CN100471563C - Catalyst for preparing low-carbon mixed alcohol by synthetic gas, its preparation method and application - Google Patents

Catalyst for preparing low-carbon mixed alcohol by synthetic gas, its preparation method and application Download PDF

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CN100471563C
CN100471563C CNB2004100924275A CN200410092427A CN100471563C CN 100471563 C CN100471563 C CN 100471563C CN B2004100924275 A CNB2004100924275 A CN B2004100924275A CN 200410092427 A CN200410092427 A CN 200410092427A CN 100471563 C CN100471563 C CN 100471563C
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synthetic gas
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CN1663683A (en
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孙予罕
钟炳
李文怀
马玉刚
张侃
肖海成
李影辉
张勇军
苑慧敏
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The invention is composition gasifying low-carbon mixing alcohol catalyst and its preparation method and utilization. The weight percentages of the catalyst are: Mo: 20-40%, Ni: 4-10%, Mn: 0.1-1.0%, K: 5-15%, Fe: 5-10%, S: 20-40%, the cohesive agent: 10-20%. The preparation method is to add ammonium molybdate to ammonium sulfide solution to react to get thiosulfate ammonium molybdate solution; drop in nickel and manganese salt solution and the thiosulfate ammonium molybdate solution, and through heating, filtering, cleaning, depositing and drying to get molybdenum nickel manganese multi-sulfur compound; mix molysite with citric acid and carry out heating reaction to get molysite C; mix molybdenum nickel manganese multi-sulfur compound, kali salt and molysite C, abrade them, lead in indifferent protective gas to burn to get molybdenum nickel manganese kalium sulfur compound; add cohesive agent to mix, press and form. The catalyst of the invention has high activity, high selectivity and good stability.

Description

A kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas and method for making thereof and application
Technical field
The invention belongs to a kind of catalyst and method for making thereof and application, relate in particular to a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas and method for making thereof and application.
Background technology
Along with the exhaustion day by day of petroleum resources, the future source of energy structure will turn to based on coal and natural gas.Coal is the main energy sources resource of China, and along with going from bad to worse of environment, the coal clean utilization has been a urgent task.Utilizing angle from resources effective, is the coal indirect reformer research of liquid fuel and chemicals, has a wide range of applications.
The application prospect of low-carbon alcohols is bright and clear day by day.The additive that acts as a fuel, it has fine solubility, volatility, driver behavior and higher octane number.In addition, it can also use as the raw material and the clean fuel of some chemical products.
At present existing in a large number by the reports of co hydrogenation synthesis of low-carbon alcohol, wherein representative have four kinds of catalyst.(1) the modified methanol synthetic catalyst (Cu-Zn/Al, Zn-Cr); This catalyst adds an amount of alkali metal or alkaline earth metal compound modification by methanol synthesis catalyst and gets, typical patent has EP-0034338-A2 people such as () C.E.Hofstadt and United States Patent (USP) 4513100 (Snam company subsidizes, and the invention people is people such as Fattore).Though this catalyst is active higher, isobutanol content height in the product, severe reaction conditions (pressure is 14-20Mpa, and temperature is 350-450 ℃), higher alcohol selectivity low (being generally less than 35%), water content height (being generally 30-50%) in the product; (2) Cu-Co catalyst: France Petroleum Institute (IFP) has at first developed Cu-Co co-precipitation low-carbon alcohol catalyst, only four catalyst patent (US Patent4122110 have just been obtained before 1985,4291126 and GB Patent 2118061,2158730) the synthetic product of this catalyst is mainly C 1-C 6The straight chain n-alkanol, accessory substance is mainly C 1-C 6Aliphatic hydrocarbon, reaction condition gentleness (similar) to the low pressure methanol synthetic catalyst.The shortcoming of this catalyst is a less stable.(3) Rh catalyst based (as US 4014913 and 4096164): after adding one to two kind of transition metal or metal oxide auxiliary agent in the support type Rh catalyst, to low-carbon alcohols is synthetic higher activity and selectivity are arranged, particularly to C 2 +The selectivity of alcohol is higher, and product is based on ethanol.But the Rh compound costs an arm and a leg, and catalyst is easily by CO 2Poison, its activity and selectivity generally do not reach industrial requirement.(4) anti-sulphur MoS 2Catalyst: being worth mentioning most is that the molybdenum of U.S. DOW company exploitation is sulfide catalyst (main patent is seen people's such as Stevens US patent 4882360), this catalyst system and catalyzing not only has anti-sulphur, product is moisture few, and higher alcohol content is higher, reaching 30-70%, wherein mainly is ethanol and normal propyl alcohol.The subject matter that this catalyst exists be wherein auxiliary element very easily and form carbonyls between the carbon monoxide, cause the loss of auxiliary element, influence activity of such catalysts and selectivity, cause catalyst stability and life-span to be restricted.
