723565A EP 4323104 A1 EP4323104 A1 EP 4323104A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- porous polymeric
- carbon sorbent
- polymeric carbon
- sorbent
- atm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002594 sorbent Substances 0.000 title claims abstract description 936
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 895
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 864
- 238000000034 method Methods 0.000 title claims abstract description 551
- 229910052751 metal Inorganic materials 0.000 claims abstract description 219
- 239000002184 metal Substances 0.000 claims abstract description 219
- 238000010438 heat treatment Methods 0.000 claims abstract description 175
- 239000007789 gas Substances 0.000 claims abstract description 169
- 239000000203 mixture Substances 0.000 claims abstract description 116
- 238000002485 combustion reaction Methods 0.000 claims abstract description 85
- 229920003023 plastic Polymers 0.000 claims abstract description 80
- 239000004033 plastic Substances 0.000 claims abstract description 80
- 239000000654 additive Substances 0.000 claims abstract description 79
- 230000000996 additive effect Effects 0.000 claims abstract description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 32
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 22
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003546 flue gas Substances 0.000 claims abstract description 13
- 238000003860 storage Methods 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 174
- 239000011148 porous material Substances 0.000 claims description 171
- 239000007825 activation reagent Substances 0.000 claims description 109
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical group [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 94
- 238000001994 activation Methods 0.000 claims description 93
- 230000004913 activation Effects 0.000 claims description 93
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 77
- 229920001903 high density polyethylene Polymers 0.000 claims description 75
- 239000004700 high-density polyethylene Substances 0.000 claims description 75
- 125000004432 carbon atom Chemical group C* 0.000 claims description 66
- 229920000877 Melamine resin Polymers 0.000 claims description 52
- 150000002739 metals Chemical class 0.000 claims description 49
- 238000001179 sorption measurement Methods 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 45
- 235000011056 potassium acetate Nutrition 0.000 claims description 44
- 239000004743 Polypropylene Substances 0.000 claims description 40
- 229920001155 polypropylene Polymers 0.000 claims description 40
- 150000003868 ammonium compounds Chemical class 0.000 claims description 39
- 229910052760 oxygen Inorganic materials 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 39
- 239000001301 oxygen Substances 0.000 claims description 38
- 229920001684 low density polyethylene Polymers 0.000 claims description 36
- 239000004702 low-density polyethylene Substances 0.000 claims description 36
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 34
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 32
- 229920002873 Polyethylenimine Polymers 0.000 claims description 31
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 31
- 239000004677 Nylon Substances 0.000 claims description 29
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 29
- 229920001778 nylon Polymers 0.000 claims description 29
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 28
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 28
- 230000036961 partial effect Effects 0.000 claims description 26
- -1 polypropylene Polymers 0.000 claims description 26
- 229920002635 polyurethane Polymers 0.000 claims description 26
- 239000004814 polyurethane Substances 0.000 claims description 26
- 238000002441 X-ray diffraction Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 230000002194 synthesizing effect Effects 0.000 claims description 24
- 239000013502 plastic waste Substances 0.000 claims description 23
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 22
- 230000003213 activating effect Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011591 potassium Substances 0.000 claims description 19
- 229910052700 potassium Inorganic materials 0.000 claims description 19
- 229910052776 Thorium Inorganic materials 0.000 claims description 18
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical group [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 17
- 239000001639 calcium acetate Substances 0.000 claims description 17
- 235000011092 calcium acetate Nutrition 0.000 claims description 17
- 229960005147 calcium acetate Drugs 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052768 actinide Inorganic materials 0.000 claims description 14
- 150000001255 actinides Chemical class 0.000 claims description 14
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 14
- 150000002602 lanthanoids Chemical class 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 150000007942 carboxylates Chemical group 0.000 claims description 12
- 238000011010 flushing procedure Methods 0.000 claims description 12
- 239000003345 natural gas Substances 0.000 claims description 12
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 12
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 10
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 239000004800 polyvinyl chloride Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229920005575 poly(amic acid) Polymers 0.000 claims description 9
- 239000004640 Melamine resin Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 230000007423 decrease Effects 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 241001507939 Cormus domestica Species 0.000 claims description 6
- GVNMYOZQCKIVOR-UHFFFAOYSA-N NO.O.NN Chemical compound NO.O.NN GVNMYOZQCKIVOR-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 159000000021 acetate salts Chemical group 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 240000006766 Cornus mas Species 0.000 claims description 2
- 235000003363 Cornus mas Nutrition 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 53
- 238000002360 preparation method Methods 0.000 abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 708
- 229910002092 carbon dioxide Inorganic materials 0.000 description 359
- 239000001569 carbon dioxide Substances 0.000 description 354
- 230000008569 process Effects 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 230000001276 controlling effect Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000000197 pyrolysis Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000005755 formation reaction Methods 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 238000002429 nitrogen sorption measurement Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
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- 230000007246 mechanism Effects 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229920000426 Microplastic Polymers 0.000 description 2
- 208000025174 PANDAS Diseases 0.000 description 2
- 208000021155 Paediatric autoimmune neuropsychiatric disorders associated with streptococcal infection Diseases 0.000 description 2
- 240000004718 Panda Species 0.000 description 2
- 235000016496 Panda oleosa Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 1
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 102100026933 Myelin-associated neurite-outgrowth inhibitor Human genes 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28088—Pore-size distribution
- B01J20/2809—Monomodal or narrow distribution, uniform pores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/202—Polymeric adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4893—Residues derived from used synthetic products, e.g. rubber from used tyres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
Porous polymeric carbon sorbents, including particularly polymeric carbon sorbents for CO2 capture for flue gas from power plants, for gases from other post combustion CO2 emission outlets, for gas storage, for direct air capture of CO2, and methods of making and using same. The porous carbon material can be prepared by heating plastic with an additive. The additive can be selected from metal hydroxide, metal carbonate, metal bicarbonate, metal oxalate, metal acetate, metal acetylacetonoate or mixtures thereof. By controlling the preparation, such as the temperature of preparation, the porous carbon sorbent can be controlled to be rigid or flexible.
Description
POROUS POLYMERIC CARBON SORBENTS AND METHODS OF MAKING AND
USING SAME
TECHNICAL FIELD
[0001] The present invention relates to porous polymeric carbon sorbents, including particularly porous polymeric carbon sorbents for sorption of gases, such as for CO2 capture for flue gas from power plants and for gases from other post-combustion CO2 emission outlets, for gas storage, and/or for direct air capture of CO2, and methods of making and using same. [0002] This application is in the same technical field as (a) PCT IntT Appl. No. PCT/US2020/055637, entitled “Porous Polymeric Carbon Sorbents For CO2 Capture And Methods Of Making And Using Same,” (b) PCT IntT Appl. No. PCT/US2020/055638, entitled “Porous Polymeric Carbon Sorbents For Gas Storage And Methods Of Making And Using Same,” and PCT IntT Appl. No. PCT/US2020/055639, entitled “Porous Polymeric Carbon Sorbents For Direct Air Capture Of CO2 And Methods Of Making And Using Same,” which were each filed on October 14, 2020, are each commonly owned by the owner of the present invention, and each claim priority to U.S. Patent Appl. Serial No. 62/914,826, filed October 14, 2019, entitled “Method To Convert Plastic Waste To Porous Polymeric Carbon Sorbents And Compositions Thereof.” All of these patent applications are incorporated herein in their entirety.
BACKGROUND
[0003] Plastic pollution and ever-raising carbon dioxide (CO2) levels are among the top environmental concerns of the 21st century. \Modak 2019; Younas 2016; Ramanathan 2009] The concentration of CO2 in the atmosphere has increased from preindustrial value of ~280 ppm to 401 ppm in 2018. [. Lindsey 2020] This increase in CO2 levels is believed to be primarily due to the continuous combustion of fossil fuels and the lack of economical CO2 capture routes. With the slow development of green and renewable energy sources, fossil fuels are expected to remain the least expensive energy source for the next 40 years. [Haszeldine
2009 ; Pacala 2004 ]. To lessen the impact caused by fossil fuel consumption, efficient and economic post-combustion CO2 capture technologies are needed to replace the expensive and energy intensive amine-based chemical absorption that has been practiced in industry for decades. [. Rochelle 2009\.
[0004] Amine-based technologies for CO2 capture rely on the chemical reaction between amines and CO2 to form a carbamate complex as shown in eq. 1. [. Rochelle 2009; Astaria 1983; Rao 2002]
2 R-NH2 + CO2 < R-NH3 + + R-NHCOO (eq. 1)
[0005] Carbamates are stable and require heating to 125°C to regenerate the amine, making it an extremely energy intensive technology given the high heat capacity of aqueous amine solution. [ Camper 2008] On top of the high regeneration cost, aqueous amines are corrosive and cause continuous equipment failures in the CO2 capture units, degrade upon heating, are expensive to replace, produce large amounts of wastewater and sludge as byproducts, and they occupy a large footprint. Thus, the development of a greener and cheaper technology is desirable. [Dutcher 2008]
[0006] Solid sorbents have received more interest in recent years due to their low heat of regeneration and high thermal stability. [Jalilov 12017; Jung 2013] Out of all reported solid sorbents, activated carbons are inexpensive, non-toxic and they have a resilient structure [Gray 2008; Jalilov 2015; Sevilla 2018; Siriwarda e 2001; Tour 2010; Xu 2018], making them great candidates for applications with severe and harsh conditions as found in crude oil desulfurization [Bandosz 2006; Wang 2007], gas storage [Sun 1996], and high-pressure CO2 capture [Jalilov 12017] The surface area and pore volume of carbonaceous materials can be easily tuned and economically tuned. [Sevilla 2018; He 20167] Moreover, carbonaceous materials can be synthesized from various feedstocks ranging from a renewable biomass like glucose [Sevilla 2018; Yue 2018; Rau 2019; Singh 2019] to industrial carbon waste like asphalt
\Jalilov II 2017], which makes the precursors of carbonaceous material highly abundant. [0007] With the increasing awareness of the harmful effects of microplastics, nanoplastics and other plastic waste [ Cox 2019 ; Tetu 2019], new technologies for plastic waste utilization are being pursued. One of the proposed technologies to treat plastic waste is pyrolysis of plastic, also called chemical recycling. [Al-Salem 2009] This method involves heating plastics in an inert atmosphere, a process which breaks up the plastic into smaller molecules such as monomers, oligomers, oils and waxes, along with a nonvolatile carbonaceous residue or char. [Al-Salem 2009; Panda 2018 \. This process occurs at -600 °C. [Panda 2018] The waxes and oil products are further cracked over acidic zeolites or bentonite clay to obtain higher value petrochemicals and fuels. [Nishino 2008; Mani 2011; Budsaereechai 2019] One of the drawbacks of pyrolysis methods is the formation of large amounts of char that currently has no significant usefulness. [Kiran Ciliz 2004]
[0008] Accordingly, there is a need for improved processes to address the large environmental issues that are being faced today, namely plastic waste pollution and the rising CO2 levels in the atmosphere.
[0009] Moreover, existing porous sorbent synthesis technologies require heating carbon source with potassium salts (KOH most often used) at 700°C -900°C, making the process very energy intensive and hard to scale up. Also, at high temperatures and mass quantities there is a risk of formation of potassium metal making the current routes for sorbent synthesis difficult to commercialize because traces of potassium can cause fires, igniting the carbon upon work-up. While in a lab the danger is small, industrially, in large scale, the danger is enormous. Thus an improved process that is safer, less energy intensive, scalable, and commercial is needed. [0010] Furthermore, while the demand for ethylene increases every year, ethylene trade is limited due to challenges in transporting and refrigerating ethylene. FIGS. 1A-1B show two current commercial processes for ethylene production, which require high temperatures greater
than 850°C to produce ethylene. Accordingly, there is a need for an improved process for ethylene production.
SUMMARY OF THE INVENTION
[0011] In general, the present description relates to methods of synthesizing porous polymeric carbon sorbents for use in gas capture. The method can include contacting an activation reagent with a polymer followed by heating to produce the porous polymeric carbon sorbent. The porous polymeric carbon sorbent can be rigid or flexible, and can have properties for enhanced sorption performance. Various optional details, aspects and embodiments will be described further herein.
[0012] In one embodiment, the invention features a method of synthesizing a rigid porous polymeric carbon sorbent. The method includes the step of mixing a polymer with an additive to form a mixture. The polymer has a polymer chain order including long range order and short range order as detected by powder X-ray diffraction (XRD). The additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal oxalate, metal acetate, metal acetylacetonoate, and mixtures thereof. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The chemical activation results in a loss of the long range order and the short range order of the polymer as detected by powder XRD such that the porous polymeric carbon sorbent material is a rigid porous polymeric carbon sorbent. The rigid porous polymeric carbon sorbent is operable for capturing CO2 at a pressure between 0.75 atm to 5 atm. The rigid polymeric carbon sorbent has a selectivity for capturing CO2 over N2 at least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0013] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any
combination in implementations of the invention:
[0014] The polymer can be selected from a group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), and combinations thereof. [0015] The polymer can be selected from a group consisting of polyvinyl chloride (PVC), nylon, melamine mixed with HDPE, melamine mixed with LDPE, melamine mixed with PP, melamine-formaldehyde resins, polyethylene imine (PEI), PEI mixed with HDPE, polyurethanes (PU), polyacrylonitrile, (PAN), and polyethyleneteraphthalte (PET) and mixtures therefrom.
[0016] The polymer can include nitrogen atoms.
[0017] The rigid polymeric carbon sorbent can have a selectivity for capturing CO2 over N2 at least 300:1 in 0.15 bar of CO2 in 0.85 bar N2 at 23°C.
[0018] The polymer can include a plastic from a waste plastic source.
[0019] The step of heating can be performed at a temperature that is between 550°C and 700°C. [0020] The step of heating can be performed at a temperature that is between 575°C and 600°C. [0021] The activation reagent can be an acetate salt of potassium or calcium.
[0022] The activation reagent can be potassium acetate.
[0023] The activation reagent can be calcium acetate.
[0024] The weight ratio of the additive and the polymer in the mixture can be between 0.5:1 and 5:1.
[0025] The weight ratio of the additive and the polymer in the mixture can be between 2: 1 and 4:1.
[0026] The rigid porous polymeric carbon sorbent can be operable for capturing CO2 from a post-combustion CO2 emission outlet gas.
[0027] The post-combustion CO2 emission outlet gas can be a flue gas.
[0028] The rigid porous polymeric carbon sorbent can be operable for capturing more than 15
wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at 1 atm.
[0029] The rigid porous polymeric carbon sorbent can be operable for releasing the CO2 captured from a post-combustion CO2 emission outlet gas by heating the rigid porous polymeric carbon sorbent to at most 110°C at 1 atm.
[0030] The rigid porous polymeric carbon sorbent can be operable for releasing the CO2 captured from a post-combustion CO2 emission outlet gas by heating the rigid porous polymeric carbon sorbent to at most 75°C at 1 atm.
[0031] The rigid porous polymeric carbon sorbent can be operable for capturing more than 18 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at most 5 atm.
[0032] The rigid porous polymeric carbon sorbent can be operable for capturing more than 100 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at most 300 atm. [0033] The method can further include controlling pore size of the rigid porous polymeric carbon sorbent by controlling pressure during the step of heating.
[0034] The step of heating the mixture can be performed at a near vacuum pressure of at least 0.01 bars.
[0035] In general, in another embodiment, the invention features a rigid porous polymeric carbon sorbent. The rigid porous polymeric carbon sorbent is operable to capture more than 15 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at 1 atm. The rigid polymeric carbon sorbent has a selectivity for capturing CO2 over N2 at least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0036] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0037] The rigid porous polymeric carbon sorbent can include a polymer that has no polymeric
long range order and no polymeric short range order detectable by powder X-ray diffraction. [0038] The rigid porous polymeric carbon sorbent can include pores having an average pore size of between 2 A and 100 A.
[0039] The rigid porous polymeric carbon sorbent can include pores having an average pore size of between 5 A and 20 A.
[0040] The rigid porous polymeric carbon sorbent can be operable for releasing the CO2 captured from post-combustion CO2 emission outlet gas by heating the rigid porous polymeric carbon sorbent to at most 110°C at about 1 atm pressure.
[0041] The rigid porous polymeric carbon sorbent can be operable for releasing the CO2 captured from post-combustion CO2 emission outlet gas by heating the rigid porous polymeric carbon sorbent to at most 75°C at about 1 atm pressure.
[0042] The rigid porous polymeric carbon sorbent can be operable for capturing more than 18 wt% CO2 from post-combustion CO2 emission outlet gas at 25°C and at 5 atm.
[0043] The rigid porous polymeric carbon sorbent can be operable for capturing more than 100 wt% CO2 from post-combustion CO2 emission outlet gas at 25°C and at 300 atm.
[0044] The rigid porous polymeric carbon sorbent can include nitrogen atoms.
[0045] The rigid polymeric carbon sorbent can have a selectivity for capturing CO2 over N2 of at least 250:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0046]
[0047] In general, in another embodiment, the invention features a method that includes selecting a rigid porous polymeric carbon sorbent having a selectivity for capturing CO2 over N2 least 40: 1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C. The method further includes utilizing the rigid porous polymeric carbon sorbent to capture more than 15 wt% CO2 from post combustion CO2 emission outlet gas.
[0048] Implementations of the invention can include one or more of the following features,
which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0049] The post-combustion CO2 emission outlet gas can be a flue gas.
[0050] The CO2 can be captured from post-combustion CO2 emission outlet gas at atmospheric pressure.
[0051] The CO2 can be captured from post-combustion CO2 emission outlet gas at room temperature at around 25°C.
[0052] The rigid porous polymeric carbon sorbent can be utilized to capture more than 18 wt% CO2 from post-combustion CO2 emission outlet gas.
[0053] The CO2 can be captured from post-combustion CO2 emission outlet gas at a pressure that is at most 5 atm.
[0054] The rigid porous polymeric carbon sorbent can be utilized to capture more than 100 wt% CO2 from post-combustion CO2 emission outlet gas.
[0055] The CO2 can be captured from post-combustion CO2 emission outlet gas at a pressure that is at most 300 atm.
[0056] The method can further include releasing the CO2 captured from post-combustion CO2 emission outlet by heating the rigid porous polymeric carbon sorbent.
[0057] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 110°C.
[0058] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 75°C.
[0059] The method can further include repeating the capture and release of the CO2 by the rigid porous polymeric carbon sorbent for at least 1000 cycles.
[0060] The method can further include repeating the capture and release of the CO2 by the rigid
porous polymeric carbon sorbent for at least 100,000 cycles.
[0061] The rigid porous polymeric carbon sorbent can have a selectivity for capturing CO2 over N2 of at least 70:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0062] The rigid porous polymeric carbon sorbent can include nitrogen atoms.
[0063] The rigid porous polymeric carbon sorbent can have a selectivity for capturing CO2 over N2 of at least 300:1 at least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0064] In general, in another embodiment, the invention feature a method of synthesizing a flexible porous polymeric carbon sorbent. The method includes the step of mixing a polymer with an additive to form a mixture. The polymer has a polymer chain order including long range order and short range order as determined by powder X-ray diffraction (XRD). The additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal oxalate, metal acetate, metal acetylacetonoate and mixtures thereof. The method further includes heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The chemical activation results in a loss of the long range order while maintaining short range order of the polymer as detected by powder XRD such that the porous polymeric carbon sorbent material is a flexible porous polymeric carbon sorbent. The flexible porous polymeric carbon sorbent is operable for storing 4.5 wt% H2 at room temperature and 100 atm.
[0065] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0066] The flexible porous polymeric carbon sorbent gas can be operable for storing each of H2, CO2, O2, methane, natural gas, and combinations thereof.
[0067] The flexible porous polymeric carbon sorbent can be independently: (a) operable to
store at least 150 wt% of CO2 at room temperature and 50 atm; (b) operable to store at least 140 wt% of O2 at room temperature and 110 atm; and (c) operable to store at least 80 wt% of CH4 at room temperature and 100 atm.
[0068] The polymer can be selected from a group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), and combinations thereof. [0069] The polymer can be selected from a group consisting of polyvinyl chloride (PVC), nylon, melamine with HDPE, melamine with LDPE, melamine with PP, melamine- formaldehyde resins, melamine resins, urea, polyurethanes (PEI), polyacrylonitrile, (PAN), polyethylene imine, polyethylene imine mixed with HDPE, and polyethyleneteraphthalte (PET) and mixtures therefrom.
[0070] The polymer can include nitrogen atoms.
[0071] The step of heating can be performed at a temperature that is between 400°C and 525°C. [0072] The step of heating can be performed at a temperature that is between 475°C and 500°C. [0073] The activation reagent can be an acetate salt of potassium or calcium.
[0074] The activation reagent can be potassium acetate.
[0075] The activation reagent can be calcium acetate.
[0076] The weight ratio of the additive and the polymer in the mixture can be between 0.5:1 and 5:1.
[0077] The weight ratio of the additive and the polymer in the mixture can be between 2: 1 and 4:1.
[0078] The flexible porous polymeric carbon sorbent can be operable for storing more than 5.5 wt% of H2 at room temperature and 100 atm.
[0079] The flexible porous polymeric carbon sorbent can be operable for storing more than 8 wt% of H2 at room temperature and 100 atm.
[0080] The flexible porous polymeric carbon sorbent can be operable for storing about 13 wt%
of H2 at room temperature and 200 atm.
[0081] The flexible porous polymeric carbon sorbent can be operable for storing about 15 wt% of H2 at room temperature and 300 atm.
[0082] The flexible porous polymeric carbon sorbent can be operable for storing more than 80 wt% of CH4 at room temperature and 100 atm.
[0083] The flexible porous polymeric carbon sorbent can be operable for storing more than 150 wt% of CH4 at room temperature and 200 atm.
[0084] The flexible porous polymeric carbon sorbent can be operable for storing more than 175 wt% of CH4 at room temperature and 300 atm.
[0085] The flexible porous polymeric carbon sorbent can be operable for releasing the stored gas by lowering the pressure back to 1 atm.
[0086] The method can further include controlling pore size of the flexible porous polymeric carbon sorbent by controlling pressure during the step of heating.
[0087] The step of heating the mixture can be performed at a near vacuum pressure of at least 0.01 bars.
[0088] In general, in another embodiment, the invention features a flexible porous polymeric carbon sorbent that is operable for storing 4.5 wt% H2 at room temperature and 100 atm. [0089] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0090] The flexible porous polymeric carbon sorbent can be independently: (a) operable to store at least 150 wt% of CO2 at room temperature and 50 atm; (b) operable to store at least 140 wt% of O2 at room temperature and 110 atm; and (c) operable to store at least 80 wt% of CH4 at room temperature and 100 atm.
[0091] The flexible porous polymeric carbon sorbent can include a polymer that has short range order and no long range order by powder X-ray diffraction (XRD).
[0092] The flexible porous polymeric carbon sorbent can include pores having an average pore size of between 2 A and 100 A.
[0093] The flexible porous polymeric carbon sorbent can include pores having an average pore size of between 5 A and 20 A.
[0094] The flexible porous polymeric carbon sorbent can be operable for storing more than 5.5 wt% of Th at room temperature and 100 atm.
[0095] The flexible porous polymeric carbon sorbent can be operable for storing more than 8 wt% of Th at room temperature and 100 atm.
[0096] The flexible porous polymeric carbon sorbent can be operable for storing more than 13 wt% of Th at room temperature and 200 atm.
[0097] The flexible porous polymeric carbon sorbent can be operable for storing more than 13 wt% of Th at room temperature and 300 atm.
[0098] The flexible porous polymeric carbon sorbent can be operable for storing more than 15 wt% of Th at room temperature and 300 atm.
[0099] The flexible porous polymeric carbon sorbent can be operable for storing about 20 wt% of Th at 100°C and 100 atm.
[0100] The flexible porous polymeric carbon sorbent can be operable for storing more than 90 wt% of CTh at room temperature and 100 atm.
[0101] The flexible porous polymeric carbon sorbent can be operable for storing more than 150 wt% of CTh at room temperature and 200 atm.
[0102] The flexible porous polymeric carbon sorbent can be operable for storing more than 175 wt% of CTh at room temperature and 300 atm.
[0103] The flexible porous polymeric carbon sorbent can include nitrogen atoms.
[0104] In general, in another embodiment, the invention features a method that includes positioning a flexible porous polymeric carbon sorbent in a container that can contain a gas under pressure. The flexible porous polymeric carbon sorbent is operable for storing 4.5 wt% ftz at room temperature and 100 atm. The method further includes storing gas in the container. The container can store more of the gas at room temperature and 100 atm than in the container without the flexible porous polymeric carbon sorbent at the same conditions.
[0105] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0106] The flexible porous polymeric carbon sorbent can be independently: (a) operable to store at least 150 wt% of CO2 at room temperature and 50 atm; (b) operable to store at least 140 wt% of O2 at room temperature and 110 atm; and (c) operable to store at least 80 wt% of CH4 at room temperature and 100 atm.
[0107] The flexible porous polymeric carbon sorbent can include a polymer that has short range order and no long range order by powder X-ray diffraction (XRD).
[0108] The flexible porous polymeric carbon sorbent can include pores having an average pore size of between 2 A and 100 A.
[0109] The flexible porous polymeric carbon sorbent can include pores having an average pore size of between 5 A and 20 A.
[0110] The flexible porous polymeric carbon sorbent can store more than 4.5 wt% H2 at room temperature and at most 100 atm.
[0111] The flexible porous polymeric carbon sorbent can store more than 13 wt% H2 at room temperature and at most 200 atm.
[0112] The flexible porous polymeric carbon sorbent can store more than 15 wt% H2 at room
temperature and at most 300 atm.
[0113] The flexible porous polymeric carbon sorbent can store at least 8 wt% of Th at room temperature and at most 100 atm.
[0114] The flexible porous polymeric carbon sorbent can store at least 10 wt% of Th at room temperature and at most 100 atm.
[0115] The flexible porous polymeric carbon sorbent can store more than 175 wt% of CH4 at room temperature and at most 300 atm.
[0116] The flexible porous polymeric carbon sorbent can store more than 175 wt% of CH4 at room temperature and at most 275 atm.
[0117] The flexible porous polymeric carbon sorbent can store more than 150 wt% of CH4 at room temperature and at most 200 atm.
[0118] The flexible porous polymeric carbon sorbent can include nitrogen atoms.
[0119] In general, in another embodiment, the invention features a vehicle comprising an onboard hydrogen storage container. The container includes a flexible porous polymeric carbon sorbent. The container includes at least 4.5 wt% of Th at a pressure below 300 atm at room temperature.
[0120] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0121] The container can include at least 4.5 wt% of H2 at a pressure below 200 atm at room temperature.
[0122] The container can include at least 4.5 wt% of H2 at a pressure below 100 atm at room temperature.
[0123] The container can include at least 5.5 wt% of H2 at a pressure below 300 atm at room
temperature.
[0124] The container can include at least 5.5 wt% of Th at a pressure below 200 atm at room temperature.
[0125] The container can include at least 5.5 wt% of Th at a pressure below 100 atm at room temperature.
[0126] The container can include at least 8 wt% of Th at a pressure below 300 atm at room temperature.
[0127] The container can include at least 8 wt% of Th at a pressure below 200 atm at room temperature.
[0128] The container can include at least 8 wt% of Th at a pressure below 100 atm at room temperature.
[0129] The container can include comprises at least 13 wt% of Th at a pressure below 300 atm at room temperature.
[0130] The container can include at least 13 wt% of Th at a pressure below 200 atm at room temperature.
[0131] The container can include at least 15 wt% of Th at a pressure below 300 atm at room temperature.
[0132] In general, in another embodiment, the invention features a method that includes selecting a flexible porous polymeric carbon sorbent. The flexible porous polymeric carbon sorbent is operable for storing 4.5 wt% Th at room temperature and 100 atm. The method further includes utilizing the flexible porous polymeric carbon sorbent to capture a gas.
[0133] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0134] The gas can be selected from the group consisting of Th, CO2, O2, methane, natural gas, and combinations thereof.
[0135] In general, in another embodiment, the invention features a method of synthesizing a porous polymeric carbon sorbent. The method includes the step of mixing a polymer with an additive to form a mixture. The polymer has a polymer chain order comprising long range order and short range order as detected by powder X-ray diffraction (XRD). The additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal oxalate, metal acetate, metal acetylacetonoate, and mixtures thereof. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The chemical activation results in a loss of the long range order and the short range order of the polymer as detected by powder XRD such that the porous polymeric carbon sorbent material is a rigid porous polymeric carbon sorbent. The porous polymeric carbon sorbent is operable for direct air capturing of at least 4 wt% of CO2 at room temperature and 4 mbar partial pressure of CO2 in air.
[0136] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0137] The polymer can be selected from a group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), and combinations thereof. [0138] The polymer can be selected from a group consisting of polyvinyl chloride (PVC), nylon, melamine mixed with HDPE, melamine mixed with LDPE, melamine mixed with PP, melamine-formaldehyde resins, polyethylene imine (PEI), PEI mixed with HDPE, polyurethanes (PU), polyacrylonitrile, (PAN), and polyethyleneteraphthalte (PET) and mixtures therefrom.
[0139] The polymer can include a plastic from a waste plastic source.
[0140] The step of heating can be performed at a temperature that is between 550°C and 700°C. [0141] The step of heating can be performed at a temperature that is between 575°C and 600°C. [0142] The activation reagent can be an acetate salt of potassium or calcium.
[0143] The activation reagent can be potassium acetate.
[0144] The activation reagent can be calcium acetate.
[0145] The weight ratio of the additive and the polymer in the mixture can be between 0.5:1 and 5:1.
[0146] The weight ratio of the additive and the polymer in the mixture can be between 2: 1 and 4:1.
[0147] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 200°C.
[0148] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 75°C.
[0149] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 100°C.
[0150] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
[0151] The polymer can include nitrogen atoms.
[0152] The porous polymeric carbon sorbent can be operable for direct air capturing of at least 6 wt% of CO2 at 4 mbar partial pressure of CO2 in air.
[0153] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 110°C.
[0154] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
[0155] The method can further include controlling pore size of the porous polymeric carbon sorbent by controlling pressure during the step of heating.
[0156] The step of heating the mixture can be performed at a near vacuum pressure of at least 0.01 bars.
[0157] In general, in another embodiment, the invention features a rigid porous polymeric carbon sorbent that is operable to direct air capture more than 4 wt% CO2 at room temperature and 4 mbar partial pressure of CO2 in air.
[0158] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0159] The rigid porous polymeric carbon sorbent can include a polymer that has no polymeric long range order and no polymeric short range order detectable by powder X-ray diffraction (XRD).
[0160] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 200°C.
[0161] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 75°C.
[0162] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 100°C.
[0163] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
[0164] The porous polymeric carbon sorbent can include nitrogen atoms.
[0165] The porous polymeric carbon sorbent can be operable for direct air capturing of at least 6 wt% of CO2 at 4 mbar partial pressure of CO2 in air.
[0166] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 110°C.
[0167] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
[0168] In general, in another embodiment, the invention features a method that includes selecting a rigid porous polymeric carbon sorbent. The porous polymeric carbon sorbent is operable for direct air capturing of at least 4 wt% of CO2 at room temperature and 4 mbar partial pressure of CO2 in air. The method further includes utilizing the rigid porous polymeric carbon sorbent to direct air capture more than 4 wt% CO2.
[0169] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0170] The method can further include releasing the direct air captured CO2 by heating the rigid porous polymeric carbon sorbent.
[0171] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 200°C.
[0172] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 75°C.
[0173] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 100°C.
[0174] The method can further include releasing the direct air captured CO2 by applying a vacuum to the rigid porous polymeric carbon sorbent.
[0175] The method can further comprising repeating the direct air capture and release of the CO2 by the porous polymeric carbon sorbent for at least 1000 cycles.
[0176] The porous polymeric carbon sorbent can include nitrogen atoms.
[0177] The porous polymeric carbon sorbent can be operable for direct air capturing of at least 6 wt% of CO2 at 4 mbar partial pressure of CO2 in air.
[0178] The rigid porous polymeric carbon sorbent can be utilized to direct air capture more than 6 wt% CO2 at 4 mbar partial pressure of CO2 in air.
[0179] The method can further include releasing the direct air captured CO2 by heating the rigid porous polymeric carbon sorbent.
[0180] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 200°C.
[0181] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 100°C.
[0182] The method can further include releasing the direct air captured CO2 by applying a vacuum to the rigid porous polymeric carbon sorbent.
[0183] In general, another embodiment, the invention features a method of synthesizing a porous carbon material. The method includes mixing a plastic with an additive. The method further includes heating the plastic and the additive to a temperature in the range of 400°C and 700°C to form the porous carbon material.
[0184] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0185] The plastic can be selected from a group consisting of HDPE, LDPE, PP, and combinations thereof.
[0186] The plastic can be selected from a group consisting of polyvinyl chloride (PVC), nylon. [0187] The plastic can be a polymer that includes nitrogen atoms.
