CN101143329A - Mo-O-K基催化剂、其制备方法及其在甲硫醇合成中的应用 - Google Patents
Mo-O-K基催化剂、其制备方法及其在甲硫醇合成中的应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 21
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- 229910004298 SiO 2 Inorganic materials 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 11
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- 238000006243 chemical reaction Methods 0.000 claims description 7
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- 238000013019 agitation Methods 0.000 description 4
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- 239000011591 potassium Substances 0.000 description 3
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- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
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Abstract
本发明涉及制备包含TeO2的Mo－O－K基催化剂的方法，其包括在多于一个步骤中用作为TeO2前体的化合物和作为K2O前体的含K化合物的水溶液并且用包含Mo化合物的溶液或者包含作为含Mo化合物的(NH4)6Mo7O24的水溶液浸渍无机载体，干燥所述经浸渍的载体，并在高温下用H2或者合成气(CO+H2)处理所述经浸渍的载体。本发明的催化剂适用于甲硫醇的合成。
Description
技术领域
本发明涉及用于从高H2S含量的合成气合成甲硫醇的Mo-O-K基催化剂的制备方法以及所述催化剂。
背景技术
作为生产甲硫氨酸、杀虫剂和医药的重要化学原料，甲硫醇主要通过硫化氢与甲醇的反应来制备。例如，美国专利申请856,232公开了基于硫化氢与甲醇或二***之间反应的甲硫醇合成方法；法国专利申请93,112,491公开了基于甲基硫醚与氢气在过渡金属催化剂上的反应的制备方法；EP167,354公开了在二氧化钛载体和NiO或MoO3活性组分上硫化氢与一氧化碳反应的合成路径；中国专利CN98118186.4和CN98118187.2公开了两种从高H2S含量的合成气合成甲硫醇的催化剂，其中由前体K2MoS4或(NH4)2MoS4加上一种钾盐形成活性组分Mo-S-K；中国专利申请200310100496.1和200310100495公开了两种用于甲硫醇合成的Mo-O-K/SiO2催化剂，其中助催化剂来自Co、Ni、Fe、Mn的氧化物或者La、Ce的稀土氧化物，Mo-O-K基活性组分由前体K2MoO4或(NH4)6Mo7O24·4H2O加上一种钾盐形成。
发明内容
本发明的目的是制备高活性和选择性的催化剂，该催化剂用于从高H2S含量的合成气一步合成甲硫醇。
具体实施方式
