CN104190457A - Catalyst in synthesis of isopropanol by virtue of hydrogenation of acetic acid and preparation method and application of catalyst - Google Patents
Catalyst in synthesis of isopropanol by virtue of hydrogenation of acetic acid and preparation method and application of catalyst Download PDFInfo
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- CN104190457A CN104190457A CN201410431776.9A CN201410431776A CN104190457A CN 104190457 A CN104190457 A CN 104190457A CN 201410431776 A CN201410431776 A CN 201410431776A CN 104190457 A CN104190457 A CN 104190457A
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Abstract
The invention relates to a catalyst in synthesis of isopropanol by virtue of hydrogenation of acetic acid, and the catalyst is a transition metal carbide, wherein the mol ratio of transition metals A, B and C is 1 to (0-0.5) to (0-0.08). The transition metal A is one or two of Fe, Co and Ni, the transition metal B is one or two of Cu, Zn and Mo, and the transition metal C is one or two of W, V and Cr. According to the invention, the advantages of low cost, mild condition, high transformation rate of the acetic acid, high selectivity of the isopropanol, and good stability of the catalyst are achieved.
Description
Technical field
The present invention relates to a kind of catalyst and method for making and application of petrohol, specifically a kind of Catalysts and its preparation method and application for acetic acid hydrogenation petrohol.
Background technology
Isopropyl alcohol (Isopropyl Alcohol, abbreviation IPA) have another name called IPA, dimethylcarbinol, it is a kind of organic solvent of function admirable, still produce the important intermediate of multiple organic compound, can be used as the raw material of synthetic glycerine, isopropyl acetate and acetone etc., also be widely used as oil-fired antifreeze additive, for aspects such as automobile and aviation fuel.In addition, isopropyl alcohol also can be used for manufacturing bactericide, pesticide, cleaning agent and disinfection preservative etc.At field tools such as agricultural chemicals, electronics industry, medicine, coating, daily-use chemical industry and organic syntheses, have been widely used, exploitation prospect is wide.
The production method of industrial isopropyl alcohol is mainly propylene hydration method and acetone hydrogenation method.Propylene hydration method can be divided into two kinds of the indirect hydration method of propylene and direct hydration methods.The indirect hydration method of propylene is that propylene is dissolved in and esterification occurs in sulfuric acid solution generates isopropyl acid sulphate and sulfuric acid diisopropyl ester, then through hydrolysis, the refining isopropyl alcohol that obtains.This method flow process is complicated, and selectively lower, equipment corrosion is serious, and waste water and exhaust-gas treatment be difficulty comparatively, after the 80's of 20th century, is eliminated gradually.Propylene direct hydration method is to make propylene that hydration reaction directly occur under catalyst exists to generate isopropyl alcohol, and by-product normal propyl alcohol, is the main method of current industrial production isopropyl alcohol simultaneously.Due to state's inner propene resource scarcity, the production cost of propylene hydration method petrohol is high.It is carried catalyst or nickel-base catalyst that acetone hydrogenation method petrohol adopts copper or zinc oxide, at 70～200 ℃, under condition of normal pressure, acetone hydrogenation generates isopropyl alcohol, (CN201110300319.4 has announced a kind of method of nickel-base catalyst catalysis acetone liquid-phase hydrogenatin petrohol can be divided into acetone gas phase hydrogenation (as CN201110293568.3 has announced a kind of method of copper nickel-base catalyst catalysis acetone gas phase hydrogenation petrohol) and liquid-phase hydrogenatin, US7799958 has announced the method for acetone liquid-phase hydrogenatin petrohol, acetone liquid-phase hydrogenatin is converted into isopropyl alcohol by least 2 hydrogenation reaction stages).Acetone liquid-phase hydrogenatin petrohol reaction pressure is high, and equipment investment is large, and cost is high, and gas phase hydrogenation petrohol reacts to such an extent that heat exchange efficiency is low, and when industrial production, heat of reaction cannot shift out, poor operability.
Summary of the invention
The object of the present invention is to provide a kind of cost low, mild condition, acetic acid conversion ratio is high, and isopropyl alcohol is selectively high, Catalysts and its preparation method and application for acetic acid direct hydrogenation petrohol that catalyst stability is good.
Catalyst of the present invention is transition metal carbide, and wherein transition metal A:B:C mol ratio is 1:0-0.5:0-0.08.
Transition metal A as described above is one or both in Fe, Co, Ni, and transition metal B is one or both in Cu, Zn, Mo, transition metal C be W, V or Cr one or both.
