CN114797903A - Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof - Google Patents
Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof Download PDFInfo
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- CN114797903A CN114797903A CN202110082561.0A CN202110082561A CN114797903A CN 114797903 A CN114797903 A CN 114797903A CN 202110082561 A CN202110082561 A CN 202110082561A CN 114797903 A CN114797903 A CN 114797903A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 58
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 44
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 150000001868 cobalt Chemical class 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 150000001298 alcohols Chemical class 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 238000000975 co-precipitation Methods 0.000 claims description 11
- 229940011182 cobalt acetate Drugs 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 30
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000000047 product Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 9
- 239000011654 magnesium acetate Substances 0.000 description 9
- 235000011285 magnesium acetate Nutrition 0.000 description 9
- 229940069446 magnesium acetate Drugs 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 5
- 229910052976 metal sulfide Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012360 testing method Methods 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C29/151—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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a catalyst for preparing low carbon alcohol from synthesis gas, a preparation method of the catalyst, and application of the catalyst in preparing low carbon alcohol from synthesis gas. The catalyst contains active components Co, Mo, K, S and an auxiliary agent M, wherein M is at least one element selected from Mg, Ca and La; based on the total amount of the catalyst, the content of Co is 5.5-17 wt%, the content of Mo is 33-47 wt%, the content of K is 4-9 wt%, the content of S is 30-50 wt%, the content of M is 0.05-0.9 wt%, wherein the molar ratio of M to Mo is 0.005-0.09: 1. the catalyst for preparing low carbon alcohol from synthesis gas is used in the reaction of preparing low carbon alcohol from synthesis gas, has high catalytic activity, and improves the selectivity of total alcohol in the product and the space-time yield of the total alcohol.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for preparing low carbon alcohol from synthesis gas, a preparation method of the catalyst and application of the catalyst in preparing low carbon alcohol from synthesis gas.
Background
Energy is the basis of human survival and civilized evolution, and China is a country lack of oil, less gas and more coal, and has important strategic significance in developing the modern coal chemical industry and developing a clean and efficient conversion technology of coal and carbon. And the synthesis gas (CO + H) is produced by coal gasification 2 ) The synthesis of low-carbon alcohol by the catalytic conversion of the synthesis gas can not only relieve the current situation of petroleum resource shortage in China, but also be one of the most practical and feasible ways for realizing the efficient and clean conversion of coal resources. The low-carbon mixed alcohol can be used as a gasoline additive and a fuel, and can be used as a high-value-added chemical after separation.
Due to the complexity of the reaction process and mechanism for preparing the lower alcohol by the synthesis gas, the target product has low selectivity, and the selectivity of the byproduct methanol and hydrocarbon is high. In the reaction process, CO is required to be subjected to dissociative adsorption so as to realize carbon chain growth, CO is required to be subjected to non-dissociative adsorption and inserted when the carbon chain is grown to a certain length so as to generate alcohol, and the two reactions are coordinated and matched so as to obtain more target products C 2 OH-C 6 OH, if the insertion capacity of CO is weaker, more hydrocarbons can be obtained after the carbon chain is increased, and if the carbon chain is weaker, CO can be hydrogenated to generate more methanol, so that the target product C is generated 2 + Alcohol selectivity is low, and therefore, the design and development of a catalyst with high selectivity and high activity and excellent stability are key factors for the breakthrough of the technology.
MoS 2 The base catalyst is considered to be one of the most promising catalyst systems for synthesizing low-carbon alcohol due to the advantages of unique sulfur resistance, higher activity, higher alcohol selectivity, long service life and the like, but the current MoS 2 The base catalyst still has the problems of low catalytic activity, low total alcohol selectivity, low total alcohol space-time yield and the like.
CN103459020A discloses a catalyst for the conversion of synthesis gas to alcohols, which comprises a combination of nickel, molybdenum, at least one metal selected from palladium, ruthenium, chromium, gold, zirconium and aluminum, and at least one of alkali metals or alkaline earth metals as promoters, although it can increase C 2 -C 4 Alcohol selectivity, but lower conversion, and lower overall alcohol selectivity.
US4882360 discloses a catalyst for preparing low carbon alcohol from synthesis gas and a preparation method thereof. The catalyst comprises at least one of molybdenum and tungsten as a first component, at least one of Fe, Co and Ni as a second component, an alkali metal or alkaline earth metal assistant as a third component, and other components and carriers as a fourth component, and the catalyst has the reaction temperature of about 300 ℃, the reaction pressure of 10MPa and the space velocity of 1000-2000 h- -1 When the method is used, the total alcohol selectivity in the product is more than 70 percent, and CH 3 OH/C 2 + Alcohol (wt%)<0.5, but the space velocity used is low, resulting in a low space-time yield of the alcohol product.
