CN102143798A - 用于从包含氢气和一氧化碳的气体生产醇的双金属Mo/Co催化剂 - Google Patents
用于从包含氢气和一氧化碳的气体生产醇的双金属Mo/Co催化剂 Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000001257 hydrogen Substances 0.000 title claims abstract description 9
- 239000003426 co-catalyst Substances 0.000 title claims description 8
- 150000001298 alcohols Chemical class 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical class [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Chemical class 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011733 molybdenum Substances 0.000 claims abstract description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011159 matrix material Substances 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000013590 bulk material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910002065 alloy metal Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 6
- 239000012018 catalyst precursor Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- -1 syngas Chemical compound 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 235000016768 molybdenum Nutrition 0.000 description 8
- 238000001994 activation Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 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
- 244000287680 Garcinia dulcis Species 0.000 description 1
- PPWHTZKZQNXVAE-UHFFFAOYSA-N Tetracaine hydrochloride Chemical compound Cl.CCCCNC1=CC=C(C(=O)OCCN(C)C)C=C1 PPWHTZKZQNXVAE-UHFFFAOYSA-N 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 238000002167 anodic stripping potentiometry Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 206010003664 atrial septal defect Diseases 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 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
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
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- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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Abstract
用于从含有氢气和一氧化碳的气体混合物，如合成气生产醇的负载催化剂是由粒状的惰性多孔催化剂基质的前体制备的，所述粒状的惰性多孔催化剂基质用约2∶1到约1∶1，优选约1.5∶1的钼对钴的摩尔比和约1∶0.08到约1∶0.30，优选约1∶0.26-0.28的钴对碱金属的摩尔比的钼、钴和助催化剂碱金属或碱土金属的氧化物或盐浸渍。通过在约600℃到约900℃，优选约800℃下，在还原性环境中还原催化剂前体材料来“活化”催化剂。通过在约240℃到约270℃和1000psi-1200psi的压力下，使包含1∶1到3∶1的比的至少CO和H2的气体混合物通过包含催化剂的反应器来生产醇。
Description
相关申请的交叉引用
本申请要求2008年7月3日提交的美国临时专利申请序列号第61/078,042号的优先权。
领域和背景
本发明涉及尤其用于促进诸如CO和H2的气体成分的反应以最终形成醇的催化剂的领域以及涉及这些催化剂的制备和用途。美国专利4825013、4752622、4882360、4831060、4752623、4607055、4607056和4661525是示例。
发明概述
本发明包括负载催化剂前体、负载催化剂和这样的催化剂的制备方法，以及使用催化剂从包含氢气和一氧化碳的气体混合物，如合成气来生产醇。负载催化剂前体包括负载钼、钴和助催化剂碱金属或碱土金属的氧化物或盐的粒状的惰性多孔催化剂基质，钼对钴的摩尔比为约2∶1到约1∶1，优选约1.5∶1，钴对碱金属摩尔比为约1∶0.08到约1∶0.30，优选约1∶0.26-0.28。
优选地，通过用以上面指出的比的钼、钴和助催化剂金属的盐浸渍多孔催化剂基质材料，并将负载盐煅烧成氧化物来制备催化剂前体，除非所使用的盐可以被还原且不会产生对催化反应的系统催化活性、反应器和/或产物有害的产物。
通过在约600℃到约900℃，优选约800℃下，在还原性环境中还原催化剂前体材料来形成或“活化”催化剂。
通过在约240℃到约270℃和1000psi-1200psi的压力下，使包含至少CO和H2的气体混合物通过包含催化剂的反应器来生产醇。
H2/CO比从1∶1到3∶1变化，优选约1-1.5∶1，且最优选约1∶1。以约0.9-1.0的高级醇(C2 +OH)对甲醇的比，醇的收率可以达到140-175g/kg催化剂小时。如果从生物质气化来生产合成气，这具有67％的碳效率，每绝干吨生物质可以生产115加仑的醇，这高于可利用的发酵过程。
参考下面的优选实施方案的详细描述将可以更充分地领会和理解本发明的这些和其他目的、特征和优势。
优选实施方案的描述
催化剂
催化剂前体制备
在优选的实施方案中，将钼、钴和碱金属或碱土金属助催化剂的盐顺次装载到多孔的惰性基质材料上。钼酸铵四水合物是优选的钼盐。硝酸钴是优选的钴盐。最优选的助催化剂是铯，且甲酸铯是优选的铯盐。
适于作为催化剂基质的示例性多孔的惰性材料包括粉末的、颗粒的或其他形式的粒状的碳、二氧化钛、二氧化锆和氧化铝。目前优选的基质是氧化铝(Al2O3)，优选是球形颗粒形式，具有约1.5到约2.0毫米(平均直径)，优选约1.8毫米的粒径，约0.63克每立方毫米的密度，约210m2每克的表面积以及约0.75立方毫米每克的孔体积。
催化剂中所使用的钼对钴对助催化剂金属的摩尔比是约：
1-2∶1∶0.08-0.30，优选约1.5∶1∶0.26-0.28。
当氧化铝用作基质时，将约5.7wt％到约11.4wt％的Mo(基于Mo对Al2O3的重量)加载到基质上且在一定程度上浸渍到基质中。换句话说，每100克基质加载约5.7到约11.4克的钼。优选地，将8.5wt％-10wt％的Mo加载到基质上。成比例地加载其他盐以获得上面指出的摩尔比。
将三种金属盐中的每一种溶解在其自己的水溶液中。加载到所使用的定量的基质上的需要量的盐溶解在一定体积的水中，该体积近似匹配所使用的量的基质将吸收的水的体积。
优选地，先用钼酸铵溶液浸渍基质。基质在60℃下干燥4小时，然后在110℃下过夜。接着，应用硝酸钴溶液并以同样的方式干燥基质。在钼和钴盐浸渍到基质中之后，在350℃空气中煅烧系统4小时。这将金属盐转化成氧化物，氧化物随后如下所述地通过在反应器内原位还原而得到活化。
接着，用铯盐浸渍基质和钼-钴组合。以相同的方式再次干燥系统。甲酸盐是可以被直接还原而不会产生对催化剂和反应器有害的产物的盐的示例。这使得在催化剂活化之前不需要煅烧甲酸铯，因为活化的热和还原将甲酸金属盐还原成元素金属，或金属氢化物，而释放出水和二氧化碳。水和二氧化碳不会污染反应器/催化剂系统或催化反应中产生的醇。