Summary of the invention
Purpose of the present invention is primarily aimed at the bad shortcoming of sulfur resistant catalyst stability, provides a kind of and has not only had high activity and high selectivity, and had the Catalysts and its preparation method and the application of fine stability.
The catalyst weight percentage of the present invention's preparation consists of: Mo:20-40%, Ni:4-10%, Mn:0.1-1.0%, K:5-15%, Fe:5-10%, S:20-40%, adhesive: 10-20%.
Preparation of catalysts method provided by the invention may further comprise the steps:
(1) preparation ammonium thiomolybdate solution ((NH 4) 2MoS 4)
With ammonium sulfide ((NH 4) 2S) solution is heated to 40-80 ℃, adds ammonium molybdate ((NH 4) 6Mo 7O 24.24H 2O) also stir, adding can make solution be neutralized to neutral dense acetic acid (CH after 10-20 minute 3COOH), and through 5-10 hour add thermal agitation, the cooling back adds deionized water, after making it to dissolve fully the ammonium thiomolybdate solution A;
(2) preparation molybdenum nickel manganese precipitation
Elder generation adds the 20-50wt% acetum toward a container, ammonium thiomolybdate solution A and the drip of preparation in nickel and manganese salt solution and (1) is gone into wherein, and be heated to 40-60 ℃ of stirring 1-10 hour;
(3) filter the also middle sediment of washing step (2), 60-150 ℃ of oven dry down, obtain molybdenum nickel manganese polysulfide B then;
(4) with molysite with etc. the weight citric acid fully mix, under inert atmosphere protection, be warmed up to 300-500 ℃, constant temperature cooled off after 1-3 hours, obtained molysite C;
(5) evenly mixed, the grinding of molybdenum nickel manganese polysulfide B and sylvite or potassium hydroxide and molysite C fed inertia protection gas at 350-650 ℃ of following roasting 0.5-3.0 hour, obtained molybdenum nickel manganese potassium sulphur compound powder D;
(6) add adhesive among the molybdenum nickel manganese potassium sulphur compound powder D and evenly mix compressing tablet, moulding then; Wherein the addition between each material consists of by catalyst weight percentage: Mo:30-50%, Ni:4-10%, Mn:0.1-1.0%, K:5-15%, Fe:4-10%, S:20-30%, adhesive: 10-20%.
The concentration range of ammonium thiomolybdate solution is 0.2-2M in the aforesaid step (1).
Aforesaid step (2) also can be used ammonium thiomolybdate solution ((NH earlier 4) 2MoS 4) obtain different sediments with nickel salt and manganese reactant salt respectively, mix oven dry then.
Aforesaid nickel and manganese salt can be acetate, oxalates.
Aforesaid step (3) must spend deionised water.
The sylvite that adds in the aforesaid step (5) can be potash (K 2CO 3).
The molysite that adds in the aforesaid step (4) is ferrous sulfide (FeS).
Aforesaid inertia protection gas can be nitrogen, also argon gas.
Aforesaid adhesive is bentonite or graphite etc.,
Application of Catalyst condition of the present invention is: reaction temperature is 290-350 ℃, and pressure is 8.0-9.5MPa, and air speed is 6000-8000h -1, H 2/ CO=1.0-1.8.
The present invention compared with prior art has following characteristics:
(a) catalyst of the present invention is to add molysite in the molybdenum nickel manganese sulfide as auxiliary agent, helps improving the stability and the life-span of catalyst.
(b) catalyst of the present invention has anti-sulphur, does not tie the characteristics of carbon.
(c) adopt catalyst of the present invention to carry out the synthetic of low-carbon alcohols, its total pure selectivity is 45-60%, and total pure space-time yield is 0.40-0.51g/h.ml cat; Water in products content is 4-10%; Higher alcohol content is 40-46%.
(c) catalyst reaction condition of the present invention is a temperature: 290-350 ℃, and pressure: 8.0-12.0MPa.
