CN107413348A - Catalyst and preparation method thereof, the method for synthesizing isobutanol - Google Patents
Catalyst and preparation method thereof, the method for synthesizing isobutanol Download PDFInfo
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- CN107413348A CN107413348A CN201710232604.2A CN201710232604A CN107413348A CN 107413348 A CN107413348 A CN 107413348A CN 201710232604 A CN201710232604 A CN 201710232604A CN 107413348 A CN107413348 A CN 107413348A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention provides a kind of preparation method of catalyst, and it includes：Graphitized carbon material is provided, and carries out activation process and obtains Activated Graphite carbon material；Copper zinc-aluminium salting liquid and alkaline solution are provided；The Activated Graphite carbon material is dispersed in water, and adds the copper zinc-aluminium salting liquid and alkaline solution simultaneously thereto and is co-precipitated to obtain presoma；And the presoma is carried out to be thermally treated resulting in required catalyst.The preparation method preparation cost of the catalyst is low, is adapted to industrialized production；Obtained catalyst prepares isobutanol particularly suitable for preparing synthesis gas, and its CO conversion ratio and isobutanol selectivity are high.The present invention also provides a kind of catalyst, and the catalyst is the compound containing copper, zinc oxide and aluminum oxide that is formed with Activated Graphite carbon material by carrier.The present invention also provides a kind of method for synthesizing isobutanol, using hydrogen and carbon monoxide as synthesis gas, synthesizes to obtain isobutanol using above-mentioned catalyst.
Description
【Technical field】
The present invention relates to chemical material technical field, and in particular to a kind of catalyst and preparation method thereof, synthesis isobutanol
Method.
【Background technology】
Since the oil crisis twice of the seventies, and lifting of the countries in the world to environmental protection attention degree, people recognize
Oil can not be relied on too much by knowing the energy and organic synthesis industry, and should adjust raw material route and product structure, to raw material
Develop with the diversification direction of product：I.e. oil, coal, gas develop simultaneously, and are directed to Optimum utilization these three inflammable minerals resources
To produce different chemicals and clean fuel.
By exploration for many years, regarding for people is entered into by the technique of producing hydrocarbon with synthetic gas, alcohols, ethers product gradually
Line.Wherein, synthesis gas is its wide material sources using hydrogen, carbon monoxide as the unstripped gas of main component, can be solid by coal or coke etc.
Fluid fuel gasification produces, and can also be produced by light hydrocarbons such as natural gas and naphthas.The technique is moving towards large-scale work at present
Industry, to promote the commercial Application of synthesis gas to create precondition, wherein research prepared by relevant low-carbon alcohols receives much concern.
Low carbon mixed alcohol refers to C1~C6 alcohol-based mixtures.And in numerous products of mixed alcohol, isobutanol has extensive
Purposes.High-quality power fuel can be such as used as；And its high-octane rating, the advantages that explosion-proof anti-seismic performance is superior can be utilized,
Substitute and the gasoline additive MTBE (methyl tertiary butyl ether(MTBE), Methyl Tert-butyl Ether) threatened be present to human health；
Also, isobutanol or basic Organic Chemicals, the synthesis available for rubber, plastics etc.；In addition isobutanol can also conduct
Excellent extractant, the extraction for rare earth metal.
Catalyst is needed to use during synthesis gas prepares isobutanol, the catalyst used at present includes modified high temperature
Methanol synthesis catalyst, modified low temperature methanol synthesis catalyst, Zirconium-base catalyst etc..Wherein, modified high temperature methanol synthesis catalytic
Agent product is mainly methanol, ethanol, normal propyl alcohol and isobutanol, and wherein methanol and isobutanol is main component, but reaction condition compared with
For harshness：400~600 DEG C of temperature, 12~16Mpa of pressure.Modified low temperature methanol synthesis catalyst synthesizes compared to high temperature methanol
Catalyst, its reaction condition are more gentle：270~300 DEG C, 6~8MPa of pressure of temperature, product based on methanol and isobutanol,
But CO conversion is not high, isobutanol is selectively relatively low.Although Zirconium-base catalyst isobutanol selectivity is high, it prepares former
Material is expensive, is not easy to realize industrialization.
【The content of the invention】
To overcome existing technical problem, the present invention provides a kind of catalyst and preparation method thereof, the side of synthesis isobutanol
Method.
To solve a kind of preparation method for catalyst that above-mentioned technical problem provides, it includes the present invention：Graphitization is provided
Carbon material, and carry out activation process and obtain Activated Graphite carbon material；Copper zinc-aluminium salting liquid and alkaline solution are provided；By the work
Property graphitized carbon material be dispersed in water, and add the copper zinc-aluminium salting liquid and alkaline solution simultaneously thereto and be co-precipitated
Obtain presoma；And the presoma is carried out to be thermally treated resulting in required catalyst.
Preferably, the adding speed of the copper zinc-aluminium salting liquid and alkaline solution is controlled, makes co-precipitation in pH value be 5.0-
Carried out under conditions of 7.0.
Preferably, the carbon content of the graphitized carbon material is more than 99%, and graphitized carbon content is more than 90%.
Preferably, the molal quantity of the graphitized carbon material is n1, copper, zinc, mole of aluminium in the copper zinc-aluminium salting liquid
Number is respectively n2、n3、n4, n1:n2:n3:n4=(10-20):(1-3):(0.5-1.5):(0.4-1.2).
Preferably, the activation process is activates using acid solution to the graphitized carbon material, the acidity
The molar concentration of solution is 10-20mol/L；Or the activation process is that the graphitized carbon material is carried out using alkaline solution
Activation, the molar concentration of the alkaline solution is 2-8mol/L.
Preferably, the activation process is specially：The acid solution that molar concentration is 10-20mol/L is provided；Make acid molten
Liquid submerges the graphitized carbon material, and the 2-4h that flowed back at 50-90 DEG C obtains activation products；Activation products are washed, and
16-24h is dried at 80-120 DEG C and obtains Activated Graphite carbon material.