Disclosure of Invention
The invention aims to overcome the MoS existing in the prior art 2 The base catalyst is used for preparing low-carbon alcohol from synthesis gas, has low total alcohol selectivity and low total alcohol space-time yield, and provides the catalyst for preparing the low-carbon alcohol from the synthesis gas as well as a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a catalyst for producing lower alcohols from synthesis gas, the catalyst comprising active components Co, Mo, K, S and an auxiliary agent M, wherein M is at least one element selected from Mg, Ca and La;
based on the total amount of the catalyst, the content of Co is 5.5-17 wt%, the content of Mo is 33-47 wt%, the content of K is 4-9 wt%, the content of S is 30-50 wt%, the content of M is 0.05-0.9 wt%, wherein the molar ratio of M to Mo is 0.005-0.09: 1.
the second aspect of the invention provides a preparation method of a catalyst for preparing low carbon alcohol from synthesis gas, which comprises the following steps:
(1) preparing an ammonium thiomolybdate solution and a mixed solution containing cobalt salt and M salt;
(2) carrying out coprecipitation reaction on the ammonium thiomolybdate solution and the mixed solution in a base solution;
(3) carrying out solid-liquid separation on a product obtained by the coprecipitation reaction, and then washing, drying and roasting the obtained solid to obtain a precursor;
wherein, the drying and the roasting are carried out under the protection of inert gas;
(4) mixing the precursor with potassium carbonate, grinding and tabletting to obtain the catalyst;
wherein M is at least one element selected from Mg, Ca and La; the use amounts of the ammonium thiomolybdate, the cobalt salt, the M salt and the potassium carbonate are used, so that in the obtained catalyst, the content of Co is 5.5-17 wt%, the content of Mo is 33-47 wt%, the content of K is 4-9 wt%, the content of S is 30-50 wt%, and the content of M is 0.05-0.9 wt%; the dosage of the ammonium thiomolybdate and the M salt satisfies the following requirements: the molar ratio of M to Mo is 0.005-0.09: 1.
the third aspect of the invention provides a catalyst for preparing low carbon alcohol from the synthesis gas prepared by the preparation method.
The fourth aspect of the invention provides an application of the catalyst for preparing low carbon alcohol from synthesis gas in preparing low carbon alcohol from synthesis gas.
Through the technical scheme, the catalyst for preparing the low-carbon alcohol from the synthesis gas is used in the reaction of preparing the low-carbon alcohol from the synthesis gas, has high catalytic activity, and improves the selectivity of the total alcohol in the product and the space-time yield of the total alcohol.
Drawings
FIG. 1 is an X-ray diffraction analysis (XRD) pattern of the catalysts prepared in examples 1-3 and comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a catalyst for preparing low carbon alcohol from synthesis gas, which comprises active components of Co, Mo, K and S and an auxiliary agent M, wherein M is at least one element selected from Mg, Ca and La;
based on the total amount of the catalyst, the content of Co is 5.5-17 wt%, the content of Mo is 33-47 wt%, the content of K is 4-9 wt%, the content of S is 30-50 wt%, the content of M is 0.05-0.9 wt%, wherein the molar ratio of M to Mo is 0.005-0.09: 1.
in some embodiments of the present invention, the foregoing catalyst composition can achieve the object of the present invention, and in order to further improve the activity of the catalyst, and further improve the selectivity of the total alcohol and the space-time yield of the total alcohol in the product, it is preferable that the content of Co is 6.5 to 16 wt%, the content of Mo is 35 to 45 wt%, the content of K is 4.5 to 7 wt%, the content of S is 35 to 45 wt%, and the content of M is 0.08 to 0.6 wt%, based on the total amount of the catalyst.
In some embodiments of the invention, in the catalyst for preparing low carbon alcohol by synthesis gas, Co, Mo and the auxiliary agent M exist in the form of sulfide, and K is K 2 S 3 O 6 Exist in the form of (1). Sulfides of Co and Mo exist in various forms, including complex metal sulfides (Co-MoS) 2 ) And independent metal sulfides (MoS) 2 、CoS 2 And Co 9 S 8 ). In which the metal sulfide phase (CoS) is present in a separate metal sulfide phase 2 、Co 9 S 8 、MoS 2 ) On the surface of the catalyst, CO dissociation and adsorption and H generation 2 Dissociative adsorption and CH x The formation reaction of the species, under the reaction evaluation conditions, over a period of about 100-200h, CoS 2 Gradually change into oppositeShould be more favorable to Co 9 S 8 (ii) a In the potassium promoted composite metal sulfide phase (Co-MoS) 2 ) Non-dissociative adsorption of CO, carbon chain growth and alcohol formation reaction.
In some embodiments of the invention, the syngas to lower alcohol catalyst of the invention is phase analyzed using an X-ray diffractometer (XRD) model D/max-2600/pc from Rigaku corporation. In an X-ray diffraction analysis (XRD) diagram, the characteristic peaks and K of the catalyst for preparing the low-carbon alcohol from the synthesis gas appear at 2 theta of 19.0 degrees, 23.9 degrees, 24.7 degrees, 24.9 degrees, 26.5 degrees, 28.1 degrees and 31.1 degrees 2 S 3 O 6 The standard card PDF-75-1479 is consistent, which shows that K is formed in the catalyst for preparing the low-carbon alcohol from the synthesis gas prepared by the invention 2 S 3 O 6 Structure; k does not appear in the catalyst for preparing the low-carbon alcohol from the synthesis gas prepared without adding the auxiliary agent M 2 S 3 O 6 Characteristic peak of (1), no formation of K 2 S 3 O 6 Structure, described in MoS 2 The addition agent M is introduced in the preparation process of the base catalyst, which can promote K on the catalyst 2 S 3 O 6 Formation of the Structure, K 2 S 3 O 6 The structure can stabilize the intermediate product of the reaction and change the electronic structure of the catalyst, so that the activation of CO becomes easy, the hydrogenation activity of alkyl species is reduced, and the addition of the auxiliary agent M is also favorable for reducing Co-MoS 2 The size of the active centers increases the number of active centers per unit weight of catalyst, thereby increasing the catalytic activity of the catalyst as well as the selectivity of the total alcohol in the product and the space time yield of the alcohol.