The analysis that the present invention adopts and being calculated as follows:
Gas and product liquid adopt the analysis of Tianjin, island GC-8A gas chromatograph.Thermal conductivity detector (TCD) (TCD) detects CO, the CO in the gas 2, H 2, CH 4Volume content and the H in the product liquid 2O, CH 3The percentage by weight of OH, its chromatographic column use carbon molecular sieve and the TDX401 packed column of 2m respectively, and column temperature is 100 ℃.Hydrocarbon in the gas and the mixed alcohol in the liquid are then detected by hydrogen flame ionization detector, and its chromatographic column is the Porapak Q packed column of 2m.
Gas is that intermediate carries out related normalizing calculating by methane gas, and liquid is that the related normalizing of intermediate calculates by methyl alcohol.
The specific embodiment
Embodiment 1
Ammonium molybdate ((NH 4) 6Mo 7O 24.24H 2O) 13.6g and concentration are 22% ammonium sulfide ((NH 4) 2S) solution 120ml 60 ℃ and stir under reaction one hour, add the dense acetic acid (CH of 50ml 3COOH) and deionized water, partly precipitated is dissolved fully, be mixed with 1.0M ammonium thiomolybdate solution.Take by weighing nickel acetate (Ni (CH 3COO) 2.4H 2O) 4.7g, manganese acetate (Mn (CH 3COO) 2.4H 2O) 1.7g is dissolved in the 150ml deionized water jointly, and this solution and ammonium thiomolybdate are molten. liquid and 300ml concentration be 30% acetum 60 ℃, stir under reaction, generate black precipitate.Washing, filtration, 120 ℃ of following vacuum drying obtain molybdenum base sediment.The citric acid that takes by weighing 1.7g ferrous sulfide and same quality fully mixes; under nitrogen protection, rise to 450 ℃; constant temperature calcining 2 hours; be cooled to room temperature; fully mix to be placed on 3.5g potash and molybdenum base sediment and be warming up to 500 ℃ under the tube furnace nitrogen protection; constant temperature 2 hours obtains black powder after the cooling.Add 0.5g bentonite compression molding, obtain catalyst 1#, its metallic element weight ratio is: Mo:Ni:Fe:Mn:K:S: bentonite=1:0.15:0.15:0.006:0.27:0.47:0.25.The evaluating catalyst condition: reaction temperature is 340 ℃, and pressure is 9.5MPa, and air speed is 7000h -1, H 2/ CO=1.3, reaction result sees Table 1.
Embodiment 2
Ammonium molybdate ((NH 4) 6Mo 7O 2424H 2O) 13.6g and concentration are 22% ammonium sulfide ((NH 4) 2S) solution 120ml 60 ℃ and stir under reaction one hour, add the dense acetic acid (CH of 50ml 3COOH) and deionized water, partly precipitated is dissolved fully, be mixed with 0.5M ammonium thiomolybdate solution.Take by weighing nickel acetate (Ni (CH 3COO) 24H 2O) 6.4g, manganese acetate (Mn (CH 3COO) 24H 2O) 3.4g is dissolved in the 150ml deionized water jointly, this solution and ammonium thiomolybdate solution and 300ml concentration be 30% acetum 60 ℃, stir under reaction, generate black precipitate.Washing, filtration, 120 ℃ of following vacuum drying obtain molybdenum base sediment.The citric acid that takes by weighing 1.15g ferrous sulfide and same quality fully mixes; under nitrogen protection, rise to 450 ℃; constant temperature calcining 2 hours; be cooled to room temperature; fully mix to be placed on 3.5g potash and molybdenum base sediment and be warming up to 500 ℃ under the tube furnace nitrogen protection; constant temperature 2 hours obtains black powder after the cooling.Add 0.5g bentonite compression molding, obtain catalyst 2#, its metallic element weight ratio is: Mo:Ni:Fe:Mn:K:S: bentonite=1:0.21:0.10:0.009:0.27:0.47:0.25.The evaluating catalyst condition: reaction temperature is 330 ℃, and pressure is 9.5MPa, and air speed is 6000h -1, H 2/ CO=1.3, reaction result sees Table 1.