根据本发明的催化剂包括活性组分、活性助催化剂(promoter)和载体材料。所述活性组分是Mo-O-K基化合物，其前体是由K2MoO4表示的钼酸钾或由MoO3表示的(NH4)6Mo7O24·4H2O加上一种由K2O表示钾盐，或者MoO3加上一种钾盐，所述钾盐是选自K2CO3、KOH和CH3COOK或者任何其它的作为K2O前体的含钾的盐中的至少一种。所述助催化剂是由TeO2和H6TeO6表示的含Te化合物，或者任何其它的作为TeO2前体的含Te盐或化合物，例如所述酸的钾盐。所述载体优选是SiO2或者氧化物载体，例如TiO2、ZrO2、Al2O3、Al2O3-SiO2、沸石、纯的所述金属氧化物或者它们的混合物。对于催化剂TeO2-K2MoO4/SiO2(从K2MoO4制备)，重量比是TeO2/K2MoO4/SiO2＝(1-20)/(1-50)/100，更优选(3-12)/(15-30)/100；对于催化剂TeO2-K2MoO4/SiO2(从(NH4)6Mo7O24·4H2O和含钾的盐制备)，重量比是TeO2/MoO3/K2O/SiO2＝(1-20)/(1-50)/(1-50)/100，更优选(3-12)/(15-30)/(8-20)/100。
本发明还涉及制备所述催化剂的方法，其包括在多于一个步骤中用作为TeO2前体的化合物和作为K2O前体的含K化合物的水溶液并且用包含Mo化合物的溶液或者作为含Mo化合物的(NH4)6Mo7O24的水溶液浸渍无机载体，干燥所述经浸渍的载体，并在高温下用H2或者合成气(CO+H2)处理所述经浸渍的载体。
未用所述气体预处理的产物也是本发明的一部分。
为了实现活性组分和助催化剂在载体表面上较好的分布，在浸渍过程中优选存在至少一种螯合剂。所述螯合剂选自例如柠檬酸的羧酸、柠檬酸三铵、L-谷氨酸、酒石酸以及例如乙二胺四乙酸(EDTA)的络合剂，同时以重量计所选螯合剂的用量为载体的0.1-0.6倍，并且更优选以重量计为0.3-0.6倍。应该添加氨水调节浸渍溶液的pH值为8-10，优选的操作工序是至少两步的浸渍方法，包括：
(1)当选择K2MoO4作为活性组分的前体时，在给定量的蒸馏水中溶解根据所需重量比的给定量的H2TeO4，产生水溶液，使用该溶液浸渍相应量的载体8-10h，然后在100-135℃下干燥4-6h，得到中间产物；然后在给定量的蒸馏水中溶解给定量的至少一种螯合剂和K2MoO4，制得水溶液，向其中添加适量的氨水，调节pH值至8-10。用所述溶液浸渍上面制得的中间产物8-10h，最后在高温，尤其是110-135℃下干燥所述浸渍的材料4-6h。
(2)当选择(NH4)6Mo7O24·4H2O加上上述钾盐之一作为活性组分的前体时，制备的次序优选如下：首先，在给定量的蒸馏水中溶解根据所需Mo和Te的重量比的一定量的所选钾盐和给定量的H2TeO4，制得混合的水溶液，使用该溶液浸渍相应量的载体8-10h，然后在高温，尤其是100-130℃下干燥4-6h，形成H2TeO4-K/SiO2中间产物；在规定量的蒸馏水中溶解一定量的所选螯合剂和(NH4)6Mo7O24·4H2O，制得混合的水溶液，向其中添加适量的氨水，调节pH值至8-10。用所述溶液浸渍上面制得的H2TeO4-K/SiO2中间产物8-10h，接着将其在高温，尤其是110-135℃下干燥4-6h。
(3)在给定量的蒸馏水中溶解给定量的(NH4)6Mo7O24·4H2O和给定量的H2TeO4，制得混合的水溶液，使用该溶液浸渍给定量的SiO28-10h，然后将其在高温，尤其是100-130℃下干燥4-6h，形成Mo-O-Te/SiO2中间产物；在给定量的蒸馏水中溶解给定量的钾盐，制得水溶液，向其中添加给定量的所选螯合剂和氨水，调节溶液的pH值至8-10，用所述溶液浸渍上面制得的Mo-O-Te/SiO28-10h，然后在110-135℃下干燥4-6h。
通过在上述催化剂的存在下，使碳氧化物、硫或硫化氢的混合物和氢气在高温高压下反应，成功地实施了制备甲硫醇的连续过程。
优选以1/0/1/0至1/10/10/10的比例向反应器中添加反应物碳氧化物、硫和/或硫化氢以及氢气。
反应条件以及产物的纯化和未反应化合物的再循环是公知的(US 4,665,245/EP-A-104507；WO 2005/040082)。
