CN106807422A - Catalyst and its preparation and application for modulation synthesis gas higher alcohol performance - Google Patents
Catalyst and its preparation and application for modulation synthesis gas higher alcohol performance Download PDFInfo
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- CN106807422A CN106807422A CN201510854580.5A CN201510854580A CN106807422A CN 106807422 A CN106807422 A CN 106807422A CN 201510854580 A CN201510854580 A CN 201510854580A CN 106807422 A CN106807422 A CN 106807422A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
Abstract
The invention discloses a kind of catalyst for modulation synthesis gas higher alcohol performance and its preparation method and application.According to the present invention, the catalyst for CO hydrogenation synthesis higher alcohols is disclosed, consisting of xM1yM2/ AC, wherein AC are carrier active carbon, the first component M1It is metallic cobalt, the second component M2For alkaline-earth metal Mg, Ca, Sr and Ba one or more.On the basis of catalyst quality percentage, its composition is the catalyst：The mass content of cobalt element is 1~30%, and the mass content of alkali earth metal is 0.01~10%.The catalyst is prepared from using infusion process, preparation method is simple, required catalytic reaction condition is gentle, suitable catalyst composition and catalyst heat treatment method can be selected according to required target product, using catalyst of the invention, the reactivity worth (including activity and selectivity of product) of higher alcohol can be prepared with modulation synthesis gas.
Description
Technical field
The present invention relates to a kind of catalyst for modulation synthesis gas higher alcohol performance.
The invention further relates to the preparation method of above-mentioned catalyst.
The invention further relates to above-mentioned catalyst in CO Hydrogenations for the application in mixed alcohol reaction.
Background technology
With the continuous progress of society, the demand of fuel and platform chemicals is improved constantly, and oil is provided
The dependence in source constantly strengthens, and the reserves of petroleum resources are constantly being reduced.On the other hand, with to ring
The requirement of guarantor is more and more harsh, develops the non-petroleum chemical industry system with coal and natural gas as raw material and is subject to more
Carry out more concerns.The national conditions of the few gas of China's richness coal determine that Coal Chemical Industry Route is more suitable for China
Non-petroleum chemical industry route.Therefore, the chemicals such as liquid fuel and oxygenatedchemicals are prepared via synthesis gas
Research become the study hotspot of academic circles at present and industrial circle due to being with a wide range of applications.
Mixing higher alcohol includes MAS (C2-C5) and high-carbon mixed alcohol (C6-C18).It is wherein low
Carbon mixed alcohol can directly as fuel or as fuel additive, it have good dissolubility,
Volatility, driver behavior and octane number higher.And high-carbon mixed alcohol have it is more distinctive excellent
Performance, is widely used in multiple fields, can serve as production plasticizer, surfactant and
The raw material of the chemical products with high added-value such as detergent.Compared with traditional artificial oil, synthol has more
Added value and more preferable application prospect high.
CO hydrogenation one-step method can be directly synthesized mixed alcohol, including MAS and high-carbon mixed alcohol etc.
Higher alcohol product.This kind of catalyst of report has following representative patent at present.
Chinese patent CN103831112A disclose a kind of catalyst for low carbon alcohol by synthetic gas and
Its preparation method and application, catalyst described in the patent are carbon nanotube loaded Cu-Co-Ce catalyst
System, the catalyst can catalyze and synthesize solid/liquid/gas reactions and obtain MAS, predominantly C1-C4Alcohol, its
Middle methanol content accounts for 20%.
Chinese patent CN103433046A discloses one kind is used for synthesis gas mixed alcohol especially high-carbon
The copper cobalt-based compound oxide catalyst and preparation method of alcohol and application.The catalyst under certain condition, can
To obtain the C of certain content2+C more than mixing higher alcohol, including 15%6+Mixing higher alcohols.
United States Patent (USP) 4504600 is reported using thallium as the ferrum-based catalyst of auxiliary agent, can obtain hydrocarbon
The C of class content 4~8%6~C12High-carbon mixed alcohol, and CO2Selectivity then up to 12~18%.
