CN1674982A - 保护床和含铜催化剂床的组合 - Google Patents
保护床和含铜催化剂床的组合 Download PDFInfo
- Publication number
- CN1674982A CN1674982A CNA038190702A CN03819070A CN1674982A CN 1674982 A CN1674982 A CN 1674982A CN A038190702 A CNA038190702 A CN A038190702A CN 03819070 A CN03819070 A CN 03819070A CN 1674982 A CN1674982 A CN 1674982A
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- China
- Prior art keywords
- bed
- lead
- combination
- oxide
- forming unit
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 21
- 229910052802 copper Inorganic materials 0.000 title abstract description 17
- 239000010949 copper Substances 0.000 title abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 35
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 5
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 22
- 239000012876 carrier material Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 33
- 239000007789 gas Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 150000002611 lead compounds Chemical class 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 4
- 229910000278 bentonite Inorganic materials 0.000 description 4
- 229960004643 cupric oxide Drugs 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- -1 halide compound Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052761 rare earth metal Chemical group 0.000 description 2
- 150000002910 rare earth metals Chemical group 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 210000000498 stratum granulosum Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Classifications
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- 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
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- 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
- B01D53/8696—Controlling the catalytic process
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/88—Handling or mounting catalysts
- B01D53/885—Devices in general for catalytic purification of waste gases
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- B01J20/0211—Compounds of Ti, Zr, Hf
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0251—Compounds of Si, Ge, Sn, Pb