In some embodiments of the present invention, if the molar ratio of M to Mo is greater than 0.09, the improvement of the total alcohol selectivity and the total alcohol space-time yield is not achieved, but the activity of the catalyst is reduced; if the molar ratio of the promoter M to Mo is less than 0.005, the content of M in the catalyst will be too low to contribute to the improvement in the selectivity for the total alcohol and the space-time yield of the total alcohol, and therefore, the molar ratio of the promoter M to Mo is controlled only to be 0.005 to 0.09: 1, to achieve an increase in the selectivity for the total alcohol and the space-time yield of the total alcohol. In order to further increase the selectivity and the space-time yield of the total alcohol, the molar ratio of the auxiliary M to Mo is preferably from 0.008 to 0.06: 1, more preferably 0.01 to 0.05: 1.
in some embodiments of the invention, to ensure two active centers (Co-MoS) 2 And MoS 2 、CoS 2 ) Preferably, the molar ratio of Co to Mo is 0.2-0.8: 1, more preferably 0.3 to 0.7: 1.
in some embodiments of the invention, in order to promote the formation of sulfides of Co, Mo active metals, increase the catalytic activity of the catalyst and the selectivity of the total alcohol in the product, it is preferred that the molar ratio of S to Mo is 2 to 4: 1, more preferably 2.5 to 3.5: 1.
the second aspect of the invention provides a preparation method of a catalyst for preparing low carbon alcohol from synthesis gas, which comprises the following steps:
(1) preparing an ammonium thiomolybdate solution and a mixed solution containing cobalt salt and M salt;
(2) carrying out coprecipitation reaction on the ammonium thiomolybdate solution and the mixed solution in a base solution;
(3) carrying out solid-liquid separation on a product obtained by the coprecipitation reaction, and then washing, drying and roasting the obtained solid to obtain a precursor;
wherein, the drying and the roasting are carried out under the protection of inert gas;
(4) mixing the precursor with potassium carbonate, grinding and tabletting to obtain the catalyst;
wherein M is at least one element selected from Mg, Ca and La; the use amounts of the ammonium thiomolybdate, the cobalt salt, the M salt and the potassium carbonate are such that in the obtained catalyst, the content of Co is 5.5-17 wt%, the content of Mo is 33-47 wt%, the content of K is 4-9 wt%, the content of S is 30-50 wt%, and the content of M is 0.05-0.9 wt%; the dosage of the ammonium thiomolybdate and the M salt satisfies the following requirements: the molar ratio of M to Mo is 0.005-0.09: 1.
in some embodiments of the present invention, the amounts of the ammonium thiomolybdate, the cobalt salt, the M salt and the potassium carbonate may be selected according to the contents and molar ratios of the foregoing components, and will not be described herein again.
In some embodiments of the present invention, the cobalt salt may be a cobalt salt that is commonly used in the art and is soluble in water, selected from water-soluble cobalt salts, and may be a commercially available product, for example, the cobalt salt may be selected from at least one of cobalt acetate, cobalt nitrate, and cobalt sulfate.
In some embodiments of the present invention, the M salt may be a water-soluble M salt commonly used in the art, selected from water-soluble salts containing an M element, and may be a commercially available product, for example, the M salt may be selected from at least one of acetate, nitrate, and sulfate containing an M element.
In some embodiments of the present invention, in step (1), the ammonium thiomolybdate solution may be prepared according to a conventional method, for example, the step of preparing the ammonium thiomolybdate solution may specifically be: reacting ammonium molybdate with ammonium sulfide solution at 50-70 deg.C for 0.2-4 h.
In some embodiments of the present invention, in the step (2), the catalyst precursor with a predetermined ratio can be obtained by using the base solution, the precipitation reaction can be maintained within a range of pH 4 to 6, and in addition, the mixed solution of the ammonium thiomolybdate solution, the cobalt salt and the M salt can be ensured to be uniformly precipitated at a set temperature when being dropped into the precipitation flask. In order to further improve the selectivity of the total alcohol in the product and the space-time yield of the total alcohol, the base solution is preferably an acetic acid solution with a mass concentration of 20-40 wt%.
In some embodiments of the present invention, preferably, in step (2), the conditions of the coprecipitation reaction include: the aging temperature is 50-60 ℃, and the aging time is 0.5-12 h.
In some embodiments of the present invention, in step (3), the solid-liquid separation may be performed by a conventional separation method to separate the solid therein. For example, solid-liquid separation can be achieved by filtration.
