CN113117692A - 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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- CN113117692A CN113117692A CN202110391625.5A CN202110391625A CN113117692A CN 113117692 A CN113117692 A CN 113117692A CN 202110391625 A CN202110391625 A CN 202110391625A CN 113117692 A CN113117692 A CN 113117692A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 53
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 24
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 24
- 238000005470 impregnation Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000010948 rhodium Substances 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 28
- 229910002651 NO3 Inorganic materials 0.000 claims description 21
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 63
- 239000000203 mixture Substances 0.000 description 29
- 238000011156 evaluation Methods 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- 229910052703 rhodium Inorganic materials 0.000 description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- 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
- C07C29/157—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 containing platinum group metals or compounds thereof
- C07C29/158—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 containing platinum group metals or compounds thereof containing rhodium or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for preparing low-carbon alcohol from synthesis gas, which comprises a multi-element metal oxide (Cu)2+Co2+M2+）M3+And supported Rh and an alkali metal promoter, where M2+Including Mn2+、Zn2+、Mg2+、Ni2+、Ca 2+One or more of, M3+Including Al3+、Fe3+、Ga3+、La3+、Cr3+One or more of them. The invention also provides a preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas, which comprises the following steps: preparing hydrotalcite-like precursor by coprecipitation method, preparing multi-element metal oxide from the precursor, impregnating Rh and alkali metal onto the multi-element metal oxide by isovolumetric impregnation method, and dryingDrying and roasting to obtain the required catalyst. The catalyst has the advantages of high activity, high total alcohol selectivity, high mass percent of ethanol in the total alcohol and the like.
Description
Technical Field
The invention relates to a catalyst for preparing low-carbon alcohol from synthesis gas, a preparation method and application thereof, belonging to the technical field of catalytic chemistry.
Background
The synthesis of low-carbon mixed alcohol from synthesis gas has developed various catalyst systems, of which 4 are representative: rhodium-based catalyst, modified methanol catalyst, modified Fischer-Tropsch synthesis catalyst and molybdenum-based catalyst. The rhodium-based catalyst has better selectivity of low-carbon alcohol, but the CO conversion rate is lower; the modified Fischer-Tropsch synthesis catalyst has high CO conversion rate, still has Fischer-Tropsch synthesis characteristics, low selectivity of low-carbon alcohol and poor stability. The development of high-performance catalysts for producing lower alcohols from synthesis gas is still a major issue facing many relevant researchers.
In the research of the modified Fischer-Tropsch catalyst for preparing low-carbon alcohol from synthesis gas, the oxide prepared by the hydrotalcite precursor method shows good catalytic performance. Layered Double Hydroxides (abbreviated as LDHs) are a general term for hydrotalcite and hydrotalcite-like compounds, and the general chemical composition formula is usually written as:
M2+and M3+Respectively represent metal cations of corresponding valence state on the main body laminate, An-Is an interlayer anion, x is M2+/(M2++M3+) The molar ratio, m, represents the amount of interlayer bound water. LDHs are typical anionic clay mineral layered materials, and have high specific surface area, controllability of interlayer ions and unique lamellar-pore structure, so that LDHs become main research objects of catalytic research. The mixture is roasted at the temperature of 400-550 ℃ to form stable bimetallic oxide, which is abbreviated as LDO (low dropout regulator), for example, the roasted product of magnesium aluminum hydrotalcite in the temperature range is Mg3A1O4(OH). The LDO can still be used asAn important class of catalysts and supports, which have a larger specific surface area than their precursors. Meanwhile, the surface of the catalyst is rich in a large number of alkaline sites (hydroxyl groups), which is beneficial to the ethanol synthesis reaction. However, in the prior art, the catalytic activity and the ethanol selectivity of the catalyst for preparing the low-carbon alcohol from the synthesis gas are both low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a catalyst for preparing low-carbon alcohol from synthesis gas, and a preparation method and application thereof, and aims to solve the problems of low catalytic activity and low ethanol selectivity of the conventional synthesis gas-prepared low-carbon alcohol.
