CN102639228B - 用于将含氧物自烯烃流移除的较低反应性吸附剂和较高含氧物容量 - Google Patents
用于将含氧物自烯烃流移除的较低反应性吸附剂和较高含氧物容量 Download PDFInfo
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- CN102639228B CN102639228B CN201080055092.3A CN201080055092A CN102639228B CN 102639228 B CN102639228 B CN 102639228B CN 201080055092 A CN201080055092 A CN 201080055092A CN 102639228 B CN102639228 B CN 102639228B
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- zeolite
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 77
- 150000001336 alkenes Chemical class 0.000 title description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000010457 zeolite Substances 0.000 claims abstract description 116
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 112
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 78
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 17
- 231100000719 pollutant Toxicity 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- 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 abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 32
- 239000002250 absorbent Substances 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- -1 hydroxide compound Chemical class 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 57
- 238000007598 dipping method Methods 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 239000000843 powder Substances 0.000 description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- 150000001342 alkaline earth metals Chemical class 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010099 solid forming Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002594 sorbent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 239000000376 reactant Substances 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910014307 bSiO Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000001745 non-dispersive infrared spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- B01J20/02—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
- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
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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
- B01J20/02—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
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明关于一种可以用于将污染物自各种烃流移除的改良吸附剂,所述吸附剂包含沸石、氧化铝和外加金属组分,所述外加金属组分是通过在初始时首先使沸石与所述外加金属接触而存在于吸附剂中。在具体应用中,将包含经钠浸渍的沸石Y和氧化铝的吸附剂用于纯化乙烯流以移除CO2、H2S、甲醇和其它含S-和含O-化合物。
Description
技术领域
本申请涉及一种吸附剂,所述吸附剂包含沸石、氧化铝组分和外加金属组分,例如,大部分含于沸石组分中的钠。这种新型吸附剂是用于将污染物自烃流移除,例如,将CO2、H2S、AsH3、甲醇、硫醇和其它含S-或O-有机化合物自乙烯、丙烯、C3至C4烃产物和其它轻质烃流移除。
发明背景
固体吸附剂常用于将污染物自诸如烯烃、天然气和轻质烃馏分移除。由于这些流可以含有不同污染物,所以需要多于一种吸附剂或吸附剂床才足以纯化所述流,以使其可以用于所需的过程中。可以存在于这些流中的污染物包括H2O、CO、O2、CO2、COS、H2S、NH3、AsH3、PH3、Hg、甲醇、硫醇和其它含S-或O-有机化合物。
各种吸附剂可以移除一种或多种污染物,同时这些吸附剂也可以移除和/或促进所需的烃的反应。例如,八面型沸石,例如,沸石13X,是用于硫和含氧化合物的良好吸附剂。但是,这些沸石也是用于烯烃的良好吸附剂,且会产热,进而可以导致高温产生和/或失控反应。此外,沸石的残余表面反应性在再生期间可以引起寡聚和聚合作用。这会导致结垢和性能劣化。
在尝试补救这个问题时,本领域已提出将沸石与氧化铝混合。美国专利公开4,762,537使用包含沸石Y和氧化铝的吸附剂来将HCl自氢气流移除。在美国专利4,686,198和4,717,483号中公开了氧化铝与钠Y沸石的混合物可以将氨水、硫化物和有机杂质自废水移除。钠Y沸石含有至少12.7重量%Na2O。也将相同吸附剂用于降低使用过的有机磷酸盐官能流体的酸度和水含量,参见美国专利4,751,211。氧化铝与碱或碱土金属用于移除HCl和其它污染物的用途公开在美国专利6,013,600中。
在归属UOP的U.S.6,632,766中,描述一种已改良的吸附剂,所述吸附剂可将多种污染物自各种烃流移除。这种吸附剂包含沸石、氧化铝和金属组分,其中所述金属组分是以占补偿沸石晶格的负电荷所需的金属(表示为氧化物)的化学计算量的至少10摩尔%的量存在。在这个专利中,将金属组分,特别是钠,同时添加至沸石和氧化铝组分。
在以上专利的发现中,UOP发现将Na(广义上来说,1A/2A族金属)添加至沸石/氧化铝复合吸附剂会使烯烃/含氧物对所述吸附剂的反应性大大下降,这由寡聚作用下降予以证明。但是,这个专利并未说明吸附剂上的甲醇容量(典型含氧物)将会损失。本发明人已确定,通过在起始时仅将钠放置在吸附剂的沸石部分上可以在指定的含氧物容量损失下获得最高反应性下降。
发明概要
本发明关于一种固体成型吸附剂,一种制备所述吸附剂的方法和一种利用所述吸附剂移除污染物的方法。因此,本发明的一个实施方案是用于纯化烃流的固体成型吸附剂,其包含氧化铝组分、沸石组分和外加金属组分,所述金属组分选自,例如,由碱金属、碱土金属及其混合物组成的组,在初始时首先将外加金属组分添加至所述沸石组分,以使在沸石中的外加金属的量相较于将相同量的初始金属添加至沸石与氧化铝的混合物的情况大。所述外加金属组分是以超过补偿沸石晶格的负电荷所需的金属的化学计算量的量存在。
