CN105646148B - A kind of method of acetic acid hydrogenation ethanol - Google Patents

A kind of method of acetic acid hydrogenation ethanol Download PDF

Info

Publication number
CN105646148B
CN105646148B CN201511029939.1A CN201511029939A CN105646148B CN 105646148 B CN105646148 B CN 105646148B CN 201511029939 A CN201511029939 A CN 201511029939A CN 105646148 B CN105646148 B CN 105646148B
Authority
CN
China
Prior art keywords
catalyst
transition metal
acetic acid
temperature
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201511029939.1A
Other languages
Chinese (zh)
Other versions
CN105646148A (en
Inventor
任杰
金辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN201511029939.1A priority Critical patent/CN105646148B/en
Publication of CN105646148A publication Critical patent/CN105646148A/en
Application granted granted Critical
Publication of CN105646148B publication Critical patent/CN105646148B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a kind of method of acetic acid hydrogenation ethanol, described method is：In 250~400 DEG C of temperature, 0.5~10.0MPa of pressure, mass space velocity 0.2~8.0 hour‑1, hydrogen and acetic acid feed mol ratio 1:1~20:Under conditions of 1, acetic acid and hydrogen are mixed, and supported transition metal carbide catalyst haptoreaction, by acetic acid hydrogenation ethanol；Present invention process flow is simple, and catalyst price is relatively low, and catalyst performance stabilised is good, device stable operation time length, can avoid reactor reaction and regeneration frequent switching operation, catalyst is renewable, and a large amount of dead catalyst can be avoided to post-process, and effect on environment is small.