In order to solve the technical problem, the invention provides a catalyst for preparing low-carbon alcohol from synthesis gas, which comprises a multi-element metal oxide (Cu)2+Co2+M2+)M3+And supported Rh and an alkali metal promoter, where M2+Including Mn2+、Zn2+、Mg2+、Ni2+、Ca2+One or more of, M3+Including Al3+、Fe3+、Ga3+、La3+、Cr3+One or more of them.
Preferably, the alkali metal comprises one or more of K, Na, Cs and Li, and the loading amount of the alkali metal is 0.01-2 wt% of the multi-element metal oxide.
Preferably, the loading amount of Rh is 0.01wt% to 3wt% of the polyvalent metal oxide.
Preferably, in the multi-element metal oxide, calculated by metal elements, Cu, Co and M2+、M3+The total mass percentage content is 100 percent, wherein the mass percentage of each component is as follows: 20-60% of Cu, 10-45% of Co and M2+10～50％、M3+10～50％。
The invention also provides a preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas, which comprises the following steps: preparing a hydrotalcite-like precursor by a coprecipitation method, preparing a multi-element metal oxide from the precursor, impregnating Rh and alkali metal on the multi-element metal oxide in an isometric impregnation mode, drying and roasting to obtain the required catalyst.
Preferably, the dipping time is 10-24 hours, the drying is carried out for 6-20 hours at the temperature of 60-80 ℃, and the roasting is carried out for 3-5 hours at the temperature of 300-500 ℃.
Preferably, the Rh is one of rhodium nitrate or rhodium chloride, the alkali metal comprises nitrate or chloride of K, Na, Cs and Li, and one or more of the alkali metal is selected.
Preferably, the preparation method of the multi-element metal oxide comprises the following steps:
dissolving the metal salt in deionized water by using water as a solvent, wherein the molar concentration of total ions is 0.3-2.0M, and the solution is A;
weighing Na2CO3、K2CO3One of NaOH and KOH is weighed, and the NaOH and the KOH are simultaneously dissolved in deionized water to be mixed to prepare a precipitator, wherein Na is2CO3Or K2CO3In a molar amount of [ M ]3+]1.5 to 2.5 times of the amount of the catalyst, the molar amount of NaOH or KOH being ([ Cu ]]+[Co]+[M2+]) 1.5 to 2.8 times of the total molar concentration of the solution B, and the total molar concentration is 0.5 to 2.0M;
and simultaneously dripping the prepared A, B solution into a four-neck flask for coprecipitation, aging the precipitate for 3-24 h at the temperature of 60-90 ℃, washing, drying and roasting to obtain the multi-element metal oxide.
Preferably, the dropping speed is 2-10 ml/min, the PH is 8-9, the reaction temperature is 60-90 ℃, and the stirring speed is 300-700 rpm; washing with equivalent deionized water for 5-10 times, drying at 60-80 ℃ for 6-20 hours, and roasting at 300-500 ℃ for 3-5 hours.
The application of the catalyst for preparing low-carbon alcohol from synthesis gas is to use H2H with the volume content of 20-100%2、N2The mixed reducing gas is used at a gas airspeed of 200-1000 h-1Reducing the catalyst for 3-6 hours under the conditions of pressure of 0.05-1.0 Mpa and temperature of 300-550 ℃; the temperature of the reduced catalyst is reduced to the reaction temperature, the reaction of preparing low carbon alcohol from the synthesis gas is carried out, and H in the reaction raw material gas2The mol ratio of/CO is 1-3, the reaction pressure is 2-5 Mpa, the reaction temperature is 200-330 ℃, and the reaction is carried outThe air space velocity is 3000-12000 h-1。
The invention achieves the following beneficial effects: utilizes the structural characteristics of hydrotalcite-like compound to synthesize multi-element metal oxide (Cu) prepared by hydrotalcite-like compound precursor with better activity on preparing low-carbon alcohol from synthesis gas2+Co2+M2+)M3+The conversion rate is improved by loading Rh and an alkali metal auxiliary agent, and the selectivity of the catalyst to low-carbon alcohol is increased, particularly the selectivity of ethanol is improved. The hydrotalcite-like precursor is prepared by a coprecipitation method, the precursor is used for preparing a multi-element metal oxide, Rh and alkali metal are impregnated on the multi-element metal oxide in an equal-volume impregnation mode, interaction between the Rh and the multi-element metal oxide is enhanced after roasting, good metal dispersibility is kept, and the performance of the catalyst in the application of preparing low-carbon alcohol and preferably producing ethanol from synthesis gas is obviously improved. The catalyst has the advantages of high activity, high total alcohol selectivity, high mass percent of ethanol in the total alcohol and the like.
