CN101939099A - 低温水煤气轮换催化剂 - Google Patents
低温水煤气轮换催化剂 Download PDFInfo
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- CN101939099A CN101939099A CN2008801262080A CN200880126208A CN101939099A CN 101939099 A CN101939099 A CN 101939099A CN 2008801262080 A CN2008801262080 A CN 2008801262080A CN 200880126208 A CN200880126208 A CN 200880126208A CN 101939099 A CN101939099 A CN 101939099A
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- gas shift
- shift catalyst
- dispersed alumina
- water gas
- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 159
- 239000010949 copper Substances 0.000 claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims description 61
- 230000009467 reduction Effects 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 25
- 238000001935 peptisation Methods 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 229960004643 cupric oxide Drugs 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 239000000725 suspension Substances 0.000 description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 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 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 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
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000009719 regenerative response Effects 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- 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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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- 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
- C01B3/16—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 using catalysts
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Abstract
公开了一种包含铜、锌、铝的低温水煤气轮换催化剂,其中铝组分由高可分散氧化铝制备。
Description
技术领域
本发明涉及一种低温水煤气轮换(WGS)催化剂,其可用于将气流中的CO和H2O转化为CO2和H2。
背景
合成气体(合成气,氢气和一氧化碳的混合物)代表最重要的化学工业原料之一。它用于合成基础化学品,例如甲醇或乙醛,以及用于生产氨和纯氢气。然而,通过蒸汽转化碳氢化合物生产的合成气体通常不宜用于一些工业应用,因为生产的合成气具有相对富集的一氧化碳和贫乏的氢气。
在工业操作中,水煤气轮换(WGS)反应(式1)用于将一氧化碳转化为二氧化碳。WGS反应的附加益处是随着一氧化碳转化同时产生氢气。
式1
水煤气轮换反应通常在两个阶段中进行:高温阶段,通常具有约350-400℃的反应温度,以及低温阶段,通常具有约180-220℃的反应温度。尽管低温反应有利于使一氧化碳更完全地转化,但是高温反应能够在足够的温度水平下再生反应热以生成高压蒸汽。为了操作的最大效率化和经济化,许多装置含有用于一氧化碳批量转化和热再生的高温反应部件,以及用于最终一氧化碳转化的低温反应部件。