在将一氧化碳、氢气和硫化氢催化转化成甲硫醇之前，应该用H2或者合成气(CO+H2)预处理催化剂8-10h，优选接着用H2S硫化，从而获得助催化剂的TeO2组分。
每次通过0.5毫升催化剂，在固定床管式反应器中进行本发明催化剂催化性能的评价。反应条件是CO/H2/H2S＝1/1/2，300℃，0.2MPa和GHSV＝2000h-1。用GC分析产物。所有数据在达到稳定状态条件下后获得。
下面借助实施例阐述本发明。
实施例1
在搅拌下，在10.0ml的蒸馏水中完全溶解0.648g的H2TeO4·2H2O，测量如此制备的H2TeO4水溶液的pH值为4.1，然后在室温下将5.000g的SiO2在该H2TeO4水溶液中浸渍8h，接着在120℃下干燥5h，制得干燥的中间产物。
在搅拌下，在5.0ml的蒸馏水中完全溶解2.068g的K2MoO4，制得K2MoO4水溶液，向其中添加5ml的NH3·H2O，测量该水溶液的pH值为11.40，然后在搅拌下，向K2MoO4加NH3·H2O的水溶液中添加3.000g的柠檬酸，测量K2MoO4加NH3·H2O溶液的pH值为9.26。最后，在室温下用含柠檬酸的K2MoO4加NH3·H2O的溶液浸渍在步骤(1)中制备的中间产物10h，接着在120℃下干燥5h，制得催化剂TeO2/K2MoO4/SiO2，其中重量比为TeO2/K2MoO4/SiO2＝9/25/100。表1中给出了如此制备的催化剂的评价结果。
实施例2
(1)在快速搅拌下，在10ml的蒸馏水中完全溶解1.468g的K2CO3和0.648g的H2TeO4·2H2O，形成水溶液，在室温下使用该溶液浸渍5.000g的SiO2，并且最后在125℃下干燥4h，制得中间产物。
(2)在搅拌下，在5.0ml的蒸馏水中完全溶解1.534g(NH4)6Mo7O24·4H2O，形成水溶液，向其中添加2.000g柠檬酸三铵，调节溶液的pH值为9.05，在室温下使用该溶液浸渍在步骤(1)中制备的中间产物9h，并且最后在125℃下干燥4h，制得催化剂K2O-MoO3-TeO2/SiO2，其中重量比为K2O/MoO3/TeO2/SiO2＝20/25/9/100。表1中给出了如此制备的催化剂的评价结果。
实施例3
除了使用2.000g的酒石酸作为螯合剂，并用γ-Al2O3代替载体SiO2外，根据在实施例1中描述的方法制备催化剂。表1中给出了如此制备的催化剂的评价结果。
实施例4和5
除了改变H2TeO4·2H2O的量分别为0.486g和0.432g，并且在两种情况中螯合剂都是EDTA外，根据在实施例1中描述的方法制备催化剂，如此制备的最终催化剂的重量比分别为TeO2/K2MoO4/SiO2＝6.75/25/100和TeO2/K2MoO4/SiO2＝6/25/100。表1中给出了如此制备的催化剂的评价结果。
实施例6
除了使用5.000g的TiO2作为载体，并且H2TeO4·2H2O的量和K2MoO4的量分别替换为0.142g和0.827g外，根据在实施例1中描述的方法制备催化剂，所制备的最终催化剂为TeO2/K2MoO4/TiO2＝2/10/100。表1中给出了如此制备的催化剂的评价结果。
实施例7
除了H2TeO4·2H2O的量和K2MoO4的量分别替换为0.071g和0.414g外，根据在实施例6中描述的方法制备催化剂，所制备的最终催化剂为TeO2/K2MoO4/ZrO2＝1/5/100。表1中给出了如此制备的催化剂的评价结果。
实施例8
除了使用5.000g的沸石MCM-41作为载体，并且K2CO3、H2TeO4·2H2O的量和(NH4)6Mo7O24·4H2O的量分别替换为1.835g、1.080g和2.454g外，根据在实施例2中描述的方法制备催化剂，所制备的最终催化剂为K2O/MoO3/TeO2/MCM-41＝25/40/15/100。表1中给出了如此制备的催化剂的评价结果。
表1实施例1-8中催化剂的评价结果.