Detailed Description
Example 1
Preparation of multi-component metal oxides from hydrotalcite-like precursors: 9.76gCu (NO) was weighed out separately3)2·3H2O、5.88gCo(NO3)2·6H2O、10.74g50％Mn(NO3)2Aqueous solution, 11.36gAl (NO)3)3·9H2And O, dissolving in 150ml of deionized water, and uniformly stirring to obtain the solution A. Then 8.82g of sodium hydroxide and 6.42g of anhydrous sodium carbonate are respectively weighed and dissolved in 180ml of deionized water, and the solution is uniformly stirred to obtain a solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 4 mL/min. The reaction temperature was controlled at 80 ℃ and aged for 5 hours. The precipitate was washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours, and calcined at 350 ℃ in air for 3 hours. The metal composition of the resulting oxide was: 41.25% of Cu (wt.), 19.10% of Co (wt.), 26.49% of Mn (wt.), and 13.16% of Al (wt.).
Impregnation of Rh and alkali metal: 0.20g Rh (NO) containing 5% Rh was weighed out3)3Aqueous solution, 0.05g of LiNO was dissolved in deionized water and stirred uniformly to obtain solution C. 5.0g of the uniformly ground multicomponent metal oxide from hydrotalcite-like precursor was weighed and added to solution C to achieve incipient wetness impregnation. After being immersed for 24 hours at room temperature, the mixture is dried for 12 hours at 60 ℃ and roasted for 3 hours at 320 ℃. The prepared catalyst is pressed into tablets, crushed and sieved by a 40-60-mesh sieve for evaluation. The supported amount of Rh and the supported amount of Li in the catalyst were 0.2 wt% and 0.1 wt%, respectively, with respect to the polyvalent metal oxide.
Evaluation of catalyst application: a fixed bed micro-reaction device is adopted, 1.0g of catalyst is filled, the dilution volume of quartz sand is 2:1, and the reduction conditions of the catalyst are as follows: vH2：VN21:4, space velocity of reducing gas 400h-1The reduction pressure is 0.3MPa, the reduction temperature is 400 ℃, and the reduction time is 3 hours. After the catalyst is reduced, the temperature is reduced to be below 100 ℃, and raw material gas H is introduced22/CO: 1, the reaction temperature is 250 ℃, the reaction pressure is 2.5MPa, and the space velocity is 4000h-1. After the reaction was stabilized for 12 hours, the raw material gas and the product were analyzed, and the results are shown in Table 1.
Example 2
Preparation of multi-component metal oxides from hydrotalcite-like precursors: separately weigh 4.88gCu (NO)3)2·3H2O、5.88gCo(NO3)2·6H2O、1.62g Fe(NO3)3·9H2O、5.05gAl(NO3)3·9H2And O, dissolving in 100ml of deionized water, and uniformly stirring to obtain the solution A. 3.92g of sodium hydroxide and 3.71g of anhydrous sodium carbonate are respectively weighed and dissolved in 110ml of water, and the solution is stirred uniformly to obtain a solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 4 mL/min. The reaction temperature was controlled at 80 ℃ and aged for 5 hours. The precipitate was washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours, and calcined at 350 ℃ in air for 3 hours. The metal composition of the resulting oxide was: 42.05% of Cu (wt.), 38.76% of Co (wt.), 7.36% of Mn (wt.) and 11.83% of Al (wt.).