Method for preparing catalyst provided by the invention is:
(1) pressing catalyst forms, soluble transition metal compound and citric acid are joined in deionized water, obtain solution A, the mol ratio of each material adding is transition metal: citric acid: deionized water=1:0.5-3.0:40-100, in solution A, add red fuming nitric acid (RFNA) regulator solution pH value for 1.0-4.5, obtain solution B, by ethylene glycol: citric acid=1-3:1, in solution B, add ethylene glycol, obtain solution C;
(2) solution C step (1) being obtained is heated to generate thick gel in 40-70 ℃, by the gel obtaining in 100-140 ℃ of dry 10-24 h, obtain solid D, solid D is warmed up to 550-750 ℃ with the speed of 0.5-3 ℃/min under inert atmosphere, and at this temperature carbonization 3-8 h, at inert atmosphere, drop to after room temperature, pass into O
2content is the O of 0.5-2.5v%
2with N
2the gaseous mixture forming, by its surface passivation, obtains metal carbides.
If the transistion metal compound in above-mentioned steps (1) is ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, ammonium molybdate, ammonium metatungstate, chromic nitrate, ammonium metavanadate.
Inert atmosphere described in above-mentioned steps (2) can be N
2, He, a kind of in Ar etc.
Catalyst application of the present invention is as follows:
Above-mentioned catalyst is applied to tubular fixed-bed reactor: reaction is front at H
2under atmosphere, with 1-3 ℃/min, be warming up to 500-600 ℃, and at this temperature, reduce 4-8 h, H
2air speed is 3000-7000 h
-1, H
2atmosphere drops to reaction temperature 280-350 ℃, passes into the acetic acid steam and the H that are preheated to 150～180 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 10～40 v%, reaction gas air speed is 3000-7000 ml/g
cat.h, operating pressure is 2.5～6.0 MPa.
The present invention's advantage is compared to the prior art:
1) method for preparing catalyst is simple, easy to operate.
2) technological process is short, produces isopropyl alcohol cost low.
3) reaction condition is gentle, and acetic acid conversion ratio is high, and isopropyl alcohol is selectively high, and catalyst stability is good.
The specific embodiment
Embodiment 1
(1) by 8.8 g cobalt nitrates, 0.23 g ammonium metatungstate, 5.8 g citric acids join that in 44.5 g deionized waters, (mol ratio of each material is: (Co+W): citric acid: water=1:1.0:80), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 1.5, obtain solution B.In solution B, add 5.5 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 2.9), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 50 ℃, and the gel obtaining, in 100 ℃ of dry 12 h, is obtained to solid D.By solid D in N
2speed with 1 ℃/min under atmosphere is warmed up to 650 ℃, and at this temperature carbonization 4 h.At N
2atmosphere drops to after room temperature, passes into O
2content is the O of 1.0 v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain cobalt tungsten carbide catalyst.Catalyst mole consists of: Co:W=1:0.03.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 1 ℃/min, be warming up to 500 ℃, and at this temperature, reduce 5 h, H
2air speed is 3000 h
-1, H
2atmosphere drops to 280 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 160 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 30 v%, reaction gas air speed is 3000 ml/g
cat.h, operating pressure is 4.0 MPa.Acetic acid conversion ratio 95.6%, isopropyl alcohol selective 65.3%.
Embodiment 2
(1) by 9.8 g ferric nitrates, 0.18 g ammonium metavanadate, 7.1 g citric acids join that in 40.1 g deionized waters, (mol ratio of each material is: (Fe+V): citric acid: water=1:1.4:86), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 2.5, obtain solution B.In solution B, add 5.7 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 2.5), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 110 ℃ of dry 24 h, is obtained to solid D.Solid D speed with 1.5 ℃/min under Ar atmosphere is warmed up to 700 ℃, and at this temperature carbonization 8 h.In Ar atmosphere, drop to after room temperature, pass into O
2content is the O of 1.5 v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain ferrovanadium carbide catalyst.Catalyst mole consists of: Fe:V=1:0.06.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 1 ℃/min, be warming up to 500 ℃, and at this temperature, reduce 10 h, H
2air speed is 5000 h
-1, H
2atmosphere drops to 290 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 150 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 20 v%, reaction gas air speed is 5000 ml/g
cat.h, operating pressure is 5.0 MPa.Acetic acid conversion ratio 99.8%, isopropyl alcohol selective 77.2%.