[0188] The polymer that includes nitrogen atoms can be a polymer selected from a group consisting of melamine mixed with HDPE, melamine mixed with LDPE, melamine mixed with PP, melamine mixed with other polymers, melamine-formaldehyde resins, urea, polyethylene imine (PEI), PEI mixed with HDPE, PEI mixed with other polymers, polyurethanes (PU), polyacrylonitrile, (PAN), and polyethyleneteraphthalte (PET).
[0189] The plastic can be from a mixture of plastic sources.
[0190] The plastic can be from at least one waste plastic source.
[0191] The plastic can be from plastic waste.
[0192] The plastic can be selected from a group consisting of plastics made from chain grow polymerization, vinyl polymerization, step growth polymerization, condensation polymerization, living polymerization, radical polymerization, cationic polymerization, anionic polymerization, synthetic polymers, naturally occurring polymers, and combinations thereof.
[0193] The additive can be potassium acetate.
[0194] The additive can be calcium acetate.
[0195] The additive can be selected from a group consisting of potassium hydroxide, potassium oxalate, potassium acetate, potassium acetylacetonoate, and mixtures thereof.
[0196] The additive can be selected from a group consisting of metal hydroxide, metal oxalate, metal acetate, metal acetylacetonoate, and mixtures thereof.
[0197] The metal can be selected from a group consisting of Groups 1A, 2A, and 3A of the Periodic Table, transitional metal, lanthanide, and actinide.
[0198] The metal can be an alkali-metal.
[0199] The metal can be lithium or cesium.
[0200] The additive can be a salt.
[0201] The weight ratio of the additive to the plastic can be between 0.5:1 and 5:1.
[0202] The weight ratio can be between 1 : 1 and 2:1.
[0203] The temperature of heating the plastic and the additive can be greater than about 550°C. The porous carbon material can be a mechanically rigid porous carbon material.
[0204] The temperature of heating the plastic and the additive can be at most about 550°C. The porous carbon material can be a mechanically flexible porous carbon material.
[0205] The temperature of heating the plastic and the additive can be at most about 500°C. [0206] The temperature of heating the plastic and the additive can be at most about 550°C. The porous carbon material can be a flexible porous carbon material.
[0207] The temperature of heating the plastic and the additive can be at most about 500°C. [0208] The diffraction bands in the X-ray diffraction analysis of the porous carbon material that are characteristic of the plastic can be remaining in the porous carbon material.
[0209] The method of any of any of the above-described methods can further include controlling pore size of the flexible porous carbon material by controlling the temperature and pressure of the method.
[0210] The method of any of the above-described methods can further include controlling pore size of the porous carbon material by controlling the temperature and pressure of the method. [0211] In general, in another embodiment, the invention features a porous carbon material that is made according to the method of one or more of the above-described methods.
[0212] In general, in another embodiment, the invention features a porous carbon material that can capture more than 15 wt% CO2 at about 25°C and at 1 atm.
[0213] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0214] The porous carbon material can release the CO2 when heating the porous carbon
material to less than 125°C.
[0215] The porous carbon material can release the CO2 when heating the porous carbon material to less than 100°C.
[0216] The porous carbon material can release the CO2 when heating the porous carbon material to about 70-75°C.
[0217] The porous carbon material of any of the above-described porous carbon materials and can be made according to any of the above-described methods.
[0218] The porous carbon material can capture more than 15 wt% CO2 at about 25°C and at a pressure less than 5 atm.
[0219] The porous carbon material can capture more than 18 wt% CO2 at about 25°C and at a pressure less than 5 atm.
[0220] The porous carbon material can capture more than 100 wt% CO2 at about 25°C and at a pressure less than 300 atm.
[0221] The porous carbon material can capture more than 100 wt% CO2 at about 25°C and at a pressure less than 50 atm.
[0222] The porous carbon material can capture up to 190 wt% CO2 at about 25°C and at a pressure less than 50 atm.
[0223] The porous carbon material can be any of the above-described porous carbon materials. The porous carbon material can be a flexible porous carbon material made by any of the above- described methods.
[0224] In general, in another embodiment, the invention features a method that includes selecting a porous carbon material selected from any of the above-described porous carbon materials. The method further includes utilizing the porous carbon material to capture more than 15 wt% CO2.
[0225] Implementations of the invention can include one or more of the following features,
which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0226] More than 15 wt% CO2 can be captured at about 25°C and at a pressure less than 5 atm.
[0227] More than 18 wt% CO2 can be captured at about 25°C and at a pressure less than 5 atm.
[0228] More than 25 wt% CO2 can be captured at about 25°C and at a pressure less than 5 atm.
[0229] More than 100 wt% CO2 can be captured at about 25°C and at a pressure less than 300 atm.
[0230] More than 100 wt% CO2 can be captured at about 25°C and at a pressure less than 50 atm.
[0231] More than 190 wt% CO2 can be captured at about 25°C and at a pressure less than 50 atm.
[0232] The CO2 can be captured from flue gas.
[0233] The CO2 can be captured from a post-combustion process.
[0234] The CO2 can be captured from a pre-combustion process.
[0235] The pre-combustion process can include separation of the CO2 from natural gas.
[0236] The CO2 can be being selectively captured over the capture of N2.
[0237] The porous carbon material can be made according to the method of one or more of the above-described methods.
[0238] The porous carbon material can be a flexible porous material.
[0239] The flexible porous carbon material can be made according to the method of one or more of the above-described methods.
[0240] In general, in another embodiment, the invention features a flexible porous carbon material made according to the method of one or more of the above-described methods. The flexible porous carbon materials has tunable pore sizes based upon the gas used, the
temperature, the pressure, or a mixture of those conditions.
[0241] In general, in another embodiment, the invention features a porous carbon material that can capture O2, methane, or natural gas at about 25°C and at 100 atm.
[0242] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0243] The porous carbon material can be a flexible porous material.
[0244] The flexible porous carbon material can be made according to the method of one or more of the above-described methods.
[0245] In general, in another embodiment, the invention features a storage container that includes a flexible porous carbon material. The storage container can store more H2, O2, methane, or natural gas at about 25°C and about 100 atm to 300 atm than in the storage container without the flexible porous carbon material at the same conditions.
[0246] In general, in another embodiment, the invention features a method that includes feeding plastic bags into a chopper. The method further includes sheering the plastic bags in the chopper to produce flakes. The method further includes utilizing a sizing mesh to allow flakes below a pre-determined size to flow out of the chopper. The flakes that are above the pre-determined size remain in the chopper for further sheering. The method further includes gathering the flakes in a receptacle.
[0247] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0248] The flakes can be utilized in a flash graphene process.
[0249] The flakes can be utilized in method to synthesize a porous carbon material.
[0250] In general, in another embodiment, the invention features a method of synthesizing a porous polymeric carbon sorbent. The method includes the step of mixing a polymer with an additive to form a mixture. The additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal carbonate, metal bicarbonate, metal oxalate, metal acetate, metal acetyl acetonoate, and mixtures thereof. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The porous polymeric carbon sorbent has a surface area between 400 m2/g and 2000 m2/g, an average pore size between 2 A and 100 A, a total pore volume between 0.2 cm3/g and 0.9 cm3/g, a microporosity greater than 60%, and an atomic percentage of carbon atoms greater than 75%. The polymeric carbon sorbent is a gas capturing sorbent.
[0251] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0252] The porous polymeric carbon sorbent can be a rigid porous polymeric carbon sorbent. [0253] The average pore size can be between 5 A and 20 A.
[0254] The average pore size can be between 6 A and 10 A.
[0255] The surface area can be between 500 m2/g and 2000 m2/g.
[0256] The surface area can be between 500 m2/g and 1100 m2/g.
[0257] The total pore volume can be between 0.25 cm3/g and 0.7 cm3/g.
[0258] The total pore volume can be between 0.25 cm3/g and 0.6 cm3/g.
[0259] The microporosity can be greater than 70%.
[0260] The microporosity can be greater than 80%.
[0261] The atomic percentage of carbon atoms can be greater than 85%.
[0262] The atomic percentage of carbon atoms can be greater than 88%.
[0263] The porous polymeric carbon sorbent can be operable for capturing CO2 at a pressure between 0.01 atm to 5 atm. The polymeric carbon sorbent can have a selectivity for capturing CO2 over N2 at least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0264] The gas can be CO2.
[0265] The porous polymeric carbon sorbent can have a density between 1.3 g/cc and 1.8 g/cc. [0266] The polymer can be selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), nylon, polyamine, polyurethane, polyamide, polyacrylonitrile, melamine resin, polyamic acid, styrene, Jeffamine, and combinations thereof.
[0267] The polymer can include HDPE.
[0268] The polymer can include nylon.
[0269] The polymer can be selected from the group consisting of polyvinyl chloride (PVC), nylon, melamine mixed with HDPE, melamine mixed with LDPE, melamine mixed with PP, melamine-formaldehyde resins, polyethylene imine (PEI), PEI mixed with HDPE, polyurethanes (PU), polyacrylonitrile (PAN), and polyethyleneteraphthalte (PET) and mixtures therefrom.
[0270] The polymer can include nitrogen atoms.
[0271] The polymeric carbon sorbent can have a selectivity for capturing CO2 over N2 at least 300:1 in 0.15 bar of CO2 in 0.85 barN2 at 23°C.
[0272] The polymer can include a plastic from a waste plastic source.
[0273] The step of heating can be performed at a temperature that is between 550°C and 700°C. [0274] The step of heating can be performed at a temperature that is between 575°C and 600°C. [0275] The activation reagent can be an acetate, carbonate, bicarbonate, or hydroxide salt of potassium or calcium.
[0276] The method of Claim 25, wherein the salt of potassium or calcium can be an acetate, carbonate, or bicarbonate.
[0277] The activation reagent can be potassium acetate.
[0278] The activation reagent can be calcium acetate.
[0279] The activation reagent can include a metal selected from the group consisting of Group 1A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
[0280] The activation reagent can include a metal hydroxide.
[0281] The activation reagent can include a metal oxalate.
[0282] The activation reagent can be a metal carbonate.
[0283] The activation reagent can include a metal bicarbonate.
[0284] The activation reagent can include a metal acetate.
[0285] The activation reagent can include a metal acetylacetonoate.
[0286] The weight ratio of the additive and the polymer in the mixture can be between 0.5:1 and 5:1.
[0287] The weight ratio of the additive and the polymer in the mixture can be between 2: 1 and 4:1.
[0288] The porous polymeric carbon sorbent can be operable for capturing CO2 from a post combustion CO2 emission outlet gas.
[0289] The post-combustion CO2 emission outlet gas can be a flue gas.
[0290] The porous polymeric carbon sorbent can be operable for capturing more than 15 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at 1 atm.
[0291] The porous polymeric carbon sorbent can be operable for releasing at least a portion of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 110°C at 1 atm.
[0292] The porous polymeric carbon sorbent can be operable for releasing at least 50% of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 110°C at 1 atm.
[0293] The porous polymeric carbon sorbent can be operable for releasing substantially all of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 110°C at 1 atm.
[0294] The porous polymeric carbon sorbent can be operable for releasing at least a portion of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 75°C at 1 atm.
[0295] The porous polymeric carbon sorbent can be operable for releasing at least 50% of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 75°C at 1 atm.
[0296] The porous polymeric carbon sorbent can be operable for releasing substantially all of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 75°C at 1 atm.
[0297] The porous polymeric carbon sorbent can be operable for capturing more than 18 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at most 5 atm.
[0298] The porous polymeric carbon sorbent can be operable for capturing more than 100 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at most 300 atm.
[0299] The method can further include controlling pore size of the porous polymeric carbon sorbent by controlling pressure during the step of heating.
[0300] The step of heating the mixture can be performed at a near vacuum pressure of at least 0.01 bars.
[0301] The step of heating the mixture can be performed at a near vacuum pressure of between
0.01 bars and 0.1 bars.
[0302] The method can further include the step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound or another modifier.
[0303] The treating of the porous polymer carbon sorbent can include soaking the porous polymer carbon sorbent utilizing the ammonium compound.
[0304] The ammonium compound can be ammonium hydroxide.
[0305] The step of modifying the porous polymeric carbon sorbent by the ammonium compound treatment can increase the surface area and/or the microporosity of the porous polymeric carbon sorbent.
[0306] The method can further include the step of modifying the porous polymeric carbon sorbent by treating with hydrazine or hydrazine hydrate.
[0307] The method can further include the step of modifying the porous polymeric carbon sorbent by treating with hydroxylamine or hydroxylamine hydrochloride.
[0308] The method can further include washing the porous polymeric carbon sorbent.
[0309] The deionized water can be used to wash the porous polymeric carbon sorbent.
[0310] The method can further include filtering the porous polymeric carbon sorbent after the step of washing.
[0311] The method can further include activating the porous polymeric carbon sorbent.
[0312] The step of activating the porous polymeric carbon sorbent can include heating to an activation temperature under an activation pressure to remove water and/or other compounds from binding sites. The step of activating the porous polymeric carbon sorbent can include flushing the porous polymeric carbon sorbent with a flush gas at a flushing pressure.
[0313] The method can further include maintaining vacuum pressures at or above a threshold pressure to prevent pore collapse of pores of the porous polymeric carbon sorbent.
[0314] The activation temperature can be in a range between 120°C and 150°C.
[0315] The heating to the activation temperature can be for 1 to 12 hours.
[0316] The activation pressure can be in a range between 1 and 100 bars.
[0317] The flush gas can be Th.
[0318] The flush gas can be at a temperature around 25°C.
[0319] The threshold pressure can be selected a group consisting of above 0.005 bar, above 0.006 bar, above 0.007 bar, above 0.008 bar, above 0.009 bar and above 0.01 bar.
[0320] The threshold pressure can be near vacuum pressure.
[0321] The step of activation can be not reducing density of the porous polymeric carbon sorbent by more than 0.4 g/cc.
[0322] The step of activation can be not reducing density of the porous polymeric carbon sorbent by more than 30%.
[0323] The step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound, hydrazine, hydrazine hydrate hydroxylamine, and/or hydroxylamine hydrochloride can occur after the step of activation. [0324] In general, in another embodiment, the invention features a method of synthesizing a porous polymeric carbon sorbent. The method includes the step of mixing a polymer with an additive to form a mixture. The additive is an activation reagent that is a metal carbon-and- oxygen containing compound. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The porous polymeric carbon sorbent has a surface area between 400 m2/g and 2000 m2/g, an average pore size between 2 A and 100 A, a total pore volume between 0.2 cm3/g and 0.9 cm3/g, a microporosity greater than 60%, and an atomic percentage of carbon atoms greater than 75%. The polymeric carbon sorbent is a gas capturing sorbent.
[0325] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all
additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0326] The metal carbon-and-oxygen containing compound can have between 1 to 6 carbon atoms.
[0327] The metal carbon-and-oxygen containing compound can have between 1 and 2 carbon atoms.
[0328] The metal carbon-and-oxygen containing compound can have 2 carbon atoms.
[0329] The metal carbon-and-oxygen containing compound can have between one and two carboxyl ate groups.
[0330] The metal carbon-and-oxygen containing compound can include a metal oxocarbon or a metal carboxyl ate.
[0331] The activation reagent can include a metal selected from the group consisting of Group 1 A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
[0332] The surface area can be between 500 m2/g and 2000 m2/g.
[0333] The surface area can be between 500 m2/g and 1100 m2/g.
[0334] The total pore volume can be between 0.25 cm3/g and 0.7 cm3/g.
[0335] The total pore volume can be between 0.25 cm3/g and 0.6 cm3/g.
[0336] The microporosity can be greater than 70%.
[0337] The microporosity can be greater than 80%.
[0338] The atomic percentage of carbon atoms can be greater than 85%.
[0339] The atomic percentage of carbon atoms can be greater than 88%.
[0340] In general, in another embodiment, the invention features a porous polymeric carbon sorbent that has a surface area between 400 m2/g and 2000 m2/g, an average pore size between 2 A and 100 A, a total pore volume between 0.2 cm3/g and 0.9 cm3/g, a microporosity greater
than 60%, and an atomic percentage of carbon atoms greater than 75%. The porous polymeric carbon sorbent is a gas capturing sorbent.
[0341] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0342] The porous polymeric carbon sorbent can be a rigid porous polymeric carbon sorbent. [0343] The average pore size can be between 5 A and 20 A.
[0344] The average pore size can be between 6 A and 10 A.
[0345] The surface area can be between 500 m2/g and 2000 m2/g.
[0346] The surface area can be between 500 m2/g and 1100 m2/g.
[0347] The total pore volume can be between 0.25 cm3/g and 0.7 cm3/g.
[0348] The total pore volume can be between 0.25 cm3/g and 0.6 cm3/g.
[0349] The microporosity can be greater than 70%.
[0350] The microporosity can be greater than 80%.
[0351] The atomic percentage of carbon atoms can be greater than 85%.
[0352] The atomic percentage of carbon atoms can be greater than 88%.
[0353] The porous polymeric carbon sorbent can be operable to capture more than 15 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at 1 atm. The porous polymeric carbon sorbent can have a selectivity for capturing CO2 overN2 at least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0354] The gas can be CO2.
[0355] The porous polymeric carbon sorbent can include a polymer that has no polymeric long range order and no polymeric short range order detectable by powder X-ray diffraction.
[0356] The porous polymeric carbon sorbent can be operable for releasing the CO2 captured
from post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 110°C at about 1 atm pressure.
[0357] The porous polymeric carbon sorbent can be operable for releasing the CO2 captured from post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 75°C at about 1 atm pressure.
[0358] The porous polymeric carbon sorbent can be operable for capturing more than 18 wt% CO2 from post-combustion CO2 emission outlet gas at 25°C and at 5 atm.
[0359] The porous polymeric carbon sorbent can be operable for capturing more than 100 wt% CO2 from post-combustion CO2 emission outlet gas at 25°C and at 300 atm.
[0360] The porous polymeric carbon sorbent can include nitrogen atoms.
[0361] The polymeric carbon sorbent can have a selectivity for capturing CO2 over N2 of at least 250:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0362] In general, in another embodiment, the invention features a method that includes selecting a porous polymeric carbon sorbent. The porous polymeric carbon sorbent has a surface area between 400 m2/g and 2000 m2/g, an average pore size between 2 A and 100 A, a total pore volume between 0.2 cm3/g and 0.9 cm3/g, a microporosity greater than 60%, and an atomic percentage of carbon atoms greater than 75%. The method further includes utilizing the porous polymeric carbon sorbent to capture more than 15 wt% CO2 from post-combustion CO2 emission outlet gas.
[0363] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0364] The porous polymeric carbon sorbent can be a rigid porous polymeric carbon sorbent. [0365] The average pore size can be between 5 A and 20 A.
[0366] The average pore size can be between 6 A and 10 A.
[0367] The surface area can be between 500 m2/g and 1100 m2/g.
[0368] The surface area can be between 500 m2/g and 1100 m2/g.
[0369] The total pore volume can be between 0.25 cm3/g and 0.7 cm3/g.
[0370] The total pore volume can be between 0.25 cm3/g and 0.6 cm3/g.
[0371] The microporosity can be greater than 70%.
[0372] The microporosity can be greater than 80%.
[0373] The atomic percentage of carbon atoms can be greater than 85%.
[0374] The atomic percentage of carbon atoms can be greater than 88%.
[0375] The porous polymeric carbon sorbent can have a selectivity for capturing CO2 over N2 least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0376] The post-combustion CO2 emission outlet gas can be a flue gas.
[0377] The CO2 can be captured from post-combustion CO2 emission outlet gas at atmospheric pressure.
[0378] The CO2 can be captured from post-combustion CO2 emission outlet gas at room temperature at around 25°C.
[0379] The porous polymeric carbon sorbent can be utilized to capture more than 18 wt% CO2 from post-combustion CO2 emission outlet gas.
[0380] The CO2 can be captured from post-combustion CO2 emission outlet gas at a pressure that is at most 5 atm.
[0381] The porous polymeric carbon sorbent can be utilized to capture more than 100 wt% CO2 from post-combustion CO2 emission outlet gas.
[0382] The CO2 can be captured from post-combustion CO2 emission outlet gas at a pressure that is at most 300 atm.
[0383] The method can further include releasing the CO2 captured from post-combustion CO2
emission outlet by heating the porous polymeric carbon sorbent.
[0384] The CO2 can be released by heating the porous polymeric carbon sorbent to at most 110°C.
[0385] The CO2 can be released by heating the porous polymeric carbon sorbent to at most 75°C.
[0386] The method can further include repeating the capture and release of the CO2 by the porous polymeric carbon sorbent for at least 1000 cycles.
[0387] The method can further include repeating the capture and release of the CO2 by the porous polymeric carbon sorbent for at least 100,000 cycles.
[0388] The porous polymeric carbon sorbent can haved a selectivity for capturing CO2 over N2 of at least 70:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0389] The porous polymeric carbon sorbent can include nitrogen atoms.
[0390] The porous polymeric carbon sorbent can have a selectivity for capturing CO2 over N2 of at least 300:1 at least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
[0391] In general, in another embodiment, the invention features a method of synthesizing a flexible porous polymeric carbon sorbent. The method includes the step of mixing a polymer with an additive to form a mixture. The additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal carbonate, metal bicarbonate, metal oxalate, metal acetate, metal acetylacetonoate, and mixtures thereof. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The porous polymeric carbon sorbent has a first stiffness at room temperature. The porous polymeric carbon sorbent has a second stiffness at 100°C. The first stiffness is at least two times more than the second stiffness.
[0392] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all
additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0393] The first stiffness can be at least three times more than the second stiffness.
[0394] The first stiffness can be at least four times more than the second stiffness.
[0395] The first stiffness can be greater than 35 N/m. The second stiffness can be less than 10 N/m.
[0396] The sorbance of the flexible porous polymeric carbon sorbent at 100°C can be substantially greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
[0397] The sorbance of the flexible porous polymeric carbon sorbent at 100°C can be at least three times greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
[0398] The flexible porous polymeric carbon sorbent can be operable for storing 4.5 wt% Th at room temperature and 100 atm.
[0399] The polymer mixed with the additive can have a polymer chain order comprising long range order and short range order as detected by powder X-ray diffraction (XRD). The chemical activation can result in a loss of the long range order while maintaining short range order of the polymer as detected by powder XRD such that the porous polymeric carbon sorbent material is a flexible porous polymeric carbon sorbent
[0400] The flexible porous polymeric carbon sorbent gas can be operable for storing each of Th, CO2, O2, methane, natural gas, and combinations thereof.
[0401] The flexible porous polymeric carbon sorbent can be independently: operable to store at least 150 wt% of CO2 at room temperature and 50 atm; operable to store at least 140 wt% of O2 at room temperature and 110 atm; and operable to store at least 80 wt% of CTri at room temperature and 100 atm.
[0402] The polymer can be selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), nylon, polyamine, polyurethane, polyamide, polyacrylonitrile, melamine resin, polyamic acid, styrene, Jeffamine, and combinations thereof.
[0403] The polymer can include HDPE.
[0404] The polymer can include nylon.
[0405] The polymer can be selected from the group consisting of polyvinyl chloride (PVC), nylon, melamine with HDPE, melamine with LDPE, melamine with PP, melamine- formaldehyde resins, melamine resins, urea, polyurethanes (PEI), polyacrylonitrile, (PAN), polyethylene imine, polyethylene imine mixed with HDPE, and polyethyleneteraphthalte (PET) and mixtures therefrom.
[0406] The polymer can include nitrogen atoms.
[0407] The step of heating can performed at a temperature that is between 400°C and 525°C. [0408] The step of heating can be performed at a temperature that is between 475°C and 500°C. [0409] The activation reagent can be an acetate, carbonate, bicarbonate, or hydroxide salt of potassium or calcium.
[0410] The salt of potassium or calcium can be an acetate, carbonate, or bicarbonate.
[0411] The activation reagent can be potassium acetate.
[0412] The activation reagent can be calcium acetate.
[0413] The activation reagent can include a metal selected from the group consisting of Group 1 A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
[0414] The activation reagent can include a metal hydroxide.
[0415] The activation reagent can include a metal oxalate.
[0416] The activation reagent can include a metal carbonate.
[0417] The activation reagent can include a metal bicarbonate.
[0418] The activation reagent can include a metal acetate.
[0419] The activation reagent can include a metal acetylacetonoate.
[0420] The weight ratio of the additive and the polymer in the mixture can be between 0.5:1 and 5:1.
[0421] The weight ratio of the additive and the polymer in the mixture can be between 2: 1 and 4:1.
[0422] The flexible porous polymeric carbon sorbent can be operable for storing more than 5.5 wt% of Th at room temperature and 100 atm.
[0423] The flexible porous polymeric carbon sorbent can be operable for storing more than 8 wt% of Th at room temperature and 100 atm.
[0424] The flexible porous polymeric carbon sorbent can be operable for storing about 13 wt% of Th at room temperature and 200 atm.
[0425] The flexible porous polymeric carbon sorbent can be operable for storing about 15 wt% of Th at room temperature and 300 atm.
[0426] The flexible porous polymeric carbon sorbent can be operable for storing more than 80 wt% of CH4 at room temperature and 100 atm.
[0427] The flexible porous polymeric carbon sorbent can be operable for storing more than 150 wt% of CH4 at room temperature and 200 atm.
[0428] The flexible porous polymeric carbon sorbent can be operable for storing more than 175 wt% of CH4 at room temperature and 300 atm.
[0429] The flexible porous polymeric carbon sorbent can be operable for releasing the stored gas by lowering the pressure back to 1 atm.
[0430] The method can further include controlling pore size of the flexible porous polymeric carbon sorbent by controlling pressure during the step of heating.
[0431] The step of heating the mixture can be performed at a near vacuum pressure of at least 0.01 bars.
[0432] The step of heating the mixture can be performed at a near vacuum pressure of between 0.01 bars and 0.1 bars.
[0433] The method can further include the step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound.
[0434] The treating of the porous polymer carbon sorbent can include soaking the porous polymer carbon sorbent utilizing the ammonium compound.
[0435] The ammonium compound can be ammonium hydroxide.
[0436] The step of modifying the porous polymeric carbon sorbent by the ammonium compound treatment can increase surface area and/or microporosity of the porous polymeric carbon sorbent.
[0437] The method can further include the step of modifying the porous polymeric carbon sorbent by treating with hydrazine or hydrazine hydrate.
[0438] The method can further include the step of modifying the porous polymeric carbon sorbent by treating with hydroxylamine or hydroxylamine hydrochloride.
[0439] The method can further include washing the porous polymeric carbon sorbent.
[0440] Deionized water can be used to wash the porous polymeric carbon sorbent.
[0441] The method can further include filtering the porous polymeric carbon sorbent after the step of washing.
[0442] The method can further include activating the porous polymeric carbon sorbent.
[0443] The step of activating the porous polymeric carbon sorbent can include heating to an activation temperature under an activation pressure to remove water and/or other compounds from binding sites. The step of activating the porous polymeric carbon sorbent can include flushing the porous polymeric carbon sorbent with a flush gas at a flushing pressure.
[0444] The method can further include maintaining vacuum pressures at or above a threshold pressure to prevent pore collapse of pores of the porous polymeric carbon sorbent.
[0445] The activation temperature can be in a range between 120°C and 150°C.
[0446] The heating to the activation temperature can be for 1 to 12 hours.
[0447] The activation pressure can be in a range between 1 and 100 bars.
[0448] The flush gas can be Th.
[0449] The flush gas can be at a temperature around 25°C.
[0450] The threshold pressure can be selected a group consisting of above 0.005 bar, above 0.006 bar, above 0.007 bar, above 0.008 bar, above 0.009 bar and above 0.01 bar.
[0451] The threshold pressure can be near vacuum pressure.
[0452] The step of activation can be not reducing density of the porous polymeric carbon sorbent by more than 0.4 g/cc.
[0453] The step of activation can be not reducing density of the porous polymeric carbon sorbent by more than 30%.
[0454] The step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound, hydrazine, hydrazine hydrate hydroxylamine, and/or hydroxylamine hydrochloride can occur after the step of activation. [0455] In general, in another embodiment, the invention features a method of synthesizing a flexible porous polymeric carbon sorbent. The method includes the step of mixing a polymer with an additive to form a mixture. The additive is an activation reagent that is a metal carbon- and-oxygen containing compound. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The porous polymeric carbon sorbent has a first stiffness at room temperature. The porous polymeric carbon sorbent has a second stiffness at 100°C. The first stiffness is at least two times more than the second stiffness.
[0456] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0457] The metal carbon-and-oxygen containing compound can have between 1 to 6 carbon atoms.
[0458] The metal carbon-and-oxygen containing compound can have between 1 and 2 carbon atoms.
[0459] The metal carbon-and-oxygen containing compound can have 2 carbon atoms.
[0460] The metal carbon-and-oxygen containing compound can have between one and two carboxyl ate groups.
[0461] The metal carbon-and-oxygen containing compound can include a metal oxocarbon or a metal carboxyl ate.
[0462] The activation reagent can include a metal selected from the group consisting of Group 1 A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
[0463] In general, in another embodiment, the invention features a flexible porous polymeric carbon sorbent that is operable to store Th. The flexible porous polymeric carbon sorbent has a first stiffness at room temperature. The porous polymeric carbon sorbent has a second stiffness at 100°C. The first stiffness is at least two times more than the second stiffness. [0464] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention.
[0465] The first stiffness can be at three times more than the second stiffness.
[0466] The first stiffness can be at four times more than the second stiffness.
[0467] The first stiffness can be greater than 35 N/m. The second stiffness can be less than 10 N/m.
[0468] The flexible porous polymeric carbon sorbent can be operable for storing 4.5 wt% Th at room temperature and 100 atm.
[0469] The sorbance of the flexible porous polymeric carbon sorbent at 100°C can be substantially greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
[0470] The sorbance of the flexible porous polymeric carbon sorbent at 100°C can be at least three times greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
[0471] The flexible porous polymeric carbon sorbent can be independently: operable to store at least 150 wt% of CO2 at room temperature and 50 atm; operable to store at least 140 wt% of O2 at room temperature and 110 atm; and operable to store at least 80 wt% of CTri at room temperature and 100 atm.
[0472] The flexible porous polymeric carbon sorbent can include a polymer that has short range order and no long range order by powder X-ray diffraction (XRD).
[0473] The flexible porous polymeric carbon sorbent can include pores having an average pore size of between 2 A and 100 A.
[0474] The flexible porous polymeric carbon sorbent can include pores having an average pore size of between 2 A and 20 A.
[0475] The flexible porous polymeric carbon sorbent can be operable for storing more than 5.5 wt% of H2 at room temperature and 100 atm.
[0476] The flexible porous polymeric carbon sorbent can be operable for storing more than 8 wt% of H2 at room temperature and 100 atm.
[0477] The flexible porous polymeric carbon sorbent can be operable for storing more than 13 wt% of Th at room temperature and 200 atm.
[0478] The flexible porous polymeric carbon sorbent can be operable for storing more than 13 wt% of Th at room temperature and 300 atm.
[0479] The flexible porous polymeric carbon sorbent can be operable for storing more than 15 wt% of Th at room temperature and 300 atm.
[0480] The flexible porous polymeric carbon sorbent can be operable for storing about 20 wt% of Th at 100°C and 100 atm.
[0481] The flexible porous polymeric carbon sorbent can be operable for storing more than 90 wt% of CH4 at room temperature and 100 atm.
[0482] The flexible porous polymeric carbon sorbent can be operable for storing more than 150 wt% of CH4 at room temperature and 200 atm.
[0483] The flexible porous polymeric carbon sorbent can be operable for storing more than 175 wt% of CH4 at room temperature and 300 atm.
[0484] The flexible porous polymeric carbon sorbent include nitrogen atoms.
[0485] In general, in another embodiment, the invention features a method that includes positioning a flexible porous polymeric carbon sorbent in a container that can contain a gas under pressure. The flexible porous polymeric carbon sorbent has a first stiffness at room temperature. The porous polymeric carbon sorbent has a second stiffness at 100°C. The first stiffness is at least two times more than the second stiffness. The method further includes storing gas in the container. The flexible porous polymeric carbon sorbent sorbs some the gas in the container.
[0486] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any
combination in implementations of the invention:
[0487] The first stiffness can be at three times more than the second stiffness.
[0488] The first stiffness can be at four times more than the second stiffness.
[0489] The first stiffness can be greater than 35 N/m. The second stiffness can be less than 10 N/m.
[0490] The temperature of the flexible porous polymeric carbon sorbent can increase during the step of storing the gas.
[0491] The temperature of the flexible porous polymeric carbon sorbent can increase by at least 20°C during the step of storing the gas.
[0492] The temperature of the flexible porous polymeric carbon sorbent can increase from below 80°C to above 100°C during the step of storing the gas.
[0493] The container can store more of the gas at room temperature and 100 atm than in the container without the flexible porous polymeric carbon sorbent at the same conditions.
[0494] The flexible porous polymeric carbon sorbent can be operable for storing 4.5 wt% Th at room temperature and 100 atm.