催化剂前体活化
催化剂前体在使用之前必须被活化。将催化剂前体-基质组合加载到反应器中，在该反应器中，所述催化剂前体-基质组合将用于生产醇。在反应器内在约600℃到约900℃，优选约800℃下，在约大气压下，在体积比为3/2的氮和氢的流动的流中，加热催化剂前体/基质组合。此处理持续约3到约10小时，优选约5小时。所使用的还原气体混合物的流速是约15cc每分钟每cc的催化剂前体-基质组合(15cc/min/cc催化剂前体-基质)。此活化过程之后，通过使用惰性气体环境来保护催化剂，然后将合成气输送到反应系统。
虽然不希望受到理论束缚，但认为氧化钴、氧化钼和甲酸铯由此被还原成元素金属、和/或金属氢化物或合金。因而，所获得的催化剂包括元素钼、钴或合金以及碱金属或碱土金属、和/或其氢化物，且元素比为约2-1∶1∶0.08-0.30，优选约1.5∶1∶0.26-0.28。将催化剂负载到多孔的惰性粒状材料，诸如氧化铝上。
按照这样的方式完成催化剂活化后，催化剂和反应器做好了使用的准备。
反应器操作
在下面提供的操作条件下，将包含氢和一氧化碳的气体混合物通过反应器。在商业气化操作中，将优选使用通过在过热蒸汽存在下，由含碳物质的热分解且通常是无氧分解产生的合成气混合物。气体混合物中氢对一氧化碳的比优选是约1-1.5∶1。
在约240℃到约270℃，优选在最高260℃的相对低的温度下操作反应器。较高的压力在理论上是需要的，但考虑到工艺成本，优选采用低压，如约1000psig到约1200psig。采用的气时空速(GHSV)是约4000h-1到约6000h-1。较低的温度和较高的压力在此过程中有利于形成高级醇。
实施例
表1-6中列出的下面的实施例显示了由本发明的催化剂获得的结果，以及Co、Mo和Cs装载量和比对催化剂活性及对醇的反应选择性的影响。在所有实施例中，试验是基于含有反应物的气体单程通过反应器来进行的。没有一种气体如将在商业操作中进行的那样被回收。
表中的醇加仑数/BDT(生物质的绝干吨)的计算按照如下方式进行：
1.测量测试时间期间引入到系统内的CO的摩尔数(A)。
2.测量离开反应器的CO的摩尔数(B)。
3.测量测试期间生产的醇的加仑数(G)。
4.G/[A-B]得到醇加仑数/转化的碳(作为CO)的摩尔数。
5.做出如下假设：在商业过程中，来自一吨生物质的所有一氧化碳最终都将通过气体循环通过反应器而被转化。
6.然后基于试验，假设667磅作为CO的碳将从气化的一吨干生物质(BDT-绝干吨)产生，G/[A-B]的比用于计算此量的碳所生产的醇的加仑数。此计算假设气化器的理论效率是66.7％，因为1BDT的生物质(不含水分和灰)通常包含1000磅的碳。
表第二列中“CO的浓度％”指CO在通过反应器时转化成其他产物的CO的重量百分比。
第三列中“醇的选择性C Mol％”指转化成所表示的醇的碳的mol％。
1.使用相同式的催化剂的结果
测试催化剂：所使用的催化剂具有1∶1∶0.27的Mo∶Co∶Cs比。以5.7wt％(每100克氧化铝基质5.7克Mo)基质，将Mo负载到优选的氧化铝基质上。
测试条件：温度：265℃。压力：1200psi。GHSV：4269-4321h-1合成气：CO/H2＝1∶1
测试时间：测试是在反应稳定之后的5小时或60小时的一段时间内进行。
冷凝器：#1，收集(60小时试验的)前21个小时的液体产物
#2，收集(60小时试验的)后13个小时的液体产物
表1.5小时测试和60小时测试的结果概述
*相同配方的催化剂测试5小时
**相同的催化剂，在60小时试验后测试5小时
按照表1的结果，显示了在开始第21个小时时获得了较高的转化率和选择性，然后反应逐渐变得稳定。当反应系统关闭并再次开启时，转化率和选择性(表1的第5行)能够达到与先前水平一样高或高于先前水平。这表明催化剂在测试期间并未失活。
基于上面的试验结果，表1结果的平均G值和醇产率是：
醇产率：119.9g/kg催化剂小时
G值：95.6加仑/BDT
2.Co装载量对催化剂的活性和对醇的选择性的影响
测试催化剂：改变所使用的Co的量，得到不同的Mo∶Co比。将Mo以5.7wt％装载到优选的氧化铝基质上，且以2.2wt％装载Cs。
测试条件：温度：260℃-272℃。压力：1200psi。GHSV：4300h-1，除了所标示的。
合成气：CO/H2＝1∶1
测试时间：5小时
表2.Co装载量对催化剂的活性和对醇的选择性的影响