由氧化铜和氧化锌的混合物组成的催化剂组合物用于促进水煤气轮换反应。这种催化剂可以通过金属盐如硝酸盐或醋酸盐的共沉淀、金属复合物的热分解、或将金属盐浸渍在载体上制备。制备后,将催化剂洗涤以去除不相干的离子、干燥并在适当的温度下锻烧以形成氧化物。然后必须在使用前用氢气将催化剂还原。还原后,二价铜形式的的氧化铜还原成金属铜。
氧化铝可以用作氧化铜/氧化锌水煤气轮换催化剂的载体。这种催化剂可以从铝盐例如硝酸铝、铝酸钠、或其组合与铜和锌的盐的混合物制备。氧化铝可以与铝盐混合以提供催化剂的铝源。
概述
下面提供本发明的简要概述以对本发明的某些方面具有基本了解。这种概述并不是本发明广泛的综述。其既不是用来确定本发明的重要或关键要素,也不是用来描绘本发明的范围。相反地,该概述的唯一目的是以简化形式提出本发明的一些概念,其为以下提出的更详细说明的前叙。
本发明提供一种水煤气轮换催化剂,包含约5-约75重量%的氧化铜、约5-约70重量%的氧化锌,和约5-约50重量%的氧化铝。该催化剂从这样的催化剂制备,即其包含在分散氧化铝存在下沉淀的铜和锌的化合物。
本发明的一方面涉及从可分散氧化铝和沉淀的铜和锌的化合物制备水煤气轮换催化剂的方法,其中该可分散氧化铝在约2-约5的pH下胶溶后在水中具有40%或更大的可分散性。
本发明的另一方面涉及通过还原水煤气轮换催化剂制备的还原的水煤气轮换催化剂,所述催化剂由可分散氧化铝和沉淀的铜和锌的化合物制备,包含约5-约75重量%的氧化铜、约5-约70重量%的氧化锌,和约5-约50重量%的氧化铝,其中该可分散氧化铝在约2-约5的pH下胶溶后在水中具有40%或更大的可分散性。含氢的气体可以用作还原剂。
本发明包括以下充分描并在权利要求中特别指出的特征。以下描述详细阐述本发明的某些例举性方面和实施方式。然而,这说明不过是可使用本发明原则的多种方式中的一些。根据本发明的以下详细说明,本发明的其他目的、优点和新的特征将变得显而易见。
发明详述
定义
术语“可分散氧化铝”是指在约2-约5的pH下胶溶后在水中具有40%或更大可分散性的氧化铝。在2-5的pH下胶溶后在水中具有50%或更大的可分散性、60%或更大的可分散性、70%或更大的可分散性、80%或更大的可分散性或90%或更大的可分散性的氧化铝也包括在该定义内。
氧化铝的百分比可分散性是指在约2-约5的pH下胶溶后,在酸性溶液中尺寸小于1微米的氧化铝的百分比。
术语“碱金属碳酸盐”是指LiHCO3、Li2CO3、NaHCO3、Na2CO3、KHCO3、K2CO3、CsHCO3、Cs2CO3及其混合物。
术语“psig”是指表压磅/平方英寸,即将海平面大气压视为零时的压力。这是样品高于海平面大气压的压力。
除非另有说明,在下列实施例及说明书和权利要求书中的其它处,所有份和百分比以重量计,所有温度为摄氏度,并且压力为大气压或接近大气压。对于既定特征的任意数字或数值范围,来自一个范围的数字或参数可与来自相同特征的不同范围的另一数字或参数组合,以生成数值范围。
说明
本发明涉及一种包含铜、锌、铝的低温水煤气轮换催化剂。该催化剂包含约5-约75重量%的氧化铜,约5-约70重量%的氧化锌,和约5-约50重量%的氧化铝。
本发明催化剂的氧化铝组分完全从可分散氧化铝制备。氧化铝组分不从由溶液作为氧化铝沉淀的铝盐制备。在约2-约5的pH下胶溶后,具有40%或更大可分散性的可分散氧化铝形成悬浮液,其中悬浮液中大于40%或更多的氧化铝颗粒的尺寸小于1微米。优选悬浮液中更大百分比的氧化铝颗粒的尺寸小于1微米。优选具有50%或更大可分散性、60%或更大可分散性、70%或更大可分散性、80%或更大可分散性或90%或或更大可分散性的氧化铝,并且其是市场上可买到的。术语如“大于40%可分散性”在其含义内包括术语如大于50%可分散性,乃至大于90%可分散性。上述的可分散性百分比是指包括在广意所述范围内的所有范围。
可以几步制备催化剂。通过使用含氢气的气体还原水煤气轮换催化剂制备还原的催化剂。
形成分散氧化铝淤浆
通过在约2-约5的pH下的酸性溶液中,使可分散氧化铝胶溶形成分散氧化铝淤浆。在胶溶过程中,将可分散氧化铝添加到然后酸化的水中。或者,将可分散氧化铝添加到酸性溶液中。在两种情况下都形成了酸的水溶液的悬浮液,其pH为2-5之间,具有约5-约35重量%的固体。优选的pH约为3。用于酸化悬浮液的酸可以强有机酸如甲酸或强无机酸如硝酸。将悬浮液在高剪切混合器中搅拌约1小时以形成可分散氧化铝的淤浆。在这些条件下,淤浆中大于40%的氧化铝是直径为1微米或更小的颗粒形式。氧化铝可分散性越高,直径为1微米或更小的颗粒的百分比越高。因此,对于70%可分散性的氧化铝,70%的氧化铝将是直径为1微米或更小的颗粒形式。
适用于本发明的可分散氧化铝通常是勃姆石或假勃姆石氧化铝,其在约2-约5的pH下胶溶后在水中的可分散性为40%或更大。优选在约2-约5的pH下胶溶后在水中的可分散性大于70%或大于90%的氧化铝。尽管在本发明实施中最常使用勃姆石或假勃姆石氧化铝,但在约2-约5的pH下胶溶后在水中的可分散性为40%或更大的任意氧化铝均可用于本发明实施中。