Embodiment 3
Ammonium molybdate ((NH 4) 6Mo 7O 2424H 2O) 13.6g and concentration are 22% ammonium sulfide ((NH 4) 2S) solution 120ml 60 ℃ and stir under reaction one hour, add the dense acetic acid (CH of 50ml 3COOH) and deionized water, partly precipitated is dissolved fully, be mixed with 0.8M ammonium thiomolybdate solution.Take by weighing nickel acetate (Ni (CH 3COO) 24H 2O) 3.2g, manganese acetate (Mn (CH 3COO) 24H 2O) 1.7g is dissolved in the 150ml deionized water jointly, this solution and ammonium thiomolybdate solution and 300ml concentration be 30% acetum 60 ℃, stir under reaction, generate black precipitate.Washing, filtration, 120 ℃ of following vacuum drying obtain molybdenum base sediment.The citric acid that takes by weighing 2.3g ferrous sulfide and same quality fully mixes; under nitrogen protection, rise to 450 ℃; constant temperature calcining 2 hours; be cooled to room temperature; fully mix to be placed on 3.5g potash and molybdenum base sediment and be warming up to 500 ℃ under the tube furnace nitrogen protection; constant temperature 2 hours obtains black powder after the cooling.Add 0.5g bentonite compression molding, obtain catalyst 3#, its metallic element weight ratio is: Mo:Ni:Fe:Mn:K:S: bentonite=1:0.10:0.20:0.006:0.27:0.47:0.25.The evaluating catalyst condition: reaction temperature is 320 ℃, and pressure is 9.5MPa, and air speed is 8000h -1, H 2/ CO=1.2, reaction result sees Table 1.
Embodiment 4
Ammonium molybdate ((NH 4) 6Mo 7O 2424H 2O) 13.6g and concentration are 22% ammonium sulfide ((NH 4) 2S) solution 120ml 60 ℃ and stir under reaction one hour, add the dense acetic acid (CH of 50ml 3COOH) and deionized water, partly precipitated is dissolved fully, be mixed with 2.0M ammonium thiomolybdate solution.Take by weighing nickel oxalate (NiC 2O 42H 2O) 2.4g, manganese oxalate (MnC 2O 42H 2O) 1.3g is dissolved in the 150ml deionized water jointly, this solution and ammonium thiomolybdate solution and 300ml concentration be 30% acetum 60 ℃, stir under reaction, generate black precipitate.Washing, filtration, 120 ℃ of following vacuum drying obtain molybdenum base sediment.The citric acid that takes by weighing 2.3g ferrous sulfide and same quality fully mixes; under nitrogen protection, rise to 450 ℃; constant temperature calcining 2 hours; be cooled to room temperature; fully mix to be placed on 3.5g potash and molybdenum base sediment and be warming up to 500 ℃ under the tube furnace nitrogen protection; constant temperature 2 hours obtains black powder after the cooling.Add 0.5g bentonite compression molding, obtain catalyst 4#, its metallic element weight ratio is: Mo:Ni:Fe:Mn:K:S: bentonite=1:0.10:0.20:0.006:0.27:0.47:0.25.The evaluating catalyst condition: reaction temperature is 335 ℃, and pressure is 9.2MPa, and air speed is 6000h -1, H 2/ CO=1.5, reaction result sees Table 1.
Embodiment 5
Ammonium molybdate ((NH 4) 6Mo 7O 2424H 2O) 13.6g and concentration are 22% ammonium sulfide ((NH 4) 2S) solution 120ml 60 ℃ and stir under reaction one hour, add the dense acetic acid (CH of 50ml 3COOH) and deionized water, partly precipitated is dissolved fully, be mixed with 2.0M ammonium thiomolybdate solution.Take by weighing nickel oxalate (NiC 2O 42H 2O) 2.4g, manganese oxalate (MnC 2O 42H 2O) 1.3g is dissolved in the 150ml deionized water jointly, this solution and ammonium thiomolybdate solution and 300ml concentration be 30% acetum 60 ℃, stir under reaction, generate black precipitate.Washing, filtration, 120 ℃ of following vacuum drying obtain molybdenum base sediment.The citric acid that takes by weighing 2.3g ferrous sulfide and same quality fully mixes; under nitrogen protection, rise to 450 ℃; constant temperature calcining 2 hours; be cooled to room temperature; fully mix to be placed on 2.9g potassium hydroxide and molybdenum base sediment and be warming up to 500 ℃ under the tube furnace nitrogen protection; constant temperature 2 hours obtains black powder after the cooling.Add 0.5g bentonite compression molding, obtain catalyst 5#, its metallic element weight ratio is: Mo:Ni:Fe:Mn:K:S: bentonite=1:0.10:0.20:0.006:0.27:0.47:0.25.The evaluating catalyst condition: reaction temperature is 330 ℃, and pressure is 9.2MPa, and air speed is 6000h -1, H 2/ CO=1.5, reaction result sees Table 1.