*温度：321℃，#239℃，GHSV：5980h-1，---痕量
在260℃-270℃的温度下，包含5.7wt％Mo和Cs 2.2wt％(不含Co)的催化剂根本无活性。在320℃的更高温度下，催化剂具有17％的CO转化率，但产物中仅有痕量的醇。当Co的装载量增大到1.75wt％时，活性和醇的选择性都显著增强。当装载量增大到3.5wt％时，醇产率达到120g/kg催化剂小时且醇的收率(G值)达到90加仑/BDT。当Co的装载量增大到5.3wt％时，活性和选择性都减弱。
3.Mo装载量对催化剂的活性和对醇的选择性的影响
测试催化剂：改变所使用的Mo的量，得到不同的Mo∶Co比。将Co以3.5wt％装载到优选的氧化铝基质上；以2.2wt％装载Cs。
测试条件：温度：241℃-255℃。压力：1200psi。GHSV：5759-6000h-1，除了所标示的。
合成气：CO/H2＝1∶1
测试时间：5小时
表3.Mo装载量对催化剂的活性和对醇的选择性的影响
*GHSV：4127h-1
Mo的装载量wt％从0-17.1wt％变化，反应选择性和醇收率先是随着Mo装载量的增加而增大，并在11.4wt％的Mo装载量时达到最高水平。在高于约11.4wt％，选择性和收率随着Mo装载量的继续增加而降低。不包含Mo的催化剂在相同的温度和压力下，且甚至在较低的GHSV和较高的温度下均无活性。因此，Mo和Co，或它们的合金在使催化剂在所应用的条件下有活性的方面起到了重要的作用。
4.Mo/Co比对催化剂的活性和反应的选择性的影响
测试催化剂：改变Mo对催化剂的比。将Cs以2.2wt％装载到基质。
测试条件：温度：250℃。压力：1200psi。GHSV：4330h-1，除了所标示的。
合成气：CO/H2＝1∶1
测试时间：5小时
表4.Mo/Co比对催化剂的性能的影响
*温度：221℃
Mo、Co的装载量和Mo/Co的比都影响催化剂的性能。不含Mo或Co的催化剂在所应用的条件下无活性的事实表明Mo和Co的一些合金在基质的表面上形成，且可能是负载金属的活性催化态。
5.Cs装载量对由合成气合成醇中Mo/Co/Cs/Al2O3的性能的影响
使用的催化剂：Mo、Co装载量相对于基质是8.5wt％、3.5wt％。
Cs装载量相对于基质从0-3.6wt％变化。
测试条件：测试温度：237℃-250℃。压力：1200psi。GHSV：6000h-1，
合成气：CO/H2＝1∶1
测试时间：5小时
表5.Cs装载量对由合成气合成醇中Mo/Co/Cs/Al2O3的性能的影响
反应对醇的选择性随着Cs的装载量而增强，且在0.73wt％-2.2wt％的Cs装载量时是最佳的。超过这些水平继续增大Cs的装载量将会降低选择性和醇的收率。当Cs装载量是0.73％-2.2％时，G值是97.6-106.6加仑/BDT的生物质。
6.所获得的醇的分布随Cs装载量的变化
表6显示了从上面的表5中显示的试验获得的醇的分布。
表6.所获得的醇的分布随Cs装载量的变化
甲醇选择性随Cs装载量的增加而减弱，但乙醇和其他高级醇随Cs的装载量增加。这表明碱性助催化剂将会增强高级醇的选择性。结合选择性和液体中醇的分布，当Cs装载量是2.2wt％时，最高可变毛利(variable margin)(VM)是$1.71每加仑。可变毛利是原材料成本与所生产的醇的销售价格之间的差。下面的销售价格以加权平均销售价格计算而使用：甲醇$1.50/加仑，乙醇$2.30/加仑，丙醇和高级醇$3.00/加仑。所使用的原材料成本假设将生物质热转化成包含氢气和一氧化碳的合成气，价格为$35每绝干吨生物质。
当然，应理解，前述内容是本发明的优选实施方案，且可以在下面的权利要求的范围内进行各种变化和改变，正如根据专利法原理，包括等同原则，所解释和应用的。
Claims (16)
1.一种负载催化剂，包括：
元素钼、钴或它们的合金和碱金属或碱土金属、和/或其氢化物，以约2-1∶1∶0.08-0.30的元素比负载到多孔的惰性粒状材料上。
2.如权利要求1所述的负载催化剂，其中所述元素比为约1.5∶1∶0.26-0.28。
3.如权利要求2所述的负载催化剂，其中所述基质是粒状的碳、二氧化钛、二氧化锆和氧化铝中的一种。
4.如权利要求3所述的负载催化剂，其中所述基质是氧化铝(Al2O3)。
5.如权利要求4所述的负载催化剂，其中所述氧化铝是球形颗粒形式，具有约1.5到约2.0毫米(平均直径)的粒径，约0.63克每立方毫米的密度，约210m2每克的表面积以及约0.75立方毫米每克的孔体积。