Description

A kind of method of acetic acid hydrogenation ethanol
(1) technical field
It is especially a kind of to be urged with supported transition metal carbide the present invention relates to a kind of method of acetic acid hydrogenation ethanol The method of agent acetic acid hydrogenation ethanol.
(2) background technology
Ethanol is a kind of high-quality liquid fuel, and sulphur content and ash content are relatively low, and combustibility is similar to gasoline, has higher contain Oxygen amount and octane number, being burnt compared with regular gasoline, complete, CO emission is low, and burning can be significantly decreased using ethanol petrol Environmental pollution caused by gasoline, ethanol are referred to as 21 century " green energy resource ".With oil supply and demand aggravation of contradictions, environmental pressure It is increasingly heavy, countries in the world common concern fungible energy source, promote the development of alcohol fuel.Existing alcohol production technology is most Using crops as raw material, limited by raw material, production cost is higher, it is difficult to meet the needs of alcohol fuel.Acetic acid catalysis adds Hydrogen is the feasible path of ethanol production, and the effective way by the indirect preparing liquid fuel of coal.With Development of Coal Chemical Industry, acetic acid supplies More than asking.Can not only solve the problems, such as alcohol production by acetic acid hydrogenation ethanol, moreover it is possible to effectively solve the problems, such as acetic acid production capacity surplus, Thus the technique turns into the focus studied both at home and abroad.
The hydrogenation catalyst and reaction process on acetic acid hydrogenation ethanol have carried out numerous studies both at home and abroad.Hydrogenation catalyst Agent is mainly urged using load type palladium or platinum catalyst, load type palladium or platinum catalyst containing other metals, and copper support type Agent.Because palladium and platinum are noble metal, load type palladium or platinum catalyst are expensive, and alcohol production cost is higher.Further, since Copper loaded catalyst less stable, the catalyst are difficult to commercial Application.Development cost is low, the base metal of stable performance adds Hydrogen catalyst and acetic acid hydrogenation technique are important developing direction.
Carbon changes the surface electronic characteristic of transition metal in transition metal carbide, is allowed to possess the property similar with platinum Can, it is a kind of non-noble metal hydrogenation catalyst active component.Transition metal carbide because specific surface area is small, its catalytic performance compared with Difference.Loaded on the porous material, prepare loaded catalyst, be the effective way of increasing specific surface area.Load hydrogenation Degree of scatter of the performance of catalyst by catalytic active component load capacity and on carrier is influenceed.
Loaded catalyst is prepared using incipient impregnation method, catalytic active component can be effectively utilized.Impregnating Source metal, by adding complexing agent into dipping solution, improves scattered journey of the source metal on carrier to during on carrier Degree, increase metal surface area, improve the high active of hydrogenation catalysis of loaded catalyst.In addition, in source metal dipping process, utilize The peptizaiton of ultrasonic wave, degree of scatter of the source metal on carrier is improved, improve the catalytic activity of loaded catalyst.In profit On the basis of the preferable transition metal carbide loaded catalyst of these method processabilities, acetic acid hydrogenation ethanol skill is developed Art has good application value.
(3) content of the invention
It is an object of the present invention to provide a kind of method of acetic acid hydrogenation ethanol, i.e., it is catalyzed with supported transition metal carbide The method of agent acetic acid hydrogenation ethanol, solves load type palladium or the expensive caused alcohol production cost of platinum catalyst is high The problem of.
The technical solution adopted by the present invention is：
The present invention provides a kind of method with supported transition metal carbide catalyst acetic acid hydrogenation ethanol, described Method is：In 250~400 DEG C of temperature, 0.5~10.0MPa of pressure, mass space velocity 0.2~8.0 hour-1, hydrogen and acetic acid feed The ratio between amount of material 1:1~20:Under conditions of 1, acetic acid and hydrogen are mixed, connect with supported transition metal carbide catalyst Touch and carry out hydrogenation reaction, obtain ethanol；Regenerate, recycle after catalyst inactivation；
The supported transition metal carbide catalyst is using transition metal carbide as active component, with silica or oxygen Change aluminium is carrier, and the transition metal carbide mass loading amount is 1%~20%；
The transition metal carbide is that one or both of carbonization nickel, molybdenum carbide, cobalt carbide, tungsten carbide are mixed above Thing.
Further, the aluminum oxide is Al2O3Or γ-Al2O3；The silica is Bio-sil, preferably Qingdao Haiyang ZCX-2 types, 20~40 mesh Bio-sils of work company production.
Further, the hydrogenation conditions be 280~380 DEG C of temperature, 0.5~5.0MPa of pressure, feedstock quality air speed 0.5~5.0 hour-1, hydrogen and acetic acid feed mol ratio 2:1~10:1,300~350 DEG C of preferably temperature, pressure 2.0~ 5.0MPa, feedstock quality air speed 0.5~2.0 hour-1, hydrogen and acetic acid feed mol ratio 5:1~10:1.
Further, the transition metal carbide mass loading amount is 5%~15%.
Supported transition metal carbide catalyst of the present invention is prepared using incipient impregnation method：By transition metal Dipping solution is made with distilled water, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water, uses at room temperature Dipping solution is stirred dipping to catalyst carrier, 3~24h (preferably 5~8h) is stored at room temperature, at a temperature of 60~100 DEG C Dry 3~24h (preferably 80~95 DEG C dry 5~8h)；400 DEG C~700 DEG C are warming up to 1~10 DEG C/min rate programs, roasting 1~10h (preferably 1~5 DEG C/min is warming up to 450 DEG C~650 DEG C, is calcined 1~5h) is burnt, obtains catalyst precursor；Then, will Catalyst precursor is fitted into tubular reactor, using pentane as carbon source, is passed through hydrogen, in 0.1~5.0MPa of pressure, positive penta 0.2~2.0h of alkane mass space velocity-1, hydrogen and pentane volume ratio 100~1000:Under the conditions of 1, with 1~10 DEG C/min speed from 100 DEG C of temperature programmings are to 500 DEG C~750 DEG C, 1~10h of constant temperature (preferably 0.5~5.0MPa, 0.5~2.0h-1, volume ratio 300~ 800:Under the conditions of 1,500 DEG C~650 DEG C are warming up to 1~5 DEG C/min speed, 2~6h of constant temperature), carry out catalyst precursor carbon Change is handled, and obtains supported transition metal carbide catalyst；Transiting metal concentration is 1.0 × 10 in the dipping solution-5~ 9.0×10-3Mol/mL (preferably 4.3 × 10-5~1.3 × 10-3Mol/mL), the dipping solution volumetric usage is with carrier quality It is calculated as 0.5~5.5mL/g (preferably 0.8~1.5mL/g).
