CN104437534B - The catalyst and preparation method of a kind of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas and application - Google Patents
The catalyst and preparation method of a kind of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas and application Download PDFInfo
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- CN104437534B CN104437534B CN201410638186.3A CN201410638186A CN104437534B CN 104437534 B CN104437534 B CN 104437534B CN 201410638186 A CN201410638186 A CN 201410638186A CN 104437534 B CN104437534 B CN 104437534B
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Abstract
A kind of catalyst weight percent of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas is constituted：Cu:18‑36%,Fe:20‑28%,Mn:10‑24%,Zn:13‑33%,Zr:1‑10%,Co:1‑10%.The present invention is low with cost, and stability is good, long lifespan, the high advantage of selectivity.
Description
Technical field
The invention belongs to it is a kind of by catalyst of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas and preparation method thereof and
Using.
Background technology
With the continuous improvement of the increasingly depleted and mankind's environmental consciousness of petroleum resources, seek the alternative fuel of novel clean
As an important energy exploitation and application subject under discussion.In view of the endowment of resources feature of China's " rich coal, oil-poor, few gas ", turns coal
The beneficial application prospect of efficient alternative fuel aspect will be produced in substitution oil by turning to clean liquid fuel and chemicals.
The low carbon mixed alcohol (C1~C5 mixed alcohols) of the preparation by coal based synthetic gas can be used as fuel additive and certain
The raw materials of a little chemical products, or even used directly as clean fuel.There is well mutual between low carbon mixed alcohol and gasoline
Dissolubility, can be effectively improved the explosion-proof of gasoline, shockproof properties and octane number.Therefore, new catalyst is developed, it is low in synthesis gas system
Coproduction gasoline can not only substantially reduce the dependence to petroleum resources while carbon mixed alcohol, and to coal/natural gas resource
Clean efficiently utilize has important practical significance.Research by the direct synthesis of low-carbon alcohol of synthesis gas is relatively broad, is formed
Catalyst system mainly has following four：
(1) modified methanol synthetic catalyst (Cu/ZnO/Al2O3,ZnO/Cr2O3)：This catalyst is by methanol synthesis catalyst
Add appropriate alkali metal or Modified With Alkali-earth Compounds and obtain, more typical patent has EP-0034338-A2
(C.E.Hofstadt et al.) and United States Patent (USP) 4513100 (Snam companies subsidize, inventor Fattore et al.).It is such to urge
Although agent activity is higher, isobutyl alcohol content is high in product, has the disadvantage that (pressure is 14-20MPa, temperature to severe reaction conditions
For 350-450 DEG C), higher alcohol is selectively low (being generally less than 35%), and water content is high (generally 30-50%) in product；(2)
Rh bases catalyst (such as US 4014913 and 4096164)：One to two kinds of transition metal or metal are added in support type Rh catalyst
After oxides additive, there is higher activity and selectivity to higher alcohols synthesis, particularly to C2 +The selectivity of alcohol is higher, product with
Based on ethanol.But Rh compounds are expensive, and catalyst is easily by CO2Poison, its activity and selectivity is typically up to raw less than industry
The requirement of production.(3) sulfur resistive MoS2Catalyst：Most be worth mentioning is that the molybdenum system sulfide catalyst of DOW companies of U.S. exploitation is (main
Patent is shown in Stevens et al. US patent 4882360), the catalyst system and catalyzing not only has resistance to SO_2, and product is aqueous few, and
And senior alcohol content is higher, up to 30-70%, wherein mainly ethanol and normal propyl alcohol.The subject matter that this catalyst is present is it
In auxiliary element carbonyls is easily formed between carbon monoxide, cause the loss of auxiliary element, influence catalyst
Activity and selectivity, cause catalyst stability and life-span to be restricted.(4) Cu-Co catalyst：France Petroleum Institute
(IFP) Cu-Co co-precipitation low-carbon alcohol catalysts are developed first, just obtain within only 1985 four catalyst patent (US
Patent 4122110,4291126 and GB Patent 2118061,2158730), the product of this catalyst synthesis is mainly
C1-C6Straight chain n-alkanol, accessory substance is mainly C1-C6Aliphatic hydrocarbon, reaction condition is gentle (with low pressure methanol synthesis catalyst phase
Like).The shortcoming of the catalyst is less stable.
At present, both at home and abroad for the catalyst research by jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas also relatively
It is few.Chinese patent CN 1736594A report catalyst of a kind of cobalt and palladium zinc supported picotite and preparation method thereof, and this is urged
Agent can selectively make synthesis gas be converted into low carbon mixed alcohol and liquid alkane mixture.The catalyst is using simple dipping
Method prepare, but catalyst activity component be cobalt and palladium, it is expensive, cause the extensive use of catalyst to be restricted.