6.如权利要求5所述的负载催化剂，其中所述氧化铝的粒径是约1.8毫米。
7.如权利要求1所述的负载催化剂，其中所述碱金属或碱土金属是铯。
8.如权利要求1所述的负载催化剂，包括负载到所述基质上的约5.7wt％到约11.4wt％的Mo。
9.如权利要求8所述的负载催化剂，包括负载到所述基质上的约1.75wt％到约3.5wt％的Co。
10.如权利要求1所述的负载催化剂，包括负载到所述载体上的约8.5wt/wt％到约10wt/wt％的钼。
11.如权利要求1所述的负载催化剂，包括Cs，其以相对于载体的约0.73wt％到约2.9wt％被装载到所述基质上。
12.如权利要求1所述的负载催化剂，包括Cs，其以相对于载体的约0.73wt％到约2.2wt％被装载到所述基质上。
13.一种用于负载催化剂的前体，包括：
钼、钴和碱金属或碱土金属助催化剂的盐或氧化物，其以约2-1∶1∶0.08-0.30的元素Mo对Co对碱金属或碱土金属的比负载到多孔的惰性粒状材料上。
14.一种用于制备负载催化剂的方法，包括：
在还原性环境中将以约2-1∶1∶0.08-0.30的元素Mo对Co对碱金属或碱土金属的比负载的、负载钼、钴和碱金属或碱土金属助催化剂的盐或氧化物的多孔的惰性粒状材料加热到约600℃到约900℃的温度，持续约3到约7小时。
15.一种用于制备负载催化剂的方法，包括：
用以约2-1∶1∶0.08-0.30的元素Mo对Co对碱金属或碱土金属的比负载的钼盐、钴盐和碱金属或碱土金属助催化剂的盐浸渍多孔的惰性粒状材料；煅烧至少浸渍的Mo和Co的盐，并在还原性气氛中将所得到的材料加热到约600℃到约900℃的温度，持续约3到约10小时。
16.一种用于从包含氢气和一氧化碳的气体制备醇的方法，包括：
在约240℃到约270℃的温度，约1000psig到约1200psig的压力和约4000h-1到约6000h-1的气时空速下，使所述气体通过包含负载催化剂的反应器，所述负载催化剂包括以约2-1∶1∶0.08-0.30的元素比负载到多孔的惰性粒状材料上的元素钼、钴和碱金属或碱土金属、和/或其氢化物。
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- 2009-06-22 EP EP09774070A patent/EP2293875A4/en not_active Withdrawn
- 2009-06-22 WO PCT/US2009/048132 patent/WO2010002618A1/en active Application Filing
- 2009-06-22 CN CN2009801343538A patent/CN102143798A/zh active Pending
- 2009-06-22 RU RU2011102051/04A patent/RU2011102051A/ru not_active Application Discontinuation
- 2009-06-22 JP JP2011516494A patent/JP2012501815A/ja active Pending
- 2009-06-22 CA CA2729477A patent/CA2729477A1/en not_active Abandoned
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112166169A (zh) * | 2018-02-09 | 2021-01-01 | 英国石油有限公司 | 费-托方法、负载型费-托合成催化剂及其用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010002618A1 (en) | 2010-01-07 |
| JP2012501815A (ja) | 2012-01-26 |
| EP2293875A4 (en) | 2012-04-25 |
| EP2293875A1 (en) | 2011-03-16 |
| CA2729477A1 (en) | 2010-01-07 |
| RU2011102051A (ru) | 2012-08-10 |
| AU2009264984A1 (en) | 2010-01-07 |
| US20120065279A1 (en) | 2012-03-15 |
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