CN111788000A - 用于去除一氧化碳的吸附剂组合物 - Google Patents
用于去除一氧化碳的吸附剂组合物 Download PDFInfo
- Publication number
- CN111788000A CN111788000A CN201980016750.9A CN201980016750A CN111788000A CN 111788000 A CN111788000 A CN 111788000A CN 201980016750 A CN201980016750 A CN 201980016750A CN 111788000 A CN111788000 A CN 111788000A
- Authority
- CN
- China
- Prior art keywords
- composition
- hours
- weight
- process stream
- stream
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims description 33
- 239000003463 adsorbent Substances 0.000 title claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title description 32
- 238000000034 method Methods 0.000 claims abstract description 88
- 239000002594 sorbent Substances 0.000 claims abstract description 42
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000013980 iron oxide Nutrition 0.000 claims abstract description 16
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005751 Copper oxide Substances 0.000 claims description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 159000000014 iron salts Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 17
- 239000011787 zinc oxide Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000004484 Briquette Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J20/28054—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
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
-
- 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
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
-
- 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
- B01J20/3007—Moulding, shaping or extruding
-
- 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
-
- 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
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
-
- 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
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
-
- 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
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- 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
- B01D2253/10—Inorganic adsorbents
- B01D2253/104—Alumina
-
- 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
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1124—Metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20792—Zinc
-
- 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
- B01D2257/502—Carbon monoxide
-
- 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
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
包含一种或多种铜氧化物和一种或多种铁氧化物的吸附剂组合物可有效地在低于100℃的温度下从例如烯烃过程流的过程流中去除CO。一种从过程流中去除CO的方法包含使所述流与包含一种或多种铜氧化物和一种或多种铁氧化物的所述吸附剂组合物接触。
Description
相关申请的交叉引用
本申请要求于2018年3月5日提交的美国临时专利申请第62/638,612号的优先权,其公开内容以全文引用的方式并入本文中。
