CN102688768A - Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof - Google Patents
Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof Download PDFInfo
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- CN102688768A CN102688768A CN2012101822606A CN201210182260A CN102688768A CN 102688768 A CN102688768 A CN 102688768A CN 2012101822606 A CN2012101822606 A CN 2012101822606A CN 201210182260 A CN201210182260 A CN 201210182260A CN 102688768 A CN102688768 A CN 102688768A
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Abstract
The invention relates to a cobalt-based catalyst for synthesizing ethanol, a preparation method and the application of the cobalt-based catalyst. The cobalt-based catalyst is characterized by comprising carbide taking Co as main transition metal, additive metal carbide and carrier, wherein the components have the weight ratio: 8.0-23.0wt% of cobalt carbide, 1.0-5.0wt% of molybdenum carbide, nickel carbide or tungsten carbide, and 75.1-91.0wt% of carrier. The invention has the advantages of being low in cost, high in activity and high in ethanol selectivity.
Description
Technical field
The present invention relates to a kind of ethanol synthetic method, is a kind of method of utilizing modified carbonize Co catalysts catalysis acetic acid hydrogenation synthesizing alcohol specifically.
Background technology
Ethanol is the important chemical product, is widely used in biological, medicine and other fields.After adding ethanol in the oil product, performance and quality can effectively be improved, and the discharging of carbon monoxide, hydrocarbon etc. can reduce.Ethanol is topmost in the world at present fuel additive.The U.S., Brazil are the maximum countries of ethanol petrol use amount in the world, and the ethanol addition is 20-30% in the oil product.The area of ten provinces and cities begins the pilot conversion work of alcohol fuel in the whole nation in China, and the ethanol addition is 10%.China's production of fuel ethanol method is mainly corn and wheat fermentation method, and the cost of grain method alcohol production is very high, and far above the market price of ethanol, country is the survival and development of protection alcohol fuel enterprise, and ethanol subsidy 1000-2000 per ton is first; In addition, China's per capita area of cultivated farmland is few, and there is the problem of " strive grain with the people, strive ground with grain " in grain method alcohol production, and this must influence national food safety.Cellulose fermentation system ethanol (patent CN101235392) technology is not directly used grain and industrial crops, and not extra use is ploughed, but cost that should technology is very high, is higher than the grain alcohol method.This is because the high two aspect factors of core technology cost that low high cost of transportation that causes of cellulose energy density and cellulase cost height cause cause.It with the synthesis gas focus that the method ethanol production of raw material becomes Recent study.Synthesis gas Ethanol Method (patent CN1225852) is from one step of synthesis gas synthesizing alcohol, and technical process is simple relatively, but this process receives the ASF distribution limitation, and the ethanol selectivity is lower.Patent U.S. Pat. No. 2,607,807, U.S. Pat. No. 4,517,391, U.S. Pat. No. 5,149,680, CN102149661, CN102271805 have reported the catalyst and the application thereof of acetic acid hydrogenation synthesizing alcohol.Above catalyst all uses expensive noble metal, has limited its industrial applications.Summary of the invention
The object of the present invention is to provide a kind of with low cost, active high, metal carbide catalyst that the ethanol selectivity is high.
Catalyst of the present invention is to be to be the carbide of Co by transition metal master metal by catalyst, and the carbide of promoter metal and carrier are formed, and the catalyst weight ratio is: cobalt carbide 8.0-23.0wt%, molybdenum carbide, carbonization nickel or tungsten carbide 1.0-5.0wt %; Carrier 75.1-91.0wt %.
Aforesaid carrier is alundum (Al, molecular sieve, silica, titanium dioxide, zirconia or diatomite etc.