本发明的另一实施方案是一种制备用于纯化烃流的固体成型吸附剂的方法,所述吸附剂包含氧化铝组分、沸石组分和外加金属组分,所述外加金属组分选自,例如,由碱金属、碱土金属及其混合物组成的组,且在初始时首先添加至沸石组分,以使沸石中的外加金属的量相较于将相同量的初始金属添加至沸石与氧化铝的混合物的情况大。所述外加金属组分是以超过补偿沸石晶格的负电荷所需的金属的化学计算量的量存在。
所述制备吸附剂的方法包括将外加金属组分放置在沸石上和随后与氧化铝聚结,和或者将其它金属组分放置在沸石上,形成呈分离珠粒形式的含金属沸石和随后将分离的氧化铝与沸石珠粒掺合以形成颗粒混合床。
本发明的又一实施方案是一种将污染物自烃流移除的方法,所述方法包括使所述流与上述固体成型吸附剂或颗粒混合吸附剂在吸附条件下接触以移除至少一部分的至少一种污染物。
这些和其它目的和实施方案将在参阅本发明的具体实施方式後变得更为明了。
具体实施方式
本发明包含异种固体成型吸附剂或颗粒吸附剂组合物,一种制备所述吸附剂的方法和利用所述吸附剂的纯化方法。就固体成型吸附剂和颗粒吸附剂组合物而言,其中的一种必要组分是活化氧化铝。活化氧化铝包括具有一般大于100m2/g且基本上在100至400m2/g范围内的表面积的氧化铝。此外,优选地通过使铝氢氧化物(例如,热气体或固体热载体流中的水铝矿的氧化铝三水合物)快速脱水获得活化氧化铝粉末。可以利用热气体或固体热载体流在任何适宜装置中实现脱水。一般而言,用于加热或与热气体接触的时间极短,基本上是几分之一秒至4或5秒。常规上,气体的温度在400℃与1000℃之间变化。所述方法常称为闪式焙烧并公开在,例如,美国专利2,915,365号中,所述专利是以引用的方式并入本文。但是,可以采用其它焙烧方法。
适宜用于本发明中的活化氧化铝的平均粒径为0.1至300微米,优选地1至100微米和基本上在1至20微米范围内。在特定情况中,宜使用平均粒径为1至10微米的的氧化铝。可以在活化之前或之后将氧化铝研磨至所需的粒径。活化氧化铝在200℃至1000℃的温度下基本上具有在约5至12%范围内的LOI(烧失量)。
活化氧化铝的一个来源是三水铝石,三水铝石是利用拜耳(Bayer)法自铝土获得的铝三水合物。但是,若通过充分焙烧,则可以使用α氧化铝单水合物、假勃姆石或其它氧化铝三水合物。也可以利用其它氧化铝来源,包括黏土和铝烷氧化物。
本发明的另一必要组分是沸石。沸石是晶状硅铝酸盐组合物,其具有微孔性且具有自AlO2与SiO2的角共用四面体形成的三维氧化物框架。沸石的特征在于具有呈均一尺寸的孔开口,具有巨大离子交换能力,且能够可逆地使分散遍布在晶体的内空隙中的吸附物脱吸而不会使构成固有沸石晶体结构的任何原子明显移位。可以用于本发明中的沸石是具有约5至约孔开口的那些沸石。
一般而言,沸石具有由以下经验式表示的组成:
M2/nO:Al2O3:bSiO2
M是具有“n”价的阳离子和“b”是约2至约500的值。优选沸石是那些具有约2:1至约6:1的SiO2/Al2O3比的沸石和/或具有沸石X、八面沸石、沸石Y、沸石A、发光沸石、ZSM-5、β和镁碱沸石晶体结构的那些沸石。特优选沸石是沸石X、Y和A。
这些沸石的制备已在本领域熟知且涉及使适当的组分来源进行水热反应形成沸石,藉此形成主要由这些组分组成的反应混合物。具体来说,沸石Y的合成描述在美国专利3,130,007和4,503,023中和沸石X的合成描述在美国专利2,883,244和3,862,900中,这些专利的公开内容是以引用的方式并入本文。
虽然沸石,特别是沸石X和Y的合成已熟知,但在完备性上将在此处给出简要描述。M的反应性来源包括碱或碱土金属的卤化物和氢氧化物化合物,如氯化钠、氢氧化钠、氢氧化钾等。铝来源包括但不限于勃姆石氧化铝、γ氧化铝和可溶性铝酸盐,如铝酸钠或铝酸四乙基铵。最后,硅来源包括硅石、硅石水溶胶、硅酸等。
将反应性来源组合成反应混合物,所述反应混合物具有如下氧化物摩尔比组成:
SiO2/Al2O3=8至12
M2O/Al2O3=2.5至4
H2O/M2O=120至180
和随后使混合物反应形成沸石。