Embodiment 3:
(1) by 10.5 g nickel nitrates, 0.33 g chromic nitrate, 8.8 g citric acids join that in 60.4 g deionized waters, (mol ratio of each material is: (Ni+Cr): citric acid: water=1:1.2:90), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 3.0, obtain solution B.In solution B, add 5.5 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 1.9), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 120 ℃ of dry 16 h, is obtained to solid D.Solid D speed with 2.0 ℃/min under inert atmosphere is warmed up to 750 ℃, and at this temperature carbonization 6 h.In He atmosphere, drop to after room temperature, pass into O
2content is the O of 1.5 v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain nickel chromium triangle carbide catalyst.Catalyst mole consists of: Ni:Cr=1:0.02.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 1 ℃/min, be warming up to 350 ℃, and at this temperature, reduce 10 h, H
2air speed is 4500 h
-1, H
2atmosphere drops to 270 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 160 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 35 v%, reaction gas air speed is 4500 ml/g
cat.h, operating pressure is 2.5 MPa.Acetic acid conversion ratio 86.5%, isopropyl alcohol selective 66.1%
Embodiment 4
(1) by 12.4 g nickel nitrates, 4.3 g zinc nitrates, 12.4 g citric acids join that in 42.4 g deionized waters, (mol ratio of each material is: (Ni+Zn): citric acid: water=1:1.1:41), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 4.0, obtain solution B.In solution B, add 6.2 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 1.6), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 70 ℃, and the gel obtaining, in 120 ℃ of dry 18 h, is obtained to solid D.By solid D in N
2speed with 1 ℃/min under atmosphere is warmed up to 550 ℃, and at this temperature carbonization 8 h.At N
2atmosphere drops to after room temperature, passes into O
2content is the O of 1.0 v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain nickel zinc carbide catalyst.Catalyst mole consists of: Ni:Zn=1:0.34.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 2 ℃/min, be warming up to 400 ℃, and at this temperature, reduce 3 h, H
2air speed is 4000 h
-1, H
2atmosphere drops to 300 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 180 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 20 v%, reaction gas air speed is 4000 ml/g
cat.h, operating pressure is 4.0 MPa.Acetic acid conversion ratio 100%, isopropyl alcohol selective 78.3%.
Embodiment 5
(1) by 13.8 g cobalt nitrates, 0.8 g ammonium metatungstate, 15.1 g citric acids join that in 70 g deionized waters, (mol ratio of each material is: (Co+W): citric acid: water=1:1.6:77), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 1.0, obtain solution B.In solution B, add 8.8 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 1.8), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 110 ℃ of dry 20 h, is obtained to solid D.Solid D speed with 1 ℃/min under Ar atmosphere is warmed up to 700 ℃, and at this temperature carbonization 4 h.In Ar atmosphere, drop to after room temperature, pass into O
2content is the O of 1.0 v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain cobalt tungsten carbide catalyst.Catalyst mole consists of: Co:W=1:0.06.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 2 ℃/min, be warming up to 550 ℃, and at this temperature, reduce 5 h, H
2air speed is 3000 h
-1, H
2atmosphere drops to 300 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 160 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 10 v%, reaction gas air speed is 3000 ml/g
cat.h, operating pressure is 4.0 MPa.Acetic acid conversion ratio 97.7%, isopropyl alcohol selective 81.3%.
Embodiment 6
(1) by 12.3 g ferric nitrates, 4.5 g cobalt nitrates, 11.5 g citric acids join that in 66 g deionized waters, (mol ratio of each material is: (Fe+Co): citric acid: water=1:1.3:80), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 1.5, obtain solution B.In solution B, add 3.9 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 1.0), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 110 ℃ of dry 20 h, is obtained to solid D.By solid D in N
2speed with 1 ℃/min under atmosphere is warmed up to 700 ℃, and at this temperature carbonization 4 h.At N
2atmosphere drops to after room temperature, passes into O
2content is the O of 1.0 v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain iron cobalt carbide catalyst.Catalyst mole consists of: Fe:Co=1:0.5.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 1 ℃/min, be warming up to 400 ℃, and at this temperature, reduce 6 h, H
2air speed is 3000 h
-1, H
2atmosphere drops to 290 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 160 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 40 v%, reaction gas air speed is 3000 ml/g
cat.h, operating pressure is 5.0 MPa.Acetic acid conversion ratio 96.6%, isopropyl alcohol selective 76.4%.