In some embodiments of the present invention, the solid obtained by solid-liquid separation may be washed with deionized water, and then dried and calcined under the protection of an inert gas to obtain the precursor. In order to prevent the catalyst from being oxidized violently and from being changed in structure, the drying and the calcination are carried out in an inert atmosphere. The inert atmosphere may be an atmosphere formed by various gases that do not react with the reactants and products, for example, an atmosphere formed by a gas such as nitrogen and/or helium and/or argon.
In some embodiments of the present invention, the drying conditions are not particularly limited as long as the solvent attached to the product can be removed, and for example, the drying conditions generally include: the drying temperature can be 40-120 ℃, and preferably 70-110 ℃; the drying time may be from 2 to 25 hours, preferably from 4 to 20 hours.
In some embodiments of the invention, the conditions for the calcination are not particularly limited, provided that the CoMoS can be made 4 Decomposition into Co-MoS 2 The excess S may be distilled off as elemental S, for example, the conditions for the calcination generally include: the roasting temperature can be 300-500 ℃, and the roasting time can be 0.3-6 h. To avoid Co-MoS 2 The activity of the active center particles is reduced, preferably, the roasting temperature is 350-400 ℃, and the roasting time is 0.5-4 h.
The third aspect of the invention provides a catalyst for preparing low-carbon alcohol from synthesis gas, which is prepared by the preparation method. The catalyst contains active components of Co, Mo, K, S and an auxiliary agent M, wherein M is at least one element selected from Mg, Ca and La;
based on the total amount of the catalyst, the content of Co is 5.5-17 wt%, the content of Mo is 33-47 wt%, the content of K is 4-9 wt%, the content of S is 30-50 wt%, the content of M is 0.05-0.9 wt%, wherein the molar ratio of M to Mo is 0.005-0.09: 1.
in some embodiments of the present invention, it is preferable that the content of Co is 6.5 to 16 wt%, the content of Mo is 35 to 45 wt%, the content of K is 4.5 to 7 wt%, the content of S is 35 to 45 wt%, and the content of M is 0.08 to 0.6 wt%, based on the total amount of the catalyst.
In some embodiments of the invention, preferably, the molar ratio of M to Mo is from 0.008 to 0.06: 1, more preferably 0.01 to 0.05: 1.
in some embodiments of the invention, the molar ratio of Co to Mo is preferably from 0.2 to 0.8: 1, more preferably 0.3 to 0.7: 1.
in some embodiments of the invention, preferably, the molar ratio of S to Mo is 2 to 4: 1, more preferably 2.5 to 3.5: 1.
in some embodiments of the invention, it is preferred that Co, Mo and M are present as sulfides and K is K 2 S 3 O 6 Exist in the form of (1).
The fourth aspect of the invention provides an application of the catalyst for preparing low carbon alcohol from synthesis gas in preparing low carbon alcohol from synthesis gas.
In some embodiments of the present invention, the method for producing lower alcohols from synthesis gas using the catalyst of the present invention may comprise: the catalyst is molded, and is loaded into a fixed bed reactor, the air in the reactor is replaced by inert gas, then the reactor is heated, and when the temperature and the pressure are raised to the temperature and the pressure required by the reaction, the reaction gas is introduced into the reactor for reaction, so that the low carbon alcohol is prepared. Wherein the reaction conditions include: the pressure is 7-10MPa, the temperature is 320-350 ℃, and the volume space velocity is 2000-4000 mL-g -1 ·h -1 Volume ratio of reaction gas H 2 0.8-1.2,: 1. the synthesis gas-to-lower alcohol may be carried out in a fixed bed or a fluidized bed, and preferably in a fixed bed.
In the present invention, the pressure is a gauge pressure.
The present invention will be described in detail by way of examples, but it should be understood that the scope of the present invention is not limited by the examples.
In the following examples and comparative examples, the raw materials used were commercially available.
Analyzing and measuring the molar (or weight) composition of the catalyst component for preparing the low-carbon alcohol from the prepared synthesis gas by using an X-ray fluorescence spectrometer (XRF) with the model ZSX Primus II purchased from Rigaku company, wherein an Updide Radiation X-ray generator and a 4kW Rh target are adopted, the category range of a test element is F-U, the diameter of a test area is 30mm, and the test method is a full-element semi-quantitative method;
the obtained catalyst for preparing lower alcohols from synthesis gas was subjected to X-ray diffraction analysis by means of an X-ray diffractometer (XRD) of model D/max-2600/pc, available from Rigaku corporation;
the microscopic morphology of the prepared catalyst for preparing the low carbon alcohol from the synthesis gas is observed and determined by a Scanning Electron Microscope (SEM) with the model number of Nova Nano SEM 450, which is purchased from FEI company, the adopted accelerating voltage is 20kV to 30kV, the resolution limit is about 1.2nm, and the magnification is 25K times to 200K times.
The catalytic performance of the catalyst for producing lower alcohols from the synthesis gas was evaluated by a four-channel reactor available from Altamira corporation.