Preparation of catalysts method provided by the invention is:
The ratio of corresponding cobalt carbide, promoter metal carbide and carrier joins in the deionized water at first cobalt nitrate and promoter metal compound being formed in catalyst; On carrier, the carrier after the load is at room temperature placed 2-5 h with the solution incipient impregnation that disposes, 30-60 ℃ of following dry 2-5 h; Dry 6-12 h under 100-120 ℃; Roasting 3-6 h in 400-600 ℃ of air obtains the metal carbides precursor again, with carbon four following hydrocarbon, CO or CO and H
2Ratio with mol ratio 1:4-10 is formed the carbonization medium, and precursor speed with 0.5-3 ℃/min under the carbonization medium is warming up to 600-800 ℃, and in this temperature, volume space velocity is 3000-9000 h
-1Carbonization 3-8 h under the condition, sample use air speed to be 1000-3000 h after carbonization medium atmosphere drops to room temperature
-1, O
2Percent by volume is the O of 0.5-2%
2/ N
2Passivation 2-5 h obtains catalyst.
Aforesaid promoter metal compound is nickel nitrate, ammonium metatungstate, ammonium molybdate etc.
Aforesaid carbon four following hydro carbons are methane, ethane, propane, butane, ethene, propylene, butylene etc. and composition thereof.
Aforesaid cobalt carbide catalyst can be applicable in the fixed-bed tube reactor.Sample is at H before the reaction
2400-600 ℃ of preliminary treatment 3-8 h under the atmosphere, H
2Gas space velocity is 1500-6000 h
-1Heating rate 0.5-3 ℃/min.Concrete reaction condition is following: in the reaction temperature 200-300 ℃ of scope, reaction pressure is at 1.0-3.5 MPa, acetic acid liquid air speed 0.5-3 h
-1, H
2: the acetic acid mol ratio is 5-50.Under reaction condition as stated, the acetic acid conversion ratio is greater than 90%, and the ethanol selectivity is greater than 90%.
The present invention's advantage compared with prior art:
Support type carbonization Co catalysts preparation method provided by the invention is simple, production cost is low.Catalyst applications of the present invention is gentle in acetic acid hydrogenation synthesizing alcohol reaction condition, and the acetic acid conversion ratio is high, the ethanol selectivity is high, catalyst stability is good.Content of reaction byproduct is low.
The specific embodiment
Embodiment 1:
Take by weighing cobalt nitrate 6.3 g, nickel nitrate 0.72 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 16 g zirconias.Zirconia behind the dipping solution is at room temperature placed 5 h, 30 ℃ of drying 3 h, 110 ℃ of drying 10 h, 450 ℃ of roasting 5 h.With the gained sample at air speed 3000 h
-1, pressure 0.1 MPa, CO
2: H
2For the heating rate with 3 ml/min under the carbonization medium of 1:7 is elevated to 600 ℃, constant temperature is handled 4 h.After sample temperature was reduced to room temperature, using air speed was 1000 h
-1, O
2Content is 0.5% O
2 /N
2Passivation 3 h.Gained catalyst carbonization cobalt percentage composition 8.0wt%, carbonization nickel percentage composition 1.0wt%, carrier zirconia percentage composition 91.0wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 6000 h
-1, pressure 0.1 MPa H
2Be elevated to 450 ℃ with 2 ℃/min under the atmosphere, reduction 8 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 260 ℃ of reaction temperatures, reaction pressure 3.0 MPa, acetic acid liquid air speed 1.0 h
-1, H
2: acetic acid mol ratio 25.Under reaction condition as stated, acetic acid conversion ratio 93.0%, ethanol selectivity 95.2%.
Embodiment 2:
Take by weighing cobalt nitrate 16.45 g, ammonium metatungstate 0.39 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 12 g silica.Silica behind the dipping solution is at room temperature placed 4 h, 40 ℃ of drying 5 h, 110 ℃ of drying 8 h, 400 ℃ of roasting 6 h.With the gained sample at air speed 4500 h
-1, pressure 0.1 MPa, methane: H
2For the heating rate with 0.5 ml/min under the carbonization medium of 1:8 is elevated to 750 ℃, constant temperature is handled 6 h.After sample temperature was reduced to room temperature, using air speed was 1500 h
-1, O
2Content is 1% O
2 /N
2Passivation 2 h.Gained catalyst carbonization cobalt percentage composition 23.0wt%, tungsten carbide percentage composition 1.9wt%, carrier silica percentage composition 75.1wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 5000 h
-1, pressure 0.1 MPa H
2Be elevated to 550 ℃ with 2 ℃/min under the atmosphere, reduction 3 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 270 ℃ of reaction temperatures, reaction pressure 1.5 MPa, acetic acid liquid air speed 2.0 h
-1, H
2: acetic acid mol ratio 10.Under reaction condition as stated, acetic acid conversion ratio 97.5%, ethanol selectivity 96.3%.