Embodiment 7
(1) by 8.6 g cobalt nitrates, 4.5 g nickel nitrates, 2.2 g ammonium molybdates, 5.8 g citric acids join that in 55g deionized water, (mol ratio of each material is: (Co+Ni+Mo): citric acid: water=1:0.5:53), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 4.5, obtain solution B.In solution B, add 5.4 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 2.9), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 110 ℃ of dry 20 h, is obtained to solid D.By solid D in N
2speed with 1 ℃/min under atmosphere is warmed up to 700 ℃, and at this temperature carbonization 4 h.At N
2atmosphere drops to after room temperature, passes into O
2content is the O of 1.0 v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain cobalt nickel molybdenum carbide catalyst.Catalyst mole consists of: (Co+Ni): Mo=1:0.26.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 3 ℃/min, be warming up to 500 ℃, and at this temperature, reduce 5 h, H
2air speed is 3000 h
-1, H
2atmosphere drops to 285 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 160 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 30 v%, reaction gas air speed is 3000 ml/g
cat.h, operating pressure is 3.0 MPa.Acetic acid conversion ratio 88.4%, isopropyl alcohol selective 62.1%
Embodiment 8
(1) by 14.5 g ferric nitrates, 2.1 g copper nitrates, 1.5 g zinc nitrates, 4.4 g citric acids join that in 60 g deionized waters, (mol ratio of each material is: (Fe+Cu+Zn): citric acid: water=1:0.5:68), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 1.0, obtain solution B.In solution B, add 2.8 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 2.0), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 120 ℃ of dry 16 h, is obtained to solid D.Solid D speed with 1.5 ℃/min under Ar atmosphere is warmed up to 750 ℃, and at this temperature carbonization 3 h.In Ar atmosphere, drop to after room temperature, pass into O
2content is the O of 1.0v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain iron copper zinc carbide catalyst.Catalyst mole consists of: Fe:(Cu+Zn)=1:0.38.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 1 ℃/min, be warming up to 450 ℃, and at this temperature, reduce 6 h, H
2air speed is 6000 h
-1, H
2atmosphere drops to 280 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 160 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 20 v%, reaction gas air speed is 6000 ml/g
cat.h, operating pressure is 4.5 MPa.Acetic acid conversion ratio 88.5%, isopropyl alcohol selective 72.3%
Embodiment 9
(1) by 8.6 g ferric nitrates, 1.9 g copper nitrates, 16.2 g citric acids join that in 50 g deionized waters, (mol ratio of each material is: (Fe+Cu): citric acid: water=1:2.9:96), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 1.5, obtain solution B.In solution B, add 14.8 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 2.8), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 120 ℃ of dry 16 h, is obtained to solid D.Solid D speed with 1.5 ℃/min under Ar atmosphere is warmed up to 750 ℃, and at this temperature carbonization 3 h.In Ar atmosphere, drop to after room temperature, pass into O
2content is the O of 1.0 v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain iron copper carbide catalyst.Catalyst mole consists of: Fe:Cu=1:0.37.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 1 ℃/min, be warming up to 400 ℃, and at this temperature, reduce 5 h, H
2air speed is 5000 h
-1, H
2atmosphere drops to 290 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 150 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 30 v%, reaction gas air speed is 4000 ml/g
cat.h, operating pressure is 3.0 MPa.Acetic acid conversion ratio 92.1%, isopropyl alcohol selective 75.3%
Embodiment 10
(1) by 21.5 g nickel nitrates, 3.5 g ammonium molybdates, 0.64 g ammonium metavanadate, 20.5 g citric acids join in 50 g deionized waters that (mol ratio of each material is (Ni+Mo+V): citric acid: water=1:1.1:67), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 1.5, obtain solution B.In solution B, add 7.4 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 1.1), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 120 ℃ of dry 16 h, is obtained to solid D.By solid D in N
2speed with 1.5 ℃/min under atmosphere is warmed up to 750 ℃, and at this temperature carbonization 3 h.At N
2atmosphere drops to after room temperature, passes into O
2content is the O of 1.0v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain nickel molybdenum vanadium carbide catalyst.Catalyst mole consists of: Ni:Mo:V=1:0.27:0.07.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 2 ℃/min, be warming up to 350 ℃, and at this temperature, reduce 5 h, H
2air speed is 4000 h
-1, H
2atmosphere drops to 290 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 150 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 35 v%, reaction gas air speed is 4000 ml/g
cat.h, operating pressure is 3.0 MPa.Acetic acid conversion ratio 94.6%, isopropyl alcohol selective 67.8%.