Impregnation of Rh and alkali metal: 0.40g of Rh (NO) containing 5% of Rh was weighed3)3Aqueous solution, 0.02gCsNO3Dissolving in deionized water, and stirring to obtain solution C. 5.0g of the uniformly ground multicomponent metal oxide from hydrotalcite-like precursor was weighed and added to solution C to achieve incipient wetness impregnation. After being soaked for 24 hours at room temperature, the mixture is dried for 12 hours at 60 ℃ and roasted for 3 hours at 350 ℃. The prepared catalyst is pressed into tablets, crushed and sieved by a 40-60-mesh sieve for evaluation. The supported amount of Rh was 0.4 wt% and the supported amount of Cs was 0.2 wt% with respect to the polyvalent metal oxide in the catalyst.
The application conditions were the same as in example 1.
Example 3
Preparation of multi-component metal oxides from hydrotalcite-like precursors: 9.76gCu (NO) was weighed out separately3)2·3H2O、5.88gCo(NO3)2·6H2O、1.73g Zn(NO3)2·6H2O、8.33gAl(NO3)3·9H2And O, dissolving in 120ml of deionized water, and uniformly stirring to obtain the solution A. Then 6.47g of sodium hydroxide and 4.71g of anhydrous sodium carbonate are respectively weighed and dissolved in 130ml of water, and the mixture is uniformly stirred to obtain a solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 3 mL/min. The reaction temperature was controlled at 80 ℃ and aged for 5 hours. The precipitate was washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours, and calcined at 400 ℃ in air for 3 hours. The metal composition of the resulting oxide was: cu (Wt.) 54.19%, Co (Wt.) 24.98%, Zn (Wt.) 8.26%, and Al (Wt.) 12.57%.
Impregnation of Rh and alkali metal: 0.30g Rh (NO) containing 5% Rh was weighed out3)3Aqueous solution, 0.02gNaNO3Dissolving in deionized water, and stirring to obtain solution C. 5.0g of the uniformly ground multicomponent metal oxide from hydrotalcite-like precursor was weighed and added to solution C to achieve incipient wetness impregnation. After being immersed for 24 hours at room temperature, the mixture is dried for 12 hours at 60 ℃ and roasted for 3 hours at 400 ℃. The prepared catalyst is pressed into tablets, crushed and sieved by a 40-60-mesh sieve for evaluation. The supported amount of Rh and the supported amount of Na in the catalyst were 0.3 wt% and 0.1 wt%, respectively, with respect to the polyvalent metal oxide.
The application conditions were the same as in example 1.
Example 4
Preparation of multi-component metal oxides from hydrotalcite-like precursors: 6.10g of Cu (NO) was weighed out separately3)2·3H2O、7.35gCo(NO3)2·6H2O、2.18g Ni(NO3)2·6H2O、8.71gAl(NO3)3·9H2And O, dissolving in 100ml of deionized water, and uniformly stirring to obtain the solution A. Then 5.63g of sodium hydroxide and 6.41g of anhydrous potassium carbonate are weighed respectively and dissolved in 110ml of water, and the mixture is stirred uniformly to obtain a solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 4 mL/min. The reaction temperature was controlled at 85 ℃ and aged for 5 hours. The precipitate is washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours and roasted at 380 ℃ in air for 3 hours. The metal composition of the resulting oxide was: 38.66% of Cu (Wt.), 35.64% of Co (Wt.), 10.69% of Ni (Wt.), and 15.01% of Al (Wt.).
Impregnation of Rh and alkali metal: 0.50g of Rh (NO) containing 5% of Rh were weighed out3)3Aqueous solution, 0.02gKNO3Dissolving in deionized water, and stirring to obtain solution C. 5.0g of the uniformly ground multicomponent metal oxide from hydrotalcite-like precursor was weighed and added to solution C to achieve incipient wetness impregnation. After being soaked for 24 hours at room temperature, the mixture is dried for hours at 60 ℃ and roasted for 3 hours at 380 ℃. The prepared catalyst is pressed into tablets, crushed and sieved by a 40-60-mesh sieve for evaluation. The supported amount of Rh and the supported amount of K in the catalyst were 0.5 wt% and 0.1 wt%, respectively, with respect to the polyvalent metal oxide.
