CN104437534A - Catalyst for producing low-carbon mixed alcohol co-produced gasoline fraction from synthesis gas as well as preparation method and application of catalyst - Google Patents
Catalyst for producing low-carbon mixed alcohol co-produced gasoline fraction from synthesis gas as well as preparation method and application of catalyst Download PDFInfo
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Abstract
The invention provides a catalyst for producing a low-carbon mixed alcohol co-produced gasoline fraction from synthesis gas. The catalyst is prepared from the following components in percentage by weight: 18%-36% of Cu, 20%-28% of Fe, 10%-24% of Mn, 13%-33% of Zn, 1%-10% of Zr and 1%-10% of Co. The catalyst has the advantages of low cost, good stability, long service life and high selectivity.
Description
Technical field
The invention belongs to a kind of Catalysts and its preparation method by jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas and application.
Background technology
Along with improving constantly of the day by day exhausted of petroleum resources and mankind's environmental consciousness, the alternative fuel of seeking novel clean becomes an important energy exploitation and application subject under discussion.In view of the endowment of resources feature of China's " rich coal, oil-poor, weak breath ", coal is converted into cleaning liquid fluid fuel and chemicals at replacement oil, will produce the application prospect that efficient alternative fuel aspect is useful.
The MAS (C1 ~ C5 mixed alcohol) of preparation by coal based synthetic gas can as the raw material of fuel additive and some chemical products, even directly uses as clean fuel.There is between MAS and gasoline good intersolubility, effectively can improve explosion-proof, shockproof properties and the octane number of gasoline.Therefore, development of new catalyst, while preparing low-carbon mixed alcohol by synthetic gas, coproduction gasoline not only can reduce the dependence to petroleum resources greatly, and has important practical significance to the clean efficiency utilization of coal/natural gas resource.Comparatively extensive by the research of the direct synthesis of low-carbon alcohol of synthesis gas, the catalyst system formed mainly contains following four kinds:
(1) modified methanol synthetic catalyst (Cu/ZnO/Al
2o
3, ZnO/Cr
2o
3): this catalyst adds appropriate alkali metal or Modified With Alkali-earth Compounds by methanol synthesis catalyst and obtains, more typical patent has EP-0034338-A2 people such as () C.E.Hofstadt and United States Patent (USP) 4513100 (Snam company subsidizes, and invention people is the people such as Fattore).Although this type of catalyst activity is higher, in product, isobutanol content is high, but shortcoming is that (pressure is 14-20MPa to severe reaction conditions, temperature is 350-450 DEG C), higher alcohol selective low (being generally less than 35%), water content high (being generally 30-50%) in product; (2) Rh catalyst based (as US 4014913 and 4096164): after adding one to two kinds of transition metal or metal oxide auxiliary agent in support type Rh catalyst, have higher activity and selectivity, particularly to C to higher alcohols synthesis
2 +alcohol selective higher, product is based on ethanol.But Rh compound is expensive, catalyst is easily by CO
2poison, its activity and selectivity does not generally reach industrial requirement.(3) sulfur resistive MoS
2catalyst: being worth mentioning most is the molybdenum system sulfide catalyst (main patent is shown in the US patent4882360 of the people such as Stevens) that DOW company of the U.S. develops, this catalyst system and catalyzing not only has resistance to SO_2, product is moisture few, and higher alcohol content is higher, reach 30-70%, wherein mainly ethanol and normal propyl alcohol.The subject matter that this catalyst exists is that auxiliary element wherein very easily and between carbon monoxide forms carbonyls, causes the loss of auxiliary element, affects the activity of catalyst and selective, causes catalyst stability and life-span to be restricted.(4) Cu-Co catalyst: France Petroleum Institute (IFP) developed in the first Cu-Co co-precipitation low-carbon alcohol catalyst, only within 1985, just obtain four catalyst patent (US Patent 4122110,4291126 and GB Patent 2118061,2158730), the product of this catalyst synthesis is mainly C
1-C
6straight chain n-alkanol, accessory substance is mainly C
1-C
6aliphatic hydrocarbon, reaction condition gentleness (similar to low pressure methanol synthesis catalyst).The shortcoming of this catalyst is less stable.