The reaction conditions include: the pressure is 8MPa, the temperature is 345 ℃, and the volume space velocity is 3000mL g -1 ·h -1 Volume ratio of reaction gas H 2 /CO＝1/1。
The evaluation process comprises the following steps: tabletting and screening the catalyst to obtain 20-40 mesh particles, fixing the catalyst in a constant-temperature section of a reactor by quartz sand, wherein the loading amount of the catalyst is 1.5 g, carrying out leak detection on the device, replacing air in the reactor by inert gas He gas for 3-5 times, then heating the reactor, and after the temperature and the pressure are increased to the temperature and the pressure required by the reaction (345 ℃, 8MPa), carrying out 37.5mL (standard condition) of H 2 And 37.5mL of CO and 3.26mL of N 2 (internal standard gas) is introduced into the reactor to carry out the reaction of preparing the low carbon alcohol by the synthesis gas.
After gas and tail gas after reaction enter a cold trap for gas-liquid separation, carrying out on-line analysis on the tail gas by adopting Agilent 7890 chromatography, wherein H 2 、CO、CH 4 、N 2 Performing TDX-01 carbon molecular sieve chromatographic column analysis, taking He as carrier gas, and detecting by TCD; c 1 -C 6 Modification of Al by hydrocarbons (alkenes, alkanes) 2 O 3 Performing packed chromatographic column analysis, using Ar as a carrier, and adopting FID for detection. The remaining product was analyzed by off-line chromatography Shimadzu GC-2010 and the liquid product by two PORpak Q column analysis using TCD (water and methanol) and FID (C), respectively 1 -C 5 Oxygenate) detector.
CO conversion, Total alcohol Selectivity and C 2 + The alcohol selectivity is used as an evaluation index of the performance of the catalyst for preparing the low-carbon alcohol from the synthesis gas. CO conversion (χ CO), product selectivity (x CO)
Carbon based selectivity based on moles of carbon) and total alcohol selectivity (S) ROH Based on the carbon-based selectivity in terms of moles of carbon) are calculated from the following equations, respectively:
wherein chi CO represents the CO conversion rate;
represents the product selectivity; s ROH Represents the total alcohol selectivity; f represents the number of moles of the substance, and i represents the number of carbon atoms of the substance;
represents the number of moles of CO at the inlet,
indicating the moles of outlet CO.
Example 1
(1) Heating 100g of 26.5 wt% ammonium molybdate solution to 60 ℃, adding 206.5g of 20 wt% ammonium sulfide solution, and reacting at 60 ℃ for 1h to obtain ammonium thiomolybdate solution; dissolving 13.2g of cobalt acetate and 0.42g of magnesium acetate in 280mL of deionized water to prepare a mixed solution;
(2) dropwise adding an ammonium thiomolybdate solution and the mixed solution into a base solution (the base solution is a 30 wt% acetic acid solution) at the same speed at the temperature of 55 ℃ for coprecipitation reaction, and aging at the temperature of 55 ℃ for 1h to obtain a precipitate;
(3) filtering and washing the precipitate, drying at 90 ℃ for 12h under the protection of nitrogen atmosphere, and then roasting at 400 ℃ for 1h under the protection of nitrogen atmosphere to obtain a precursor;
(4) 9g of precursor was mixed with 1g of K 2 CO 3 The catalyst was mixed, milled and tableted to give the catalyst designated S1.
Wherein the molar ratio of Mg to Mo is 0.011: 1; the molar ratio of Co to Mo is 0.35: 1; the molar ratio of S to Mo is 2.7: 1, the content of Mo was 42.43 wt%, the content of Co was 9.12 wt%, the content of Mg was 0.12 wt%, the content of K was 5.66 wt%, and the content of S was 38.33 wt%.
Example 2
(1) Heating 100g of 26.5 wt% ammonium molybdate solution to 60 ℃, adding 340.5g of 20 wt% ammonium sulfide solution, and reacting at 65 ℃ for 1h to obtain ammonium thiomolybdate solution; dissolving 30.5g of cobalt nitrate and 0.94g of lanthanum acetate in 320mL of deionized water to prepare a mixed solution;
(2) dropwise adding an ammonium thiomolybdate solution and the mixed solution into a base solution (the base solution is a 30 wt% acetic acid solution) at the same speed at the temperature of 55 ℃ for coprecipitation reaction, and aging at the temperature of 55 ℃ for 2 hours to obtain a precipitate;
(3) filtering and washing the precipitate, drying at 90 ℃ for 12h under the protection of nitrogen atmosphere, and then roasting at 390 ℃ for 1.5h under the protection of nitrogen atmosphere to obtain a precursor;
(4) 9g of precursor was mixed with 1g of K 2 CO 3 The catalyst was mixed, milled and tableted to give the catalyst designated S2.
Wherein the molar ratio of La to Mo is 0.01: 1; the molar ratio of Co to Mo is 0.7: 1; the molar ratio of S to Mo is 3.4: 1, Mo content 34.86 wt%, Co content 14.99 wt%, La content 0.50 wt%, K content 5.66 wt%, and S content 39.65 wt%.