技术领域
本发明涉及吸附剂组合物和从例如烃过程流的过程流中去除一氧化碳(CO)的方法。
背景技术
理想地,用于化学过程的流基本上不含有可能妨碍所需化学反应的杂质。例如,烯烃聚合过程使用诸如茂金属的催化剂,其容易因烯烃过程进料流中仅微量的杂质而中毒。因此,用于聚合过程的烯烃进料流必须含有不超过ppb(十亿分之几)水平的杂质;这些流称为“聚合物级”烯烃。来自包括蒸汽裂化器、流化催化裂化器、脱氢、甲醇到烯烃(MTO)过程等典型来源的烯烃通常含有高的多水平的诸如CO或氧气的非所需杂质,例如ppm(百万分之几)或更高水平;这些流称为“化学级”烯烃。
待纯化的流包括空气、氮气、氩气和包括烯烃(如乙烯、丙烯、1-丁烯、2-丁烯、1,3-丁二烯或苯乙烯)的烃。包含氧化铜、氧化锌和氧化铝的吸附剂用于从烯烃流中去除CO。这些吸附剂需要约90℃至约150℃的过程温度。需要有效地在较低温度下从过程流中去除CO的吸附剂。
发明内容
本文公开了能够在低于100℃的温度下从过程流中去除CO的吸附剂组合物。一方面,所述吸附剂组合物包含一种或多种铜氧化物和一种或多种铁氧化物。
在某些实施例中,所述一种或多种铜氧化物与所述一种或多种铁氧化物的重量/重量比为约20/80至约80/20。
在某些实施例中,所述组合物包含按所述组合物的总重量计约0.2重量%至约99.8重量%所述一种或多种铜氧化物。在某些实施例中,所述组合物包含按所述组合物的总重量计约0.2重量%至约99.8重量%所述一种或多种铁氧化物。
在某些实施例中,所述组合物还包含载体或填料。在某些实施例中,所述载体或填料选自由以下组成的组:氧化铝、二氧化硅、氧化镁、氧化锆、铝硅酸盐、粘土、分子筛、活性炭和其组合。
在某些实施例中,所述组合物还包含按所述组合物的总重量计约0.1重量%至约10.0重量%ZnO。在某些实施例中,所述组合物基本上不含ZnO。
在某些实施例中,所述组合物还包含一种或多种选自由以下组成的组的促进剂:钾、钠、锰、铬、钴、钨、钼、镍、镁和钙。在某些实施例中,所述一种或多种促进剂的存在量按所述组合物的总重量计为约0.05重量%至约5.0重量%。
在某些实施例中,所述组合物呈选自由以下组成的组的形式:片剂、团块、环形物、星形物、车轮、挤出物、棒、圆柱体和丸粒。
在某些实施例中,所述组合物呈选自由以下组成的组的形式:片剂、团块、圆柱体和丸粒,其平均最大直径为约1mm至约25mm。
在某些实施例中,当包含CO的过程流在相同条件下在约30℃的温度下与组合物接触时,所述组合物的CO去除效率是包含40重量%CuO、40重量%ZnO和19.9重量%氧化铝的吸附剂组合物的CO去除效率的≥1.5倍。
另一方面,一种用于制备所述组合物的方法包含:制备包含铜和铁盐的溶液;从所述溶液中沉淀固体;分离并干燥所述固体;和煅烧干燥的固体。
在某些实施例中,所述方法还包含随后使干燥的煅烧固体成型。
在某些实施例中,所述方法还包含在所述煅烧步骤之前使所述干燥的固体成型。
在某些实施例中,所述方法还包含:随后使所述干燥的煅烧固体成型以形成成型固体;且煅烧所述成型固体。
在某些实施例中,所述一个或多个煅烧步骤在约250℃至约700℃的温度下进行,持续约0.1小时至约12小时的时段。
在某些实施例中,所述成型包含挤出、压片或造粒。
在某些实施例中,所述方法还包含将载体添加至包含所述铜和铁盐的所述溶液中。
另一方面,一种从气态或液态过程流中去除CO的方法包含使所述流与上述吸附剂组合物中的任一种接触。在某些实施例中,过程流是烃流。在某些实施例中,过程流是烯烃流。在某些实施例中,过程流是丙烯或乙烯流。
在某些实施例中,所述接触在约0℃至约110℃的温度下进行。在某些实施例中,所述接触在约1巴至约80巴的压力下进行。
在某些实施例中,在接触期间,所述气态过程流在所述吸附剂组合物上的流动速率为约1000小时-1至约5000小时-1,并且所述液态过程流在所述吸附剂组合物上的流动速率为约1小时-1至约10小时-1。
在某些实施例中,所述过程流是烯烃流,并且以重量计≤1000ppm的烯烃在所述接触期间被氧化。
在某些实施例中,在相同条件下,在约30℃的接触温度下从所述过程流中去除CO的效率是在相同条件下包含40重量%CuO、40重量%ZnO和19.9重量%氧化铝的吸附剂组合物的CO去除效率的≥1.5倍。在某些实施例中,包含所述铜氧化物和铁氧化物的所述吸附剂组合物和包含40重量%CuO、40重量%ZnO和19.9重量%氧化铝的所述吸附剂组合物以相同方式成型。
具体实施方式
本发明的吸附剂组合物包含一种或多种铜氧化物和一种或多种铁氧化物。在某些实施例中,铜氧化物包含CuO,且铁氧化物包含Fe2O3。在某些实施例中,铜氧化物与铁氧化物的重量/重量比为约99.8/0.2、约99.5/0.5、约99/1、约98/2、约95/5、约90/10、约85/15、约80/20、约75/25、约70/30、约65/35、约60/40、约55/45、或约50/50中的任一者至约45/55、约40/60、约35/65、约30/70、约25/75、约20/80、约15/75、约10/90、约5/95、约2/98、约1/99、约0.5/99.5或约0.2/99.8中的任一者。
组合物还可包含一种或多种金属(元素)铜、金属铁、碱式碳酸铁(Fe2(OH)2CO3)、碱式碳酸铜(Cu2(OH)2CO3)、Fe3O4或Cu2O。在某些实施例中,这些其它形式的铜和/或铁在吸附剂组合物中的存在量按组合物的总重量计为约0.02重量%(重量百分比)、约0.05重量%、约0.10重量%、约0.25重量%、约0.33重量%、约0.40重量%、约0.55重量%、约0.65重量%、约0.75重量%、约0.90重量%、约1.0重量%或约1.5重量%中的任一者至约2.0重量%、约2.5重量%、约3.0重量%、约3.5重量%、约4.0重量%、约4.5重量%或约5.0重量%中的任一者。
在某些实施例中,吸附剂组合物包含按组合物的总重量计约0.2重量%、约0.5重量%(重量百分比)、约0.7重量%、约1.0重量%、约2.5重量%、约4.0重量%、约5.0重量%、约6.0重量%、约8.0重量%、约10重量%、约12重量%、约15重量%、约20重量%、约25重量%或约30重量%中的任一者至约35重量%、约40重量%、约45重量%、约50重量%、约55重量%、约60重量%、约65重量%、约70重量%、约75重量%、约80重量%、约85重量%、约90重量%、约95重量%、约96重量%、约97重量%、约98重量%、约99重量%或约99.8重量%中的任一者的铜氧化物。