At present, also relatively less for the catalyst research by jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas both at home and abroad.Chinese patent CN 1736594A reports the Catalysts and its preparation method of a kind of cobalt and palladium zinc supported picotite, and this catalyst can selectively make Synthetic holography be MAS and liquid alkane mixture.This catalyst adopts simple infusion process to prepare, but catalyst activity component is cobalt and palladium, expensive, causes the extensive use of catalyst to be restricted.
Summary of the invention
The object of this invention is to provide a kind of cost low, good stability, the life-span is long, under mild reaction conditions high selectivity by the method for preparing catalyst of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas and application.
Super absorbent resin (Super Absorbent Resin is called for short SAR) is also referred to as super strength water absorbent, superabsorbency resin, high water absorbency polymer etc.It contains strongly hydrophilic group (-OH ,-COOH ,-CONH
2,-SO
3h etc.) and have certain degree of cross linking, occurring swelling after contacting with water in the short time, and form both water insoluble gels being also insoluble to organic solvent after water suction, is a kind of novel functional high molecule material.
The object of the present invention is achieved like this, using super absorbent resin (SAR) as skeleton, Fe, Cu base inorganic salt solution is impregnated in SAR framework material, then precipitates, calcine shaping.And introduce the VIII element with stronger carbochain growing ability in catalyst promoter, and transition metal, alkali metal, alkaline-earth metal or rare earth metal, thus improve the activity of CO hydrogenation reaction, improve C
2 +alcohol and C
4 +hydrocarbon selective, and suppress CO simultaneously
2with the generation of the accessory substances such as methane.
Catalyst weight percent of the present invention consists of: Cu:18-36%, Fe:20-28%, Mn:10-24%, Zn:13-33%, Zr:1-10%, Co:1-10%.
The preparation method of catalyst provided by the invention comprises the following steps:
Under temperature is 20-90 DEG C of condition, now super absorbent resin is added in distilled water, be made into 0.1wt% ~ 10wt% Matrix Solution, under 15-30r/min stir speed (S.S.), by catalyst form metal nitrate be dissolved in Matrix Solution mix formed nitrate concentration be the mixed solution of 30wt% ~ 60wt%, and be the ammonia spirit of 30wt% or soluble carbonate salt with concentration and stream precipitates, stir speed (S.S.) during precipitation controls at 30-45r/min, precipitation temperature is 40-80 DEG C, keep pH value of solution=6-10, aging 3-5h after precipitation, precipitate through distilled water washing to neutrality.Wet cake after 80-120 DEG C of drying under 350-500 DEG C of air atmosphere roasting 6h, be crushed to 40-60 order.
SAR is super absorbent resin, comprises polyvinyl alcohol type, polyacrylie-type, polyacrylamide and and poly-cellulose type four class.Polyvinyl alcohol is the same with the polysaccharide such as starch, cellulose, is the macromolecular compound containing great amount of hydroxy group; Polyacrylic is high hydroscopic resin acrylic acid or Acrylates monomer being carried out being polymerized, being cross-linked under crosslinking agent effect.With the polyelectrolyte of ionization property group (-COONa), and there is slight cross-linked structure macromolecule; Polyacrylamide is for being the non-ionic polyalcohol with hydrophilic radical (-CONH2).Adopt acrylamide, Methacrylamide etc. as monomer through polymerization synthesizing high-hydroscopicity resin; Poly-cellulose type is skeleton based on cellulose, by a kind of super absorbent polymer formed with other monomer-grafted copolymerization.
SAR is polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, fat acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM), acrylic acid-copolymer-maleic anhydride high hydroscopic resin P (AA/MA), one or more in cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin.
Soluble carbonate salt as above is more particularly sodium carbonate or potash etc.
The application conditions of catalyst of the present invention is:
Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h
-1, H
2/ CO (mole)=0.5-3.0.
Reaction temperature is 210-280 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h
-1, H
2/ CO (mole)=0.5-3.0.
Carry out the synthesis of low-carbon alcohols with catalyst of the present invention, CO conversion ratio 15-45%, total alcohol is selective is 35-65%, total hydrocarbon-selective 30-45%, CO
2selective 9-20%.Total alcohol space-time yield is 0.15-0.45g/h.mL.cat; Water in products content is 25-40%; C
2 +alcohol content is 40-60%, C
4 +hydrocarbon is shared percentage composition 55-70% in total hydrocarbon.