[0495] The flexible porous polymeric carbon sorbent can be independently: operable to store at least 150 wt% of CO2 at room temperature and 50 atm; operable to store at least 140 wt% of O2 at room temperature and 110 atm; and operable to store at least 80 wt% of CTri at room temperature and 100 atm.
[0496] The flexible porous polymeric carbon sorbent can include a polymer that has short range order and no long range order by powder X-ray diffraction (XRD).
[0497] The flexible porous polymeric carbon sorbent can include pores having an average pore size of between 2 A and 100 A.
[0498] The flexible porous polymeric carbon sorbent can include pores having an average pore size of between 5 A and 20 A.
[0499] The flexible porous polymeric carbon sorbent can store more than 4.5 wt% Th at room temperature and at most 100 atm.
[0500] The flexible porous polymeric carbon sorbent can store more than 13 wt% Th at room temperature and at most 200 atm.
[0501] The flexible porous polymeric carbon sorbent can store more than 15 wt% Th at room temperature and at most 300 atm.
[0502] The flexible porous polymeric carbon sorbent can store at least 8 wt% of Th at room temperature and at most 100 atm.
[0503] The flexible porous polymeric carbon sorbent can store at least 10 wt% of Th at room temperature and at most 100 atm.
[0504] The flexible porous polymeric carbon sorbent can store more than 175 wt% of CH4 at room temperature and at most 300 atm.
[0505] The flexible porous polymeric carbon sorbent can store more than 175 wt% of CH4 at room temperature and at most 275 atm.
[0506] The flexible porous polymeric carbon sorbent can store more than 150 wt% of CH4 at room temperature and at most 200 atm.
[0507] The flexible porous polymeric carbon sorbent can include nitrogen atoms.
[0508] In general, in another embodiment, the invention features a vehicle that includes an onboard hydrogen storage container. The container includes a flexible porous polymeric carbon sorbent. The flexible porous polymeric carbon sorbent has a first stiffness at room temperature. The flexible porous polymeric carbon sorbent has a second stiffness at 100°C. The first stiffness is at least two times more than the second stiffness. The container includes Th with at least some of the Th sorbed by the flexible flexible porous polymeric carbon sorbent.
[0509] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all
additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0510] The first stiffness can be at three times more than the second stiffness.
[0511] The first stiffness can be at four times more than the second stiffness.
[0512] The first stiffness can be greater than 35 N/m. The second stiffness can be less than 10 N/m.
[0513] The sorbance of the flexible porous polymeric carbon sorbent at 100°C can be substantially greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
[0514] The sorbance of the flexible porous polymeric carbon sorbent at 100°C can be at least three times greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
[0515] The container can include at least 4.5 wt% of Th at a pressure below 300 atm at room temperature.
[0516] The container can include at least 4.5 wt% of Th at a pressure below 200 atm at room temperature.
[0517] The container can include at least 4.5 wt% of Th at a pressure below 100 atm at room temperature.
[0518] The container can inlcude at least 5.5 wt% of Th at a pressure below 300 atm at room temperature.
[0519] The container can include at least 5.5 wt% of Th at a pressure below 200 atm at room temperature.
[0520] The container can include at least 5.5 wt% of Th at a pressure below 100 atm at room temperature.
[0521] The container can include at least 8 wt% of Th at a pressure below 300 atm at room
temperature.
[0522] The container can include at least 8 wt% of Th at a pressure below 200 atm at room temperature.
[0523] The container can include at least 8 wt% of Th at a pressure below 100 atm at room temperature.
[0524] The container can include at least 13 wt% of Th at a pressure below 300 atm at room temperature.
[0525] The container can include at least 13 wt% of Th at a pressure below 200 atm at room temperature.
[0526] The container can include at least 15 wt% of Th at a pressure below 300 atm at room temperature.
[0527] In general, in another embodiment, the invention features a method that includes selecting a flexible porous polymeric carbon sorbent. The flexible porous polymeric carbon sorbent has a first stiffness at room temperature. The flexible porous polymeric carbon sorbent has a second stiffness at 100°C. The first stiffness is at least two times more than the second stiffness. The method further includes utilizing the flexible porous polymeric carbon sorbent to capture a gas.
[0528] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0529] The first stiffness can be at three times more than the second stiffness.
[0530] The first stiffness can be at four times more than the second stiffness.
[0531] The first stiffness can be greater than 35 N/m. The second stiffness can be less than 10
N/m.
[0532] The sorbance of the flexible porous polymeric carbon sorbent at 100°C can be substantially greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
[0533] The sorbance of the flexible porous polymeric carbon sorbent at 100°C can be at least three times greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
[0534] The temperature of the flexible porous polymeric carbon sorbent can increase during the step of utilizing the flexible porous polymeric carbon sorbent to capture the gas.
[0535] The temperature of the flexible porous polymeric carbon sorbent can increase by at least 20°C during the step of utilizing the flexible porous polymeric carbon sorbent to capture the gas.
[0536] The temperature of the flexible porous polymeric carbon sorbent can increase from below 80°C to above 100°C during the step of storing the gas.
[0537] The flexible porous polymeric carbon sorbent can be operable for storing 4.5 wt% Th at room temperature and 100 atm.
[0538] The gas can be selected from the group consisting of Th, CO2, O2, methane, natural gas, and combinations thereof.
[0539] In general, in another embodiment, the invention features a method of synthesizing a porous polymeric carbon sorbent. The method includes the step of mixing a polymer with an additive to form a mixture. The additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal oxalate, metal carbonate, metal bicarbonate, metal acetate, metal acetyl acetonoate, and mixtures thereof. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The porous polymeric carbon sorbent has a surface area between 400 m2/g and 2000 m2/g, an average pore size between 2 A and 100 A, a total pore volume between 0.2 cm3/g and 0.9
cm3/g, a microporosity greater than 60%, and an atomic percentage of carbon atoms greater than 75%. The porous polymeric carbon sorbent is operable for direct air capturing of CO2. [0540] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0541] The porous polymeric carbon sorbent can be a rigid porous polymeric carbon sorbent. [0542] The average pore size can be between 5 A and 20 A.
[0543] The average pore size can be between 6 A and 10 A.
[0544] The surface area can be between 500 m2/g and 2000 m2/g.
[0545] The surface area can be between 500 m2/g and 1100 m2/g.
[0546] The total pore volume can be between 0.25 cm3/g and 0.7 cm3/g.
[0547] The total pore volume can be between 0.25 cm3/g and 0.6 cm3/g.
[0548] The microporosity can be greater than 70%.
[0549] The microporosity can be greater than 80%.
[0550] The atomic percentage of carbon atoms can be greater than 85%.
[0551] The atomic percentage of carbon atoms can be greater than 88%.
[0552] The porous polymeric carbon sorbent can be operable for direct air capturing of at least 4 wt% of CO2 at room temperature and 4 mbar partial pressure of CO2 in air.
[0553] The polymer can be selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), nylon, polyamine, polyurethane, polyamide, polyacrylonitrile, melamine resin, polyamic acid, styrene, Jeffamine, and combinations thereof.
[0554] The polymer can include HDPE.
[0555] The polymer can inlcude nylon.
[0556] The polymer can be selected from the group consisting of polyvinyl chloride (PVC), nylon, melamine mixed with HDPE, melamine mixed with LDPE, melamine mixed with PP, melamine-formaldehyde resins, polyethylene imine (PEI), PEI mixed with HDPE, polyurethanes (PU), polyacrylonitrile, (PAN), and polyethyleneteraphthalte (PET) and mixtures therefrom.
[0557] The polymer can include a plastic from a waste plastic source.
[0558] The step of heating can be performed at a temperature that is between 550°C and 700°C. [0559] The step of heating can be performed at a temperature that is between 575°C and 600°C. [0560] The activation reagent can be an acetate salt of potassium or calcium.
[0561] The activation reagent can be potassium acetate.
[0562] The activation reagent can be calcium acetate.
[0563] The activation reagent can include a metal selected from the group consisting of Group 1 A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
[0564] The activation reagent can include a metal hydroxide.
[0565] The activation reagent can include a metal oxalate.
[0566] The activation reagent can include a metal carbonate.
[0567] The activation reagent can include a metal bicarbonate.
[0568] The activation reagent can include a metal acetate.
[0569] The activation reagent can include a metal acetylacetonoate.
[0570] The weight ratio of the additive and the polymer in the mixture can be between 0.5:1 and 5:1.
[0571] The weight ratio of the additive and the polymer in the mixture can be between 2: 1 and 4:1.
[0572] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air
captured by heating the porous polymeric carbon sorbent to at most 200°C.
[0573] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 75°C.
[0574] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 100°C.
[0575] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
[0576] The polymer can include nitrogen atoms.
[0577] The porous polymeric carbon sorbent can be operable for direct air capturing of at least 6 wt% of CO2 at 4 mbar partial pressure of CO2 in air.
[0578] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 110°C.
[0579] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
[0580] The method can further include controlling pore size of the porous polymeric carbon sorbent by controlling pressure during the step of heating.
[0581] The step of heating the mixture can be performed at a near vacuum pressure of at least 0.01 bars.
[0582] The step of heating the mixture can be performed at a near vacuum pressure of between 0.01 bars and 0.1 bars.
[0583] The method can further include the step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound.
[0584] The treating of the porous polymer carbon sorbent can include soaking the porous polymer carbon sorbent utilizing the ammonium compound.
[0585] The ammonium compound can be ammonium hydroxide.
[0586] The step of modifying the porous polymeric carbon sorbent by the ammonium compound treatment can increase the surface area and/or the microporosity of the porous polymeric carbon sorbent.
[0587] The method can further include the step of modifying the porous polymeric carbon sorbent by treating with hydrazine or hydrazine hydrate.
[0588] The method can further comprising the step of modifying the porous polymeric carbon sorbent by treating with hydroxylamine or hydroxylamine hydrochloride.
[0589] The method can further comprising washing the porous polymeric carbon sorbent. [0590] Deionized water can be used to wash the porous polymeric carbon sorbent.
[0591] The method can further include filtering the porous polymeric carbon sorbent after the step of washing.
[0592] The method can further include activating the porous polymeric carbon sorbent.
[0593] The step of activating the porous polymeric carbon sorbent can include heating to an activation temperature under an activation pressure to remove water and/or other compounds from binding sites. The step of activating the porous polymeric carbon sorbent can include flushing the porous polymeric carbon sorbent with a flush gas at a flushing pressure.
[0594] The method can further include maintaining vacuum pressures at or above a threshold pressure to prevent pore collapse of pores of the porous polymeric carbon sorbent.
[0595] The activation temperature can be in a range between 120°C and 150°C.
[0596] The heating to the activation temperature can be for 1 to 12 hours.
[0597] The activation pressure can be in a range between 1 and 100 bars.
[0598] The flush gas can be Th.
[0599] The flush gas can be at a temperature around 25°C.
[0600] The threshold pressure can be selected a group consisting of above 0.005 bar, above 0.006 bar, above 0.007 bar, above 0.008 bar, above 0.009 bar and above 0.01 bar.
[0601] The threshold pressure can be near vacuum pressure.
[0602] The step of activation can be not reducing density of the porous polymeric carbon sorbent by more than 0.4 g/cc.
[0603] The step of activation can be not reducing density of the porous polymeric carbon sorbent by more than 30%.
[0604] The step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound, hydrazine, hydrazine hydrate hydroxylamine, and/or hydroxylamine hydrochloride can occur after the step of activation. [0605] In general, in another embodiment, the invention features a method of synthesizing a porous polymeric carbon sorbent. The method includes the step of mixing a polymer with an additive to form a mixture. The additive is an activation reagent a metal carbon-and-oxygen containing compound. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The porous polymeric carbon sorbent has a surface area between 400 m2/g and 2000 m2/g, an average pore size between 2 A and 100 A, a total pore volume between 0.2 cm3/g and 0.9 cm3/g, a microporosity greater than 60%, and an atomic percentage of carbon atoms greater than 75%. The porous polymeric carbon sorbent is operable for direct air capturing of CO2.
[0606] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0607] The metal carbon-and-oxygen containing compound can have between 1 to 6 carbon atoms.
[0608] The metal carbon-and-oxygen containing compound can have between 1 and 2 carbon atoms.
[0609] The metal carbon-and-oxygen containing compound can have 2 carbon atoms.
[0610] The metal carbon-and-oxygen containing compound can have between one and two carboxyl ate groups.
[0611] The metal carbon-and-oxygen containing compound can include a metal oxocarbon or a metal carboxyl ate.
[0612] The activation reagent can include a metal selected from the group consisting of Group 1 A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
[0613] The surface area can be between 500 m2/g and 2000 m2/g.
[0614] The surface area can be between 500 m2/g and 1100 m2/g.
[0615] The total pore volume can be between 0.25 cm3/g and 0.7 cm3/g.
[0616] The total pore volume can be between 0.25 cm3/g and 0.6 cm3/g.
[0617] The microporosity can be greater than 70%.
[0618] The microporosity can be greater than 80%.
[0619] The atomic percentage of carbon atoms can be greater than 85%.
[0620] The atomic percentage of carbon atoms can be greater than 88%.
[0621] In general, in another embodiment, the invention features a porous polymeric carbon sorbent. The porous polymeric carbon sorbent has a surface area between 400 m2/g and 2000 m2/g, average pore size between 2 A and 100 A, a total pore volume between 0.2 cm3/g and 0.9 cm3/g, a microporosity greater than 60%, and an atomic percentage of carbon atoms greater than 75%. The porous polymeric carbon sorbent is operable to direct air capture CO2.
[0622] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0623] The porous polymeric carbon sorbent can be a rigid porous polymeric carbon sorbent. [0624] The average pore size can be between 5 A and 20 A.
[0625] The average pore size can be between 6 A and 10 A.
[0626] The surface area can be between 500 m2/g and 2000 m2/g.
[0627] The surface area can be between 500 m2/g and 1100 m2/g.
[0628] The total pore volume can be between 0.25 cm3/g and 0.7 cm3/g.
[0629] The total pore volume can be between 0.25 cm3/g and 0.6 cm3/g.
[0630] The microporosity can be greater than 70%.
[0631] The microporosity can be greater than 80%.
[0632] The atomic percentage of carbon atoms can be greater than 85%.
[0633] The atomic percentage of carbon atoms can be greater than 88%.
[0634] The porous polymeric carbon sorbent can be operable to direct air capture more than 4 wt% CO2 at room temperature and 4 mbar partial pressure of CO2 in air.
[0635] The porous polymeric carbon sorbent can include a polymer that has no polymeric long range order and no polymeric short range order detectable by powder X-ray diffraction (XRD). [0636] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 200°C.
[0637] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 75°C.
[0638] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 100°C.
[0639] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
[0640] The porous polymeric carbon sorbent can include nitrogen atoms.
[0641] The porous polymeric carbon sorbent can be operable for direct air capturing of at least
6 wt% of CO2 at 4 mbar partial pressure of CO2 in air.
[0642] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 110°C.
[0643] The porous polymeric carbon sorbent can be operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
[0644] In general, in another embodiment, the invention features a method that includes selecting a porous polymeric carbon sorbent. The porous polymeric carbon sorbent has a surface area between 400 m2/g and 2000 m2/g, an average pore size between 2 A and 100 A, a total pore volume between 0.2 cm3/g and 0.9 cm3/g, a microporosity greater than 60%, and an atomic percentage of carbon atoms greater than 75%. The method further includes utilizing the porous polymeric carbon sorbent to direct air capture CO2.
[0645] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0646] The porous polymeric carbon sorbent can be a rigid porous polymeric carbon sorbent. [0647] The average pore size can be between 5 A and 20 A.
[0648] The average pore size can be between 6 A and 10 A.
[0649] The surface area can be between 500 m2/g and 2000 m2/g.
[0650] The surface area can be between 500 m2/g and 1100 m2/g.
[0651] The total pore volume can be between 0.25 cm3/g and 0.7 cm3/g.
[0652] The total pore volume can be between 0.25 cm3/g and 0.6 cm3/g.
[0653] The microporosity can be greater than 70%.
[0654] The microporosity can be greater than 80%.
[0655] The atomic percentage of carbon atoms can be greater than 85%.
[0656] The atomic percentage of carbon atoms can be greater than 88%.
[0657] The porous polymeric carbon sorbent can be operable for direct air capturing of at least 4 wt% of CO2 at room temperature and 4 mbar partial pressure of CO2 in air.
[0658] The step of utilizing the porous polymeric carbon sorbent can include utilizing the porous polymeric carbon sorbent to direct air capture more than 4 wt% CO2.
[0659] The method can further include releasing the direct air captured CO2 by heating the rigid porous polymeric carbon sorbent.
[0660] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 200°C.
[0661] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 75°C.
[0662] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 100°C.
[0663] The method can further include releasing the direct air captured CO2 by applying a vacuum to the rigid porous polymeric carbon sorbent.
[0664] The method can further include repeating the direct air capture and release of the CO2 by the porous polymeric carbon sorbent for at least 1000 cycles.
[0665] The porous polymeric carbon sorbent can include nitrogen atoms.
[0666] The porous polymeric carbon sorbent can be operable for direct air capturing of at least 6 wt% of CO2 at 4 mbar partial pressure of CO2 in air.
[0667] The porous polymeric carbon sorbent can be utilized to direct air capture more than 6 wt% CO2 at 4 mbar partial pressure of CO2 in air.
[0668] The method can further include releasing the direct air captured CO2 by heating the porous polymeric carbon sorbent.
[0669] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at
most 200°C.
[0670] The CO2 can be released by heating the rigid porous polymeric carbon sorbent to at most 100°C.
[0671] The method can further include releasing the direct air captured CO2 by applying a vacuum to the porous polymeric carbon sorbent.
[0672] The method can simultaneously capture and convert the CO2 to ethylene.
[0673] In general, in another embodiment, the invention features a method of synthesizing a porous polymeric carbon sorbent. The method includes the step ofmixing a polymer with an additive to form a mixture, wherein the additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal carbonate, metal bicarbonate, metal oxalate, metal acetate, metal acetylacetonoate, and mixtures thereof. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The method further includes the step of modifying the porous polymeric carbon sorbent by treating the porous polymeric carbon sorbent with a nitrogen compound to increase the surface area and/or microporosity of the porous polymeric carbon sorbent. The nitrogen compound is selected from the group consisting of an ammonium compound, hydrazine, hydrazine hydrate, hydroxylamine, and hydroxylamine hydrochloride.
[0674] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0675] The porous polymeric carbon sorbent can be a rigid porous polymeric carbon sorbent. [0676] The porous polymeric carbon sorbent can be a flexible porous polymeric carbon sorbent.
[0677] The polymer can be plastic waste.
[0678] The plastic waste can be selected from the group consisting of packaging plastic, textile plastic and construction plastic.
[0679] The treating of the porous polymer carbon sorbent can include soaking the porous polymer carbon sorbent utilizing the nitrogen compound.
[0680] The nitrogen compound can be an ammonium compound [0681] The ammonium compound can be ammonium hydroxide.
[0682] The nitrogen compound can be hydrazine or hydrazine hydrate.
[0683] The nitrogen compound can be hydroxylamine or hydroxylamine hydrochloride. [0684] The method can further include activating the sorbent after heating and before modifying.
[0685] In general, in another embodiment, the invention features a method of synthesizing a porous polymeric carbon sorbent. The method includes mixing a polymer with an activation reagent to form a mixture. The method further includes heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The method further includes removing sorbates from the porous polymeric carbon sorbent under partial vacuum above a threshold pressure to maintain open pore structures of the porous polymeric carbon sorbent.
[0686] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0687] The heating can be conducted at a temperature between 400°C and 525°C and the threshold pressure is 0.01 bar.
[0688] The activation reagent can be a metal carbon-and-oxygen compound.
[0689] The method can further include modifying the porous polymeric carbon sorbent
produced by contacting with a modifier compound to increase the surface area and/or microporosity of the porous polymeric carbon sorbent.
[0690] The modifier can include comprises a nitrogen-containing compound.
[0691] The nitrogen-containing compound can be selected from the group consisting of an ammonium compound, a hydrazine compound, and a hydroxylamine compound.
[0692] The threshold pressure canbe sufficiently high to avoid collapse of the open pore structures of the porous polymeric carbon sorbent that would decrease a gas sorption capacity of the porous polymeric carbon sorbent by more than an amount selected from the group consisting of 10%, 15%, 20%, 25%, 30% and 35%.
[0693] In general, in another embodiment, the invention features a method of synthesizing a porous polymeric carbon sorbent. The method includes the step of determining a target characteristic of the porous polymeric carbon sorbet. The target characteristic is selected from the group consisting of surface area, average pore size, total pore volume, microporosity, nitrogen content, regeneration temperature, and combinations thereof. The method further includes the step of mixing a polymer with an additive to form the mixture. The additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal carbonate, metal bicarbonate, metal oxalate, metal acetate, metal acetylacetonoate, and mixtures thereof. The method further includes the step of heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation. The method further includes the step of tuning the mixing step and/or the heating step to form porous polymeric carbon sorbent having the target characteristic.
[0694] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0695] The tuning step can include selecting the polymer based upon the target characteristic. [0696] The tuning step can include N-doping the polymer.
[0697] The polymer can be selected a group consisting of nylon, polyamine, polyurethane, polyamide, polyacrylonitrile, melamine resin, polyamic acid, styrene, Jeffamine,, and combinations thereof.
[0698] The polymer can include HDPE.
[0699] The polymer can include nylon.
[0700] The porous polymeric carbon sorbent can have a CO2 uptake of more than 20% at 1 bar and more than 5% at 0.1 bar.
[0701] In general, in another embodiment, the invention features a method that includes selecting a pressure vessel that includes a flexible porous polymeric carbon sorbent. The flexible porous polymeric carbon sorbent is at a first temperature in the pressure vessel. The flexible porous polymeric carbon sorbent is capable of sorbing a gas. The method further includes flowing the gas into the pressure vessel at a velocity that results in the temperature inside the pressure vessel to increase. The increase of temperature within the pressure vessel increases the temperature of the flexible porous polymeric carbon sorbent to a second temperature. The sorbance of flexible porous polymeric carbon sorbent at the second temperature is greater than the sorbance of the flexible porous polymeric carbon sorbent at the first temperature.
[0702] Implementations of the invention can include one or more of the following features, which following features set forth in the subsequent paragraphs below (as well as any and all additional applicable features described throughout this application) can be combined in any combination in implementations of the invention:
[0703] The second temperature can be at least 20°C greater than the first temperature.
[0704] The first temperature can be below 80°C and the second temperature is above 100°C.
[0705] The stiffness of the flexible porous polymeric carbon sorbent can substantially decrease between the first temperature and the second temperature.
[0706] The stiffness of the flexible porous polymeric carbon sorbent at the second temperature can be less than 50% of the stiffness of the flexible porous polymeric carbon sorbent at room temperature
[0707] The stiffness of the flexible porous polymeric carbon sorbent at the second temperature can be less than 33% of the stiffness of the flexible porous polymeric carbon sorbent at room temperature.
[0708] The stiffness of the flexible porous polymeric carbon sorbent at the second temperature can be less than 25% of the stiffness of the flexible porous polymeric carbon sorbent at room temperature.
[0709] The container can store more of the gas at room temperature and 100 atm than in the pressure vessel without the flexible porous polymeric carbon sorbent at the same conditions.
BRIEF DESCRIPTION OF THE DRAWINGS [0710] FIG. 1A is a flow diagram of a generalized steam cracker process (known in the prior art) for ethylene production from natural gas and oil.
[0711] FIG. IB is a flow diagram of a coal to olefin process (known in the prior art) for ethylene production from coal.
[0712] FIG. 2 is a scheme of the post-combustion process and the CO2 capture unit.
[0713] FIG. 3 illustrates an embodiment of the present invention showing a one-step activation method of plastic waste to produce a solid sorbent with high CO2 capacity at room temperature and pressure along with monomer and oligomer that can be recycled or used for other chemical applications.
[0714] FIG. 4 is the CO2 sorption isotherm of activated polypropylene at 700°C using potassium oxalate (2,l-A-PP-700) and potassium acetate (2,l-A-PP-700) at 2:1 base: plastic
ratio.
[0715] FIG. 5A is the CO2 sorption isotherms of HDPE activated at 500°C (2,1-A-HDPE- 500), 600°C (2, 1 - A-HDPE-600), 700°C (2,l-A-HDPE-700), 800°C (2,l-A-HDPE-800) at 2:1 acetate: plastic ratio.
[0716] FIG. 5B is the CO2 sorption isotherms of HDPE samples activated at different acetate: polymer ratio of 2:1 (2,1 -A-HDPE-600), 1:1 (1,1 -A-HDPE-600), and 1:2 (1,2- A-HDPE-600) all activated at 600°C.
[0717] FIG. 6A is nitrogen sorption isotherm for 2,1 -A-HDPE-600 at 77 K.
[0718] FIG. 6B is the DFT-cal culated pore size distribution for FIG. 6A.
[0719] FIG. 6C is the X-ray diffraction pattern of 2,1 -A-HDPE-600 after washing with DI water.
[0720] FIG. 6D is survey scan XPS of 2,1 -A-HDPE-600.
[0721] FIG. 6E is the high resolution XPS Cls spectrum of 2,1 -A-HDPE-600.
[0722] FIGS. 7A-7C are ESEM images of 2,1 -A-HDPE-600 showing the highly porous structure of the sorbent.
[0723] FIG. 8A is the XRD pattern of unwashed 2,1 -A-HDPE-600 showing peaks characteristic of K2CO3 (stars).
[0724] FIG. 8B is the TGA of potassium acetate demonstrating mass losses consistent with proposed decomposition mechanism; an initial -10% mass reduction is due to dehydration of hygroscopic potassium acetate.
[0725] FIG. 8C is TGA profile of potassium acetate/HDPE (2:1) mixture showing the mass change and the rate of mass change as a function of temperature.
[0726] FIG. 9A is the CO2 sorption isotherm LDPE and PP all activated at 600°C and 2: 1 ratio of potassium acetate to plastic.
[0727] FIG. 9B is CO2 sorption isotherm of sorbent synthesized from a PP and HDPE mixture.
[0728] FIG. 9C is a CO2 sorption isotherm of sorbent synthesized from wax activated at 600°C and 2: 1 various ratios of potassium acetate to wax.
[0729] FIG. 10A is the CO2 and N2 sorption isotherms of activated 2,l-HDPE-600.
[0730] FIG. 10B is a graph of the calculated ideal adsorbed solution theory (IAST) selectivity of 2, 1 - A-HDPE-600.
[0731] FIGS. 11A is CO2 sorption isotherm of 2,l-HDPE-600 at 25 °C and 20 °C.
[0732] FIGS. 11B is a graph of calculated isosteric heat of adsorption of 2,l-HDPE-600 showing an overall decrease of the heat of adsorption as the surface of the sorbent gets occupied by CO2 molecules.
[0733] FIG. llC is a graph of CO2 release from the pores of 2,l-PP-600 after saturation as function of temperature showing full release of CO2 at 70-75 °C.
[0734] FIG. 11D is a graph showing 10-cycles of adsorption and desorption of 2,l-HDPE-600 showing high stability in performance over the cycles.
[0735] FIG. HE is a graph of CO2 release from the pores of 2,1 -wax-600 and 4,1 -wax 600 after saturation as function of temperature showing full release of CO2 at 80°C.
[0736]
[0737] FIG. 12A is the MS of the evolved gases during potassium acetate /HOPE (2: 1) mixture pyrolysis at 600°C showing ethylene formation as a gas.
[0738] FIG. 12B is the FTIR spectrum of the waxes formed as a byproduct of potassium acetate /HOPE (2:1) mixture pyrolysis at 600°C showing typical hydrocarbon profile.
[0739] FIG. 13A is the CO2 sorption isotherm of activated 2,l-HDPE-500 compared to 2,1- HDPE-600.
[0740] FIG. 13B is nitrogen sorption isotherm for 2,l-A-HDPE-500 at 77 K.
[0741] FIG. 13C is the DFT-calculated pore size distribution for FIG. 13B.
[0742] FIG. 13D is the XRD patterns of 2,l-HDPE-500 compared to and 2,l-HDPE-600 the
starting HDPE after twin-screw blending with potassium acetate.
[0743] FIG. 13E is the FTIR spectra of the CO2 captured within the pores of 2,l-HDPE-500 in a high pressure IR cell.
[0744] FIG. 14A is the CO2 sorption isotherm of activated 2,l-HDPE-500 at 20°C, 25°C, 40°C, and 100°C.
[0745] FIG. 14B is CO2 sorption isotherm of activated 2,l-HDPE-500 at different temperatures showing the change in density as the temperature and pressure increase.
[0746] FIG. 15 is a scheme of the scale-up reactor to get porous carbon and high value chemicals from plastic waste.
[0747] FIG. 16A is the hydrogen sorption isotherm 2,l-HDPE-500 at 25°C.
[0748] FIG. 16B is the hydrogen uptakes of 2,l-HDPE-500 when cycled 8 times where the uptake increases with each cycle as the sorbed water is purged out.
[0749] FIG. 16C is hydrogen uptakes at different temperatures at 100 bar, showing a sharp increase in hydrogen uptake at 96°C to 100°C.
[0750] FIG. 16D is a hydrogen sorption isotherm of 2,l-HDPE-500 at 100°C.
[0751] FIG. 17 is methane and methane mixed gas sorption isotherm of 2,l-HDPE-500 at 25°C.
[0752] FIG. 18 is the oxygen sorption isotherm 2,l-HDPE-500 at 25°C showing an uptake of 155 wt% at 125 bar.
[0753] FIG. 19 is a scheme of N-doping of mesoporous sorbent to get microporous carbon. [0754] FIGS. 20A-20B are CO2 sorption isotherms of N-doped sorbent at low and high pressure, respectively.
[0755] FIG. 20C shows CO2 isotherm of NH + exchanged 4,l-HDPE-600.
[0756] FIG. 21A is the TGA-DSC profile of 2,l-HDPE-500 showing a glass transition temperature around 96 °C.
[0757] FIG. 21B is the CO2 sorption isotherms of 2,1-HDPE pyrolized at 600°C and 500°C. [0758] FIG. 21C is the CO2 sorption isotherms of 2,l-HDPE-500 and 2,l-HDPE-600,
[0759] FIG. 22 is the CO2 sorption isotherm of 2,l-HDPE-500 after subjecting the sorbent to 0.01 bar and then 0.005 bar showing the catastrophic destruction of the material at this small pretreatment pressure declination.
[0760] FIG. 23 is a schematic of the pressure control manifold installed on the Rubotherm gravimetric uptake measurement system in order to monitor the precise pressure on the sample during the evacuation pre-treatment.
[0761] FIG. 24 is a digital picture of the actual pressure control manifold with valve labeling as installed on the Rubotherm gravimetric uptake system.
[0762] FIG. 25 is an alternative schematic for the pressure control manifold made of stainless steel.
[0763] FIG. 26 is an illustration of an embodiment of a system and method for converting plastic bags into flakes.
[0764] FIG. 27 is an illustration of a second embodiment of a system and method for converting plastic bags into flakes.
[0765] FIG. 28A is the C02 isotherms of rigid sorbents synthesized at different potassium acetate/HDPE ratios.
[0766] FIG. 28B is the gravimetric and volumetric CO2 isotherms of 4,l-HDPE-600 showing that the two are in close agreement.
[0767] FIG. 29A is the CO2 uptake and change in pressure overtime of a rigid sorbent of the present invention demonstrating the fast kinetics of the uptake.
[0768] FIG. 29B is the CO2 capacity change with time upon subjecting a rigid sorbent to CO2. [0769] FIG. 29C is the CO2 and N2 sorption isotherms for 4,l-HDPE-600.
[0770] FIG. 29D is the N2 and N2 + CO2 sorption isotherms for 4, l-HDPE-600.
[0771] FIG. 29E are ideal adsorbed solution theory (IAST) selectivity for 4,l-HDPE-600. [0772] FIG. 30A is the TGA/DSC of HDPE and potassium acetate mixture showing weight loss and heat required to synthesize rigid sorbent of the present invention.
[0773] FIG. 30B is the heat loss and heat gain over time during the pyrolysis of HDPE+ acetate to synthesize rigid sorbent of the present invention.
[0774] FIG. 31A is the isosteric heat versus uptake of CO2 for 4,l-HDPE-600.
[0775] FIG. 31B is the CO2 capacity of 4, l-HDPE-600 upon the first, second, and third times. [0776] FIG. 31C is the CO2 capacity of 4, l-HDPE-600 upon cycling 110 times. The small decline occurs only because there was fast cycling in this test so complete CO2 was not extracted between the runs.
[0777] FIG. 32 shows the change in the micropores (< lnm in radius) percentage upon changing the potassium acetate/HDPE ratio.
[0778] FIG. 33 is the CO2 isotherm of plastic obtained from mixed post-consumer waste plastic.
[0779] FIG. 34A is the CO2 isotherm of sorbent activated with calcium acetate in replacement of potassium acetate.