Supported transition metal carbide catalyst of the present invention can also use complexing dipping method to prepare：By transition Metal, citric acid and distilled water prepare dipping solution, and dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water, Dipping is stirred to catalyst carrier with dipping solution at room temperature, is stored at room temperature 3~24h (preferably 5~8h), 60~ 3~24h (preferably 80~95 DEG C dry 5~8h) is dried at a temperature of 100 DEG C；400 DEG C are warming up to 1~10 DEG C/min rate programs ~700 DEG C, 1~10h of roasting (preferably 1~5 DEG C/min is warming up to 450 DEG C~650 DEG C, is calcined 1~5h), obtain complex catalyst precursor Body；Then, catalyst precursor is fitted into tubular reactor, using pentane as carbon source, is passed through hydrogen, pressure 0.1~ 5.0MPa, 0.2~2.0h of pentane mass space velocity-1, hydrogen and pentane volume ratio 100~1000:Under the conditions of 1, with 1~10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C~750 DEG C, 1~10h of constant temperature (preferably 0.5~5.0MPa, 0.5~2.0h-1, volume ratio 300~800:Under the conditions of 1,500 DEG C~650 DEG C are warming up to 1~5 DEG C/min speed, 2~6h of constant temperature), urged Agent presoma carbonization treatment, obtains supported transition metal carbide catalyst, citric acid and transition in the dipping solution The mol ratio of metal is 1:1~4:1, transiting metal concentration is 1.0 × 10 in the dipping solution-5~9.0 × 10-3mol/mL (preferably 4.3 × 10-5~1.3 × 10-3Mol/mL), the dipping solution volumetric usage is calculated as 0.5~5.5mL/ with carrier quality G (preferably 0.8~1.5mL/g).
Supported transition metal carbide catalyst of the present invention can also use ultrasonic immersing method to prepare：By transition Metal prepares dipping solution with distilled water, and dipping solution volume is 1~3 times of catalyst carrier maximum adsorption water volume, in room Dipping is stirred to catalyst carrier with dipping solution under temperature, after adding dipping solution, in room temperature, 30~100W of ultrasonic power Under the conditions of be ultrasonically treated 10~60min (preferably 40~80W, 15~40min)；3~24h (preferably 5~8h) is stored at room temperature, 60 3~24h (preferably 80~95 DEG C dry 5~8h) is dried at a temperature of~100 DEG C；400 are warming up to 1~10 DEG C/min rate programs DEG C~700 DEG C, 1~10h of roasting (preferably 1~5 DEG C/min is warming up to 450 DEG C~650 DEG C, is calcined 1~5h), before obtaining catalyst Drive body；Then, catalyst precursor is fitted into tubular reactor, using pentane as carbon source, is passed through hydrogen, in pressure 0.1 ~5.0MPa, 0.2~2.0h of pentane mass space velocity-1, hydrogen and pentane volume ratio 100~1000:Under the conditions of 1, with 1~10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C~750 DEG C, 1~10h of constant temperature (preferably 0.5~5.0MPa, 0.5~2.0h-1, volume ratio 300~800:Under the conditions of 1,500 DEG C~650 DEG C are warming up to 1~5 DEG C/min speed, 2~6h of constant temperature), urged Agent presoma carbonization treatment, obtains supported transition metal carbide catalyst；Transiting metal concentration in the dipping solution For 1.0 × 10-5~9.0 × 10-3Mol/mL (preferably 4.3 × 10-5~1.3 × 10-3Mol/mL), the dipping solution volume is used Amount is calculated as 0.5~5.5mL/g (preferably 0.8~1.5mL/g) with carrier quality.
Further, the transition metal source is in one or both of nickel nitrate, ammonium molybdate, ammonium metatungstate, cobalt nitrate Mixture above, preferably ammonium metatungstate or ammonium molybdate.
Further, the renovation process of described supported transition metal carbide catalyst is off into acetic acid raw material, after It is continuous to be passed through hydrogen, it is 100~1000h in 300 DEG C~600 DEG C of temperature, 0.8~6.0MPa of pressure, hydrogen volume air speed-1Under the conditions of 3~24h of hydrogenation regeneration in reactor is carried out to decaying catalyst.
Further, described reaction is carried out in the reactor of two or more serial or parallel connections, each reactor The identical or different catalyst of interior filling.
The optional fixed bed of reactor, expanded bed, fluid bed, stirred-tank reactor used by present invention reaction, and Catalytic distillation reactor.Reaction unit can have multiple reactors to operate in parallel or series.Material in reactor can be taken Upstriker, downstriker can also be used.
A kind of beneficial effect of the method for acetic acid hydrogenation ethanol of the present invention is mainly reflected in：
(1) supported transition metal carbide catalyst price is relatively low, and alcohol production cost is relatively low；
(2) catalyst activity stability is good, device stable operation time length, reactor reaction and regeneration can be avoided frequently to cut Change operation；
(3) catalyst is renewable, and a large amount of dead catalyst can be avoided to post-process, and effect on environment is small.
(4) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in This：
Carrying alumina production procedure is to mix 30 grams of monohydrate aluminas (Shandong Aluminum Co., Ltd. group company), 3 grams of field mountain valley with clumps of trees and bamboo powder Close uniformly, add 18 grams of distilled water and 21 gram mass fractions as 5% aqueous solution of nitric acid, be kneaded into walk, extruded moulding, dry Temperature programming is calcined 4 hours to 550 DEG C afterwards, and through crushing, sieve takes 20~40 particles, obtains Al2O3Carrier.Through above-mentioned extruded moulding, Dry rear temperature programming to be calcined 4 hours to 850 DEG C, through crushing, sieve takes 20~40 mesh particles, obtains γ-Al2O3Carrier.
SiO used in embodiment2ZCX-2 types, 20~40 mesh Bio-sils produced for Qingdao Haiyang chemical company, Liquid volume is with solid masses than 50:Under the conditions of 1 (mL/g), 80 DEG C of temperature, with the aqueous solution of nitric acid of mass concentration 10% to it 8h is handled, is separated by filtration；Filter cake is in liquid volume and solid masses than 50:By 2 steamings under the conditions of 1 (mL/g), 80 DEG C of temperature Distilled water agitator treating 3h, it is separated by filtration, 120 DEG C of dry 3h, then is calcined 1h by 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C respectively, The SiO handled2, as catalyst carrier.
Nickel nitrate (Ni (NO used3)2·6H2O), ammonium molybdate ((NH4)6Mo7O24·4H2O), ammonium metatungstate ((NH4)6H2W12O40·nH2O), cobalt nitrate (Co (NO3)2·6H2O), it is limited to be purchased from Chinese medicines group chemical reagent for citric acid, pentane The chemically pure reagent of company.Hydrogen comes from Hangzhou Jin Gong special gases Co., Ltd, purity ＞ 99.99%.
Acetic acid hydrogenation reaction experiment is carried out using fixed-bed reactor, stainless steel tubular type reactor size is：Internal diameter 10mm, external diameter 14mm, long 100cm, by Catalyst packing, inertia quartz sand is filled up at portion, reactor both ends in the reactor.Reaction Temperature is controlled by temperature control instrument, by back pressure valve regulation hydrogenation reaction pressure.
Being formed with Japanese Shimadzu GC-2014C chromatographics reaction product, chromatographic detector is thermal conductivity detector (TCD), Chromatographic column is 2m × 4mm GDX-102 packed columns, and injector temperature is 140 DEG C, and column temperature is 120 DEG C, detector temperature 130 DEG C, chromatographic data processing method is rectification area normalization method.Reaction product contains unconverted acetic acid (HAc), ethanol (EtOH), ethyl acetate (EtOAc), acetone (Acetone), acetaldehyde (Acetal), relative acetic acid total organic matter in reaction product Amount (T0) be：