Embodiment 6
Ammonium molybdate ((NH 4) 6Mo 7O 2424H 2O) 13.6g and concentration are 22% ammonium sulfide ((NH 4) 2S) solution 120ml 60 ℃ and stir under reaction one hour, add the dense acetic acid (CH of 50ml 3COOH) and deionized water, partly precipitated is dissolved fully, be mixed with 0.5M ammonium thiomolybdate solution.Take by weighing nickel acetate (Ni (CH 3COO) 24H 2O) 6.4g, manganese acetate (Mn (CH 3COO) 24H 2O) 3.4g is dissolved in the 150ml deionized water jointly, this solution and ammonium thiomolybdate solution and 300ml concentration be 30% acetum 60 ℃, stir under reaction, generate black precipitate.Washing, filtration, 120 ℃ of following vacuum drying obtain molybdenum base sediment.The citric acid that takes by weighing 1.15g ferrous sulfide and same quality fully mixes; under argon shield, rise to 450 ℃; constant temperature calcining 2 hours; be cooled to room temperature; fully mix to be placed on 3.5g potash and molybdenum base sediment and be warming up to 500 ℃ under the tube furnace argon shield; constant temperature 2 hours obtains black powder after the cooling.Add 0.5g bentonite compression molding, obtain catalyst 6#, its metallic element weight ratio is: Mo:Ni:Fe:Mn:K:S: bentonite=1:0.21:0.10:0.009:0.27:0.47:0.25.The evaluating catalyst condition: reaction temperature is 330 ℃, and pressure is 9.5MPa, and air speed is 7000h -1, H 2/ CO=1.3, reaction result sees Table 1.
Embodiment 7
Ammonium molybdate ((NH 4) 6Mo 7O 2424H 2O) 13.6g and concentration are 22% ammonium sulfide ((NH 4) 2S) solution 120ml 60 ℃ and stir under reaction one hour, add the dense acetic acid (CH of 50ml 3COOH) and deionized water, partly precipitated is dissolved fully, be mixed with 0.8M ammonium thiomolybdate solution.Take by weighing nickel acetate (Ni (CH 3COO) 24H 2O) 3.2g, manganese acetate (Mn (CH 3COO) 24H 2O) 1.7g is dissolved in the 150ml deionized water jointly, this solution and ammonium thiomolybdate solution and 300ml concentration be 30% acetum 60 ℃, stir under reaction, generate black precipitate.Washing, filtration, 120 ℃ of following vacuum drying obtain molybdenum base sediment.The citric acid that takes by weighing 2.3g ferrous sulfide and same quality fully mixes; under nitrogen protection, rise to 450 ℃; constant temperature calcining 2 hours; be cooled to room temperature; fully mix to be placed on 2.9g potassium hydroxide and molybdenum base sediment and be warming up to 500 ℃ under the tube furnace nitrogen protection; constant temperature 2 hours obtains black powder after the cooling.Add 0.5g graphite compression molding, obtain catalyst 7#, its metallic element weight ratio is: Mo:Ni:Fe:Mn:K:S: graphite=1:0.10:0.20:0.006:0.27:0.47:0.25.The evaluating catalyst condition: reaction temperature is 320 ℃, and pressure is 9.5MPa, and air speed is 8000h -1, H 2/ CO=1.2, reaction result sees Table 1.