Embodiment 11
(1) by 16.3 g cobalt nitrates, 6.5 g copper nitrates, 0.25 g ammonium metatungstate, 8.5 g citric acids join that in 71 g deionized waters, (mol ratio of each material is: (Co+Cu+W): citric acid: water=1:0.5:47), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 3.0, obtain solution B.In solution B, add 3.5 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 1.3), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 120 ℃ of dry 16 h, is obtained to solid D.By solid D in N
2speed with 1.5 ℃/min under atmosphere is warmed up to 750 ℃, and at this temperature carbonization 3 h.At N
2atmosphere drops to after room temperature, passes into O
2content is the O of 1.0v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain cobalt copper tungsten carbide catalyst.Catalyst mole consists of Co:Cu:W=1:0.48:0.02.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 3 ℃/min, be warming up to 400 ℃, and at this temperature, reduce 5 h, H
2air speed is 7000 h
-1, H
2atmosphere drops to 330 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 150 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 35 v%, reaction gas air speed is 7000 ml/g
cat.h, operating pressure is 3.0 MPa.Acetic acid conversion ratio 100%, isopropyl alcohol selective 62.5%.
Embodiment 12
(1) by 15.3 g cobalt nitrates, 2.2 g zinc nitrates, 0.98 g chromic nitrate, 8.0 g citric acids join that in 50 g deionized waters, (mol ratio of each material is: (Co+Zn+Cr): citric acid: water=1:0.9:58), obtain solution A.To adding red fuming nitric acid (RFNA) regulator solution pH value in solution A, be 2.0, obtain solution B.In solution B, add 6.4 g ethylene glycol (mol ratio of ethylene glycol and citric acid is 2.5), obtain solution C.
(2) solution C step (1) being obtained is heated to generate thick gel in 60 ℃, and the gel obtaining, in 120 ℃ of dry 16 h, is obtained to solid D.By solid D in N
2speed with 1.5 ℃/min under atmosphere is warmed up to 750 ℃, and at this temperature carbonization 3 h.At N
2atmosphere drops to after room temperature, passes into O
2content is the O of 1.0v%
2with N
2the gaseous mixture forming, by its surface passivation, can obtain cobalt zinc chrome carbide catalyst.In catalyst, mole consist of: Co:Zn:Cr=1:0.2:0.06.
By catalyst application tubular fixed-bed reactor obtained above: before reaction at H
2under atmosphere, with 2 ℃/min, be warming up to 350 ℃, and at this temperature, reduce 5 h, H
2air speed is 5000 h
-1, H
2atmosphere drops to 330 ℃ of reaction temperatures.Pass into the acetic acid steam and the H that are preheated to 150 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 30 v%, reaction gas air speed is 5000 ml/g
cat.h, operating pressure is 6.0 MPa.Acetic acid conversion ratio 99.5%, isopropyl alcohol selective 80.2%.
Claims (8)
1. a catalyst for acetic acid hydrogenation petrohol, is characterized in that catalyst is transition metal carbide, and wherein transition metal A:B:C mol ratio is 1:0-0.5:0-0.08.
2. the catalyst of a kind of acetic acid hydrogenation petrohol as claimed in claim 1, is characterized in that described transition metal A is one or both in Fe, Co, Ni.
3. the catalyst of a kind of acetic acid hydrogenation petrohol as claimed in claim 1, is characterized in that described transition metal B is one or both in Cu, Zn, Mo.
4. the catalyst of a kind of acetic acid hydrogenation petrohol as claimed in claim 1, it is characterized in that described transition metal C be W, V or Cr one or both.
5. the preparation method of the catalyst of a kind of acetic acid hydrogenation petrohol as described in claim 1-4 any one, is characterized in that comprising the steps:
(1) pressing catalyst forms, soluble transition metal compound and citric acid are joined in deionized water, obtain solution A, the mol ratio of each material adding is transition metal: citric acid: deionized water=1:0.5-3.0:40-100, in solution A, add red fuming nitric acid (RFNA) regulator solution pH value for 1.0-4.5, obtain solution B, by ethylene glycol: citric acid=1-3:1, in solution B, add ethylene glycol, obtain solution C;
(2) solution C step (1) being obtained is heated to generate thick gel in 40-70 ℃, by the gel obtaining in 100-140 ℃ of dry 10-24 h, obtain solid D, solid D is warmed up to 550-750 ℃ with the speed of 0.5-3 ℃/min under inert atmosphere, and at this temperature carbonization 3-8 h, at inert atmosphere, drop to after room temperature, pass into O
2content is the O of 0.5-2.5v%
2with N
2the gaseous mixture forming, by its surface passivation, obtains metal carbides.