在某些实施例中,组合物包含按组合物的总重量计约0.2重量%、约0.5重量%、约0.7重量%、约1.0重量%、约2.5重量%、约4.0重量%、约5.0重量%、约6.0重量%、约8.0重量%、约10重量%、约12重量%、约15重量%、约20重量%、约25重量%或约30重量%中的任一者至约35重量%、约40重量%、约45重量%、约50重量%、约55重量%、约60重量%、约65重量%、约70重量%、约75重量%、约80重量%、约85重量%、约90重量%、约95重量%、约96重量%、约97重量%、约98重量%、约99重量%或约99.8重量%中的任一者的铁氧化物。
在某些实施例中,吸附剂组合物可基本上由以下组成或由以下组成:CuO和Fe2O3以及一种或多种金属(元素)铜、金属铁、碱式碳酸铁(Fe2(OH)2CO3)、碱式碳酸铜(Cu2(OH)2CO3)、Fe3O4或Cu2O;或者组合物可以基本上由CuO和Fe2O3组成或由CuO和Fe2O3组成。
在某些实施例中,组合物还可包含载体和/或填料。在某些实施例中,载体和填料选自由以下组成的组:氧化铝、二氧化硅、氧化镁、氧化锆、铝硅酸盐、粘土、分子筛、活性炭和其组合。在某些实施例中,组合物可以包含氧化铝和/或二氧化硅。载体和/或填料的存在量按组合物的总重量计为约0.2重量%、约0.5重量%、约0.7重量%、约1.0重量%、约2.5重量%、约4.0重量%、约5.0重量%、约6.0重量%、约8.0重量%、约10重量%、约12重量%、约15重量%、约20重量%、约25重量%或约30重量%中的任一者至约35重量%、约40重量%、约45重量%、约50重量%、约55重量%、约60重量%、约65重量%、约70重量%、约75重量%、约80重量%、约85重量%、约90重量%、约95重量%、约96重量%、约97重量%或约98重量%中的任一者。
在某些实施例中,吸附剂组合物可包含ZnO,例如其中ZnO的存在量按组合物的总重量计为约0.1重量%、约0.3重量%、约0.5重量%、约0.7重量%、约1.0重量%、约1.5重量%、约2.0重量%或约2.5重量%中的任一者至约3.0重量%、约3.5重量%、约4.0重量%、约4.5重量%、约5.0重量%、约5.5重量%、约6.0重量%、约6.5、约7.0重量%、约7.5重量%、约8.0重量%、约8.5重量%、约9.0重量%、约9.5重量%或约10.0重量%中的任一者。
在某些实施例中,吸附剂组合物基本上不含ZnO或不含有ZnO。
在某些实施例中,吸附剂组合物可包含一种或多种选自由以下组成的组的促进剂的氧化物:钾、钠、锰、铬、钴、钨、钼、镍、镁和钙。在某些实施例中,一种或多种促进剂在吸附剂组合物中的存在量按组合物的总重量计为0.05重量%、约0.10重量%、约0.25重量%、约0.33重量%、约0.40重量%、约0.55重量%、约0.65重量%、约0.75重量%、约0.90重量%、约1.0重量%或约1.5重量%中的任一者至约2.0重量%、约2.5重量%、约3.0重量%、约3.5重量%、约4.0重量%、约4.5重量%或约5.0重量%中的任一者。
在某些实施例中,吸附剂组合物可包含一种或多种选自氧化锰、氧化钴、氧化铈或氧化锆的促进剂。
吸附剂组合物可有利地呈成型形式,例如呈选自由以下组成的组的形式:形成的凝结物、片剂、环形物、星形物、车轮、挤出物、棒、圆柱体、团块和丸粒。片剂、团块、圆柱体和丸粒的平均最大直径可为约1mm、约2mm、约3mm、约4mm、约5mm、约6mm、约7mm、约8mm、约9mm或约10mm中的任一者至约12mm、约14mm、约16mm、约18mm、约20mm、约22mm、约24mm或约25mm中的任一者。最大直径是指形式的最大测量值。可以通过包括挤出、造粒或压片的过程由粉末制备成型形式。
在某些实施例中,组合物可以呈片剂、团块或挤出物的成型形式,其具有约1mm、约2mm、约3mm、约4mm或约5mm中的任一者乘以约1mm、约2mm、约3mm、约4mm或约5mm中的任一者的最大直径和长度尺寸。
在某些实施例中,当在约30℃、约40℃或约50℃的温度下使包含CO的过程流与组合物接触时,从所述流中去除CO的效率是包含40重量%CuO、40重量%ZnO和19.9重量%氧化铝的吸附剂组合物的CO去除效率的≥1.5倍、≥2.0倍、≥2.5倍、≥3.0倍、≥3.5倍、≥4.0倍、≥4.5倍、≥5.0倍、≥5.5倍或≥6.0倍。在这些比较中,接触是在相同的时间、温度、压力和物流流动速率下进行的,并且吸附剂组合物呈相同的成型形式。例如在美国专利第7,314,965号的实例1中公开了包含40重量%CuO、40重量%ZnO和19.9重量%氧化铝的比较吸附剂。
本发明的吸附剂组合物可通过包含以下的方法制备:制备包含铜和铁盐的溶液;从溶液中沉淀固体;分离并干燥固体;和煅烧干燥的固体。可以对分离的干燥固体进行煅烧步骤。在其它实施例中,可以使分离的干燥固体成型,并且可以对成型的吸附剂进行煅烧步骤。在某些实施例中,可以将分离的干燥固体进行煅烧,可以使煅烧的固体成型,并且可以将成型的形式进一步煅烧(即,两个煅烧步骤)。
合适的铜和铁盐包括硝酸盐、卤化物和硫酸盐。铜和铁盐可以具有相同或不同的阴离子。在某些实施例中,将盐溶液加热到约30℃、约35℃、约40℃或约45℃中的任一者至约50℃、约55℃、约60℃、约65℃、约70℃或约75℃中的任一者。
可以通过添加碱性溶液(例如碱或碱土氢氧化物、碳酸盐或碳酸氢盐溶液,诸如氢氧化钠或碳酸钠)来进行沉淀。可以在约30℃、约35℃、约40℃或约45℃中的任一者至约50℃、约55℃、约60℃、约65℃、约70℃或约75℃中的任一者的温度下,在低于7.0的pH下,例如在约5.8、约6.0、约6.2或约6.3至约6.5或约6.7的pH下进行沉淀。沉淀也可以进行约0.2小时(h)、约0.3小时、约0.4小时、约0.5小时、约0.7小时、约1.0小时或约1.3至约1.5小时、约1.7、约1.9小时、约2.1小时、约2.3小时、约2.5小时、约3小时、约4小时或约5小时中的任一者的时段。