[0780] FIG. 34B are XRD pattern of unwashed sorbent activated with calcium acetate.
[0781] FIG. 35 is the CO2 isotherm of N-doped sorbent by the addition of polyethyleneimine. [0782] FIGS. 36A-36B are, respectively, the survey XPS scan and high resolution N Is XPS of the N-doped sorbent.
[0783] FIG. 37 are ideal sorbed solution theory (IAST) selectivity of the sorbent.
[0784] FIGS. 38A-38B are CO2 sorption isotherm of 1,1-polyamic acid and 1,1 -nylon acid, respectively.
[0785] FIG. 39 is isosteric heat of adsorption and regeneration temperature of the N-doped sorbent.
[0786] FIGS. 40A-40B are, respectively, the gravimetric and volumetric Hz isotherm of 2,1- HDPE-500.
[0787] FIG. 41 is the H2 isotherm of 2,l-HDPE-500.
[0788] FIG. 42 is CH isotherm of 2,l-HDPE-500.
[0789] FIGS. 43A-43B are the Eh isotherm of 2,l-HDPE-500 at room temperature.
[0790] FIGS. 43C-43D are the H2 isotherm of 2,l-HDPE-500 at 100°C.
[0791] FIG. 44A is the CH isotherm of 2,l-HDPE-500.
[0792] FIG. 44B is the 02 isotherm of 2,l-HDPE-500.
[0793] FIG. 44C is the isotherm of 2,l-HDPE-500 for interchanged gases (C02, H2, 02, and CH ).
[0794] FIGS. 45A-45B are the change in heat observed during Eh cycling.
[0795] FIG. 46A is the methane C02 isotherm of different sorbent in very low pressure. [0796] FIGS. 46B-46C are the C02 isotherm in very low pressure.
[0797] FIGS. 47A-47B are atomic force microscopy (AFM) performed using normal force (FN = 400 nN) at different temperatures on sorbent 2,l-HDPE-500.
[0798] FIGS. 48A-48C are Raman spectra of 2,l-HDPE-500 at different temperature.
[0799] FIGS. 48D-48E are the fullwidth-half maximum of the D-band observed upon heating and cooling, respectively.
[0800] FIGS. 49A-49C shows characterizations of sorbents. FIG. 49A shows N2 sorption isotherms at 77K of sorbents synthesized at different KOAc:HDPE ratios and prepared at different activation temperatures. FIG. 49B shows pore size distribution of sorbents synthesized at different temperature showing larger pores formation at higher temperatures. FIG. 49C shows XRD of 4,l-HDPE-600 showing an amorphous carbon-like pattern.
[0801] FIGS. 50A-50D show images of sorbents. FIG. 50A is an ESEM image of 4,1-HDPE- 600 showing the highly porous structure of the amorphous carbon product. FIG. 50B is an
ESEM image of 4,l-HDPE-600 showing the porous structure. FIGS. 50C-50D are TEM images of 4,l-HDPE-400 showing amorphous carbon morphology.
[0802] FIGS. 51A-51D show CO2 sorption capacities of sorbents. FIG. 51A shows gravimetric CO2 sorption isotherm of 4,l-HDPE-600. FIG. 51B shows gravimetric CO2 capacity of activated HDPE sorbent synthesized at 600 °C with different KOAc:HDPE ratios. FIG. 51C shows gravimetric CO2 capacity of activated HDPE synthesized at different temperatures with a KOAc:HDPE ratio = 4:1. FIG. 51D shows gravimetric CO2 capacity sorbent synthesized using different plastics (KOAc:plastic ratio = 4:1).
[0803] FIG. 52 shows gravimetric CO2 sorption isotherms of sorbents prepared at different KOAc:HDPE ratios and different temperatures.
[0804] FIG. 53 shows gravimetric CO2 isotherms of 4,l-HDPE-600 and 4,l-HDPE-700 at 25°C, showing improved uptake at high pressure with 4,l-HDPE-700 compared to 4,1-HDPE- 600.
[0805] FIG. 54A shows gravimetric CO2 sorption isotherms of sorbents prepared from different activated plastics.
[0806] FIG. 54B shows volumetric CO2 sorption isotherms of sorbents prepared from different activated plastics.
[0807] FIGS. 55A-55D show pyrolysis mechanism of the sorbent. FIG. 55A is the TGA thermogram of KOAc + HDPE (25 °C/min, nitrogen) showing the different stages of pyrolysis. FIG. 55B is the mass spectrum of the evolved gases during sorbent synthesis of 4,1-HDPE- 600. FIG. 55C is the unwashed adsorbent XRD spectrum showing peaks characteristic of K2CO3. FIG. 55D is the literature survey of the activation temperature versus the uptake of some reported sorbents.
[0808] FIG. 56 shows a CO2 sorption isotherm of waxes.
[0809] FIG. 57 shows gravimetric CO2 and N2 isotherm of the 4,l-HDPE-600.
[0810] FIGS. 58A-58D show CO2 capture from flue gas. FIG. 58A shows the calculated IAST selectivity of 4,l-HDPE-600 showing high selectivity at low pressure. FIG. 58B shows the breakthrough curve for 4,l-HDPE-600 showing the separation of CO2 from flue gas. FIG. 58C shows the isosteric heat of adsorption of 4,l-HDPE-600. FIG. 58D shows the adsorption isobar showing the change of CO2 uptake upon heating with full regeneration at 70°C.
[0811] FIGS. 59A-59B show CO2 uptake of 4,l-HDPE-600 against time.
[0812] FIG. 60 shows a schematic of a CO2 capture/regeneration system in which CO2 is captured and released without the need of an external heating source.
[0813] FIGS. 61A-61I are the chemical structures of polymers that can be used in the synthesis processes of the present invention.
[0814] FIGS. 62A-62F show characteristics relating to the sorbents made from different N- containing plastics. FIG. 62A shows TGA of the different N-containing plastics. FIG. 62B shows XRD of the sorbents. FIG. 62C shows overlayed N2 sorption isotherm of the sorbents showing type I isotherm for all. FIG. 62D-6E shows DFT pore size distribution of the sorbents (with FIG. 62E being a magnified portion of FIG. 62D). FIG. 62F shows high resolution NS1 XPS of the sorbent.
[0815] FIG. 63 shows volumetric CO2 isotherm of nylon sorbent activated using different activation reagents.
[0816] FIGS. 64A-64B shows, respectively, volumetric and gravimetric CO2 sorption isotherms of the different N-containing plastics.
[0817] FIG. 64C shows correlation between the uptake and micropores of the different N- containing plastics.
[0818] FIG. 65A-65B shows N2 sorption isotherms of 4,l-HDPE-600 before and after NH4OH treatment.
[0819] FIG. 65C shows DFT pore size distribution of 4,l-HDPE-600 before and after NH4OH
treatment.
[0820] FIGS. 66A-66B show volumetric CO2 isotherm of HDPE and Nylon sorbent.
DETAILED DESCRIPTION
[0821] The present invention relates to porous polymeric carbon sorbents for CO2, H2, and other gases, and methods of making and using same.
[0822] For instance, in some embodiments, the present invention relates to a cost-effective way to process plastic waste (such as, for example, waste plastic milk jugs, which are high density polyethylene, HDPE) to produce value added chemicals and products that can capture >17 wt% CO2 at room temperature and 1 atm. Such processes easily release the captured CO2 at 70°C and are reversible in this capture and release cycling. Plastic waste is an example starting material that can be used to produce porous polymeric carbon sorbents that have various properties and can be used in particular gas sorption applications, as will be described in further detail below.
Synthesis Processes
[0823] Embodiments of the present invention encompass an alternative approach to plastic pyrolysis of the prior art, which alternative approach results in obtaining a porous carbon that has high CO2 capture capacity. The developed approach also results in thermal cracking of the polymer, yielding the typical chemicals and fuels that are usually produced with the conventional pyrolysis including monomers and oligomers. One advantage of this technology over conventional pyrolysis is the elimination of an unusable char by simply adding potassium acetate (or other metal salt, such as an alkali-metal salt) to the process. The process produces a high surface area carbonaceous residue that is an effective CO2 sorbent. This addresses two enormous environmental issues, namely the reuse of waste plastics and the capture of post combustion or pre-combustion CO2 from a single new technological approach.
[0824] In embodiments of the present invention, thermal cracking of polymers and plastic
waste is used to emit chemicals including monomers, oligomers and high surface porous carbon. While thermal cracking of plastic waste is known in the prior art, the prior art processes do not produce the porous carbon like obtained using embodiments of the present invention when cracking the plastic waste over potassium acetate and/or other potassium salt additives like potassium hydroxide, potassium oxalate, potassium acetylacetonoate, etc. In lieu of (or in addition to) such additives, the additives include other metal hydroxides, metal oxalates, metal acetates, metal acetylacetonoates, and mixtures thereof (including those in which the metal is one or more of Group 1 A, 2A, and 3A from the periodic table, transitional metals, lanthanide, and actinide). A particular good one is calcium acetate.
[0825] The porous carbon can be used as a CO2 sorbent while it has a much higher sorbing affinity to CO2 than to N2, thus making it useful to even capture CO2 from flue gas, such as the evolved CO2 from a power plant stack (such as the scheme of the post-combustion process and C02 capture unit shown in FIG. 2) and from gases from other post-combustion CO2 emission outlets. As used herein, the term “sorbing” includes physisorbing (noncovalent), chemisorbing (covalent), adsorbing (within), and absorbing (on the surface). The term “sorb” and “capture” are also used interchangeably herein. Here, “atm” is used interchangeably with “bar”. While other metal salts (such as alkali-metal salts and calcium acetate) can be utilized in the present invention, embodiments utilizing potassium salts will be described in more detail herein. [0826] Since the cracking temperature is maintained below 700°C (and typically below 600°C, and even more typically at or below 500°C), the potassium in the additive {i.e., the potassium salt) does not reduce to potassium metal. So, there is little, if any, risk of generating H2 gas with ignition upon washing with water to remove the remaining additive after the cracking process. Hence, this has an additional benefit of lessening production costs.
[0827] In embodiments of the present invention the same porous carbon generated via the process can also sorb H2 gas. A goal is to make a material that is both dense (i.e., density ~1
g/cc) and can sorb 5.5 wt% Eb at room temperature and 100 atm of pressure. In this invention, the carbon materials have a density greater than 1.5 g/cc and even 1.7 g/cc. So unlike an aerogel which is too low density and therefore voluminous to be easily used in mobile tanks, the carbon material here, though porous, is high density so low in overall volume. The material porous carbon made using embodiments of the present invention captures ~7 wt% to 8 wt% Eb at room temperature and 100 atm and ~15 wt% at room temperature and 300 atm, and oddly ~20 wt% Eb at 100°C and 100 atm. This is counterintuitive since most materials capture less gas at higher temperature. But this goes back to the interesting behavior of the materials of the present invention, as described and discussed below. The 5.5 wt% is an essential goal set by the US Department of Energy to make hydrogen fuel cell vehicles widely available. Presently they can only use Eh tanks that are 5000-10,000 psi (340-680 atm) to provide the range needed in a car. But those tanks are spherical to handle the high pressures, and therefore hard to fit in vehicles, and considered dangerous. If Eh is liquefied, the density is low and 30% of the energy content is lost in the liquefaction process. So to be able to store Eh at 100 atm (1470 psi) is a huge advance since light weight composite tanks can be used. Although the results here can be advantageous even up to 300 atm where the Eh storage starts to saturate at ~13 wt%.
[0828] Moreover, embodiments of the present invention shows that the properties of the resultant material can be tunable by simply controlling the activation temperature or the pressure or a combination of both temperature and pressure. For example, a porous carbon obtained by activating high density polyethylene (HDPE plastic at ~475-500°C shows properties that are similar to porous polymers (rather than porous carbons) where they are mechanically flexible in that the pores can vary in sizes depending upon the pressure and temperature used during the sorption process. This allows the polymer to tune its pore sizes for a particular gas at a particular pressure and temperature. So at 500°C, the material has both the properties of a porous carbon and the properties of a porous polymer. If however, a higher
temperature is utilized (such as ~575-600°C), the resulting materials is stiff, rather than flexible.
[0829] Further embodiments include sorbing of other gases, such as O2 and methane. O2 sorbing can be very useful in that if one can add even obtain 20% more O2 to a compressed cylinder, at the same pressure, then it would enormously reduce the price of O2 gas cylinder deliveries. But since this material can be flexible like a polymer, it can sorb most any gas since it can accommodate variable size molecules due to its mechanical flexibility. The sorption of methane has also been seen with the flexible porous polymer here, and that could increase the amount of methane that can be contained in a methane or natural gas tank. Again, lowering cost of deliver per amount of gas in the cylinder and making the use of natural gas more attractive for vehicular (car and truck) and maritime (boat and ship) use.
[0830] Embodiment of the present invention encompass a one-step activation method of plastic waste to produce a solid sorbent with high CO2 capacity at room temperature and pressure along with monomer and oligomer that can be recycled or used for other chemical applications. See FIG. 3. The CO2 capacity of sorbent can go up to 17 wt% (3.8 mmol/g) at 25 °C and 1 bar. The process is green and relies on the mild decomposition of potassium acetate (or other potassium additives, or calcium acetate), which is a nontoxic activation reagent. The sorbent can be synthesized at 475°C-600°C via pyrolysis of plastic waste such as HDPE (such as bottle waste), LDPE (such as plastic bag waste) and PP (polypropylene), (low density polypropylene and polypropylene) to get a highly porous sorbent with surface area of 930 m2/g.
[0831] The ability to synthesize sorbent <700°C eliminates the possibility of potassium metal formation, making the scale up of this process highly attractive since there is no formation of potassium metal at these temperatures. The nature of the sorbent can be manipulated by changing the activation temperature. For example, activating at around 600°C can yield a rigid porous carbon while activating below 550°C, and more preferably 475 to 500°C, can yield an
sorbent with porous polymer-like properties. TG-MS data of the evolved gases during the synthesis of the sorbent showed that the predominant product in the gas phase is propylene and ethylene, which are monomers that can potentially be used to synthesize fresh plastics. The synthesized sorbent has a selectivity of CO2 over N2 of 230 at 0.1 bar, and the sorbent is stable upon cycling. The sorbent has low heat of sorption, making it possible to regenerate at 70 to 75°C using waste heat from power plants and refineries. In comparison, one of the dominant technologies used today for CO2 capture at 1 bar is aqueous amine towers. These trap 13 wt%, they are corrosive, require a large footprint, and they need to be heated to 120-140°C to yield the CO2. Moreover, since aqueous amine towers have a high heat capacity (water), the amount of energy needed to heat them to 120-140°C is exceedingly high.
[0832] Porous sorbents were prepared by carbonization of plastic waste (polyolefins) at below 700°C under inert atmosphere (such as argon or nitrogen) in the presence of activation reagents. High density polyethylene (HDPE) was utilized. It was found that the same conditions can be used to activate plastic cups (PP) and plastic bags (LDPE), the latter being one of the most challenging materials to recycle and is one of the main sources of microplastics after polyethylene terephthalate (PET). Samples were named so that the first two numbers represent the activation reagent to polymer ratio followed by the plastic type and the numbers after the plastic type represents the activation temperature. I.e., “2-1-A-HDPE-500” represents a 2:1 activation reagent to polymer ratio, “A” for thermally activated, a plastic type of HDPE, and an activation temperature of 500°C. In some cases the “A” is not used since “activation” can be understood in the context here.
[0833] Different activation agents can be utilized, including potassium hydroxide, potassium oxalate, potassium acetate, and calcium acetate. See FIG. 4. It was found that, in some embodiments, activating with potassium acetate can yield the most effective sorbent with a CCk-capacity as high as 17 wt% at 1 bar and 25 °C. (Generally, potassium acetate is more
effective at making porous carbon with high CO2 capacity than potassium oxalate).
[0834] This adsorption capacity surpasses amine scrubbing which has 13 wt% CCk-capacity at 1 bar at 25 °C. While KOH is commonly reported in literature as an effective activation reagent for high surface area porous carbon synthesis [He 2016 ; Otowa 1997]; it is corrosive, hard to handle in large quantities and can have detrimental human health effects. The utilization of potassium acetate or calcium acetate as an activation reagent in embodiments of the present invention is highly advantageous because potassium acetate is a greener and nontoxic activation reagent and calcium salts are green and even less toxic that most other metal salts. In fact, potassium acetate is commonly used as food additive as acidity regulator and flavor enhancer.
[0835] Synthesis was carried at different temperatures (FIG. 5A) and various salt: plastic ratios (FIG. 5B) to find that a good sorbent can be synthesized at temperatures as low as 500°C. The activation method for this synthesis process require much lower synthesis temperature than other reported synthesis methods that require activation at 700°C-900°C. [Zhu 2014] The ability to synthesize sorbents at such low temperatures eliminates the risk of potassium metal formation, thereby mitigating one of the biggest risks associated with scaling up such activation methods. Also, the utilization of lower activation temperature of the polymer lowers the overall cost of the synthesis. The CO2 uptake and synthesis conditions were analyzed carefully to find the plastic is treated at 600°C with salt. In this embodiment, a plastic ratio of 2: 1 was the most attractive sorbent commercially with a CO2 capacity of 16 % at 1 bar and 25°C.
[0836] In exemplar methods of the present invention, plastic waste was chemically activated using potassium acetate. 8 grams of plastic cups and milk bottles were cut into small 2 cm2 pieces and the plastic mixture was processed at 160°C -180°C in a Brabender melt mixer (model type 808-400-DTI). Once melted, potassium acetate was added to the polymer melt at salt: plastic weight ratio of 0.5-2. After adding potassium acetate to the polymer melt, the
mixture was mixed in the Brabender at 50 RPM for 15 min to form a homogenous blend. The mixture was cool before transferring the polymer-based mixture to a ceramic boat and heating in a tube furnace at rate of 20 °C/min under argon atmosphere. Once the targeted temperature was reached, the temperature was held for 50 min to obtain 6 grams of product. The mixture was washed with DI water to obtain 0.8 g of porous carbon. While heating, the polymer was observed to crack and some liquids distilled out into the cool region of the tube. These are the volatile fractions that have ancillary commercial value in the pyrolysis.
Structural and Chemical Properties
[0837] The structural and chemical properties of the synthesized sorbent is presented in
TABLE I
TABLE I
Structural and chemical properties of the porous carbon obtained via chemical activation of
HDPE waste
[0838] The Brunauer-Emmett-Teller (BET) surface area were characterized via N2 physisorption analysis at 87 K. The results show that the surface area and total pore volume decrease as temperature increase indicating a collapse in the pore structure as temperature increase (TABLE I). Pore size distribution was studied via DFT theory to find that sorbents activated 600°C have pores diameter of 10, 25 and 30 A. Samples activated at higher temperatures have larger pore diameter that could go up to 100 A. While larger pore diameter is favorable for high pressure CO2 capture, narrow pore diameter is better for CO2 capture at 1
bar.
[0839] FIGS. 6A-6E a show the N2 sorption isotherm for 2,l-HDPE-600 showing a surface area of 950 rrrg 1 Moreover, adding less than 2 equivalent potassium acetate to the polymer mixture was shown to yield sorbents with lower surface area and total pore volume, which is expected since higher amount of activation reagent leads to higher porosity and thus, higher surface area. XRD patterns of the sorbent showed broad signals with no sharp lines, indicating the amorphous nature of the sorbent. The elemental composition of the sorbent was studied using XPS. The oxygen content was observed to decrease as the synthesis temperature increased, which was expected since a higher degree of carbonization is obtained at higher temperatures. High resolution XPS and survey scan of 2,l-HDPE-600 (FIG. 6D-6E) showed Ols and Cls signals with 10% O and 89% C. Detailed analysis of the O type is shown in FIG. 6E.
[0840] The morphology of the sorbent was studied using environmental scanning electron microscope (ESEM). FIGS. 7A-7C show ESEM images of 2,l-A-HDPE-600 with pores and pockets throughout the material. Due to the mild decomposition of potassium acetate, the sorbent exhibited a porous structure; this highly porous morphology differs from other reported carbon sorbents, which are characterized by their structural irregularity. [Sevilla 2018]. The average particle size was found to be around 250 pm. It is worth noting that activation at higher temperatures yield an sorbent with sheet-like morphology. This might be due to the formation of potassium metal at elevated temperature (>700°C), which induces the formation of the sheet like morphology.
[0841] XRD and TGA were utilized to study the activation mechanism of the sorbent. XRD of the unwashed sorbent after synthesis at 600°C indicates the formation of potassium carbonate (FIG. 8A). This suggests that from ~450°C to 520°C, potassium acetate decomposes into K2CO3 and acetone [Cheng 2014], a process which results in -30% weight loss due to acetone
volatilization as shown in the TGA profile of potassium acetate (FIG. 8B).
[0842] At 400°C, while some of the polymer decomposes to monomers, the carbon material is oxidized, and the formed CO is subsequently oxidized to generate CO2 and H2 gas (2-3).
C + H2O -> CO + H2 † T= ~400°C-460°C (2)
[0843] This process occurs from ~400°C-460°C in the carbon material (FIG. 8C). Potassium metal is formed by reduction of KzCCbby carbon above 700°C (4). That is something that we avoid in our process to minimize the risks of working with potassium metal which flame on contact with water.
[0844] Therefore, synthesizing an sorbent at temperatures lower 700°C is highly advantageous because it eliminate the risk forming potassium metal, (potassium is flammable and can even be explosive upon contact with air or water), which is one of the biggest challenges standing before commercializing the synthesis of porous carbon. Moreover, the use of potassium acetate instead of potassium hydroxide as an activation reagent is advantageous because potassium acetate is non-corrosive. Unlike potassium hydroxide, potassium acetate is easy to handle and will not cause continuous corrosion in the scale-up rector. Moreover, the use of potassium acetate is environmentally favorable because it is non-toxicity and the byproduct of the activation reaction is potassium carbonate, which is non-toxic, too, making it simple to deal with the waste product of this reaction.
Varying Plastic Waste Types
[0845] Embodiments of the present invention (and its method of activation) can utilize different plastic types, including LDPE and PP (see FIG. 9A), which LDPE and PP are commonly used in plastic bags and plastic cups, respectively. Due to the softness and
stretchiness of LDPE, it is known to be one of the most problematic waste types making it is hard to handle and recycle, which embodiments of the present invention offer solutions to. Moreover, different plastic waste products (PP, HDPE, LDPE) were mixed, melted, and activated together to yield an sorbent with a CO2 capacity of 15 wt% (FIG. 9B) indicating the possibility of single streaming waste product into one pot. Thus, embodiments of the present invention can eliminate the necessary separation and sorting steps present in conventional recycling.
[0846] As shown in FIG. 9C, waxes can be activated just like plastic.
Sorbent Selectivity And Heat Of Sorption
[0847] Post-combustion streams are made of around 10% CO2 and 90% N2. Therefore, selectivity is an important parameter for sorbent quality. FIG. 10A shows sorption isotherm of 2, l-HDPE-600 CO2 and N2 with far more CO2 capacity than N2 capacity. Ideal sorbed solution theory (IAST) was used to calculate the selectivity of the sorbent (eq. 2).
where,
SIAST is the selectivity, nCQ2 is the number of moles sorbent uptakes of CO2 without the presence nitrogen, nW2 is the number of moles of nitrogen in the sorbent without the presence of nitrogen,
PCo2 and PNzi s the partial pressure of CO2 and N2, respectively, in the desired stream. [Myers 1965\.
[0848] The IAST selectivity of the sorbent was found to be 150 at 0.1 bar and 58 at 1 bar (FIG. 10B). Since the partial pressure of CO2 is 0.1 bar in post-combustion steams, the selectivity at low partial pressure is important when designing an sorbent for flue gas CO2 capture. The selectivity at low pressure is high and comparable to the selectivity of metal organic
frameworks (MOFs) and zeolites.
[0849] To understand the nature of interactions between the CO2 gas and the sorbent, isosteric heat of absorption (Qst) was calculated using Clausius-Clapeyron equation (eq.3) using the isotherms collected at 20 °C and 25 °C (FIG. 11 A).
where,
P is the pressure of the sorbate,
Tis the temperature at which the adsorption took place, and R is the universal gas constant.
[0850] The sorbent has a maximum heat of adsorption of 51 kJ/mol (FIG. 11B), which is a typical heat of adsorption obtained from weak physical interactions. This heat of adsorption is well below that of MOF and zeolites, which usually have heat of adsorptions at 50 kJ/mol and 90 kJ/mol, respectively. [Modak 2019] The unique nature of interactions between the sorbent and the CO2 allows the regeneration of the sorbent by subjecting the sorbent to vacuum or heating the sorbent to 70°C to release trapped CO2 from the pores as shown in FIG. 11C. This indicated that sorbent regeneration can be easily achieved using waste heat in power plants and refineries at 70-75°C. Moreover, the sorbent is stable upon cycling (FIG. 11D); 10 adsorption cycles were tested and no loss in the CO2 capacity was observed.
[0851] FIG. HE shows that sorbent made by activating waxes can also be regenerated by releasing the trapped CO2 from the pores at around 80°C.
Byproducts Of Reaction when making the carbon materials.
[0852] The prior art shows the feasibility of cracking plastic waste over zeolites or bentonite clay to get liquid fuels and an ash that has no significant use. \Budsaereechai 2019; Kumar 2011\. The activation process disclosed and taught herein allows one to produce monomers as a gas and oligomers as solid, waxy or oily deposits in the cool regions of the furnace without
the generation of the undesirable ash that is usually obtained in conventional methods of plastic pyrolysis. FIG. 12A shows TG-MS of the evolved gases of HDPE/potassium acetate mixture with the highest abundance signal obtained from the ethylene (m/z=28) monomers, which could be polymerized to fresh HDPE polymer. Also, the TG-MS of FIG. 12A shows small traces of methanol (m/z=32), indicating partial oxidation of the carbon in the presence of potassium acetate to yield methanol. FIG. 12B shows FTIR spectrum of waxy deposits showing a typical hydrocarbon spectrum.
[0853] Ethylene can be reacted with other chemical feedstocks to produce polyvinyl chloride, polystyrene, and polyester resin. Therefore, the demand of ethylene is high worldwide. Currently, large-scale production of ethylene is carried in steam cracker where naphtha and paraffin hydrocarbon are pyrolyzed in the presence of steam. The temperatures in a typical steam cracker that could reach 850°C and the yield of ethylene is only 30% ethylene when naphtha is cracked at high severity. While the demand for ethylene increases every year, ethylene trade is limited due to challenges in transporting and refrigerating ethylene. The pyrolysis method disclosed and taught herein is simple and allows for ethylene production on site using plastic waste, making ethylene production not limited to large petrochemicals companies. The beauty of this process is what can be done with the remaining carbon when it is mixed with an additive that will make the carbon porous while remaining flexible in desired cases.
Synthesis Conditions And Characterization Of The Sorbent For Gas Storage At High Pressure
[0854] While activating plastic waste at 600°C yields rigid porous carbon that is attractive for CO2 capture at low pressure, it was found that activating the plastic waste at temperatures around 500°C yields carbon materials that behave like a metal organic framework (MOF) and porous polymers. FIG. 13A shows CO2 sorption profiles of a sorbent activated at 500°C and 600°C. The sample activated at 500°C shows extremely high capacities at high pressures. The
sample activated at 600°C showed an uptake of ~4 mmol/g of CO2, which is around 18 wt%. The BET surface area of the sorbent was -355 m2/g with wide distribution of pores ranging from micropores to mesopores (FIGS. 13B-13C). FIG. 13D shows XRD of 2,l-HDPE-500 shows sharp signals at 40° indicating short-range order due to the presence of plastic domains within the amorphous carbon region. If the heating is performed at 600°C, all short range order is lost. It is suggested that this preservation of short range order that affords a flexible nature to the pores of this material. Without the short range order, this flexible polymer-like behavior has not been seen from these porous carbons. In-situ FTIR analysis of the pore filling process from 1-50 bar indicates that the captured CO2 is in gas phase within the pores (FIG. 13E). As shown in FIG. 13D, upon heating to 500°C, the short range order of the polymer remains while the long range order is lost. Upon heating to 600°C, all of the original polymer chain ordering has been lost. This underscores the dramatic difference between the flexible and the rigid carbon materials made at these two different temperatures.
[0855] The CO2 sorption process was evaluated at different temperatures and it was found that high temperatures increased the CO2 uptakes at lower pressure, as shown in FIG. 14A. Moreover, it was found that the density of the materials decreased as temperature increased, which could be due to the expansion of the pores of the sorbent (FIG. 14B). The densities are greater than 1 g/cc and have been seen to be 1.7 g/cc by density measurements in liquid standards.
Scale-Up
[0856] The scale up of the synthesis process was considered. FIG. 15 shows a simplified scale-up design of the synthesis processes described herein, in which a fixed bed batch reactor is utilized to mix and pyrolyze the plastic waste with potassium acetate to get the porous carbon. The evolved gases can go to a distillation unit for separating the effluent’s components to get petrochemicals of high value at low cost.
[0857] As the synthesis process disclosed and taught herein involve synthesis of high surface area sorbent at 475-600° C, this eliminate the risk of forming undesired materials, such as potassium metal. For instance, in embodiments of the present invention, potassium acetate can be utilized. Potassium acetate is non-toxic and cheap as compared to potassium, which is corrosive and has determine health effects.
Uses
[0858] Embodiments of the present invention can be used as a technology for chemical recycling of plastics via thermal cracking of plastic wastes to get oligomers, monomers and porous sorbent. Furthermore, the resultant sorbent has properties, such as the high porosity and electrical conductivity, which can be utilized.
Batteries/Cathodes
[0859] The porous carbon obtained from the processes described herein is a good CO2 sorbent and has high capacity when used as a anode or cathode for batteries.
Hydrogen Storage
[0860] The porous carbon can be utilized for hydrogen storage. The low activation temperature of 2, l-HDPE-500 allows for the formation of micropores that are ideal for hydrogen storage at 100 bar. FIG. 16A shows hydrogen sorption isotherm of 2,1-HDPE with a capacity that can go up to 6.7 wt%, which is greater than 5.5 wt% at 100 bar, which is a Department of Energy target for such uses. Moreover, when the sorbent was allowed 15 minutes contact time with hydrogen, the uptakes were ranging from 3.4-6.5 wt% when cycled 8 times (FIG 16B). FIG. 16C shows temperature depended uptakes at 100 bar to find that the uptake increases significantly at 100°C. FIG. 16D shows the hydrogen sorption profile of 2, l-HDPE-500 collected at 100°C. Interestingly, when one seeks to fill a tank containing a good sorbent, the heat release upon gas binding to the sorbent heats the system, therefore restricting the rate at which the gas can enter the tank because higher temperature lowers usually sorption capacity.
But here, on the contrary, at 100°C, there is a marked increase in H2 uptake (FIG 16C). Therefore, heat release upon sorption of H2 can actually increase the efficiency of uptake with these materials. This is a highly unusual property that can be exceedingly advantageous during gas refilling.
Methane and Mix Gases Storage
As show in FIG. 17 (methane and methane mixed gas sorption isotherm of 2,l-HDPE-500 at 25°C), the flexible sorbent showed high storage capacity for methane. The observed capacity is around -100 wt% making this sorbent superb for methane and natural gas storage in tanks and operated vehicles.
Oxygen Storage Tanks
[0861] The flexible sorbent shows high oxygen capacity reaching an uptake of 155 wt% oxygen at 125 bars as shown in FIG. 18. This makes the sorbent ideal for increasing the storage capacity per tank and decreasing the overall shipping cost of oxygen to medical facilities and homes. Moreover, adding the sorbent to the oxygen tank can be utilized as a safety mechanism, because the oxygen desorption is endothermic, which minimize the chance of explosion in case of accidental release.
N-Doped Materials
[0862] The sorbent described herein can be nitrogen-doped (N-doped) for further uses. FIG. 19 shows a scheme for N-doping a mesoporous sorbent to get microporous carbon. The sorbent was N-doped by heating the sample up to 700°C in an ammonia atmosphere (which yielded a rigid sorbent). While the uptake at low pressure decreased due to converting some of the micropores to mesopores as shown in FIG. 19, the uptake at high pressure increased from to 25 wt% to 700 wt% at 30 bars and 25°C. FIGS. 20A-20B show CO2 sorption isotherm of N- doped sorbent at low and high pressure, respectively. The nitrogen containing material, need a higher temperature, however, to remove the CO2, generally exceeding 100°C. Other ways to
have nitrogen in these is to use nitrogen-containing polymers such as PET or nylons or polyurethanes, or mixtures of polyethylene and polyethylene imine. Or, the applicants can treat the rigid polymer made at 600°C as described above with a combination of aqueous ammonium hydroxide and HC1 or ammonium chloride at room temperature then drying. CO2 uptakes can be obtained at room temperature and 1 atm as high as 27 wt% CO2. See FIG. 20C.