Embodiment 3:
Take by weighing cobalt nitrate 13.07 g, ammonium molybdate 0.95 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 16 g zirconias.Zirconia behind the dipping solution is at room temperature placed 3 h, 45 ℃ of drying 3 h, 120 ℃ of drying 11 h, 450 ℃ of roasting 3 h.With the gained sample at air speed 6000 h
-1, pressure 0.1 MPa, ethane: H
2For the heating rate with 2 ml/min under the carbonization medium of 1:9 is elevated to 650 ℃, constant temperature is handled 3 h.After sample temperature was reduced to room temperature, using air speed was 2000 h
-1, O
2Content is 1.5% O
2 /N
2Passivation 3 h.Gained catalyst carbonization cobalt percentage composition 15.0wt%, molybdenum carbide percentage composition 2.8wt%, carrier silica percentage composition 82.2wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 4500 h
-1, pressure 0.1 MPa H
2Be elevated to 400 ℃ with 0.5 ℃/min under the atmosphere, reduction 7 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 280 ℃ of reaction temperatures, reaction pressure 2.5 MPa, acetic acid liquid air speed 2.5 h
-1, H
2: acetic acid mol ratio 50.Under reaction condition as stated, acetic acid conversion ratio 94.7%, ethanol selectivity 91.2%.
Embodiment 4:
Take by weighing cobalt nitrate 9.32 g, nickel nitrate 2.99 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 18 g alundum (Als.Alundum (Al behind the dipping solution is at room temperature placed 2 h, 55 ℃ of drying 2 h, 100 ℃ of drying 12 h, 600 ℃ of roasting 4 h.With the gained sample at air speed 9000 h
-1, pressure 0.1 MPa, propane: H
2For the heating rate with 1 ml/min under the carbonization medium of 1:10 is elevated to 750 ℃, constant temperature is handled 6 h.After sample temperature was reduced to room temperature, using air speed was 3000 h
-1, O
2Content is 2% O
2 /N
2Passivation 4 h.Gained catalyst carbonization cobalt percentage composition 10.0wt%, carbonization nickel percentage composition 3.5wt%, carrier alundum percentage composition 86.5wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 1500 h
-1, pressure 0.1 MPa H
2Be elevated to 450 ℃ with 1 ℃/min under the atmosphere, reduction 6 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 290 ℃ of reaction temperatures, reaction pressure 1 MPa, acetic acid liquid air speed 3.0 h
-1, H
2: acetic acid mol ratio 5.Under reaction condition as stated, acetic acid conversion ratio 100%, ethanol selectivity 96.3%.
Embodiment 5:
Take by weighing cobalt nitrate 10.07 g, ammonium metatungstate 0.33 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 10 g titanium dioxide.Titanium dioxide behind the dipping solution is at room temperature placed 5 h, 30 ℃ of drying 2 h, 120 ℃ of drying 6 h, 550 ℃ of roasting 6 h.With the gained sample at air speed 7500 h
-1, pressure 0.1 MPa, butane: H
2For the heating rate with 1 ml/min under the carbonization medium of 1:9 is elevated to 650 ℃, constant temperature is handled 5 h.After sample temperature was reduced to room temperature, using air speed was 2500 h
-1, O
2Content is 0.5% O
2 /N
2Passivation 5 h.Gained catalyst carbonization cobalt percentage composition 18.0wt%, tungsten carbide percentage composition 2.0wt%, carrier titanium dioxide percentage composition 80.0wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 3000 h
-1, pressure 0.1 MPa H
2Be elevated to 600 ℃ with 1 ℃/min under the atmosphere, reduction 4 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 300 ℃ of reaction temperatures, reaction pressure 2.5 MPa, acetic acid liquid air speed 1.5 h
-1, H
2: acetic acid mol ratio 45.Under reaction condition as stated, acetic acid conversion ratio 95.6%, ethanol selectivity 97.5%.