在沉淀看起来完成之后,可以使混合物在如沉淀所述的温度下再“老化”一段时间。
可以通过过滤或倾析分离或收集固体沉淀物,并且通常用去离子(DI)水洗涤所述固体沉淀物,以去除诸如钠盐的任何水溶性盐。
可通过加热至约60℃、约65℃、约70℃、约75℃、约80℃或约90℃中的任一者至约100℃、约110℃、约120℃、约130℃、约1400℃或约150℃中的任一者的温度,持续约.1小时、约0.25小时、约0.4小时、约0.5小时、约0.75小时、约1小时、约1.5小时、约2小时或约2.5小时中的任一者至约3小时、约4小时、约5小时、约6小时、约7小时、约8小时、约9小时、约10小时、约11小时、约12小时、约13小时、约14小时或约15小时中的任一者的时间,来对分离的固体进行干燥。
在其它实施例中,可以将分离的沉淀物喷雾干燥以形成粉末。
在某些实施例中,方法包含分离和干燥固体;煅烧干燥的固体;和使干燥的煅烧固体成型。
在某些实施例中,方法包含分离和干燥固体;使干燥的固体成型;并且煅烧干燥的成型固体。
在某些实施例中,方法包含分离和干燥固体;煅烧干燥的固体;使干燥的煅烧固体成型;和进一步煅烧成型固体。
也就是说,有至少一个对分离的粉末或成型的形式进行的煅烧步骤。可能有两个对分离的粉末和也对成型的粉末进行的煅烧步骤。
在某些实施例中,一个或多个煅烧步骤在约250℃、约300℃、约350℃或约400℃中的任一者至约450℃、约500℃、约550℃、约600℃、约650℃或约700℃中的任一者的温度下进行,持续约0.1小时、约0.25小时、约0.45小时、约0.6小时、约0.75小时或约1小时中的任一者至约1.5小时、约2小时、约2.5小时、约3小时、约4小时、约5小时、约6小时、约7小时、约8小时、约9小时、约10小时、约11小时或约12小时中的任一者的时段。
在某些实施例中,煅烧步骤例如,在约250℃、约300℃或约350℃至约400℃或约450℃中的任一者的温度下将是“温和的”。温和煅烧可用于防止烧结,并且可导致最终组合物中存在少量残留的碱式碳酸铁(Fe2(OH)2CO3)和/或碱式碳酸铜。
成型步骤可以包含挤出、压片或造粒。
在某些实施例中,可以将载体和/或填料添加至铜和铁盐溶液中。可以在沉淀步骤之前将载体或填料作为水中的分散体添加至盐溶液中。也可以将载体或填料作为不可分散的固体或作为例如硝酸铝的盐添加至溶液中。
在某些实施例中,可以在沉淀铜和铁盐之前或之后添加载体或填料。
如果存在载体,则铜氧化物和铁氧化物可浸渍于载体中或沉积于载体上。
在其它实施例中,可以通过简单地物理混合一种或多种铜氧化物、一种或多种铁氧化物的干燥粉末和任选地一种或多种载体或填料来制备吸附剂组合物。可以使物理混合物成型为所需形式,如片剂、团块或挤出物。
本发明的又一目的是从过程流中去除CO的方法,所述方法包含使所述流与本发明的吸附剂组合物接触。过程流可以是需要从其中去除CO的任何组合物。在某些实施例中,过程流是烃流,例如烯烃流。烯烃流包括例如乙烯、丙烯、1-丁烯、2-丁烯、1,3-丁二烯或苯乙烯。
本发明的方法可以提供聚合物级烯烃,例如可以提供来自化学级烯烃的聚合物级烯烃。方法可以提供含有<1000ppb、<900ppm、<800ppb、<700ppb、<600ppb、<500ppb、<400ppb、<300ppb、<200ppb、<100ppb、<50ppb、<25ppb或<10ppb CO的纯化的烯烃流。
吸附剂组合物对CO具有高亲和力,并且同时对氧化烯烃没有活性。例如,以重量计≤1000ppm、≤750ppm、≤500ppm、≤400ppm、≤300ppm、≤200ppm、≤150ppm、≤100ppm、≤75ppm、≤50ppm或≤10ppm的烯烃在烯烃纯化方法中被氧化。
在某些实施例中,可以在约0℃、约10℃、约15℃、约20℃、约25℃、约30℃、约35℃、约40℃、约45℃、约50℃、约55℃或约60℃中的任一者至约65℃、约70℃、约75℃、约80℃、约85℃、约90℃、约95℃、约100℃或约110℃中的任一者的温度下进行接触或过程流纯化。
在某些实施例中,可以在约1巴、约2巴、约4巴、约5巴、约7巴、约9巴、约12巴或约15巴中的任一者至约20巴、约25巴、约30巴、约35巴、约40巴、约45巴、约50巴、约55巴、约60巴、约65巴、约70巴、约75巴或约80巴中的任一者的压力下进行过程流纯化。
在某些实施例中,在接触期间,气态过程流在吸附剂组合物上的流动速率是以约900小时-1、约1000小时-1、约1500小时-1、约2000小时-1、约2500小时-1中的任一者至约3000小时-1、约3500小时-1、约4000小时-1、约4500小时-1、约5000小时-1或约5500小时-1中的任一者的气时空速(GHSV)。
在某些实施例中,在接触期间,液态过程流在吸附剂组合物上的流动速率是以约0.9小时-1、约1.0小时-1、约1.5小时-1、约2.0小时-1或约2.5小时-1中的任一者至约3.0小时-1、约3.5小时-1、约4.0小时-1、约4.5小时-1、约5.0小时-1、约5.5小时-1、6.0小时-1、约6.5小时-1、约7.0小时-1、约7.5小时-1、约8.0小时-1、约8.5小时-1、约9.0小时-1、约9.5小时-1、约10.0小时-1或约10.5小时-1中的任一者的液时空速(LHSV)。
在某些实施例中,从乙烯中去除CO在气相中进行,并且从丙烯中去除CO在液相中进行。
可以在使用后例如通过进行温和的再氧化而再生吸附剂组合物。在某些实施例中,可以通过在例如约150℃的加工温度下用低浓度的氧气来处理而再生吸附剂组合物。
在某些实施例中,过程流是烯烃流,并且以重量计≤1000ppm、≤750ppm、≤500ppm、≤400ppm、≤300ppm、≤200ppm、≤150ppm、≤100ppm、≤75ppm、≤50ppm、≤10ppm、≤5ppm、≤3ppm或≤1ppm的烯烃在接触期间被氧化。
在某些实施例中,在约30℃、约40℃或约50℃的接触温度下从过程流中去除CO的效率是按组合物的重量计包含40重量%CuO、40重量%ZnO和19.9重量%氧化铝的吸附剂组合物的CO去除效率的≥1.5倍、≥2.0倍、≥2.5倍、≥3.0倍、≥3.5倍、≥4.0倍、≥4.5倍、≥5.0倍、≥5.5倍或≥6.0倍。在相同条件下进行接触,例如对于相同的过程流以相同的流动速率和在相同的时间、温度和压力下进行接触,并且其中吸附剂组合物呈相同的成型形式。