| 实施例(催化剂) | 选择性(％) | CO2/CH3SH | 产率(g.mlcat -1.h-1) | CO的转化率(％) | ||||||
| CH4 | CH3SH | COS | CO2 | CH4 | CH3SH | COS | CO2 | |||
| 1，K2MoO4/TeO2/SiO2＝25/9/100 | 0.23 | 55.21 | 10.70 | 33.86 | 0.61 | 5.29E-04 | 0.38 | 0.09 | 0.21 | 59.29 |
| 2，K2O/MoO3/TeO2/SiO2＝15/25/9/100 | 0.25 | 55.15 | 11.30 | 33.30 | 0.60 | 5.32E-04 | 0.35 | 0.09 | 0.19 | 57.26 |
| 3，K2MoO4/TeO2/γ-Al2O3＝25/9/100 | 0.30 | 48.70 | 17.91 | 33.08 | 0.68 | 4.90E-04 | 0.24 | 0.09 | 0.21 | 56.02 |
| 4，K2MoO4/TeO2/SiO2＝25/6.75/100 | 0.24 | 54.74 | 10.72 | 34.90 | 0.60 | 5.20E-04 | 0.35 | 0.09 | 0.21 | 56.02 |
| 5，K2MoO4/TeO2/SiO2＝25/6/100 | 0.24 | 54.50 | 10.50 | 35.02 | 0.66 | 5.25E-04 | 0.36 | 0.09 | 0.22 | 57.52 |
| 6，K2MoO4/TeO2/TiO2＝10/2/100 | 0.08 | 48.40 | 14.05 | 37.47 | 0.77 | 5.12E-04 | 0.31 | 0.09 | 0.24 | 48.4 |
| 7，K2MoO4/TeO2/ZrO2＝5/1/100 | 0.09 | 48.17 | 17.84 | 33.90 | 0.70 | 5.01E-04 | 0.27 | 0.10 | 0.19 | 39.6 |
| 8，K2O/MoO3/TeO2/MCM-41＝25/40/15/100 | 0.07 | 51.28 | 11.83 | 36.82 | 0.72 | 4.97E-04 | 0.39 | 0.09 | 0.28 | 61.5 |
实施例9
图1中与原材料和催化剂K2MoO4/SiO2及CoO-K2MoO4/SiO2相比较，给出了通过在150℃下干燥催化剂并在400℃下煅烧制备的催化剂TeO2-K2MoO4/SiO2的X射线衍射图[A]载体SiO2；B]H6TeO6(H2TeO4·2H2O)；C]K2MoO4/SiO2；D]TeO2-K2MoO4/SiO2(用柠檬酸制备的；在150℃下干燥)；E]TeO2-K2MoO4/SiO2(用HNO3制备的且不用螯合剂)；F)CoO-K2MoO4/SiO2；G)TeO2-K2MoO4/SiO2(在400℃下煅烧)；H)CoO-K2MoO4/SiO2(在500℃下煅烧)]。与基于K2MoO4/SiO2体系制备的其它催化剂相比，X射线衍射图清晰地表明了含Te催化剂的特性。
Claims (14)
1.一种负载型催化剂，其包括
a)作为活性组分的Mo化合物，
b)助催化剂，其中所述助催化剂包含TeO2和含氧的钾化合物，及
c)载体。
2.根据权利要求1的催化剂，其中所述组分的重量比为
TeO2/KMoO4/载体＝(1-20)/(1-50)/100或者
TeO2/MoO3/K2O/载体＝(1-20)/(1-50)/(1-50)/100。
3.根据权利要求2的催化剂，其中所述组分的重量比为
(1)TeO2/KMoO4/载体＝(3-12)/(15-30)/100或者
(2)TeO2/MoO3/K2O/载体＝(3-12)/(15-30)/(8-20)/100。
4.根据权利要求1的催化剂，其中所述载体选自SiO2、TiO2、Al2O3-SiO2、沸石或者它们的混合物。
5.根据权利要求1的催化剂，其中所述催化剂包含活性Mo-O-K中心。
6.一种制备根据权利要求1的催化剂的方法，其包括以下步骤：在多于一个步骤中用作为TeO2前体的Te化合物和作为K2O前体的含K化合物的水溶液以及用作为含Mo化合物的KMoO4溶液或者(NH4)6Mo7O24的水溶液浸渍无机载体；干燥经浸渍的载体并在高温下用H2或者合成气(CO+H2)处理所述经浸渍的载体。
7.根据权利要求6的方法，其包括以下步骤：
a1)用作为TeO2前体的含Te化合物的水溶液浸渍所述载体，在高温下干燥所述经浸渍的载体，制得中间产物(a)；
a2)用根据重量比(1)的KMoO4水溶液浸渍所述产物(a)，并在高温下干燥所制备的产物(b)；或者
b1)用作为TeO2前体的含Te化合物和作为K2O前体的含K化合物的水溶液浸渍载体，在高温下干燥所述经浸渍的载体，制得中间产物(c)；
b2)用根据重量比(2)的(NH4)6Mo7O24·4H2O水溶液浸渍所述产物(c)，并干燥所述浸渍的产物(d)，其中调节在第二个浸渍步骤a2)和b2)期间的pH值在8-10的范围内。
8.根据权利要求7的方法，其中通过添加适量的氨水或氨来实现所述pH值的调节。
9.根据权利要求7的方法，其中在用所述含Mo化合物浸渍期间添加至少一种螯合剂。
10.根据权利要求7和9之一的方法，其中以重量计所述螯合剂的添加量相对于载体为0.1-0.6/1。
11.根据权利要求7-10之一的方法，其中所述螯合剂选自柠檬酸、柠檬酸三铵、L-谷氨酸和酒石酸或者乙二胺四乙酸(EDTA)。
12.一种通过使碳氧化物、硫和/或硫化氢和氢气反应而在催化过程中制备甲硫醇的方法，其包括：
a)提供负载型催化剂，其包含作为活性组分的Mo化合物、助催化剂和载体，其中所述助催化剂包含TeO2和含氧的钾化合物；
b)在所述催化过程中使用所述催化剂。
13.权利要求12的方法，其中所述各组分的重量比为
TeO2/KMoO4/载体＝(3-12)/(15-30)/100或者
TeO2/MoO3/K2O/载体＝(3-12)/(15-30)/(8-20)/100。
14.权利要求12的方法，其中所述载体选自SiO2、TiO2、Al2O3、Al2O3-SiO2、沸石或者它们的混合物。