Flexibility
[0863] Differential scanning calorimetry was used to determine the glass-transition temperature of the sorbent 2,l-HDPE-500. FIG. 21 A shows an endothermic phase transition of the sorbent occurring at 96 °C (with plots 2101-2103 showing weight, heat flow, and derivative of heat flow, respectively). This phase transition agrees with the gas sorption finding that shows higher uptake at higher temperature and a sudden increase in the storage capacity at around 100°C.
[0864] FIGS. 21B shows that partial pyrolysis of HDPE yields a flexible materials (comparing HDPE pyrolyzed at 600°C (rigid skeleton ploy 2111) with HDPE pyrolyzed at 500°C (flexible linkers plot 2111)). FIG. 21C shows that flexibility does result in a change in storage capacity.
Stiffness/Structure Due To Temperature Changes
[0865] Stiffness measurement was performed on in 2,l-HDPE-500 at different temperature. A study of atomic force microscopy (AFM) was performed using normal force (FN = 400 nN) at different temperatures on sorbent 2, 1 -HDPE-500. FIG. 47A shows the change in the vertical displacement on the surface of the sorbent upon applying pressure at different temperatures (with curves 4701-4705 corresponding to 30°C, 50°C, 70°C, 90°C, and 105°C, respectively). FIG. 47B shows the change in of sorbent stiffness upon changing the temperature. These show that as temperature increases, the stiffness of the 2,1 -HDPE-500 decreases (indicating the softening of the sorbent as temperature increases, i.e., the sorbent become more flexible as temperature increases). These show a slight decrease in stiffness between 25°C-90°C.
However, a large decrease in stiffness (i.e., a large increase in flexibility) was observed when heating above 100°C.
[0866] This characteristic is unusual and also can explain why the flexible sorbents act contrary (and counterintuitive) since, again, most materials capture less gas at higher temperature. [0867] Raman spectroscopy was used to examine the change in the spectra of the sorbent as temperature changes. FIGS. 48A-48C are Raman spectra of 2,l-HDPE-500 at different temperatures 22°C, 50°C, and 100°C, respectively. As shown in FIG. 48A, plot 4801 (22°C) has D-peak 4802 and G-peak 4803, with a Lorentzian fit 4804. As shown in FIG. 48B, plot 4805 (22°C) has D-peak 4806 and G-peak 4807, with a Lorentzian fit 4808. As shown in FIG. 48C, plot 4809 (22°C) has D-peak 4810 and G-peak 4811, with a Lorentzian fit 4812.
[0868] FIGS. 48D-48E show the fullwidth-half maximum of the D-band observed upon heating and cooling, respectively, indicating that a change in the sorbent structure upon heating. It is believe that this change in sorbent structure contributed to the strong decrease in the stiffness.
[0869] Because of this unusual ability of the carbon-based sorbent to sorb gases at higher temperatures, this is highly advantageous in that it provides the ability to charge gases into tanks (such as light-weight tanks used in hydrogen fuel cell vehicles) more rapidly. Generally, charging such tanks rapidly is avoided because of the increase in temperature that results, which would be detrimental for sorbents. However, for the flexible carbon-based sorbents herein, this actually works in favor of increasing the sorbents ability to sorb the gas. As the temperatures reached are still well below the decomposing temperature for the sorbent, this provides for a faster re-charge. Such tanks can be insulated to lessen the reduction of temperature, which would tend to decrease the sorbence of the sorbent, leading to an increase in pressure in the vessel. As the gas is discharged, temperature in the tank would be decreased, but as the amount of gas is reduced due the discharge (thereby acting to reduce the pressure) and the reduction in
pressure due to the reduction in temperature, these will act to offset the effects of pressure increase resulting from the decrease in sorbence of the sorbent at the lower temperature.
Effect of Vacuum on the Sorbent
[0870] It is standard in the practice of gas uptake measurement to subject the material to an absolute pressure of at around 0.00013 bar (0.1 mmHg) or lower absolute pressure. This is done to remove any remaining sorbates from the material in order to get an accurate uptake of gas in the subsequent experiment. This is also done in BET surface area determination equipment before the surface area is determined. While low absolute pressure activation is fine for the rigid carbon materials that were prepare at around 600°C, it is destructive to the flexible carbons made at around 500°C. The applicants discovered that these low absolute pressures cause destruction of this flexible carbon material presumably by collapse of the framework. One should exercise care in the pressure control of these carbon frameworks in order to preserve their structure. The uptake capacity of the flexible sorbent is dependent on the level of vacuum applied as a pre-treatment to activate the materials by removing the traces of sorbates like water, i.e., the absolute pressure before the sorbent gas is introduced. If the sample is subjected to even slightly more vacuum (lower absolute pressure), then the capacity to sorb the gas is drastically reduced since the material undergoes a catastrophic change in structure wherein its density lessens (from about 1.5 g/cc to less than 1.0 g /cc) and its gas uptake capacity plummets. The absolute pressure (or level of vacuum) during this pretreatment where the failure occurs is also temperature dependent. However, when the quality of the vacuum is poorer ( i.e . at slightly higher absolute pressure) then the uptake is high when the gas is introduced. FIG. 22 shows the CO2 sorption isotherm of the sorbent when subjected to 0.01 bar (7.5 mmHg, 1 hour) and 0.005 bar (3.5 mm Hg, overnight) both at room temperature of 23°C. It is observed that the high sorbent capacity plummets after subjecting it to higher vacuum (lower absolute pressure) for long periods of time on the order of hours. The typical
measurement instruments that reduce the pressure to around 0.00013 bar (0.1 mmHg) or lower destroy this type of carbon material since even at 0.005 bar destruction can occur. It is noted that 0.005 bar may not destroy the structure for all embodiments of the sorbent and therefore, in some embodiments, the pressure threshold above which the vacuum pressure is kept can be lower than this value and can be determined by routine testing.
Sorption mechanism
[0871] Collapse upon drying or removal of sorbates is a known phenomenon with some metal organic frameworks (MOFs). MOF is an example of a sorbent with pores that have unique interaction with the solvent. Complete removal of the solvent from pores results, in some cases, in pore collapse. The pore collapse and interactions between the different MOFs and solvents has been studied extensively. \Hisaki 2018; Dodson 2018 ]. To prevent the MOFs pore collapse the pores can be supported with polymer or covalent interactions. [ Peng 2019 ]. Furthermore, porous polymeric membranes have been reported to demonstrate unique solvent-pores interactions. It has been shown that solvent choice, heating time and temperature affect the pores interconnectivity. [ Lu 2018] Moreover, the interactions between the polymers strands also plays a role in preserving the porous structure. Strong polymer-polymer interaction may lead to pore collapse. [Lu 2018; Bhattacharjee 2018] Pore collapse in carbon materials: (A) Cellulose cell wall pore collapse in wood derived porous structure upon drying; some work shows that drying water from the nanopores in wood leads to the collapse of the pores. [ Papadopoulos 2018] (B) Templated porous carbon can collapse upon drying. Thus, cationic polyelectrolyte template or surfactant can be used to stabilize the porous structure. [Dutta 2014 ]. The “pore collapse during the drying step due to large capillary forces imposed at the liquid-vapor interface” is known. [Lee 2002] Functionalized pores collapse due to drying is known. Some structural deterioration of functionalized porous carbon is known when a hydrophilic porous carbon is dried. The work shows a decrease in the surface area and pore
volume upon drying water or solvent exchange with ethanol. Freeze drying was found to be effective at preserving the porous structure. Hydrophobic porous carbons were found to remain intact upon drying and are not affected by water removal. [Zhang 2019 ]. Note that the porous carbons in that work by Zhang 2019 was prepared by a silicon templating method. This is distinct from embodiments of the present invention which were porous carbon that was hydrophobic with very little non-carbon content. Further, there are no known reports of porous carbon collapse in carbons prepared by potassium salt activation.
[0872] The results as described herein show that higher vacuum (lower absolute pressure) pre treatment could alter the structure of the sorbent material and lowering its uptake capacity. Three possible mechanisms are suggested below:
[0873] First possible mechanism: after the starting polymer has been subject to partial thermal decomposition at elevated temperatures in argon, when the tube furnace is opened, room air displaces the argon. Atmospheric moisture is likely to be strongly sorbed into the pores. The material was further submersed in water to remove excess salts after the carbonization step, then the material is put in an oven at 100 °C to give it a dry surface appearance. Yet sorbed water will remain in the pores. Upon lowering the absolute pressure, the nitrogen, oxygen, argon, and similar non-polar species will be quickly pumped away, whereas water is quite “sticky,” meaning that its polar interactions keep to sorbed to the carbon. This makes water the overwhelming favorite as the sorbed species that give rise to this observation. Inside the pores, the water has a vapor pressure, but is much lower than liquid water because the water molecules are sorbed onto the surface. Let us assume for this argument that the average vapor pressure of the sorbed water in the sample is 7 mbar. If the needle valve is used to keep the pressure at 10 mbar in the pre-treatment chamber, then little water vapor escapes from the sample because there is not enough pressure to displace the external surrounding gas. A small amount will be lost due to diffusion, but nearly all water molecules that desorb will just re-sorb. When the
pressure is reduced to 4 mbar (well below the internal vapor pressure), it is believed that the 7- mbar internal vapor pressure can displace the lower external pressure, and water molecules will freely escape from the sample into the chamber. The sample is quickly dehydrated, and the nano-sized pores collapse once the sorbed water is gone and cannot be re-opened.
[0874] The second possible mechanism is similar to the first: the polymer is partially decomposed, will likely leave many reactive sites, with radicals and multiple bond structures. The highly polar water molecule will adhere due to van der Waals attractions of the water to these sites. So, water is keeping the reactive sites from binding to each other. However, if the water is completely removed, then these nanoscale pores are likely to collapse, and gas species cannot pry the pores open again. In effect, this becomes a new material, with the partially decomposed hydrocarbon chains that are propped apart by water molecule.
[0875] A third possible mechanism is that at the lower absolute pressures, the flexible domains from the remaining short range polymer order (as described in FIG. 13D), become evacuated and they irreversible collapse or break, like a balloon being evacuated until the rubber splits.
External vacuum control system
[0876] The Rubotherm system determines gas uptake by weight increase. As is the case for most gas uptake measuring systems, it is designed to evacuate the sample to a low absolute pressure of 0.1 mmHg or less, which has the built-in assumption that vacuum will not alter the material morphology. Hence, the sample is exposed to the best vacuum (lowest absolute pressure) that the pump can generate. For a mechanical pump, this is 0.1 mmHg (0.13 mbar) and likely lower. The limit of resolution of the Rubotherm gauge is 0.01 bar, which does not allow useful pressure measurements in the range of interest when the water is outgassing. A high vacuum gauge can be installed on the pumpout line, but the many tubes, valves, and fittings in the control box will have a low gas conductance, whereas the tube connecting to the vacuum pump has a high gas conductance. Therefore, the gauge is measuring the pressure of
the pump, not the sample, which could be one to two orders of magnitude higher than the gauge reading. Since it is not feasible to connect directly to the sample chamber, which is designed for greater than 200 bar, then the gauge system should be mounted external to the Rubotherm control box.
[0877] In order to measure the sample pressure so far from the gauge, it is necessary to introduce a restricted conductance with an external vacuum manifold. FIG. 23 shows schematic of the pressure control manifold 2300 that was installed on the Rubotherm with arrows 2301a-2301g showing gas flow direction (with needle valve control) from Rubotherm to vacuum pump. Pressure control manifold 2300 includes vacuum gauge 2302 (Bourdon vacuum gauge), absolute pressure gauge 2303, ball valves 2304a-2304b (on-off and 3-way), needle valves 2305a-2305c (for fine control), reducers/adapters 2306, piston snubber 2307, tubing 2308a-2308d (various diameters, such as 1/8 inch 3/16 inch, 1/4 inch, and 1/2 inch, respectively), and air inlet 2309. FIG. 24 shows a picture of the actual pressure controlling system installed on the Rubotherm.
[0878] In embodiments of the present invention, ball valve 2304a can be main pumpout valve, 1/4 turn, 1/2 inch tube (Swagelok B-8P6T). Ball valve 2304a can be open for total pumpdown and closed for measurements. Ball valve 2304b can be a three-way 1/4 turn valve (Swagelok SS-41-XS2 or SS-41-GSX2). The middle position with the handle perpendicular to the tubing is the off position, 1/4 turn up to open to the manifold, and 1/4 turn down to vent absolute pressure gauge 2303. This isolates and protects absolute pressure gauge 2303 until conditions are appropriate for a measurement. Needle valve 2305a can be a regulating needle valve in parallel (Swagelok SS-ORS2) and can be a multi-turn adjustable valve. This valve provides fine control on pumpout rate when ball valve 2304a is closed. Ball valve 2305b can be a vent valve for absolute pressure gauge 2303. Needle valve 2305b is typically barely open. When the handle for ball valve 2304b is turned to the down position, needle valve 2305b lets air in
slowly to bring the needle for absolute pressure gauge 2303 to full scale in about 5 seconds. Then ball valve 2304b is closed. Needle valve 2305c is a manifold vent valve that is normally kept closed.
[0879] Vacuum gauge 2302 can be a Bourdon tube gauge, which measures pressure relative to atmospheric pressure. “0” is the reading when open to air. -30 inches Hg is full vacuum, and 15 psi about 1 atmosphere above room pressure. This is termed a combination gauge. A conventional Bourdon-tube gauge is used to measure from atmosphere to vacuum and it is not suitable for an accurate measure of the absolute pressure. The term “vacuum gauge” implies that the gauge is measuring a decrease in pressure relative to atmospheric pressure and the numerals have a minus (-) sign. When the vacuum gauge 2302 goes below -25 inches Hg (-130 Torr remaining) then the 3-way valve can be switched to absolute pressure gauge 2303. The reason for using a combination gauge rather than vacuum only, is that this provides a check to see if the Rubotherm is venting to the pump while under pressure. Since this gauge is referenced to atmospheric pressure (which changes with the weather) it is not suitable for low-pressure measurements. Absolute pressure gauge 2303 (Edwards Vacuum) has an internal evacuated “can” with a “lid” that is mechanically connected to the pointer. This reference is sealed high vacuum, and it is unaffected by the barometric pressure or temperature. The gauge glass is much thicker since the entire volume of the gauge is evacuated. The absolute pressure gauge 2303 used can be a 25 mbar (absolute) full scale, which is the most sensitive available. This type of gauge is easily damaged by the shock wave if atmospheric pressure is allowed to rush in when it is evacuated. The needle will move with extreme speed and can bend or break off. The Rubotherm pumpout valve just pops open, which will ruin the gauge, as a discussion with the manufacturer confirmed. Hence there are protective devices incorporated in the design. The connecting tube can be at least 3/16 inch OD, which can be shaped by hand. 1/4 inch SS tube needs a tube bender. 40 mbar and 100 mbar ranges can alternatively utilized.
[0880] The first level of protection for the absolute pressure gauge is ball valve 2304b that has two quarter turn motions. The protective air inlet needle valve 2305b is used to control the air inlet to the absolute pressure gauge 2303 when the 3-way valve is switched to the vent position; this low-flow needle valve is the primary protection for absolute pressure gauge 2303. One position vents absolute pressure gauge 2303 to air, the opposite position connects to the vacuum manifold, with off in the middle position. Needle valve 2305b attached to the vent connection restricts the airflow to the absolute pressure gauge 2303. The absolute pressure gauge 2303 is vented through needle valve 2305b to reach full scale (but does not need to be more than 25 mbar); and then shut off ball valve 2304b. When the Rubotherm has opened to the pump, and vacuum gauge 2302 is below 25 inches Hg (typical units for Bourdon vacuum gauges) or about 100 Torr, then ball valve 2304b can be switched to connect to the manifold and measure the absolute pressure, and comes on scale at 25 mbar absolute.
[0881] Snubber 2307 (such as McMaster-Carr 4072K6 with the most restrictive "A" piston) provides a second layer of protection. There is a small piston that is pushed upward into an orifice to restrict flow when there is a fast inrush of air and protects the absolute pressure gauge 2303. With the piston engaged, it typically takes about 2 seconds for absolute pressure gauge 2303 to go to the peg at 25 mbar. A simple version of a snubber is a fitting with a pinhole passage, but this also restricts pump down rate. The largest orifice available from McMaster- Carr is 0.015", which is too small, and it was drilled out to 0.025" with a #72 drill in a hand held pin vise (an electric drill would break the bit). The second option is a piston snubber that is mounted in the vertical direction. When the airflow is too fast, it lifts the piston and plugs the orifice.
[0882] However, the surface of the orifice apparently was not smooth and did not seal well, allowing the gauge to move too fast. Since the orifice is brass and the piston is steel, a pin punch and hammer were used to gently flatten the brass orifice for a better seal. With this
modified piston snubber, the evacuated gauge can be switched suddenly to atmospheric pressure without damage. When the piston is in the lower (normal) position, the pump down rate of the gauge is adequate. This piston “vibration damper” is also available from McMaster Carr (which is what is used in the described system). Normally, the 3-way valve is turned off once the needle reaches the 25 mbar peg, leaving the gauge under partial vacuum. It is kept in the off position until the manifold pumpout pressure is below 25 inches Hg and then switched to the manifold to read the decreasing pressure. For pressures below 2 mbar, it may take the gauge a minute or more to settle down. Also, it is beneficial to gently tap the gauge after a minute to help it settle. The absolute pressure is controlled with needle valve 2305a. The desired pressure can be approached gradually to allow equilibration between the sample and the absolute pressure gauge 2303. For lower pressures in the range of a few mbar, more time is needed because the pressure drop is so small and the flow rates are likewise small. Gently tap the gauge to help it settle. If the pressure rises when the bypass valve is closed, this indicates outgassing of the sample and the rise will slow down. In contrast, if there is a leak the pressure will rise at a steady rate until the gauge reaches its maximum. When the pressure is steady for 30 seconds to a minute, then this is also the pressure of the sample.
[0883] For pressure control manifold 2300, a ½ inch tube goes to the oil-type rotary vacuum pump, and the manifold is fitted with a 1/4-tum ball valve 2304a for unrestricted pumping and will achieve < 0.1 mbar in seconds when opened. Since needle valve 2305a bypasses ball valve 2304a, when ball valve 2304a is closed, needle valve 2305a can then be used to reduce conductance or even stop pumping action altogether to control the pressure in the sample. As needle valve 2305a is closed down and the conductance becomes much less than that through the control box, vacuum gauge 2302 will come into equilibrium with the sample. Outgassing may cause the pressure to drift upwards, and a slight opening of needle valve 2305a can compensate to keep the pressure stable. While ball valve 2304a can be used for quick pump
down, needle valve 2305a is normally used to slowly approach the desired manifold pressure, and because the pressure is approached slowly, it is also close to the sample pressure.
[0884] For water outgassing, all manifold components can be brass with copper tubing. However, other polar molecules may be introduced as proppants. Ammonia, NO2 and halogen acids will attack copper and brass, and in this case, stainless steel is preferred. All fittings are Swagelok fittings. FIG. 25 shows a generic schematic for the pressure control manifold 2500 to be used for corrosive gases with arrows 2501a-2501g showing gas flow direction (with needle valve control) from Rubotherm to vacuum pump. Like pressure control manifold 2300, pressure control manifold 2500 includes vacuum gage 2302 (Bourdon vacuum gauge), absolute pressure gauge 2303, ball valves 2304a-2304b (on-off and 3 -way), needle valves 2305a-2305c (for fine control), reducers/adapters 2306, piston snubber 2307 tubing 2308a-2308d (various diameters, such as 1/8 inch 3/16 inch, 1/4 inch, and 1/2 inch, respectively), and air inlet 2309. Converting Plastic Bags To Flakes
[0885] Embodiments of the present invention can encompass converting plastic bags to flakes for use in the synthesis processes described herein or for use to make in other synthesis process, such as in the flash Joule heating synthesis method described in PCT International Patent Appl. Serial No. PCT/US19/47967, filed August 23, 2019, to Tour et al. (which describe and teach among other things, methods for making flash graphene). Of the many problems with recycling plastic, plastic shopping bags are among the worst of the problems. Conventional recycling machines cannot handle the bags because they get entangled in the slow turning shredders that are made for harder plastics. And bags left in the open are degraded by sunlight and air, and because they are lightweight, can easily be dispersed by wind. Unfortunately, the bags do not break down completely but instead photo-degrade, becoming microplastics that absorb toxins and continue to pollute the environment. Microplastics and nanoplastics adversely affect the food chain and they degrade the immune system. \Allen 2019\.
[0886] A bag flaker device utilizing the processes of the present invention can be located at a store entry to minimize employee work and allow the customer to know that the customer’s efforts are directly contributing to the recycling effort.
[0887] FIG. 26 shows a simple hopper device for converting plastic flakes, which flakes can be then used to form other materials (such as graphene). The hopper used here is commercial sold to shred hemp or related fibrous plant products.
[0888] As shown in FIG. 26, in step 2601 the store employee/customer/efc. loads the plastic bags 2617 into a hopper 2610.
[0889] In step 2602, the bags 2617 are feed into the chopper 2618 using rollers 2611, which feed the bags 2617 into the chopper 2618 at a constant feed rate.
[0890] In step 2603, chopper 2618 is used to sheer the bags to plastic flakes 2619. The chopper 2618 includes a high speed rotor with rotating knives 2613, which are close in tolerance to fixed knives 2614.
[0891] In step 2604, the smaller flakes 2619 will pass through sizing mesh 2614 located at the bottom of chopper 2618. The larger flakes 2619 (too big to pass through sizing mesh 2614) will circulate in chopper 2618 so that they can be cut smaller.
[0892] In step 2605, the flakes 2619 (that pass through sizing mesh 2614) will fall by gravity into a receptacle, such as barrel 2615. A bag 2616 is lined inside barrel 2615.
[0893] In step 2606, once barrel 2615 is full, the bag 2616 is removed with the flakes 2619 (and replaced with a new bag 2616). The flakes 2619 can then be utilized in a synthesis process as described above.
[0894] For safety and other reasons, equipment may be added to prevent/ avoid customers (and especially children) from throwing foreign objects into the device.
[0895] FIG. 27 shows an alternative device that includes an inverted funnel design that will only pick up lightweight bags.
[0896] In step 2701, the store employee/customer/efc. feeds the plastic bags 2617 into the inverted funnel 2720.
[0897] In step 2702, bag sensors 2721 search for foreign objects. Bag sensors 2721 may use light scattering, radio waves, ultrasound and/or millimeter waves to determine that the item is a bag and does not contain foreign objects.
[0898] In step 2703 after determining that the bag 2617 is empty and there are no foreign objects, controls 2722 turn on the suction. Controls 2722 do not switch on the suction until the bag is positively identified.
[0899] In step 2704, suction pulls the bag 2617 into and through pipe 2723, and the bag is carried by the air flow to the rollers 2611.
[0900] In step 2705, the bags 2617 are feed into the chopper 2618 using rollers 2611, similar as described above in step 2602 for FIG. 26.
[0901] In step 2706, chopper 2618 is used to sheer the bags to plastic flakes 2619, similar as described above in step 2603 for FIG. 26.
[0902] In step 2707, the smaller flakes 2619 will pass through sizing mesh 2614 located at the bottom of chopper 2618, similar as described above in step 2604 for FIG. 26.
[0903] In step 2708 a suction pipe (or exit hose) 2724 is utilized to deliver the flakes 2619 to a receptacle, such as vacuum canister 2725, which can be nearby. (Alternatively, the vacuum canister 2725 can be located at a remote location, such as in the stockroom at the back of the store. The latter case will reduce employee time and could allow central collection for several bag cutters if the store has multiple entries). The vacuum canister 2725 is lined with a bag, similar to as shown in FIG. 26.
[0904] In step 2709, vacuum canister 2725 collects flakes 2619.
[0905] In step 2710, the bag is removed from the vacuum canister 2725 (such as by an employee removing it and tying it off).
[0906] The bagged flakes (such as produced from the above systems/methods of FIGS. 26- 27), can then be utilized in the processes described herein or for some other processes, such as to make flash graphene. I.e., the store can sell the bags of flakes, as there is a market for these materials. As it is believed that customer participation is easy and straightforward, and the store (or other entity) has a marketable product instead of harmful waste, this is a resolution for the microplastic problem from discarded plastic bags.
[0907] Further advantages for the store (as well as other similarly situated users) include:
(i) The volume of plastic material is greatly reduced.
(ii) The flakes are collected and bagged, like emptying normal trash barrels.
(iii) A waste material has been turned into a saleable feedstock, such as for making flash graphene.
(iv) The resultant material can be sold to a graphene production center, rather than paying to haul it to landfill.
(v) If there is high customer participation in returning bags (which is believed will be the case), then plastic bag bans will be reduced/eliminated, which will reduce the use of trees for paper bags.
CO2 Capture From Post-Combustion CO2 Emission Outlet Gas And CO2 Captured Directly From Air [Direct Air Capture!
[0908] As discussed above, the present invention relates to porous polymeric carbon sorbents for CO2 capture and methods of making and using same. The porous polymeric carbon sorbent is rigid and the CO2 captured from the flue gas and for gases from other post-combustion CO2 emission outlets can be released at low temperature (such as around 70°C to 75 °C) when there are no nitrogen atoms as part of the polymeric carbon sorbant and at around 110°C when there are nitrogen atoms as part of the polymeric carbon sorbent. Or one can reduce the pressure to release the captured CO2 from the porous polymeric carbon sorbent. The term “post combustion CO2 emission outlet gas” refers to the exhaust gases (which include CO2) that
evolved from any combustion process, such as industrial applications, like flue gas from a power plant or other fossil fuel -based large point source, from a factory, exhaust from a vehicle, and the burning of oil, natural gas, gasoline, diesel, etc) The term “rigid” as used herein when referring to the porous polymeric sorbent refers to that the polymer of the sorbent having lost its long range order and short range order as detected by powder X-ray diffraction (XRD). The term “flexible” as used herein when referring to the porous polymeric sorbent refers to the polymer of the sorbent having lost its long range order while retaining its short range order as detected by powder XRD.
[0909] HDPE, PP and LDPE may be used for this rigid polymer system.
[0910] In an example utilizing a melt mixing procedure, 8 g of plastic was cut into small 2 cm2 pieces and melted at 150°C-170°C in a Brabender melt mixer (model type 808-400-DTI). This took less than 5 minutes. Once melted, potassium acetate was added to the polymer melt as salt: plastic weight ratio of 4: 1 (salt to polymer) and was mixed at 50 RPM for 10 min at 150°C to form a homogenous blend. Then, 2 g of the polymer-based mixture was transferred to a ceramic boat and heated in a tube furnace at a rate of 25 °C /min under argon atmosphere. The temperature was held at 620°C for 45 min to carbonize the plastic and get porous carbon. After cooling down, 1.5 g of sorbent/salt product was recovered. The product was washed with DI water and filtered using a 0.22 pm PTFE filter to obtain 0.07 g of porous carbon after drying at 100 °C overnight.
[0911] In an example that utilized an alternative approach using powdered plastic, to make plastic powder, plastic waste was chilled in liquid nitrogen before it was ground using a commercial mill. After that, 8 g of plastic powder was mixed with potassium acetate at salt: plastic weight ratio of 4:1. Using a mortar and pestle, the plastic/salt mixture was mixed until a homogeneous blend is formed. Then, 2 g of the polymer-based mixture was transferred to a ceramic boat and heated in a tube furnace at rate of 25°C /min under argon atmosphere. The
temperature was held at 600°C for 45 min to carbonize the plastic and get porous carbon. After cooling down, 1.5 g of sorbent/salt product was recovered. The product was washed with DI water and filtered using a 0.22 pm PTFE filter to obtain 0.07 g of porous carbon after drying at 100°C overnight.
[0912] To activate the sorbent, heat the sample at a temperature of 120°C and pressure of 1 mbar (full vacuum) for at least 1 hour.
[0913] FIG. 28A shows CO2 isotherms of sorbents synthesized at different potassium acetate: HDPE ratios at 2:1 to 6:1, with the 4:1 ratio reflecting the uptake (wt%) in this range. This shows that 4, l-HDPE-600 captures 18 wt% CO2. FIG. 28B is the gravimetric and volumetric CO2 isotherms of 4, l-HDPE-600 (plots 2801-2802, respectively). The agreement of the volumetric and gravimetric data further confirms the reliability of the results (i.e., 4, l-HDPE- 600 captures 18 wt% CO2 by volume).
[0914] FIG. 29A shows the CO2 uptake and change in pressure overtime (plots 2901-2902, respectively) of a rigid sorbent that shows the fast sorption kinetics upon exposing the sorbent to CO2. Kinetics is one important parameter to look at for any sorbent for the CO2 capture market. The results show that the sorbent exhibit fast sorption kinetics. High sorption rate allows for high number for sorbent cycling in a day and thus more CO2 can be captured per ton of sorbent in a day.
[0915] FIG. 29B shows the CO2 capacity change with time upon subjecting a rigid sorbent to CO2 (plots 2911-2912 for pressure and uptake, respectively). FIG. 29B shows that the rigid sorbent staturates after ~ 4 min of exposure to CO2. As for selectivity, the rigid sorbent (such as 4- l-HDPE-600) was highly selective to CO2, as shown in FIGS. 29A-29C.
[0916] FIG. 30 A shows the TGA/DSC of HDPE and potassium acetate mixture showing weight loss and heat required (plots 3001-3002, respectively) to synthesize the rigid sorbent. FIG. 30B is the heat loss (endothermic plot 3111) and heat gain (exothermic plot 3112) over
time during the pyrolysis of HDPE+ acetate to synthesize the sorbent. Using the heat loss and heat gain data from FIG. 30B, this estimates a cost for sorbent synthesis to be around $34 per ton from HDPE.
[0917] As shown in FIGS. 31A-31C, 4,l-HDPE-600 has low binding energy and cycles well. FIG. 31C shows the CO2 capacity of 4,l-HDPE-600 upon cycling 110 time and demonstrates great stability in the CO2 capacity. Thus, the rigid sorbent of the present invention can be repeatedly cycled over and over again while maintaining its capacity. The slight decrease is due to the rapidity in which we did the cycling. (This is because time was not given for full CO2 desorption; however, more time would have shown greater stability to the system).
[0918] FIG. 32 shows the change in the micropores (< 1 nm in radius) percentage upon changing the potassium acetate/HDPE ratio showing that ultra-high micro-porosity can be attained with 4: 1 potassium acetate: HDPE ratio. Higher micro porosity can be obtained with increasing the HDPE ratio to reach 90% when the potassium acetate: HDPE is 4: 1.
[0919] FIG. 33 shows the CO2 isotherm of plastic obtained from mixed post consumer plastic. This demonstrates that the rigid sorbent of the present invention can be synthesized from all kinds of plastic including plastic from end-of-life cars.
[0920] Calcium acetate can be utilized in lieu of potassium acetate to make the rigid sorbents. FIG. 34A shows the CO2 isotherm of sorbent activated with calcium acetate in replacement of potassium acetate showing efficient CO2 uptake compared to different sorbents activated with potassium acetate (plots 3401-3403 for (a) 2, l-HDPE-600 Ca acetate, (b) 2, l-HDPE-PEI-600, and (c) 4, l-HDPE-600, respectively). Accordingly, calcium acetate is a possible activation reagent for the rigid sorbent. Washing the calcium salts from the sorbent will require an acidic water-based solution.
[0921] FIG. 34B show XRD pattern of unwashed sorbent activated with calcium acetate showing the formation of calcite and calcium oxide at 600 °C and 800 °C (plots 3411-3412,
respectively). The byproducts of pyrolysis of calcium acetate with HDPE are calcite and calcium oxide, which are noncorrosive and safe to handle. In addition, the pyrolysis of calcium acetate does not yield reactive metal that ignite upon contact with moisture (which is another advantage of the present invention). If washed with dilute aqueous acid, such a 1 M hydrochloric acid, these salts can be efficiently removed.
[0922] In some embodiments, the rigid sorbent can be N-doped by adding N-containing polymers to the HDPE (or other polymer). FIG. 35 show CO2 isotherm of N-doped sorbent by the addition of polyethyleneimine. FIG. 36A shows the survey XPS scan of the N-doped sorbent. FIG. 36B shows high resolution N Is XPS showing that the sorbent has nitrogen in the pyrrolic and pyridinic form. Blocks 3601 show the spectrum. Areas 3602-3604 are pyridinic N (28%), pyrollic N (54%), and N-oxide (17%). Plot 3605 is the sum. Pyrrolic and pyridinic nitrogen are a preferred form of nitrogen for CO2 capture. FIG.37 shows ideal sorbed solution theory (IAST) selectivity of the sorbent showing great increase in the selectivity upon N-doping (plot 3701) as compared to without N-doping (plot 3702).
[0923] N-doped sorbent can also be synthesized from different N-containing polymers to have an uptake of 20 wt% at 1 bar. FIGS. 38A-38B are CO2 sorption isotherm of 1,1-polyamic acid and 1,1 -nylon acid, respectively.
[0924] N-doping further allows for tuning heat of adsorption and will lead to higher regeneration temperature. FIG. 39 shows isosteric heat of adsorption and regeneration temperature which reveals an increase in the regeneration temperature with isosteric heat of energy.