向铜和锌的盐添加氧化铝
将可分散氧化铝的淤浆添加到铜和锌的盐如硝酸盐、乙酸盐或其组合中。可将混合物在约3的pH下混合约30-约60分钟以形成包含氧化铝、铜和锌的盐的淤浆。
沉淀铜和锌
将包含氧化铝、铜盐和锌盐的淤浆缓慢添加到含一定量水(a heal ofwater)的容器中。同时,向容器中添加碱金属碳酸盐的水溶液。保持恒温在约35℃-约90℃。通过调整淤浆悬浮液的流速和碱金属碳酸盐的流速使容器中混合物的pH保持在pH 7。这产生不溶的铜和锌的化合物的沉淀,如碳酸盐、混合碳酸盐和氢氧化物,并且由此获得含有除氧化铝以外的这些不溶化合物的淤浆。搅拌含有沉淀的淤浆并使其在约35℃-约90℃的温度下老化约15分钟-约3小时,保持pH为7-9。
形成催化剂
将沉淀过滤、洗涤并在约80℃-约200℃的温度下干燥粉末。洗涤沉淀以使Na2O水平小于0.2重量%、优选小于0.1重量%。可将干燥的粉末在约200℃-约600℃温度下锻烧约30分钟-约5小时以获得催化剂。锻烧的催化剂粉末然后可形成任何大小与形状,如根据工业应用需要的片状或粒料或挤出物。
形成还原的催化剂
在约100℃-约300℃下用含氢气的气体还原催化剂以形成还原的水煤气轮换催化剂。在还原过程中,二价铜形式的氧化铜还原成金属铜。可使用纯氢气,或可将氢气用惰性气体如氮气、氦气、氖气、氩气、氪气或氙气稀释。合成气(含氢气和一氧化碳的混合物)是还原催化剂的适宜气体。
还原的催化剂的铜表面积在还原的催化剂的活性方面很重要。这种Cu表面积不同于总BET表面积,而是必须单独测量的。通过其中CO和H2O转化成CO2和H2的试验来测量还原的催化剂活性。
下列实施例说明了本发明。
实施例1
制备催化剂
制备两种催化剂。催化剂1和催化剂2是本发明的实施例。还制备比较催化剂催化剂3,其不是本发明的实施例。
从勃姆石氧化铝CatapalB在水中的663.16克悬浮液制备催化剂1。该悬浮液含19%的表示为Al2O3的氧化铝。将悬浮液用硝酸酸化到pH3。将混合物在高剪切混合器中搅拌一小时以形成分散氧化铝淤浆。CatapalB氧化铝的可分散性大于90%。将分散氧化铝淤浆添加到含307.14克硝酸铜和151.85克硝酸锌的溶液中以形成含氧化铝、硝酸铜和硝酸锌的淤浆。将该淤浆保持在pH 3并搅拌60分钟。向含2124.58克水的容器中缓慢添加含氧化铝、硝酸铜和硝酸锌的淤浆。同时添加含1433.3克碳酸钠溶液的溶液。调整碳酸钠溶液的流速以便将pH控制到pH 7。将温度保持在60℃,同时搅拌混合物并老化1.5小时。将淤浆过滤、洗涤并将粉末干燥。将干燥的粉末在400℃煅烧2小时以形成催化剂。
从1667.07克含4%Al的硝酸铝溶液制备催化剂3。将硝酸铝添加到含307.14克硝酸铜和151.85克硝酸锌的溶液中。将该溶液保持在pH 3并搅拌60分钟。向含2124.58克水的容器中缓慢添加含硝酸铝、硝酸铜和硝酸锌的溶液。同时,添加含1433.3克碳酸钠溶液的溶液。调整碳酸钠溶液的流速以便将pH控制到pH 7。将温度保持在60℃,同时搅拌混合物并老化1.5小时。将淤浆过滤、洗涤并将粉末干燥。将干燥的粉末在400℃煅烧2小时以形成催化剂。
在制备催化剂时使用的材料概括在表1中。表2给出了催化剂的性能,以及组分的测量值。表2还提供了还原催化剂而形成的催化剂的数据。
表1
表2
实施例2
测量铜表面积
通过G.C.Chinchen等人在Journal of Catalysis(1987),103卷,第79-86页中描述的标准方法测量在实施例1中制备的还原的催化剂1、还原的催化剂2和还原的催化剂3的铜表面积。首先使用在氮气中含5%氢气的气体在约210℃下还原催化剂。获得还原的金属Cu表面。使在氦气中含2重量%N2O的气体在60℃下流过还原的催化剂10分钟。一氧化二氮在催化剂的铜表面上分解,通过热导检测器测量释放出的所形成的N2,并且氧原子仍然是结合于铜。每个氧原子接合2个表面Cu原子。释放出的氮气量给出了氧原子数以及由此可在催化剂表面上获得的铜原子的数目的度量。Cu原子的表面积为6.8×10-16cm2/原子。通过铜原子的数目乘以每个原子的面积,获得催化剂的铜表面积。显示在表2中的结果表明尽管催化剂1、催化剂2和催化剂3的组成非常类似,催化剂1和催化剂2具有大很多的铜表面积。
实施例3
测量催化剂的活性
通过用含3mol%氢气的He气处理1小时、含5mot%氢气的He气处理2小时和含20mol%氢气的He气处理1小时,将催化剂1、催化剂2和催化剂3在170℃下还原。将温度升高到200℃,用含20mol%氢气的He气对催化剂另外处理1小时。
对还原的催化剂进行催化剂活性的测试。在200℃、25psig总压力下,在固定床反应器中进行还原的催化剂的测试。使用的所有催化剂的粒度为50-100目。通过催化剂的气体含有12mol%的CO、8mol%的CO2、55mol%的H2和25mol%的N2;蒸汽/干燥气体的摩尔比为0.5。在各种空速下测试每种还原的催化剂,并且在40%的CO转化率下获得每种催化剂的反应速率。这种转化率远离反应的热力平衡,由此给出了用于比较的反应速率。