Dalian Inst of Chemicophysics, Chinese Academy of Sciences have developed and prepare height for the step of CO hydrogenation reactions one
The catalyst of level mixed alcohol, wherein US 7670985 and CN101310856 disclose its catalyst system and catalyzing is
Activated carbon supported cobalt-base catalyst, in the product of the CO hydrogenation reactions of the catalyst, C2~C18
Higher alcohol accounts for 60% or so of total product liquid.Their patent CN103586060A discloses one afterwards
Plant and improve catalyst and its preparation method and application that FT synthesizes higher alcohols selectivity processed.The catalyst is adopted
Activated carbon supported Co catalysts are modified with one or more in Al, B or Ga, are obtained more
Excellent catalytic effect.
The present invention discloses one kind and directly prepares Higher Mixed Alcohols coproduction cleaning diesel oil, stone brain for modulation CO
The catalyst system of oiliness energy.Using catalyst system of the invention, different alkaline-earth metal kinds are selected
Class and load capacity, the catalyst of preparation is used for CO hydrogenation reactions can obtain the higher alcohol of correspondence cut.
The content of the invention
It is an object of the invention to provide a kind of catalyst for modulation synthesis gas higher alcohol performance and
Its preparation method and application, the application are to be directly synthesized C in CO hydrogenation one-step method2~C18Straight chain mixes
Primary alconol, can obtain C higher2~C5And C6~C18Higher alcohol yield, wherein described higher alcohol is former carbon
Primary alconol of the subnumber more than 2, described catalyst can be with coproduction clean fuel liquid and mixing primary alconol, choosing
Suitable catalyst composition and heat treatment method are selected, the selectivity of correspondence target product can be improved.
The technical solution adopted in the present invention is：
The catalyst includes active component, auxiliary agent and carrier, and wherein active component is metallic cobalt and carbon
Change cobalt, auxiliary agent is the combination of one or more of alkaline-earth metal Mg, Ca, Sr and Ba, the carrier
It is activated carbon.
On the basis of above-mentioned technical proposal, further, the cobalt content in the catalyst is catalysis
The 1~30% of agent quality；It is preferred that 10~20%, alkaline earth metal content is the 0.01~10% of catalyst quality,
It is preferred that 0.1~1.0%, remaining is activated carbon.
On the basis of above-mentioned technical proposal, further, wherein described carrier is active fruit shell carbon,
The specific surface area of the activated carbon is 200~2000m2/ g, average pore size is 0.5~30nm, and pore volume is
0.1~2ml/g.
Another aspect provides a kind of method for preparing catalyst for preparing above-mentioned catalyst, in
The method of carrying metal component is two kinds on carrier, and method one is that will be again heat-treated after slaine co-impregnation
Carrying metal component, method two is to be impregnated slaine and be heat-treated two step operations by several times to support
Metal component：
Method one：
A) deionized water boiling washing absorbent charcoal carrier；
B) soluble salt of active component and auxiliary agent is dissolved in solvent and is stirred, obtain metal front
Body salting liquid, the absorbent charcoal carrier after washing is slowly added to be stirred in salting liquid, obtains sample
1；
C) sample 1 is heat-treated, is obtained sample 2；
D) by sample 2 by activation process be obtain for modulation synthesis gas higher alcohol catalyst；
Method two：
A) deionized water boiling washing absorbent charcoal carrier；
B) soluble salt of active component or auxiliary agent is dissolved in solvent and is stirred, obtain metal front
Body salting liquid, the absorbent charcoal carrier after washing is slowly added to be stirred in salting liquid, obtains sample
A；
C) sample A is heat-treated, is obtained sample B；
D) soluble salt of auxiliary agent or active component is dissolved in solvent and is stirred, obtain metal front
Body salting liquid, sample B is slowly added to be stirred in salting liquid, obtains sample C；
E) sample C is heat-treated, is obtained sample D；
F) by sample D by activation process be obtain for modulation synthesis gas higher alcohol catalyst；
In method two, slaines step b) different with d) middle selection are supported, and slaine is activity
The soluble salt of component or auxiliary agent.