当合成时,沸石将在通道和/或孔中含有“M”金属。金属阳离子的功能是平衡沸石晶格的负电荷。由于这些阳离子不是框架中的一部分,所以这些阳离子可交换且据称会占据交换位点。存在于沸石中的金属阳离子的量称为沸石的化学计算量或最大离子交换能力。这个量常以摩尔表示。
由于起始时便存在于沸石中的金属阳离子可交换,所以这些金属阳离子可交换成其它(不同)的碱金属、碱土金属、水合氢离子、铵离子或它们的混合物。如果所使用的沸石部分或完全地含有水合氢或铵离子,那么这些离子应在制备复合吸附剂之前与碱金属、碱土金属或它们的混合物充分交换。
本发明的成型吸附剂的另一必要组分是外加金属组分,其选自由碱、碱土金属及其混合物组成的组。这个外加金属组分是除存在于沸石交换位点中的金属阳离子(M)以外的金属组分。所述外加金属可以与M金属相同或不同。
外加金属的具体实例包括但不限于钠、钾、锂、铷、铯、钙、锶、镁、钡、锌和铜。外加金属的来源(金属组分前体)可以是在活化条件下(参见下文)分解成金属氧化物的任何化合物。这些来源的实例是这些金属的硝酸盐、氢氧化物、羧酸盐、碳酸盐和氧化物。
所述成型吸附剂可以依照以下方式组合三种组分制备:使沸石中的外加金属组分的量相较于将相同量的外加金属添加至沸石与氧化铝的混合物的情况大。优选避免有意使氧化铝与外加金属接触的制备方法,以使仅有沸石被处理成含有金属,且因此仅有沸石在初始加工期间含有外加金属。但是,在如下文所述的形成过程期间,一定量的外加金属将不可避免地迁移至氧化铝。但是,最终产物将使沸石中的外加金属组分的量相较于使相同量的初始金属与沸石和氧化铝的混合物接触的情况大。
在一种方法中,将沸石和所需的金属化合物的水溶液混合以利用外加金属浸渍沸石。移除水分对改良沸石浸渍有用。在约150℃的温度下将沸石加热1至2小时将服务这个目的。在金属转化为氧化物之前或之后,将浸渍过的沸石与氧化铝混合并使混合物形成成型物件。例如,可以将沸石Y和乙酸钠溶液组合以浸渍沸石。可以将浸渍过的沸石Y和γ氧化铝组合并形成面团和随后通过为本领域所熟知的方式(例如,通过油滴方法)挤压或形成为诸如小球、小丸、扁片或微球的形状。形成大体圆化形状或实体的优选方法涉及使用盘式造粒机。这个技术使用一个旋转盘或盘式造粒机,将氧化铝组分、浸渍过的沸石组分和,任选地,粘结剂供料至其中,藉此形成大体圆化的物件或实体。常见粘结剂包括硅酸钠、粘土和用于组合组分以成型的可蒸发液体,例如,水、醇。或者,氧化铝本身在特定氧化铝浓度(例如,至少50重量%,一般而言,至少65重量%)下可以用作粘结剂。
使成型物件在环境温度在至高约200℃下固化或干燥约5分钟至约25小时。可以利用转鼓或移动带分批(例如,成箱或成盘)或以连续方法固化成型物件。成型物件固化之后,通过在约275℃至约600℃的温度下将已固化物件加热约5至约600分钟时间来活化该成型物件。可以在转鼓或移动带中通过直接燃烧物件来加热所述物件以提供成品固体吸附剂。还可以首先在所提及的升高温度下活化外加金属并将其转化为氧化物,然后将含有外加金属的干燥沸石与氧化铝混合,但这并非优选做法。
氧化铝和浸渍过的沸石组分的相对量可在宽广范围内极大地变化。一般而言,氧化铝的量在约40至约90%,常见地在50至80重量%内变化。浸渍过的沸石的量在吸附剂的约10至60重量%内变化。外加金属组分的量也可以变化,但应以等于存在于沸石交换位点中的金属阳离子M的化学计算量的至少10%的量存在。由于已发现应在起始时使外加金属束缚于沸石以获得较低反应性和改良的含氧物(如甲醇)吸附,所以需将较上述UOP专利所要求的少的外加金属并入吸附剂中。因此,从绝对意义上来说,优选地,外加金属是以约0.0075至约0.05摩尔外加金属/100mg吸附剂的量存在。更优选地,外加金属的量是约0.0075至0.0135摩尔/100mg吸附剂。M和外加金属的量是以金属氧化物,例如,Na2O的形式给出或表示。
成品吸附剂现在可以用于将污染物自各种烃流移除。可以处理的流包括,但不限于,烃流,尤其是含有饱和和/或不饱和烃的那些流。尤其可以利用所述吸附剂处理诸如乙稀、丙烯和丁烯的烯烃流。这些流可能含有以下污染物中的一种或多种:H2O、CO、O2、CO2、COS、H2S、NH3、AsH3、PH3、Hg、甲醇、硫醇和其它含S-或O-有机化合物。