The content of the invention
It is an object of the invention to provide a kind of cost is low, stability is good, long lifespan, under mild reaction conditions high selectivity
Method for preparing catalyst by jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas and application.
Super absorbent resin (Super Absorbent Resin abbreviation SAR) is also referred to as super strength water absorbent, super-strong moisture absorbing
Property resin, high water absorbency polymer etc..It contains strongly hydrophilic group (- OH ,-COOH ,-CONH2、-SO3H etc.) and have certain
The degree of cross linking, be swelled after being contacted with water in the short time, and formed after water suction and both water insoluble be also insoluble in organic solvent
Gel, be a kind of new functional high molecule material.
The object of the present invention is achieved like this, using super absorbent resin (SAR) as skeleton, by Fe, Cu base inorganic salts
Solution is impregnated into SAR framework materials, is then precipitated, is calcined shaping.And being introduced in catalyst promoter, there is stronger carbochain to increase
The VIII element of long ability, and transition metal, alkali metal, alkaline-earth metal or rare earth metal, so as to improve CO hydrogenation reactions
Activity, improve C2 +Alcohol and C4 +The selectivity of hydrocarbon, and suppress CO simultaneously2With the generation of the accessory substance such as methane.
Catalyst weight percent of the present invention is constituted：Cu:18-36%, Fe:20-28%, Mn:10-24%, Zn:13-
33%, Zr:1-10%, Co:1-10%.
The preparation method for the catalyst that the present invention is provided comprises the following steps：
Temperature be 20-90 DEG C under the conditions of, now will super absorbent resin add distilled water in, be made into 0.1wt%~
10wt% Matrix Solutions, under 15-30r/min stir speed (S.S.)s, the metal nitrate that catalyst is constituted is dissolved in Matrix Solution
It is well mixed to form the mixed solution that nitrate concentration is 30wt%~60wt%, and with concentration for 30wt% ammonia spirit or
Soluble carbonate salt cocurrent is precipitated, and stir speed (S.S.) control during precipitation is in 30-45r/min, and precipitation temperature is 40-80 DEG C,
Aging 3-5h after pH value of solution=6-10, precipitation is kept, precipitation is through distilling water washing untill neutrality.Wet cake is dry through 80-120 DEG C
6h is calcined under 350-500 DEG C of air atmosphere after dry, 40-60 mesh is crushed to.
SAR is super absorbent resin, including polyvinyl alcohol type, polyacrylie-type, polyacrylamide and and poly- cellulose
The class of type four.It is the high-molecular compound containing great amount of hydroxy group as the polysaccharides such as polyvinyl alcohol and starch, cellulose；Poly- third
Olefin(e) acid class is the high hydroscopic resin that acrylic acid or Acrylates monomer are polymerize, are crosslinked under crosslinking agent effect.
Polyelectrolyte with ionization property group (- COONa), and with slight cross-linked structure macromolecule；Polyacrylamide
To be the non-ionic polyalcohol with hydrophilic radical (- CONH2).Monomer is used as using acrylamide, Methacrylamide etc.
Aggregated and synthesizing high-hydroscopicity resin；Poly- cellulose type be based on cellulose be skeleton, by with other monomer graft copolymerizations
A kind of super absorbent polymer formed.
SAR is polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA, fat propylene
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 resins.
Soluble carbonate salt as described above is more specifically sodium carbonate or potassium carbonate etc..
The application conditions of catalyst of the present invention are：
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 temperature is 210-280 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1,H2/ CO (mole)
=0.5-3.0.
The synthesis of low-carbon alcohols, CO conversion ratios 15-45% are carried out with catalyst of the present invention, total alcohol is selectively 35-65%, always
Hydrocarbon-selective 30-45%, CO2Selective 9-20%.Total alcohol space-time yield is 0.15-0.45g/h.mL.cat；Water in products contains
Measure as 25-40%；C2 +Alcohol content is 40-60%, C4 +Hydrocarbon shared percentage composition 55-70% in total hydrocarbon.
The invention has the advantages that：
1st, preparation method is simple, it is easy to operate, and catalyst reaction performance reproducibility is than good.
2nd, the present invention is due to the pore passage structure of the stabilization by high water absorption molecule (SAR), and catalyst components distribution is compared
Uniformly, and between each component there is strong interaction, sedimentation effect is good, and anti-sintering property is relatively good, and cost is low, and stability is good, the longevity
Life length.
3rd, catalyst of the invention is in reduction and course of reaction, it is not necessary to add CO2Gas, greatly reduces operating cost
With.
