CN101502806B - Supported non-precious metal catalyst for synthesizing acetic anhydride as well as production method and use - Google Patents
Supported non-precious metal catalyst for synthesizing acetic anhydride as well as production method and use Download PDFInfo
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- CN101502806B CN101502806B CN2009100739544A CN200910073954A CN101502806B CN 101502806 B CN101502806 B CN 101502806B CN 2009100739544 A CN2009100739544 A CN 2009100739544A CN 200910073954 A CN200910073954 A CN 200910073954A CN 101502806 B CN101502806 B CN 101502806B
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Abstract
The invention relates to a loaded non-precious metal catalyst for synthesizing acetic anhydride, which comprises the following components in percentage by mass: 20 to 30 percent of chloride or oxide of Ni, 10 to 20 percent of chloride or oxide of Sn, 15 to 30 percent of chloride, oxide or sulfide of Cr, and 30 to 55 percent of carrier. The catalyst is prepared by adopting an impregnation method. The catalyst has the advantage of higher activity, the conversion rate of reactant methyl acetate can achieve 20 to 40 percent, and the selectivity of the acetic anhydride can achieve more than 80 percent.
Description
Technical field
The present invention relates to a kind of supported non-precious metal catalyst and method for making and application of synthetic aceticanhydride.
Background technology
Aceticanhydride is a kind of colourless transparent liquid, and the pungent pungent flavor of smelling is arranged.Aceticanhydride and ether can be dissolved in that to emit branch in the second alcohol and water analgesic with arbitrary proportion, and hydrolysis generates acetic acid, is dissolved in alcohol, ether, acetone and other organic solvent.Aceticanhydride is a kind of important Organic Chemicals and organic synthesis intermediate, has purposes very widely.Aceticanhydride is mainly with being acetylation reagent, dehydrating agent, solvent etc.Aceticanhydride is a primary raw material of producing cellulose acetate, and aceticanhydride also is widely used in fields such as medicine, dyestuff, agricultural chemicals, light industry, weaving in addition.
At present, the main production method of aceticanhydride has acetaldehyde oxidation, ketenes method, oxo synthesis.There are many unfavorable factors such as production cost is higher, of poor benefits, environmental pollution serious, small scale in acetaldehyde oxidation and ketenes method, and have overcome the part shortcoming of preceding two kinds of methods and the researchers' that are subjected to getting more and more attention as the oxo synthesis that rises the eighties in 20th century.The flow process that has of the synthetic aceticanhydride of carbonylation is lacked, good product quality, and energy consumption is low, and three waste discharge is few, and can realize the advantages such as coproduction of acetic acid and aceticanhydride.The catalyst system that is applied to study oxo-acetic anhydride mainly comprises VIIIB noble metal and base metal two big classes.Wherein adopt the research of the synthetic aceticanhydride aspect of noble metal catalyst to obtain bigger progress and realized industrialization.In recent years, Jiang of Institute of Chemistry, Academia Sinica pansophy etc. is being obtained aspect the research of Noble Metal Rhodium System Catalyst than quantum jump, and successfully is used for industrial production.Rhodium base catalyst is had other metallic catalyst incomparable advantage aspect catalytic activity and the selectivity, but rhodium is limited as its resource reserve of noble metal, cost an arm and a leg, thereby cause the Catalyst Production cost higher, therefore exploitation is applicable to that the non-precious metal catalyst of the synthetic aceticanhydride of carbonylation has important practical significance.In recent years, nickel-base catalyst is applied to the research that acetate carbonyl is combined to aceticanhydride and has obtained certain progress, yet industrialized report is not arranged as yet.Tsutomu Shlkada etc. (In.Eng.Chem.Prod.Res.Dev.1985,24,521-525) reported the nickel catalyst carried methyl acetate vapor phase carbonylation prepared in reaction aceticanhydride that is applied to, but the yield of the conversion ratio of methyl acetate and aceticanhydride is lower.
Summary of the invention
The purpose of this invention is to provide supported non-precious metal catalyst and the method for making and the application of the synthetic aceticanhydride that a kind of catalytic activity is higher, preparation is simple, with low cost.
Each constituent mass percentage of catalyst of the present invention consists of chloride or the oxide of Ni: the chloride of the chloride of Sn or oxide: Cr, oxide or sulfide: carrier=20～30%: 10～20%: 15～30%: 30～55%.
Aforesaid carrier is active carbon, magnesia or carborundum.
Preparation of catalysts method: Ni presoma, Sn presoma, Cr presoma are mixed with mixed solution by the catalyst composition, carrier is added the mixed solution dipping that contains catalyst precursor, left standstill 4～25 hours, in 80～130 ℃ of oven dry, in N2 atmosphere,, can make required catalyst in 400～800 ℃ of roastings 4～6 hours.