Acetic acid conversion (X) is：
Ethanol selectivity (SEtOH) be：
Ethyl acetate selectivity (SEtOAc) be：
Acetone selectivity (SAcetone) be：
Acetaldehyde selectivity (SAcetal) be：
In formula, AiDivide rate, M for i component color area under spectrumsiFor i component molar quality；λiFor i component chromatogram correction factors, its Middle λHAc=1.0208, λEtOH=1.3158, λEtOAc=2.9321, λAcetone=0.9763.
Room temperature of the present invention refers to 25 DEG C.
Embodiment 1：1%WC/SiO2Catalyst preparation
Weighing 10g Bio-sil carrier, (its specific surface area is 480m2/ g), by 0.13g (4.3974 × 10-5Mol) Ammonium metatungstate and distilled water prepare 12mL dipping solutions, and its tungsten concentration is 4.3974 × 10-5Mol/mL, dipping solution volume is with urging The volume of agent carrier maximum adsorption water is equal.Room temperature immersion is carried out by incipient impregnation method, 12mL is added dropwise into 10g carriers Dipping solution, and be stirred continuously.After being added dropwise, 3h is stored at room temperature, 3h is dried at a temperature of 90 DEG C；With 1 DEG C/min speed journeys Sequence is warming up to 400 DEG C, is calcined 10h.Then, dry catalyst precursor is fitted into tubular reactor, using pentane as Carbon source, hydrogen is passed through, in pressure 0.1MPa, pentane mass space velocity 0.2h-1, hydrogen and pentane volume ratio 100：Under the conditions of 1, With 10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C, constant temperature 10h, catalyst precursor carbonization treatment is carried out, obtains carbon Change the loaded catalyst of tungsten load mass fraction 1%, be designated as 1%WC/SiO2。
Embodiment 2：5%WC/SiO2Catalyst preparation
10g Bio-sil carrier is weighed, by 0.65g (2.1987 × 10-4It is prepared by ammonium metatungstate and distilled water mol) 12mL dipping solutions, its tungsten concentration are 2.1987 × 10-4Mol/mL, dipping solution volume and catalyst carrier maximum adsorption water Volume is equal.Room temperature immersion is carried out by incipient impregnation method, 12mL dipping solutions are added dropwise into 10g carriers, and be stirred continuously. After being added dropwise, 24h is stored at room temperature, 24h is dried at a temperature of 60 DEG C；700 DEG C are warming up to 2 DEG C/min rate programs, roasting 1h.Then, dry catalyst precursor is fitted into tubular reactor, using pentane as carbon source, hydrogen is passed through, in pressure 0.5MPa, pentane mass space velocity 0.5h-1, hydrogen and pentane volume ratio 500：Under the conditions of 1, with 5 DEG C/min speed from 100 DEG C Temperature programming carries out catalyst precursor carbonization treatment to 550 DEG C, constant temperature 6h, obtains the negative of Tungsten Carbides mass fraction 5% Supported catalyst, it is designated as 5%WC/SiO2。
Embodiment 3：10%WC/SiO2Catalyst preparation
10g Bio-sil carrier is weighed, by 1.3g (4.3974 × 10-4It is prepared by ammonium metatungstate and distilled water mol) 12mL dipping solutions, its tungsten concentration are 4.3974 × 10-4Mol/mL, dipping solution volume and catalyst carrier maximum adsorption water Volume is equal.Room temperature immersion is carried out by incipient impregnation method, 12mL dipping solutions are added dropwise into 10g carriers, and be stirred continuously. After being added dropwise, 6h is stored at room temperature, 12h is dried at a temperature of 80 DEG C；650 DEG C are warming up to 5 DEG C/min rate programs, roasting 4h.Then, dry catalyst precursor is fitted into tubular reactor, using pentane as carbon source, hydrogen is passed through, in pressure 5.0MPa, pentane mass space velocity 2.0h-1, hydrogen and pentane volume ratio 1000：Under the conditions of 1, with 10 DEG C/min speed from 100 DEG C temperature programming carries out catalyst precursor carbonization treatment, obtains Tungsten Carbides mass fraction 10% to 750 DEG C, constant temperature 1h Loaded catalyst, be designated as 10%WC/SiO2。
Embodiment 4：20%WC/SiO2Catalyst preparation
10g Bio-sil carrier is weighed, by 2.6g (8.7948 × 10-4It is prepared by ammonium metatungstate and distilled water mol) 12mL dipping solutions, its tungsten concentration are 8.7948 × 10-4Mol/mL, dipping solution volume and catalyst carrier maximum adsorption water Volume is equal.Room temperature immersion is carried out by incipient impregnation method, 12mL dipping solutions are added dropwise into 10g carriers, and be stirred continuously. After being added dropwise, 4h is stored at room temperature, 3h is dried at a temperature of 100 DEG C；600 DEG C are warming up to 10 DEG C/min rate programs, roasting 6h.Then, dry catalyst precursor is fitted into tubular reactor, using pentane as carbon source, hydrogen is passed through, in pressure 5.0MPa, pentane mass space velocity 2.0h-1, hydrogen and pentane volume ratio 500：Under the conditions of 1, with 5 DEG C/min speed from 100 DEG C Temperature programming carries out catalyst precursor carbonization treatment, obtains Tungsten Carbides mass fraction 20% to 550 DEG C, constant temperature 6h Loaded catalyst, it is designated as 20%WC/SiO2。
Embodiment 5：10%WC/ γ-Al2O3Catalyst preparation
Weigh 10g γ-Al2O3(its specific surface area is 296m to carrier2/ g), by 1.3g (4.3974 × 10-4Mol) inclined Ammonium tungstate and distilled water prepare 8mL dipping solutions, and its tungsten concentration is 6.5961 × 10-4Mol/mL, dipping solution volume and catalysis The volume of agent carrier maximum adsorption water is equal.Room temperature immersion is carried out by incipient impregnation method, 8mL leachings are added dropwise into 10g carriers Stain solution, and be stirred continuously.After being added dropwise, 24h is stored at room temperature, 24h is dried at a temperature of 60 DEG C；With 2 DEG C/min speed journeys Sequence is warming up to 700 DEG C, is calcined 1h.Then, dry catalyst precursor is fitted into tubular reactor, carbon is used as using pentane Source, hydrogen is passed through, in pressure 0.5MPa, pentane mass space velocity 0.5h-1, hydrogen and pentane volume ratio 500：Under the conditions of 1, with 5 DEG C/min speed carries out catalyst precursor carbonization treatment, obtains tungsten carbide from 100 DEG C of temperature programmings to 550 DEG C, constant temperature 6h The loaded catalyst of load quality fraction 10%, it is designated as 10%WC/ γ-Al2O3。
Embodiment 6：10%WC/Al2O3Catalyst preparation
Weigh 10g Al2O3(its specific surface area is 302m to carrier2/ g), by 1.3g (4.3974 × 10-4Mol metatungstic acid) Ammonium and distilled water prepare 8mL dipping solutions, and its tungsten concentration is 6.5961 × 10-4Mol/mL, dipping solution volume carry with catalyst The volume of body maximum adsorption water is equal.Room temperature immersion is carried out by incipient impregnation method, it is molten that 8mL dippings are added dropwise into 10g carriers Liquid, and be stirred continuously.After being added dropwise, 24h is stored at room temperature, 24h is dried at a temperature of 60 DEG C；With 2 DEG C/min rate program liters Temperature is calcined 1h to 700 DEG C.Then, dry catalyst precursor is fitted into tubular reactor, using pentane as carbon source, Hydrogen is passed through, in pressure 0.5MPa, pentane mass space velocity 0.5h-1, hydrogen and pentane volume ratio 500：Under the conditions of 1, with 5 DEG C/min speed from 100 DEG C of temperature programmings to 550 DEG C, constant temperature 6h, carry out catalyst precursor carbonization treatment, obtain tungsten carbide and bear The loaded catalyst of mounted mass fraction 10%, is designated as 10%WC/Al2O3。