Embodiment
Embodiment 1
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, wt0.1% macromolecules are made into distilled water molten
Liquid, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:
0.1:0.2 is dissolved in the nitrate mixed solution that wt30% is formed among the solution.At 70 DEG C with 30wt% sodium carbonate liquors simultaneously
Stream precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is passed through
6h is calcined under 400 DEG C of air atmospheres after 120 DEG C of dryings, 40-60 mesh is crushed to, obtains catalyst.Each element group in catalyst
As 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, pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition is such as
Under：T=260 DEG C, P=6.0MPa, GHSV=8000h-1,H2/ CO (mole)=2.0.Reaction result is shown in Table 1.
Embodiment 2
First by PAA high hydroscopic resin PAA, wt0.15% Polymer Solutions are made into distilled water, by following metal
Atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=0.5:1.0:0.5:1.0:0.1:0.2 is dissolved in distillation
Wt45% nitrate mixed solution is formed among water.With 30wt% sodium carbonate liquor parallel-flow precipitations, precipitation process at 70 DEG C
It need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is after 120 DEG C of dryings 400
6h is calcined under DEG C air atmosphere, 40-60 mesh is crushed to, obtains catalyst.Each element composition is Cu in catalyst: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, 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,H2/ CO (mole)=2.0.Reaction result is shown in Table 1.
Embodiment 3
Acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) will be made into wt0.2% with distilled water high first
Molecular solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn：Zr:Co=1.5:1.0:
0.5:1:0.1:0.2 is dissolved in the nitrate mixed solution that wt50% is formed among in Polymer Solution.With 30wt% at 70 DEG C
Sodium carbonate liquor parallel-flow precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitate and be through distilling water washing to neutrality
Only.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Catalyst
Middle each element is constituted.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.Instead
Answer condition as follows：T=260 DEG C, P=6.0MPa, GHSV=8000h-1,H2/ CO (mole)=2.0.Reaction result is shown in Table 1.
Embodiment 4
First by acrylic acid-copolymer-maleic anhydride high hydroscopic resin P (AA/MA), wt0.25% is made into distilled water high
Molecular solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
1.0:1:0.2:0.2 is dissolved in the nitrate mixed solution that wt30% is formed among Polymer Solution.With 20wt% carbon at 70 DEG C
Sour potassium solution parallel-flow precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.
Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.In catalyst
Each element composition is Cu:23.7%, Fe:20.7%, Mn:20.0%, Zn:24.1%, Zr:6.7%, Co:4.4%.Reduction temperature
Spend for 210-300 DEG C, pressure is 4.0-12.0MPa, 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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 5
First by cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resins, wt0.3% is made into distilled water
Polymer Solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
1.0:1:0.3:0.2 is dissolved in the nitrate mixed solution that wt60% concentration is formed among Polymer Solution.At 70 DEG C with
20wt% solution of potassium carbonate parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing extremely
Untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.
Each element composition is Cu in catalyst: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,H2/ CO (mole)=2.0, reaction knot
Fruit is shown in Table 1.
Embodiment 6
Polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and PAA high hydroscopic resin PAA is pressed 1 first:1 ratio
Example, wt0.35% Polymer Solutions are made into distilled water, after by following metallic atom Cu in molar ratio in the form of nitrate:
Fe:Mn:Zn:Zr:Co=1.0:1.0:1.0:0.1:0.3 nitrate for being dissolved in formation wt50% concentration among Polymer Solution is mixed
Close solution.With 20wt% solution of potassium carbonate parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and keep pH=8-9.It is heavy
Form sediment through distilling water washing untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-
60 mesh, obtain catalyst.Each element composition is Cu in catalyst: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,H2/ CO (mole)
=2.0, reaction result is shown in Table 1.
Embodiment 7
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high water absorption
Resin P (AAAM) presses 1:1 ratio, wt0.4% Polymer Solutions are made into distilled water, by following metallic atom with the shape of nitrate
Formula Cu in molar ratio:Fe:Mn:Zn：Zr:Co=1.0:1.0:1.0:0.5:0.1:0.4 is dissolved in formation among Polymer Solution
The nitrate mixed solution of wt55% concentration.With 20%wt solution of potassium carbonate parallel-flow precipitations at 70 DEG C, precipitation process needs abundant
Stirring, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is after 120 DEG C of dryings in 400 DEG C of air
6h is calcined under atmosphere, 40-60 mesh is crushed to, obtains catalyst.Each element composition is Cu in catalyst: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, 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,H2/ CO=2.0 (mole), reaction result is shown in Table 1.