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| MX2009002454A MX2009002454A (es) | 2006-09-11 | 2007-05-25 | Catalizador que contiene molibdeno, metodo de preparacion y metodo para preparar metilmercaptano. |
| PCT/EP2007/055078 WO2008031637A1 (en) | 2006-09-11 | 2007-05-25 | Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan |
| JP2009527755A JP5550340B2 (ja) | 2006-09-11 | 2007-05-25 | Ｍｏ含有触媒、製造方法およびメチルメルカプタンの製造方法 |
| RU2009113256/04A RU2436626C2 (ru) | 2006-09-11 | 2007-05-25 | Молибденсодержащий катализатор, способ его получения и способ получения метилмеркаптана |
| EP07729507.9A EP2061592B1 (en) | 2006-09-11 | 2007-05-25 | Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan |
| US12/439,926 US8883670B2 (en) | 2006-09-11 | 2007-05-25 | Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan |
| CN200780033646.8A CN101511472B (zh) | 2006-09-11 | 2007-05-25 | 含Mo催化剂、其制备方法和甲硫醇的制备方法 |
| MYPI20090949A MY186831A (en) | 2006-09-11 | 2007-05-25 | Mo containing catalyst, a preparation method and a method for preparing methyl mercaptan |
| ES07729507.9T ES2591027T3 (es) | 2006-09-11 | 2007-05-25 | Un catalizador que contiene Mo, un método para su preparación y un método para la preparación de metil mercaptano |
| BRPI0716632-0A BRPI0716632A2 (pt) | 2006-09-11 | 2007-05-25 | catalisador contendo mo, método de preparação e método para preparar metil mercaptano |
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| CN200780033646.8A Expired - Fee Related CN101511472B (zh) | 2006-09-11 | 2007-05-25 | 含Mo催化剂、其制备方法和甲硫醇的制备方法 |
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| EP (1) | EP2061592B1 (zh) |
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| CN (2) | CN101143329A (zh) |
| BR (1) | BRPI0716632A2 (zh) |
| ES (1) | ES2591027T3 (zh) |
| MX (1) | MX2009002454A (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114308080A (zh) * | 2022-01-14 | 2022-04-12 | 中国科学院大学 | 以二氧化碳、硫化氢和氢气合成甲硫醇的催化剂及其制备方法和应用 |
| CN115228504A (zh) * | 2022-01-30 | 2022-10-25 | 昆明理工大学 | 一种负载型Mo催化剂及其应用 |
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| FR2938535B1 (fr) * | 2008-11-20 | 2012-08-17 | Arkema France | Procede de fabrication de methylmercaptopropionaldehyde et de methionine a partir de matieres renouvelables |
| CN102861612A (zh) * | 2012-09-27 | 2013-01-09 | 合肥工业大学 | 一种用于含硫合成气制备甲硫醇的改性催化剂及制备方法 |
| FR3003773B1 (fr) | 2013-03-29 | 2016-12-30 | Arkema France | Catalyseur pour la synthese de methyl mercaptan et procede de production de methyl mercaptan a partir de gaz de synthese et de sulfure d'hydrogene |
| FR3023288B1 (fr) | 2014-07-04 | 2016-07-15 | Arkema France | Procede de preparation de disulfure de dimethyle |
| FR3023287B1 (fr) | 2014-07-04 | 2016-07-22 | Arkema France | Procede de preparation de methylmercaptan |