Embodiment 7：10%Ni2C/SiO2Catalyst preparation
Using Bio-sil as carrier, with Ni (NO3)2·6H2O is as nickel source.10g Bio-sil is weighed, by 4.5g (1.5474×10-2Mol Ni (NO)3)2·6H2O and distilled water prepare 12mL dipping solutions, and its nickel concentration is 1.2895 × 10-3Mol/mL, dipping solution volume are equal with the volume of catalyst carrier maximum adsorption water.Room temperature is carried out by incipient impregnation method Dipping, 12mL dipping solutions are added dropwise into 10g carriers, and are stirred continuously.After being added dropwise, 5h is stored at room temperature, in 90 DEG C of temperature Lower dry 24h；650 DEG C are warming up to 5 DEG C/min rate programs, is calcined 4h.Then, by dry catalyst precursor loading tube In formula reactor, using pentane as carbon source, hydrogen is passed through, in pressure 1.0MPa, pentane mass space velocity 2.0h-1, hydrogen with Pentane volume ratio 1000：Under the conditions of 1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, it is catalyzed Agent presoma carbonization treatment, obtains the loaded catalyst of Tungsten Carbides mass fraction 10%, is designated as 10%Ni2C/SiO2。
Embodiment 8：10%MoC/SiO2Catalyst preparation
Using Bio-sil as carrier, with (NH4)6Mo7O24·4H2O is as molybdenum source.10g Bio-sil is weighed, by 1.64g(1.327×10-3Mol (NH)4)6Mo7O24·4H2O and distilled water prepare 12mL dipping solutions, and its molybdenum concentration is 7.7409×10-4Mol/mL, dipping solution volume are equal with the volume of catalyst carrier maximum adsorption water.By incipient impregnation side Method carries out room temperature immersion, 12mL dipping solutions is added dropwise into 10g carriers, and be stirred continuously.After being added dropwise, 5h is stored at room temperature. 24h is dried at a temperature of 60 DEG C；650 DEG C are warming up to 5 DEG C/min rate programs, is calcined 10h.Then, by dry catalyst Presoma is fitted into tubular reactor, using pentane as carbon source, is passed through hydrogen, in pressure 1.0MPa, pentane mass space velocity 2.0h-1, under the conditions of hydrogen and pentane volume ratio 1000, with 2 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, catalyst precursor carbonization treatment is carried out, the loaded catalyst of molybdenum carbide load quality fraction 10% is obtained, is designated as 10% MoC/SiO2。
Embodiment 9：10%Co2C/SiO2Catalyst preparation
Using Bio-sil as carrier, with Co (NO3)2·6H2O is as cobalt source.10g Bio-sil is weighed, by 4.48g (1.5391×10-2Mol Co (NO)3)2·6H2O and distilled water prepare 12mL dipping solutions, and its cobalt concentration is 1.2826 × 10-3Mol/mL, dipping solution volume are equal with the volume of catalyst carrier maximum adsorption water.Room temperature is carried out by incipient impregnation method Dipping, 12mL dipping solutions are added dropwise into 10g carriers, and are stirred continuously.After being added dropwise, 5h is stored at room temperature.In 90 DEG C of temperature Lower dry 6h；650 DEG C are warming up to 5 DEG C/min rate programs, is calcined 10h.Then, by dry catalyst precursor loading tube In formula reactor, using pentane as carbon source, hydrogen is passed through, in pressure 1.0MPa, pentane mass space velocity 2.0h-1, hydrogen with Under the conditions of pentane volume ratio 1000, with 2 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, catalyst is carried out Presoma carbonization treatment, the loaded catalyst of cobalt carbide load quality fraction 10% is obtained, is designated as 10%Co2C/SiO2。
Embodiment 10：10%WC/SiO2- L1 catalyst preparations
10g Bio-sil carrier is weighed, by 1.3g (4.3974 × 10-4Mol ammonium metatungstate, 1.1089g (5.277) ×10-3Mol citric acid and distilled water) prepares 12mL dipping solutions, and its tungsten and citric acid concentration are 4.3974 × 10- 4Mol/mL, the mol ratio of citric acid and tungsten in ammonium metatungstate is 1 in dipping solution:1, dipping solution volume and catalyst carrier The volume of maximum adsorption water is equal.Room temperature immersion is carried out by incipient impregnation method, it is molten that 12mL dippings are added dropwise into 10g carriers Liquid, and be stirred continuously.After being added dropwise, 6h is stored at room temperature, 12h is dried at a temperature of 80 DEG C；Heated up with 5 DEG C/min rate programs To 650 DEG C, 4h is calcined.Then, dry catalyst precursor is fitted into tubular reactor, using pentane as carbon source, led to Enter hydrogen, in pressure 1.0MPa, pentane mass space velocity 2.0h-1, hydrogen and pentane volume ratio 1000：Under the conditions of 1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, carry out catalyst precursor carbonization treatment, obtain tungsten carbide and bear The loaded catalyst of mounted mass fraction 10%, is designated as 10%WC/SiO2-L1。
Embodiment 11：10%WC/SiO2- L4 catalyst preparations
10g Bio-sil carrier is weighed, by 1.3g (4.3974 × 10-4Mol ammonium metatungstate, 4.4356g (2.1108) ×10-2Mol citric acid and distilled water) prepares 12mL dipping solutions, and its tungsten and citric acid concentration are respectively 4.3974 × 10- 4Mol/mL and 1.759 × 10-3Mol/mL, the mol ratio of citric acid and tungsten in ammonium metatungstate is 4 in dipping solution:1, dipping is molten Liquid product is equal with the volume of catalyst carrier maximum adsorption water.Room temperature immersion is carried out by incipient impregnation method, toward 10g carriers Middle dropwise addition 12mL dipping solutions, and be stirred continuously.After being added dropwise, 6h is stored at room temperature, 12h is dried at a temperature of 80 DEG C；With 5 DEG C/min rate programs are warming up to 650 DEG C, it is calcined 4h.Then, dry catalyst precursor is fitted into tubular reactor, with Pentane is passed through hydrogen, in pressure 1.0MPa, pentane mass space velocity 2.0h as carbon source-1, hydrogen and pentane volume ratio 1000：Under the conditions of 1, with 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, catalyst precursor carbonization is carried out Processing, obtains the loaded catalyst of Tungsten Carbides mass fraction 10%, is designated as 10%WC/SiO2-L4。
Embodiment 12：10%WC/SiO2- U30 catalyst preparations