Tool of the present invention has the following advantages:
1, preparation method is simple, be easy to operation, and catalyst reaction performance reproducibility is than good.
2, the present invention is due to the stable pore passage structure by high water molecules (SAR), and catalyst components distribution is relatively more even, and there is strong interaction between each component, sedimentation effect is good, and anti-sintering property is relatively good, and cost is low, good stability, the life-span is long.
3, catalyst of the present invention is in reduction and course of reaction, does not need to add CO
2gas, greatly reduces operating cost.
Detailed description of the invention
Embodiment 1
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, be made into wt0.1% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:0.1:0.2 be dissolved in the nitrate mixed solution forming wt30% in the middle of this solution.With 30wt% sodium carbonate liquor parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=6.0MPa, GHSV=8000h
-1, H
2/ CO (mole)=2.0.Reaction result is in table 1.
Embodiment 2
First by PAA high hydroscopic resin PAA, be made into wt0.15% Polymer Solution with distilled water, by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=0.5:1.0:0.5:1.0:0.1:0.2 be dissolved in the nitrate mixed solution forming wt45% in the middle of distilled water.With 30wt% sodium carbonate liquor parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:15.9%, Fe:27.8%, Mn:13.7%, Zn:32.3%, Zr:4.5%, Co:5.8%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=6.0MPa, GHSV=8000h
-1, H
2/ CO (mole)=2.0.Reaction result is in table 1.
Embodiment 3
First just acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM), be made into wt0.2% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.5:1.0:0.5:1:0.1:0.2 form the nitrate mixed solution of wt50% in the middle of being dissolved in Polymer Solution.With 30wt% sodium carbonate liquor parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes.Cu:36.0％,Fe:21.2％,Mn:10.5％,Zn:24.5％,Zr:3.4％,Co:4.4％。Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=6.0MPa, GHSV=8000h
-1, H
2/ CO (mole)=2.0.Reaction result is in table 1.
Embodiment 4
First by acrylic acid-copolymer-maleic anhydride high hydroscopic resin P (AA/MA), be made into wt0.25% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:1.0:1:0.2:0.2 be dissolved in the nitrate mixed solution forming wt30% in the middle of Polymer Solution.With 20wt% solution of potassium carbonate parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:23.7%, Fe:20.7%, Mn:20.0%, Zn:24.1%, Zr:6.7%, Co:4.4%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 5
First by cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin, be made into wt0.3% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:1.0:1:0.3:0.2 be dissolved in the nitrate mixed solution forming wt60% concentration in the middle of Polymer Solution.With 20wt% solution of potassium carbonate parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:22.9%, Fe:20.1%, Mn:20.0%, Zn:23.3%, Zr:9.8%, Co:4.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 6
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and PAA high hydroscopic resin PAA in 1:1 ratio, be made into wt0.35% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:1.0:0.1:0.3 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.With 20wt% solution of potassium carbonate parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:24.0%, Fe:21.0%, Mn:20.6%, Zn:24.4%, Zr:3.4%, Co:6.6%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 7
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) in 1:1 ratio, be made into wt0.4% Polymer Solution with distilled water, by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:1.0:0.5:0.1:0.4 be dissolved in the nitrate mixed solution forming wt55% concentration in the middle of Polymer Solution.With 20%wt solution of potassium carbonate parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:26.6%, Fe:23.3%, Mn:22.9%, Zn:13.5%, Zr:3.9%, Co:9.8%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=6.0MPa, GHSV=6000h
-1, H
2/ CO=2.0 (mole), reaction result is in table 1.
Embodiment 8
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, be made into wt0.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.With 20wt% solution of potassium carbonate parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=10MPa, GHSV=6000h
-1, H
2/ CO=2.0 (mole), reaction result is in table 1.
Embodiment 9
First by cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin, be made into wt0.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt45% concentration in the middle of Polymer Solution.With 20wt% solution of potassium carbonate parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=4000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 10
Will first by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, be made into wt0.6% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.With 20wt% solution of potassium carbonate parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=8000h
-1, H
2/ CO=2.0 (mole), reaction result is in table 1.