通过使流与固体吸附剂在吸附条件下接触来纯化烃流。可以利用分批或连续方法实施接触,优选是连续方法。所述吸附剂可以呈固定床、移动床或半径流动床的方式存在,优选是固定床。当使用固定床时,原料流可以沿上流或下流方向流动,对于液体原料来说,基本上以上流为优选。如果使用移动床,则原料流可以顺行或逆行地流动。此外,当使用固定床时,可以使用多个床且可以将这些床放置在一个或多个反应容器中。吸附条件包括约环境至约80℃的温度,约大气压至约100atm(1.01×104kPa)的压力和视烃流是液态或气态流而定的接触时间。对于液态流来说,以液体小时空间速度(LHSV)表示的接触时间是约0.01至约10小时-1,而对于气态流来说,气体小时空间速度在约500至约10,000小时-1内变化。
在一段特定时间之后(该时间视污染物的浓度、床的大小和空间速度而定),吸附剂将大部分消耗,即,已吸附一定量的污染物,如此一来,经纯化的流中的污染物浓度高于可接受浓度。此时,移除吸附剂并以新吸附剂替代。可以通过为本领域熟知的方式再生已消耗的吸附剂并随后再次使用。在常见再生流程中,首先排出吸附剂并减压,接着以惰性流进行冷净化。然后,在80至150℃下沿下流方向进行的暖净化会将留存的烃自床移除。最后,使温度缓慢升高至280至320℃并维持至少2小时和随后冷却至环境温度。
描述以下实施例以更全面地说明本发明。应理解,这些实例仅以说明方式使用且不应视为对附接权利要求中所描述的本发明广义范围进行过度限制。
实施例1
如下制备八个吸附剂样品:通过将沸石Y粉末与氧化铝混合来制备样品。所有样品的沸石Y和氧化铝来源相同。
样品1是通过添加188lbs.的沸石Y和624lbs.的氧化铝并在流化床中混合制成。在混合粉末之后,使这些粉末聚结,固化和通过具有350℉、450℉、600℉、750℉和875℉的区温度的皮带驱动活化器并使材料在各区中停留大致相同的时间来进行活化。在皮带上的总停留时间是2.5小时。
样品2是仅由氧化铝粉末形成的1/8英寸珠粒。使粉末进行盘式聚结,固化和通过具有350℉、450℉、650℉、750℉和775℉的区温度的皮带驱动活化器,并使材料在各区中停留大致相同的时间来进行活化。在皮带上的总停留时间是2.5小时。
样品3是通过将2.25克沸石Y与7.75克氧化铝混合制成。将6克浓度为9%的NaOH水溶液添加至组合粉末以使在组合混合物上获得4%Na2O浓度。在混合并浸渍粉末之后,使用卡佛(Carver)压缩机制备材料以形成大型小球,将所得的小球打碎成块并通过10×12网进行筛分。经筛分之后,在烘箱中,在320℃下将材料焙烧2小时。
样品4是通过将21.75克乙酸钠以水溶液(22.8重量%CH3COONa)方式添加至63克沸石Y制成。将浸渍过的沸石添加至216克氧化铝。在混合粉末之后,使材料进行盘式聚结。经聚结之后,使材料在180℉下熟化4小时,通过10×12网筛滤,并在烘箱中在150℃下焙烧1小时,接着在420℃下焙烧1小时。
样品5是通过将188lb的沸石Y和624lb的氧化铝组合和在流化床中混合制成。在混合粉末之后,使粉末聚结和随后通过具有350℉、450℉、600℉、750℉和875℉的区温度的皮带驱动活化器并使材料在各区中停留大致相同的时间来进行活化。在皮带上的总停留时间是2.5小时。
样品6是在V-掺合机中制备:首先添加331kg沸石Y。当旋转达5分钟时,将72.2kg的23.74%乙酸Na喷洒至沸石中。在将材料自容器排出之后,取样浸渍过的沸石材料。然后,在实验室规模(0.7ft3)V-掺合机中将59.6g水含量为27.8%的的浸渍过的沸石与150.8g氧化铝混合30分钟。在混合粉末之后,使粉末进行盘式聚结。经聚结之后,使材料在180℉下熟化4小时。随后通过10×12网筛滤材料,和在烘箱中在150℃下焙烧1小时,接着在420℃下焙烧1小时。
样品7是通过在Eirich混合机中将239克沸石Y与761克氧化铝混合1组合1分钟制备。在1分钟之后,将7重量%CH3COONa水溶液喷洒至旋转中的Eirich混合机中。在3分钟内总共将208.5克溶液喷洒至氧化铝与沸石Y的混合物中。在浸渍之后,使混合物进行盘式聚结。经聚结之后,使微粒在180℉下熟化4小时。随后通过10×12网筛滤材料,和在烘箱中在150℃下焙烧1小时,接着在420℃下焙烧1小时。