- B01J20/0255—Compounds of Pb
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- 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
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- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
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Abstract
一种催化剂床的组合,它包括粒状含铜催化剂的床,和在该催化剂床上游的由氧化铅颗粒和粒状载体材料形成的成型单元形式的保护床。该保护床通过吸收在工艺蒸汽内的卤化物污染物,从而延长铜催化剂的寿命。
Description
本发明涉及催化剂床的组合,尤其涉及铜催化剂和其保护床的组合。
铜催化剂常用于牵涉氢气的反应,例如简单的氢化反应,如醛氢化成醇,以供甲醇合成(其中碳的氧化物与氢气反应)、甲醇的分解(其中甲醇(通常与蒸汽混合)分解,形成氢气和碳的氧化物),和转移反应(其中一氧化碳与蒸汽反应,生产氢气和二氧化碳)和逆转移反应。通常为了获得催化剂的最佳活性和稳定性,用高度分散形式的铜,例如通过铜化合物在一种或多种载体材料,特别是锌、镁、铬和/或铝化合物存在下沉淀,或者与之一起沉淀,从而制造催化剂。紧跟在这种沉淀之后,加热组合物,使铜化合物,和视需要的载体材料,转化成相应的氧化物。在所需的反应上使用之前,将氧化铜还原成金属铜。上述反应的特别合适的催化剂是铜/氧化锌/氧化铝和铜/氧化锌/氧化铬组合物。有时,一部分锌可被镁替代,和/或一部分氧化铝或氧化铬可被铈土或稀土金属如氧化镧替代。
在经历该反应的工艺气体(process gas)内,在卤化物化合物和尤其氯化物化合物,如氯化氢存在下,铜催化剂容易失活。痕量的这种氯化物化合物可来自于制造工艺气体所使用的材料,例如烃原料、蒸汽或空气内的污染物。这种氯化物化合物与活性铜反应,形成氯化铜。由于氯化铜的熔点相对低,在催化剂通常被使用的温度,例如150-300℃下,铜移动并倾向于聚结,从而导致铜的分散度的丧失和因此催化剂活性的丧失。另外,在其中锌和/或氧化镁为催化剂组分的情况下,同样可能形成相应的氯化物,和这些同样易于移动,从而导致氧化锌或氧化镁的稳定效果的丧失,结果又是铜的分散度和活性的丧失。
在PCT申请WO 01/17674中已提出了在铜催化剂的上游使用保护床,其中保护床是含有铅化合物及其载体的粒状组合物。该申请公开了通过用合适的铅盐溶液,例如硝酸铅浸渍载体颗粒,通过在载体材料的颗粒存在下,沉淀合适的铅化合物,或通过共沉淀铅化合物和载体,或载体的前体,从而可制造保护床颗粒。优选的铅化合物是硝酸铅。然而,当使用硝酸铅时,存在的危险是,万一设备失常(upset),水可能在保护床上冷凝并从载体中浸出硝酸铅和将它洗涤到下游的铜催化剂上。铅化合物倾向于使铜催化剂中毒,因此存在铜催化剂的活性可能降低的危险。为此可以优选使用不溶于水的铅化合物。
在前述PCT申请WO 0l/17674中,发现与所测试的其它铅化合物相比,承载在氧化铝上且含有20.4wt%铅的商业氧化铅是差的保护床材料,它提供仅仅勉强好于氧化铝颗粒的活性。
我们已发现,可简单地由细分的(finely divided)氧化铅颗粒和载体材料的颗粒制造适合用作保护床的成型单元。
因此,本发明提供一种催化剂床的组合,它包括粒状含铜催化剂床,和在该催化剂床上游的由氧化铅颗粒和粒状载体材料形成的成型单元的保护床。
“氧化铅”,我们是指含氧的铅化合物,其中包括部分水合的氧化铅。这种化合物包括PbO、Pb3O4和PbO2。优选氧化铅是PbO。氧化铅颗粒的平均(重量)粒度特别是低于50微米,更特别是25微米,和优选基本上所有颗粒的尺寸低于120微米。保护床为成型单元的形式:这些优选具有在1.5-20mm,特别是3-6mm范围内的最大和最小尺寸。成型单元的长径比,即最大对最小尺寸之比优选小于2。
成型单元可以具有规则形状,例如球形、柱形等,和可以通过“干法”技术来制造,其中将含有粒状氧化铅和粒状载体材料的粉末组合物在例如造粒机内压紧成所需的形状;或者可以通过“湿法”来制造,其中将粉末组合物与合适的液体混合,形成糊剂,然后将所述糊剂挤出成所需的截面,并将挤出料切割或破碎成所要求长度的单元;或者可以使用粒化方法,其中将粉末组合物与不足以得到糊剂的小量液体(通常是水)混合,和藉助粒料研磨机,例如动物饲料切粒所使用的那种类型,造粒或粒化所得潮湿的混合物,其中将待造粒的混合物经孔眼引入到旋转的穿孔圆柱体内,其中在该圆柱体内,通过棒或辊,使混合物受迫穿过该圆柱体中的孔眼。通过为得到所需长度粒料而布置的刮刀,从旋转圆柱体的表面处切割所得挤出的混合物。或者,粒化材料可用作造粒机的原料。取决于含湿量,粒化材料在使用之前可以需要或者可以不需要干燥。此外,希望可焙烧成型单元。术语“焙烧”,我们是指在含氧气体如空气中加热到高于200℃的温度。