[0925] Because the rigid sorbent material can release the captured CO2 at low temperature, waste heat or recycle streams can then be utilized.
Gas Storage
[0926] As discussed above, embodiments of the present invention relates to flexible porous
polymeric carbon sorbents for gas storage. The gas can be, for example, Th, CO2, O2, methane, and natural gas. The gas can be contained in containing that includes the flexible sorbent, and an increased amount of gas can be stored in the container as compared to the container without the flexible sorbent. I.e., the storage container can store more Th, O2, methane, or natural gas at about 25°C and about 100 atm than in the storage container without the flexible porous carbon material at the same conditions. For instance, the container can be a hydrogen storage vessel to contain Fh for an automobile that runs on Fh. And even much more storage can be achieved at 300 atm.
[0927] In example utilizing HDPE, 8 g of plastic was cut into small 2 cm2 pieces and melted at 150-170°C in a Brabender melt mixer (model type 808-400-DTI). This took less than 5 minutes. Once melted, potassium acetate was added to the polymer melt at salt: plastic weight ratio of 4: 1 and was mixed at 50 RPM for 10 min at 150°C to form a homogenous blend. Then, 2 g of the polymer-based mixture was transferred to a ceramic boat and heated in a tube furnace at rate of 25°C /min under argon atmosphere. The temperature was held at 500°C for 40 min to carbonize the plastic and get porous carbon. After cooling down, 1.5 g of sorbent/salt product was recovered. The product was washed with DI water and filtered using a 0.22 pm PTFE filter to obtain 0.08 g of porous carbon after drying at 100 °C overnight.
[0928] To activate the sorbent, one of the following can be performed:
(a) Heat the sample at a temperature of 120°C and a pressure of 15-10 mbar (a higher vacuum cannot be applied without destruction of the material) for at least 1 hour. As the material activates, water is removed from the binding site, causing pressure to slightly increase. Be sure to adjust the vacuum to back to 10 mbar all the time during the activation process.
(b) Heat the sample at 120°C and flush the sorbent with CO2 three times going from
1 bar to 50 bars in each round.
(c) Do not pull high vacuum on this material as it results on pores collapse and thus sorbent failure.
[0929] The United States Department of Energy (DOE) goal for 2020 for onboard hydrogen storage for light-duty vehicles is 4.5 wt% at 100 atm and room temperature. The DOE’s goal for 2025 is 5.5 wt% at 100 atm, with an ultimate goal of 6.5 wt% at 100 atm and room temperature. [DOE Technical Targets ]. Embodiments of the present invention have already exceeded the 2025 goal and the ultimate goal with their 8 wt% capture at 100 atm and room temperature, thereby underscoring the novelty of the advance described here. FIG. 40A is the gravimetric Eh isotherm of 2,l-HDPE-500 showing an uptake of 8 wt% at 100 bars at room temperature. FIG. 40B is the volumetric Eh isotherm of 2,l-HDPE-500 showing an uptake of 8 wt% at 100 bars at room temperature. FIG. 41 is the Eh isotherm of 2,l-HDPE-500 showing an uptake of 13 wt% at 200 bar at room temperature and 15 wt% at 300 bar. The sorbent is approaching saturation at around 300 bar. FIG. 42 is CEh isotherm of 2,l-HDPE-500 at room temperature reach 160 wt%. The sorbent begins to saturate at around 275 bar.
[0930] FIGS. 43A-43B shows that 2,l-HDPE-500 has high hydrogen storage capacity at room temperature. FIGS. 43C-43D show that 2,l-HDPE-500 has ultra-high storage capacity at 100°C. As shown in FIGS. 44A-44C, 2,l-HDPE-500 can have high storage capacity for CEh and O2, and can capture CO2, Eh, O2, and CEh interchangeably.
[0931] FIGS. 45A-45B show the change of temperature (plots 4501 and 4511) and corresponding change of pressure (plots 4502 and 4512) during Eh cycling. FIG. 45A show the heat gain during the sorption process; and FIG. 45B shows the heat loss during the desorption process.
Direct Air Capture
[0932] The present invention relates to porous polymeric carbon sorbents for direct air capture (DAC). The results reveal that the porous polymeric carbon sorbents perform better than
sorbents with metal-organic framework (MOF), but with none of the high-cost, water instability, and volumetric problems associated with MOFs. Direct air capture of CO2 (and other gases) from air is a technological goal important to large-scale industrial processes such as gas purification and the mitigation of carbon emissions. Moreover, the porous polymeric carbon sorbents can selectively sorb the gases from air.
[0933] In example utilizing HDPE and/or LDPE, to make plastic powder, plastic waste was chilled in liquid nitrogen before it was grounded using a commercial mill. After that, 1 g of plastic powder was mixed with potassium acetate at salt: plastic weight ratio of 4:1. For N- doping, 1 g of N-containing feedstock was added to the plastic/salt mixture. Using a mortar and pestle, the plastic/salt mixture was mixed until a homogeneous blend is formed. Then, 2 g of the polymer-based mixture was transferred to a ceramic boat and heated in a tube furnace at rate of 25°C/min under argon atmosphere. The temperature was held at 620°C for 45 min to carbonize the plastic and get porous carbon. After cooling down, 1.5 g of sorbent/salt product was recovered. The product was washed with DI water and filtered using a 0.22 pm PTFE filter to obtain 0.07 g of porous carbon after drying at 100°C overnight.
[0934] To activate the sorbent, heat the sample at 120°C under vacuum (lxlO 3 mbar) for at least 4 hours. Possible N-containing chemicals include melamine resin, polyethylenimine (most effective), urea, nylon, and NEE gas (during the furnace stage).
[0935] FIG. 46A is the CO2 isotherm of different sorbent in very low pressure showing great capacity at 4 mbar (plots 4601-4602 for HDPE-PEI-600 and HDPE-600, respectively). FIGS. 46B-4C are the CO2 isotherms in very low pressure showing great capacity at 4 mbar which is the partial pressure of CO2 in the air (plots 4611 and 4621 for 2,l-HDPE-600 (Ca OAc), plots 4612 and 4622 for 2,l-HDPE-2-PEI-600, and plots 4613 and 4623 for 2,1 -PEI-600, respectively). Thus, high uptake at very low pressure was obtained, especially for 2,1-HDPE- 2-PEI-600 at 6.1 wt% CO2 uptake at 4 mbar in the nitrogen containing polymer (which takes
110°C for regeneration) whereas without the N-doping it has about 4.4 wt% uptake at 4 mbar but requires only 75°C for regeneration. N-doped sorbent can also be used for DAC. FIG. 20C shows CO2 isotherm of NH4+ exchanged 4, 1 -HDPE-600. An uptake of 27% was obtained when NH4OH is used to wash the sorbent. And it took 95°C to regenerate the material by expelling the CO2.
Plastic Waste Product For Carbon Dioxide Capture
[0936] The present invention also relates to processes to handle plastic waste from different applications, such as packaging plastic, textile plastic and construction plastic, for direct carbon dioxide capture. The processes can results in thermal cracking of the plastic waste, yielding the typical chemicals and fuels that are usually produced with conventional pyrolysis.
[0937] The activated pyrolysis product of plastic waste can produce a solid sorbent with high CO2 uptake capacity at room temperature. In embodiments, the CO2 capacity of the adsorbent can be 18 wt% (4.1 mmol/g) at 25 °C and 1 bar. The sorbent can be synthesized at 600°C via pyrolysis of plastic waste in the presence of potassium acetate. The plastic can be range from high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), or mixture of thereof, to obtain a highly microporous adsorbent with a surface area of -1000 to -1300 m2/g. The ability to synthesize adsorbent at temperatures less than 700°C eliminates the possibility of potassium metal formation, making the scale-up of this process far safer than higher temperature activation. The synthesized adsorbent can have a selectivity of CO2 over N2 of 150 at 0.1 bar, and the adsorbent is stable to repeated cycling. The adsorbent can have low heat of adsorption (24 kJ/mol), making it possible to regenerate at 70°C using waste heat from power plants and refineries. The CO2 capture cost via this technology can be less than $ 10/ton CO2, which is much lower than competing CO2 capture technologies. Hence this plastic waste-derived material should find utility in the capture of from point sources such as flue gas. [0938] For instance, ultra-mi croporous sorbents were prepared by a single-step carbonization
of plastic waste at 600°C under inert atmosphere in the presence of activation reagents. Different activation agents, including potassium hydroxide (KOH), potassium oxalate (K2C2O4), and potassium acetate (KOAc) were explored. See FIG. 4. KOH is an effective agent for carbon activation that has been reported in the literature, [. Jalilov 12017 ; Xu 2018 \ but it is corrosive, difficult to handle in large quantities and has detrimental human health effects, which made the scale-up of materials utilizing KOH as an activator less attractive. Here, the usefulness of KOAc has been shown as an environmentally appealing activating reagent because of its nontoxicity.
[0939] The sorbent was prepared by mixing the plastic waste with the KOAc to obtain a homogenous mixture. The mixture was then carbonized in argon (Ar) atmosphere, washed with deionized water (DI) water, and dried to get the final sorbent.
[0940] Different KOAc:HDPE ratios and activation temperatures were explored to optimize synthesis conditions. FIG. 49A shows the nitrogen (N2) sorption isotherm of the sorbents prepared at different salfHDPE ratios and temperatures, all having type I isotherms (namely, 4,l-HDPE-700, 4,l-HDPE-500, 5,l-HDPE-600, 4,l-HDPE-600, 6,l-HDPE-300, and 2,1- HDPE-600 corresponding to plots 4901-4906, respectively). A type I isotherm is typical for microporous materials with pores less than 2 nm in width. TABLE I below contains the calculated Brunauer-Emmett-Teller (BET) surface area from the N2 isotherms, average pore width, total pore volume, and percentage of microporosity.
Table II
CO2 uptake, pore volume and elemental analysis of the prepared sorbents
[0941] When the different samples were prepared at 600°C, the surface area increased with the increase of KOAc:HDPE ratio, reaching a maximum of 1055 m2/g with 4,l-HDPE-600. Materials prepared with ratios greater than 4 had a collapsed structure and resulted in a decrease in surface area as shown by 5,l-HDPE-600, where the surface area was only 407 m2/g. This data shows that the activation temperature plays a role in the surface area of the sorbent; higher activation temperature leads to higher surface area. The highest surface area of 1293 m2/g was achieved with 4,l-HDPE-700.
[0942] Heating above 700 °C leads to full decomposition of the carbon sorbent, while heating below 600 °C leads to a decrease in the surface area as observed with 4,l-HDPE-500 in
TABLE II
[0943] FIG. 49B shows the density functional theory (DFT) pore width distribution of the sorbents; the highest pore width population is at -0.7 nm. Increasing synthesis temperature and KOAc:HDPE ratios leads to the formations of pore widths of -1.1 nm and 1.4 nm, depending on the temperature. Higher temperature leads to wider pore formation. While pore size distribution varied from one sample to the other based on the synthesis condition, the percentage of micropores was found to be high across all samples as shown in TABLE II.
Characterization
[0944] The elemental composition of the sorbent was studied using X-ray photoelectron spectroscopy (XPS). Oxygen and carbon were the two most abundant elements in the sorbent as shown in the survey scan of 4,l-HDPE-600 in FIGS. 6D-6E. The oxygen content decreased as the synthesis temperature increased, an expected trend since a higher degree of carbonization occurs at higher temperatures (TABLE 2). High resolution Cl XPS showed the presence of
different oxygen functionality, suggesting that KOAc oxidizes the surface of the sorbent during the synthesis. X-ray diffraction (XRD) patterns of the adsorbent showed broad bands with no sharp lines, indicating the amorphous nature of the sorbent. See FIG. 49C.
[0945] The morphology of the adsorbent was studied using environmental scanning electron microscopy (ESEM). FIGS. 50A-50B show ESEM images of 4,l-HDPE-600 with pores and pockets throughout the material. FIGS. 50C-50D show TEM images of 4,l-HDPE-400 that indicate amorphous carbon structures presumably due to the lower non-graphitizing synthesis temperature.
CO2 capacity of the sorbent
[0946] The CO2 capacity of the sorbent was studied using a Rubotherm gravimetric uptake analyzer equipped with a suspended magnetic balance to offer maximum sensitivity. The CO2 isotherms show Langmuir curves (type I isotherms) reaching saturation ~10 bar. FIG. 51A shows a great Langmuir fitting (plot 5101) along with the experimental data (points 5102). Activating HDPE with KOAc yields sorbents with different CO2 capacities, reaching a maximum of 18 wt% at 1 bar and 25 °C with 4,l-HDPE-600. FIG. 52 shows the full isotherms of 4,l-HDPE-700, 4,l-HDPE-600, 3,l-HDPE-600, 2,l-HDPE-600, 5,l-HDPE-600, 4,1- HDPE-500, and l,l-HDPE-600.
[0947] The CO2 uptake was observed to increase with surface area. The uptake increases with an increase in the KOAc:HDPE ratio before it drops when KOAc:HDPE ratio is 5. FIG. 51B (with dots 5103 showing the micropore surface). While the increase in temperature showed a good increase in surface area, no significant enhancement in the CO2 uptake at 1 bar was observed when the activation temperature was greater than 600 °C. FIG. 51C (with dots 5104 showing the micropore surface). This could be due to the formation of larger pores at high temperatures [ Yue 2018\ , which are useful for uptake at high pressure (greater than 1 bar) rather than at low pressure. FIG. 53.
[0948] In general, the CO2 capacity was found to correlate to the micropore surface area; higher micropore surface area usually produced higher CO2 capacity. The volumetric CO2 capacity of 4,l-HDPE-600 was tested to show a capacity of 18% at 1 bar, confirming that the sorbent performance is good both gravimetrically and volumetrically. FIG. 28B.
[0949] Synthesis parameters were optimized using HDPE plastic bottles, nonetheless, the same conditions can be used to activate a mixture of postconsumer plastic (PCP), polypropylene (PP, from plastic cups) and low-density polyethylene (LDPE, from single use plastic bags), which are some of the most challenging materials to recycle and one of the main sources of microplastics. \Yurtsever 2018; Kalogerakis 2017] FIG. 51D. FIGS. 54A-54B show full isotherms for PP, PDPE, HDPE and PCP.
Reaction mechanism
[0950] XRD and thermal gravimetric analyzer-mass spectrometer (TGA-MS) were used to study the activation mechanism of the sorbent. FIGS. 55A-55C. Upon heating, the reaction starts by the decomposition of KOAc to potassium carbonate and acetone at -430 °C, as shown in (5). [ Singh 2019; Cheng 2014]
2CH3COO K+ -> K2CO3 + CH3COCH3 † T = - 430 °C (5)
[0951] The decomposition of KOAc induces the carbonization of HDPE, forming highly microporous carbon around the K2CO3 particles at -500 °C. This step is highly exothermic due to the oxidation reactions that occur upon heating. FIG. 30B.
[0952] In addition, HDPE, (C2Hi)n, undergoes thermal degradation via a free-radical mechanism, producing ethylene and short paraffin chains, (C2H4)m and (C2Hi)p , as described in (6) and (7). [ Tsuchiya 1968]
(C2H4)n (C2H4)m· + (C2H )p· (6)
[0953] The short paraffin chains are collected as a wax deposited in the cold region of the
furnace, while ethylene is volatilized in the gas phase.
[0954] When the evolved gases were analyzed via mass spectroscopy, a large amount of ethylene (m/z=28) and methanol (m/z=32) was detected. The formation of methanol indicated KOAc oxidized and cracked HDPE, thereby releasing methanol, while ethylene evolved due to thermal cracking of HDPE as shown in FIG 55B.
[0955] XRD of the unwashed adsorbent after synthesis at 600°C showed the formation of K2CO3. FIG 55C (with plots 5501-5502 for unwashed sorbent and potassium carbonate, respectively). This supports the mechanism deduced from TGA-MS analysis.
[0956] XPS analysis of the sorbent reveals the presence significant amount of oxygen, indicating oxidation by KOAc. Upon continuous heating, KOAc is reduced to form potassium metal at temperatures above 700 °C as shown in (8). \Coromina 2016; Singh 2017]
T > 720 °C (4)
[0957] Having an understanding of the synthesis mechanism provides insight into the advantages of this technology over existing porous carbon production technologies. Since this technology requires heating plastic waste with KOAc up to 600 °C, the risk of potassium metal formation is lessened, potentially making the process safe to scale up. FIG. 55D shows the synthesis temperature of sorbents reported in the literature, most of which require temperatures above 700 °C to synthesize the porous material. [Yuan 2019; Hong 2016; Bail 2014; Li 2019] Squares 5503a-5503f (KOH) correspond to Ramanathan 2009, Astaria 1983, Jalilov 2015, Yuan 2019, Hong 2016, and Li 2019, respectively. Diamond 5504 (K2CO3) corresponds to Yue 2018. Stars 5505a-5505b (CH3CO2K) correspond to Rao 2019 and 4,l-HDPE-600, respectively. Triangle 5506 (K2C2O4) corresponds to Tsuchiya 1968.
[0958] At such high temperatures, potassium metal formation is one of the safety hazards of scaling up the sorbent production, since potassium metal ignites upon air or moisture exposure.
Pyrolysis cost and assessment of the byproducts
[0959] Differential scanning calorimetry (DSC) curve of the KOAc/HDPE was used to estimate the energy cost to process HDPE using this technology. It was found that 4.5 kJ/g are required to process the KOAc and HDPE mixture. Using natural gas as a fuel to drive the pyrolysis, the process would cost ~$29/ton of HDPE (5 tons total, 1 HDPE and 4 KOAc). The overall cost to process plastic waste is low and competitive compared to existing plastic waste upcycling technologies.
[0960] This synthesis cost is believed to be a fraction of that of metal-organic frameworks (MOFs) or covalent-organic frameworks (COFs) that are difficult to scale up due to the cost and sensitivity to contaminants. [ Ding 2019; Rubio-Martinez 2017; National Academies 2019; Sinha 2017] In large scale production, 4,l-HDPE-600 would presently cost an estimated amount of $35/kg to produce. The net cost of the sorbent could be only $ 19/kg when the value of the byproducts is accounted for, whereas the cost of synthesizing MOFs goes up to $13, 000/kg of MOF with harmful solvents and byproducts produced.
[0961] When synthesizing the sorbent, the initial HDPE is cracked to produced waxes (50%) and gases (38%) as a byproduct. The waxes show similar composition to HDPE with low degree of oxidation when analyzed by FTIR. FIG. 56 (with plots 5601-5602 for wax and HDPE, respectively). The oxidation is probably due to the reaction with KOAc upon heating. [0962] To determine the usefulness of these waxes, they were collected, mixed with KOAc and pyrolyzed to yield a sorbent with similar uptake capacity as the parent activated plastic. See FIG. 9C (4,1 -wax-600). As discussed above, the gas phase byproducts are predominantly ethylene and methanol. Currently, large-scale production of ethylene is carried out in steam crackers via pyrolysis of naphtha and paraffin hydrocarbons in the presence of steam at 850°C to yield -30% ethylene. [Gao 2019] Lower temperature activated pyrolysis of plastic waste could lead to the production of ethylene from waste materials at facilities that could be built near the point of use in support of a circular economy. [ Beston 2021 \.
CO2 capture from flue gas and regeneration
[0963] The sorbent effectiveness for CO2 capture from flue gas streams tested in breakthrough experiments with a 10% CO2 in N2 stream. In such applications, gas selectivity can be a significant parameter to consider when assessing sorbent viability. The selectivity was predicted from the individual pure isotherm of the gases using the ideal adsorbed solution theory (IAST). [Myers 1965\. FIG. 57 shows the CO2 and N2 sorption isotherm of 4,1-HDPE- 600, with greater CO2 capacity than N2 capacity (i.e., high uptake of CO2 in plot 5701 as compared to N2 in plot 5702).
[0964] 4,l-HDPE-600 was found to have a IAST selectivity of 150 at 0.1 bar and 58 at 1 bar. FIG. 58A. Consistent with the high IAST selectivities at 0.1 bar CO2, a negligible difference in the breakthrough times of N2 and the inert tracer (argon) were observed, combined with a finite breakthrough time for CO2 (~ 65 s) (FIG 58B). It is believed that the high selectively of the sorbent may be due to the presence of ultra-micropores the sorbent. The selectivity at low pressure is high and comparable to the selectivity of MOFs [Shi 2020] and zeolites.
[0965] In addition, the sorbent demonstrates fast sorption kinetics, as shown in FIG. 29A. Sorption kinetics is a key parameter in low pressure CO2 adsorption applications since it determines working capacities (and hence, capture cost) in adsorption processes with rapid cycling. Lastly, CO2 breakthrough curves were found to be relatively insensitive to the presence of water vapor at a partial pressure of 0.026 bar (70% relative humidity), evidencing the potential of the sorbent to function effectively under humid conditions. See FIGS. 59A-59B (showing CO2 uptake of 4,l-HDPE-600 against time showing fast sorption dynamics). FIG. 59A shows the normalized concentration over time with plots 5901-5904 for Ar, CO2, H2O, and H2O (empty tube), respectively. FIG. 59B shows the H2O adsorbed over time with plots 5905-5906 for H2O and H2O (empty tube), respectively. In FIG. 59B, the H2O absorbed was corrected for the quantity absorbed during analysis with a blank tube.
[0966] To further understand the nature of interactions between the CO2 gas and the adsorbent, isosteric heat of absorption (Qst) was calculated using the Clausius-Clapeyron eq at 20°C and 25°C. The adsorbent has a maximum heat of adsorption of 24 kJ/mol (FIG. 58C), which is a typical heat of adsorption obtained from weak physical interactions. This heat of adsorption was well below that of MOF and zeolites, which usually have heat of adsorptions at 50 kJ/mol and 90 kJ/mol, respectively. [Modak 2019\. The nature of interactions between the adsorbent and the CO2 allows the regeneration of the adsorbent by subjecting the adsorbent to vacuum, or heating the adsorbent to 70 °C to release trapped CO2 from the pores (FIG. 59D). The ability to regenerate the sorbent at lower temperature reduces the cost of CO2 capture, a factor delaying the deployment of CO2 capture technologies in the market.
[0967] FIG. 60 shows a schematic for CO2 capture/regeneration system utilizing the hot flue gas and interchangeable sorbent chambers, in which the CO2 can be captured in the CO2 capture unit 6001, and regenerated in regeneration unit 6002. In CO2 capture unit 6001, flue gas 6006 (including CO2 and N2) is flowed through a vessel 6005 packed with sorbent while air 6007 for cooling is flowed by the vessel 6005. The CO2 from flue gas 6006 is capture while output gas 6004 containing the N2 flows out of vessel 6005. In regeneration unit 6002, the hot flue gas 6009 is passed through heat exchangers 6010 resulting in cooled flue gas 6012 and output gas 6011 containing CO2.
Highly Tunable Carbon Dioxide Sorbent from Construction/Textile Waste [0968] The present invention relates also to processes to handle plastic waste from different applications, such as packaging plastic, textile plastic and construction plastic in which the properties of the sorbent are tuned by changing the parent plastic type to get varying degrees of microporosity, surface area and nitrogen content. The process relies of the thermal pyrolysis of plastic waste to obtain N-doped porous carbon along with other chemicals as byproducts. With a great control over the pore width, the binding energy of CO2 to the sorbent surface can
be tuned and thus, sorbent with different regeneration temperature can be synthesized from different plastics. For instance, sorbent derived from Nylon 6,6 can have a CO2 uptake of 21% and 6% at 1 bar and 0.1 bar. The cost of synthesizing the sorbent is low making this sorbent very low and competitive compared to other solid sorbents costs.
[0969] N-doped sorbent can be synthesized from construction and textile waste product. For instance, potassium acetate was used as an activating reagent to synthesize the porous sorbent. Examples of the polymers utilized in this synthesis can include melamine resin (MR), polyacrylonitrile (PAN), polyamic acid (PAA), Jeffamine (JA), polyethyleneimine (PEI), acrylonitrile butadiene styrene (ABS), Nylon 6,6, polyurethane (PEI), and Nylon 6,12, which are shown in FIGS. 61A-61I. These polymers for this work are widely used in constructions and textile industry. These polymers are often produced in large quantities and are not usually physically or chemically recycled. Thus, this technology offers a great utilization of the unique backbone of the polymers to synthesize N-doped sorbent in one step activation process. Characterization
[0970] TGA of the tested polymers is shown in FIG 62A (with plots 6201-6209 for Nylon 6,6, Nylon 6,12, MR, PAN, JA M-1000, open cell PU, ABS, PA, and PEI-600, respectively). FIG. 62A shows TGA of the different N-containing plastics showing a decomposition temperature close to that of potassium acetate. Most of the polymers decomposed between 400-600°C. Different activating reagent were explored, including potassium acetate, potassium carbonate, and potassium bicarbonate. All resulted in synthesizing microporous sorbent effectively. FIG. 63 (with plots 6301-6303 for potassium bicarbonate, potassium carbonate, and potassium acetate, respectively).
[0971] In some embodiments, potassium acetate was used with a polymer ratio of 4:1 and synthesis temperature of 600°C were used to prepared sorbent from nine different N-containing polymers. XRD of the produced sorbent showed amorphous carbon structure. FIG. 62B (with
plots 6211-6221 for Nylon 6,6, Nylon 6,12, MR, PAN, JA M-1000, open cell PU, ABS, PAA, PEI-600, PA 12, and PA 6, respectively) shows XRD of the sorbents showing amorphous carbon profile except for PAN, which tended to graphitize.
[0972] Surface area and pore volume of the sorbent were calculated from the N2 sorption isotherm at 77 K. The collected isotherms are shown in FIG. 62C (with plots 6231-6238 for JA, PAN, PA 6/12, OCPU, PA 6/6, ABS, PAA, and MR, respectively) showing type 1 isotherm for all indicating the microporous nature of the sorbent. The surface area of the synthesized sorbent falls between 900 m2/g and 1400 m2/g. Pore size distribution of the sorbent shows high percentage of microporosity with high distribution at 0.75 nm, 1.5 nm, and 1.56 nm, as shown in FIGS. 62D-62E (with plots 6241-6248 for PAA, PA 6/12, OCPU, PA 6/6, ABS, JA, PAN, and MR, respectively). It was found that contribution of microporous to surface area was high and above 90% in some of the sorbent.
[0973] X-photon spectroscopy was used to analyze the elemental composition of the sorbent. FIG. 62F shows the N content along with the nitrogen type for each of the synthesized sorbent. Non-graphitizing polymers shows a N content between 1.5-2% N content, while graphitizing polymer (PAN and MR) have 8 to 9.5% N content.
CO2 capacity of the sorbents
[0974] The CO2 capacity of the sorbent was evaluated using a volumetric analysis setup. Nylon was found to have the highest uptake 0.1 and 1 bar as shown in FIG. 64A. The high uptake is attributed to the high micropore surface area of the nylon derived sorbent. FIG. 64B (with squares 6401-6409 corresponding to Nylon 6,6, Nylon 6, 12, PU, PAA, JA, MR, PEI, ABS, and PAN, respectively) shows the correlation between the microporosity of the sorbent and uptake. High micropore surface area leads to high uptake. This data reveals that the uptake of the sorbent is dictated by the tendency of the polymer to form microspores. It was found that the nitrogen content does not play a big role in increasing the uptake. For example, PAN has 10%
N (one of the highest N content) but shows only 14% uptake at 1 bar (lowest CO2 uptake of all polymers).
[0975] The isosteric heat of binding was calculated for each of the sorbent. Different sorbent was found to have different heat of binding. This could be due to the difference in the average pore size and nitrogen content. Higher heat of regeneration was found to lead to higher regeneration temperature of the sorbent was shown in FIG. 64C (with squares 6411-6418 corresponding to Nylon 6,6, PU, PAA, JA, MR, PEI, PAN, and without doping, respectively). Modification of the sorbent using NH4OH
[0976] FIG. 65A-65B shows N2 sorption isotherms of 4,l-HDPE-600 before and after NH4OH treatment (with plots 6501 and 6503 with NH4OH and plots 6502 and 6504 without NH4OH). FIG. 65C shows DFT pore size distribution of 4,l-HDPE-600 before and after NH4OH treatment (with plots 6505-6506 with NH4OH and without NH4OH, respectively). The surface area and microporosity of the sorbent can be increased by soaking in NH4OH. XPS data shows no significant change in the nitrogen content of the sorbent upon contact with NH4OH. The surface area on the other hand shows big change upon exposure to NH4OH.
Direct air capture
[0977] FIGS. 66A-66B show volumetric CO2 isotherm of HDPE and Nylon sorbent (with plots 6601 and 6603 for 4,1 -Nylon-600 and plots 6602 and 6604 for 4,l-HDPE-600). The nylon sorbent (4,1 -Nylon-600) appears to have excellent uptake at ultra-low pressure compared to HDPE sorbent (4,l-HDPE-600). This could allow it to be effective for direct air capture of CO2.
Advantages For Synthesis of Sorbents From Product Waste
[0978] Embodiments of the present invention can be used as a technology for chemical recycling of plastics via thermal cracking of plastic wastes to get oligomers, monomers, and porous adsorbent. The sorbent can be used for CO2 capture from pre- and post- combustion
CO2 rich steams. Sorbent can be used for direct CO2 capture form air. The sorbent has interesting properties, such as the high porosity and electrical conductivity, making it suitable for simultaneous CO2 capture and conversion to ethylene. The flexible sorbent can be used for hydrogen, methane, oxygen storage, natural gas and more.
[0979] The present invention offers a solution to two of the world’s largest environmental concerns: plastic waste and the rising CO2 levels. The process can be considered green. Zero waste in chemicals and zero net carbon emissions can be achieved. Most plastic recycling technologies fail to recycle/upcycle plastic waste from the construction and textile industry. This present invention offers a great utility of this plastic where it could be upcycled to high value N-doped sorbent. The pyrolysis process of the present invention takes place at temperature less than 600°C, making it very attractive to scaleup. Most porous sorbent synthesis technologies requires temperatures greater than 700°C where risk of formation of potassium metal is high, making the current routes for adsorbent synthesis impossible to commercialize.
[0980] Moreover, because the present invention utilize non-corrosive potassium salts, including potassium acetate, potassium carbonate, and potassium bicarbonate, in thermal processing of plastic waste and because the treatment temperature is kept below 700°C (such that the potassium in the salt will not reduce to potassium metal), there is little, if any, risk of generating H2 gas with ignition upon washing with water to remove the remaining salts after the cracking process. This would greatly lessen the production costs.
[0981] Furthermore, the microporosity of the sorbent can be modified by socking the sorbent in ammonium hydroxide solution. Higher microporosity leads usually to higher uptake at low pressure.
[0982] Moveover, flexible sorbent can be obtained by changing the temperature of synthesis below 550°C. The sorbent can be activated using supercritical CO2 to avoid pores collapse and
allowing for H2 gas storage with high capacity. The Department of Energy goal is to make a material that is both dense (i.e., density ~1 g/cc) and can sorb 5.5 wt% Eb at room temperature and 100 atm of pressure. Embodiments of the present application can capture more than that, such as 7 wt% Eb at room temperature.
[0983] Additional variations of these embodiments will be obvious to those of ordinary skill in the art. Therefore, the spirit and scope of the appended claims should not be limited to the foregoing description. Only those claims specifically reciting “means for” or “step for” should be construed in the manner required under the sixth paragraph of 35 U.S.C. §112.
[0984] While embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described and the examples provided herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. The scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims.
[0985] The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated herein by reference in their entirety, to the extent that they provide exemplary, procedural, or other details supplementary to those set forth herein.
[0986] Amounts and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of approximately 1 to approximately 4.5 should be interpreted to include not only the explicitly recited limits of 1 to approximately 4.5, but also to include individual
numerals such as 2, 3, 4, and sub-ranges such as 1 to 3, 2 to 4, etc. The same principle applies to ranges reciting only one numerical value, such as “less than approximately 4.5,” which should be interpreted to include all of the above-recited values and ranges. Further, such an interpretation should apply regardless of the breadth of the range or the characteristic being described. The symbol
is the same as “approximately”.
[0987] Moreover amounts and other numerical data set forth in the various example embodiments described and taught herein, unless otherwise indicated therein, can be understood to reflect a range of amounts that are ± 10% of the amounts recited in such examples for additional implementations of embodiments of the present invention.
[0988] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently disclosed subject matter belongs. Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the presently disclosed subject matter, representative methods, devices, and materials are now described. [0989] Following long-standing patent law convention, the terms “a” and “an” mean “one or more” when used in this application, including the claims.
[0990] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification are approximations that can vary depending upon the desired properties sought to be obtained by the presently disclosed subject matter.
[0991] As used herein, the term “and/or” when used in the context of a listing of entities, refers to the entities being present singly or in combination. Thus, for example, the phrase “A, B, C, and/or D” includes A, B, C, and D individually, but also includes any and all combinations and subcombinations of A, B, C, and D.