Embodiment 11
First by acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM), be made into wt0.7% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt30% concentration in the middle of Polymer Solution.With 20wt% Lithium carbonate solution parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO=2.0 (mole), reaction result is in table 1.Embodiment 12
First by acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM), be made into 0.8wt% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt40% concentration in the middle of Polymer Solution.With 20wt% Lithium carbonate solution parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO=2.0 (mole), reaction result is in table 1.
Embodiment 13
First by PAA high hydroscopic resin PAA, be made into wt0.9% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=0.5:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt60% concentration in the middle of Polymer Solution.With 20wt% Lithium carbonate solution parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO=2.0 (mole), reaction result is in table 1.
Embodiment 14
First by PAA high hydroscopic resin PAA, be made into wt1.0% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=0.5:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt45% concentration in the middle of Polymer Solution.With 30wt% cesium carbonate solution parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO=2.0 (mole), reaction result is in table 1.
Embodiment 15
First by PAA high hydroscopic resin PAA, be made into wt1.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.With 30wt% cesium carbonate solution parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality, wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO=2.0 (mole), reaction result is in table 1.
Embodiment 16
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and PAA high hydroscopic resin PAA in 1:1 ratio, be made into wt2.0% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt60% concentration in the middle of Polymer Solution.With 30wt% cesium carbonate solution parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.Catalyst each element composition Cu:15.9%, Fe:27.7%, Mn:13.7%, Zn:32.2%, Zr:4.5%, Co:5.8%, Cs:0.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 17
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and PAA high hydroscopic resin PAA in 1:1 ratio, be made into wt2.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:0.1:0.2 be dissolved in the nitrate mixed solution forming wt55% concentration in the middle of Polymer Solution.With 20wt% solution of potassium carbonate parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality, wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 18
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and PAA high hydroscopic resin PAA in 1:1 ratio, be made into wt3.0% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:0.1:0.2 be dissolved in the nitrate mixed solution forming wt35% concentration in the middle of Polymer Solution.With 20wt% solution of potassium carbonate parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality, wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 19
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) in 1:1 ratio, be made into wt3.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:0.1:0.2 be dissolved in the nitrate mixed solution forming wt40% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 20
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) in 1:1 ratio, be made into wt4.0% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 21
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) in 1:1 ratio, be made into wt4.0% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt55% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 22
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) in 1:1 ratio, be made into wt4.4% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:0.1:0.2 be dissolved in the nitrate mixed solution forming wt60% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 23
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA and acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) are mixed in 1:1:1 ratio, be made into wt4.8% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt40% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 24
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA and acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) are mixed in 1:1:1 ratio, be made into wt5.0% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 25
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA and acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) are mixed in 1:1:1 ratio, be made into wt5.2% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1:1:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt55% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 26
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA and acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) are mixed in 1:1:1 ratio, be made into wt5.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt60% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 27
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt5.7% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt45% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 28
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt6.0% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 29
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt6.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt55% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 30
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt7.2% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt60% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 31
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt7.4% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 32
First PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1 ratio, be made into wt7.4% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt30% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 33
First PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1 ratio, be made into wt7.7% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt55% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 34
First PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1 ratio, be made into wt7.7% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt40% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 35
First PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1 ratio, be made into wt8.0% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt60% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 36
First PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin mix in 1:1:1 ratio, wt8.0% Polymer Solution will be made into distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt60% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 37
First PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1 ratio, be made into wt8.3% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 38
First PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1 ratio, be made into wt8.3% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt55% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.Each element composition Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2% in catalyst.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 39
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt8.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt35% concentration in the middle of Polymer Solution.With 35wt% ammonia spirit parallel-flow precipitation at 70 DEG C, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 40
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt8.7% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt45% concentration in the middle of Polymer Solution.A certain amount of 35wt% ammonia spirit is mixed to form the homogeneous alkaline solution of concentration, and by above-mentioned metal-nitrate solutions and alkaline solution at 70 DEG C of parallel-flow precipitations, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 41
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt9.0% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.A certain amount of 35wt% ammonia spirit is mixed to form the homogeneous alkaline solution of concentration, and by above-mentioned metal-nitrate solutions and alkaline solution at 70 DEG C of parallel-flow precipitations, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 42
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt9.2% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt55% concentration in the middle of Polymer Solution.A certain amount of 35wt% ammonia spirit is mixed to form the homogeneous alkaline solution of concentration, and by above-mentioned metal-nitrate solutions and alkaline solution at 70 DEG C of parallel-flow precipitations, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 43
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt9.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.A certain amount of 35wt% ammonia spirit is mixed to form the homogeneous alkaline solution of concentration, and by above-mentioned metal-nitrate solutions and alkaline solution at 70 DEG C of parallel-flow precipitations, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 44
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt9.5% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.A certain amount of 35wt% ammonia spirit is mixed to form the homogeneous alkaline solution of concentration, and by above-mentioned metal-nitrate solutions and alkaline solution at 70 DEG C of parallel-flow precipitations, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Embodiment 45
First polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resin are mixed in 1:1:1:1 ratio, be made into wt10% Polymer Solution with distilled water, after by following metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 be dissolved in the nitrate mixed solution forming wt50% concentration in the middle of Polymer Solution.A certain amount of 35wt% ammonia spirit is mixed to form the homogeneous alkaline solution of concentration, and by above-mentioned metal-nitrate solutions and alkaline solution at 70 DEG C of parallel-flow precipitations, precipitation process needs fully to stir, and keeps pH=8-9.Precipitate through distilled water washing to neutrality.Wet cake after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst.In catalyst, each element set becomes Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is as follows: T=260 DEG C, P=4.0MPa, GHSV=6000h
-1, H
2/ CO (mole)=2.0, reaction result is in table 1.
Table 1 embodiment reaction result
Claims (5)
1. a catalyst for jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas, is characterized in that catalyst weight percent consists of: Cu:18-36%, Fe:20-28%, Mn:10-24%, Zn:13-33%, Zr:1-10%, Co:1-10%.
2. the preparation method of the catalyst of a kind of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas as claimed in claim 1, is characterized in that comprising the following steps:
Under temperature is 20-90 DEG C of condition, now super absorbent resin is added in distilled water, be made into 0.1wt% ~ 10wt% Matrix Solution, under 15-30r/min stir speed (S.S.), the metal nitrate that catalyst forms is dissolved in Matrix Solution mix and forms the mixed solution that nitrate concentration is 30wt% ~ 60wt %, and be the ammonia spirit of 30wt% or soluble carbonate salt with concentration and stream precipitates, stir speed (S.S.) during precipitation controls at 30-45r/min, precipitation temperature is 40-80 DEG C, keep pH value of solution=6-10, aging 3-5h after precipitation, precipitate through distilled water washing to neutrality,
Wet cake after 80-120 DEG C of drying under 350-500 DEG C of air atmosphere roasting 6h, be crushed to 40-60 order.
3. the preparation method of the catalyst of a kind of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas as claimed in claim 2, it is characterized in that super absorbent resin is polyvinyl alcohol type high hydroscopic resin, PAA high hydroscopic resin, fat acrylic acid-acrylamide copolymer high hydroscopic resin, acrylic acid-copolymer-maleic anhydride high hydroscopic resin, one or more in cellulose family sodium carboxymethylcellulose high hydroscopic resin.
4. the preparation method of the catalyst of a kind of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas as claimed in claim 2, is characterized in that described soluble carbonate salt is sodium carbonate or potash.
5. the application of the catalyst of a kind of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas as claimed in claim 1, is characterized in that comprising following condition:
Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h
-1, H
2/ CO mole is 0.5-3.0;
Reaction temperature is 210-280 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h
-1, H
2/ CO mole is 0.5-3.0.
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| CN105289677A (en) * | 2015-11-11 | 2016-02-03 | 中国科学院山西煤炭化学研究所 | SiC supported catalyst for preparing low-carbon mixed alcohol by utilizing synthesis gas, preparation method and application |
| CN110975934A (en) * | 2019-11-28 | 2020-04-10 | 中国科学院山西煤炭化学研究所 | Cation exchange resin-based catalyst for preparing low-carbon mixed alcohol from synthesis gas, preparation method and application thereof |
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| CN110975934A (en) * | 2019-11-28 | 2020-04-10 | 中国科学院山西煤炭化学研究所 | Cation exchange resin-based catalyst for preparing low-carbon mixed alcohol from synthesis gas, preparation method and application thereof |
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