表3显示了在40%CO转化下的反应速率。该速率以每克催化剂每小时反应的CO摩尔量(速率A)的形式给出,和以每Cu(金属形式)总摩尔量每小时反应的CO摩尔量(速率B)的形式给出。在两种情况下,从可分散氧化铝制备的本发明的催化剂(还原的催化剂1和2)的速率比从硝酸铝制备的对比例的还原的催化剂3高大于40%。
表3
速率A | 速率B | |
样品编号 | mol CO/g.h | mol CO/mol Cu.h |
还原的催化剂1 | 24.5×10-2 | 33.9 |
还原的催化剂2 | 24.3×10-2 | 32.4 |
还原的催化剂3 | 16.9×10-2 | 22.5 |
尽管已经结合某些实施方案对本发明进行了说明,但应当理解在阅读本说明书时,其各种改进对于本领域技术人员是显而易见的。因此,应当理解在此公开的本发明是涵盖了这种落入所附权利要求书的范围内的改进的。
Claims (22)
1.一种水煤气轮换催化剂,包含约5-约75重量%的氧化铜,约5-约70重量%的氧化锌和约5-约50重量%的氧化铝,其从可分散氧化铝制备,其中可分散氧化铝在约2-约5的pH下胶溶后在水中具有40%或更大的可分散性。
2.根据权利要求1的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有50%或更大的百分比可分散性。
3.根据权利要求1的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有60%或更大的百分比可分散性。
4.根据权利要求1的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有70%或更大的百分比可分散性。
5.根据权利要求1的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有80%或更大的百分比可分散性。
6.根据权利要求1的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有90%或更大的百分比可分散性。
7.根据权利要求1的水煤气轮换催化剂,其中可分散氧化铝选自勃姆石氧化铝、假勃姆石氧化铝及其混合物组成的组。
8.根据权利要求7的水煤气轮换催化剂,其中可分散氧化铝包含勃姆石氧化铝。
9.根据权利要求7的水煤气轮换催化剂,其中可分散氧化铝包含假勃姆石氧化铝。
10.一种还原的水煤气轮换催化剂,其从水煤气轮换催化剂制备,包含约5-约75重量%的氧化铜,约5-约70重量%的氧化锌和约5-约50重量%的氧化铝,其中水煤气轮换催化剂从可分散氧化铝制备,所述可分散氧化铝在约2-约5的pH下胶溶后在水中具有40%或更大的百分比可分散性。
11.根据权利要求10的还原的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有50%或更大的百分比可分散性。
12.根据权利要求10的还原的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有60%或更大的百分比可分散性。
13.根据权利要求10的还原的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有70%或更大的百分比可分散性。
14.根据权利要求10的还原的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有80%或更大的百分比可分散性。
15.根据权利要求10的还原的水煤气轮换催化剂,其从可分散氧化铝制备,所述可分散氧化铝在pH2-5下胶溶后在水中具有90%或更大的百分比可分散性。
16.根据权利要求10的还原的水煤气轮换催化剂。其中可分散氧化铝选自勃姆石氧化铝、假勃姆石氧化铝及其混合物组成的组。
17.根据权利要求16的还原的水煤气轮换催化剂,其中可分散氧化铝包含勃姆石氧化铝。
18.根据权利要求16的还原的水煤气轮换催化剂,其中可分散氧化铝包含假勃姆石氧化铝。
19.一种用于从可分散氧化铝和沉淀的铜和锌的化合物制备水煤气轮换催化剂的方法,包括:
(a)向铜和锌的盐的溶液中添加分散氧化铝淤浆以形成氧化铝与铜和锌的盐的淤浆;
(b)形成碱金属碳酸盐的水溶液;
(c)将氧化铝与铜和锌的盐的淤浆和碱金属碳酸盐的水溶液同时与水混合以形成沉淀;使该沉淀老化;和
(d)将沉淀过滤、洗涤、干燥和锻烧以形成水煤气轮换催化剂。
20.根据权利要求19的方法,还包括将水煤气轮换催化剂还原以形成还原的水煤气轮换催化剂。
21.一种产品,其通过如下生产:
(a)向铜和锌的盐的溶液中添加从可分散氧化铝制备的分散氧化铝淤浆以形成氧化铝与铜和锌的盐的淤浆;
(b)形成碱金属碳酸盐的水溶液;