样品8是通过以159克的23%CH3COONa水溶液将700克水分含量为15%的沸石Y(干基)浸渍3分钟来制备。在3分钟之后,添加1300克水分含量为6%的氧化铝(干基)和在Eirich混合机中混合3分钟。在混合粉末之后,使粉末进行盘式聚结。经聚结之后,使材料在180℉下熟化4小时。随后通过10×12网筛滤材料,和在烘箱中在150℃下焙烧1小时,接着在420℃下焙烧1小时。
实施例2
在如下文实施例4所描述的快速去活化测试之后,通过分析吸附剂上的残余碳来测定来自实施例1的样品1、2和4的反应性。
结果显示在表1中。
表1
如上所示,添加有钠的样品4的反应性较样品1低,这由降低的焦炭予以证明。重要的是,使用未经钠浸渍的纯氧化铝的样品2具有最小焦炭形成,说明氧化铝对这类反应性不产生显著作用。因此,以钠仅处理沸石会降低反应性且保持氧化铝的吸附强度。
碳是利用碳、氢和氮分析仪测定,该分析仪是设计用以测定各种不同化合物中的碳、氢和氮含量的非色散红外(IR)微电脑型仪器。
开始分析时,称出样品重量并放置于样品架中。将样品转移至一燃烧室,该燃烧室的熔炉温度(约900℃)和氧气流动会导致样品燃烧。所述过程将任何元素碳、氢和氮转化为CO2、H2O、N2和NOx。随后使这些气体经过IR元件以确定碳和氢含量并经过一导热性(TC)元件以确定氮含量。
实施例3
使30克/分钟的85%正丁烷、15%1-丁烯与1000ppm(摩尔)甲醇一起流过含有2克吸附剂的床。床的尺寸为0.5”ID×3”长。将玻璃珠放置在该床的首个1英寸中,接着放置玻璃棉,然后是吸附剂,和随后将更多的玻璃珠用于填充床直至顶部。使原料在30分钟的时间内通过床。在这个过程之后,终止原料并封闭吸附剂床的出口。使床向连接至一干燥测试仪(DTM)的一个收集罐敞开。随后液体经DTM迅驰离开到达大气压并通过DTM测定总量。
在液体迅驰至大气压之后,将床自收集罐隔离。随后利用真空排空该收集罐和再次使吸附剂床向收集罐敞开。以氦气将收集罐加压至1000至2000托。随后利用气相色谱(GC)分析收集罐混合物。然后,利用电缆加热器将吸附剂床加热至270℃的温度,且当床达到该温度之后,再次排空收集罐。随后进行以下流程:
1)使吸附剂床向收集罐敞开60秒。
2)以氦气将收集罐加压至1000至2000托。
3)通过GC分析收集罐混合物。
4)再次排空收集罐。
重复以上步骤1至4所指出的流程直至所测得的吸附剂床压力低于5托。
可以通过记录具有固定体积的收集罐的各次压力和温度来计算所吸附的材料的总量(摩尔)。这个总和以及通过GC测得的组成能够确定所吸附的各种物质的总摩尔量。当知晓被吸附的各种物质的总摩尔量和吸附剂的克数之后,便可以计算在迅驰通过DTM之后留存的材料的量。我们报告的吸附摩尔量并不包括迅驰离去并通过DTM的液体。已进一步假定,在270℃和5托下,可以忽略留存在吸附剂上的材料的量。
收集罐体积为300cm3。所吸附的甲醇(MeOH)在GC中被视为三种物质:二甲醚(DME)、MeOH和水。不测定水但假定其存在。通过化学计算法,所测得的每摩尔DME代表2摩尔甲醇被吸附。所吸附的甲醇的量的报告值表示液体经DTM迅驰至大气之后留存的量。
实施例4
在快速去活化测试中,使吸附步骤进行10分钟。随后吸附剂床的内容物迅驰至大气并将流动引导至DTM持续10分钟。在迅驰至大气压之后,利用电缆加热器将吸附剂床加热至270℃并维持20分钟。随后关闭电缆加热器,并自收集罐抽真空10分钟。以上步骤顺序表示一个循环。完成多个循环(80或180个)以模拟吸附剂床的熟化。
表2提供来自实施例3流程的新材料和来自以上段落流程的已熟化材料的吸附剂容量的结果。自表可见,样品1具有最高新容量和样品4具有次高新容量。但是,在熟化后样品4具有比样品1(市售吸附剂)优的容量。且,以钠浸渍沸石Y,然后将其与氧化铝混合而得的样品4展现比样品3高的新容量。
表2
原料甲醇1000ppm
实施例5
表3提供新材料和已熟化材料的吸附剂容量的更多结果。样品5和8具有最高新MeOH容量和样品7具有最低新MeOH容量。样品6和7具有相同Y含量,但是,样品7具有较低新MeOH容量和较大的随时间MeOH容量损失,表明在起始时使钠仅与沸石接触的优势。为了与样品5的较高新MeOH容量相一致,以较高浓度的沸石Y制备样品8。在这种情况中,样品5的MeOH容量衰减,而样品8维持高的MeOH容量。