Example 3
(1) Heating 100g of 26.5 wt% ammonium molybdate solution to 55 ℃, adding 206.5g of 20 wt% ammonium sulfide solution, and reacting at 55 ℃ for 1h to obtain ammonium thiomolybdate solution; dissolving 18.9g of cobalt acetate and 0.87g of calcium sulfate in 280mL of deionized water to prepare a mixed solution;
(2) dropwise adding an ammonium thiomolybdate solution and the mixed solution into a base solution (the base solution is a 30 wt% acetic acid solution) at the same speed at the temperature of 55 ℃ for coprecipitation reaction, and aging at the temperature of 55 ℃ for 1h to obtain a precipitate;
(3) filtering and washing the precipitate, drying the precipitate for 8 hours at 100 ℃ under the protection of nitrogen atmosphere, and then roasting the precipitate for 4 hours at 360 ℃ under the protection of nitrogen atmosphere to obtain a precursor;
(4) 8.9g of precursor was mixed with 1.1g of K 2 CO 3 The catalyst was mixed, milled and tableted to give the catalyst designated S3.
Wherein the molar ratio of Ca to Mo is 0.03: 1; the molar ratio of Co to Mo is 0.5: 1; the molar ratio of S to Mo is 3: 1, the content of Mo is 38.32 wt%, the content of Co is 11.75 wt%, the content of Ca is 0.48 wt%, the content of K is 6.22 wt%, and the content of S is 38.45 wt%.
Example 4
The procedure is as in example 1, except that in step (1) 2.3g of magnesium acetate are added and the catalyst obtained is designated S4.
Wherein the molar ratio of Mg to Mo is 0.06: 1.
example 5
The procedure is as in example 1, except that in step (1) 3.4g of magnesium acetate are added and the catalyst obtained is designated S5.
Wherein the molar ratio of Mg to Mo is 0.09: 1.
example 6
The procedure of example 1 was followed except that in step (1), 30.2g of cobalt acetate was added and the resulting catalyst was designated S6.
Wherein the molar ratio of Co to Mo is 0.8: 1.
example 7
The procedure is as in example 1, except that, in step (1), 5.7g of cobalt acetate are added and the catalyst obtained is reported as S7.
Wherein the molar ratio of Co to Mo is 0.15: 1.
example 8
The procedure is as in example 1, except that in step (1), 175.9g of ammonium sulfide solution are added and the catalyst obtained is reported as S8.
Wherein the molar ratio of S to Mo is 2.3: 1.
example 9
The procedure is as in example 1, except that in step (1), 321.2g of ammonium sulfide solution are added and the catalyst is reported as S9.
Wherein the molar ratio of S to Mo is 4.2: 1.
example 10
The procedure is as in example 1, except that in step (1) 3.5g of magnesium acetate are added and the catalyst obtained is reported as S10.
Wherein the Mg content is 0.9 wt%.
Example 11
The procedure is as in example 1, except that in step (4), 1.70g of potassium carbonate are added and the catalyst obtained is reported as S11.
Wherein the content of K is 9 wt%.
Example 12
The procedure is as in example 1 except that in step (1), 13.2g of cobalt acetate, 0.22g of magnesium acetate, and 0.12g of lanthanum acetate are dissolved in 280mL of deionized water to prepare a mixed solution, and the resulting catalyst is designated S12.
Wherein, the content of Mg is 0.06wt percent, and the content of La is 0.06wt percent.
Example 13
The procedure is as in example 1 except that in step (1), 13.2g of cobalt acetate, 0.13g of calcium acetate, and 0.12g of lanthanum acetate are dissolved in 280mL of deionized water to prepare a mixed solution, and the resulting catalyst is designated S13.
Wherein, the content of Ca is 0.06wt percent, and the content of La is 0.06wt percent.
Example 14
The procedure of example 1 was followed except that in step (1), 13.2g of cobalt acetate, 0.22g of magnesium acetate, 0.13g of calcium acetate, and 0.12g of lanthanum acetate were dissolved in 280mL of deionized water to prepare a mixed solution, and the resulting catalyst was designated S14.
Wherein, the content of Mg is 0.06 wt%, the content of Ca is 0.06 wt%, and the content of La is 0.06 wt%.
Comparative example 1
The procedure is as in example 1, except that the mixed solution of step (1) contains no magnesium acetate and the catalyst obtained is designated D1.
Comparative example 2
The procedure is as in example 1, except that in step (1) 3.7g of magnesium acetate are added and the catalyst obtained is designated D2. Wherein the Mg content is 1 wt%.
Comparative example 3
The procedure is as in example 2, except that, in step (1), 2.3g of lanthanum acetate are added and the catalyst obtained is reported as D3. Wherein the La content was 1.2 wt%.
Comparative example 4
The procedure is as in example 1, except that in step (1) 0.11g of magnesium acetate are added and the catalyst obtained is designated D4. Wherein the molar ratio of Mg to Mo is 0.003: 1.
the catalysts for producing lower alcohols from synthesis gas obtained in examples 1 to 3 and comparative example 1 were subjected to X-ray diffraction analysis (XRD), and the results are shown in FIG. 1.