吸附剂组合物还可适合于从液氮流中去除氧气。在此情况下,组合物可有效地针对在低至约77K的温度下从过程流中去除氧气。
在某些实施例中,本发明的吸附剂组合物的累积孔隙体积可为约0.20cm3/g、约0.25cm3/g、或约0.30cm3/g中的任一者至约0.35cm3/g、约0.40cm3/g、约0/45cm3/g或约0.50cm3/g中的任一者。
在某些实施例中,吸附剂组合物的N2布鲁尼尔-埃密特-特勒(BET)表面积可为约130m2/g、140m2/g、约145m2/g、约150m2/g或约155m2/g中的任一者至约160m2/g、约165m2/g、约170m2/g、约175m2/g、约180m2/g或约190m2/g中的任一者。
在某些实施例中,吸附剂组合物的平均孔隙尺寸可以为约20埃、约25埃、约30埃或约35埃中的任一者至约40埃、约45埃、约50埃、约55埃或约60埃中的任一者。如本文所用,“孔隙尺寸”是指孔径。
说明性实例
提出以下实例以帮助理解本公开,并且以下实例当然不应被解释为特定地限制本文描述和主张的实施例。将在本领域技术人员的范围内的包括替换现在已知或以后开发的所有等效物的实施例的此类变化和调配物的改变或实验设计的微小改变都视为属于并入本文中的实施例的范围内。
样品A:将一份199.7g的硝酸铜溶液(17重量%Cu)、208.3g的硝酸铁溶液(10重量%Fe)和252.5g的去离子(DI)水混合在一起且加热到60℃。使用实验室掺合器将一份39.5g的D氧化铝粉末(D50粒径为40μm,BET表面积为220m2/g,孔隙体积为0.55mL/g)分散在127.9g的DI水中,并且将所得的分散体添加到硝酸铜和硝酸铁中。用3000mL的DI水稀释混合物,且随后将其加入到反应器中。在pH 6.5下且在60℃下,添加约650g碳酸钠(24重量%Na2CO3)使硝酸铜和硝酸铁沉淀约1小时的时段。沉淀完成后,使混合物在60℃下再老化2小时。将固体沉淀物过滤,用DI水洗涤,且在110℃下干燥过夜。在300℃下将固体在马弗炉中煅烧2小时。所得的混合金属氧化物介质含有37重量%CuO、27重量%Fe2O3和36重量%Al2O3。
样品B:重复样品A的程序,但改为使用一份199.7g的硝酸铜溶液(17重量%Cu)、277.3g的硝酸铁溶液(10重量%Fe)和208.2g的DI水来提供铜硝酸铜和硝酸铁混合物,并且将一份26g的氧化铝粉末分散在85.3g的DI水中。所得的混合金属氧化物介质含有39重量%CuO、36.9重量%Fe2O3和22.5重量%Al2O3。
样品C:重复样品A的程序,但改为不使用氧化铝。使用一份250g的硝酸铜溶液(17重量%Cu)、347.8g的硝酸铁溶液(10重量%Fe)和149.8g的DI水,并且将其沉淀、老化、过滤、洗涤、干燥且煅烧。所得的混合金属氧化物介质含有51重量%CuO和49重量%Fe2O3。
样品D:重复样品A的程序,但改为使用一份194.7g的硝酸铜溶液(17重量%Cu)、一份48.7g的硝酸锌溶液(16.5重量%Zn)、一份209.5g的硝酸铁溶液(10重量%Fe)和241.3g的DI水来提供混合金属硝酸盐溶液,并且将一份27.6g的氧化铝粉末分散在89.5g的DI水中。所得的混合金属氧化物介质含有37重量%CuO、10重量%ZnO、28.8重量%Fe2O3和24.2重量%Al2O3。
样品A、B和C各自的N2 BET表面积为160m2/g至170m2/g,孔隙体积为0.25cm3/g至0.45cm3/g,并且平均孔隙尺寸为约30埃至50埃。
在测试之前,用卡沃压机(Carver press)压实样品A-D的粉末且将其筛至+20/-30US目的级分。使用约1立方厘米(cc)的吸附剂通过活塞流反应器来评估去除CO的性能。在150℃下在氮气下将样品预处理数小时,以去除任何水分,然后对过程温度进行温度调节。随后,以3500小时-1的气时空速将157ppm CO/N2气体引入反应器中,并且用CO分析仪和气相色谱法监测流出气体组合物。特定样品的CO容量定义为5ppm CO穿过时消耗/转化的CO总量。100℃下和30℃下的CO容量(L/kg)的结果展示于表1。比较样品是包含CuO、ZnO和氧化铝且不含Fe2O3的商业吸附剂。
表1
在前面的描述中,阐述了许多诸如具体的材料、尺寸、过程参数等的具体细节,以提供对本公开的实施例的透彻理解。在一个或多个实施例中,特定特征、结构、材料或特性可以以任何合适的方式组合。如本文所用的词语“实例”或“例示性”是指用作实例、例子或说明。本文中描述为“实例”或“例示性”的任何方面或设计并不一定被解释为优于或胜于其它方面或设计。实际上,词语“实例”或“例示性”的使用旨在以具体方式呈现概念。如在本申请中所使用,术语“或”旨在是指包括性的“或”而非排除性的“或”。也就是说,除非另有说明或从上下文显而易见,否则“X包括A或B”旨在是指任何自然的包括性排列。也就是说,如果X包括A;X包括B;或X包括A和B两者,那么“X包括A或B”在上述任何情况下都满足。另外,除非本文中另外指示或明显与上下文相矛盾,否则在描述本文中所述的材料和方法的上下文中(尤其在以下权利要求书的上下文中)使用术语“一(a/an)”和“所述”以及类似指示物应被解释为涵盖单数和复数。
通篇使用的术语“约”用于描述和说明小波动。举例来说,“约”可指的是数值可由±5%、±4%、±3%、±2%、±1%、±0.5%、±0.4%、±0.3%、±0.2%、±0.1%或±0.05%修饰。无论是否明确指出,所有数值均由术语“约”修饰。由术语“约”修饰的数值包括特定的识别值。举例来说,“约5.0”包括5.0。
术语“基本上没有”、“大体上没有”、“基本上不含”等是指“不特意添加”,并且可能存在仅微量或非故意的量,例如按提及的组合物的重量计,例如按总吸附剂组合物的重量计,为≤5重量%、≤4重量%、≤3重量%、≤2重量%、≤1重量%、≤0.5重量%或≤0.25重量%
本文中所讨论的美国专利、美国专利申请和公开的美国专利申请特此以全文引用的方式并入本文中。
除非另外指示,否则所有份数和百分比都按重量计。如果未另外指示,那么重量百分比(重量%)是按不含任何挥发物的整个组合物计,也就是说,按干燥固体含量计。