由氧化铅颗粒和载体材料的颗粒的混合物形成成型单元。术语“载体材料”,我们是指惰性材料的细分的载体材料。合适的惰性材料包括氧化铝、水合氧化铝、氧化铬、氧化锆、氧化钛,或不那么优选的氧化硅。氧化铝、水合氧化铝和这些的混合物是优选的载体材料。最优选,载体材料是水合氧化铝,如三水合氧化铝(Al(OH)3)和勃姆石(AlO(OH))和这些的混合物。水合氧化铝优选重均粒度低于100微米,更特别的是低于50微米,和优选基本上所有颗粒的尺寸低于200微米。我们已发现,两种或多种水合氧化铝的混合物可提供具有较好物理性能,例如抗碎强度的成型单元。在使用两种水合氧化铝的混合物的情况下,相对用量可在10∶90到90∶10,优选60∶40到40∶60的重量范围内变化。
不管使用哪种成型方法形成成型单元,加工助剂如润滑剂和/或粘合剂可掺入到该粉末组合物内。当使用“干法”加工路线,如造粒时,可使用的润滑剂包括石墨、脂肪酸及其盐如硬脂酸盐。优选的润滑剂是石墨。可以使用的粘合剂可以是无机粘合剂,例如粘土,如绿坡缕石、膨润土、海泡石或胶态硅酸铝镁,或水泥,例如铝酸钙水泥,或者有机粘合剂,例如可溶碳水化合物,如淀粉、藻酸盐或黄原胶;纤维素醚例如羟甲基纤维素;蛋白质;聚乙烯醇、酯、缩醛,或醚或混合衍生物,例如部分水解的聚乙酸乙烯酯;聚氧化烯;聚丙烯酸酯或甲基丙烯酸酯;或聚丙烯酰胺或聚甲基丙烯酰胺。若使用的话,优选有机粘合剂。
所使用的加工助剂的用量可以是0.5-10%,尤其1-5wt%,基于铅化合物、载体和加工助剂的结合重量。优选的组合物含有加工助剂,尤其润滑剂如石墨。因此由氧化铅、水合氧化铝和石墨形成特别优选的成型单元。
优选的组合物的铅含量为5-75%,尤其10-60%,更尤其30-75%,和特别是40-75wt%的铅(以金属来表达),基于铅化合物、载体和若存在的润滑剂和/或粘合剂的结合重量。通过提供由氧化铅颗粒和粒状载体材料形成的成型单元的保护床,成型单元可有利地含有比通常使用浸渍技术可能的负载量高的氧化铅负载。与仅仅氧化铅颗粒可能具有的表面积和孔隙度相比,粒状载体材料还提供具有改进的表面积和孔隙度的成型单元。
使用包括粒状氧化铅、载体材料和润滑剂如石墨的成型单元的进一步的优点是,成型单元在使用之前不需要干燥或焙烧。然而,若使用有机粘合剂,则不管使用湿法成型还是干法成型方法,优选在空气中焙烧成型单元,以烧毁粘合剂。使用氧化铅,而不是其它铅化合物如碳酸铅或碱性碳酸铅的优点是,它的较高的热稳定性,这允许使用较高的温度以烧毁粘合剂。优选的是,可使用温度大于200℃的温度和更优选大于400℃。
保护床和催化剂床用作固定床,和可以在相同的容器或在不同的容器内,其中保护床在催化剂床的上游。优选工艺气体向下流经催化剂床,从而在保护床和催化剂床在相同的容器内的情况下,保护床可以是在催化剂床颗粒上面的保护床颗粒层。视需要,可以在保护床和催化剂床之间存在一层惰性材料,例如氧化铝球或环,以便于在没有干扰催化剂床的情况下补充保护床。
保护床有效地从工艺气体中,尤其从其中氯化物化合物的存在量大于0.5ppm体积的工艺气体中吸收氯化物化合物。通过吸收氯化物化合物,可有效地延长含铜催化剂的寿命。
因此,根据本发明进一步的方面,我们提供使用含铜催化剂床进行催化反应的方法,该方法包括使工艺气体流经由氧化铅颗粒和粒状载体材料形成的成型单元的保护床,然后使所述工艺气体流经含铜催化剂床。
本发明在涉及转移反应方面尤其具有实用性。在该方法中,在150-300℃的温度范围内,特别是150-250℃范围内的入口温度下,含有一氧化碳和蒸汽,和通常其它组分如氢气、二氧化碳、甲烷和/或氮气的工艺气体流,流经含铜催化剂,特别是铜/氧化锌/氧化铝或铜/氧化锌/氧化铬催化剂的床,其中一些氧化锌可用氧化镁替代和/或一些氧化铝和/或氧化铬可用稀土来替代。工艺气体含有1-4%体积的一氧化碳,和至少1mol蒸汽/mol一氧化碳。优选工艺气体含有20-50%体积的蒸汽。典型地,在2000-5000h-1范围内的湿气空速下,和在范围为大气压-50bar(绝压)的压力下操作该方法。
要理解,成型单元除了吸收氯化物化合物以外,还吸收硫化合物,因此该床可起到硫保护床的作用。
通过下述实施例进一步阐述本发明。
实施例1
由氧化铅(PbO)和水合氧化铝粉末制造氯化物吸收剂样品。样品1(a)的氧化铅的重均粒度为13.6微米,和基本上所有颗粒的尺寸在6.3-29.4微米范围内。实施例1(b)的氧化铅粉末的重均粒度为8.5微米,和基本上所有颗粒的尺寸在3.6-19.5微米范围内。三水合氧化铝(Al(OH)3)粉末的BET表面积为0.5m2/g,和重均粒度为21微米,且基本上所有颗粒的尺寸在5.1-54.3微米范围内。膨润土(AlO(OH))粉末的BET表面积为228m2/g,和重均粒度为31.2微米,且基本上所有颗粒的尺寸在5.8-71.2微米范围内。