10g Bio-sil carrier is weighed, by 1.3g (4.3974 × 10-4It is prepared by ammonium metatungstate and distilled water mol) 12mL dipping solutions, its tungsten concentration are 4.3974 × 10-4Mol/mL, dipping solution volume and catalyst carrier maximum adsorption water Volume is equal.In the KQ-100DE type numerical control ultrasonic cleaners of Kunshan Ultrasonic Instruments Co., Ltd.'s production, burnt in room temperature 17mL dipping solutions are added dropwise to 10g carriers in cup, and are stirred continuously；After adding dipping solution, room temperature, supersonic frequency 40kHz, 60min is ultrasonically treated under the conditions of ultrasonic power 30W；6h is stored at room temperature, 12h is dried at a temperature of 80 DEG C；With 5 DEG C/min speed journeys Sequence is warming up to 650 DEG C, is calcined 4h.Then, dry catalyst precursor is fitted into tubular reactor, carbon is used as using pentane Source, hydrogen is passed through, in pressure 1.0MPa, pentane mass space velocity 2.0h-1, hydrogen and pentane volume ratio 1000：Under the conditions of 1, With 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, catalyst precursor carbonization treatment is carried out, is carbonized The loaded catalyst of tungsten load mass fraction 10%, is designated as 10%WC/SiO2-U30。
Embodiment 13：10%WC/SiO2- U100 catalyst preparations
10g Bio-sil carrier is weighed, by 1.3g (4.3974 × 10-4It is prepared by ammonium metatungstate and distilled water mol) 36mL dipping solutions, its tungsten concentration are 1.4658 × 10-4Mol/mL, dipping solution volume are catalyst carrier maximum adsorption water bodys Long-pending 3 times.In the KQ-100DE type numerical control ultrasonic cleaners of Kunshan Ultrasonic Instruments Co., Ltd.'s production, in room temperature beaker It is middle that 36mL dipping solutions are added dropwise to 10g carriers, and be stirred continuously；After adding dipping solution, in room temperature, supersonic frequency 40kHz, surpass 10min is ultrasonically treated under the conditions of acoustical power 100W；6h is stored at room temperature, 12h is dried at a temperature of 80 DEG C；With 5 DEG C/min speed journeys Sequence is warming up to 650 DEG C, is calcined 4h.Then, dry catalyst precursor is fitted into tubular reactor, carbon is used as using pentane Source, hydrogen is passed through, in pressure 1.0MPa, pentane mass space velocity 2.0h-1, hydrogen and pentane volume ratio 1000：Under the conditions of 1, With 10 DEG C/min speed from 100 DEG C of temperature programmings to 750 DEG C, constant temperature 1h, catalyst precursor carbonization treatment is carried out, is carbonized The loaded catalyst of tungsten load mass fraction 10%, is designated as 10%WC/SiO2-U100。
Embodiment 14：Catalyst performance evaluation
Using fixed-bed reactor, in 320 DEG C of temperature, pressure 2.0MPa, quality of acetic acid air speed 0.5h-1, hydrogen and second Sour raw materials components mole ratio 10:Under 1 reaction condition, acetic acid hydrogenation reaction is carried out with the catalyst of above-mentioned preparation, evaluates catalyst Catalytic performance, experimental result are listed in table 1.
The acetic acid hydrogenation reaction result of 1 various catalyst of table
As it can be seen from table 1 as catalyst transition metal carbide load capacity increases, acetic acid conversion gradually increases, Catalyst hydrogenation catalytic activity gradually steps up, and ethanol selectivity has increased, and ethyl acetate, acetone and acetaldehyde selectivity are Reduce.In the case where transition metal carbide load quality fraction is 10%, with SiO2For the catalyst activity and second of carrier Alcohol selectivity is somewhat quite a lot of.Compare the catalyst performance that transition metal carbide load quality fraction is 10%, catalyst activity Order from high to low is WC, MoC, Co2C、Ni2C, the order of ethanol selectivity from high to low are MoC, Co2C、Ni2C、WC.Always For body, the catalytic performance of WC loaded catalysts is preferable.The acetic acid of catalyst is prepared with complexing infusion process and ultrasonic immersing method Conversion ratio and ethanol selectivity are better than the catalyst of equi-volume impregnating preparation, and with citric acid complexing agent dosage and surpass Acoustical power increases, and catalyst performance makes moderate progress.On the whole, acetone and acetaldehyde selectivity numerical value are smaller, and ethanol selectivity is big In 80%.
Embodiment 15：Hydrogenation conditions are investigated
Using fixed-bed reactor, in 10%WC/SiO2Under catalyst action, the acetic acid hydrogenation for carrying out different condition is anti- Should, single factor exploration temperature, pressure, mass space velocity, the reaction condition of hydrogen and acetic acid feed mol ratio are influenceed, and experimental result is shown in Table 2.As known from Table 2, as reaction temperature improves, pressure increases, mass space velocity reduces, hydracid mol ratio increases, acetic acid conversion Rate and ethanol selectivity increase, and ethyl acetate selectively reduces, this explanation, strengthen hydrogenation conditions and are advantageous to acetic acid conversion For ethanol.
Table 2 investigates the experimental result that hydrogenation conditions influence
Embodiment 16：Catalyst performance stabilised is investigated
Using fixed-bed reactor, in 10%WC/SiO2Under catalyst action, 350 DEG C of temperature, pressure 5.0MPa, Mass space velocity 0.5h-1, hydracid mol ratio 5:Under 1 reaction condition, acetic acid hydrogenation sustained response is carried out, investigates the performance of catalyst Stability, experimental result are shown in Table 3.From table 3 it can be seen that it is determined that the acetic acid hydrogenation that 1000h is persistently carried out under reaction condition is anti- Should, acetic acid conversion and each selectivity of product are basically unchanged, and illustrate that catalyst has good stability.
The investigation result of the catalyst activity stability of table 3
Embodiment 17：Hydrogenation catalyst regenerates and its performance evaluation
Using fixed-bed reactor, in 10%WC/SiO2Under catalyst action, 350 DEG C of temperature, pressure 5.0MPa, Mass space velocity 0.5h-1, hydracid mol ratio 5:Acetic acid hydrogenation reaction is persistently carried out under 1 reaction condition, treats acetic acid conversion reduction To stopping input acetic acid raw material when 90%；Continue to be passed through hydrogen, regeneration stage is hydrogenated with into decaying catalyst, in pressure 5.0MPa, hydrogen volume air speed 200h-1Under the conditions of, temperature is increased to 400 DEG C of constant temperature hydrogenation regeneration 3h, then temperature is brought up to 500 DEG C of constant temperature regenerate 24h.Then, in 350 DEG C of temperature, pressure 5.0MPa, mass space velocity 0.5h-1, hydracid mol ratio 5:1 it is anti- Acetic acid and hydrogen are inputted under the conditions of answering, catalytic hydrogenation reaction is persistently carried out, is as a result listed in table 4.
The performance evaluation of the regenerated catalyst of table 4
As known from Table 4, decaying catalyst brings up to 99.22% by hydrogenation regenerative operation, acetic acid conversion from 90%.This Illustrate, inactivation loaded catalyst is regenerated by hydrogenation, and catalyst activity is substantially recovered.Comparison sheet 3 and the data of table 4 can be with Find out, the activity stability and selectivity of product of regenerated catalyst are suitable with fresh catalyst.
It is above-mentioned test result indicates that, acetic acid effectively can be converted into ethanol by catalytic hydrogenation reaction method of the invention, The high active of hydrogenation catalysis and reaction selectivity of catalyst are higher, and activity stability is good, and can regenerate.The inventive method is The effective ways of acetic acid hydrogenation ethanol, there is application value.