The presoma of the aforesaid Ni of containing is nickel nitrate, nickelous sulfate, nickel chloride or nickel acetate.
The presoma of the aforesaid Sn of containing is stannic chloride, stannous chloride or nitric acid tin.
The presoma of the aforesaid Cr of containing is chromic nitrate, chromium sulfate or chromium chloride.
Application of Catalyst method of the present invention is: the mol ratio of reactant methyl acetate and auxiliary agent iodomethane is 4: 1～9: 1, and the mol ratio of reactor feed gas carbon monoxide and hydrogen is 5: 1～12: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 1～1: 4.Be reflected on the fixed bed reactors and carry out, the reacting gas air speed is 900～1700h
-1, reaction temperature is 185～220 ℃, reaction pressure 4～8MPa, reaction time 4～22h.
Advantage of the present invention is as follows:
1. catalyst has higher activity, and the conversion ratio of reactant methyl acetate can reach 20-40%, and the selectivity of product aceticanhydride can reach more than 80%.
2. the catalyst raw material is cheap and easy to get, greatly reduces catalyst production cost, helps large-scale production.
3. technology of the present invention is simple, easy to operate.
4. gas-solid heterogeneous reaction makes that product is easy to separate, and has alleviated the corrosion to equipment.
The specific embodiment
Embodiment 1:
1. preparation catalyst: press the composition of nickel nitrate 20%, chromic nitrate 12%, stannic chloride 30%, carborundum 38%, carborundum is added the mixed solution dipping that contains catalyst precursor, left standstill 12 hours, in 115 ℃ of oven dry, N
2In 600 ℃ of roastings 5 hours, can make the required catalyst of reaction under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 8: 1, and the mol ratio of carbon monoxide and hydrogen is 8.5: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 1.Reaction velocity is 1100h
-1, reaction temperature is 180 ℃, and reaction pressure is 6.0MPa, and the reaction time is 7 hours, gets final product to such an extent that selectivity is 58.6% aceticanhydride, and the methyl acetate conversion ratio is 26.2%.
Embodiment 2:
1. preparation catalyst: press the composition of nickel nitrate 24%, chromic nitrate 18%, stannic chloride 20%, active carbon 38%, active carbon is added the mixed solution dipping that contains catalyst precursor, left standstill 12 hours, in 120 ℃ of oven dry, N
2In 650 ℃ of roastings 6 hours, can make required catalyst under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 7.5: 1, and the mol ratio of carbon monoxide and hydrogen is 12: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 3, and reaction velocity is 1400h
-1, reaction temperature is 195 ℃, and reaction pressure is 6.3MPa, and the reaction time is 10 hours, gets final product to such an extent that selectivity is 72.3% aceticanhydride, and the methyl acetate conversion ratio is 27.5%.
Embodiment 3:
1. preparation catalyst: press the composition of nickel nitrate 20%, chromic nitrate 18%, nitric acid tin 20%, active carbon 42%, active carbon is added the mixed solution dipping that contains catalyst precursor, left standstill 12 hours, in 120 ℃ of oven dry, N
2In 600 ℃ of roastings 4.5 hours, can make required catalyst under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 8: 1, and the mol ratio of carbon monoxide and hydrogen is 11: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 3, and reaction velocity is 1300h
-1, reaction temperature is 210 ℃, and reaction pressure is 5.3MPa, and the reaction time is 9 hours, gets final product to such an extent that selectivity is 63.2% aceticanhydride, and the conversion ratio of methyl acetate is 20.8%.
Embodiment 4:
1. preparation catalyst: press the composition of nickel acetate 22%, chromic nitrate 18%, nitric acid tin 20%, active carbon 40%, active carbon is added the mixed solution dipping that contains catalyst precursor, left standstill 10 hours, in 120 ℃ of oven dry, N
2In 600 ℃ of roastings 4 hours, can make required catalyst under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 7: 1, and the mol ratio of carbon monoxide and hydrogen is 6: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 4, and reaction velocity is 1200h
-1, reaction temperature is 210 ℃, and reaction pressure is 5.8MPa, and the reaction time is 7 hours, gets final product to such an extent that selectivity is 70.9% aceticanhydride, and the conversion ratio of methyl acetate is 31.2%.
