CN106807421A - A kind of catalyst for synthesis gas mixed alcohol and its preparation method and application - Google Patents
A kind of catalyst for synthesis gas mixed alcohol and its preparation method and application Download PDFInfo
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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Abstract
The invention discloses a kind of catalyst for synthesis gas mixed alcohol and its preparation method and application.According to the present invention, the catalyst for CO hydrogenation synthesis mixed alcohols is disclosed, the catalyst includes the first active component, the second active component and carrier, wherein the first active component is metallic cobalt and iron, second active component is cobalt carbide and ferro-cobalt, and the carrier is activated carbon.On the basis of catalyst quality percentage, its composition is：The mass content of cobalt element is 1~30%, and the mass content of ferro element is 0.1~10%.The catalyst is prepared from using infusion process, and preparation method is simple, and required catalytic reaction condition is gentle, the C with catalysis activity is high, in product2~C18The selectivity of higher alcohol advantage higher, using catalyst of the invention, can improve the alcohol yield that synthesis gas system mixes primary alconol, with good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of catalyst for synthesis gas mixed alcohol.
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
It is increasingly exhausted with petroleum resources, increasingly harsh, fuel and the platform chemicals demand of environmental requirement
Continuous growth, the chemical industry system of Non oil-based route is developed to seek to substitute the part of petroleum resources ten
Divide urgent.Energy resource structure wherein based on coal and natural gas will occupy prior status.And China's richness coal
The national conditions of few gas, will further facilitate development and progress of the Coal Chemical Industry in China.Wherein converted via synthesis gas
Route be very important part in Coal Chemical Industry system.Coal is converted into liquid fuel and height through synthesis gas
The correlative study of the chemicals such as level alcohol, there is application prospect widely.
Mixing higher alcohol includes MAS (C2-C5) and high-carbon mixed alcohol (C6-C18).Wherein low-carbon (LC) mixing
Alcohol can be directly as fuel or as fuel additive, and it has good dissolubility, volatility, drives
Sail operational and higher octane number.And high-carbon mixed alcohol has more distinctive premium properties, led in multiple
It is widely used in domain, can serve as the high added values such as production plasticizer, surfactant and detergent
The raw material of chemical product.Compared with traditional artificial oil, synthol has added value higher and preferably application
Prospect.
At present, higher alcohols are industrially mainly produced by ziegler process and hydroformylation of higher olefins method.
Ziegler process is carried out with ethene as raw material by catalyst reaction of triethyl aluminum, then by aoxidizing,
Hydrolysis and separating technology, are obtained C6~C12Straight-chain even primary alconol.But the technological process is long, technical sophistication is urged
The consumption of agent triethyl aluminum is very big and security is poor.
Hydroformylation of higher olefins method is the production method as representative with South Africa Sasol techniques, is closed by Fischer-Tropsch
Into alkane and olefin product, separation of olefins is out used as raw material, then it is high in high temperature by catalyst of carbonyl cobalt
Depressing the alkene and synthesis gas carries out hydroformylation reaction and produces high-elastic complete, and finally hydrogenation obtains higher alcohols.But
It is that the technological process is long, severe reaction conditions, catalyst separates complexity, relatively costly.
Therefore, the higher alcohols production new technology that an urgent demand process is simple, reaction condition be gentle, raw material is easy to get.
CO hydrogenation one-step method can be directly synthesized mixed alcohol, senior including MAS and high-carbon mixed alcohol etc.
Alcohol product.This kind of catalyst of report has following representative patent at present.
Chinese patent CN103831112A discloses a kind of catalyst for low carbon alcohol by synthetic gas and its preparation
Methods and applications, catalyst described in the patent is carbon nanotube loaded Cu-Co-Ce catalyst systems, and this is urged
Agent can catalyze and synthesize solid/liquid/gas reactions and obtain MAS.
Chinese patent CN103433046A discloses a kind of copper for synthesis gas mixed alcohol especially higher alcohols
Cobalt-based compound oxide catalyst and preparation method and application.The catalyst under certain condition, can obtain certain
The C of content2+C more than mixing higher alcohol, including 15%6+Mixing higher alcohols.