表3
500ppmMeOH原料
Claims (14)
1.一种用于纯化烃流的固体吸附剂,所述吸附剂包含氧化铝组分、沸石组分和金属组分,其中所述金属组分是在初始时首先添加至所述沸石,以使所述金属以相较于将相同量初始金属添加至所述沸石与所述氧化铝的混合物的情况大的量存在于所述沸石组分中,其中所述金属组分是以0.0075至0.05摩尔金属氧化物/100g吸附剂的量存在,其中所述氧化铝是以所述吸附剂的40至90重量%的量存在。
2.根据权利要求1所述的吸附剂,其中所述沸石选自由沸石X、沸石Y、沸石A、ZSM-5、沸石β及其混合物组成的组。
3.根据权利要求2所述的吸附剂,其中所述沸石是沸石Y。
4.根据权利要求1所述的吸附剂,其中所述金属组分是选自由钠、钾、锂、铷、铯及其混合物组成的组的碱金属。
5.根据权利要求4所述的吸附剂,其中所述金属组分是钠。
6.根据权利要求1所述的吸附剂,其中所述金属组分是以0.0075至0.0135摩尔金属氧化物/100g吸附剂的量存在。
7.一种制备用于纯化烃流的固体吸附剂的方法,其中所述吸附剂包含氧化铝组分、沸石组分和金属组分,其中所述金属组分是在初始时首先添加至所述沸石,以使所述金属以相较于将相同量初始金属添加至所述沸石与所述氧化铝的混合物的情况大的量存在于所述沸石组分中,其中所述金属组分是以0.0075至0.05摩尔金属氧化物/100g吸附剂的量存在,其中所述氧化铝是以所述吸附剂的40至90重量%的量存在;所述方法包括将沸石组分与金属组分前体组合以形成浸渍过的沸石,将所述浸渍过的沸石与氧化铝组合以形成成型物件并且在活化条件下活化所述物件以获得所述固体吸附剂。
8.根据权利要求7所述的方法,其中所述金属组分是以0.0075至0.0135摩尔金属氧化物/100g吸附剂的量存在。
9.根据权利要求7所述的方法,其中所述沸石组分选自由沸石X、沸石Y、沸石A、ZSM-5、沸石β及其混合物组成的组。
10.根据权利要求7所述的方法,其中所述金属组分前体选自所述金属组分的羧酸盐、碳酸盐和氢氧化物化合物。
11.根据权利要求7所述的方法,其中所述金属组分是碱金属。
12.根据权利要求7所述的方法,所述方法包括在活化前,使所述成型物件在环境至200℃的温度下固化5分钟至25小时的时间。
13.根据权利要求7所述的方法,其中活化条件包括275℃至600℃的温度和5至70分钟的时间。
14.一种将污染物自烃流移除的方法,所述方法包括使所述烃流与权利要求1的吸附剂接触。
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US20110079145A1 (en) | 2011-04-07 |
EP2485834A4 (en) | 2014-10-15 |
TWI526428B (zh) | 2016-03-21 |
EP2485834B1 (en) | 2016-08-24 |
KR20120084757A (ko) | 2012-07-30 |
EP2485834A2 (en) | 2012-08-15 |
TW201129542A (en) | 2011-09-01 |
US8147588B2 (en) | 2012-04-03 |
EP3112019B1 (en) | 2019-03-27 |
JP5827231B2 (ja) | 2015-12-02 |
PL3112019T3 (pl) | 2019-09-30 |
WO2011043974A2 (en) | 2011-04-14 |
RU2560360C2 (ru) | 2015-08-20 |
WO2011043974A3 (en) | 2011-08-25 |
KR101854924B1 (ko) | 2018-05-04 |
CN102639228A (zh) | 2012-08-15 |
EP3112019A1 (en) | 2017-01-04 |
RU2012118494A (ru) | 2013-11-20 |
JP2013506554A (ja) | 2013-02-28 |
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