Embodiment 8
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, wt0.5% macromolecules are made into distilled water molten
Liquid, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:
0.1:0.2 is dissolved in the nitrate mixed solution that wt50% concentration is formed among Polymer Solution.With 20wt% carbonic acid at 70 DEG C
Potassium solution parallel-flow precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.It is wet
Filter cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.It is each in catalyst
Element composition is Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature
For 210-300 DEG C, pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.React bar
Part is as follows：T=260 DEG C, P=10MPa, GHSV=6000h-1,H2/ CO=2.0 (mole), reaction result is shown in Table 1.
Embodiment 9
First by cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resins, wt0.5% is made into distilled water
Polymer Solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
0.5:1:0.1:0.2 is dissolved in the nitrate mixed solution that wt45% concentration is formed among Polymer Solution.At 70 DEG C with
20wt% solution of potassium carbonate parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing extremely
Untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.
Each element composition is Cu in catalyst: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,H2/ CO (mole)=2.0, reaction knot
Fruit is shown in Table 1.
Embodiment 10
Wt0.6% macromolecules will be made into distilled water molten first by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA
Liquid, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:
0.1:0.2 is dissolved in the nitrate mixed solution that wt50% concentration is formed among Polymer Solution.With 20wt% carbonic acid at 70 DEG C
Potassium solution parallel-flow precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.It is wet
Filter cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.It is each in catalyst
Element composition is Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature
For 210-300 DEG C, pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.React bar
Part is as follows：T=260 DEG C, P=4.0MPa, GHSV=8000h-1,H2/ CO=2.0 (mole), reaction result is shown in Table 1.
Embodiment 11
First by acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM), wt0.7% high scores are made into distilled water
Sub- solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:
1:0.1:0.2 is dissolved in the nitrate mixed solution that wt30% concentration is formed among Polymer Solution.With 20wt% carbon at 70 DEG C
Sour lithium solution parallel-flow precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.
Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.In catalyst
Each element composition is Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature
Spend for 210-300 DEG C, pressure is 4.0-12.0MPa, 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,H2/ CO=2.0 (mole), reaction result is shown in Table 1.Implement
Example 12
First by acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM), 0.8wt% high scores are made into distilled water
Sub- solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:
1:0.1:0.2 is dissolved in the nitrate mixed solution that wt40% concentration is formed among Polymer Solution.With 20wt% carbon at 70 DEG C
Sour lithium solution parallel-flow precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.
Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.In catalyst
Each element composition is Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature
Spend for 210-300 DEG C, pressure is 4.0-12.0MPa, 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,H2/ CO=2.0 (mole), reaction result is shown in Table 1.
Embodiment 13
First by PAA high hydroscopic resin PAA, wt0.9% Polymer Solutions are made into distilled water, after by following gold
Belong to atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=0.5:1.0:0.5:1:0.1:0.2 is dissolved in high score
The nitrate mixed solution of wt60% concentration is formed among sub- solution.With 20wt% Lithium carbonate solution parallel-flow precipitations at 70 DEG C,
Precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is through 120 DEG C of dryings
6h is calcined under 400 DEG C of air atmospheres afterwards, 40-60 mesh is crushed to, obtains catalyst.Each element composition is Cu in catalyst:
27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, pressure
Power 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,H2/ CO=2.0 (mole), reaction result is shown in Table 1.
Embodiment 14
First by PAA high hydroscopic resin PAA, wt1.0% Polymer Solutions are made into distilled water, after by following gold
Belong to atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn：Zr:Co=0.5:1.0:0.5:1:0.1:0.2 is dissolved in high score
The nitrate mixed solution of wt45% concentration is formed among sub- solution.With 30wt% cesium carbonate solution parallel-flow precipitations at 70 DEG C,
Precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is through 120 DEG C of dryings
6h is calcined under 400 DEG C of air atmospheres afterwards, 40-60 mesh is crushed to, obtains catalyst.Each element composition is Cu in catalyst:
27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, pressure
Power 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,H2/ CO=2.0 (mole), reaction result is shown in Table 1.
Embodiment 15
First by PAA high hydroscopic resin PAA, wt1.5% Polymer Solutions are made into distilled water, after by following gold
Belong to atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in high score
The nitrate mixed solution of wt50% concentration is formed among sub- solution.With 30wt% cesium carbonate solution parallel-flow precipitations at 70 DEG C,
Precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality, and wet cake is through 120 DEG C of dryings
6h is calcined under 400 DEG C of air atmospheres afterwards, 40-60 mesh is crushed to, obtains catalyst.Each element composition is Cu in catalyst:
27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Reduction temperature is 210-300 DEG C, pressure
Power 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,H2/ CO=2.0 (mole), reaction result is shown in Table 1.