Table 1 embodiment reaction result
Figure C200410092427D00091

Claims (11)

1. catalyst for preparing low-carbon mixed alcohol by synthetic gas is characterized in that:
Catalyst weight percentage consists of: Mo:20-40%, Ni:4-10%, Mn:0.1-1.0%, K:5-15%, Fe:5-10%, S:20-40%, adhesive: 10-20%; Prepare by following method: (1) preparation ammonium thiomolybdate solution
Ammonium sulfide solution is heated to 40-80 ℃, add ammonium molybdate and stir, add after 10-20 minute and can make solution be neutralized to neutral dense acetic acid, and through 5-10 hour the thermal agitation that adds, the cooling back adds deionized water, gets the ammonium thiomolybdate solution A after making it to dissolve fully;
(2) preparation molybdenum nickel manganese precipitation
Elder generation adds the 20-50wt% acetum toward a container, ammonium thiomolybdate solution A and the drip of preparation in nickel and manganese salt solution and (1) is gone into wherein, and be heated to 40-60 ℃ of stirring 1-10 hour;
(3) filter the also middle sediment of washing step (2), 60-150 ℃ of oven dry down, obtain molybdenum nickel manganese polysulfide B then;
(4) with molysite with etc. the weight citric acid fully mix, under inert atmosphere protection, be warmed up to 300-500 ℃, constant temperature cooled off after 1-3 hours, obtained molysite C;
(5) evenly mixed, the grinding of molybdenum nickel manganese polysulfide B and sylvite or potassium hydroxide and molysite C fed inertia protection gas at 350-650 ℃ of following roasting 0.5-3.0 hour, obtained molybdenum nickel manganese potassium sulphur compound powder D;
(6) add adhesive among the molybdenum nickel manganese potassium sulphur compound powder D and evenly mix compressing tablet, moulding then; Wherein the addition between each material is formed adding by catalyst weight percentage.
2, a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas as claimed in claim 1 is characterized in that described adhesive is bentonite or graphite.
3, the preparation method of a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas as claimed in claim 1 or 2 is characterized in that comprising the steps:
(1) preparation ammonium thiomolybdate solution
Ammonium sulfide solution is heated to 40-80 ℃, add ammonium molybdate and stir, add after 10-20 minute and can make solution be neutralized to neutral dense acetic acid, and through 5-10 hour the thermal agitation that adds, the cooling back adds deionized water, gets the ammonium thiomolybdate solution A after making it to dissolve fully;
(2) preparation molybdenum nickel manganese precipitation
Elder generation adds the 20-50wt% acetum toward a container, ammonium thiomolybdate solution A and the drip of preparation in nickel and manganese salt solution and (1) is gone into wherein, and be heated to 40-60 ℃ of stirring 1-10 hour;
(3) sediment and in the washing step (2) 60-150 ℃ of down oven dry, obtains molybdenum nickel manganese polysulfide B then;
(4) with molysite with etc. the weight citric acid fully mix, under inert atmosphere protection, be warmed up to 300-500 ℃, constant temperature cooled off after 1-3 hours, obtained molysite C;
(5) evenly mixed, the grinding of molybdenum nickel manganese polysulfide B and sylvite or potassium hydroxide and molysite C fed inertia protection gas at 350-650 ℃ of following roasting 0.5-3.0 hour, obtained molybdenum nickel manganese potassium sulphur compound powder D;
(6) add adhesive among the molybdenum nickel manganese potassium sulphur compound powder D and evenly mix compressing tablet, moulding then; Wherein the addition between each material is formed adding by catalyst weight percentage.
4, the preparation method of a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas as claimed in claim 3 is characterized in that described step (2) can also obtain different sediments with nickel salt and manganese reactant salt respectively with ammonium thiomolybdate solution earlier, mixes oven dry then.
5,, it is characterized in that the concentration range of ammonium thiomolybdate solution in the described step (1) is 0.2-2M as the preparation method of claim 3 or 4 described a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas.
6,, it is characterized in that described nickel and manganese salt are acetate or oxalates as the preparation method of claim 3 or 4 described a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas.
7,, it is characterized in that described step (3) washing washs with deionized water as the preparation method of claim 3 or 4 described a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas.
8,, it is characterized in that the sylvite that adds in the described step (5) is potash as the preparation method of claim 3 or 4 described a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas.
9,, it is characterized in that the molysite that adds in the described step (4) is a ferrous sulfide as the preparation method of claim 3 or 4 described a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas.
10,, it is characterized in that described inertia protection gas is nitrogen or argon gas as the preparation method of claim 3 or 4 described a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas.
11, the application process of a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas as claimed in claim 1 or 2 is characterized in that reaction temperature is 290-350 ℃, and pressure is 8.0-9.5MPa, and air speed is 6000-8000h -1, H 2/ CO=1.0-1.8.
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CN105668628B (en) * 2016-03-01 2017-04-26 中国海洋石油总公司 Preparation method of ATTM (Ammonium Tetrathiomolybdate)

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