(c)将氧化铝与铜和锌的盐的淤浆和碱金属碳酸盐的水溶液同时与水混合以形成沉淀;使该沉淀老化;和
(d)将沉淀过滤、洗涤、干燥和锻烧以形成水煤气轮换催化剂。
22.一种产品,其通过如下生产:
(a)向铜和锌的盐的溶液中添加从可分散氧化铝制备的分散氧化铝淤浆以形成氧化铝与铜和锌的盐的淤浆;
(b)形成碱金属碳酸盐的水溶液;
(c)将氧化铝与铜和锌的盐的淤浆和碱金属碳酸盐的水溶液同时与水混合以形成沉淀;使该沉淀老化;
(d)将沉淀干燥和锻烧以形成水煤气轮换催化剂;和
(e)在含氢气的气体中还原该水煤气轮换催化剂以形成还原的水煤气轮换催化剂。
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CN2008801262080A Pending CN101939099A (zh) | 2007-12-05 | 2008-12-03 | 低温水煤气轮换催化剂 |
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US (2) | US20090149324A1 (zh) |
EP (1) | EP2240273A1 (zh) |
KR (1) | KR101551509B1 (zh) |
CN (1) | CN101939099A (zh) |
EA (1) | EA014964B1 (zh) |
RU (1) | RU2491119C2 (zh) |
WO (1) | WO2009076119A1 (zh) |
ZA (1) | ZA201004667B (zh) |
Cited By (1)
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CN105536803A (zh) * | 2016-01-22 | 2016-05-04 | 盘锦迪宝催化剂技术有限公司 | 一种铜系一氧化碳中温变换催化剂及其制备方法 |
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US20070196268A1 (en) * | 2006-02-22 | 2007-08-23 | Smith John R | Thermal activation of photocatalytic generation of hydrogen |
US20090321244A1 (en) * | 2008-06-25 | 2009-12-31 | Hydrogen Generation Inc. | Process for producing hydrogen |
MY162750A (en) * | 2009-10-23 | 2017-07-14 | Mitsubishi Gas Chemical Co | Methanol synthesis catalyst |
US8778833B2 (en) | 2010-11-11 | 2014-07-15 | Basf Corporation | Copper-zirconia catalyst and method of use and manufacture |
CN102423623B (zh) * | 2011-08-29 | 2013-07-10 | 华烁科技股份有限公司 | 一种多功能原料气净化剂及其制备和应用方法 |
EP2599541B1 (en) | 2011-12-02 | 2017-05-03 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for preparing a water gas shift catalyst operating at medium temperatures |
US9295978B2 (en) | 2012-02-15 | 2016-03-29 | Basf Corporation | Catalyst and method for the direct synthesis of dimethyl ether from synthesis gas |
CN105214671B (zh) * | 2015-10-20 | 2017-10-20 | 福州大学 | 一种耐热型Cu/ZnAl2O4低温水煤气变换催化剂 |
GB201519133D0 (en) | 2015-10-29 | 2015-12-16 | Johnson Matthey Plc | Process |
CA3001506A1 (en) | 2015-10-29 | 2017-05-04 | Johnson Matthey Public Limited Company | Water-gas shift catalyst |
GB201519139D0 (en) | 2015-10-29 | 2015-12-16 | Johnson Matthey Plc | Process |