In FIG. 1, S1 is the X-ray diffraction curve of the lower alcohol catalyst prepared from synthesis gas obtained in example 1, S2 is the X-ray diffraction curve of the lower alcohol catalyst prepared from synthesis gas obtained in example 2, S3 is the X-ray diffraction curve of the lower alcohol catalyst prepared from synthesis gas obtained in example 3, and D1 is the X-ray diffraction curve of the lower alcohol catalyst prepared from synthesis gas obtained in comparative example 1. As can be seen from FIG. 1, the implementationThe characteristic peaks 2 θ of the low-carbon alcohol catalysts prepared in examples 1 to 3 (corresponding to curves S1, S2 and S3 in the figures) were 19.0 °, 23.9 °, 24.7 °, 24.9 °, 26.5 °, 28.1 °, 31.1 ° and K 2 S 3 O 6 The standard card PDF-75-1479 is consistent, which shows that K is formed in the catalyst for preparing the low-carbon alcohol from the synthesis gas prepared by the invention 2 S 3 O 6 Structure; while K does not appear in the catalyst for preparing lower alcohol from synthesis gas (corresponding to curve D1 in the figure) prepared in comparative example 1 2 S 3 O 6 Characteristic peak of (1), no formation of K 2 S 3 O 6 Structure shows that the addition of the auxiliary agent M can promote K on the catalyst 2 S 3 O 6 Formation of the Structure, K 2 S 3 O 6 The structure can stabilize the intermediates of the reaction and change the electronic structure of the catalyst, so that the activation of CO becomes easy and the hydrogenation activity of alkyl species is reduced, thereby improving the catalytic activity of the catalyst, the selectivity of total alcohol in the product and the space-time yield of the total alcohol. The remaining examples are similar and the results are not shown.
The catalysts for producing lower alcohols from synthesis gas obtained in examples 1 to 14 and comparative examples 1 to 4 were evaluated for their catalytic performance, and the results are shown in Table 1.
TABLE 1
It can be seen from the results in Table 1 that the catalysts containing the auxiliary M are superior to the catalysts not containing the auxiliary M in catalytic activity, selectivity of the total alcohols in the product and space-time yield of the total alcohols.
In particular, as can be seen from the results of the evaluations of comparative examples 1 to 5, controlling the molar ratio of the promoter M to Mo within the preferred range of the present invention, the activity, the total alcohol selectivity and the total alcohol space-time yield of the prepared catalyst were further improved;
comparing the evaluation results of example 1 and examples 6 to 7, it can be seen that controlling the molar ratio of Co to Mo within the preferred range of the present invention can further improve the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol;
comparing the evaluation results of example 1 and examples 8 to 9, it can be seen that controlling the molar ratio of S to Mo within the preferred range of the present invention can further improve the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol;
comparing the evaluation results of example 1 and example 10, it can be seen that the content of the auxiliary M in the preferred range of the present invention can further improve the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol;
comparing the evaluation results of example 1 and example 11, it can be seen that the content of K within the preferred range of the present invention can further improve the catalytic activity of the catalyst, the selectivity of total alcohols in the product and the space-time yield of total alcohols;
comparing the evaluation results of examples 1 to 3 and examples 12 to 14, it can be seen that when the assistant M is two or three of Mg, Ca and La, the activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol can be further improved.
Comparing the evaluation results of example 1 and comparative example 1, it can be seen that the catalyst containing no auxiliary M fails to improve the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol.
Comparing the results of the evaluations of example 1 and comparative examples 2 to 3, it can be seen that the content of the auxiliary M in the catalyst is within the range defined in the present invention, so that the catalytic activity of the catalyst can be improved, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol can be increased, and that the content of the auxiliary M is too high, so that the catalytic performance cannot be improved, but the catalytic activity of the catalyst, the selectivity of the total alcohol in the product and the space-time yield of the total alcohol can be reduced.
Comparing the evaluation results of example 1 and comparative example 4, it can be seen that the catalyst in which the molar ratio of the assistant M to Mo is not within the range defined in the present invention has no significant effect on the improvement of the catalytic activity of the catalyst, the selectivity of the total alcohol in the product, and the space-time yield of the total alcohol.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The catalyst for preparing the low-carbon alcohol from the synthesis gas is characterized by comprising active components of Co, Mo, K and S and an auxiliary agent M, wherein M is at least one element selected from Mg, Ca and La;
based on the total amount of the catalyst, the content of Co is 5.5-17 wt%, the content of Mo is 33-47 wt%, the content of K is 4-9 wt%, the content of S is 30-50 wt%, the content of M is 0.05-0.9 wt%, wherein the molar ratio of M to Mo is 0.005-0.09: 1.
2. the catalyst according to claim 1, wherein the content of Co is 6.5 to 16 wt%, the content of Mo is 35 to 45 wt%, the content of K is 4.5 to 7 wt%, the content of S is 35 to 45 wt%, and the content of M is 0.08 to 0.6 wt%, based on the total amount of the catalyst;
preferably, the molar ratio of M to Mo is from 0.008 to 0.06: 1, more preferably 0.01 to 0.05: 1;
preferably, the molar ratio of Co to Mo is 0.2-0.8: 1, more preferably 0.3 to 0.7: 1;
preferably, the molar ratio of S to Mo is 2-4: 1, more preferably 2.5 to 3.5: 1;
preferably, Co, Mo and M are present in sulfide form and K is K 2 S 3 O 6 Exist in the form of (1).