除非在本文中另外指示,否则对本文中值的范围的叙述仅旨在充当分别提及属于所述范围的每一单独值的速记方法,并且每一单独值并入本说明书中,如同在本文中分别叙述一样。除非在本文中另外指示或另外明显与上下文相矛盾,否则本文中所述的所有方法可以任何适合的顺序进行。
整个说明书中提及的“一个实施例”、“某些实施例”、“一个或多个实施例”、“一实施例”或“某些实施例”是指结合实施例描述的特定特征、结构、材料或特性包括于本公开的至少一个实施例中。因此,在整个说明书中各处出现的短语,如“在一个或多个实施例中”、“在某些实施例中”、“在一个实施例中”或“在一实施例中”并不一定指代本公开的相同的实施例。此外,在一个或多个实施例中,特定特征、结构、材料或特性可以以任何合适的方式组合。
应理解,以上描述旨在为说明性的而非限制性的。在阅读和理解以上描述之后,许多其它实施例对于本领域的技术人员将是显而易见的。因此,应参考所附权利要求书以及此类权利要求书所赋予的等效物的全部范围来确定本公开的范围。本文所提供的任何和所有实例或例示性语言(例如“诸如”)的使用仅旨在更好地说明材料和方法,并且除非另外要求,否则并不对范围造成限制。本说明书中的语言不应解释为指示任何未要求的元件是本公开的材料和方法的实践所必需的。
尽管已经参考特定实施例描述了本文公开的实施例,但应理解,这些实施例仅是说明本公开的原理和应用。对于本领域技术人员将显而易见的是,在不脱离本公开的精神和范围的情况下,可以对本公开的方法和装置进行各种修改和变化。因此,希望本公开包括在所附权利要求书及其等效物的范围内的修改和变化,并且出于说明而非限制的目的呈现上述实施例。
Claims (30)
1.一种能够在低于100℃的温度下从过程流中去除CO的吸附剂组合物,所述组合物包含一种或多种铜氧化物和一种或多种铁氧化物。
2.根据权利要求1所述的组合物,其中所述一种或多种铜氧化物与所述一种或多种铁氧化物的重量/重量比为约20/80至约80/20。
3.根据权利要求1或2所述的组合物,其包含按所述组合物的总重量计约0.2重量%至约99.8重量%所述一种或多种铜氧化物。
4.根据前述权利要求中任一项所述的组合物,其包含按所述组合物的总重量计约0.2重量%至约99.8重量%所述一种或多种铁氧化物。
5.根据前述权利要求中任一项所述的组合物,其还包含载体或填料。
6.根据权利要求5所述的组合物,其中所述载体或填料选自由以下组成的组:氧化铝、二氧化硅、氧化镁、氧化锆、铝硅酸盐、粘土、分子筛、活性炭和其组合。
7.根据前述权利要求中任一项所述的组合物,其还包含按所述组合物的总重量计约0.1重量%至约10.0重量%ZnO。
8.根据权利要求1至6中任一项所述的组合物,所述组合物基本上不含ZnO。
9.根据前述权利要求中任一项所述的组合物,其还包含一种或多种选自由以下组成的组的促进剂:钾、钠、锰、铬、钴、钨、钼、镍、镁和钙。
10.根据权利要求9所述的组合物,其中所述一种或多种促进剂的存在量按所述组合物的总重量计为约0.05重量%至约5.0重量%。
11.根据前述权利要求中任一项所述的组合物,其中所述组合物呈选自由以下组成的组的形式:片剂、团块、环形物、星形物、车轮、挤出物、棒、圆柱体和丸粒。
12.根据前述权利要求中任一项所述的组合物,其中所述组合物呈选自由以下组成的组的形式:片剂、团块、圆柱体和丸粒,其平均最大直径为约1mm至约25mm。
13.根据前述权利要求中任一项所述的组合物,其中当包含CO的过程流在相同条件下在约30℃的温度下与组合物接触时,所述组合物的CO去除效率是包含40重量%CuO、40重量%ZnO和19.9重量%氧化铝的吸附剂组合物的CO去除效率的≥1.5倍。
14.一种制备根据前述权利要求中任一项所述的组合物的方法,所述方法包含:
制备包含铜和铁盐的溶液;
从所述溶液中沉淀固体;
分离并干燥所述固体;和
煅烧干燥的固体。
15.根据权利要求14所述的方法,其还包含:
随后使干燥的煅烧固体成型。
16.根据权利要求14所述的方法,其还包含:
在所述煅烧步骤之前使所述干燥的固体成型。
17.根据权利要求14所述的方法,其还包含:
随后使所述干燥的煅烧固体成型以形成成型固体;且
煅烧成型固体。
18.根据权利要求14至17中任一项所述的方法,其中所述煅烧步骤在约250℃至约700℃的温度下进行,持续约0.1小时至约12小时的时段。
19.根据权利要求15至18中任一项所述的方法,其中所述成型步骤包含挤出、压片或造粒。
20.根据权利要求14至19中任一项所述的方法,其还包含:
将载体添加至包含所述铜和铁盐的所述溶液中。
21.一种从气态或液态过程流中去除CO的方法,所述方法包含使所述流与根据权利要求1至13中任一项所述的吸附剂组合物接触。
22.根据权利要求21所述的方法,其中所述过程流是烃流。
23.根据权利要求21或22所述的方法,其中所述过程流是烯烃流。
24.根据权利要求21至23中任一项所述的方法,其中所述过程流是丙烯或乙烯流。
25.根据权利要求21至24中任一项所述的方法,其中所述接触在约0℃至约110℃的温度下进行。
26.根据权利要求21至25中任一项所述的方法,其中所述接触在约1巴至约80巴的压力下进行。
27.根据权利要求21至26中任一项所述的方法,其中在所述接触期间,所述气态过程流在所述吸附剂组合物上的流动速率为约1000小时-1至约5000小时-1,并且所述液态过程流在所述吸附剂组合物上的流动速率为约1小时-1至约10小时-1。
28.根据权利要求21至27中任一项所述的方法,其中所述过程流是烯烃流,并且其中以重量计≤1000ppm的烯烃在所述接触期间被氧化。
29.根据权利要求21至28中任一项所述的方法,其中在约30℃的接触温度下从所述过程流中去除CO的效率是在相同条件下包含40重量%CuO、40重量%ZnO和19.9重量%氧化铝的吸附剂组合物的CO去除效率的≥1.5倍。
30.根据权利要求29所述的方法,其中包含所述铜氧化物和所述铁氧化物的所述吸附剂组合物和包含40重量%CuO、40重量%ZnO和19.9重量%氧化铝的所述吸附剂组合物以相同方式成型。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201862638612P | 2018-03-05 | 2018-03-05 | |