Embodiment 6:
Take by weighing cobalt nitrate 10.16 g, ammonium metatungstate 0.84 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 16 g molecular sieves.Molecular sieve behind the dipping solution is at room temperature placed 5 h, 50 ℃ of drying 3 h, 110 ℃ of drying 7 h, 500 ℃ of roasting 3 h.With the gained sample at air speed 6000 h
-1, pressure 0.1 MPa, ethene: H
2For the heating rate with 3 ml/min under the carbonization medium of 1:8 is elevated to 600 ℃, constant temperature is handled 4 h.After sample temperature was reduced to room temperature, using air speed was 2000 h
-1, O
2Content is 1% O
2 /N
2Passivation 5 h.Gained catalyst carbonization cobalt percentage composition 12.0wt%, tungsten carbide percentage composition 3.4wt%, carrier molecule sieve percentage composition 84.6wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 4500 h
-1, pressure 0.1 MPa H
2Be elevated to 400 ℃ with 3 ℃/min under the atmosphere, reduction 5 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 250 ℃ of reaction temperatures, reaction pressure 3.5 MPa, acetic acid liquid air speed 0.5 h
-1, H
2: acetic acid mol ratio 50.Under reaction condition as stated, acetic acid conversion ratio 100%, ethanol selectivity 92.4%.
Embodiment 7:
Take by weighing cobalt nitrate 17.51 g, nickel nitrate 2.18 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 20 g diatomite.Diatomite behind the dipping solution is at room temperature placed 2 h, 45 ℃ of drying 4 h, 100 ℃ of drying 6 h, 400 ℃ of roasting 4 h.With the gained sample at air speed 3000 h
-1, pressure 0.1 MPa, propylene: H
2For the heating rate with 1.5 ml/min under the carbonization medium of 1:7 is elevated to 650 ℃, constant temperature is handled 5 h.After sample temperature was reduced to room temperature, using air speed was 1000 h
-1, O
2Content is 1.5% O
2 /N
2Passivation 4 h.Gained catalyst carbonization cobalt percentage composition 16.0wt%, carbonization nickel percentage composition 2.2wt%, carrier diatomite percentage composition 81.8wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 6000 h
-1, pressure 0.1 MPa H
2Be elevated to 600 ℃ with 1.5 ℃/min under the atmosphere, reduction 5 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 240 ℃ of reaction temperatures, reaction pressure 2.5 MPa, acetic acid liquid air speed 0.5 h
-1, H
2: acetic acid mol ratio 20.Under reaction condition as stated, acetic acid conversion ratio 100%, ethanol selectivity 97.4%.
Embodiment 8:
Take by weighing cobalt nitrate 12.56 g, nickel nitrate 3.19 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 12 g silica.Silica behind the dipping solution is at room temperature placed 3 h, 60 ℃ of drying 4 h, 120 ℃ of drying 10 h, 450 ℃ of roasting 4 h.With the gained sample at air speed 3000 h
-1, pressure 0.1 MPa, butylene: H
2For the heating rate with 1.5 ml/min under the carbonization medium of 1:6 is elevated to 600 ℃, constant temperature is handled 6 h.After sample temperature was reduced to room temperature, using air speed was 1500 h
-1, O
2Content is 2% O
2 /N
2Passivation 4 h.Gained catalyst carbonization cobalt percentage composition 18.0wt%, carbonization nickel percentage composition 5.0wt%, carrier silica percentage composition 77.0wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 1500 h
-1, pressure 0.1 MPa H
2Be elevated to 400 ℃ with 0.5 ℃/min under the atmosphere, reduction 6 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 230 ℃ of reaction temperatures, reaction pressure 2 MPa, acetic acid liquid air speed 1.0 h
-1, H
2: acetic acid mol ratio 30.Under reaction condition as stated, acetic acid conversion ratio 92.5%, ethanol selectivity 95.4%.