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Claims
WHAT IS CLAIMED IS:
1. A method of synthesizing a porous polymeric carbon sorbent, wherein the method comprises the steps of:
(a) mixing a polymer with an additive to form a mixture, wherein the additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal carbonate, metal bicarbonate, metal oxalate, metal acetate, metal acetyl acetonoate, and mixtures thereof; and
(b) heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation, wherein
(i) the porous polymeric carbon sorbent comprises
(A) a surface area between 400 m2/g and 2000 m2/g,
(B) an average pore size between 2 A and 100 A,
(C) a total pore volume between 0.2 cm3/g and 0.9 cm3/g,
(D) a microporosity greater than 60%, and
(E) an atomic percentage of carbon atoms greater than 75%, and
(ii) the polymeric carbon sorbent is a gas capturing sorbent.
2. The method of Claim 1, wherein the porous polymeric carbon sorbent is a rigid porous polymeric carbon sorbent.
3. The method of any one of Claims 1-2, wherein the average pore size is between 5 A and 20 A.
4. The method of any one of Claims 1-2, wherein the average pore size is between 6 A and 10 A.
5. The method of any one of Claims 1-4, wherein the surface area is between 500 m2/g and 2000 m2/g.
6. The method of any one of Claims 1-4, wherein the surface area is between 500 m2/g and 1100 m2/g.
7. The method of any one of Claims 1-6, wherein the total pore volume is between 0.25 cm3/g and 0.7 cm3/g.
8. The method of any one of Claims 1-6, wherein the total pore volume is between 0.25 cm3/g and 0.6 cm3/g.
9. The method of any one of Claims 1-8, wherein the microporosity is greater than 70%.
10. The method of any one of Claims 1-8, wherein the microporosity is greater than 80%.
11. The method of any one of Claims 1-10, wherein the atomic percentage of carbon atoms is greater than 85%.
12. The method of any one of Claims 1-10, wherein the atomic percentage of carbon atoms can greater than 88%.
13. The method of any one of Claims 1-12, wherein
(a) the porous polymeric carbon sorbent is operable for capturing CO2 at a pressure
between 0.01 atm to 5 atm, and
(b) the polymeric carbon sorbent has a selectivity for capturing CO2 over N2 at least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
14. The method of any one of Claims 1-13, wherein the gas is CO2.
15. The method of any one of Claims 1-14, wherein the porous polymeric carbon sorbent has a density between 1.3 g/cc and 1.8 g/cc.
16. The method of any one of Claims 1-15, wherein the polymer is selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), nylon, polyamine, polyurethane, polyamide, polyacrylonitrile, melamine resin, polyamic acid, styrene, Jeffamine, and combinations thereof.
17. The method of Claim 16, wherein the polymer comprises HDPE.
18. The method of Claim 16, wherein the polymer comprises nylon.
19. The method of any one of Claims 1-18, wherein the polymer is selected from the group consisting of polyvinyl chloride (PVC), nylon, melamine mixed with HDPE, melamine mixed with LDPE, melamine mixed with PP, melamine-formaldehyde resins, polyethylene imine (PEI), PEI mixed with HDPE, polyurethanes (PU), polyacrylonitrile (PAN), and polyethyleneteraphthalte (PET) and mixtures therefrom.
20. The method of any one of Claims 1-19, wherein the polymer comprises nitrogen atoms.
21. The method of Claim 20, wherein the polymeric carbon sorbent has a selectivity for capturing CO2 over N2 at least 300:1 in 0.15 bar of CO2 in 0.85 bar N2 at 23°C.
22. The method of any one of Claims 1-21, wherein the polymer comprises a plastic from a waste plastic source.
23. The method of any one of Claims 1-22, wherein the step of heating is performed at a temperature that is between 550°C and 700°C.
24. The method of Claim 23, wherein the step of heating is performed at a temperature that is between 575°C and 600°C.
25. The method of any one of Claims 1-24, wherein the activation reagent is an acetate, carbonate, bicarbonate, or hydroxide salt of potassium or calcium.
26. The method of Claim 25, wherein the salt of potassium or calcium is an acetate, carbonate, or bicarbonate.
27. The method of any one of Claims 1-24, wherein the activation reagent is potassium acetate.
28. The method of any one of Claims 1-24, wherein the activation reagent is calcium acetate.
29. The method of any one of Claims 1-24, wherein the activation reagent comprises a metal selected from the group consisting of Group 1A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
30. The method of any one of Claims 1-24, wherein the activation reagent comprises a metal hydroxide.
31. The method of any one of Claims 1-24, wherein the activation reagent comprises a metal oxalate.
32. The method of any one of Claims 1-24, wherein the activation reagent comprises a metal carbonate.
33. The method of any one of Claims 1-24, wherein the activation reagent comprises a metal bicarbonate.
34. The method of any one of Claims 1-24, wherein the activation reagent comprises a metal acetate.
35. The method of any one of Claims 1-24, wherein the activation reagent comprises a metal acetyl acetonoate.
36. The method of any one of Claims 1-35, wherein weight ratio of the additive and the polymer in the mixture is between 0.5:1 and 5:1.
37. The method of Claim 36, wherein weight ratio of the additive and the polymer in the mixture is between 2: 1 and 4:1.
38. The method of any one of Claims 1-37, wherein the porous polymeric carbon sorbent is operable for capturing CO2 from a post-combustion CO2 emission outlet gas.
39. The method of Claim 38, wherein the post-combustion CO2 emission outlet gas is a flue gas.
40. The method of any one of Claims 1-39, wherein the porous polymeric carbon sorbent is operable for capturing more than 15 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at 1 atm.
41. The method of Claim 40, wherein the porous polymeric carbon sorbent is operable for releasing at least a portion of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 110°C at 1 atm.
42. The method of Claim 41, wherein the porous polymeric carbon sorbent is operable for releasing at least 50% of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 110°C at 1 atm.
43. The method of Claim 41, wherein the porous polymeric carbon sorbent is operable for releasing substantially all of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 110°C at 1 atm.
44. The method of Claim 40, wherein the porous polymeric carbon sorbent is operable for releasing at least a portion of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 75°C at 1 atm.
45. The method of Claim 44, wherein the porous polymeric carbon sorbent is operable for releasing at least 50% of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 75°C at 1 atm.
46. The method of Claim 44, wherein the porous polymeric carbon sorbent is operable for releasing substantially all of the CO2 captured from a post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 75°C at 1 atm.
47. The method of any one of Claims 1-146, wherein the porous polymeric carbon sorbent is operable for capturing more than 18 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at most 5 atm.
48. The method of any one of Claims 1-46, wherein the porous polymeric carbon sorbent is operable for capturing more than 100 wt% CO2 from a post-combustion CO2 emission outlet gas at 25°C and at most 300 atm.
49. The method of any one of Claims 1-48 further comprising controlling pore size of the porous polymeric carbon sorbent by controlling pressure during the step of heating.
50. The method of any one of Claims 1-49, wherein the step of heating the mixture is performed at a near vacuum pressure of at least 0.01 bars.
51. The method of Claim 50, wherein the step of heating the mixture is performed at a near vacuum pressure of between 0.01 bars and 0.1 bars.
52. The method of any one of Claims 1-51 further comprising the step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound or another modifier.
53. The method of Claim 52, wherein the treating of the porous polymer carbon sorbent comprises soaking the porous polymer carbon sorbent utilizing the ammonium compound.
54. The method of any of Claims 52-53, wherein the ammonium compound is ammonium hydroxide.
55. The method of any of Claims 52-54, wherein the step of modifying the porous polymeric carbon sorbent by the ammonium compound treatment increases the surface area and/or the microporosity of the porous polymeric carbon sorbent.
56. The method of any one of Claims 1-50 further comprising the step of modifying the porous polymeric carbon sorbent by treating with hydrazine or hydrazine hydrate.
57. The method of any one of Claims 1-50 further comprising the step of modifying the porous polymeric carbon sorbent by treating with hydroxylamine or hydroxylamine hydrochloride.
58. The method of any of Claims 1-57 further comprising washing the porous polymeric carbon sorbent.
59. The method of Claim 58, wherein deionized water is used to wash the porous polymeric carbon sorbent.
60. The method of any of Claims 58-59 further comprising filtering the porous polymeric carbon sorbent after the step of washing.
61. The method of any of Claims 1-60 further comprising activating the porous polymeric carbon sorbent.
62. The method of Claim 61, wherein the step of activating the porous polymeric carbon sorbent comprises:
(a) heating to an activation temperature under an activation pressure to remove water and/or other compounds from binding sites; and
(b) flushing the porous polymeric carbon sorbent with a flush gas at a flushing pressure.
63. The method of Claim 62 further comprising maintaining vacuum pressures at or above a threshold pressure to prevent pore collapse of pores of the porous polymeric carbon sorbent.
64. The method of any one of Claims 62-63, wherein the activation temperature is in a range between 120°C and 150°C.
65. The method of any one of Claims 62-64, wherein the heating to the activation temperature is for 1 to 12 hours.
66. The method of any one of Claims 62-65, wherein the activation pressure is in a range between 1 and 100 bars.
67. The method of any one of Claims 62-66, wherein the flush gas is Th.
68. The method of any one of Claims 62-66, wherein the flush gas is at a temperature around 25 °C.
69. The method of any one of Claims 62-68, wherein the threshold pressure is selected a group consisting of above 0.005 bar, above 0.006 bar, above 0.007 bar, above 0.008 bar, above 0.009 bar and above 0.01 bar.
70. The method of Claims 62-69, wherein the threshold pressure is near vacuum pressure.
71. The method of any one of Claims 63-70, wherein the step of activation does not reduce density of the porous polymeric carbon sorbent by more than 0.4 g/cc.
72. The method of any one of Claims 63-71, wherein the step of activation does not reduce density of the porous polymeric carbon sorbent by more than 30%.
73. The method of Claim 62-72, wherein the step of modifying the porous polymeric
carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound, hydrazine, hydrazine hydrate hydroxylamine, and/or hydroxylamine hydrochloride occurs after the step of activation.
74. A method of synthesizing a porous polymeric carbon sorbent, wherein the method comprises the steps of:
(a) mixing a polymer with an additive to form a mixture, wherein the additive is an activation reagent that is a metal carbon-and-oxygen containing compound; and
(b) heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation, wherein
(i) the porous polymeric carbon sorbent comprises
(A) a surface area between 400 m2/g and 2000 m2/g,
(B) an average pore size between 2 A and 100 A,
(C) a total pore volume between 0.2 cm3/g and 0.9 cm3/g,
(D) a microporosity greater than 60%, and
(E) an atomic percentage of carbon atoms greater than 75%, and
(ii) the polymeric carbon sorbent is a gas capturing sorbent.
75. The method of Claim 74, wherein the metal carbon-and-oxygen containing compound has between 1 to 6 carbon atoms.
76. The method of Claim 75, wherein the metal carbon-and-oxygen containing compound has between 1 and 2 carbon atoms.
77. The method of Claim 76, wherein the metal carbon-and-oxygen containing compound
has 2 carbon atoms.
78. The method of Claim 74, wherein the metal carbon-and-oxygen containing compound has between one and two carboxylate groups.
79. The method of claim 74, wherein the metal carbon-and-oxygen containing compound comprises a metal oxocarbon or a metal carboxylate.
80. The method of any one of Claims 74-79, wherein the activation reagent comprises a metal selected from the group consisting of Group 1A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
81. The method of any one of Claims 74-80, wherein the surface area is between 500 m2/g and 2000 m2/g.
82. The method of any one of Claims 74-80, wherein the surface area is between 500 m2/g and 1100 m2/g.
83. The method of any one of Claims 74-82, wherein the total pore volume is between 0.25 cm3/g and 0.7 cm3/g.
84. The method of any one of Claims 74-82, wherein the total pore volume is between 0.25 cm3/g and 0.6 cm3/g.
85. The method of any one of Claims 74-84, wherein the microporosity is greater than
70%.
86. The method of any one of Claims 74-84, wherein the microporosity is greater than 80%.
87. The method of any one of Claims 74-86, wherein the atomic percentage of carbon atoms is greater than 85%.
88. The method of any one of Claims 74-86, wherein the atomic percentage of carbon atoms is greater than 88%.
89. A porous polymeric carbon sorbent that comprises
(a) a surface area between 400 m2/g and 2000 m2/g,
(b) an average pore size between 2 A and 100 A,
(c) a total pore volume between 0.2 cm3/g and 0.9 cm3/g,
(d) a microporosity greater than 60%, and
(e) an atomic percentage of carbon atoms greater than 75%, wherein
(i) the porous polymeric carbon sorbent is a gas capturing sorbent.
90. The porous polymeric carbon sorbent of Claim 89, wherein the porous polymeric carbon sorbent is a rigid porous polymeric carbon sorbent.
91. The porous polymeric carbon sorbent of any one of Claims 89-90, wherein the average pore size is between 5 A and 20 A.
92. The porous polymeric carbon sorbent of any one of Claims 89-91, wherein the average pore size is between 6 A and 10 A.
93. The porous polymeric carbon sorbent of any one of Claims 89-92, wherein the surface area is between 500 m2/g and 2000 m2/g.
94. The porous polymeric carbon sorbent of any one of Claims 89-92, wherein the surface area is between 500 m2/g and 1100 m2/g.
95. The porous polymeric carbon sorbent of any one of Claims 89-94, wherein the total pore volume is between 0.25 cm3/g and 0.7 cm3/g.
96. The porous polymeric carbon sorbent of any one of Claims 89-94, wherein the total pore volume is between 0.25 cm3/g and 0.6 cm3/g.
97. The porous polymeric carbon sorbent of any one of Claims 89-96, wherein the microporosity is greater than 70%.
98. The porous polymeric carbon sorbent of any one of Claims 89-96, wherein the microporosity is greater than 80%.
99. The porous polymeric carbon sorbent of any one of Claims 89-98, wherein the atomic percentage of carbon atoms is greater than 85%.
100. The porous polymeric carbon sorbent of any one of Claims 89-98, wherein the atomic
percentage of carbon atoms is greater than 88%.
101. The porous polymeric carbon sorbent of any one of Claims 89-100, wherein
(a) the porous polymeric carbon sorbent is operable to capture more than 15 wt%
CO2 from a post-combustion CO2 emission outlet gas at 25°C and at 1 atm, and
(b) the polymeric carbon sorbent has a selectivity for capturing CO2 over N2 at least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
102. The porous polymeric carbon sorbent of any one of Claims 89-101, wherein the gas is CO2.
103. The porous polymeric carbon sorbent of any one of Claims 89-102, wherein the porous polymeric carbon sorbent comprises a polymer that has no polymeric long range order and no polymeric short range order detectable by powder X-ray diffraction.
104. The porous polymeric carbon sorbent of any one of Claims 89-103, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 captured from post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 110°C at about 1 atm pressure.
105. The porous polymeric carbon sorbent of any one of Claims 89-103, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 captured from post-combustion CO2 emission outlet gas by heating the porous polymeric carbon sorbent to at most 75°C at about 1 atm pressure.
106. The porous polymeric carbon sorbent of any one of Claims 89-105, wherein the porous polymeric carbon sorbent is operable for capturing more than 18 wt% CO2 from post combustion CO2 emission outlet gas at 25°C and at 5 atm.
107. The porous polymeric carbon sorbent of any one of Claims 89-106, wherein the porous polymeric carbon sorbent is operable for capturing more than 100 wt% CO2 from post combustion CO2 emission outlet gas at 25°C and at 300 atm.
108. The porous polymeric carbon sorbent of any one of Claims 89-107, wherein the porous polymeric carbon sorbent comprises nitrogen atoms.
109. The porous polymeric carbon sorbent of Claim 108, wherein the polymeric carbon sorbent has a selectivity for capturing CO2 over N2 of at least 250: 1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23 °C.
110. A method compri sing :
(a) selecting a porous polymeric carbon sorbent comprising
(i) a surface area between 400 m2/g and 2000 m2/g,
(ii) an average pore size between 2 A and 100 A,
(iii) a total pore volume between 0.2 cm3/g and 0.9 cm3/g,
(iv) a microporosity greater than 60%, and
(v) an atomic percentage of carbon atoms greater than 75%, and
(b) utilizing the porous polymeric carbon sorbent to capture more than 15 wt% CO2 from post-combustion CO2 emission outlet gas.
111. The method of Claim 110, wherein the porous polymeric carbon sorbent is a rigid porous polymeric carbon sorbent.
112. The method of any one of Claims 110-111, wherein the average pore size is between 5 A and 20 A.
113. The method of any one of Claims 110-111, wherein the average pore size is between 6 A and 10 A.
114. The method of any one of Claims 110-113, wherein the surface area is between 500 m2/g and 1100 m2/g.
115. The method of any one of Claims 1105-113, wherein the surface area is between 500 m2/g and 1100 m2/g.
116. The method of any one of Claims 110-115, wherein the total pore volume is between 0.25 cm3/g and 0.7 cm3/g.
117. The method of any one of Claims 110-115, wherein the total pore volume is between 0.25 cm3/g and 0.6 cm3/g.
118. The method of any one of Claims 110-117, wherein the microporosity is greater than 70%.
119. The method of any one of Claims 110-117, wherein the microporosity is greater than
80%.
120. The method of any one of Claims 110-119, wherein the atomic percentage of carbon atoms is greater than 85%.
121. The method of any one of Claims 110-119, wherein the atomic percentage of carbon atoms is greater than 88%.
122. The method of any one of Claims 110-121, wherein the porous polymeric carbon sorbent has a selectivity for capturing CO2 over N2 least 40: 1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
123. The method of any one of Claims 110-122, wherein the post-combustion CO2 emission outlet gas is a flue gas.
124. The method of any one of Claims 110-123, wherein the CO2 is captured from post combustion CO2 emission outlet gas at atmospheric pressure.
125. The method of any one of Claims 110-124, wherein the CO2 is captured from post combustion CO2 emission outlet gas at room temperature at around 25°C.
126. The method of any one of Claims 110-125, wherein the porous polymeric carbon sorbent is utilized to capture more than 18 wt% CO2 from post-combustion CO2 emission outlet gas.
127. The method of Claim 126, wherein the CO2 is captured from post-combustion CO2 emission outlet gas at a pressure that is at most 5 atm.
128. The method of any one of Claims 110-127, wherein the porous polymeric carbon sorbent is utilized to capture more than 100 wt% CO2 from post-combustion CO2 emission outlet gas.
129. The method of Claim 128, wherein the CO2 is captured from post-combustion CO2 emission outlet gas at a pressure that is at most 300 atm.
130. The method of any one of Claims 110-129 further comprising releasing the CO2 captured from post-combustion CO2 emission outlet by heating the porous polymeric carbon sorbent.
131. The method of Claim 130, wherein the CO2 is released by heating the porous polymeric carbon sorbent to at most 110°C.
132. The method of Claim 130, wherein the CO2 is released by heating the porous polymeric carbon sorbent to at most 75°C.
133. The method of any one of Claims 130-132 further comprising repeating the capture and release of the CO2 by the porous polymeric carbon sorbent for at least 1000 cycles.
134. The method of any one of Claims 130-132 further comprising repeating the capture and release of the CO2 by the porous polymeric carbon sorbent for at least 100,000 cycles.
135. The method of any one of Claims 110-134, wherein the porous polymeric carbon sorbent having a selectivity for capturing CO2 over N2 of at least 70:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23°C.
136. The method of any one of Claims 110-135, wherein the porous polymeric carbon sorbent comprises nitrogen atoms.
137. The method of Claim 136, wherein the porous polymeric carbon sorbent having a selectivity for capturing CO2 over N2 of at least 300:1 at least 40:1 at 0.15 bar of CO2 in 0.85 bar of N2 at 23 °C.
138. A method of synthesizing a flexible porous polymeric carbon sorbent, wherein the method comprises the steps of:
(a) mixing a polymer with an additive to form a mixture, wherein the additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal carbonate, metal bicarbonate, metal oxalate, metal acetate, metal acetyl acetonoate, and mixtures thereof; and
(b) heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation, wherein
(i) the porous polymeric carbon sorbent has a first stiffness at room temperature,
(ii) the porous polymeric carbon sorbent has a second stiffness at 100°C,
(iii) the first stiffness is at least two times more than the second stiffness.
139. The method of Claim 1338, wherein the first stiffness is at least three times more than
the second stiffness.
140. The method of any one of Claims 138-139, wherein the first stiffness is at least four times more than the second stiffness.
141. The method of any one of Claims 138-140, wherein
(a) the first stiffness is greater than 35 N/m; and
(b) the second stiffness is less than 10 N/m.
142. The method of any one of Claims 138-141, wherein sorbance of the flexible porous polymeric carbon sorbent at 100°C is substantially greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
143. The method of any one of Claims 138-142, wherein sorbance of the flexible porous polymeric carbon sorbent at 100°C is at least three times greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
144. The method of any one of Claims 138-143, wherein the flexible porous polymeric carbon sorbent is operable for storing 4.5 wt% Th at room temperature and 100 atm.
145. The method of any one of Claims 138-144, wherein
(a) the polymer mixed with the additive has a polymer chain order comprising long range order and short range order as detected by powder X-ray diffraction (XRD); and
(b) the chemical activation results in a loss of the long range order while
maintaining short range order of the polymer as detected by powder XRD such that the porous polymeric carbon sorbent material is a flexible porous polymeric carbon sorbent
146. The method of any one of Claims 138-145, wherein the flexible porous polymeric carbon sorbent gas is operable for storing each of Th, CO2, O2, methane, natural gas, and combinations thereof.
147. The method of any one of Claims 138-146, wherein the flexible porous polymeric carbon sorbent is independently:
(a) operable to store at least 150 wt% of CO2 at room temperature and 50 atm;
(b) operable to store at least 140 wt% of O2 at room temperature and 110 atm; and
(c) operable to store at least 80 wt% of CH4 at room temperature and 100 atm.
148. The method of any one of Claims 138-147, wherein the polymer is selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), nylon, polyamine, polyurethane, polyamide, polyacrylonitrile, melamine resin, polyamic acid, styrene, Jeffamine, and combinations thereof.
149. The method of Claim 148, wherein the polymer comprises HDPE.
150. The method of Claim 148, wherein the polymer comprises nylon.
151. The method of any one of Claims 138-150, wherein the polymer is selected from the group consisting of polyvinyl chloride (PVC), nylon, melamine with HDPE, melamine with
LDPE, melamine with PP, melamine-formaldehyde resins, melamine resins, urea, polyurethanes (PU), polyacrylonitrile, (PAN), polyethylene imine, polyethylene imine mixed with HDPE, and polyethyleneteraphthalte (PET) and mixtures therefrom.
152. The method of any one of Claims 138-151, wherein the polymer comprises nitrogen atoms.
153. The method of any one of Claims 139-152, wherein the step of heating is performed at a temperature that is between 400°C and 525°C.
154. The method of any one of Claims 138-152, wherein the step of heating is performed at a temperature that is between 475°C and 500°C.
155. The method of any one of Claims 138-154, wherein the activation reagent is an acetate, carbonate, bicarbonate, or hydroxide salt of potassium or calcium.
156. The method of Claim 155, wherein the salt of potassium or calcium is an acetate, carbonate, or bicarbonate.
157. The method of any one of Claims 138-154, wherein the activation reagent is potassium acetate.
158. The method of any one of Claims 138-154, wherein the activation reagent is calcium acetate.
159. The method of any one of Claims 138-154, wherein the activation reagent comprises a metal selected from the group consisting of Group 1A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
160. The method of any one of Claims 138-154, wherein the activation reagent comprises a metal hydroxide.
161. The method of any one of Claims 138-154, wherein the activation reagent comprises a metal oxalate.
162. The method of any one of Claims 138-154, wherein the activation reagent comprises a metal carbonate.
163. The method of any one of Claims 138-154, wherein the activation reagent comprises a metal bicarbonate.
164. The method of any one of Claims 138-154, wherein the activation reagent comprises a metal acetate.
165. The method of any one of Claims 138-154, wherein the activation reagent comprises a metal acetyl acetonoate.
166. The method of any one of Claims 138-165, wherein weight ratio of the additive and the polymer in the mixture is between 0.5:1 and 5:1.
167. The method of Claim 166, wherein weight ratio of the additive and the polymer in the mixture is between 2: 1 and 4:1.
168. The method of any one of Claims 138-167, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 5.5 wt% of Th at room temperature and 100 atm.
169. The method of Claim 168, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 8 wt% of Th at room temperature and 100 atm.
170. The method of any one of Claims 138-169, wherein the flexible porous polymeric carbon sorbent is operable for storing about 13 wt% of Th at room temperature and 200 atm.
171. The method of any one of Claims 138-170, wherein the flexible porous polymeric carbon sorbent is operable for storing about 15 wt% of Th at room temperature and 300 atm.
172. The method of any one of Claims 138-171, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 80 wt% of CTri at room temperature and 100 atm.
173. The method of any one of Claims 138-172, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 150 wt% of CTri at room temperature and 200 atm.
174. The method of Claim 173, wherein the flexible porous polymeric carbon sorbent is
operable for storing more than 175 wt% of CH4 at room temperature and 300 atm.
175. The method of any one of Claims 138-174, wherein the flexible porous polymeric carbon sorbent is operable for releasing the stored gas by lowering the pressure back to 1 atm.
176. The method of any one of Claims 138-175 further comprising controlling pore size of the flexible porous polymeric carbon sorbent by controlling pressure during the step of heating.
177. The method of any one of Claims 138-176, wherein the step of heating the mixture is performed at a near vacuum pressure of at least 0.01 bars.
178. The method of Claim 177, wherein the step of heating the mixture is performed at a near vacuum pressure of between 0.01 bars and 0.1 bars.
179. The method of any one of Claims 138-178 further comprising the step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound.
180. The method of Claim 179, wherein the treating of the porous polymer carbon sorbent comprises soaking the porous polymer carbon sorbent utilizing the ammonium compound.
181. The method of any one of Claims 179-180, wherein the ammonium compound is ammonium hydroxide.
182. The method of any one of Claims 179-181, wherein the step of modifying the porous
polymeric carbon sorbent by the ammonium compound treatment increases surface area and/or microporosity of the porous polymeric carbon sorbent.
183. The method of any one of Claims 138-178 further comprising the step of modifying the porous polymeric carbon sorbent by treating with hydrazine or hydrazine hydrate.
184. The method of any one of Claims 138-178 further comprising the step of modifying the porous polymeric carbon sorbent by treating with hydroxylamine or hydroxylamine hydrochloride.
185. The method of any one of Claims 138-184 further comprising washing the porous polymeric carbon sorbent.
186. The method of Claim 185, wherein deionized water is used to wash the porous polymeric carbon sorbent.
187. The method of any one of Claims 185-186 further comprising filtering the porous polymeric carbon sorbent after the step of washing.
188. The method of any one of Claims 138-187 further comprising activating the porous polymeric carbon sorbent.
189. The method of Claim 188, wherein the step of activating the porous polymeric carbon sorbent comprises:
(a) heating to an activation temperature under an activation pressure to remove
water and/or other compounds from binding sites; and (b) flushing the porous polymeric carbon sorbent with a flush gas at a flushing pressure.
190. The method of Claim 189 further comprising maintaining vacuum pressures at or above a threshold pressure to prevent pore collapse of pores of the porous polymeric carbon sorbent.
191. The method of any one of Claims 189-190, wherein the activation temperature is in a range between 120°C and 150°C.
192. The method of any one of Claims 189-191, wherein the heating to the activation temperature is for 1 to 12 hours.
193. The method of any one of Claims 189-192, wherein the activation pressure is in a range between 1 and 100 bars.
194. The method of any one of Claims 189-193, wherein the flush gas is Th.
195. The method of any one of Claims 189-194, wherein the flush gas is at a temperature around 25 °C.
196. The method of any one of Claims 190-195, wherein the threshold pressure is selected a group consisting of above 0.005 bar, above 0.006 bar, above 0.007 bar, above 0.008 bar, above
0.009 bar and above 0.01 bar.
197. The method of Claims 190-196, wherein the threshold pressure is near vacuum pressure.
198. The method of any one of Claims 189-197, wherein the step of activation does not reduce density of the porous polymeric carbon sorbent by more than 0.4 g/cc.
199. The method of any one of Claims 189-198, wherein the step of activation does not reduce density of the porous polymeric carbon sorbent by more than 30%.
200. The method of Claim 189-199, wherein the step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound, hydrazine, hydrazine hydrate hydroxylamine, and/or hydroxylamine hydrochloride occurs after the step of activation.
201. A method of synthesizing a flexible porous polymeric carbon sorbent, wherein the method comprises the steps of:
(a) mixing a polymer with an additive to form a mixture, wherein the additive is an activation reagent that is a metal carbon-and-oxygen containing compound; and
(b) heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation, wherein
(i) the porous polymeric carbon sorbent has a first stiffness at room temperature,
(ii) the porous polymeric carbon sorbent has a second stiffness at 100°C,
(iii) the first stiffness is at least two times more than the second stiffness.
202. The method of Claim 201 , wherein the metal carbon-and-oxygen containing compound has between 1 to 6 carbon atoms.
203. The method of Claim 202, wherein the metal carbon-and-oxygen containing compound has between 1 and 2 carbon atoms.
204. The method of Claim 203, wherein the metal carbon-and-oxygen containing compound has 2 carbon atoms.
205. The method of Claim 201 , wherein the metal carbon-and-oxygen containing compound has between one and two carboxylate groups.
206. The method of claim 201, wherein the metal carbon-and-oxygen containing compound comprises a metal oxocarbon or a metal carboxylate.
207. The method of any one of Claims 201-206, wherein the activation reagent comprises a metal selected from the group consisting of Group 1A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
208. A flexible porous polymeric carbon sorbent that is operable to store Th, wherein
(i) the flexible porous polymeric carbon sorbent has a first stiffness at room temperature,
(ii) the porous polymeric carbon sorbent has a second stiffness at 100°C, and
(iii) the first stiffness is at least two times more than the second stiffness.
209. The flexible porous polymeric carbon sorbent of Claim 208, wherein the first stiffness is at three times more than the second stiffness.
210. The flexible porous polymeric carbon sorbent of any one of Claims 208-209, wherein the first stiffness is at four times more than the second stiffness.
211. The flexible porous polymeric carbon sorbent of any one of Claims 210, wherein
(a) the first stiffness is greater than 35 N/m; and
(b) the second stiffness is less than 10 N/m.
212. The flexible porous polymeric carbon sorbent of any one of Claims 208-211, wherein the flexible porous polymeric carbon sorbent is operable for storing 4.5 wt% Th at room temperature and 100 atm.
213. The flexible porous polymeric carbon sorbent of any one of Claims 208-211, wherein sorbance of the flexible porous polymeric carbon sorbent at 100°C is substantially greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
214. The flexible porous polymeric carbon sorbent of any one of Claims 208-213, wherein sorbance of the flexible porous polymeric carbon sorbent at 100°C is at least three times greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
215. The flexible porous polymeric carbon sorbent of any one of Claims 208-213, wherein the flexible porous polymeric carbon sorbent is independently:
(a) operable to store at least 150 wt% of CO2 at room temperature and 50 atm;
(b) operable to store at least 140 wt% of O2 at room temperature and 110 atm; and
(c) operable to store at least 80 wt% of CH4 at room temperature and 100 atm.
216. The flexible porous polymeric carbon sorbent of any one of Claims 208-215, wherein the flexible porous polymeric carbon sorbent comprises a polymer that has short range order and no long range order by powder X-ray diffraction (XRD).
217. The flexible porous polymeric carbon sorbent of any one of Claims 208-216, wherein the flexible porous polymeric carbon sorbent comprises pores having an average pore size of between 2 A and 100 A.
218. The flexible porous polymeric carbon sorbent of any one of Claims 208-216, wherein the flexible porous polymeric carbon sorbent comprises pores having an average pore size of between 2 A and 20 A.
219. The flexible porous polymeric carbon sorbents of any one of Claims 208-218, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 5.5 wt% of H2 at room temperature and 100 atm.
220. The flexible porous polymeric carbon sorbent of any one of Claims 208-219, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 8 wt% of H2 at room temperature and 100 atm.
221. The flexible porous polymeric carbon sorbent of any one of Claims 208-220, wherein
the flexible porous polymeric carbon sorbent is operable for storing more than 13 wt% of H2 at room temperature and 200 atm.
222. The flexible porous polymeric carbon sorbent of any one of Claims 208-221, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 13 wt% of H2 at room temperature and 300 atm.
223. The flexible porous polymeric carbon sorbent of any one of Claims 208-221, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 15 wt% of H2 at room temperature and 300 atm.
224. The flexible porous polymeric carbon sorbent of any one of Claims 208-223, wherein the flexible porous polymeric carbon sorbent is operable for storing about 20 wt% of H2 at 100°C and 100 atm.
225. The flexible porous polymeric carbon sorbent of any one of Claims 208-224, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 90 wt% of CH4 at room temperature and 100 atm.
226. The flexible porous polymeric carbon sorbent of any one of Claims 208-225, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 150 wt% of CTU at room temperature and 200 atm.