The soluble salt of the auxiliary agent or active component is its nitrate, carbonate or oxalates；It is described molten
The solvent of enzymolysis auxiliary agent or active component soluble salt is deionized water or organic solvent, the organic solvent
For it is any it is known can be used to as solvent compound and it is two or more can mutual solvents mixture,
May be selected from methyl alcohol, ethanol, isopropanol, acetone, one or several the mixture in ethylene glycol.
Described method, wherein, absorbent charcoal carrier is the active fruit shell carbon such as coconut husk charcoal or almond charcoal.
The heat treatment condition of wherein catalyst is divided into following two：
A) impregnated sample is dried into 8-24h in air atmosphere at a temperature of 323~373K, that is, is done
Dry half-dried catalyst precursors；
B) 8-24h or by impregnated sample is dried in air atmosphere at a temperature of 323~373K, then
2~48h is calcined under the inert atmosphere of 473~773K nitrogen, argon gas or helium, that is, is obtained and is loaded with living
The catalyst precursors of property component oxide, wherein, 573~673K of preferable temperature during roasting is preferably roasted
3~10h of burning time.
Activation process condition is carried out under the mixed atmosphere of hydrogen, the hydrogen content of hydrogeneous gaseous mixture
It is 1~100%, other gases are nitrogen, argon gas or helium beyond hydrogen in gaseous mixture；Hydrogeneous gaseous mixture
Air speed be 500~10000h-1, activation temperature is 473K~1073K, and soak time is 2~48 hours,
Activation pressure is 0.1~1.0MPa；The activation process of catalyst uses Activated in Vitro or in-situ activation.
In above-mentioned technical proposal, further preferred activation condition:The hydrogen content of hydrogeneous gaseous mixture is
50~100%, other gases are argon gas beyond hydrogen in gaseous mixture；The air speed of hydrogeneous gaseous mixture is
1000~5000h-1, activation temperature is 573K~773K, and soak time is 10~20 hours, activation pressure
It is 0.1~0.3MPa；The activation process of catalyst uses in-situ activation.
Another aspect of the invention, there is provided a kind of catalyst is used for the standby mixing of modulation CO Hydrogenations
The application of primary alconol performance, the application is included in the presence of catalyst described above, CO and H2Reaction life
Linear C1~C18Mixing primary alconol, wherein C2+Senior alcohol content is higher above.
In a preferred embodiment of the invention, methods described is carried out under the following conditions：
Reaction temperature is 473K~543K, and reaction pressure is 0.5~6.0MPa, and air speed is 500-5000h-1, its
Middle H2/ CO mol ratios are 0.5~4:1.
Reaction is carried out in fixed bed reactors, and wherein reaction end gas and gas-phase product persistently flow out,
And higher boiling and low boiling liquid product are collected respectively with hot trap and cold-trap.
Catalyst of the present invention can prepare the reactivity worth of higher alcohol with modulation synthesis gas, including activity and
Selectivity of product.The appropriate alkaline-earth metal species of selection, and the alkaline-earth metal is suitable with metallic cobalt
Mol ratio, the catalyst of the specific composition for preparing can obtain proper ratio in activation process
Metallic cobalt and cobalt carbide, catalyst CO add hydroformylation step can be obtained when preparing mixed alcohol correspondence
Alcohol product.
Beneficial effects of the present invention are：
Using the catalyst prepared by catalyst of the invention or preparation method of the invention or using this hair
It is bright for CO Hydrogenations for mixed alcohol method, methanol content in the liquid product that CO is hydrogenated to
It is 5% or so, C2~C5Straight chain mixing primary alconol content is 11~58%, C6-C18Straight chain mixing primary alconol content is
8~25%；Total alcohol content highest can reach 75% or so in liquid product；C2+The yield of higher alcohol is roasting
50g/kg-cath can be reached on the basis of burning sample quality.It is straight that the catalyst can be used for CO hydrogenation
It is bonded into C2~C18Straight chain mixing primary alconol coproduction naphtha and diesel oil, with CO conversion ratios higher and
C2~C18The selectivity of straight chain mixing primary alconol, can simultaneously obtain C higher2~C5And C6~C18Higher alcohol is produced
Rate.
Specific embodiment
Below by specific embodiment, the present invention will be further described.