Claims (5)

  1. A kind of 1. method of acetic acid hydrogenation ethanol, it is characterised in that methods described is：In 250~400 DEG C of temperature, pressure 0.5 ~10.0MPa, mass space velocity 0.2~8.0 hour-1, hydrogen and acetic acid feed material the ratio between amount 1:1~20:Under conditions of 1, Acetic acid and hydrogen are mixed, is contacted with supported transition metal carbide catalyst and carries out hydrogenation reaction, obtains ethanol；Catalyst Regenerate, recycle after inactivation；
    Described supported transition metal carbide catalyst is using transition metal carbide as active component, with silica or oxidation Aluminium is carrier, and the transition metal carbide mass loading amount is 1%~20%；
    The transition metal carbide is one or both of carbonization nickel, molybdenum carbide, cobalt carbide, tungsten carbide thing mixed above；
    The aluminum oxide is γ-Al2O3；The silica is Bio-sil；
    The supported transition metal carbide catalyst is prepared using one of following method：
    (1) prepared using incipient impregnation method：Dipping solution is made by transition metal and distilled water, it is molten with impregnating at room temperature Liquid is stirred dipping to carrier, is stored at room temperature 3~24h, and 3~24h is dried at a temperature of 60~100 DEG C；With 1~10 DEG C/min Rate program is warming up to 400 DEG C~700 DEG C, is calcined 1~10h, obtains catalyst precursor；Then, catalyst precursor is filled Enter in tubular reactor, using pentane as carbon source, be passed through hydrogen, in 0.1~5.0MPa of pressure, pentane mass space velocity 0.2 ~2.0h-1, hydrogen and pentane volume ratio 100~1000：Under the conditions of 1, with 1~10 DEG C/min speed from 100 DEG C of temperature programmings To 500 DEG C~750 DEG C, 1~10h of constant temperature, supported transition metal carbide catalyst is obtained；Transition gold in the dipping solution It is 1.0 × 10 to belong to concentration-5~9.0 × 10-3Mol/mL, the dipping solution volumetric usage is calculated as 0.5 with carrier quality~ 5.5mL/g；
    (2) prepared using complexing dipping side：Dipping solution is prepared by transition metal, citric acid and distilled water, at room temperature with leaching Stain solution is stirred dipping to carrier, is stored at room temperature 3~24h, and 3~24h is dried at a temperature of 60~100 DEG C；With 1~10 DEG C/min rate programs are warming up to 400 DEG C~700 DEG C, 1~10h is calcined, obtains catalyst precursor；Then, by before catalyst Drive body to be fitted into tubular reactor, using pentane as carbon source, be passed through hydrogen, it is empty in 0.1~5.0MPa of pressure, pentane quality 0.2~2.0h of speed-1, hydrogen and pentane volume ratio 100~1000:Under the conditions of 1, with 1~10 DEG C/min speed from 100 DEG C of programs 500 DEG C~750 DEG C are warming up to, 1~10h of constant temperature, obtains supported transition metal carbide catalyst；Lemon in the dipping solution The ratio between amount of material of lemon acid and transition metal is 1:1~4:1, transiting metal concentration is 1.0 × 10 in the dipping solution-5~ 9.0×10-3Mol/mL, the dipping solution volumetric usage are calculated as 0.5~5.5mL/g with carrier quality；
    (3) prepared using ultrasonic immersing method:Dipping solution is prepared by transition metal and distilled water, uses dipping solution at room temperature Dipping is stirred to carrier, after adding dipping solution, under the conditions of room temperature, 30~100W of ultrasonic power be ultrasonically treated 10~ 60min；3~24h is stored at room temperature, 3~24h is dried at a temperature of 60~100 DEG C；It is warming up to 1~10 DEG C/min rate programs 400 DEG C~700 DEG C, 1~10h is calcined, obtains catalyst precursor；Then, catalyst precursor is fitted into tubular reactor, Using pentane as carbon source, hydrogen is passed through, in 0.1~5.0MPa of pressure, 0.2~2.0h of pentane mass space velocity-1, hydrogen with just Pentane volume ratio 100~1000：It is permanent with 1~10 DEG C/min speed from 100 DEG C of temperature programmings to 500 DEG C~750 DEG C under the conditions of 1 1~10h of temperature, catalyst precursor carbonization treatment is carried out, obtains supported transition metal carbide catalyst；The dipping solution Middle transiting metal concentration is 1.0 × 10-5~9.0 × 10-3Mol/mL, the dipping solution volumetric usage are calculated as with carrier quality 0.5~5.5mL/g；
    Described transition metal derives from more than one or both of nickel nitrate, ammonium molybdate, ammonium metatungstate, cobalt nitrate mixed Close.
  2. 2. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterised in that the hydrogenation conditions are temperature 280 ~380 DEG C, 0.5~5.0MPa of pressure, feedstock quality air speed 0.5~5.0 hour-1, hydrogen and acetic acid feed mol ratio 2:1~ 10:1。
  3. 3. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterised in that the transition metal carbide quality is born Carrying capacity is 5%~15%.
  4. 4. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterised in that described carrier-borne transition metal carbonization The renovation process of thing catalyst is off into acetic acid raw material, continues to be passed through hydrogen, 300 DEG C~600 DEG C of temperature, pressure 0.8~ 6.0MPa, hydrogen volume air speed are 100~1000h-1Under the conditions of to decaying catalyst carry out reactor in hydrogenation regeneration 3~24h.
  5. 5. the method for acetic acid hydrogenation ethanol as claimed in claim 1, it is characterised in that described reaction is at two or two Carried out in the reactor of above serial or parallel connection, the identical or different catalyst of filling in each reactor.
CN201511029939.1A 2015-12-31 2015-12-31 A kind of method of acetic acid hydrogenation ethanol Active CN105646148B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201511029939.1A CN105646148B (en) 2015-12-31 2015-12-31 A kind of method of acetic acid hydrogenation ethanol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201511029939.1A CN105646148B (en) 2015-12-31 2015-12-31 A kind of method of acetic acid hydrogenation ethanol