Embodiment 16
Polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and PAA high hydroscopic resin PAA is pressed 1 first:1 ratio
Example, wt2.0% Polymer Solutions are made into distilled water, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:
Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 nitrate for being dissolved in formation wt60% concentration among Polymer Solution is mixed
Close solution.With 30wt% cesium carbonate solution parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and keep pH=8-9.It is heavy
Form sediment through distilling water washing untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-
60 mesh, obtain catalyst.Catalyst each element constitutes 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,
H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 17
Polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and PAA high hydroscopic resin PAA is pressed 1 first:1 ratio
Example, wt2.5% Polymer Solutions are made into distilled water, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:
Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:0.1:0.2 is dissolved in the nitrate that wt55% concentration is formed among Polymer Solution
Mixed solution.With 20wt% solution of potassium carbonate parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and keep pH=8-9.
Precipitation is through distilling water washing untill neutrality, and wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to
40-60 mesh, obtains catalyst.Each element composition is Cu in catalyst: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,
H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 18
Polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and PAA high hydroscopic resin PAA is pressed 1 first:1 ratio
Example, wt3.0% Polymer Solutions are made into distilled water, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:
Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:0.1:0.2 is dissolved in the nitrate that wt35% concentration is formed among Polymer Solution
Mixed solution.With 20wt% solution of potassium carbonate parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and keep pH=8-9.
Precipitation is through distilling water washing untill neutrality, and wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to
40-60 mesh, obtains catalyst.Each element composition is Cu in catalyst: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,
H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 19
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high water absorption
Resin P (AAAM) presses 1:1 ratio, wt3.5% Polymer Solutions are made into distilled water, after by following metallic atom with nitrate
Form Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:0.1:0.2 is dissolved in formation among Polymer Solution
The nitrate mixed solution of wt40% concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be stirred fully
Mix, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is after 120 DEG C of dryings in 400 DEG C of air gas
6h is calcined under atmosphere, 40-60 mesh is crushed to, obtains catalyst.Each element composition is Cu in catalyst: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,
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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 20
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high water absorption
Resin P (AAAM) presses 1:1 ratio, wt4.0% Polymer Solutions are made into distilled water, after by following metallic atom with nitrate
Form Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation among Polymer Solution
The nitrate mixed solution of wt50% concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be stirred fully
Mix, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is after 120 DEG C of dryings in 400 DEG C of air gas
6h is calcined under atmosphere, 40-60 mesh is crushed to, obtains catalyst.Each element composition is Cu in catalyst: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,
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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 21
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high water absorption
Resin P (AAAM) presses 1:1 ratio, wt4.0% Polymer Solutions are made into distilled water, after by following metallic atom with nitrate
Form Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation among Polymer Solution
The nitrate mixed solution of wt55% concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be stirred fully
Mix, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is after 120 DEG C of dryings in 400 DEG C of air gas
6h is calcined under atmosphere, 40-60 mesh is crushed to, obtains catalyst.Each element composition is Cu in catalyst: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,
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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 22
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA and acrylic acid-acrylamide copolymer high water absorption
Resin P (AAAM) presses 1:1 ratio, wt4.4% Polymer Solutions are made into distilled water, after by following metallic atom with nitrate
Form Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1.0:0.1:0.2 is dissolved in formation among Polymer Solution
The nitrate mixed solution of wt60% concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be stirred fully
Mix, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is after 120 DEG C of dryings in 400 DEG C of air gas
6h is calcined under atmosphere, 40-60 mesh is crushed to, obtains catalyst.Each element composition is Cu in catalyst: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,
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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 23
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA and propylene
Acid-acrylamide copolymer high hydroscopic resin P (AAAM) presses 1:1:1 ratio is mixed, and wt4.8% macromolecules is made into distilled water molten
Liquid, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:
0.1:0.2 is dissolved in the nitrate mixed solution that wt40% concentration is formed among Polymer Solution.With 35wt% ammoniacal liquor at 70 DEG C
Solution parallel-flow precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet filter
Cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Each member in catalyst
Element composition is 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, pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition
It is as follows：T=260 DEG C, P=4.0MPa, GHSV=6000h-1,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 24
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA and propylene
Acid-acrylamide copolymer high hydroscopic resin P (AAAM) presses 1:1:1 ratio is mixed, and wt5.0% macromolecules is made into distilled water molten
Liquid, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:
0.1:0.2 is dissolved in the nitrate mixed solution that wt50% concentration is formed among Polymer Solution.With 35wt% ammoniacal liquor at 70 DEG C
Solution parallel-flow precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet filter
Cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Each member in catalyst
Element composition is 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, pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition
It is as follows：T=260 DEG C, P=4.0MPa, GHSV=6000h-1,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 25