Embodiment 1
1000 grams of coconut activated high-area carbons carry out carrying out washing treatment three by the way of deionized water boiling washing
Secondary, 393K is dried 12 hours, obtains preparing the carrier material of catalyst.
The composition of catalyst A is 15Co0.05Ca/AC, and wherein metallic cobalt content is catalyst quality
15%, alkaline-earth metal calcium content is the 0.05% of catalyst quality, with the activated carbon that 40~60 mesh are treated
It is carrier, method for preparing catalyst is carried out in the steps below.Weigh 5 grams of activated carbons handled well.Claim
Take 4.35 grams of Co (NO3)2·6H2O and 0.02 gram of Ca (NO3)2·4H2O, dissolves them in 4.0 grams
Solution is made in deionized water.Obtained solution is supported on absorbent charcoal carrier with infusion process.Then
Dried 12 hours at a temperature of air atmosphere 333K, obtain the predecessor of catalyst A.
Embodiment 2
The composition of catalyst B is 15Co0.1Ca/AC.Except weighing 4.36 grams of Co (NO3)2·6H2O generations
For 4.35 grams of Co (NO3)2·6H2O, weighs 0.04 gram of Ca (NO3)2·4H2O replaces 0.02 gram
Ca(NO3)2·4H2Outside O, other steps are with embodiment 1.
Embodiment 3
The composition of catalyst C is 15Co0.5Ca/AC.Except weighing 4.38 grams of Co (NO3)2·6H2O generations
For 4.35 grams of Co (NO3)2·6H2O, weighs 0.17 gram of Ca (NO3)2·4H2O replaces 0.02 gram
Ca(NO3)2·4H2Outside O, other steps are with embodiment 1.
Embodiment 4
The composition of catalyst D is Co-Mg/AC, and wherein the mass content of metallic cobalt is 15%, alkaline earth gold
The mol ratio of category magnesium and metallic cobalt is 0.04, is carrier with the activated carbon that 40~60 mesh are treated, catalysis
Agent preparation method is carried out in the steps below.Weigh 5 grams of activated carbons handled well.Weigh 0.11 gram
Mg(NO3)2·2H2O, to dissolve it in and be made solution in 6.0 grams of deionized waters.To be obtained with infusion process
Solution be supported on absorbent charcoal carrier.Above-mentioned catalyst sample is dried at a temperature of air atmosphere 333K
12 hours, then 393K was dried 2 hours in argon gas atmosphere, the last 873K temperature in argon gas atmosphere
The lower roasting of degree 3 hours, obtains final product the absorbent charcoal carrier of magnesium oxide modification.
Then, 3.49 grams of Co (NO are weighed3)2·6H2O is made in dissolving it in 5.0 grams of deionized waters
Solution.Obtained solution is supported on the activity of magnesium oxide modification prepared by preceding method with infusion process
On charcoal.The sample is dried 12 hours at a temperature of air atmosphere 333K, then in argon gas atmosphere
393K is dried 2 hours, and finally 623K roasting temperatures 3 hours in argon gas atmosphere, obtain activity
The cobalt/cobalt oxide presoma of the magnesium oxide modification of charcoal load.
Embodiment 5
The composition of catalyst E is Co-Ca/AC, and wherein the mass content of metallic cobalt is 15%, alkaline earth gold
The mol ratio of category calcium and metallic cobalt is 0.04, except weighing 0.14 gram of Ca (NO3)2·4H2O replaces 0.11
Gram Mg (NO3)2·2H2Outside O, other steps are with embodiment 4.
Embodiment 6
The composition of catalyst F is Co-Sr/AC, and wherein the mass content of metallic cobalt is 15%, alkaline earth gold
The mol ratio of category strontium and metallic cobalt is 0.04, except weighing 0.13 gram of Sr (NO3)2Instead of 0.11 gram
Mg(NO3)2·2H2Outside O, other steps are with embodiment 4.
Embodiment 7
The composition of catalyst G is Co-Ba/AC, and wherein the mass content of metallic cobalt is 15%, alkaline earth gold
The mol ratio of category barium and metallic cobalt is 0.04, except weighing 0.16 gram of Ba (NO3)2Instead of 0.11 gram
Mg(NO3)2·2H2Outside O, other steps are with embodiment 4.