CN105833876B (zh) * | 2016-04-15 | 2019-03-26 | 西安向阳航天材料股份有限公司 | 一种高活性铜锌铝低温变换催化剂及其制备方法 |
KR102233613B1 (ko) * | 2018-10-15 | 2021-03-30 | 재단법인 포항산업과학연구원 | 중온용 수성가스 전환 반응 촉매, 이의 제조방법, 및 이를 이용한 수소 제조방법 |
KR102199485B1 (ko) * | 2018-10-18 | 2021-01-06 | 연세대학교 원주산학협력단 | 일단 수성가스 전이 반응을 위한 촉매의 제조 방법 |
GB201905293D0 (en) * | 2019-04-15 | 2019-05-29 | Johnson Matthey Plc | Copper-containing catalysts |
US11045793B1 (en) * | 2020-07-24 | 2021-06-29 | Qatar University | Controlled on-pot design of mixed copper/zinc oxides supported aluminum oxide as an efficient catalyst for conversion of syngas to heavy liquid hydrocarbons and alcohols under ambient conditions feasible for the Fischer-Tropsch synthesis |
CN114250095B (zh) * | 2022-01-17 | 2022-10-14 | 江西颖南原环能有限公司 | 一种腐植酸络合铜基催化剂及其制备方法和应用 |
US20230398519A1 (en) * | 2022-06-09 | 2023-12-14 | Clariant International Ltd | Hydrotalcite-precursor based catalyst with improved performance for lts reaction |
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2008
- 2008-12-03 CN CN2008801262080A patent/CN101939099A/zh active Pending
- 2008-12-03 KR KR1020107014693A patent/KR101551509B1/ko not_active IP Right Cessation
- 2008-12-03 WO PCT/US2008/085329 patent/WO2009076119A1/en active Application Filing
- 2008-12-03 EP EP08859023A patent/EP2240273A1/en not_active Withdrawn
- 2008-12-03 RU RU2010127370/04A patent/RU2491119C2/ru not_active IP Right Cessation
- 2008-12-05 EA EA200802290A patent/EA014964B1/ru not_active IP Right Cessation
-
2009
- 2009-12-30 US US12/650,110 patent/US20100102278A1/en not_active Abandoned
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2010
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Also Published As
Publication number | Publication date |
---|---|
RU2010127370A (ru) | 2012-01-10 |
KR101551509B1 (ko) | 2015-09-08 |
US20100102278A1 (en) | 2010-04-29 |
US20090149324A1 (en) | 2009-06-11 |
WO2009076119A1 (en) | 2009-06-18 |
EP2240273A1 (en) | 2010-10-20 |
RU2491119C2 (ru) | 2013-08-27 |
KR20100100934A (ko) | 2010-09-15 |
EA200802290A1 (ru) | 2009-06-30 |
ZA201004667B (en) | 2011-09-28 |
EA014964B1 (ru) | 2011-04-29 |
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