227. The flexible porous polymeric carbon sorbent of any one of Claims 208-226, wherein the flexible porous polymeric carbon sorbent is operable for storing more than 175 wt% of CTU
at room temperature and 300 atm.
228. The flexible porous polymeric carbon sorbent of any one of Claims 208-227, wherein the flexible porous polymeric carbon sorbent comprises nitrogen atoms.
229. A method compri sing :
(a) positioning a flexible porous polymeric carbon sorbent in a container that can contain a gas under pressure, wherein
(i) the flexible porous polymeric carbon sorbent has a first stiffness at room temperature,
(ii) the porous polymeric carbon sorbent has a second stiffness at 100°C, and
(iii) the first stiffness is at least two times more than the second stiffness; and
(b) storing gas in the container, wherein the flexible porous polymeric carbon sorbent sorbs some the gas in the container.
230. The method of Claim 229, wherein the first stiffness is at three times more than the second stiffness.
231. The method of any one of Claims 229-230, wherein the first stiffness is at four times more than the second stiffness.
232. The method of any one of Claims 229-231, wherein
(a) the first stiffness is greater than 35 N/m; and
(b) the second stiffness is less than 10 N/m.
233. The method of any one of Claims 229-232, wherein the temperature of the flexible porous polymeric carbon sorbent increases during the step of storing the gas.
234. The method of Claim 233, wherein the temperature of the flexible porous polymeric carbon sorbent increases by at least 20°C during the step of storing the gas.
235. The method of any one of Claims 229-234, wherein the temperature of the flexible porous polymeric carbon sorbent increases from below 80°C to above 100°C during the step of storing the gas.
236. The method of any one of Claims 229-235, wherein the container can store more of the gas at room temperature and 100 atm than in the container without the flexible porous polymeric carbon sorbent at the same conditions.
237. The method of any one of Claims 229-236, wherein the flexible porous polymeric carbon sorbent is operable for storing 4.5 wt% Th at room temperature and 100 atm.
238. The method of any one of Claims 229-237, wherein, the flexible porous polymeric carbon sorbent is independently:
(a) operable to store at least 150 wt% of CO2 at room temperature and 50 atm;
(b) operable to store at least 140 wt% of O2 at room temperature and 110 atm; and
(c) operable to store at least 80 wt% of CTri at room temperature and 100 atm.
239. The method of any one of Claims 229-238, wherein the flexible porous polymeric
carbon sorbent comprises a polymer that has short range order and no long range order by powder X-ray diffraction (XRD).
240. The method of any one of Claims 229-239, wherein the flexible porous polymeric carbon sorbent comprises pores having an average pore size of between 2 A and 100 A.
241. The method of any one of Claims 229-239, wherein the flexible porous polymeric carbon sorbent comprises pores having an average pore size of between 5 A and 20 A.
242. The method of any one of Claims 229-241, wherein the flexible porous polymeric carbon sorbent stores more than 4.5 wt% Th at room temperature and at most 100 atm.
243. The method of Claim 242, wherein the flexible porous polymeric carbon sorbent stores more than 13 wt% Th at room temperature and at most 200 atm.
244. The method of Claim 243, wherein the flexible porous polymeric carbon sorbent stores more than 15 wt% Th at room temperature and at most 300 atm.
245. The method of any one of Claims 229-243, wherein the flexible porous polymeric carbon sorbent stores at least 8 wt% of Th at room temperature and at most 100 atm.
246. The method of Claim 245, wherein the flexible porous polymeric carbon sorbent stores at least 10 wt% of Th at room temperature and at most 100 atm.
247. The method of any one of Claims 229-246, wherein the flexible porous polymeric
carbon sorbent stores more than 175 wt% of CH4 at room temperature and at most 300 atm.
248. The method of Claim 247, wherein the flexible porous polymeric carbon sorbent stores more than 175 wt% of CTri at room temperature and at most 275 atm.
249. The method of any one of Claims 247-248, wherein the flexible porous polymeric carbon sorbent stores more than 150 wt% of CTU at room temperature and at most 200 atm.
250. The method of any one of Claims 229-249, wherein the flexible porous polymeric carbon sorbent comprises nitrogen atoms.
251. A vehicle comprising an onboard hydrogen storage container, wherein
(a) the container comprises a flexible porous polymeric carbon sorbent, wherein
(i) the flexible porous polymeric carbon sorbent has a first stiffness at room temperature,
(ii) the flexible porous polymeric carbon sorbent has a second stiffness at 100°C, and
(iii) the first stiffness is at least two times more than the second stiffness, and
(b) the container comprises H2 with at least some of the H2 sorbed by the flexible flexible porous polymeric carbon sorbent.
252. The vehicle of Claim 251, wherein the first stiffness is at three times more than the second stiffness.
253. The vehicle of any one of Claims 251-252, wherein the first stiffness is at four times
more than the second stiffness.
254. The vehicle of any one of Claims 251-253, wherein
(a) the first stiffness is greater than 35 N/m; and
(b) the second stiffness is less than 10 N/m.
255. The vehicle of any one of Claims 251-254, wherein sorbance of the flexible porous polymeric carbon sorbent at 100°C is substantially greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
256. The vehicle of any one of Claims 251-255, wherein sorbance of the flexible porous polymeric carbon sorbent at 100°C is at least three times greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
257. The vehicle of any one of Claims 251-256, wherein the container comprises at least 4.5 wt% of Th at a pressure below 300 atm at room temperature.
258. The vehicle of Claim 257, wherein the container comprises at least 4.5 wt% of Th at a pressure below 200 atm at room temperature.
259. The vehicle of Claim 257, wherein the container comprises at least 4.5 wt% of Th at a pressure below 100 atm at room temperature.
260. The vehicle of any one of Claims 251-259, wherein the container comprises at least 5.5 wt% of Th at a pressure below 300 atm at room temperature.
261. The vehicle of Claim 260, wherein the container comprises at least 5.5 wt% of Th at a pressure below 200 atm at room temperature.
262. The vehicle of Claim 260, wherein the container comprises at least 5.5 wt% of Th at a pressure below 100 atm at room temperature.
263. The vehicle of any one of Claims 251-262, wherein the container comprises at least 8 wt% of Th at a pressure below 300 atm at room temperature.
264. The vehicle of Claim 263, wherein the container comprises at least 8 wt% of Th at a pressure below 200 atm at room temperature.
265. The vehicle of Claim 263, wherein the container comprises at least 8 wt% of Th at a pressure below 100 atm at room temperature.
266. The vehicle of any one of Claims 251-265, wherein the container comprises at least 13 wt% of Th at a pressure below 300 atm at room temperature.
267. The vehicle of Claim 266, wherein the container comprises at least 13 wt% of Th at a pressure below 200 atm at room temperature.
268. The vehicle of any one of Claims 251-267, wherein the container comprises at least 15 wt% of Th at a pressure below 300 atm at room temperature.
269. A method compri sing :
(a) selecting a flexible porous polymeric carbon sorbent, wherein
(i) the flexible porous polymeric carbon sorbent has a first stiffness at room temperature,
(ii) the flexible porous polymeric carbon sorbent has a second stiffness at 100°C,
(iii) the first stiffness is at least two times more than the second stiffness, and
(b) utilizing the flexible porous polymeric carbon sorbent to capture a gas.
270. The method of Claim 269, wherein the first stiffness is at three times more than the second stiffness.
271. The method of any one of Claims 269-270, wherein the first stiffness is at four times more than the second stiffness.
272. The method of any one of Claims 269-271, wherein
(a) the first stiffness is greater than 35 N/m; and
(b) the second stiffness is less than 10 N/m.
273. The method of any one of Claims 269-272, wherein sorbance of the flexible porous polymeric carbon sorbent at 100°C is substantially greater than sorbance of the flexible porous polymeric carbon sorbent at room temperature.
274. The method of any one of Claims 269-273, wherein sorbance of the flexible porous polymeric carbon sorbent at 100°C is at least three times greater than sorbance of the flexible
porous polymeric carbon sorbent at room temperature.
275. The method of any one of Claims 269-274, wherein the temperature of the flexible porous polymeric carbon sorbent increases during the step of utilizing the flexible porous polymeric carbon sorbent to capture the gas.
276. The method of Claim 275, wherein the temperature of the flexible porous polymeric carbon sorbent increases by at least 20°C during the step of utilizing the flexible porous polymeric carbon sorbent to capture the gas.
277. The method of any one of Claims 269-276, wherein the temperature of the flexible porous polymeric carbon sorbent increases from below 80°C to above 100°C during the step of storing the gas.
278. The method of any one of Claims 269-277, wherein the flexible porous polymeric carbon sorbent is operable for storing 4.5 wt% Th at room temperature and 100 atm; and
279. The method of any one of Claims 269-278, wherein the gas is selected from the group consisting of Th, CO2, O2, methane, natural gas, and combinations thereof.
280. A method of synthesizing a porous polymeric carbon sorbent, wherein the method comprises the steps of:
(a) mixing a polymer with an additive to form a mixture, wherein the additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal oxalate, metal carbonate, metal bicarbonate, metal acetate, metal
acetyl acetonoate, and mixtures thereof; and (b) heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation, wherein
(i) the porous polymeric carbon sorbent comprises
(A) a surface area between 400 m2/g and 2000 m2/g,
(B) an average pore size between 2 A and 100 A,
(C) a total pore volume between 0.2 cm3/g and 0.9 cm3/g,
(D) a microporosity greater than 60%, and
(E) an atomic percentage of carbon atoms greater than 75%, and
(ii) the porous polymeric carbon sorbent is operable for direct air capturing of C02.
281. The method of Claim 280, wherein the porous polymeric carbon sorbent is a rigid porous polymeric carbon sorbent.
282. The method of any one of Claims 280-281, wherein the average pore size is between 5 A and 20 A.
283. The method of any one of Claims 280-281, wherein the average pore size is between 6 A and 10 A.
284. The method of any one of Claims 280-283, wherein the surface area is between 500 m2/g and 2000 m2/g.
285. The method of any one of Claims 280-283, wherein the surface area is between 500
m2/g and 1100 m2/g.
286. The method of any one of Claims 280-286, wherein the total pore volume is between 0.25 cm3/g and 0.7 cm3/g.
287. The method of any one of Claims 280-286, wherein the total pore volume is between 0.25 cm3/g and 0.6 cm3/g.
288. The method of any one of Claims 286-287, wherein the microporosity is greater than 70%.
289. The method of any one of Claims 286-287, wherein the microporosity is greater than 80%.
290. The method of any one of Claims 280-289, wherein the atomic percentage of carbon atoms is greater than 85%.
291. The method of any one of Claims 280-289, wherein the atomic percentage of carbon atoms is greater than 88%.
292. The method of any one of Claims 280-291, wherein the porous polymeric carbon sorbent is operable for direct air capturing of at least 4 wt% of CO2 at room temperature and 4 mbar partial pressure of CO2 in air.
293. The method of any one of Claims 280-292, wherein the polymer is selected from the
group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), nylon, polyamine, polyurethane, polyamide, polyacrylonitrile, melamine resin, polyamic acid, styrene, Jeffamine, and combinations thereof.
294. The method of Claim 293, wherein the polymer comprises HDPE.
295. The method of Claim 293, wherein the polymer comprises nylon.
296. The method of any one of Claims 280-295, wherein the polymer is selected from the group consisting of polyvinyl chloride (PVC), nylon, melamine mixed with HDPE, melamine mixed with LDPE, melamine mixed with PP, melamine-formaldehyde resins, polyethylene imine (PEI), PEI mixed with HDPE, polyurethanes (PU), polyacrylonitrile, (PAN), and polyethyleneteraphthalte (PET) and mixtures therefrom.
297. The method of any one of Claims 280-296, wherein the polymer comprise a plastic from a waste plastic source.
298. The method of any one of Claims 280-297, wherein the step of heating is performed at a temperature that is between 550°C and 700°C.
299. The method of Claim 298, wherein the step of heating is performed at a temperature that is between 575°C and 600°C.
300. The method of any one of Claims 280-299, wherein the activation reagent is an acetate salt of potassium or calcium.
301. The method of any one of Claims 280-299, wherein the activation reagent is potassium acetate.
302. The method of any one of Claims 280-299, wherein the activation reagent is calcium acetate.
303. The method of any one of Claims 280-299, wherein the activation reagent comprises a metal selected from the group consisting of Group 1A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
304. The method of any one of Claims 280-299, wherein the activation reagent comprises a metal hydroxide.
305. The method of any one of Claims 280-299, wherein the activation reagent comprises a metal oxalate.
306. The method of any one of Claims 280-299, wherein the activation reagent comprises a metal carbonate.
307. The method of any one of Claims 280-299, wherein the activation reagent comprises a metal bicarbonate.
308. The method of any one of Claims 280-299, wherein the activation reagent comprises a metal acetate.
309. The method of any one of Claims 280-300, wherein the activation reagent comprises a metal acetyl acetonoate.
310. The method of any one of Claims 280-309, wherein weight ratio of the additive and the polymer in the mixture is between 0.5:1 and 5:1.
311. The method of Claim 310, wherein weight ratio of the additive and the polymer in the mixture is between 2: 1 and 4:1.
312. The method of any one of Claims 280-311, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 200°C.
313. The method of any one of Claims 280-312, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 75°C.
314. The method of any one of Claims 280-313, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 100°C.
315. The method of any one of Claims 280-314, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
316. The method of any one of Claims 280-315, wherein the polymer comprises nitrogen atoms.
317. The method of Claim 316, wherein the porous polymeric carbon sorbent is operable for direct air capturing of at least 6 wt% of CO2 at 4 mbar partial pressure of CO2 in air.
318. The method of any one of Claims 316-317, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 110°C.
319. The method of any one of Claims 316-318, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
320. The method of any one of Claims 280-319 further comprising controlling pore size of the porous polymeric carbon sorbent by controlling pressure during the step of heating.
321. The method of any one of Claims 280-320, wherein the step of heating the mixture is performed at a near vacuum pressure of at least 0.01 bars.
322. The method of Claim 321, wherein the step of heating the mixture is performed at a near vacuum pressure of between 0.01 bars and 0.1 bars.
323. The method of any one of Claims 280-322 further comprising the step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound.
324. The method of Claim 323, wherein the treating of the porous polymer carbon sorbent comprises soaking the porous polymer carbon sorbent utilizing the ammonium compound.
325. The method of any one of Claims 323-324, wherein the ammonium compound is ammonium hydroxide.
326. The method of any one of Claims 323-324, wherein the step of modifying the porous polymeric carbon sorbent by the ammonium compound treatment increases the surface area and/or the microporosity of the porous polymeric carbon sorbent.
327. The method of any one of Claims 280-323 further comprising the step of modifying the porous polymeric carbon sorbent by treating with hydrazine or hydrazine hydrate.
328. The method of any one of Claims 280-323 further comprising the step of modifying the porous polymeric carbon sorbent by treating with hydroxylamine or hydroxylamine hydrochloride.
329. The method of any one of Claims 280-328 further comprising washing the porous polymeric carbon sorbent.
330. The method of Claim 329, wherein deionized water is used to wash the porous polymeric carbon sorbent.
331. The method of any one of Claims 329-330 further comprising filtering the porous
polymeric carbon sorbent after the step of washing.
332. The method of any one of Claims 280-332 further comprising activating the porous polymeric carbon sorbent.
333. The method of Claim 332, wherein the step of activating the porous polymeric carbon sorbent comprises:
(a) heating to an activation temperature under an activation pressure to remove water and/or other compounds from binding sites; and
(b) flushing the porous polymeric carbon sorbent with a flush gas at a flushing pressure.
334. The method of Claim 333 further comprising maintaining vacuum pressures at or above a threshold pressure to prevent pore collapse of pores of the porous polymeric carbon sorbent.
335. The method of any one of Claims 333-334, wherein the activation temperature is in a range between 120°C and 150°C.
3336. The method of any one of Claims 333-335, wherein the heating to the activation temperature is for 1 to 12 hours.
337. The method of any one of Claims 333-336, wherein the activation pressure is in a range between 1 and 100 bars.
338. The method of any one of Claims 333-337, wherein the flush gas is Th.
339. The method of any one of Claims 3337-338, wherein the flush gas is at a temperature around 25 °C.
340. The method of any one of Claims 334-339, wherein the threshold pressure is selected a group consisting of above 0.005 bar, above 0.006 bar, above 0.007 bar, above 0.008 bar, above 0.009 bar and above 0.01 bar.
341. The method of Claims 334-340, wherein the threshold pressure is near vacuum pressure.
342. The method of any one of Claims 334-341, wherein the step of activation does not reduce density of the porous polymeric carbon sorbent by more than 0.4 g/cc.
343. The method of any one of Claims 334-342, wherein the step of activation does not reduce density of the porous polymeric carbon sorbent by more than 30%.
344. The method of Claim 333-343, wherein the step of modifying the porous polymeric carbon sorbent by treating the porous polymer carbon sorbent with an ammonium compound, hydrazine, hydrazine hydrate hydroxylamine, and/or hydroxylamine hydrochloride occurs after the step of activation.
345. A method of synthesizing a porous polymeric carbon sorbent, wherein the method comprises the steps of:
(a) mixing a polymer with an additive to form a mixture, wherein the additive is an activation reagent a metal carbon-and-oxygen containing compound; and (b) heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation, wherein
(i) the porous polymeric carbon sorbent comprises
(A) a surface area between 400 m2/g and 2000 m2/g,
(B) an average pore size between 2 A and 100 A,
(C) a total pore volume between 0.2 cm3/g and 0.9 cm3/g,
(D) a microporosity greater than 60%, and
(E) an atomic percentage of carbon atoms greater than 75%, and
(ii) the porous polymeric carbon sorbent is operable for direct air capturing of C02.
346. The method of Claim 345, wherein the metal carbon-and-oxygen containing compound has between 1 to 6 carbon atoms.
347. The method of Claim 346, wherein the metal carbon-and-oxygen containing compound has between 1 and 2 carbon atoms.
348. The method of Claim 347, wherein the metal carbon-and-oxygen containing compound has 2 carbon atoms.
349. The method of Claim 345, wherein the metal carbon-and-oxygen containing compound has between one and two carboxylate groups.
350. The method of claim 345, wherein the metal carbon-and-oxygen containing compound comprises a metal oxocarbon or a metal carboxylate.
351. The method of any one of Claims 345-350, wherein the activation reagent comprises a metal selected from the group consisting of Group 1A metals, Group 2A metals, Group 3A metals, transitional metals, lanthanide, actinide, and combinations thereof.
352. The method of any one of Claims 345-351, wherein the surface area is between 500 m2/g and 2000 m2/g.
353. The method of any one of Claims 345-351, wherein the surface area is between 500 m2/g and 1100 m2/g.
354. The method of any one of Claims 345-353, wherein the total pore volume is between 0.25 cm3/g and 0.7 cm3/g.
355. The method of any one of Claims 345-353, wherein the total pore volume is between 0.25 cm3/g and 0.6 cm3/g.
356. The method of any one of Claims 345-355, wherein the microporosity is greater than 70%.
357. The method of any one of Claims 345-355, wherein the microporosity is greater than
80%.
358. The method of any one of Claims 345-357, wherein the atomic percentage of carbon atoms is greater than 85%.
359. The method of any one of Claims 345-357, wherein the atomic percentage of carbon atoms is greater than 88%.
360. A porous polymeric carbon sorbent that comprises:
(a) a surface area between 400 m2/g and 2000 m2/g,
(b) an average pore size between 2 A and 100 A,
(c) a total pore volume between 0.2 cm3/g and 0.9 cm3/g,
(d) a microporosity greater than 60%, and
(e) an atomic percentage of carbon atoms greater than 75%, and wherein
(i) the porous polymeric carbon sorbent is operable to direct air capture CO2.
361. The porous polymeric carbon sorbent of Claim 360, wherein the porous polymeric carbon sorbent is a rigid porous polymeric carbon sorbent.
362. The porous polymeric carbon sorbent of any one of Claims 360-361, wherein the average pore size is between 5 A and 20 A.
363. The porous polymeric carbon sorbent of any one of Claims 360-362, wherein the average pore size is between 6 A and 10 A.
364. The porous polymeric carbon sorbent of any one of Claims 360-363, wherein the
surface area is between 500 m2/g and 2000 m2/g.
365. The porous polymeric carbon sorbent of any one of Claims 360-363, wherein the surface area is between 500 m2/g and 1100 m2/g.
366. The porous polymeric carbon sorbent of any one of Claims 360-365, wherein the total pore volume is between 0.25 cm3/g and 0.7 cm3/g.
367. The porous polymeric carbon sorbent of any one of Claims 360-366, wherein the total pore volume is between 0.25 cm3/g and 0.6 cm3/g.
368. The porous polymeric carbon sorbent of any one of Claims 360-367, wherein the microporosity is greater than 70%.
369. The porous polymeric carbon sorbent of any one of Claims 360-367, wherein the microporosity is greater than 80%.
370. The porous polymeric carbon sorbent of any one of Claims 360-369, wherein the atomic percentage of carbon atoms is greater than 85%.
371. The porous polymeric carbon sorbent of any one of Claims 360-369, wherein the atomic percentage of carbon atoms is greater than 88%.
372. The porous polymeric carbon sorbent of any one of Claims 360-371, wherein the porous polymeric carbon sorbent is operable to direct air capture more than 4 wt% CO2 at room
temperature and 4 mbar partial pressure of CO2 in air.
372. The porous polymeric carbon sorbent of any one of Claims 360-372, wherein the porous polymeric carbon sorbent comprises a polymer that has no polymeric long range order and no polymeric short range order detectable by powder X-ray diffraction (XRD).
374. The porous polymeric carbon sorbent of Claim 360-373, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 200°C.
375. The porous polymeric carbon sorbent of any one of Claims 360-374, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by heating the porous polymeric carbon sorbent to at most 75°C.
376. The porous polymeric carbon sorbent of Claim 360-375, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 100°C.
377. The porous polymeric carbon sorbent of any one of Claims 360-376, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
378. The porous polymeric carbon sorbent of any one of Claims 360-377, wherein the porous polymeric carbon sorbent comprises nitrogen atoms.
379. The porous polymeric carbon sorbent of Claim 378, wherein the porous polymeric carbon sorbent is operable for direct air capturing of at least 6 wt% of CO2 at 4 mbar partial pressure of CO2 in air.
380. The porous polymeric carbon sorbent of any one of Claims 379, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by heating the rigid porous polymeric carbon sorbent to at most 110°C.
381. The porous polymeric carbon sorbent of any one of Claims 379, wherein the porous polymeric carbon sorbent is operable for releasing the CO2 direct air captured by removing the CO2 with vacuum.
382. A method compri sing :
(a) selecting a porous polymeric carbon sorbent, wherein, the porous polymeric carbon sorbent comprises
(i) a surface area between 400 m2/g and 2000 m2/g,
(ii) an average pore size between 2 A and 100 A,
(iii) a total pore volume between 0.2 cm3/g and 0.9 cm3/g,
(iv) a microporosity greater than 60%, and
(v) an atomic percentage of carbon atoms greater than 75%, and
(b) utilizing the porous polymeric carbon sorbent to direct air capture CO2.
383. The method of Claim 382, wherein the porous polymeric carbon sorbent is a rigid porous polymeric carbon sorbent.
384. The method of any one of Claims 382-383, wherein the average pore size is between 5 A and 20 A.
385. The method of any one of Claims 382-383, wherein the average pore size is between 6 A and 10 A.
386. The method of any one of Claims 382-385, wherein the surface area is between 500 m2/g and 2000 m2/g.
387. The method of any one of Claims 382-385, wherein the surface area is between 500 m2/g and 1100 m2/g.
388. The method of any one of Claims 382-387, wherein the total pore volume is between 0.25 cm3/g and 0.7 cm3/g.
389. The method of any one of Claims 382-387, wherein the total pore volume is between 0.25 cm3/g and 0.6 cm3/g.
390. The method of any one of Claims 382-389, wherein the microporosity is greater than 70%.
391. The method of any one of Claims 382-389, wherein the microporosity is greater than 80%.
392. The method of any one of Claims 382-391, wherein the atomic percentage of carbon
atoms is greater than 85%.
393. The method of any one of Claims 382-391, wherein the atomic percentage of carbon atoms is greater than 88%.
394. The method of any one of Claims 382-393, wherein the porous polymeric carbon sorbent is operable for direct air capturing of at least 4 wt% of CO2 at room temperature and 4 mbar partial pressure of CO2 in air.
395. The method of any one of Claims 382-394, wherein the step of utilizing the porous polymeric carbon sorbent comprises utilizing the porous polymeric carbon sorbent to direct air capture more than 4 wt% CO2.
396. The method of any one of Claims 382-395 further comprising releasing the direct air captured CO2 by heating the rigid porous polymeric carbon sorbent.
397. The method of Claim 396, wherein the CO2 is released by heating the rigid porous polymeric carbon sorbent to at most 200°C.
398. The method of Claim 396, wherein the CO2 is released by heating the rigid porous polymeric carbon sorbent to at most 75°C.
399. The method of Claim 396, wherein the CO2 is released by heating the rigid porous polymeric carbon sorbent to at most 100°C.
400. The method of any one of Claims 382-399 further comprising releasing the direct air captured CO2 by applying a vacuum to the rigid porous polymeric carbon sorbent.
401. The method of any one of Claims 382-400 further comprising repeating the direct air capture and release of the CO2 by the porous polymeric carbon sorbent for at least 1000 cycles.
402. The method of any one of Claims 382-401, wherein the porous polymeric carbon sorbent comprises nitrogen atoms.
403. The method of Claim 402, wherein the porous polymeric carbon sorbent is operable for direct air capturing of at least 6 wt% of CO2 at 4 mbar partial pressure of CO2 in air.
404. The method of any one of Claims 402-403, wherein the porous polymeric carbon sorbent is utilized to direct air capture more than 6 wt% CO2 at 4 mbar partial pressure of CO2 in air.
405. The method of any one of Claims 402-404 further comprising releasing the direct air captured CO2 by heating the porous polymeric carbon sorbent.
406. The method of Claim 405, wherein the CO2 is released by heating the rigid porous polymeric carbon sorbent to at most 200°C.
407. The method of Claim 405, wherein the CO2 is released by heating the rigid porous polymeric carbon sorbent to at most 100°C.
408. The method of Claim 402-407 further comprising releasing the direct air captured CO2 by applying a vacuum to the porous polymeric carbon sorbent.
409. The method of any one of Claims 382-408, wherein the method simultaneously captures and converts the CO2 to ethylene.
410. A method of synthesizing a porous polymeric carbon sorbent, wherein the method comprises the steps of:
(a) mixing a polymer with an additive to form a mixture, wherein the additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal carbonate, metal bicarbonate, metal oxalate, metal acetate, metal acetyl acetonoate, and mixtures thereof;
(b) heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation; and
(c) modifying the porous polymeric carbon sorbent by treating the porous polymeric carbon sorbent with a nitrogen compound to increase the surface area and/or microporosity of the porous polymeric carbon sorbent, wherein
(i) the nitrogen compound is selected from the group consisting of an ammonium compound, hydrazine, hydrazine hydrate, hydroxylamine, and hydroxylamine hydrochloride.
411. The method of Claim 410, wherein the porous polymeric carbon sorbent is a rigid porous polymeric carbon sorbent.
412. The method of Claim 410, wherein the porous polymeric carbon sorbent is a flexible porous polymeric carbon sorbent.
413. The method of any one of Claims 410-412, wherein the polymer is plastic waste.
414. The method of Claim 413, wherein the plastic waste is selected from the group consisting of packaging plastic, textile plastic and construction plastic.
415. The method of Claim 414, wherein the treating of the porous polymer carbon sorbent comprises soaking the porous polymer carbon sorbent utilizing the nitrogen compound.
416. The method of any one of Claims 414-415, wherein the nitrogen compound is an ammonium compound
417. The method of Claim 416, wherein the ammonium compound is ammonium hydroxide.
418. The method of any one of Claims 414-415, wherein the nitrogen compound is hydrazine or hydrazine hydrate.
419. The method of any one of Claims 414-415, wherein the nitrogen compound is hydroxylamine or hydroxylamine hydrochloride.
420. The method of any one of Claims 410-419 further comprising activating the sorbent after heating and before modifying.
421. A method of synthesizing a porous polymeric carbon sorbent, wherein the method comprises:
(a) mixing a polymer with an activation reagent to form a mixture;
(b) heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation;
(c) removing sorbates from the porous polymeric carbon sorbent under partial vacuum above a threshold pressure to maintain open pore structures of the porous polymeric carbon sorbent.
422. The method of Claim 421, wherein the heating is conducted at a temperature between 400°C and 525°C and the threshold pressure is 0.01 bar.
423. The method of any one of Claims 421-422, wherein the activation reagent is a metal carbon-and-oxygen compound.
424. The method of any one of Claims 421-422 further comprising modifying the porous polymeric carbon sorbent produced in step (c) by contacting with a modifier compound to increase the surface area and/or microporosity of the porous polymeric carbon sorbent.
425. The method of Claim 424, wherein the modifier compound comprises a nitrogen- containing compound.
426. The method of Claim 425, wherein the nitrogen-containing compound is selected from the group consisting of an ammonium compound, a hydrazine compound, and a hydroxylamine compound.
427. The method of any one of Claims 421-426, wherein the threshold pressure is sufficiently high to avoid collapse of the open pore structures of the porous polymeric carbon
sorbent that would decrease a gas sorption capacity of the porous polymeric carbon sorbent by more than an amount selected from the group consisting of 10%, 15%, 20%, 25%, 30% and
35%.
428. A method of synthesizing a porous polymeric carbon sorbent, wherein the method comprises the steps of:
(a) determining a target characteristic of the porous polymeric carbon sorbet, wherein the target characteristic is selected from the group consisting of surface area, average pore size, total pore volume, microporosity, nitrogen content, regeneration temperature, and combinations thereof;
(b) mixing a polymer with an additive to form the mixture, wherein the additive is an activation reagent that is selected from the group consisting of metal hydroxide, metal carbonate, metal bicarbonate, metal oxalate, metal acetate, metal acetyl acetonoate, and mixtures thereof;
(c) heating the mixture to a temperature to form a porous polymeric carbon sorbent via chemical activation, and
(d) tuning the mixing step and/or the heating step to form porous polymeric carbon sorbent having the target characteristic.
429. The method of Claim 428, wherein the tuning step comprises selecting the polymer based upon the target characteristic.
430. The method of any one of Claims 428-429, wherein the tuning step comprises N- doping the polymer.
431. The method of any one of Claims 428-430, wherein the polymer is selected a group consisting of nylon, polyamine, polyurethane, polyamide, polyacrylonitrile, melamine resin, polyamic acid, styrene, Jeffamine,, and combinations thereof.
432. The method of Claim 431, wherein the polymer comprises HDPE.
433. The method of Claim 431, wherein the polymer comprises nylon.
434. The method of any one of Claims 428-433, wherein the porous polymeric carbon sorbent comprises a CO2 uptake of more than 20% at 1 bar and more than 5% at 0.1 bar.
435. A method compri sing :
(a) selecting a pressure vessel that comprises a flexible porous polymeric carbon sorbent, wherein
(i) the flexible porous polymeric carbon sorbent is at a first temperature in the pressure vessel, and
(ii) the flexible porous polymeric carbon sorbent is capable of sorbing a gas;
(b) flowing the gas into the pressure vessel at a velocity that results in the temperature inside the pressure vessel to increase, wherein
(i) the increase of temperature within the pressure vessel increases the temperature of the flexible porous polymeric carbon sorbent to a second temperature, and
(ii) the sorbance of flexible porous polymeric carbon sorbent at the second temperature is greater than the sorbance of the flexible porous polymeric carbon sorbent at the first temperature.
436. The method of Claim 435, wherein the second temperature is at least 20°C greater than the first temperature.
437. The method of Claim 435, wherein the first temperature is below 80°C and the second temperature is above 100°C.
438. The method of any one of Claims 435-437, wherein stiffness of the flexible porous polymeric carbon sorbent substantially decreases between the first temperature and the second temperature.
439. The method of Claim 438, wherein the stiffness of the flexible porous polymeric carbon sorbent at the second temperature is less than 50% of the stiffness of the flexible porous polymeric carbon sorbent at room temperature.
440. The method of Claim 438, wherein the stiffness of the flexible porous polymeric carbon sorbent at the second temperature is less than 33% of the stiffness of the flexible porous polymeric carbon sorbent at room temperature.
441. The method of Claim 438, wherein the stiffness of the flexible porous polymeric carbon sorbent at the second temperature is less than 33% of the stiffness of the flexible porous polymeric carbon sorbent at room temperature.
442. The method of any one of Claims 435-441, wherein the container can store more of the gas at room temperature and 100 atm than in the pressure vessel without the flexible porous
polymeric carbon sorbent at the same conditions.
443. The sorbents or methods of any one of the preceding claims, further comprising one or more features as defined herein.
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