The application conditions were the same as in example 1.
Example 5
Preparation of multi-component metal oxides from hydrotalcite-like precursors: weighing 7.32gCu (NO) respectively3)2·3H2O、5.88gCo(NO3)2·6H2O、10.74g50％Mn(NO3)2Aqueous solution, 2.42g Cr (NO)3)3·9H2O、16.29gAl(NO3)3·9H2And O, dissolving in 150ml of deionized water, and uniformly stirring to obtain the solution A. Then respectively weighing 7.84g of hydrogen hydroxideSodium, 13.66g anhydrous potassium carbonate, dissolved in 170ml water and stirred well, this is solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 4 mL/min. The reaction temperature is controlled at 80 ℃, and the aging is carried out for 5 hours. The precipitate is washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours and roasted at 380 ℃ in air for 3 hours. The metal composition of the resulting oxide was: 30.85% of Cu (wt.), 18.96% of Co (wt.), 26.51% of Mn (wt.), 5.01% of Cr (wt.), and 18.66% of Al (wt.).
Impregnation of Rh and alkali metal: 0.40g of Rh (NO) containing 5% of Rh was weighed3)3The aqueous solution and 0.03g LiCl were dissolved in deionized water and stirred well to give solution C. 5.0g of the uniformly ground multicomponent metal oxide from hydrotalcite-like precursor was weighed and added to solution C to achieve incipient wetness impregnation. After being soaked for 24 hours at room temperature, the mixture is dried for 12 hours at the temperature of 60 ℃ and roasted for 3 hours at the temperature of 380 ℃. The prepared catalyst is pressed into tablets, crushed and sieved by a 40-60-mesh sieve for evaluation. The supported amount of Rh and the supported amount of Li in the catalyst were 0.4 wt% and 0.1 wt%, respectively, with respect to the polyvalent metal oxide.
The application conditions were the same as in example 1.
Example 6
Preparation of multi-component metal oxides from hydrotalcite-like precursors: weighing 7.32gCu (NO) respectively3)2·3H2O、5.88gCo(NO3)2·6H2O、10.74g50％Mn(NO3)2Aqueous solution, 0.95g Ca (NO)3)2·4H2O、10.61gAl(NO3)3·9H2And O, dissolving in 150ml of deionized water, and uniformly stirring to obtain the solution A. Then 6.86g of sodium hydroxide and 6.0g of anhydrous sodium carbonate are respectively weighed and dissolved in 170ml of water, and the mixture is uniformly stirred to obtain solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 4 mL/min. The reaction temperature was controlled at 80 ℃ and aged for 5 hours. The precipitate is washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours and roasted at 380 ℃ in air for 3 hours. The metal composition of the resulting oxide was: cu (wt.) 32.71%, Co (wt.) 20.1%, Mn (wt.)28.11％、Ca(Wt.)6.20％、Al(Wt.)12.88％。
Impregnation of Rh and alkali metal: 0.70g Rh (NO) containing 5% Rh was weighed out3)3Aqueous solution, 0.09gKNO3Dissolving in deionized water, and stirring to obtain solution C. 5.0g of the uniformly ground multicomponent metal oxide from hydrotalcite-like precursor was weighed and added to solution C to achieve incipient wetness impregnation. After being soaked for 24 hours at room temperature, the mixture is dried for 12 hours at the temperature of 60 ℃ and roasted for 3 hours at the temperature of 380 ℃. The prepared catalyst is pressed into tablets, crushed and sieved by a 40-60-mesh sieve for evaluation. The supported amount of Rh and the supported amount of K in the catalyst were 0.7 wt% and 0.7 wt%, respectively, with respect to the polyvalent metal oxide.
The application conditions were the same as in example 1.