3. A preparation method of a catalyst for preparing low-carbon alcohol from synthesis gas is characterized by comprising the following steps:
(1) preparing an ammonium thiomolybdate solution and a mixed solution containing cobalt salt and M salt;
(2) carrying out coprecipitation reaction on the ammonium thiomolybdate solution and the mixed solution in a base solution;
(3) carrying out solid-liquid separation on a product obtained by the coprecipitation reaction, and then washing, drying and roasting the obtained solid to obtain a precursor;
wherein, the drying and the roasting are carried out under the protection of inert gas;
(4) mixing the precursor with potassium carbonate, grinding and tabletting to obtain the catalyst;
wherein M is at least one element selected from Mg, Ca and La; the use amounts of the ammonium thiomolybdate, the cobalt salt, the M salt and the potassium carbonate are such that in the obtained catalyst, the content of Co is 5.5-17 wt%, the content of Mo is 33-47 wt%, the content of K is 4-9 wt%, the content of S is 30-50 wt%, and the content of M is 0.05-0.9 wt%; the dosage of the ammonium thiomolybdate and the M salt satisfies the following requirements: the molar ratio of M to Mo is 0.005-0.09: 1.
4. the preparation method according to claim 3, wherein the ammonium thiomolybdate and the M salt are used in amounts satisfying: the molar ratio of M to Mo is 0.008-0.06: 1, preferably 0.01 to 0.05: 1;
preferably, the ammonium thiomolybdate and the cobalt salt are used in amounts such that: the molar ratio of Co to Mo is 0.2-0.8: 1, more preferably 0.3 to 0.7: 1;
preferably, the ammonium thiomolybdate is used in an amount such that the molar ratio of S to Mo in the obtained catalyst is 2-4: 1, more preferably 2.5 to 3.5: 1.
5. the preparation method according to claim 3 or 4, wherein the ammonium thiomolybdate, the cobalt salt, the M salt and the potassium carbonate are used in amounts such that the catalyst is obtained in which the content of Co is 6.5 to 16 wt%, the content of Mo is 35 to 45 wt%, the content of K is 4.5 to 7 wt%, the content of S is 35 to 45 wt%, and the content of M is 0.08 to 0.6 wt%.
6. The production method according to any one of claims 3 to 5, wherein in the step (1), the step of preparing the ammonium thiomolybdate solution is specifically: reacting ammonium molybdate with an ammonium sulfide solution at the temperature of 50-70 ℃ for 0.2-4 h;
preferably, in the step (2), the base solution is an acetic acid solution with a mass concentration of 20-40 wt%.
7. The production method according to any one of claims 3 to 6, wherein the cobalt salt is selected from water-soluble cobalt salts, preferably at least one of cobalt acetate, cobalt nitrate, and cobalt sulfate;
the M salt is selected from water-soluble salts containing M element, preferably at least one of acetate, nitrate and sulfate containing M element.
8. The production method according to any one of claims 3 to 7, wherein the conditions of the coprecipitation reaction include: the aging temperature is 50-60 ℃, and the aging time is 0.5-12 h;
preferably, the drying conditions include: the temperature is 40-120 ℃, and the preferable temperature is 70-110 ℃; the time is 2 to 25 hours, preferably 4 to 20 hours;
preferably, the conditions of the calcination include: the temperature is 300-500 ℃, preferably 350-400 ℃; the time is 0.3-6h, preferably 0.5-4 h.
9. A catalyst for preparing lower alcohol from synthesis gas prepared by the preparation method of any one of claims 3-8.
10. Use of the catalyst for producing lower alcohols from synthesis gas according to any of claims 1 to 2 and 9 in the production of lower alcohols from synthesis gas.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428229A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof |
| US20100280287A1 (en) * | 2008-09-04 | 2010-11-04 | Range Fuels, Inc. | Cobalt-molybdenum sulfide catalyst materials and methods for stable alcohol production from syngas |
| CN108325548A (en) * | 2018-03-15 | 2018-07-27 | 内蒙古大学 | A kind of molybdenum sulphide and preparation method thereof for low carbon alcohol by synthetic gas |
| CN111420689A (en) * | 2020-03-26 | 2020-07-17 | 内蒙古大学 | Preparation method and application of catalyst for preparing low-carbon alcohol from synthesis gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428229A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof |
| US20100280287A1 (en) * | 2008-09-04 | 2010-11-04 | Range Fuels, Inc. | Cobalt-molybdenum sulfide catalyst materials and methods for stable alcohol production from syngas |
| CN108325548A (en) * | 2018-03-15 | 2018-07-27 | 内蒙古大学 | A kind of molybdenum sulphide and preparation method thereof for low carbon alcohol by synthetic gas |
| CN111420689A (en) * | 2020-03-26 | 2020-07-17 | 内蒙古大学 | Preparation method and application of catalyst for preparing low-carbon alcohol from synthesis gas |
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