Embodiment 8
The composition of catalyst H be 15Co/AC, the cocoanut active charcoal handled well with embodiment 1 as carrier,
Catalyst is prepared according to the following steps.Weigh 5 grams of activated carbons handled well.Weigh 4.35 grams
Co(NO3)2·6H2O, to dissolve it in and be made solution in 4.0 grams of deionized waters.To be obtained with infusion process
Solution be supported on absorbent charcoal carrier, then at a temperature of air atmosphere 333K dry 12 hours,
Obtain catalyst precursor.
Embodiment 9
The composition of catalyst I is 15Co/AC, and the cocoanut active charcoal handled well with embodiment 1 is load
Body, catalyst is prepared according to the following steps.Weigh 5 grams of activated carbons handled well.Weigh 4.35 grams
Co(NO3)2·6H2O, to dissolve it in and be made solution in 4.0 grams of deionized waters.To be obtained with infusion process
Solution be supported on absorbent charcoal carrier, then at a temperature of air atmosphere 333K dry 12 hours,
Then 393K is dried 2 hours in argon gas atmosphere, last 623K roasting temperatures in argon gas atmosphere
Obtain catalyst precursor within 3 hours.
The CO Hydrogenations of above-described embodiment catalyst for linear hybrid alcohol catalytic performance test in fixation
Carried out in bed reactor.Respectively take catalyst 2ml to be seated in fixed bed reactors, fixed bed reactors
Internal diameter be 9mm, length is 400mm.Catalyst needs to carry out in-situ activation before the reaction, and original position is living
The condition of change is pure hydrogen atmosphere, and pressure is 0.1MPa, and air speed is 1000h-1, temperature is 703K, also
It is former 10 hours.Obtain the presoma that activity master is divided into metallic state.Reaction bed temperature drop after activation
As little as 353K or so, switching and merging gas (H2/ CO mol ratios are reacted to be 493K in temperature 2/1)
Pressure is 3.0MPa, and air speed is 1000h-1Or 2000h-1Reacted under conditions of continuous feed,
Reaction end gas and gas-phase product are persistently discharged, and higher boiling and low boiling liquid are collected respectively with hot trap and cold-trap
Phase product, hot trap temperature is 393K, and condenser temperature is 273~293K.React steady by 24 hours
After fixed, the product of 24 hours is analyzed calculating after collection stationary phase.The composition of catalyst A-I and comment
Valency result is listed in table 1.
Table 1：Catalyst (A-I) is catalyzed CO hydrogenation synthesis mixed alcohol reactivity worth
*Reaction condition：Temperature 493K；Pressure 3.0MPa；Air speed 2000h-1；48 hours reaction time；
Calculation of yield is to be calcined on the basis of sample quality.
#Reaction condition：Temperature 493K；Pressure 3.0MPa；Air speed 1000h-1；48 hours reaction time；
Calculation of yield is on the basis of drying sample quality.
Claims (10)
1. a kind of catalyst for modulation synthesis gas higher alcohol performance, it is characterised in that：The catalyst
Including active component, auxiliary agent and carrier, wherein active component is metallic cobalt and cobalt carbide, and auxiliary agent is alkaline earth gold
Belong to the combination of one or more of Mg, Ca, Sr and Ba, the carrier is activated carbon, wherein described height
Level alcohol is primary alconol of the carbon number more than 2.
2. catalyst according to claim 1, it is characterised in that：Cobalt content in the catalyst is
The 1~30% of catalyst quality；Alkaline earth metal content is the 0.01~10% of catalyst quality, and remaining is activated carbon.
3. catalyst according to claim 1 and 2, wherein described carrier is active fruit shell carbon, institute
The specific surface area for stating activated carbon is 200~2000m2/ g, average pore size is 0.5~30nm, and pore volume is 0.1~2ml/g.