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA and propylene
Acid-acrylamide copolymer high hydroscopic resin P (AAAM) presses 1:1:1 ratio is mixed, and wt5.2% macromolecules is made into distilled water molten
Liquid, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1:1:0.5:1:0.1:0.2
It is dissolved in the nitrate mixed solution that wt55% concentration is formed among Polymer Solution.With 35wt% ammonia spirit cocurrents at 70 DEG C
Precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is through 120
DEG C dry after be calcined 6h under 400 DEG C of air atmospheres, be crushed to 40-60 mesh, obtain catalyst.Each element composition is in catalyst
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, 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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 26
First by polyvinyl alcohol type high hydroscopic resin P (AA-SSS)/PVA, PAA high hydroscopic resin PAA and propylene
Acid-acrylamide copolymer high hydroscopic resin P (AAAM) presses 1:1:1 ratio is mixed, and wt5.5% macromolecules is made into distilled water molten
Liquid, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:
0.1:0.2 is dissolved in the nitrate mixed solution that wt60% concentration is formed among Polymer Solution.With 35wt% ammoniacal liquor at 70 DEG C
Solution parallel-flow precipitation, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet filter
Cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Each member in catalyst
Element composition is 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, pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/CO (mole)=0.5-3.0.Reaction condition
It is as follows：T=260 DEG C, P=4.0MPa, GHSV=6000h-1,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 27
First by 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 resins are pressed
1:1:1:1 ratio mix, wt5.7% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt45% among Polymer Solution
The nitrate mixed solution of concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and be protected
Hold pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is calcined after being dried through 120 DEG C under 400 DEG C of air atmospheres
6h, is crushed to 40-60 mesh, obtains catalyst.Each element composition is Cu in catalyst: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, air speed
For 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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 28
First by 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 resins are pressed
1:1:1:1 ratio mix, wt6.0% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt50% among Polymer Solution
The nitrate mixed solution of concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and be protected
Hold pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is calcined after being dried through 120 DEG C under 400 DEG C of air atmospheres
6h, is crushed to 40-60 mesh, obtains catalyst.Each element composition is Cu in catalyst: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, air speed
For 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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 29
First by 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 resins are pressed
1:1:1:1 ratio mix, wt6.5% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt55% among Polymer Solution
The nitrate mixed solution of concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and be protected
Hold pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is calcined after being dried through 120 DEG C under 400 DEG C of air atmospheres
6h, is crushed to 40-60 mesh, obtains catalyst.Each element composition is Cu in catalyst: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, air speed
For 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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 30
First by 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 resins are pressed
1:1:1:1 ratio mix, wt7.2% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt60% among Polymer Solution
The nitrate mixed solution of concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and be protected
Hold pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is calcined after being dried through 120 DEG C under 400 DEG C of air atmospheres
6h, is crushed to 40-60 mesh, obtains catalyst.Each element composition is Cu in catalyst: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, air speed
For 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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 31
First by 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 resins are pressed
1:1:1:1 ratio mix, wt7.4% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt50% among Polymer Solution
The nitrate mixed solution of concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and be protected
Hold pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is calcined after being dried through 120 DEG C under 400 DEG C of air atmospheres
6h, is crushed to 40-60 mesh, obtains catalyst.Each element composition is Cu in catalyst: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, air speed
For 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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 32
First by PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and
Cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resins press 1:1:1 ratio is mixed, and wt7.4% is made into distilled water
Polymer Solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
0.5:1:0.1:0.2 is dissolved in the nitrate mixed solution that wt30% concentration is formed among Polymer Solution.At 70 DEG C with
35wt% ammonia spirit parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing into
Untill property.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Urge
Each element composition is Cu in agent: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,H2/ CO (mole)=2.0, reaction result is shown in
Table 1.
Embodiment 33
First by PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and
Cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resins press 1:1:1 ratio is mixed, and wt7.7% is made into distilled water
Polymer Solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
0.5:1:0.1:0.2 is dissolved in the nitrate mixed solution that wt55% concentration is formed among Polymer Solution.At 70 DEG C with
35wt% ammonia spirit parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing into
Untill property.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Urge
Each element composition is Cu in agent: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,H2/ CO (mole)=2.0, reaction result is shown in
Table 1.
Embodiment 34
First by PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and
Cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resins press 1:1:1 ratio is mixed, and wt7.7% is made into distilled water
Polymer Solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
0.5:1:0.1:0.2 is dissolved in the nitrate mixed solution that wt40% concentration is formed among Polymer Solution.At 70 DEG C with
35wt% ammonia spirit parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing into
Untill property.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Urge
Each element composition is Cu in agent: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,H2/ CO (mole)=2.0, reaction result is shown in
Table 1.