United States Patent (USP) 4504600 is reported using thallium as the chalybeate catalyst of auxiliary agent, can be obtained hydro carbons and be contained
The C of amount 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 senior mixing for the step of CO hydrogenation reactions one
The catalyst of alcohol, it is activated carbon supported that wherein US 7670985 and CN101310856 disclose its catalyst system and catalyzing
Cobalt-base catalyst, in the product of the CO hydrogenation reactions of the catalyst, C2~C18Higher alcohol accounts for total liquid and produces
60% or so of thing.Their patent CN103586060A discloses a kind of raising FT synthesis higher alcohols processed afterwards
The catalyst of selectivity and its preparation method and application.The catalyst is using the one kind or several in Al, B or Ga
Plant and activated carbon supported Co catalysts are modified, obtain more excellent catalytic effect.
Rarely has the report that Higher Mixed Alcohols are prepared for load ferro-cobalt bicomponent catalyst in published patent.
Therefore the present invention disclose it is a kind of directly prepared for CO Higher Mixed Alcohols coproduction clean diesel oil, the Co-Fe of naphtha
Bimetallic catalyst system.
The content of the invention
It is an object of the invention to provide a kind of catalyst for synthesis gas mixed alcohol and preparation method thereof and should
With the catalyst can coproduction clean fuel liquid and mixing primary alconol, especially, C in product2+It is senior above
Alcohol content is higher, and the reactivity worth of CO hydrogenation reactions can be improved using the catalyst, improves CO hydrogenation and closes
Into the economic prospect of mixed alcohol.
The technical solution adopted by the present invention is：
A kind of CO hydrogenation one-step method that is used for is provided and is directly synthesized C2~C18The catalyst of straight chain mixing primary alconol, it is described
Catalyst includes the first active component, the second active component and carrier, wherein the first active component is metallic cobalt
And iron, the second active component is cobalt carbide and ferro-cobalt, and the carrier is activated carbon.
On the basis of above-mentioned technical proposal, further, cobalt content is catalyst quality in the catalyst
1~30%, preferably 10~20%；Iron content is the 0.1~10%, preferably 0.1~5% of catalyst quality, remaining
It is activated carbon.
On the basis of above-mentioned technical proposal, further, described carrier is active fruit shell carbon, the work
Property charcoal specific surface area be 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, the side
Method is carried out by the one kind in following two methods：
Method one：
A) deionized water boiling washing absorbent charcoal carrier；
B) molysite and salt solubility are stirred in solvent, obtains metal precursor salting liquid, will washed
Absorbent charcoal carrier afterwards is slowly added to be stirred in salting liquid, obtains sample 1；
C) sample 1 is dried in the shade at room temperature；At a temperature of 323~373K, in air atmosphere, 8~24h is dried,
2~48h is calcined under the inert atmosphere of 473~773K nitrogen, argon gas or helium, sample 2 is obtained；Wherein,
Preferable temperature 573K~623K, preferably 3~10h of roasting time during roasting；
D) by sample 2 by activation process be obtain for synthesis gas higher alcohol catalyst；
Method two：
A) deionized water boiling washing absorbent charcoal carrier；
B) molysite or salt solubility are stirred in solvent, obtains metal precursor salting liquid, will washed
Absorbent charcoal carrier afterwards is slowly added to be stirred in salting liquid, obtains sample A；
C) sample A is dried in the shade at room temperature；At a temperature of 323~373K, in air atmosphere, 8~24h is dried,
2~48h is calcined under the inert atmosphere of 473~773K nitrogen, argon gas or helium, sample B is obtained；Wherein,
Preferable temperature 573K~623K, preferably 3~10h of roasting time during roasting；
D) cobalt salt or iron salt dissolved are stirred in solvent, metal precursor salting liquid is obtained, by sample
B is slowly added to be stirred in salting liquid, obtains sample C；
E) sample C is dried in the shade at room temperature；8~24h is dried in air atmosphere at a temperature of 323~373K,
2~48h is calcined under the inert atmosphere of 473~773K nitrogen, argon gas or helium, sample D is obtained；Wherein, it is calcined
When preferable temperature 573K~623K, preferably 3~10h of roasting time；
F) by sample D by activation process be obtain for synthesis gas higher alcohol catalyst；
In method two, slaines step b) different with d) middle selection are supported, and slaine is cobalt salt or iron
Salt.