6. the preparation method of the catalyst of a kind of acetic acid hydrogenation petrohol as claimed in claim 5, it is characterized in that the soluble transition metal compound in step (1) is ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, ammonium molybdate, ammonium metatungstate, chromic nitrate or ammonium metavanadate.
7. the preparation method of the catalyst of a kind of acetic acid hydrogenation petrohol as claimed in claim 5, is characterized in that the inert atmosphere described in step (2) is N
2, He, a kind of in Ar.
8. the application of the catalyst of a kind of acetic acid hydrogenation petrohol as described in claim 1-4 any one, is characterized in that comprising the steps:
Catalyst is applied to tubular fixed-bed reactor, and reaction is front at H
2under atmosphere, with 1-3 ℃/min, be warming up to 500-600 ℃, and at this temperature, reduce 4-8 h, H
2air speed is 3000-7000 h
-1, H
2atmosphere drops to reaction temperature 280-350 ℃, passes into the acetic acid steam and the H that are preheated to 150～180 ℃
2gaseous mixture, acetic acid steam shared volume in reaction gas is 10～40%, reaction gas air speed is 3000-7000 ml/g
cat.h, operating pressure is 2.5～6.0 MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857981A (en) * | 2015-04-24 | 2015-08-26 | 中国科学院山西煤炭化学研究所 | Metal nitride catalyst for acetic acid hydrogenation synthesis of isopropanol and manufacturing method and application thereof |
| CN109529854A (en) * | 2018-12-10 | 2019-03-29 | 西南化工研究设计院有限公司 | The non-precious metal catalyst and its preparation method of a kind of acetic acid preparation of ethanol by hydrogenating and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394684A (en) * | 2002-04-10 | 2003-02-05 | 中国科学院大连化学物理研究所 | Preparation method of transition metal carbide catalyst and its catalytic performance |
| WO2012138540A1 (en) * | 2011-04-04 | 2012-10-11 | Celanese International Corporation | Ethanol production from acetic acid utilizing a molybdenum carbide catalyst |
-
2014
- 2014-08-29 CN CN201410431776.9A patent/CN104190457B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394684A (en) * | 2002-04-10 | 2003-02-05 | 中国科学院大连化学物理研究所 | Preparation method of transition metal carbide catalyst and its catalytic performance |
| WO2012138540A1 (en) * | 2011-04-04 | 2012-10-11 | Celanese International Corporation | Ethanol production from acetic acid utilizing a molybdenum carbide catalyst |
Non-Patent Citations (3)
| Title |
|---|
| H.H.STADELMAIER ET.AL.: "TERNARY CARBIDES OF THE TRANSITION METALS NICKEL, COBALT, IRON, MANGANESE WITH ZINC AND TIN", 《ACTA METALLURGICA》 * |
| LIHONG ZHAO ET.AL.: "Sol–gel derived Ni–Mo bimetallic carbide catalysts and their performance for CO hydrogenation", 《CATALYSIS TODAY》 * |
| MASSTOSHI NAGAI ET.AL.: "Low-temperature water–gas shift reaction over cobalt–molybdenum carbide catalyst", 《JOURNAL OF CATALYSIS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857981A (en) * | 2015-04-24 | 2015-08-26 | 中国科学院山西煤炭化学研究所 | Metal nitride catalyst for acetic acid hydrogenation synthesis of isopropanol and manufacturing method and application thereof |
| CN104857981B (en) * | 2015-04-24 | 2017-12-19 | 中国科学院山西煤炭化学研究所 | A kind of metal nitride catalyst of acetic acid hydrogenation synthesis isopropanol and its preparation method and application |
| CN109529854A (en) * | 2018-12-10 | 2019-03-29 | 西南化工研究设计院有限公司 | The non-precious metal catalyst and its preparation method of a kind of acetic acid preparation of ethanol by hydrogenating and application |
| CN109529854B (en) * | 2018-12-10 | 2020-08-04 | 西南化工研究设计院有限公司 | Non-noble metal catalyst for preparing ethanol by acetic acid hydrogenation and preparation method and application thereof |
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| CN104190457B (en) | 2016-09-21 |
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