Example 7
Preparation of multi-component metal oxides from hydrotalcite-like precursors: respectively called 9.76gCu (NO)3)2·3H2O、5.88gCo(NO3)2·6H2O、10.74g50％Mn(NO3)2Aqueous solution, 2.62g La (NO)3)3·6H2O、9.74gAl(NO3)3·9H2And O, dissolving in 150ml of deionized water, and uniformly stirring to obtain the solution A. Then 7.34g of sodium hydroxide and 6.79g of anhydrous sodium carbonate are respectively weighed and dissolved in 170ml of water, and the mixture is uniformly stirred to obtain solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 4 mL/min. The reaction temperature was controlled at 80 ℃ and aged for 5 hours. The precipitate is washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours and roasted at 380 ℃ in air for 3 hours. The metal composition of the resulting oxide was: 37.00% of Cu (wt.), 17.06% of Co (wt.), 23.85% of Mn (wt.), 12.06% of La (wt.), and 10.04% of Al (wt.).
Impregnation of Rh and alkali metal: 0.60g Rh (NO) containing 5% Rh was weighed out3)3Aqueous solution, 0.2g LiNO3Dissolving in deionized water, and stirring to obtain solution C. 5.0g of the uniformly ground multicomponent metal oxide from hydrotalcite-like precursor was weighed and added to solution C to achieve incipient wetness impregnation. Soaking at room temperature for 24 hr, oven drying at 60 deg.C for 12 hr, and calcining at 380 deg.CFor 3 hours. The prepared catalyst is pressed into tablets, crushed and sieved by a 40-60-mesh sieve for evaluation. The supported amount of Rh and the supported amount of Li in the catalyst were 0.6 wt% and 0.4 wt%, respectively, with respect to the polyvalent metal oxide.
The application conditions were the same as in example 1.
Example 8
Preparation of multi-component metal oxides from hydrotalcite-like precursors: 9.76gCu (NO) was weighed out separately3)2·3H2O、5.88gCo(NO3)2·6H2O、2.56g Mg(NO3)2·6H2O、8.84gAl(NO3)3·9H2And O, dissolving in 120ml of deionized water, and uniformly stirring to obtain the solution A. Then 8.0g of potassium hydroxide and 5.0g of anhydrous sodium carbonate are respectively weighed and dissolved in 130ml of deionized water, and the mixture is uniformly stirred to obtain solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 4 mL/min. The reaction temperature was controlled at 80 ℃ and aged for 5 hours. The precipitate was washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours, and calcined at 350 ℃ in air for 3 hours. The metal composition of the resulting oxide was: 55.53% of Cu (wt.), 25.60% of Co (wt.), 5.21% of Mg (wt.) and 13.67% of Al (wt.).
Impregnation of Rh and alkali metal: 0.50g of Rh (NO) containing 5% of Rh were weighed out3)3Aqueous solution, 0.1g LiNO3Dissolving in deionized water, and stirring to obtain solution C. 5.0g of the uniformly ground multicomponent metal oxide from hydrotalcite-like precursor was weighed and added to solution C to achieve incipient wetness impregnation. After being soaked for 24 hours at room temperature, the mixture is dried for 12 hours at 60 ℃ and roasted for 3 hours at 350 ℃. The prepared catalyst is pressed into tablets, crushed and sieved by a 40-60-mesh sieve for evaluation. The supported amount of Rh and the supported amount of Li in the catalyst were 0.5 wt% and 0.2 wt%, respectively, with respect to the polyvalent metal oxide.
The application conditions were the same as in example 1.