Described method, wherein, absorbent charcoal carrier is the active fruit shell carbon such as coconut husk charcoal or apricot shell charcoal.
The molysite or cobalt salt are its nitrate, carbonate or oxalates；It is described dissolving cobalt salt or molysite it is molten
Agent is deionized water or organic solvent, and the organic solvent is any known can be used to as the change of solvent
Compound and it is two or more can mutual solvents mixture, can be selected from methyl alcohol, ethanol, isopropanol, acetone,
One or several mixture in ethylene glycol.
The condition of catalyst activation treatment is carried out under the mixed atmosphere of hydrogen, the hydrogen of hydrogeneous gaseous mixture
Content is 1~100%, and 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.
In above-mentioned technical proposal, further preferred activation condition is：The hydrogen content of hydrogeneous gaseous mixture is
70~100%, other gases are argon gas beyond hydrogen in gaseous mixture；The air speed of hydrogeneous gaseous mixture is 1000~4000h-1,
Activation temperature is 573K~773K, and soak time is 10~30 hours, and activation pressure is 0.1~0.3MPa..
The activation of catalyst uses Activated in Vitro or in-situ activation.
Another aspect of the invention, there is provided a kind of catalyst is used for answering for the standby mixing primary alconol of CO Hydrogenations
With the application is included in the presence of catalyst described above, CO and H2The linear C of reaction generation1~C18Mixing
Primary alconol, wherein C2+Senior alcohol content is higher above, and the mixed alcohol is primary alconol of the carbon number more than 2.
The reaction is carried out under the following conditions:Reaction temperature is 473K~543K, and reaction pressure is
0.5~6.0MPa, air speed be 1~8L synthesis gas/gram-catalyst hour, wherein H2/ CO mol ratios are
0.5~4:1.
In a preferred embodiment of the invention, the reaction is carried out in fixed bed reactors, tail gas
Persistently discharged with gas-phase product, and higher boiling and low boiling liquid product are collected respectively with hot trap and cold-trap.
Beneficial effects of the present invention are：
Using the catalyst prepared by catalyst of the invention or preparation method of the invention or using of the invention
For CO Hydrogenations for mixed alcohol method, methyl alcohol is distributed as 10~20%, C in the alcohol that CO is hydrogenated to2~C5
Alcohol is distributed as 46~58%, C6-C18Straight chain mixing primary alconol is distributed as 20~43%.C2+The yield of higher alcohol can reach
50g/kgh, the catalyst can be used for CO hydrogenation and be directly synthesized 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 obtain simultaneously
C higher2~C5And C6~C18Higher alcohol yield.
Specific embodiment
Below by specific embodiment and comparative example, the present invention will be further described.
Embodiment 1
1000 grams of coconut activated high-area carbons carry out carrying out washing treatment three times by the way of deionized water boiling washing,
393K is dried 12 hours, obtains preparing the carrier material of catalyst.
The composition of catalyst A is 15Co0.1Fe/AC, is carrier with the AC activated carbons that 40~60 mesh are treated,
Method for preparing catalyst is carried out in the steps below.Weigh 5 grams of activated carbons handled well.Weigh 4.36 grams
Co(NO3)2·6H2O and 0.04 gram of Fe (NO3)3·9H2O, it is strong they be dissolved in 4.0 grams of deionized waters in be made
Solution.Obtained solution is supported on absorbent charcoal carrier with infusion process.Dry in the shade at room temperature, the time is being catalyzed
Agent reaches that dry condition is time-consuming to be defined, and is then dried 12 hours at a temperature of air atmosphere 333K, then exists
393K is dried 2 hours in argon gas atmosphere, and finally 623K roasting temperatures 3 hours in argon gas atmosphere, obtain
It is the catalyst A oxide precursor things that 15%, Fe mass contents are 0.1% to Co mass contents.
Embodiment 2
The composition of catalyst B is 15Co0.5Fe/AC.Except weighing 4.38 grams of Co (NO3)2·6H2O replaces 4.36
Gram Co (NO3)2·6H2O, weighs 0.21 gram of Fe (NO3)3·9H2O replaces 0.04 gram of Fe (NO3)3·9H2Outside O,
Other steps are with embodiment 1.