(a)60g三水合氧化铝粉末与40g氧化铅粉末和2g作为润滑剂的石墨一起混合5分钟,和使用造粒机,在20吨的负载下,将混合物形成为直径25mm和高度10-20mm的短粗圆柱形粒料。粒料的标称铅含量为36.4wt%和密度为约3.5g/ml。
(b)292g三水合氧化铝粉末和233g膨润土粉末与475g氧化铅粉末和10g作为润滑剂的石墨一起混合5分钟,和使用造粒机,在20吨的负载下,将混合物形成为直径62.5mm和高度10-20mm的短粗圆柱形粒料。粒料的标称铅含量为43.7wt%和密度为约3.5g/ml。
实施例2
通过在微型反应器中引入0.50g(约0.4ml)含约50wt%氧化铜和粒度范围为0.6-1.0mm的氧化铜/氧化锌/氧化铝低温转移催化剂前体颗粒,和在该转移催化剂前体上面作为一层布置的0.25g(约0.1ml)粒度为0.6-1.0mm的煅制氧化铝颗粒,以及在该煅制氧化铝颗粒上面的0.2ml(约0.36g)粒度为0.6-1.0mm的保护材料颗粒,得到体积为约0.70ml的总催化剂床,从而测试实施例1的保护床材料(在测试之前,保护床材料的粒料破碎成0.6-1mm的粒度)。
在约28bar(绝压)的压力下,在15L/h的流速(在NTP下)下,通过使含有2%体积氢气的氮气向下流经微型反应器,同时加热微型反应器从环境温度到220℃和在该温度下保持95分钟,得到3.5小时的总还原时间,从而将在催化剂前体内的氧化铜被还原为金属铜。
在220℃的温度下和在约28bar(绝压)的压力下,通过使50L/h(在NTP下)含1体积份的蒸汽/2体积份体积组成为H2 55%、CO2 15%、CO 5%和N2 25%的气体的气体混合物流经微型反应器,测定水气转移反应的催化剂活性。
为了模拟氯化物化合物的污染,在气体混合物流经催化剂床约6小时之后,将氯化氢(HCl)加入到该气体混合物中,在湿气体内得到1ppm体积的HCl浓度。在这些固定的试验条件下,使用在线红外检测,测量CO的转化率随联机时间的变化。CO转化率随时间下降是催化剂活性丧失的表征。
为了比较目的,还使用相同方法测试下述保护床:
实施例2(a)的低温转移催化剂床;
实施例2(b)含商业吸收剂的床,所述吸收剂包括标称铅含量为约20.5wt%的在氧化铝上的氧化铅;和
实施例2(c)通过如下所述浸渍制备的含承载在氧化铝颗粒上的氧化铅的床:将303g尺寸为0.6-1.0mm和BET表面积为350m2/g的γ-氧化铝颗粒浸渍在每100ml溶液中硝酸铅(II)的近似浓度为55g的800ml60-70℃的硝酸铅(II)的水溶液中。30分钟之后,从溶液中取出该材料、沥干、在110℃下干燥2小时,然后在烘箱中,在300℃下焙烧2小时。使用以上制备的焙烧的硝酸铅浸渍的氧化铝和新鲜的适量硝酸铅溶液,重复上述方法。在300℃下焙烧之后,再次使用新鲜适量的硝酸铅溶液,再浸渍所得材料第三次。在300℃下焙烧2小时之后,材料的铅含量为25.5wt%。然后在550℃下进一步焙烧一部分材料2小时,使硝酸铅分解成氧化铅和得到铅含量为28.7wt%的产物。铅含量的增加表明形成了氧化铅。
由于实施例2(b)的材料具有比实施例1的材料显著较低的堆积密度,因此,在此情况下,使用类似的吸收剂体积(约0.2ml),但其重量仅为约0.19g。
在数天的时间段内测量%CO转化率,且以规则的时间间隔进行测量。为了评价这一比较,将CO转化率的测量值对联机时间作图,和对于每一样品,通过这些点画出光滑的曲线(根据该光滑曲线,各点表明很少有变化)。根据这些图表,测定每24小时的转化率,和下表示出了结果,其中%CO转化率的数字已近似为最接近的整数。
联机时间(天) | CO转化率(%) | ||||
实施例1(a) | 实施例1(b) | 对比实施例 | |||
实施例2(a) | 实施例2(b) | 实施例2(c) | |||
12345678910 | 84817978767574747157 | 8481797776757367420 | 847975623430000 | 85817250700000 | 868577571300000 |
结果证明,含氧化铅颗粒和粒状载体的保护床材料优于商业承载的PbO和通过浸渍制备的含承载PbO的材料。
实施例3
根据实施例1(b)的方法制备具有如下所述组成的一系列承载的氧化铅保护床材料。
样品 | PbO(g) | 三水合氧化铝(g) | 膨润土(g) | 石墨(g) | 标称Pb含量(%) |
实施例3(a) | 18.75 | 17.5 | 14 | 0.5 | 34.3 |
实施例3(b) | 28.5 | 12 | 9.5 | 0.5 | 52.4 |
实施例3(c) | 33.5 | 9.25 | 7.25 | 0.5 | 61.6 |
根据实施例2的方法进行测试。结果如下所述。
联机时间(天) | CO转化率(%) | ||