Comparative example 1
Preparation of multi-component metal oxides from hydrotalcite-like precursors: 9.76gCu (NO) was weighed out separately3)2·3H2O、5.88gCo(NO3)2·6H2O、10.74g50％Mn(NO3)2Aqueous solution, 11.37gAl (NO)3)3·9H2And O, dissolving in 150ml of deionized water, and uniformly stirring to obtain the solution A. Then 8.82g of sodium hydroxide and 6.42g of anhydrous sodium carbonate are respectively weighed and dissolved in 180ml of deionized water, and the mixture is uniformly stirred to obtain solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 4 mL/min. The reaction temperature was controlled at 80 ℃ and aged for 5 hours. The precipitate was washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours, and calcined at 350 ℃ in air for 3 hours. After being pressed and crushed, the mixture is sieved by a 40-60 mesh sieve for evaluation. The metal composition of the resulting oxide was: 41.25% of Cu (wt.), 19.10% of Co (wt.), 26.49% of Mn (wt.), and 13.16% of Al (wt.).
The application conditions were the same as in example 1.
Comparative example 2
Preparation of the multinary metal oxide from non-hydrotalcite-like precursors: weighing 7.32gCu (NO) respectively3)2·3H2O、5.88gCo(NO3)2·6H2O、10.74g50％Mn(NO3)2Aqueous solution, 2.42g Cr (NO)3)3·9H2O、16.29gAl(NO3)3·9H2And O, dissolving in 130ml of deionized water, and uniformly stirring to obtain the solution A. 16.06g of anhydrous potassium carbonate was weighed, dissolved in 150ml of water, and stirred uniformly, thereby obtaining a solution B. Under the condition of stirring, the solution A and the solution B are dropwise added into a four-neck flask containing 10mL of deionized water in a concurrent flow mode, and the dropping speed is 4 mL/min. The reaction temperature is controlled at 80 ℃, and the aging is carried out for 5 hours. The precipitate is washed 8 times with equal amount of deionized water, dried at 60 ℃ for 12 hours and roasted at 380 ℃ in air for 3 hours. After being pressed and crushed, the mixture is sieved by a 40-60 mesh sieve for evaluation. The metal composition of the resulting oxide was: 30.85% of Cu (wt.), 18.96% of Co (wt.), 26.51% of Mn (wt.), 5.01% of Cr (wt.), and 18.66% of Al (wt.).
Impregnation of Rh and alkali metal: 0.40g of Rh (NO) containing 5% of Rh was weighed3)3The aqueous solution and 0.03g LiCl were dissolved in deionized water and stirred well to give solution C. 5.0g of a uniformly ground multi-component hydrotalcite-like precursor prepared from hydrotalcite-like precursor was weighedMetal oxide, to which solution C was added to achieve incipient wetness impregnation. After being soaked for 24 hours at room temperature, the mixture is dried for 12 hours at the temperature of 60 ℃ and roasted for 3 hours at the temperature of 380 ℃. The prepared catalyst is pressed into tablets, crushed and sieved by a 40-60-mesh sieve for evaluation. The supported amount of Rh and the supported amount of Li in the catalyst were 0.4 wt% and 0.1 wt%, respectively, with respect to the polyvalent metal oxide.
The application conditions were the same as in example 1.
The evaluation results of the synthesis gas for producing lower alcohols are shown in table 1.
TABLE 1 evaluation results of Low carbon alcohol production from Synthesis gas
From the evaluation results of comparative example 1 and example 1, it can be seen that the addition of Rh and Li to the multi-metal oxide prepared from the hydrotalcite-like precursor significantly improves the CO conversion and increases the yield of alcohol. Wherein the mass percentage of the ethanol in the alcohol product can reach 70 percent.
Comparison of the evaluation results of comparative example 2 and example 5 shows that the performance of the catalyst prepared from the hydrotalcite-like precursor having the same element composition and loaded with the multi-metal oxide is superior to that of the catalyst prepared from the non-hydrotalcite-like precursor and loaded with the multi-metal oxide.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The catalyst for preparing low-carbon alcohol from synthesis gas is characterized by comprising a multi-element metal oxide (Cu)2+Co2+M2+）M3+And supported Rh and an alkali metal promoter, where M2+Including Mn2+、Zn2+、Mg2+、Ni2+、Ca 2+One or more of, M3+Including Al3+、Fe3+、Ga3+、La3+、Cr3+One or more of them.
2. The catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the alkali metal comprises one or more of K, Na, Cs and Li, and the loading amount of the alkali metal is 0.01-2 wt% of the multi-element metal oxide.
3. The catalyst for preparing low carbon alcohol from synthesis gas as claimed in claim 1, wherein the loading of Rh is 0.01wt% to 3wt% of the multi-component metal oxide.
4. The catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, wherein the multi-element metal oxide comprises Cu, Co and M in terms of metal elements2+、M3+The total mass percentage content is 100 percent, wherein the mass percentage of each component is as follows: 20-60% of Cu, 10-45% of Co and M2+ 10～50%、M3+ 10～50%。
5. The method for preparing the catalyst for preparing the lower alcohol from the synthesis gas according to any one of claims 1 to 4, which is characterized by comprising the following steps: preparing a hydrotalcite-like precursor by a coprecipitation method, preparing a multi-element metal oxide from the precursor, impregnating Rh and alkali metal on the multi-element metal oxide in an isometric impregnation mode, drying and roasting to obtain the required catalyst.
6. The method according to claim 5, wherein the dipping time is 10 to 24 hours, the drying is performed at 60 to 80 ℃ for 6 to 20 hours, and the baking is performed at 300 to 500 ℃ for 3 to 5 hours.
7. The preparation method according to claim 5, wherein Rh is one of rhodium nitrate and rhodium chloride, the alkali metal comprises nitrate or chloride of K, Na, Cs and Li, and one or more of the nitrate or chloride is selected.
8. The method according to claim 5, wherein the method for preparing the multi-component metal oxide comprises:
dissolving the metal salt in deionized water by using water as a solvent, wherein the molar concentration of total ions is 0.3-2.0M, and the solution is A;
weighing Na2CO3、K2CO3One of NaOH and KOH is weighed, and the NaOH and the KOH are simultaneously dissolved in deionized water to be mixed to prepare a precipitator, wherein Na is2CO3Or K2CO3In a molar amount of [ M ]3+]1.5 to 2.5 times of the amount of the catalyst, the molar amount of NaOH or KOH being ([ Cu ]]+ [Co] +[ M2+]) 1.5 to 2.8 times of the total molar concentration of the solution B, and the total molar concentration is 0.5 to 2.0M;
and simultaneously dripping the prepared A, B solution into a four-neck flask for coprecipitation, aging the precipitate for 3-24 h at the temperature of 60-90 ℃, washing, drying and roasting to obtain the multi-element metal oxide.
9. The preparation method according to claim 8, wherein the dropping speed is 2 to 10ml/min, the pH is 8 to 9, the reaction temperature is 60 to 90 ℃, and the stirring speed is 300 to 700 rpm; washing with equivalent deionized water for 5-10 times, drying at 60-80 ℃ for 6-20 hours, and roasting at 300-500 ℃ for 3-5 hours.
10. Use of a catalyst according to any one of claims 1 to 4 for the production of lower alcohols from synthesis gas, characterised in that H is used2H with the volume content of 20-100%2 、N2The mixed reducing gas is used at a gas airspeed of 200-1000 h-1Reducing the catalyst for 3-6 hours under the conditions of pressure of 0.05-1.0 Mpa and temperature of 300-550 ℃; the temperature of the reduced catalyst is reduced to the reaction temperature, the reaction of preparing low carbon alcohol from the synthesis gas is carried out, and H in the reaction raw material gas2The mol ratio of/CO is 1-3, the reaction pressure is 2-5 Mpa, the reaction temperature is 200-330 ℃, and the airspeed of the reaction gas is 3000-12000 h-1。
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| CN115007161A (en) * | 2022-07-18 | 2022-09-06 | 中国五环工程有限公司 | Catalyst for preparing succinic anhydride by maleic anhydride hydrogenation and preparation method and using method thereof |
| CN115007161B (en) * | 2022-07-18 | 2023-10-27 | 中国五环工程有限公司 | Catalyst for preparing succinic anhydride by maleic anhydride hydrogenation, and preparation method and application method thereof |
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Application publication date: 20210716 |