Embodiment 9:
Take by weighing cobalt nitrate 9.16 g, ammonium molybdate 1.18 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 20 g diatomite.Diatomite behind the dipping solution is at room temperature placed 3 h, 55 ℃ of drying 4 h, 100 ℃ of drying 9 h, 500 ℃ of roasting 6 h.With the gained sample at air speed 9000 h
-1, pressure 0.1 MPa, CO:H
2For the heating rate with 2.5 ml/min under the carbonization medium of 1:5 is elevated to 650 ℃, constant temperature is handled 7 h.After sample temperature was reduced to room temperature, using air speed was 3000 h
-1, O
2Content is 0.5% O
2 /N
2Passivation 3 h.Gained catalyst carbonization cobalt percentage composition 9.0wt%, molybdenum carbide percentage composition 3.0wt%, carrier diatomite percentage composition 88.0wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 5000 h
-1, pressure 0.1 MPa H
2Be elevated to 450 ℃ with 1.5 ℃/min under the atmosphere, reduction 8 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 220 ℃ of reaction temperatures, reaction pressure 1 MPa, acetic acid liquid air speed 2.5 h
-1, H
2: acetic acid mol ratio 20.Under reaction condition as stated, acetic acid conversion ratio 98.2%, ethanol selectivity 94.4%.
Embodiment 10:
Take by weighing cobalt nitrate 17.44 g, ammonium molybdate 1.77 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 18 g alundum (Als.Alundum (Al behind the dipping solution is at room temperature placed 2 h, 45 ℃ of drying 3 h, 110 ℃ of drying 6 h, 550 ℃ of roasting 5 h.With the gained sample at air speed 3000 h
-1, pressure 0.1 MPa, CO
2: H
2For the heating rate with 0.5 ml/min under the carbonization medium of 1:6 is elevated to 800 ℃, constant temperature is handled 4 h.After sample temperature was reduced to room temperature, using air speed was 1000 h
-1, O
2Content is 1% O
2 /N
2Passivation 2 h.Gained catalyst carbonization cobalt percentage composition 17.0wt%, molybdenum carbide percentage composition 4.5wt%, carrier alundum percentage composition 78.5wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 3000 h
-1, pressure 0.1 MPa H
2Be elevated to 500 ℃ with 2.5 ℃/min under the atmosphere, reduction 4 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 210 ℃ of reaction temperatures, reaction pressure 2 MPa, acetic acid liquid air speed 0.5 h
-1, H
2: acetic acid mol ratio 40.Under reaction condition as stated, acetic acid conversion ratio 100%, ethanol selectivity 92.5%.
Embodiment 11:
Take by weighing cobalt nitrate 11.65 g, nickel nitrate 1.66 g respectively, above-mentioned salt is joined in the deionized water, incipient impregnation is on 10 g titanium dioxide.Titanium dioxide behind the dipping solution is at room temperature placed 5 h, 30 ℃ of drying 5 h, 120 ℃ of drying 10 h, 500 ℃ of roasting 3 h.With the gained sample at air speed 7500 h
-1, pressure 0.1 MPa, methane: H
2For the heating rate with 3 ml/min under the carbonization medium of 1:7 is elevated to 700 ℃, constant temperature is handled 8 h.After sample temperature was reduced to room temperature, using air speed was 2500 h
-1, O
2Content is 1.5% O
2 /N
2Passivation 5 h.Gained catalyst carbonization cobalt percentage composition 20.0wt%, carbonization nickel percentage composition 3.1wt%, carrier titanium dioxide percentage composition 76.9wt%.
Above-mentioned catalyst 2 ml are filled in the fixed-bed tube reactor.With sample at air speed 4500 h
-1, pressure 0.1 MPa H
2Be elevated to 550 ℃ with 3 ℃/min under the atmosphere, reduction 7 h cool the temperature to the hydrogenation reaction temperature then under this temperature.Acetic acid hydrogenation synthesizing alcohol reaction condition is following: 200 ℃ of reaction temperatures, reaction pressure 1.5 MPa, acetic acid liquid air speed 3.0 h
-1, H
2: acetic acid mol ratio 50.Under reaction condition as stated, acetic acid conversion ratio 98.3%, ethanol selectivity 94.9%.