4. the preparation method of any catalyst of a kind of claims 1 to 3, it is characterised in that：In carrier
The method of upper carrying metal component is two kinds, and method one is by reheating treatment carrying metal after slaine co-impregnation
Component, method two is to impregnate slaine by several times and be heat-treated two step operation carrying metal components：
Method one：
A) deionized water boiling washing absorbent charcoal carrier；
B) soluble salt of active component and auxiliary agent is dissolved in solvent and is stirred, obtain metal precursor salt
Solution, the absorbent charcoal carrier after washing is slowly added to be stirred in salting liquid, obtains sample 1；
C) sample 1 is heat-treated, is obtained sample 2；
D) by sample 2 by activation process be obtain for modulation synthesis gas higher alcohol catalyst；
Method two：
A) deionized water boiling washing absorbent charcoal carrier；
B) soluble salt of active component or auxiliary agent is dissolved in solvent and is stirred, obtain metal precursor salt
Solution, the absorbent charcoal carrier after washing is slowly added to be stirred in salting liquid, obtains sample A；
C) sample A is heat-treated, is obtained sample B；
D) soluble salt of auxiliary agent or active component is dissolved in solvent and is stirred, obtain metal precursor salt
Solution, sample B is slowly added to be stirred in salting liquid, obtains sample C；
E) sample C is heat-treated, is obtained sample D；
F) by sample D by activation process be obtain for modulation synthesis gas higher alcohol catalyst；
In method two, slaines step b) different with d) middle selection are supported, and slaine is active component
Or the soluble salt of auxiliary agent.
5. preparation method according to claim 4, it is characterised in that：The auxiliary agent or active component
Soluble salt is its nitrate, carbonate or oxalates；The solvent of the dissolution aids or active component soluble salt
It is deionized water or organic solvent, the organic solvent may be selected from methyl alcohol, ethanol, isopropanol, acetone,
One or several mixture in ethylene glycol.
6. preparation method according to claim 4, it is characterised in that：The wherein heat treatment bar of catalyst
Part is divided into following two：
A) impregnated sample is dried into 8-24h in air atmosphere at a temperature of 323~373K, that is, obtains dry half
Dry catalyst predecessor；
B) 8-24h or by impregnated sample is dried in air atmosphere at a temperature of 323~373K, is then existed
2~48h is calcined under the inert atmosphere of 473~773K nitrogen, argon gas or helium, that is, is obtained and is loaded with active component
The catalyst precursors of oxide.
7. preparation method according to claim 4, it is characterised in that：Activation process condition is hydrogeneous
Carried out under the mixed atmosphere of gas, the hydrogen content of hydrogeneous gaseous mixture is 1~100%, in gaseous mixture beyond hydrogen other
Gas is nitrogen, argon gas or helium；The air speed of hydrogeneous gaseous mixture is 500~10000h-1, activation temperature is
473K~1073K, soak time is 2~48 hours, and activation pressure is 0.1~1.0MPa；At the activation of catalyst
Reason uses Activated in Vitro or in-situ activation.
8. application of any catalyst of a kind of claim 1-3 in CO Hydrogenations react for mixed alcohol.
9. application according to claim 8, it is characterised in that：The reaction is carried out under the following conditions:
Reaction temperature is 473K~543K, and reaction pressure is 0.5~6.0MPa, and air speed is 500-5000h-1, wherein
H2/ CO mol ratios are 0.5~4:1.
10. application according to claim 9, it is characterised in that：Reaction is in fixed bed reactors
Carry out, wherein reaction end gas and gas-phase product persistently flow out, and higher boiling is collected respectively with hot trap and cold-trap
With low boiling liquid product.
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| CN107744810A (en) * | 2017-11-06 | 2018-03-02 | 江南大学 | A kind of catalyst and its technological process by synthesis gas higher alcohol |
| CN112275304A (en) * | 2020-11-09 | 2021-01-29 | 济南大学 | Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof |
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| CN107744810A (en) * | 2017-11-06 | 2018-03-02 | 江南大学 | A kind of catalyst and its technological process by synthesis gas higher alcohol |
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| CN112275304A (en) * | 2020-11-09 | 2021-01-29 | 济南大学 | Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof |
| CN112275304B (en) * | 2020-11-09 | 2023-03-24 | 济南大学 | Carbon-supported cobalt carbide catalyst containing auxiliary agent and preparation method and application thereof |
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