US62/638,612 | 2018-03-05 | ||
PCT/US2019/020521 WO2019173201A1 (en) | 2018-03-05 | 2019-03-04 | Adsorbent compositions for carbon monoxide removal |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111788000A true CN111788000A (zh) | 2020-10-16 |
Family
ID=67846313
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201980016750.9A Pending CN111788000A (zh) | 2018-03-05 | 2019-03-04 | 用于去除一氧化碳的吸附剂组合物 |
Country Status (11)
Country | Link |
---|---|
US (1) | US20210101112A1 (zh) |
EP (1) | EP3762140A4 (zh) |
JP (1) | JP2021516149A (zh) |
KR (1) | KR20200126986A (zh) |
CN (1) | CN111788000A (zh) |
BR (1) | BR112020018012A2 (zh) |
CA (1) | CA3091360A1 (zh) |
MX (1) | MX2020009136A (zh) |
RU (1) | RU2020132505A (zh) |
SG (1) | SG11202007692QA (zh) |
WO (1) | WO2019173201A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114452811A (zh) * | 2021-12-27 | 2022-05-10 | 深圳华明环保科技有限公司 | 一种脱硫脱硝剂及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04150940A (ja) * | 1990-10-09 | 1992-05-25 | Osaka Gas Co Ltd | 吸着剤及びその製造方法 |
US20060276332A1 (en) * | 2005-06-01 | 2006-12-07 | Lawrence Shore | Preferential oxidation catalyst containing platinum, copper and iron |
DE102005061322A1 (de) * | 2005-12-20 | 2007-06-21 | Basf Ag | Verfahren zur Entfernung von Kohlenmonoxid aus Stoffströmen |
CN101384356A (zh) * | 2006-02-14 | 2009-03-11 | 巴斯夫欧洲公司 | 吸附组合物和从物流中去除co的方法 |
CN101954283A (zh) * | 2010-09-25 | 2011-01-26 | 东华大学 | 一种常温消除一氧化碳的硅藻土催化剂及其制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4964889A (en) * | 1989-12-04 | 1990-10-23 | Uop | Selective adsorption on magnesium-containing clinoptilolites |
JP3139124B2 (ja) * | 1992-04-20 | 2001-02-26 | 昭和電工株式会社 | 液相炭化水素中の溶存ガス吸着剤 |
US20030105376A1 (en) * | 2001-11-30 | 2003-06-05 | Foral Michael J. | Purification of polyolefin feedstocks using multiple adsorbents |
DE10241529A1 (de) * | 2002-09-05 | 2004-03-11 | Basf Ag | Adsorptionsmasse und Verfahren zur Entfernung von Kohlenmonoxid aus Stoffströmen |
-
2019
- 2019-03-04 RU RU2020132505A patent/RU2020132505A/ru unknown
- 2019-03-04 CN CN201980016750.9A patent/CN111788000A/zh active Pending
- 2019-03-04 SG SG11202007692QA patent/SG11202007692QA/en unknown
- 2019-03-04 KR KR1020207025333A patent/KR20200126986A/ko not_active Application Discontinuation
- 2019-03-04 BR BR112020018012-2A patent/BR112020018012A2/pt not_active Application Discontinuation
- 2019-03-04 WO PCT/US2019/020521 patent/WO2019173201A1/en unknown
- 2019-03-04 MX MX2020009136A patent/MX2020009136A/es unknown
- 2019-03-04 CA CA3091360A patent/CA3091360A1/en active Pending
- 2019-03-04 US US16/971,090 patent/US20210101112A1/en not_active Abandoned