Publications (2)

Publication Number Publication Date
CN105646148A CN105646148A (en) 2016-06-08
CN105646148B true CN105646148B (en) 2017-12-29

Family

ID=56491162

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201511029939.1A Active CN105646148B (en) 2015-12-31 2015-12-31 A kind of method of acetic acid hydrogenation ethanol

Country Status (1)

Country Link
CN (1) CN105646148B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106563480A (en) * 2016-11-16 2017-04-19 中国科学院山西煤炭化学研究所 Catalyst for synthesis of methyl acetate and ethanol through hydrogenation of dimethyl oxalate, and preparation method and application thereof
CN108014789B (en) * 2017-12-06 2020-03-10 福州大学 Supported catalyst for preparing polycyclohexylethylene by polystyrene hydrogenation and preparation method thereof
CN109772396B (en) * 2019-03-04 2021-10-26 浙江工业大学 Metal carbide catalyst for catalyzing CFC-113a hydrogenation coupling reaction and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8350098B2 (en) * 2011-04-04 2013-01-08 Celanese International Corporation Ethanol production from acetic acid utilizing a molybdenum carbide catalyst
CN102688768B (en) * 2012-06-05 2014-04-16 中国科学院山西煤炭化学研究所 Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof

Also Published As

Publication number Publication date
CN105646148A (en) 2016-06-08

Similar Documents

Publication Publication Date Title
CN105669372B (en) Utilize the method for transition metal phosphide catalyst catalysis acetic acid hydrogenation ethanol
CN102861593B (en) Hydrofining catalyst and preparation method thereof
WO2012027948A1 (en) Method for treating sulfur-containing gas and hydrogenation catalyst used in the method
CN105646148B (en) A kind of method of acetic acid hydrogenation ethanol
CN105669347B (en) A kind of method for reducing linear alkylbenzene (LAB) unsaturated hydrocarbons content
Venkatesha et al. Citric acid-assisted synthesis of nanoparticle copper catalyst supported on an oxide system for the reduction of furfural to furfuryl alcohol in the vapor phase
CN101428228A (en) Selective hydrogenation catalyst and method of producing the same
JP2019530572A (en) Fixed catalyst bed containing metal foam
CN109806885A (en) A kind of monatomic catalyst of Pdx/Cu and preparation method thereof adding hydrogen for C4 selection
CN114950419A (en) Metal catalyst for preparing methanol by carbon dioxide hydrogenation and application thereof
CN108579742B (en) Dehydrogenation catalyst and method for preparing same
CN104815664B (en) Attapulgite-based composite material loaded Cu-Zn-Fe based catalyst, preparation method and applications thereof
CN104549345B (en) Active hydrocracking proppant and preparation method thereof
JP2007270049A (en) Method for producing hydrocarbon by reduction of carbon monoxide
CN106810419A (en) For graphene-supported metal composite in acetic acid preparation of ethanol through hydrogenation catalyst and preparation method thereof
CN104399477B (en) A kind of fischer-tropsch synthetic catalyst of metal active centres non-uniform Distribution and preparation method thereof
CN105709753A (en) Integrally extruded catalyst and preparation method and application thereof
CN103566933B (en) A kind of acetate preparation of ethanol by hydrogenating catalyst and preparation method thereof
CN103721718B (en) A kind of Catalysts and its preparation method producing higher hydrocarbons for Fiscber-Tropscb synthesis
CN109847777A (en) A kind of solid-carrying type Cu base catalyst and its preparation method and application
CN105312092B (en) A kind of catalyst and preparation method thereof and Fischer-Tropsch synthesis method
CN106238048B (en) Catalyst for synthesizing oxide, method for producing same, apparatus for producing oxide, and method for producing oxide
CN102641735B (en) Oxalate hydrogenated Au-Ag bimetallic catalyst and preparation method thereof
CN103638943B (en) A kind of co-based fischer-tropsch fixed bde catalyst for biomass synthesis gas and preparation method thereof
CN108786803B (en) Supported nano Pt catalyst and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant