CN102631941B - Catalyst for synthesizing ethanol as well as preparation method and application of catalyst - Google Patents
Catalyst for synthesizing ethanol as well as preparation method and application of catalyst Download PDFInfo
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- CN102631941B CN102631941B CN201210058210.7A CN201210058210A CN102631941B CN 102631941 B CN102631941 B CN 102631941B CN 201210058210 A CN201210058210 A CN 201210058210A CN 102631941 B CN102631941 B CN 102631941B
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Abstract
The invention provides a catalyst for synthesizing ethanol as well as a preparation method and application of the catalyst. According to the invention, the molar ratio of transition metals A to B to C is (8-10): (0-2): (0-1), wherein the transition metal A is Ni, Co, Fe or W; the transition metal B is V, Mo or Nb; and the transition metal C is Cr or Ta. The catalyst has the advantages of low cost, high acetic acid conversion rate and high ethanol selectivity.
Description
Technical field
The present invention relates to a kind of ethanol synthetic method, is a kind of method of utilizing transition metal phosphide catalyst catalysis acetic acid hydrogenation synthesizing alcohol specifically.
Background technology
Ethanol is the important source material of chemical industry, agricultural, medicine and other fields, is called alcohol fuel while using as power fuel.Ethanol has many good physics and chemistry characteristics, adds by a certain percentage in gasoline, be not simply as alternative oil product, to use, but good oil quality modifying agent not only has oxygenation effect to oil product, or the high-octane rating blending component of gasoline.In regular gasoline, add 10% alcohol fuel, formed ethanol petrol has the advantages such as energy utilization efficiency is high, pollution emission is few.
Alcohol fuel country with fastest developing speed is the U.S. and Brazil in the world, and U.S.'s ethanol petrol accounts for its domestic gasoline and uses 25% of total amount, and Brazil is unique country that uses ethanol petrol in the world.China has 10 provinces and regions using ethanol petrol at present, year consumption ethanol petrol 1,700 ten thousand t.Along with research field and the range of application of alcohol fuel are constantly expanded, alcohol fuel will occupy critical role in oil product market, and development prospect is wide.At present the production method of alcohol fuel is mainly that to take corn and wheat be staple food grain food fermentation method in the world.China is populous, and cultivated area is few, and grain method ethanol exists the problem of " strive grain with people, strive ground with grain ".The national conditions of China determined China can not walk the U.S., Brazil grain method ethanol route.The impact that national food caused safely for China recent years grain method ethanol, National Development and Reform Committee issued < < about the emergency notice > > that suspends corn processing project to control the food problem that takies in alcohol production.
Develop petroleum resources shortage that non-grain alcohol fuel both can solve China, be conducive to guarantee national energy security, be also applicable to the national conditions that China has a large population and a few land, the industrial expansions such as China's energy, agricultural and animal husbandry are also significant.
Non-grain route alcohol production technology comprises following several: cellulose fermentation method (patent CN101235392), the direct synthesizing alcohol method of synthesis gas (patent CN1225852), acetic acid hydrogenation synthesizing alcohol method (patent U.S. Pat. No. 2,607,807, U.S. Pat. No. 4,517,391, U.S. Pat. No. 5,149,680, CN102149661, CN102271805) etc.Cellulose fermentation ethanol processed is because raw material compiling costs and high, the current cost of cellulase cost are higher than grain alcohol.Synthesis gas Ethanol Method is from synthesis gas one-step synthesis ethanol, and technical process is relatively simple, but ethanol is selectively 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 catalyst and the application thereof of acetic acid hydrogenation synthesizing alcohol.These catalyst are all used expensive noble metal, have limited its industrial applications.
Summary of the invention
The object of the present invention is to provide a kind of with low cost, acetic acid conversion ratio is high, selective high metal phosphide Catalysts and its preparation method and the application of ethanol.
Catalyst of the present invention is transition metal phosphide, and wherein the mol ratio of transition metal A:B:C is 8-10:0-2:0-1;
Transition metal A as above is Ni, Co, Fe or W; Transition metal B is V, Mo or Nb; Transition metal C is Cr or Ta.
The preparation method of catalyst provided by the invention comprises the following steps:
One or more transistion metal compounds and diammonium hydrogen phosphate are joined in deionized water by the stoichiometry mol ratio of catalyst composition, and add citric acid, wherein the mol ratio of citric acid and transition metal is 0.5-3:1, the solution obtaining is stirred at 50-90 ℃ to 8-24 h, dry 18-24 h at 100-110 ℃, afterwards by sample foamed solidification 10-20 h at 120-150 ℃, by the sample roasting 3-6 h in 400-650 ℃ of air after solidifying, by the sample after roasting at H
2under atmosphere, with the heating rate of 0.5-3 ℃/min, rise to 400-800 ℃, constant temperature 3-8 h, H
2gas space velocity is 3000-9000 h
-1, sample is at H
2atmosphere drops to after room temperature, uses O
2content is the O of 0.5-2%
2 /n
2passivation 2-5 h.
Transistion metal compound as above is nickel nitrate, cobalt nitrate, ferric nitrate, ammonium metatungstate, ammonium metavanadate, ammonium molybdate, niobium oxalate, chromic nitrate, ethanol tantalum etc.
All kinds of transition metal phosphide catalyst as above can be applicable in fixed-bed tube reactor.Reducing condition is: at H
2speed with 0.5-3 ℃/min under atmosphere is warming up to 400-600 ℃, and constant temperature is processed 3-8 h, H
2gas space velocity is 1500-6000 h
-1; Hydrogenation conditions is: reaction temperature is within the scope of 200-300 ℃, and reaction pressure is at 1-3.5 MPa, acetic acid liquid air speed 0.5-3 h
-1, H
2: acetic acid mol ratio is 5-50:1.
Under reaction condition as mentioned above, acetic acid conversion ratio is greater than 90%, and ethanol is selectively greater than 90%.
The present invention's advantage compared with prior art:
Transition metal phosphide catalyst preparation method provided by the invention is simple, production cost is low.It is gentle that catalyst of the present invention is applied to acetic acid hydrogenation synthesizing alcohol reaction condition, acetic acid conversion ratio is high, ethanol selective high, catalyst stability is good.
The specific embodiment
Embodiment 1:
The mol ratio that takes respectively nickel nitrate 29.1 g, diammonium hydrogen phosphate 6.6 g, citric acid 38.4 g(citric acids and metal is 2).Above-claimed cpd is joined in 200 ml deionized waters, at 65 ℃, stir 15 h, by dry 18 h at 100 ℃ of the solution after stir process, foamed solidification 19 h at 120 ℃, afterwards roasting 6 h at 400 ℃.By gained sample, in air speed, be 4500 h
-1, pressure is the H of 0.1 MPa
2heating rate with 0.5 ml/min under atmosphere is elevated to 750 ℃, and constant temperature is processed 4 h.Sample temperature is down to after room temperature, uses O
2content is 1% O
2 /n
2passivation 3 h.The mol ratio of each element of gained catalyst is Ni:P=2:1.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 2500 h
-1h
2under atmosphere, with 2 ℃/min, be elevated to 550 ℃, at this temperature, reduce 7 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 250 ℃, and reaction pressure is adjusted into 1.5 MPa, in acetic acid liquid air speed, is 3 h
-1, H
2: acetic acid mol ratio is 10 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 95.8%, ethanol selective 98.5%.
Embodiment 2:
The mol ratio that takes respectively cobalt nitrate 28.5 g, ammonium metavanadate 0.2 g, diammonium hydrogen phosphate 6.7 g, citric acid 48.0 g(citric acids and metal is 2.5).Above-claimed cpd is joined in 200 ml deionized waters, at 50 ℃, stir 19 h, by dry 22 h at 105 ℃ of the solution after stir process, foamed solidification 18 h at 130 ℃, afterwards roasting 6 h at 400 ℃.By gained sample, in air speed, be 3000 h
-1, pressure is the H of 0.1 MPa
2heating rate with 3 ml/min under atmosphere is elevated to 400 ℃, and constant temperature is processed 6 h.Sample temperature is down to after room temperature, uses O
2content is 0.5% O
2 /n
2passivation 2 h.The mol ratio of each element of gained catalyst is Co:V:P=9.8:0.2:5.1.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 6000 h
-1h
2under atmosphere, with 1.5 ℃/min, be elevated to 450 ℃, at this temperature, reduce 3 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 260 ℃, and reaction pressure is adjusted into 2.5 MPa, in acetic acid liquid air speed, is 0.5 h
-1, H
2: acetic acid mol ratio is 25 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 91.0%, ethanol selective 96.5%.
Embodiment 3:
The mol ratio that takes respectively ferric nitrate 38.4 g, ammonium metavanadate 0.6 g, diammonium hydrogen phosphate 13.2 g, citric acid 19.2 g(citric acids and metal is 1).Above-claimed cpd is joined in 200 ml deionized waters, at 70 ℃, stir 13 h, by dry 18 h at 110 ℃ of the solution after stir process, foamed solidification 13 h at 150 ℃, afterwards roasting 3 h at 450 ℃.By gained sample, in air speed, be 3750 h
-1, pressure is the H of 0.1 MPa
2heating rate with 1 ml/min under atmosphere is elevated to 550 ℃, and constant temperature is processed 3 h.Sample temperature is down to after room temperature, uses O
2content is 1% O
2 /n
2passivation 3 h.The mol ratio of each element of gained catalyst is Fe:V:P=9.5:0.5:10.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 1500 h
-1h
2under atmosphere, with 0.5 ℃/min, be elevated to 450 ℃, at this temperature, reduce 8 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 250 ℃, and reaction pressure is adjusted into 2.5 MPa, in acetic acid liquid air speed, is 1 h
-1, H
2: acetic acid mol ratio is 5 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 93.2%, ethanol selective 97.2%.
Embodiment 4:
The mol ratio that takes respectively ammonium metatungstate 23.0 g, ammonium metavanadate 1.2 g, diammonium hydrogen phosphate 13.2 g, citric acid 38.4 g(citric acids and metal is 2).Above-claimed cpd is joined in 200 ml deionized waters, at 55 ℃, stir 20 h, by dry 20 h at 105 ℃ of the solution after stir process, foamed solidification 14 h at 120 ℃, afterwards roasting 4 h at 400 ℃.By gained sample, in air speed, be 9000 h
-1, pressure is the H of 0.1 MPa
2heating rate with 2 ml/min under atmosphere is elevated to 450 ℃, and constant temperature is processed 6 h.Sample temperature is down to after room temperature, uses O
2content is 1.5% O
2 /n
2passivation 4 h.The mol ratio of each element of gained catalyst is W:V:P=9:1:10.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 4500 h
-1h
2under atmosphere, with 1 ℃/min, be elevated to 400 ℃, at this temperature, reduce 6 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 300 ℃, and reaction pressure is adjusted into 1 MPa, in acetic acid liquid air speed, is 1.5 h
-1, H
2: acetic acid mol ratio is 50 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 97.5%, ethanol selective 97.1%.
Embodiment 5:
The mol ratio that takes respectively nickel nitrate 23.3 g, ammonium molybdate 3.5 g, diammonium hydrogen phosphate 7.9 g, citric acid 57.6 g(citric acids and metal is 3).Above-claimed cpd is joined in 200 ml deionized waters, at 65 ℃, stir 24 h, by dry 24 h at 110 ℃ of the solution after stir process, foamed solidification 10 h at 120 ℃, afterwards roasting 6 h at 650 ℃.By gained sample, in air speed, be 7500 h
-1, pressure is the H of 0.1 MPa
2heating rate with 2 ml/min under atmosphere is elevated to 650 ℃, and constant temperature is processed 5 h.Sample temperature is down to after room temperature, uses O
2content is 2% O
2 /n
2passivation 5 h.The mol ratio of each element of gained catalyst is Ni:Mo:P=8:2:6.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 3000 h
-1h
2under atmosphere, with 1 ℃/min, be elevated to 400 ℃, at this temperature, reduce 4 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 240 ℃, and reaction pressure is adjusted into 3.5 MPa, in acetic acid liquid air speed, is 1 h
-1, H
2: acetic acid mol ratio is 45 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 96.3%, ethanol selective 92.9%.
Embodiment 6:
The mol ratio that takes respectively cobalt nitrate 27.9 g, ammonium molybdate 0.7 g, diammonium hydrogen phosphate 6.9 g, citric acid 48.0 g(citric acids and metal is 2.5).Above-claimed cpd is joined in 200 ml deionized waters, at 60 ℃, stir 8 h, by dry 18 h at 100 ℃ of the solution after stir process, foamed solidification 17 h at 140 ℃, afterwards roasting 4 h at 500 ℃.By gained sample, in air speed, be 3000 h
-1, pressure is the H of 0.1 MPa
2heating rate with 1.5 ml/min under atmosphere is elevated to 400 ℃, and constant temperature is processed 4 h.Sample temperature is down to after room temperature, uses O
2content is 1% O
2 /n
2passivation 5 h.The mol ratio of each element of gained catalyst is Co:Mo:P=9.6:0.4:5.2.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 4500 h
-1h
2under atmosphere, with 1.5 ℃/min, be elevated to 600 ℃, at this temperature, reduce 5 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 210 ℃, and reaction pressure is adjusted into 2.5 MPa, in acetic acid liquid air speed, is 0.5 h
-1, H
2: acetic acid mol ratio is 50 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 92.6%, ethanol selective 95.3%.
Embodiment 7:
The mol ratio that takes respectively ferric nitrate 33.1 g, ammonium molybdate 3.2 g, diammonium hydrogen phosphate 13.2 g, citric acid 38.4 g(citric acids and metal is 2).Above-claimed cpd is joined in 200 ml deionized waters, at 90 ℃, stir 14 h, by dry 22 h at 110 ℃ of the solution after stir process, foamed solidification 20 h at 130 ℃, afterwards roasting 4 h at 500 ℃.By gained sample, in air speed, be 6750 h
-1, pressure is the H of 0.1 MPa
2heating rate with 3 ml/min under atmosphere is elevated to 400 ℃, and constant temperature is processed 5 h.Sample temperature is down to after room temperature, uses O
2content is 2% O
2 /n
2passivation 4 h.The mol ratio of each element of gained catalyst is Fe:Mo:P=8.2:1.8:10.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 1500 h
-1h
2under atmosphere, with 3 ℃/min, be elevated to 450 ℃, at this temperature, reduce 5 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 280 ℃, and reaction pressure is adjusted into 2.5 MPa, in acetic acid liquid air speed, is 0.5 h
-1, H
2: acetic acid mol ratio is 30 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 95.6%, ethanol selective 97.6%.
Embodiment 8:
The mol ratio that takes respectively ammonium metatungstate 21.7 g, ammonium molybdate 2.7 g, diammonium hydrogen phosphate 13.2 g, citric acid 19.2 g(citric acids and metal is 1).Above-claimed cpd is joined in 200 ml deionized waters, at 85 ℃, stir 21 h, by dry 20 h at 100 ℃ of the solution after stir process, foamed solidification 11 h at 150 ℃, afterwards roasting 5 h at 450 ℃.By gained sample, in air speed, be 4500 h
-1, pressure is the H of 0.1 MPa
2heating rate with 2.5 ml/min under atmosphere is elevated to 650 ℃, and constant temperature is processed 6 h.Sample temperature is down to after room temperature, uses O
2content is 1.5% O
2 /n
2passivation 4 h.The mol ratio of each element of gained catalyst is W:Mo:P=8.5:1.5:10.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 6000 h
-1h
2under atmosphere, with 0.5 ℃/min, be elevated to 400 ℃, at this temperature, reduce 4 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 300 ℃, and reaction pressure is adjusted into 2 MPa, in acetic acid liquid air speed, is 0.5 h
-1, H
2: acetic acid mol ratio is 20 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 94.4%, ethanol selective 93.4%.
Embodiment 9:
The mol ratio that takes respectively nickel nitrate 25.6 g, niobium oxalate 7.5 g, diammonium hydrogen phosphate 7.4 g, citric acid 28.8 g(citric acids and metal is 1.5).Above-claimed cpd is joined in 200 ml deionized waters, at 50 ℃, stir 9 h, by dry 24 h at 110 ℃ of the solution after stir process, foamed solidification 12 h at 130 ℃, afterwards roasting 6 h at 450 ℃.By gained sample, in air speed, be 4500 h
-1, pressure is the H of 0.1 MPa
2heating rate with 1.5 ml/min under atmosphere is elevated to 450 ℃, and constant temperature is processed 7 h.Sample temperature is down to after room temperature, uses O
2content is 0.5% O
2 /n
2passivation 3 h.The mol ratio of each element of gained catalyst is Ni:Nb:P=8.8:1.2:5.6.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 4500 h
-1h
2under atmosphere, with 2.5 ℃/min, be elevated to 600 ℃, at this temperature, reduce 8 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 200 ℃, and reaction pressure is adjusted into 1 MPa, in acetic acid liquid air speed, is 2.5 h
-1, H
2: acetic acid mol ratio is 20 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 94.6%, ethanol selective 94.2%.
Embodiment 10:
The mol ratio that takes respectively cobalt nitrate 24.4 g, niobium oxalate 10.0 g, diammonium hydrogen phosphate 7.7 g, citric acid 28.8 g(citric acids and metal is 1.5).Above-claimed cpd is joined in 200 ml deionized waters, at 85 ℃, stir 22 h, by dry 20 h at 105 ℃ of the solution after stir process, foamed solidification 16 h at 120 ℃, afterwards roasting 5 h at 600 ℃.By gained sample, in air speed, be 3750 h
-1, pressure is the H of 0.1 MPa
2heating rate with 0.5 ml/min under atmosphere is elevated to 800 ℃, and constant temperature is processed 4 h.Sample temperature is down to after room temperature, uses O
2content is 0.5% O
2 /n
2passivation 2 h.The mol ratio of each element of gained catalyst is Co:Nb:P=8.4:1.6:5.8.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 5000 h
-1h
2under atmosphere, with 1.5 ℃/min, be elevated to 500 ℃, at this temperature, reduce 6 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 200 ℃, and reaction pressure is adjusted into 1.5 MPa, in acetic acid liquid air speed, is 3 h
-1, H
2: acetic acid mol ratio is 50 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 100%, ethanol selective 96.1%.
Embodiment 11:
The mol ratio that takes respectively ferric nitrate 38.0 g, niobium oxalate 3.8 g, diammonium hydrogen phosphate 13.2 g, citric acid 9.6 g(citric acids and metal is 0.5).Above-claimed cpd is joined in 200 ml deionized waters, at 75 ℃, stir 15 h, by dry 24 h at 100 ℃ of the solution after stir process, foamed solidification 15 h at 130 ℃, afterwards roasting 3 h at 500 ℃.By gained sample, in air speed, be 5250 h
-1, pressure is the H of 0.1 MPa
2heating rate with 2 ml/min under atmosphere is elevated to 800 ℃, and constant temperature is processed 8 h.Sample temperature is down to after room temperature, uses O
2content is 1% O
2 /n
2passivation 5 h.The mol ratio of each element of gained catalyst is Fe:Nb:P=9.4:0.6:10.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 3000 h
-1h
2under atmosphere, with 3 ℃/min, be elevated to 550 ℃, at this temperature, reduce 7 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 270 ℃, and reaction pressure is adjusted into 2 MPa, in acetic acid liquid air speed, is 1.5 h
-1, H
2: acetic acid mol ratio is 40 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 91.8%, ethanol selective 94.6%.
Embodiment 12:
The mol ratio that takes respectively ammonium metatungstate 22.2 g, niobium oxalate 8.2 g, diammonium hydrogen phosphate 13.2 g, citric acid 19.2 g(citric acids and metal is 1).Above-claimed cpd is joined in 200 ml deionized waters, at 75 ℃, stir 10 h, by dry 22 h at 110 ℃ of the solution after stir process, foamed solidification 12 h at 140 ℃, afterwards roasting 3 h at 450 ℃.By gained sample, in air speed, be 6000 h
-1, pressure is the H of 0.1 MPa
2heating rate with 3 ml/min under atmosphere is elevated to 700 ℃, and constant temperature is processed 8 h.Sample temperature is down to after room temperature, uses O
2content is 1.5% O
2 /n
2passivation 4 h.The mol ratio of each element of gained catalyst is W:Nb:P=8.7:1.3:10.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 4500 h
-1h
2under atmosphere, with 2.5 ℃/min, be elevated to 600 ℃, at this temperature, reduce 8 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 280 ℃, and reaction pressure is adjusted into 3.5 MPa, in acetic acid liquid air speed, is 0.5 h
-1, H
2: acetic acid mol ratio is 45 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 95.9%, ethanol selective 98.8%.
Embodiment 13:
The mol ratio that takes respectively cobalt nitrate 26.2 g, ammonium metavanadate 0.6 g, chromic nitrate 2.0 g, diammonium hydrogen phosphate 7.3 g, citric acid 19.2 g(citric acids and metal is 1).Above-claimed cpd is joined in 200 ml deionized waters, at 80 ℃, stir 17 h, by dry 18 h at 105 ℃ of the solution after stir process, foamed solidification 16 h at 120 ℃, afterwards roasting 4 h at 450 ℃.By gained sample, in air speed, be 4500 h
-1, pressure is the H of 0.1 MPa
2heating rate with 2.5 ml/min under atmosphere is elevated to 500 ℃, and constant temperature is processed 3 h.Sample temperature is down to after room temperature, uses O
2content is 2% O
2 /n
2passivation 2 h.The mol ratio of each element of gained catalyst is Co:V:Cr:P=9:0.5:0.5:5.5.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 6000 h
-1h
2under atmosphere, with 2 ℃/min, be elevated to 450 ℃, at this temperature, reduce 4 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 240 ℃, and reaction pressure is adjusted into 2 MPa, in acetic acid liquid air speed, is 2 h
-1, H
2: acetic acid mol ratio is 30 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 97.3%, ethanol selective 95.6%.
Embodiment 14:
The mol ratio that takes respectively ferric nitrate 32.3 g, ammonium molybdate 1.8 g, ethanol tantalum 4.1 g, diammonium hydrogen phosphate 13.2 g, citric acid 38.4 g(citric acids and metal is 2).Above-claimed cpd is joined in 200 ml deionized waters, at 90 ℃, stir 18 h, by dry 20 h at 100 ℃ of the solution after stir process, foamed solidification 15 h at 140 ℃, afterwards roasting 5 h at 500 ℃.By gained sample, in air speed, be 3750 h
-1, pressure is the H of 0.1 MPa
2heating rate with 1.5 ml/min under atmosphere is elevated to 750 ℃, and constant temperature is processed 8 h.Sample temperature is down to after room temperature, uses O
2content is 1.5% O
2 /n
2passivation 3 h.The mol ratio of each element of gained catalyst is Fe:Mo:Ta:P=8:1:1:10.
By getting 2ml after above-mentioned catalyst breakage, fill in fixed-bed tube reactor.By sample at pressure 0.1 MPa, air speed 2000 h
-1h
2under atmosphere, with 0.5 ℃/min, be elevated to 400 ℃, at this temperature, reduce 5 h.Acetic acid hydrogenation synthesizing alcohol reaction condition is as follows: reaction temperature is adjusted into 230 ℃, and reaction pressure is adjusted into 3.5 MPa, in acetic acid liquid air speed, is 2.5 h
-1, H
2: acetic acid mol ratio is 50 times reactions.Under reaction condition as mentioned above, acetic acid conversion ratio 100%, ethanol selective 93.6%.
Claims (2)
1. an application for the catalyst of synthesizing alcohol, is characterized in that catalyst is applied in fixed-bed tube reactor, and reducing condition is: at H
2speed with 0.5-3 ℃/min under atmosphere is warming up to 400-600 ℃, and constant temperature is processed 3-8 h, H
2gas space velocity is 1500-6000 h
-1; Hydrogenation conditions is: reaction temperature is within the scope of 200-300 ℃, and reaction pressure is at 1-3.5 MPa, acetic acid liquid air speed 0.5-3 h
-1, H
2: acetic acid mol ratio is 5-50:1;
Catalyst as above is transition metal phosphide, and wherein the mol ratio of transition metal A:B:C is 8-10:0-2:0-1;
Described transition metal A is Ni, Co, Fe or W; Transition metal B is V, Mo or Nb; Transition metal C is Cr or Ta;
Described catalyst is also prepared by following methods:
One or more transistion metal compounds and diammonium hydrogen phosphate are joined in deionized water by the stoichiometry mol ratio of catalyst composition, and add citric acid, wherein the mol ratio of citric acid and transition metal is 0.5-3:1, the solution obtaining is stirred at 50-90 ℃ to 8-24 h, dry 18-24 h at 100-110 ℃, afterwards by sample foamed solidification 10-20 h at 120-150 ℃, by the sample roasting 3-6 h in 400-650 ℃ of air after solidifying, by the sample after roasting at H
2under atmosphere, with the heating rate of 0.5-3 ℃/min, rise to 400-800 ℃, constant temperature 3-8 h, H
2gas space velocity is 3000-9000 h
-1, sample is at H
2atmosphere drops to after room temperature, uses O
2content is the O of 0.5-2%
2/ N
2passivation 2-5 h.
2. the application of the catalyst of a kind of synthesizing alcohol as claimed in claim 1, is characterized in that described transistion metal compound is nickel nitrate, cobalt nitrate, ferric nitrate, ammonium metatungstate, ammonium metavanadate, ammonium molybdate, niobium oxalate, chromic nitrate or ethanol tantalum.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210058210.7A CN102631941B (en) | 2012-03-07 | 2012-03-07 | Catalyst for synthesizing ethanol as well as preparation method and application of catalyst |
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|---|---|---|---|
| CN201210058210.7A CN102631941B (en) | 2012-03-07 | 2012-03-07 | Catalyst for synthesizing ethanol as well as preparation method and application of catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN102631941A CN102631941A (en) | 2012-08-15 |
| CN102631941B true CN102631941B (en) | 2014-04-16 |
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| CN201210058210.7A Active CN102631941B (en) | 2012-03-07 | 2012-03-07 | Catalyst for synthesizing ethanol as well as preparation method and application of catalyst |
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| EP2218502A3 (en) * | 1999-09-30 | 2010-09-22 | Ifp | Transition metal phosphide catalysts |
| CN1492025A (en) * | 2003-08-27 | 2004-04-28 | 大连理工大学 | Process for preparing load type transition metal phoshpide deep hydrogenation desulfurizing catalyst |
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN1327958C (en) * | 2004-03-12 | 2007-07-25 | 中国科学院大连化学物理研究所 | Method for preparing transition metal phosphide |
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