- 2019-03-04 EP EP19764595.5A patent/EP3762140A4/en not_active Withdrawn
- 2019-03-04 JP JP2020546471A patent/JP2021516149A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04150940A (ja) * | 1990-10-09 | 1992-05-25 | Osaka Gas Co Ltd | 吸着剤及びその製造方法 |
US20060276332A1 (en) * | 2005-06-01 | 2006-12-07 | Lawrence Shore | Preferential oxidation catalyst containing platinum, copper and iron |
DE102005061322A1 (de) * | 2005-12-20 | 2007-06-21 | Basf Ag | Verfahren zur Entfernung von Kohlenmonoxid aus Stoffströmen |
CN101384356A (zh) * | 2006-02-14 | 2009-03-11 | 巴斯夫欧洲公司 | 吸附组合物和从物流中去除co的方法 |
CN101954283A (zh) * | 2010-09-25 | 2011-01-26 | 东华大学 | 一种常温消除一氧化碳的硅藻土催化剂及其制备方法 |
Non-Patent Citations (1)
Title |
---|
JIAN-LIANG CAO ET AL.: "Mesoporous CuO–Fe2O3 composite catalysts for low-temperature carbon monoxide oxidation", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114452811A (zh) * | 2021-12-27 | 2022-05-10 | 深圳华明环保科技有限公司 | 一种脱硫脱硝剂及其制备方法 |
CN114452811B (zh) * | 2021-12-27 | 2023-03-17 | 深圳华明环保科技有限公司 | 一种脱硫脱硝剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2021516149A (ja) | 2021-07-01 |
EP3762140A4 (en) | 2021-12-08 |
SG11202007692QA (en) | 2020-09-29 |
US20210101112A1 (en) | 2021-04-08 |
EP3762140A1 (en) | 2021-01-13 |
RU2020132505A (ru) | 2022-04-06 |
MX2020009136A (es) | 2020-09-28 |
KR20200126986A (ko) | 2020-11-09 |
BR112020018012A2 (pt) | 2020-12-22 |
WO2019173201A1 (en) | 2019-09-12 |
CA3091360A1 (en) | 2019-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0568003B1 (en) | Absorption of hydrogen sulfide and absorbent composition therefor | |
KR100976438B1 (ko) | 흡착 조성물 및 물질 스트림으로부터 일산화탄소를 제거하는 방법 | |
CA2320035C (en) | Copper-containing materials | |
US20070034552A1 (en) | Process for sulfur adsorption using copper-containing catalyst | |
US20110226700A1 (en) | Reduced copper sulphide sorbent for removing heavy metals | |
JP5198441B2 (ja) | 液体プロピレン流からcoを除去するための方法 | |
JP2012515645A (ja) | 重金属用の混合原子価金属硫化物ソーベント | |
CN101384356A (zh) | 吸附组合物和从物流中去除co的方法 | |
AU2013294803A1 (en) | Process | |
EP2158021A1 (en) | Process for reducing carbon monoxide in olefin-containing hydrocarbon feedstocks | |
JP5619788B2 (ja) | 物質流からcoを除去するための吸着体及びその除去方法 | |
JP2009541025A (ja) | 吸収組成物及び水銀の除去方法 | |
CN111788000A (zh) | 用于去除一氧化碳的吸附剂组合物 | |
US20200324267A1 (en) | Adsorbent for hydrocarbon purification | |
CN109772436B (zh) | 一种芳烃合成用催化剂及其制备方法 | |
TWI648246B (zh) | 用於烴純化之方法 | |
RU2662540C2 (ru) | Способы и активные материалы для снижения концентрации галогенида в газовых потоках | |
CN115335352A (zh) | 低级烯烃的纯化 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201016 |
|
WD01 | Invention patent application deemed withdrawn after publication |