Embodiment 3
The composition of catalyst C is 15Co1Fe/AC.Except weighing 4.41 grams of Co (NO3)2·6H2O replaces 4.36
Gram Co (NO3)2·6H2O, weighs 0.43 gram of Fe (NO3)3·9H2O replaces 0.04 gram of Fe (NO3)3·9H2Outside O,
Other steps are with embodiment 1.
Embodiment 4
The composition of catalyst D is 15Co3Fe/AC, except weighing 4.51 grams of Co (NO3)2·6H2O replaces 4.36
Gram Co (NO3)2·6H2O, weighs 1.32 grams of Fe (NO3)3·9H2O replaces 0.04 gram of Fe (NO3)3·9H2Outside O,
Other steps are with embodiment 1.
Embodiment 5
The composition of catalyst E is 15Co5Fe/AC, except weighing 4.63 grams of Co (NO3)2·6H2O replaces 4.36
Gram Co (NO3)2·6H2O, weighs 2.26 grams of Fe (NO3)3·9H2O replaces 0.04 gram of Fe (NO3)3·9H2Outside O,
Other steps are with embodiment 1.
Embodiment 6
The composition of catalyst F is 15Co-5Fe/AC, is carrier with the AC activated carbons that 40~60 mesh are treated,
Method for preparing catalyst is carried out in the steps below.Weigh 5 grams of activated carbons handled well.Weigh 4.63 grams
Co(NO3)2·6H2O, to dissolve it in and be made solution in 4.0 grams of deionized waters.Will be obtained molten with infusion process
Liquid is supported on absorbent charcoal carrier.Dry in the shade at room temperature, reach that dry condition is time-consuming to be defined the time by catalyst,
Then dried at a temperature of air atmosphere 333K 12 hours, then 393K is dried 2 hours in argon gas atmosphere,
Last 623K roasting temperatures 3 hours in argon gas atmosphere, obtain activated carbon supported cobalt/cobalt oxide presoma.
Then, 2.26 grams of Fe (NO are weighed3)3·9H2O is made solution in dissolving it in 4.0 grams of deionized waters.
With infusion process by obtained solution be supported on preceding method prepare be supported with the activated carbon of cobalt/cobalt oxide.Room
Dried in the shade under temperature, reach that dry condition is time-consuming to be defined the time by catalyst, then at a temperature of air atmosphere 333K
Dry 12 hours, then 393K is dried 2 hours in argon gas atmosphere, the last 623K temperature in argon gas atmosphere
The lower roasting of degree 3 hours, obtains activated carbon supported cobalt iron oxide presoma.
Embodiment 7
The composition of catalyst G is 5Fe-15Co/AC, except first impregnating iron nitrate solution, cobalt nitrate is impregnated afterwards molten
Outside liquid, other steps are with embodiment 6.
Comparative example 1
The composition of catalyst H is 15Co/AC, and the cocoanut active charcoal handled well with embodiment 1 is urged as carrier
Agent is prepared according to the following steps.Weigh 5 grams of activated carbons handled well.Weigh 4.35 grams of Co (NO3)2·6H2O,
Dissolve it in and be made solution in 4.0 grams of deionized waters.Obtained solution is supported on activated carbon with infusion process
On carrier.Dry in the shade at room temperature, reach that dry condition is time-consuming to be defined the time by catalyst, then in air atmosphere
Dried at a temperature of 333K 12 hours, then 393K is dried 2 hours in argon gas atmosphere, finally in argon gas gas
623K roasting temperatures 3 hours in atmosphere, obtain activated carbon supported cobalt/cobalt oxide presoma.
Comparative example 2
The composition of catalyst I is 15Fe/AC, except weighing 6.38 grams of Fe (NO3)3·9H2O replaces 4.35 grams
Co(NO3)2·6H2Outside O, other steps are with comparative example 1.
Comparative example 3
The composition of catalyst J is 15Co5Fe/SiO2, except the carrier for using is by undressed commercial silica gel
Outside instead of treated activated carbon, other steps are with embodiment 5.
The CO Hydrogenations of above-described embodiment and comparative example catalyst are being consolidated for the catalytic performance test of linear hybrid alcohol
Carried out in fixed bed reactor.Catalyst 2ml is respectively taken to be seated in fixed bed reactors, fixed bed reactors
Internal diameter is 9mm, and length is 400mm.Catalyst needs to carry out in-situ activation, the bar of in-situ activation before the reaction
Part is pure hydrogen atmosphere, and pressure is 0.1MPa, and air speed is 1000h-1, temperature is 703K, is reduced 10 hours.