Embodiment 35
First by PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and
Cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resins press 1:1:1 ratio is mixed, and wt8.0% is made into distilled water
Polymer Solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
0.5:1:0.1:0.2 is dissolved in the nitrate mixed solution that wt60% concentration is formed among Polymer Solution.At 70 DEG C with
35wt% ammonia spirit parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing into
Untill property.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Urge
Each element composition is Cu in agent: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,H2/ CO (mole)=2.0, reaction result is shown in
Table 1.
Embodiment 36
PAA high hydroscopic resin PAA first, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and fibre
The plain class sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resins of dimension press 1:1:1 ratio is mixed, and will be made into wt8.0% with distilled water
Polymer Solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
0.5:1:0.1:0.2 is dissolved in the nitrate mixed solution that wt60% concentration is formed among Polymer Solution.At 70 DEG C with
35wt% ammonia spirit parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing into
Untill property.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Urge
Each element composition is Cu in agent: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,H2/ CO (mole)=2.0, reaction result is shown in
Table 1.
Embodiment 37
First by PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and
Cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resins press 1:1:1 ratio is mixed, and wt8.3% is made into distilled water
Polymer Solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
0.5:1:0.1:0.2 is dissolved in the nitrate mixed solution that wt50% concentration is formed among Polymer Solution.At 70 DEG C with
35wt% ammonia spirit parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing into
Untill property.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Urge
Each element composition is Cu in agent: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,H2/ CO (mole)=2.0, reaction result is shown in
Table 1.
Embodiment 38
First by PAA high hydroscopic resin PAA, acrylic acid-acrylamide copolymer high hydroscopic resin P (AAAM) and
Cellulose family sodium carboxymethylcellulose/AM-AA-SSS high hydroscopic resins press 1:1:1 ratio is mixed, and wt8.3% is made into distilled water
Polymer Solution, after by following metallic atom Cu in molar ratio in the form of nitrate:Fe:Mn:Zn:Zr:Co=1.0:1.0:
0.5:1:0.1:0.2 is dissolved in the nitrate mixed solution that wt55% concentration is formed among Polymer Solution.At 70 DEG C with
35wt% ammonia spirit parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation is through distilling water washing into
Untill property.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60 mesh, obtains catalyst.Urge
Each element constitutes Cu in agent:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%.Also
Former 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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 39
First by 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 resins are pressed
1:1:1:1 ratio mix, wt8.5% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt35% among Polymer Solution
The nitrate mixed solution of concentration.With 35wt% ammonia spirit parallel-flow precipitations at 70 DEG C, precipitation process need to be sufficiently stirred for, and be protected
Hold pH=8-9.Precipitation is through distilling water washing untill neutrality.Wet cake is calcined after being dried through 120 DEG C under 400 DEG C of air atmospheres
6h, is crushed to 40-60 mesh, obtains catalyst.Each element composition is Cu in catalyst: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, air speed
For 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,H2/ CO (mole)=2.0, reaction result is shown in Table 1.
Embodiment 40
First by 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 resins are pressed
1:1:1:1 ratio mix, wt8.7% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt45% among Polymer Solution
The nitrate mixed solution of concentration.A certain amount of 35wt% ammonia spirits are mixed to form the homogeneous alkaline solution of concentration, will be upper
Metal-nitrate solutions are stated with alkaline solution in 70 DEG C of parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.It is heavy
Form sediment through distilling water washing untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-
60 mesh, obtain catalyst.Each element composition is Cu in catalyst: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,H2/ CO (mole)
=2.0, reaction result is shown in Table 1.
Embodiment 41
First by 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 resins are pressed
1:1:1:1 ratio mix, wt9.0% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt50% among Polymer Solution
The nitrate mixed solution of concentration.A certain amount of 35wt% ammonia spirits are mixed to form the homogeneous alkaline solution of concentration, will be upper
Metal-nitrate solutions are stated with alkaline solution in 70 DEG C of parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.It is heavy
Form sediment through distilling water washing untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-
60 mesh, obtain catalyst.Each element composition is Cu in catalyst: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,H2/ CO (mole)
=2.0, reaction result is shown in Table 1.
Embodiment 42
First by 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 resins are pressed
1:1:1:1 ratio mix, wt9.2% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt55% among Polymer Solution
The nitrate mixed solution of concentration.A certain amount of 35wt% ammonia spirits are mixed to form the homogeneous alkaline solution of concentration, will be upper
Metal-nitrate solutions are stated with alkaline solution in 70 DEG C of parallel-flow precipitations, precipitation process need to be sufficiently stirred for, and keep pH=8-9.It is heavy
Form sediment through distilling water washing untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-
60 mesh, obtain catalyst.Each element composition is Cu in catalyst: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,H2/ CO (mole)
=2.0, reaction result is shown in Table 1.