实施例3(a) | 实施例3(b) | 实施例3(c) | |
1 | 85 | 85 | 86 |
2 | 83 | 82 | 83 |
3 | 79 | 79 | 80 |
4 | 78 | 78 | 79 |
5 | 74 | 76 | 76 |
6 | 68 | 76 | 76 |
7 | 42 | 75 | 76 |
8 | 2 | 72 | 73 |
9 | 0 | 52 | 66 |
10 | 0 | 17 | 50 |
结果证明了含较高氧化铅含量的材料的特殊有效性。
Claims (9)
1.一种催化剂床的组合,它包括粒状含铜催化剂床,和在该催化剂床上游的由氧化铅颗粒和粒状载体材料形成的成型单元的保护床。
2.权利要求1的组合,其中载体材料选自氧化铝、水合氧化铝、氧化铬、氧化锆和氧化钛。
3.权利要求1或2的组合,其中载体材料包括两种或多种水合氧化铝的混合物。
4.权利要求1-3任何一项的组合,其中由含加工助剂的组合物形成成型单元。
5.权利要求1-4任何一项的组合,其中成型单元的铅含量为5-75wt%的铅(以金属来表达)。
6.权利要求1-5任何一项的组合,其中成型单元的铅含量为30-75wt%的铅(以金属来表达)。
7.权利要求4-6任何一项的组合,其中由氧化铅、水合氧化铝和石墨形成成型单元。
8.权利要求1-7任何一项的组合,其中形成成型单元所使用的氧化铅的平均(重量)粒度低于50微米。
9.一种使用含铜催化剂床进行催化反应的方法,该方法包括使工艺气体流经由氧化铅和粒状载体材料形成的成型单元的保护床,然后使所述工艺气体流经含铜催化剂床。
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CN109121400A (zh) * | 2016-06-28 | 2019-01-01 | 雪佛龙美国公司 | 通过使用大孔贵金属催化剂氢化再生离子液体催化剂 |
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UA103079C2 (uk) * | 2009-03-19 | 2013-09-10 | Шелл Інтернаціонале Рісерч Маатшаппідж Б.В. | Процес одержання багатої воднем газової суміші |
US9573861B2 (en) | 2011-07-25 | 2017-02-21 | Exxonmobil Chemical Patents Inc. | Olefin oligomerization process |
US9550705B2 (en) | 2011-07-25 | 2017-01-24 | Exxonmobill Chemical Patents Inc. | Olefin oligomerization process |
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GB1357335A (en) | 1970-07-22 | 1974-06-19 | Ici Ltd | Hydrogen |
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CN109121400B (zh) * | 2016-06-28 | 2021-10-01 | 雪佛龙美国公司 | 通过使用大孔贵金属催化剂氢化再生离子液体催化剂 |
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DE60303612T2 (de) | 2006-09-14 |
ES2257701T3 (es) | 2006-08-01 |
EP1545766B1 (en) | 2006-02-15 |
US7148178B2 (en) | 2006-12-12 |
GB0218785D0 (en) | 2002-09-18 |
ATE317723T1 (de) | 2006-03-15 |
AU2003260693A1 (en) | 2004-02-25 |
BR0313410A (pt) | 2005-07-12 |
WO2004014546A1 (en) | 2004-02-19 |
CN100389866C (zh) | 2008-05-28 |
DE60303612D1 (de) | 2006-04-20 |
US20050271580A1 (en) | 2005-12-08 |
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EG23619A (en) | 2006-11-30 |
CA2494393C (en) | 2011-02-01 |
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