Obtain the presoma that main activity is divided into metallic state.Reaction bed temperature is reduced to 353K or so after activation,
Switching and merging gas (H2To be 493K in temperature 2/1), reaction pressure is 3.0MPa, air speed to/CO mol ratios
To be reacted under conditions of 4L syngas/gh continuous feeds, reaction end gas and gas-phase product persistently discharge,
Higher boiling and low boiling liquid product are collected respectively with hot trap and cold-trap, and hot trap temperature is 393K, condenser temperature
It is 273~293K.Reaction product of 24 hours after after the stabilization of 24 hours, collecting stationary phase is divided
Analysis is calculated.The composition and evaluation result of catalyst A-J are listed in table 1.
Table 1：Catalyst (A-J) is catalyzed CO hydrogenation synthesis mixed alcohol reactivity worth
Reaction condition：Temperature 493K；Pressure 3.0MPa；Air speed 4L syngas/gh；Reaction time is 48 small
When.
Conclusion：
When iron content is higher, the catalyst that step impregnation method is obtained, component metals distribution in the catalyst
More rationally, the metallic cobalt constituent element with high activity is more distributed in catalyst surface, and the catalyst is in catalysis
Reactivity and higher alcohol yield higher is shown in the reaction of CO hydrogenation synthesis mixed alcohol.
When iron content is relatively low, the Co catalysts that the metallic iron that co-impregnation is obtained promotes show metal high
Decentralization and good reducing property, the catalyst show ratio in the mixed alcohol reaction of catalysis CO hydrogenation synthesis
Reactivity higher.
The active fruit shell carbon with property is make use of in the present invention as carrier, and one has been carried out to carrier
Fixed purification process.The carrier loaded ferro-cobalt bimetallic catalyst, can be with by after suitable activation process
There is metallic cobalt simultaneously, metallic iron, the catalyst of cobalt carbide and ferro-cobalt component, catalyst exists
Reactivity and higher alcohol yield high is shown in CO hydrogenation reactions.
Claims (10)
1. a kind of catalyst for synthesis gas mixed alcohol, it is characterised in that：The catalyst includes first
Active component, the second active component and carrier, wherein the first active component is metallic cobalt and iron, the second activity
Component is cobalt carbide and ferro-cobalt, and the carrier is activated carbon.
2. catalyst according to claim 1, it is characterised in that：Cobalt content is to urge in the catalyst
The 1~30% of agent quality, preferably 10~20%；Iron content is the 0.1~10%, preferably 0.1~5% of catalyst quality,
Remaining is activated carbon.
3. catalyst according to claim 1 and 2, it is characterised in that：Wherein described carrier is fruit
Shell activated carbon, the specific surface area of the activated carbon is 200~2000m2/ g, average pore size is 0.5~30nm, hole
It is 0.1~2ml/g to hold.
4. the preparation method of any catalyst of a kind of claims 1 to 3, it is characterised in that：The side
Method is carried out by the one kind in following two methods：
Method one：
A) deionized water boiling washing absorbent charcoal carrier；
B) molysite and salt solubility are stirred in solvent, obtains metal precursor salting liquid, will washed
Absorbent charcoal carrier afterwards is slowly added to be stirred in salting liquid, obtains sample 1；
C) sample 1 is dried in the shade at room temperature；At a temperature of 323~373K, in air atmosphere, 8~24h is dried,
2~48h is calcined under the inert atmosphere of 473~773K nitrogen, argon gas or helium, sample 2 is obtained；
D) by sample 2 by activation process be obtain for synthesis gas higher alcohol catalyst；
Method two：
A) deionized water boiling washing absorbent charcoal carrier；
B) molysite or salt solubility are stirred in solvent, obtains metal precursor salting liquid, will washed
Absorbent charcoal carrier afterwards is slowly added to be stirred in salting liquid, obtains sample A；
C) sample A is dried in the shade at room temperature；At a temperature of 323~373K, in air atmosphere, 8~24h is dried,
2~48h is calcined under the inert atmosphere of 473~773K nitrogen, argon gas or helium, sample B is obtained；
D) cobalt salt or iron salt dissolved are stirred in solvent, metal precursor salting liquid is obtained, by sample
B is slowly added to be stirred in salting liquid, obtains sample C；
E) sample C is dried in the shade at room temperature；8~24h is dried in air atmosphere at a temperature of 323~373K,
2~48h is calcined under the inert atmosphere of 473~773K nitrogen, argon gas or helium, sample D is obtained；
F) by sample D by activation process be obtain for synthesis gas higher alcohol catalyst；
In method two, slaines step b) different with d) middle selection are supported, and slaine is cobalt salt or iron
Salt.