Embodiment 43
First by 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 resins are pressed
1:1:1:1 ratio mix, wt9.5% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt50% among Polymer Solution
The nitrate mixed solution of concentration.A certain amount of 35wt% ammonia spirits are mixed to form the homogeneous alkaline solution of concentration, will be above-mentioned
Metal-nitrate solutions are with alkaline solution in 70 DEG C of parallel-flow precipitations, and precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation
Through distilling water washing untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60
Mesh, obtains catalyst.Each element composition is Cu in catalyst: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,H2/ CO (mole)=
2.0, reaction result is shown in Table 1.
Embodiment 44
First by 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 resins are pressed
1:1:1:1 ratio mix, wt9.5% Polymer Solutions are made into distilled water, after by following metallic atom in the form of nitrate
Cu in molar ratio:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved in formation wt50% among Polymer Solution
The nitrate mixed solution of concentration.A certain amount of 35wt% ammonia spirits are mixed to form the homogeneous alkaline solution of concentration, will be above-mentioned
Metal-nitrate solutions are with alkaline solution in 70 DEG C of parallel-flow precipitations, and precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation
Through distilling water washing untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60
Mesh, obtains catalyst.Each element composition is Cu in catalyst: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,H2/ CO (mole)=
2.0, reaction result is shown in Table 1.
Embodiment 45
First by 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 resins are pressed
1:1:1:1 ratio mix, wt10% Polymer Solutions are made into distilled water, after following metallic atom is pressed in the form of nitrate
Mol ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:1.0:0.5:1:0.1:0.2 is dissolved among Polymer Solution that to form wt50% dense
The nitrate mixed solution of degree.A certain amount of 35wt% ammonia spirits are mixed to form the homogeneous alkaline solution of concentration, by above-mentioned gold
Genus nitrobacter solution is with alkaline solution in 70 DEG C of parallel-flow precipitations, and precipitation process need to be sufficiently stirred for, and keep pH=8-9.Precipitation warp
Water washing is distilled untill neutrality.Wet cake is calcined 6h after being dried through 120 DEG C under 400 DEG C of air atmospheres, is crushed to 40-60
Mesh, obtains catalyst.Each element composition is Cu in catalyst: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,H2/ CO (mole)=
2.0, reaction result is shown in Table 1.
The embodiment reaction result of table 1
Claims (4)
1. a kind of catalyst of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas, it is characterised in that catalyst weight percent group
Turn into：Cu:18-36%, Fe:20-28%, Mn:10-24%, Zn:13-33%, Zr:1-10%, Co:1-10%；
And prepared by following steps：
Under the conditions of temperature is 20-90 DEG C, first super absorbent resin is added in distilled water, 0.1wt%~10wt% matrixes are made into
Solution, under 15-30r/min stir speed (S.S.), the metal nitrate that catalyst is constituted is dissolved in Matrix Solution and is well mixed shape
It is 30wt% ammonia spirit or soluble carbonic acid into the mixed solution that nitrate concentration is 30wt%~60wt %, and with concentration
Salt cocurrent is precipitated, and stir speed (S.S.) control during precipitation is in 30-45r/min, and precipitation temperature is 40-80 DEG C, and holding pH value of solution=
Aging 3-5h after 6-10, precipitation, precipitation is through distilling water washing untill neutrality, and wet cake is after 80-120 DEG C of drying in 350-
6h is calcined under 500 DEG C of air atmospheres, 40-60 mesh is crushed to.
2. a kind of catalyst of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas as claimed in claim 1, it is characterised in that
Super absorbent resin is polyvinyl alcohol type high hydroscopic resin, and PAA high hydroscopic resin, acrylic acid-acrylamide copolymer is high
One or more in water-absorbing resin, acrylic acid-copolymer-maleic anhydride high hydroscopic resin, cellulose family high hydroscopic resin.
3. a kind of catalyst of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas as claimed in claim 1, it is characterised in that
Described soluble carbonate salt is sodium carbonate or potassium carbonate.
4. a kind of catalyst of jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas as described in claim any one of 1-3 should
With, it is characterised in that including following condition：
Reduction temperature is 210-300 DEG C, and pressure is 4.0-12.0MPa, and air speed is 1000-10000h-1, H2/ CO mol ratios are
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, H2/ CO mol ratios are
0.5-3.0。
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