| FR3041635B1 (fr) | 2015-09-30 | 2019-01-25 | Arkema France | Procede de production de mercaptans par hydrogenolyse enzymatique de disulfures |
| FR3041636B1 (fr) | 2015-09-30 | 2018-11-16 | Arkema France | Procede de production de mercaptans par hydrogenolyse enzymatique de disulfures a l'aide d'hydrogene |
| MX2018012649A (es) | 2016-05-31 | 2019-01-30 | Novus Int Inc | Proceso para producir metil mercaptano a partir de sulfuro de dimetilo. |
| FR3075791A1 (fr) * | 2017-12-22 | 2019-06-28 | Arkema France | Procede de preparation de methylmercaptan |
| EP3689451A1 (en) * | 2019-01-29 | 2020-08-05 | Evonik Operations GmbH | Catalyst for the synthesis of alkyl mercaptan and process for its preparation |
| FR3117883B1 (fr) | 2020-12-17 | 2024-02-23 | Arkema France | Procede de sechage du methylmercaptan par distillation azeotropique |
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2006
- 2006-09-11 CN CN200610151777.3A patent/CN101143329A/zh active Pending
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- 2007-05-25 MX MX2009002454A patent/MX2009002454A/es not_active Application Discontinuation
- 2007-05-25 WO PCT/EP2007/055078 patent/WO2008031637A1/en active Application Filing
- 2007-05-25 JP JP2009527755A patent/JP5550340B2/ja not_active Expired - Fee Related
- 2007-05-25 CN CN200780033646.8A patent/CN101511472B/zh not_active Expired - Fee Related
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- 2007-05-25 ES ES07729507.9T patent/ES2591027T3/es active Active
- 2007-05-25 BR BRPI0716632-0A patent/BRPI0716632A2/pt not_active Application Discontinuation
- 2007-05-25 MY MYPI20090949A patent/MY186831A/en unknown
- 2007-05-25 RU RU2009113256/04A patent/RU2436626C2/ru not_active IP Right Cessation
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114308080A (zh) * | 2022-01-14 | 2022-04-12 | 中国科学院大学 | 以二氧化碳、硫化氢和氢气合成甲硫醇的催化剂及其制备方法和应用 |
| CN114308080B (zh) * | 2022-01-14 | 2023-08-04 | 中国科学院大学 | 以二氧化碳、硫化氢和氢气合成甲硫醇的催化剂及其制备方法和应用 |
| CN115228504A (zh) * | 2022-01-30 | 2022-10-25 | 昆明理工大学 | 一种负载型Mo催化剂及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0716632A2 (pt) | 2013-01-01 |
| CN101511472A (zh) | 2009-08-19 |
| US20100094059A1 (en) | 2010-04-15 |
| EP2061592A1 (en) | 2009-05-27 |
| CN101511472B (zh) | 2013-03-27 |
| WO2008031637A1 (en) | 2008-03-20 |
| JP5550340B2 (ja) | 2014-07-16 |
| ES2591027T3 (es) | 2016-11-24 |
| MX2009002454A (es) | 2009-03-20 |
| US8883670B2 (en) | 2014-11-11 |
| JP2010502440A (ja) | 2010-01-28 |
| EP2061592B1 (en) | 2016-06-29 |
| RU2009113256A (ru) | 2010-10-20 |
| RU2436626C2 (ru) | 2011-12-20 |
| MY186831A (en) | 2021-08-24 |
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