Claims (6)
1. cobalt-base catalyst that is used for synthesizing alcohol; It is characterized in that catalyst is is the carbide of Co by transition metal master metal; The carbide of promoter metal and carrier are formed, and the catalyst weight ratio is: cobalt carbide 8.0-23.0wt%, molybdenum carbide, carbonization nickel or tungsten carbide 1.0-5.0wt %; Carrier 75.1-91.0wt %.
2. a kind of cobalt-base catalyst that is used for synthesizing alcohol as claimed in claim 1 is characterized in that described carrier is alundum (Al, molecular sieve, silica, titanium dioxide, zirconia or diatomite.
3. according to claim 1 or claim 2 a kind of preparation method who is used for the cobalt-base catalyst of synthesizing alcohol is characterized in that comprising the steps:
The ratio of corresponding cobalt carbide, promoter metal carbide and carrier joins in the deionized water at first cobalt nitrate and promoter metal compound being formed in catalyst; On carrier, the carrier behind the carrying transition metal compound is at room temperature placed 2-5 h with the solution incipient impregnation that disposes, 30-60 ℃ of following dry 2-5 h; Dry 6-12 h under 100-120 ℃; Roasting 3-6 h in 400-600 ℃ of air obtains the metal carbides precursor again, with carbon four following hydrocarbon, CO or CO and H
2Ratio with mol ratio 1:4-10 is formed the carbonization medium, and precursor speed with 0.5-3 ℃/min under the carbonization medium is warming up to 600-800 ℃, and in this temperature, volume space velocity is 3000-9000 h
-1Carbonization 3-8 h under the condition, sample use air speed to be 1000-3000 h after carbonization medium atmosphere drops to room temperature
-1, O
2Percent by volume is the O of 0.5-2%
2/ N
2Passivation 2-5 h obtains catalyst.
4. a kind of preparation method who is used for the cobalt-base catalyst of synthesizing alcohol as claimed in claim 3 is characterized in that described promoter metal compound is nickel nitrate, ammonium metatungstate, ammonium molybdate.
5. a kind of preparation method who is used for the cobalt-base catalyst of synthesizing alcohol as claimed in claim 3 is characterized in that described carbon four following hydrocarbon are methane, ethane, propane, butane, ethene, propylene, butylene and composition thereof.
6. according to claim 1 or claim 2 a kind of application that is used for the cobalt-base catalyst of synthesizing alcohol is characterized in that comprising the steps:
Catalyst applications is in fixed-bed tube reactor, and sample is at H before the reaction
2400-600 ℃ of preliminary treatment 3-8 h under the atmosphere, H
2Gas space velocity is 1500-6000 h
-1, heating rate 0.5-3 ℃/min, concrete reaction condition is following: in the reaction temperature 200-300 ℃ of scope, reaction pressure is at 1.0-3.5 MPa, acetic acid liquid air speed 0.5-3 h
-1, H
2: the acetic acid mol ratio is 5-50.
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| CN102941108A (en) * | 2012-10-18 | 2013-02-27 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing ethyl acetate and ethanol from hydrogenation of acetic acid, and preparation method and application thereof |
| CN103240108A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Molybdenum carbide catalyst for hydrogen production from formic acid and preparation method thereof |
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
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| CN105646148A (en) * | 2015-12-31 | 2016-06-08 | 浙江工业大学 | Method for preparing ethanol by hydrogenating acetic acid |
| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
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| 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 |
| CN107866250A (en) * | 2016-09-27 | 2018-04-03 | 中国科学院上海高等研究院 | The preparation method of carbon bag noble metal nano catalyst |
| CN111185209A (en) * | 2018-11-14 | 2020-05-22 | 中国科学院大连化学物理研究所 | Preparation of molybdenum carbide supported nickel-based catalyst and application of catalyst in preparation of ethanol by hydrogenation of carbon dioxide |
| CN114505085A (en) * | 2022-02-21 | 2022-05-17 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing straight-chain alkane, preparation method and application |
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