The present invention also provides a kind of catalyst, and the catalyst is is contained with Activated Graphite carbon material by what carrier was formed
There is the compound of copper, zinc oxide and aluminum oxide, be expressed as Cu/ZnO/Al2O3/ x%C.
Preferably, the mass fraction of Activated Graphite carbon material is 10-50% in the catalyst.
The present invention also provides a kind of method for synthesizing isobutanol, using hydrogen and carbon monoxide as synthesis gas, is urged using above-mentioned
Agent is 250-360 DEG C in reaction temperature, and pressure synthesizes under conditions of being 3-5Mpa and obtains isobutanol.
Relative to prior art, the preparation method of catalyst provided by the present invention, first, it uses graphitized carbon material
It is raw material with copper zinc-aluminium salting liquid, preparation cost is low, is adapted to industrialized production；Secondly, obtained catalyst is particularly suitable for using
Isobutanol is prepared in preparing synthesis gas, its CO conversion ratio and isobutanol selectivity are high；In addition, obtained catalyst is used to close
It is gentle into isobutanol, reaction condition.
The present invention also provides a kind of catalyst, and the catalyst is is contained with Activated Graphite carbon material by what carrier was formed
There is the compound of copper, zinc oxide and aluminum oxide, the catalyst prepares isobutanol particularly suitable for preparing synthesis gas, and its CO turns
Rate and isobutanol selectivity are high；Also, obtained catalyst is used to synthesize isobutanol, reaction condition is gentle.
The present invention also provides a kind of method for synthesizing isobutanol, using hydrogen and carbon monoxide as synthesis gas, is urged using above-mentioned
Agent is 250-360 DEG C in reaction temperature, and pressure synthesizes under conditions of being 3-5Mpa and obtains isobutanol.First, reaction condition temperature
With, and CO conversion ratios and isobutanol selectivity are high.
【Brief description of the drawings】
Fig. 1 is the schematic flow sheet of the preparation method of catalyst provided by the present invention.
Fig. 2 be catalyst provided by the present invention preparation method in step S1 schematic flow sheet.
Fig. 3 be catalyst provided by the present invention preparation method in step S4 schematic flow sheet.
Fig. 4 is the schematic flow sheet of the method for synthesis isobutanol provided by the present invention.
【Embodiment】
In order that the purpose of the present invention, technical scheme and advantage are more clearly understood, below in conjunction with accompanying drawing and embodiment,
The present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.
Embodiment one
As shown in figure 1, a kind of preparation method of catalyst, it includes：
Step S1：Graphitized carbon material is provided, and carries out activation process and obtains Activated Graphite carbon material；
Step S2：Copper zinc-aluminium salting liquid and alkaline solution are provided；
Step S3：The Activated Graphite carbon material is dispersed in water, and adds the copper zinc-aluminium salt simultaneously thereto
Solution and alkaline solution are co-precipitated to obtain presoma；
Step S4：The presoma is carried out to be thermally treated resulting in required catalyst.
Wherein step S1 and step S2 can be carried out simultaneously, can also be carried out respectively, and not limit order.
To be dispersed with the aqueous solution of Activated Graphite carbon material as carrier in wherein step S3, while it is molten to add copper zinc-aluminium salt
Liquid and alkaline solution, copper ion, zinc ion and the aluminium ion contained in copper zinc-aluminium salting liquid and the hydroxyl in alkaline solution from
Son combines to form precipitation, and the precipitation forms compound further combined with the Activated Graphite carbon material disperseed in water.
Then catalyst is obtained after passing through step S4, namely heat treatment, the catalyst is with Activated Graphite carbon material
The compound containing copper, zinc oxide and aluminum oxide formed by carrier, can be expressed as Cu/ZnO/Al2O3/ x%C.Wherein
Cu/ZnO/Al2O3For active material, Activated Graphite carbon material (namely C) is used as carrier, and x% represents active stone in catalyst
The mass fraction of inkization carbon material.In the present invention, preferably x% is 10-50%.
The preparation method of catalyst provided by the present invention, there is advantages below：
(1) graphitized carbon material and copper zinc-aluminium salting liquid are used as raw material, preparation cost is low, is adapted to industrialized production.
(2) catalyst obtained by prepares isobutanol particularly suitable for preparing synthesis gas, its CO conversion ratio and isobutanol
Selectivity is high.
(3) catalyst obtained by is used to synthesize isobutanol, and reaction condition is gentle.
It is further expalined herein, the Cu/ZnO/Al in the catalyst2O3For active material, the active material is easily sent out
Raw agglomeration, its activity is influenceed, and then influence catalyst performance；And it is carrier to utilize Activated Graphite carbon material, Ke Yiyou
Effect alleviates Cu/ZnO/Al2O3The phenomenon easily reunited, promote active component to disperse, ensure that the activity of active material is able in catalyst
Middle embodiment, and then ensure that the performance of catalyst.Described catalyst performance includes conversion ratio, selectivity and anti-herein
Answer condition whether gentle etc..
And In-situ reaction obtains required catalyst, namely step S3 by the way of co-precipitation, ensureing active stone
On the premise of inkization carbon material can be combined well with active material, it is further ensured that active material can be uniformly dispersed.In addition by
Contain graphitized carbon material in preparation-obtained catalyst, in the big pi bond effect of the delocalization of graphitized carbon material, can promote
Electronics shift, therefore by by catalyst prepares isobutanol for synthesis gas made from the preparation method of described catalyst when,
CO conversion ratios and isobutanol selectivity can effectively be improved.
In some specific embodiments, also referring to Fig. 2, step S1 includes：
Step S11：Graphitized carbon material is provided.
Preferably, the carbon content of the graphitized carbon material is more than 99%, and graphitized carbon content is more than 90%.The stone
Inkization carbon material can be one or more of combinations in mesoporous carbon, graphite, carbon fiber, carbon black.Wherein preferably it is, it is described
Graphitized carbon material selects graphite, due to graphite electric conductivity more preferably, can preferably ensure CO conversion ratios and isobutanol selection
Property.It is further that the specific surface area of the graphitized carbon material is more than 80m2/ g, granularity are 6-32 μm, pore volume 0.4-
0.6cm3·g-1, aperture 10-15nm.By determining above-mentioned parameter, the performance of obtained catalyst can be further ensured that.
Step S12：The graphitized carbon material is activated using acid solution or alkaline solution.
The tube wall that can destroy graphitized carbon material of activation process, to increase the functional group on its surface, and then it is beneficial to it
Unloaded metal as carrier.
In certain embodiments, the activation process is that the graphitized carbon material is activated using alkaline solution,
The molar concentration of the alkaline solution is 2-8mol/L；Wherein, it is conventional for potassium hydroxide.
In some preferred embodiments, the activation process is that the graphitized carbon material is carried out using acid solution
Activation, the molar concentration of the acid solution is 10-20mol/L.The graphitization carbon materials are activated compared to using alkaline solution
Material, the surface using the Activated Graphite carbon material obtained by the acid solution activation graphitized carbon material is defective, can
It is combined with sediment, promotes the electronics transfer of active component in catalyst, and then ensures CO conversion ratios and isobutanol selectivity.
It is preferred that the acid solution is strong acid, the preferably mixed acid of nitric acid or nitric acid and sulfuric acid.Nitric acid has very with sulfuric acid
Good corrosivity, so as to obtain more surface functional groups.Wherein nitric acid can use mass fraction for 65% concentrated nitric acid,
Sulfuric acid is the concentrated sulfuric acid that mass fraction is 98%.When using the mixed acid of nitric acid and sulfuric acid, it is preferable that the nitric acid and sulfuric acid
Volume ratio be 1:(2-5).
It is further that the activation process is specially：The acid solution that molar concentration is 10-20mol/L is provided；Make acid
Property solution submerge the graphitized carbon material, the 2-4h that flowed back at 50-90 DEG C obtains activation products；Activation products are washed
Wash, and dry 16-24h at 80-120 DEG C and obtain Activated Graphite carbon material.By return acid solution, and further really
Determine temperature and time, ensure the activation effect of graphitized carbon material.
Step S13：Activation products are washed, and dries 16-24h at 80-120 DEG C and obtains Activated Graphite carbon materials
Material.Wherein washing can filter either centrifugal filtration etc., and it is primarily to remove the acid solution of residual, the work of gained
Property graphitized carbon material be about neutrality.
As described in the text, Cu/ZnO/Al in catalyst2O3For active material, and in active material Cu/ZnO/Al2O3
In, Cu/ZnO is difunctional component.Cu is main activated centre, plays activation Dissociative H2Effect；ZnO promotes Cu's
It is scattered, while sulfur poisoning-resistant is played, extend the effect such as catalyst life；Al2O3It is structural promoter, plays divided active component, prevents
The effects such as active component sintering.
In some preferred embodiments, copper, zinc, the molal quantity of aluminium are respectively n in the copper zinc-aluminium salting liquid2、n3、n4,
n2:n3:n4=(1-3):(0.5-1.5):(0.4-1.2).By determining the mole ratio of copper, zinc, aluminium in copper zinc-aluminium salting liquid,
Also active material Cu/ZnO/Al in gained catalyst has been determined that2O3Composition, so as to preferably ensure catalyst activity.It is excellent
Choosing, n2:n3:n4=(1.5-2.5):(0.8-1.2):(0.6-1)；It is more highly preferred to, n2:n3:n4=2:1:0.8.The copper
Zinc-aluminium salting liquid can be soluble in water i.e. available by corresponding soluble-salt, and preferably using identical the moon from
Son, such as copper nitrate, zinc nitrate and aluminum nitrate, either copper sulphate, zinc sulfate or aluminum sulfate or copper chloride, zinc chloride and chlorine
Change aluminium.
And Activated Graphite carbon material is as carrier in obtained catalyst, if content is too low, it is impossible to very well
Reach and active material is uniformly dispersed, and promote electronics transfer and other effects；If content is too high, then active matter accordingly
Matter content is low, influences the activity of obtained catalyst.Therefore by determining that the quality of Activated Graphite carbon material in catalyst is divided
Number, can preferably ensure to obtain catalytic performance preferably catalyst.Wherein, Activated Graphite carbon materials in the preferable catalyst
The mass fraction of material is 10-50%.It is appreciated that when the molal quantity of copper in the copper zinc-aluminium salting liquid, zinc, aluminium determines, i.e.,
It can determine that catalyst activity substance C u/ZnO/Al2O3Quality, and then can be by adjusting the quality of graphitized carbon material
Determine the mass fraction of Activated Graphite carbon material in catalyst.It is therefore preferred that the molal quantity of the graphitized carbon material is
n1, then n1:n2:n3:n4=(10-20):(1-3):(0.5-1.5):(0.4-1.2).Preferably, n1:n2:n3:n4=(12-
18):(1.5-2.5):(0.8-1.2):(0.6-1).It is appreciated that it is in the preparation method of catalyst provided by the present invention
Physical reactions, each component (namely carbon, copper, zinc and aluminium) equal free of losses, therefore each component in final obtained catalyst
Molal quantity be also such.
In some preferred embodiments, in step s3, the addition of the copper zinc-aluminium salting liquid and alkaline solution is controlled
Speed, co-precipitation is set to be carried out under conditions of pH value is 5.0-7.0.It is appreciated that the copper zinc-aluminium salting liquid due to metal from
The hydrolysis of son is that can determine that both addition speed by monitoring pH value in adding procedure in alkalescence in acidity, alkaline solution
Degree and addition, so as to ensure being smoothed out and obtaining required reaction product for co-precipitation.Wherein described alkaline solution can
To be NaOH, KOH, Na2CO3、K2CO3In one or more of mixing, specifically, the alkaline solution be NaOH solution,
KOH solution, NaOH and Na2CO3Mixed solution, KOH and K2CO3Mixed solution.Preferably, presoma is entered before being heat-treated
Row is stirred and washed to neutrality, in general needs stirring 0.5-2h to obtain dispersed presoma；Washing can be used
Centrifugal filtration or suction filtration etc..
Preferably, carry out being thermally treated resulting in required catalysis also referring to Fig. 3, step S4 namely to the presoma
Agent, further comprise：
Step S41：The presoma is dried into 10-20h at 60-100 DEG C, obtains desciccate；And
Step S42：Desciccate is calcined 3-5h at 300-500 DEG C, obtains required catalyst.
Embodiment two
The present invention also provides a kind of catalyst, and the catalyst is is contained with Activated Graphite carbon material by what carrier was formed
There is the compound of copper, zinc oxide and aluminum oxide, can also use the preparation method of the catalyst provided in embodiment one
It is prepared.The catalyst can be expressed as Cu/ZnO/Al2O3/ x%C.Wherein Cu/ZnO/Al2O3For active material, active stone
Inkization carbon material (namely C) is used as carrier, and x% is the mass fraction for representing Activated Graphite carbon material in catalyst.The catalysis
Agent prepares isobutanol particularly suitable for preparing synthesis gas, and its CO conversion ratio and isobutanol selectivity are high；Also, will be obtained
Catalyst is used to synthesize isobutanol, and reaction condition is gentle.
Activated Graphite carbon material is as carrier in the catalyst, if content is too low, it is impossible to which reach makes well
Active material is uniformly dispersed, and promotes electronics transfer and other effects；If content is too high, then activity substance content accordingly
It is low, influence the activity of obtained catalyst.Therefore, can be preferably by determining the mass fraction of graphitized carbon material in catalyst
Guarantee obtains catalytic performance preferably catalyst.Wherein, the quality of Activated Graphite carbon material is divided in the preferable catalyst
Number is 10-50%.It is preferred that the mass fraction of graphitized carbon material is 20-40% in the catalyst；It is specifically, described
The mass fraction of graphitized carbon material can be 20%, 25%, 30%, 35%, 40% in catalyst.
Preferably, Cu, ZnO, Al in the catalyst2O3The ratio between molal quantity be (1-3):(0.5-1.5):(0.4-
1.2)；So also determine that active material Cu/ZnO/Al2O3Composition, so as to preferably ensure catalyst activity.It is more excellent
Choosing, Cu, ZnO, Al in the catalyst2O3The ratio between molal quantity be (1.5-2.5):(0.8-1.2):(0.6-1)；Optimal
It is Cu, ZnO, Al in the catalyst2O3The ratio between molal quantity be 2:1:0.8.
Embodiment three
The present invention also provides a kind of method for synthesizing isobutanol, using hydrogen and carbon monoxide as synthesis gas, is urged using above-mentioned
Agent synthesizes to obtain isobutanol, namely synthesizes to obtain isobutanol using the catalyst provided in embodiment two.First, in utilization
Catalyst is stated, reaction condition is gentle, and CO conversion ratios and isobutanol selectivity are high.Required reaction condition is：Reaction temperature is
250-360 DEG C, pressure 3-5Mpa.Its CO conversion ratio can reach 61.14%, and isobutanol selectively can reach 17.0%.
Specifically, as shown in figure 4, the method for the synthesis isobutanol includes：
Step T1：Catalyst reduction；Above-mentioned catalyst is placed in N2:H2=(3-5):At 1 atmosphere and 250-350 DEG C
Reductase 12-10h；
Step T2：Reacted to obtain isobutanol, reaction temperature 250- using the catalyst after reduction and synthesis gas
360 DEG C, pressure 3-5Mpa.The synthesis gas includes hydrogen and carbon monoxide, and the volume ratio of the hydrogen and carbon monoxide
For (0.5-2.5):1.
Specific experimental group is further provided below：
Experimental group 1-1
The graphited mesoporous carbons of 2g are weighed, and take appropriate concentrated nitric acid, is advisable with submerging mesoporous carbon, is flowed back at 60 DEG C
3h.Then filtering and washing, 12h is dried at 80 DEG C, obtains Activated Graphite mesoporous carbon, and be scattered in distilled water, i.e.,
Obtain solution A.
Weigh 9.6gCu (NO3)2·3H2O、6g Zn(NO3)2·6H2O and 6g Al (NO3)3·9H2O is configured to mix molten
Liquid, that is, obtain solution B.
0.5mol/L NaOH solution is taken, or prepares 0.5mol/L NaOH solution, that is, provides or obtain solution C.
Add solution B and solution C simultaneously into solution A, and cause pH value be 5.0 and temperature be 25 DEG C under conditions of enter
Row co-precipitation, precipitation finish to obtain presoma.And 0.5h is stirred, wash to neutrality；Then 10h is dried at 60 DEG C, at 300 DEG C
3h is calcined, obtains catalyst.
It is appreciated that weighed 9.6g Cu (NO3)2·3H2O、6g Zn(NO3)2·6H2O and 6g Al (NO3)3·
9H2The active material Cu/ZnO/Al ultimately formed in O2O3About 4.98g, therefore the mass fraction of catalyst intermediary hole carbon is about
2/ (2+4.98)=29%.
Isobutanol is synthesized using obtained catalyst
Catalyst reduction：Catalyst is placed in fixed bed, N2:H2=3:Under 1 atmosphere, 5 DEG C/min heating rate liter
To 250 DEG C of reductase 12 h.
Reacted to obtain isobutanol using the catalyst after reduction and synthesis gas：Reaction temperature is 250 DEG C, and pressure is
3Mpa, H2:CO=0.5:Under conditions of 1, synthetic reaction is carried out.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 42.55%, hydro carbons 12.05%,
CO210.56%th, total alcohol selectivity 77.39%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 71.32%, 3.44%, 1.52%, 3.67%, 18.24%, 1.81%, that is, the selectivity of isobutanol is
14.2%.
Experimental group 1-2
Experimental group 1-2 is distinguished as with experimental group 1-1's：Weigh the preparation that the graphited mesoporous carbons of 2.5g carry out catalyst；
The mass fraction of catalyst intermediary hole carbon is about 33%.
On-line testing is finally carried out using GC9560 gas-chromatographies, CO conversion ratios are 42.36%, hydro carbons 10.85%,
CO29.51%th, total alcohol selectivity 74.02%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol point of n-butanol in total alcohol
Cloth is respectively 70.69%, 3.51%, 1.41%, 3.56%, 19.05%, 1.78%, that is, the selectivity of isobutanol is
14.1%.
Experimental group 1-3
Experimental group 1-3 is distinguished as with experimental group 1-1's：Weigh the preparation that the graphited mesoporous carbons of 3g carry out catalyst；Urge
The mass fraction of agent intermediary hole carbon is about 38%.
On-line testing is finally carried out using GC9560 gas-chromatographies, CO conversion ratios are 40.79%, hydro carbons 12.85%,
CO210.78%th, total alcohol selectivity 76.37%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 71.01%, 3.75%, 1.47%, 3.76%, 18.32%, 1.69%, that is, the selectivity of isobutanol is
13.9%.
Experimental group 1-4
Experimental group 1-4 is distinguished as with experimental group 1-1's：Weigh the preparation that the graphited mesoporous carbons of 1.5g carry out catalyst；
The mass fraction of catalyst intermediary hole carbon is about 23%.
On-line testing is finally carried out using GC9560 gas-chromatographies, CO conversion ratios are 39.16%, hydro carbons 13.47%,
CO211.85%th, total alcohol selectivity 74.68%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 72.25%, 3.68%, 1.69%, 3.91%, 16.72%, 1.75%, that is, the selectivity of isobutanol is
12.5%.
Experimental group 1-1,1-2,1-3,1-4 experiment condition and experimental result are shown in Table 1.As shown in table 1, experimental group 1-1,
It is to prepare catalyst using mesoporous carbon in 1-2,1-3,1-4, but the dosage of mesoporous carbon is different, it is real it was found from experimental result
When the mass fraction for testing group 1-1 namely catalyst intermediary hole carbon is 29%, the selectivity of CO conversion ratios and isobutanol is higher, respectively
For 42.55%, 14.2%.
Table 1
Experimental group 2-1
2.5g graphite is weighed, and takes appropriate concentrated nitric acid and concentrated sulfuric acid mixed acid (volume ratio 1:3), using submerge graphite as
Preferably, flowed back 2h at 80 DEG C, filtering and washing, and 10h is dried at 80 DEG C, obtains Activated Graphite, and is scattered in distilled water,
Obtain solution A.
Weigh 9.0g Cu (NO3)2·3H2O、6.5g Zn(NO3)2·6H2O and 6.5g Al (NO3)3·9H2O is configured to mix
Solution is closed, that is, obtains solution B.
Take 1mol/L NaOH/Na2CO3Mixed ammonium/alkali solutions, or prepare 1mol/L NaOH/Na2CO3Mixed ammonium/alkali solutions, i.e.,
There is provided or obtain solution C.
Add solution B and solution C simultaneously into solution A, and cause pH value be 5.5 and temperature be 30 DEG C under conditions of enter
Row co-precipitation, precipitation finish to obtain presoma.And 1h is stirred, wash to neutrality；Then 12h is dried at 80 DEG C, is roasted at 400 DEG C
3h is burnt, obtains catalyst.
It is appreciated that weighed 9.0g Cu (NO3)2·3H2O、6.5g Zn(NO3)2·6H2O and 6.5g Al
(NO3)3·9H2The active material Cu/ZnO/Al ultimately formed in O2O3About 5.02g, therefore the quality of graphite is divided in catalyst
Number is about 2.5/ (2.5+5.02)=33%.
Isobutanol is synthesized using obtained catalyst
Catalyst reduction：Catalyst is placed in fixed bed, N2:H2=3.5:Under 1 atmosphere, 5 DEG C/min heating rate
Rise to 280 DEG C of reduction 5h.
Reacted to obtain isobutanol using the catalyst after reduction and synthesis gas：Reaction temperature is 280 DEG C, and pressure is
4Mpa, H2:CO=1:Under conditions of 1, synthetic reaction is carried out.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 55.25%, hydro carbons 11.23%,
CO28.72%th, total alcohol selectivity 80.05%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol point of n-butanol in total alcohol
Cloth is respectively 68.26%, 3.98%, 1.74%, 3.24%, 21.22%, 1.56%, that is, the selectivity of isobutanol is
17.0%.
Experimental group 2-2
Experimental group 2-2 is distinguished as with experimental group 2-1's：Weigh the preparation that 3g graphite carries out catalyst；Graphite in catalyst
Mass fraction be about 37%.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 54.28%, hydro carbons 11.50%,
CO28.96%th, total alcohol selectivity 79.54%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol point of n-butanol in total alcohol
Cloth is respectively 69.13%, 3.94%, 1.68%, 3.16%, 21.04%, 1.05%, that is, the selectivity of isobutanol is
16.7%.
Experimental group 2-3
Experimental group 2-3 is distinguished as with experimental group 2-1's：Weigh the preparation that 3.5g graphite carries out catalyst；Stone in catalyst
The mass fraction of ink is about 41%.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 52.14%, hydro carbons 12.52%,
CO29.45%th, total alcohol selectivity 78.03%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol point of n-butanol in total alcohol
Cloth is respectively 69.41%, 3.87%, 1.75%, 3.45%, 20.42%, 1.10%, that is, the selectivity of isobutanol is
15.9%.
Experimental group 2-4
Experimental group 2-4 is distinguished as with experimental group 2-1's：Weigh the preparation that 2g graphite carries out catalyst；Graphite in catalyst
Mass fraction be about 28%.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 53.68%, hydro carbons 11.61%,
CO29.13%th, total alcohol selectivity 79.26%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol point of n-butanol in total alcohol
Cloth is respectively 70.02%, 4.12%, 1.62%, 3.18%, 20.75%, 1.11%, that is, the selectivity of isobutanol is
16.4%.
Experimental group 2-1,2-2,2-3,2-4 experiment condition and experimental result are shown in Table 2.As shown in table 2, experimental group 2-1,
It is to prepare catalyst using graphite in 2-2,2-3,2-4, but the dosage of graphite is different, it was found from experimental result, experimental group
When the mass fraction of graphite is 33% in 2-1 namely catalyst, the selectivity of CO conversion ratios and isobutanol is higher, is respectively
55.25%th, 17.0%.
Table 2
Experimental group 3-1
2g carbon fibers are weighed, and take appropriate concentrated nitric acid and concentrated sulfuric acid mixed acid (volume ratio 1:4), submergence carbon fiber is
Preferably, flowed back 2h at 100 DEG C, filtering and washing, and 12h is dried at 90 DEG C, obtains activated carbon fiber, and be scattered in distilled water
In, that is, obtain solution A.
Weigh 10g Cu (NO3)2·3H2O、7.8g Zn(NO3)2·6H2O and 7.8g Al (NO3)3·9H2O is configured to mix
Solution is closed, that is, obtains solution B.
1mol/L KOH solution is taken, or prepares 1mol/L KOH solution, that is, provides or obtain solution C.
Add solution B and solution C simultaneously into solution A, and cause pH value be 6 and temperature be 35 DEG C under conditions of carry out
Co-precipitation, precipitation finish to obtain presoma.And 1.5h is stirred, wash to neutrality；Then 18h is dried at 80 DEG C, is roasted at 500 DEG C
3h is burnt, obtains catalyst.
It is appreciated that weighed 10g Cu (NO3)2·3H2O、7.8g Zn(NO3)2·6H2O and 7.8g Al (NO3)3·
9H2The active material Cu/ZnO/Al ultimately formed in O2O3About 5.82g, therefore the mass fraction of carbon fiber is about in catalyst
2/ (2+5.82)=26%.
Isobutanol is synthesized using obtained catalyst
Catalyst reduction：Catalyst is placed in fixed bed, N2:H2=4:Under 1 atmosphere, 5 DEG C/min heating rate liter
To 300 DEG C of reduction 8h.
Reacted to obtain isobutanol using the catalyst after reduction and synthesis gas：Reaction temperature is 300 DEG C, and pressure is
5Mpa, H2:CO=2:Under conditions of 1, synthetic reaction is carried out.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 52.11%, hydro carbons 13.54%,
CO213.21%th, total alcohol selectivity 73.25%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 72.41%, 2.55%, 2.04%, 3.21%, 18.01%, 1.78%, that is, the selectivity of isobutanol is
13.2%.
Experimental group 3-2
Experimental group 3-2 is distinguished as with experimental group 3-1's：Weigh the preparation that 1.5g carbon fibers carry out catalyst；In catalyst
The mass fraction of carbon fiber is about 20%.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 50.67%, hydro carbons 13.76%,
CO214.04%th, total alcohol selectivity 72.20%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 71.78%, 2.77%, 2.25%, 3.29%, 17.97%, 1.94%, that is, the selectivity of isobutanol is
13.0%.
Experimental group 3-3
Experimental group 3-3 is distinguished as with experimental group 3-1's：Weigh the preparation that 2.5g carbon fibers carry out catalyst；In catalyst
The mass fraction of carbon fiber is about 30%.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 51.45%, hydro carbons 13.23%,
CO213.99%th, total alcohol selectivity 72.78%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 71.97%, 2.71%, 1.98%, 3.34%, 18.03%, 1.97%, that is, the selectivity of isobutanol is
13.1%.
Experimental group 3-4
Experimental group 3-4 is distinguished as with experimental group 3-1's：Weigh the preparation that 3g carbon fibers carry out catalyst；Carbon in catalyst
The mass fraction of fiber is about 34%.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 49.94%, hydro carbons 14.05%,
CO214.27%th, total alcohol selectivity 71.68%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 72.12%, 2.69%, 2.31%, 3.48%, 17.44%, 1.96%, that is, the selectivity of isobutanol is
12.5%.
Experimental group 3-1,3-2,3-3,3-4 experiment condition and experimental result are shown in Table 3.As shown in table 3, experimental group 3-1,
It is to prepare catalyst using carbon fiber in 3-2,3-3,3-4, but the dosage of carbon fiber is different, it is real it was found from experimental result
When the mass fraction for testing carbon fiber in group 3-1 namely catalyst is 25%, the selectivity of CO conversion ratios and isobutanol is higher, respectively
For 52.11%, 13.2%.
Table 3
Experimental group 4-1
The graphited carbon blacks of 2.5g are weighed, and take appropriate concentrated nitric acid, are advisable with submerging carbon black, flow back 3h at 70 DEG C,
Filtering and washing, 20h is dried at 100 DEG C, activated carbon black is obtained, is scattered in distilled water, that is, obtain solution A.
Weigh 9.2g Cu (NO3)2·3H2O、5.9g Zn(NO3)2·6H2O and 5.5g Al (NO3)3·9H2O is configured to mix
Solution is closed, that is, obtains solution B.
Take 2mol/L KOH/K2CO3Mixed ammonium/alkali solutions, or prepare 2mol/L KOH/K2CO3Mixed ammonium/alkali solutions, that is, provide
Or obtain solution C.
Add solution B and solution C simultaneously into solution A, and cause pH value be 7.0 and temperature be 40 DEG C under conditions of enter
Row co-precipitation, precipitation finish to obtain presoma.And 2h is stirred, wash to neutrality；Then 24h is dried at 90 DEG C, is roasted at 300 DEG C
3h is burnt, obtains catalyst.
It is appreciated that weighed 9.2g Cu (NO3)2·3H2O、5.9g Zn(NO3)2·6H2O and 5.5g Al
(NO3)3·9H2The active material Cu/ZnO/Al ultimately formed in O2O3About 4.78g, therefore the quality of carbon black is divided in catalyst
Number is about 2.5/ (2.5+4.78)=34%.
Isobutanol is synthesized using obtained catalyst
Catalyst reduction：Catalyst is placed in fixed bed, N2:H2=4.5:Under 1 atmosphere, 5 DEG C/min heating rate
Rise to 360 DEG C of reduction 10h.
Reacted to obtain isobutanol using the catalyst after reduction and synthesis gas：Reaction temperature is 360 DEG C, and pressure is
3Mpa, H2:CO=2.5:Under conditions of 1, synthetic reaction is carried out.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 61.14%, hydro carbons 18.05%,
CO210.15%th, total alcohol selectivity 71.80%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 69.99%, 3.17%, 1.82%, 2.79%, 20.56%, 1.67%, that is, the selectivity of isobutanol is
14.8%.
Experimental group 4-2
Experimental group 4-2 is distinguished as with experimental group 4-1's：Weigh the preparation that 3g carbon blacks carry out catalyst；Carbon black in catalyst
Mass fraction be about 39%.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 60.53%, hydro carbons 18.75%,
CO211.12%th, total alcohol selectivity 70.13%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 70.41%, 3.54%, 1.96%, 2.93%, 19.25%, 1.91%, that is, the selectivity of isobutanol is
13.5%.
Experimental group 4-3
Experimental group 4-3 is distinguished as with experimental group 4-1's：Weigh the preparation that 3.5g carbon blacks carry out catalyst；Charcoal in catalyst
Black mass fraction is about 42%.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 59.42%, hydro carbons 20.12%,
CO212.76%th, total alcohol selectivity 67.12%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 70.52%, 3.71%, 1.94%, 3.04%, 18.77%, 2.02%, that is, the selectivity of isobutanol is
12.6%.
Experimental group 4-4
Experimental group 4-4 is distinguished as with experimental group 4-1's：Weigh the preparation that 2g carbon blacks carry out catalyst；Carbon black in catalyst
Mass fraction be about 29%.
On-line testing is carried out using GC9560 gas-chromatographies, CO conversion ratios are 59.13%, hydro carbons 20.71%,
CO212.88%th, total alcohol selectivity 66.41%, methanol, ethanol, isopropanol, normal propyl alcohol, isobutanol, the alcohol of n-butanol in total alcohol
Distribution is respectively 70.48%, 3.83%, 2.10%, 3.24%, 18.37%, 1.98%, that is, the selectivity of isobutanol is
12.2%.
Experimental group 4-1,4-2,4-3,4-4 experiment condition and experimental result are shown in Table 4.As shown in table 4, experimental group 4-1,
It is to prepare catalyst using carbon black in 4-2,4-3,4-4, but the dosage of carbon black is different, it was found from experimental result, experimental group
When the mass fraction of carbon black is 34% in 4-1 namely catalyst, the selectivity of CO conversion ratios and isobutanol is higher, is respectively
61.14%th, 14.8%.
Table 4
In addition, the experimental group tested for different graphitized carbon materials is analyzed.Herein only to wherein
Best one group of result of the test is contrasted, namely is contrasted for experimental group 1-1,2-1,3-1,4-1.Experimental group 1-1,2-
1st, 3-1,4-1 experiment condition and experimental result are shown in Table 5.
Table 5
Contrast all experimental groups to understand, the catalyst being prepared using graphite, during for synthesizing isobutanol, isobutanol
Selective highest, can reach 17.0%；The catalyst being prepared using carbon black, during for synthesizing isobutanol, CO conversion ratios
Highest, it can reach 61.14%.Also, the catalyst being prepared using different types of graphitized carbon material, it is different for synthesizing
During butanol, preferably catalyst reduction condition and synthesis condition are different, specific i.e. as shown in table 5.
Compared with prior art, the preparation method of catalyst provided by the present invention, it includes：Graphitization carbon materials are provided
Material, and carry out activation process and obtain Activated Graphite carbon material；Copper zinc-aluminium salting liquid and alkaline solution are provided；By the active stone
Inkization carbon material is dispersed in water, and is added the copper zinc-aluminium salting liquid and alkaline solution simultaneously thereto and be co-precipitated to obtain
Presoma；And the presoma is carried out to be thermally treated resulting in required catalyst.First, it uses graphitized carbon material and copper zinc
Aluminum salt solution is raw material, and preparation cost is low, is adapted to industrialized production；Secondly, obtained catalyst is particularly suitable for preparing
Synthesis gas prepares isobutanol, and its CO conversion ratio and isobutanol selectivity are high；In addition, obtained catalyst is used to synthesize isobutyl
Alcohol, reaction condition are gentle.
It is further the adding speed for controlling the copper zinc-aluminium salting liquid and alkaline solution, makes the co-precipitation be in pH value
Carried out under conditions of 5.0-7.0.Both adding speeds and addition are can determine that by monitoring pH value in adding procedure,
So as to ensure being smoothed out and obtaining required reaction product for co-precipitation.
It is further that the carbon content of the graphitized carbon material is more than 99%, and graphitized carbon content is more than 90%.So
The degree of graphitization and its effective mass of graphitized carbon material can be ensured well, so as to ensure catalyst performance.
Preferably, the molal quantity of the graphitized carbon material is n1, copper, zinc, mole of aluminium in the copper zinc-aluminium salting liquid
Number is respectively n2、n3、n4, n1:n2:n3:n4=(10-20):(1-3):(0.5-1.5):(0.4-1.2).By determining copper zinc-aluminium
The mole ratio of copper, zinc, aluminium in salting liquid, active material Cu/ZnO/Al in gained catalyst is also determined that2O3Composition, from
And preferably ensure the activity of catalyst.By determining that the molal quantity of graphitized carbon material can determine that Activated Graphite in catalyst
Change the mass fraction of carbon material, can preferably ensure to obtain catalytic performance preferably catalyst.
Preferably, the activation process is activates using acid solution to the graphitized carbon material, the acidity
The molar concentration of solution is 10-20mol/L；Or the activation process is that the graphitized carbon material is carried out using alkaline solution
Activation, the molar concentration of the alkaline solution is 2-8mol/L.Activation degree is so can guarantee that, wherein being preferably to utilize acidity
Solution activates the graphitized carbon material, and the surface of its Activated Graphite carbon material obtained is defective, can be with sediment phase
With reference to, promote the electronics of active component in catalyst to shift, and then guarantee CO conversion ratios and isobutanol selectivity.
Preferably, the activation process is specially：The acid solution that molar concentration is 10-20mol/L is provided；Make acid molten
Liquid submerges the graphitized carbon material, and the 2-4h that flowed back at 50-90 DEG C obtains activation products；Activation products are washed, and
16-24h is dried at 80-120 DEG C and obtains Activated Graphite carbon material.By return acid solution, and further determine that temperature
Degree and time, ensure the activation effect of graphitized carbon material.
The present invention also provides a kind of catalyst, and the catalyst is is contained with Activated Graphite carbon material by what carrier was formed
There is the compound of copper, zinc oxide and aluminum oxide, be expressed as Cu/ZnO/Al2O3/ x%C.The catalyst is particularly suitable for preparing
Synthesis gas prepares isobutanol, and its CO conversion ratio and isobutanol selectivity are high；Also, obtained catalyst is used to synthesize isobutyl
Alcohol, reaction condition are gentle.
It is further that the mass fraction of Activated Graphite carbon material is 10-50% in the catalyst.Obtained
Activated Graphite carbon material is as carrier in catalyst, if content is too low, it is impossible to which reach disperses active material well
Uniformly, and promotion electronics shifts and other effects；If content is too high, then activity substance content is low accordingly, influences obtained
The activity of catalyst.Therefore by determining the mass fraction of Activated Graphite carbon material in catalyst, can preferably ensure to obtain
Catalytic performance preferably catalyst.
The present invention also provides a kind of method for synthesizing isobutanol, using hydrogen and carbon monoxide as synthesis gas, is urged using above-mentioned
Agent is 250-360 DEG C in reaction temperature, and pressure synthesizes under conditions of being 3-5Mpa and obtains isobutanol.First, reaction condition temperature
With, and CO conversion ratios and isobutanol selectivity are high.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all originals in the present invention
Any modification made within then, equivalent substitution and improvement etc. all should be included within protection scope of the present invention.
Claims (10)
- A kind of 1. preparation method of catalyst, it is characterised in that：Including：Graphitized carbon material is provided, and carries out activation process and obtains To Activated Graphite carbon material；Copper zinc-aluminium salting liquid and alkaline solution are provided；The Activated Graphite carbon material is dispersed in water, and adds the copper zinc-aluminium salting liquid and alkalescence is molten simultaneously thereto Liquid is co-precipitated to obtain presoma；AndThe presoma is carried out to be thermally treated resulting in required catalyst.
- 2. the preparation method of catalyst as described in the appended claim 1, it is characterised in that：Control the copper zinc-aluminium salting liquid and alkalescence The adding speed of solution, co-precipitation is set to be carried out under conditions of pH value is 5.0-7.0.
- 3. the preparation method of catalyst as described in the appended claim 1, it is characterised in that：The carbon content of the graphitized carbon material is big In 99%, graphitized carbon content is more than 90%.
- 4. the preparation method of catalyst as described in the appended claim 1, it is characterised in that：The molal quantity of the graphitized carbon material is n1, copper, zinc, the molal quantity of aluminium are respectively n in the copper zinc-aluminium salting liquid2、n3、n4, n1:n2:n3:n4=(10-20):(1-3): (0.5-1.5):(0.4-1.2)。
- 5. the preparation method of catalyst as described in the appended claim 1, it is characterised in that：The activation process is to utilize acid solution The graphitized carbon material is activated, the molar concentration of the acid solution is 10-20mol/L；Or the activation process To be activated using alkaline solution to the graphitized carbon material, the molar concentration of the alkaline solution is 2-8mol/L.
- 6. the preparation method of catalyst as claimed in claim 5, it is characterised in that：The activation process is specially：Offer rubs The acid solution that your concentration is 10-20mol/L；Acid solution is set to submerge the graphitized carbon material, flow back 2- at 50-90 DEG C 4h obtains activation products；Activation products are washed, and dries 16-24h at 80-120 DEG C and obtains Activated Graphite carbon materials Material.
- 7. the preparation method of catalyst as recited in claim 6, it is characterised in that：The acid solution be nitric acid or nitric acid with The mixed acid of sulfuric acid.
- A kind of 8. catalyst, it is characterised in that：The catalyst is is contained with Activated Graphite carbon material by what carrier was formed The compound of copper, zinc oxide and aluminum oxide, is expressed as Cu/ZnO/Al2O3/ x%C.
- 9. catalyst as claimed in claim 8, it is characterised in that：The quality of Activated Graphite carbon material point in the catalyst Number is 10-50%.
- A kind of 10. method for synthesizing isobutanol, it is characterised in that：, will using such as right using hydrogen and carbon monoxide as synthesis gas Ask catalyst described in 8 reaction temperature be 250-360 DEG C, pressure be 3-5Mpa under conditions of synthesis obtain isobutanol.
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