5. preparation method according to claim 4, it is characterised in that：The molysite or cobalt salt are its nitre
Hydrochlorate, carbonate or oxalates；It is described dissolving cobalt salt or molysite solvent be deionized water or organic solvent,
The organic solvent may be selected from methyl alcohol, ethanol, isopropanol, acetone, in ethylene glycol one or several
Mixture.
6. preparation method according to claim 4, it is characterised in that：The condition of catalyst activation treatment
It is to be carried out under the mixed atmosphere of hydrogen, the hydrogen content of hydrogeneous gaseous mixture is 1~100%, hydrogen in gaseous mixture
Other gases are nitrogen, argon gas or helium in addition；The air speed of hydrogeneous gaseous mixture is 500~10000h-1, activation
Temperature is 473K~1073K, and soak time is 2~48 hours, and activation pressure is 0.1~1.0MPa.
7. preparation method according to claim 6, it is characterised in that：The activation of catalyst is using external
Activation 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 be 473K~543K, reaction pressure be 0.5~6.0MPa, air speed be 1~8L synthesis gas/gram-catalysis
Agent hour, wherein H2/ CO mol ratios are 0.5~4:1.
10. application according to claim 8, it is characterised in that：Reaction is entered in fixed bed reactors
Capable, wherein reaction end gas and gas-phase product persistently flow out, and with hot trap and cold-trap collect respectively higher boiling and
Low boiling liquid product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675597A (en) * | 2019-02-28 | 2019-04-26 | 福州大学 | A kind of preparation method of porous silicon carbide cobalt |
| CN111375400A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof |
| CN112892543A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Catalyst for co-production of synthetic gas oil and alcohol and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101310856A (en) * | 2007-05-24 | 2008-11-26 | 中国科学院大连化学物理研究所 | Catalyst for directly synthesizing high carbon primary alcohol using CO hydrogenation and preparation method thereof |
| CN102641737A (en) * | 2012-03-21 | 2012-08-22 | 中国科学院大连化学物理研究所 | Catalyst for directly synthesizing C2-C10 straight-chain hybrid primary alcohol by CO hydrogenation and preparation method and application thereof |
| CN103648639A (en) * | 2011-04-19 | 2014-03-19 | 沙特基础工业公司 | Carbon supported cobalt and molybdenum catalyst |
-
2015
- 2015-11-30 CN CN201510849406.1A patent/CN106807421B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101310856A (en) * | 2007-05-24 | 2008-11-26 | 中国科学院大连化学物理研究所 | Catalyst for directly synthesizing high carbon primary alcohol using CO hydrogenation and preparation method thereof |
| CN103648639A (en) * | 2011-04-19 | 2014-03-19 | 沙特基础工业公司 | Carbon supported cobalt and molybdenum catalyst |
| CN102641737A (en) * | 2012-03-21 | 2012-08-22 | 中国科学院大连化学物理研究所 | Catalyst for directly synthesizing C2-C10 straight-chain hybrid primary alcohol by CO hydrogenation and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111375400A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof |
| CN111375400B (en) * | 2018-12-29 | 2023-01-10 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof |
| CN109675597A (en) * | 2019-02-28 | 2019-04-26 | 福州大学 | A kind of preparation method of porous silicon carbide cobalt |
| CN109675597B (en) * | 2019-02-28 | 2021-09-28 | 福州大学 | Preparation method of porous cobalt carbide |
| CN112892543A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Catalyst for co-production of synthetic gas oil and alcohol and preparation and application thereof |
| CN112892543B (en) * | 2019-12-03 | 2022-06-14 | 中国科学院大连化学物理研究所 | Catalyst for co-production of synthetic gas oil and alcohol and preparation and application thereof |
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