Embodiment 5:
1. preparation catalyst: press the composition of nickel acetate 25%, chromic nitrate 18%, nitric acid tin 16%, magnesia 41%, magnesia is added the mixed solution dipping that contains catalyst precursor, left standstill 18 hours, in 90 ℃ of oven dry, N
2In 750 ℃ of roastings 6 hours, can make required catalyst under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 9: 1, and the mol ratio of carbon monoxide and hydrogen is 5: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 4, and reaction velocity is 1000h
-1, reaction temperature is 200 ℃, and reaction pressure is 5.3MPa, and the reaction time is 4 hours, gets final product to such an extent that selectivity is 46.5% aceticanhydride, and the conversion ratio of methyl acetate is 15.7%.
Embodiment 6:
1. preparation catalyst: press the composition of nickel acetate 25%, chromic nitrate 20%, stannous chloride 20%, carborundum 35%, carborundum is added the mixed solution dipping that contains catalyst precursor, left standstill 20 hours, in 110 ℃ of oven dry, N
2In 600 ℃ of roastings 6 hours, can make required catalyst under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 8: 1, and the mol ratio of carbon monoxide and hydrogen is 11: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 2.5, and reaction velocity is 950h
-1, reaction temperature is 220 ℃, and reaction pressure is 6.3MPa, and the reaction time is 22 hours, gets final product to such an extent that selectivity is 40.5% aceticanhydride, and the conversion ratio of methyl acetate is 10.2%.
Embodiment 7:
1. preparation catalyst: press the composition of nickel chloride 20%, chromium chloride 20%, nitric acid tin 20%, magnesia 40%, magnesia is added the mixed solution dipping that contains catalyst precursor, left standstill 15 hours, in 100 ℃ of oven dry, N
2In 500 ℃ of roastings 4 hours, can make required catalyst under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 4: 1, and the mol ratio of carbon monoxide and hydrogen is 12: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 2.5, and reaction velocity is 1500h
-1, reaction temperature is 190 ℃, and reaction pressure is 4.5MPa, and the reaction time is 10 hours, gets final product to such an extent that selectivity is 53.4% aceticanhydride, and the conversion ratio of methyl acetate is 28.4%.
Embodiment 8:
1. preparation catalyst: press the composition of nickelous sulfate 28%, chromium sulfate 10%, stannous chloride 17%, active carbon 45%, active carbon is added the mixed solution dipping that contains catalyst precursor, left standstill 4 hours, in 90 ℃ of oven dry, N
2In 400 ℃ of roastings 5 hours, can make required catalyst under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 6.5: 1, and the mol ratio of carbon monoxide and hydrogen is 8.4: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 2.5, and reaction velocity is 1300h
-1, reaction temperature is 200 ℃, and reaction pressure is 7.5MPa, and the reaction time is 7 hours, gets final product to such an extent that selectivity is 70.5% aceticanhydride, and the conversion ratio of methyl acetate is 29.8%.
Embodiment 9:
1. preparation catalyst: press the composition of nickel nitrate 20%, chromic nitrate 12%, butter of tin 16%, active carbon 52%, active carbon is added the mixed solution dipping that contains catalyst precursor, left standstill 24 hours, in 130 ℃ of oven dry, N
2In 800 ℃ of roastings 4 hours, can make required catalyst under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 7: 1, and the mol ratio of carbon monoxide and hydrogen is 6.6: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 1, and reaction velocity is 1600h
-1, reaction temperature is 190 ℃, and reaction pressure is 7.5MPa, and the reaction time is 13 hours, gets final product to such an extent that selectivity is 63.1% aceticanhydride, and the conversion ratio of methyl acetate is 26.2%.
Embodiment 10:
1. preparation catalyst: press the composition of nickel nitrate 26%, chromium sulfate 16%, butter of tin 25%, active carbon 33%, active carbon is added the mixed solution dipping that contains catalyst precursor, left standstill 9 hours, in 120 ℃ of oven dry, N
2In 600 ℃ of roastings 4 hours, can make required catalyst under the atmosphere.
2. be reflected in the continuous fixed bed reactor and carry out: the mole proportioning of methyl acetate and iodomethane is 7: 1, and the mol ratio of carbon monoxide and hydrogen is 7.6: 1, and the mol ratio of methyl acetate and carbon monoxide is 1: 3, and reaction velocity is 1155h
-1, reaction temperature is 205 ℃, and reaction pressure is 5.5MPa, and the reaction time is 7 hours, gets final product to such an extent that selectivity is 81.1% aceticanhydride, and the conversion ratio of methyl acetate is 38.8%.
Claims (4)
1. the supported non-precious metal catalyst of a synthetic aceticanhydride is characterized in that each constituent mass percentage of catalyst consists of:
The chloride of the chloride of the chloride of Ni or oxide: Sn or oxide: Cr, oxide or sulfide: carrier=20～30%: 10～20%: 15～30%: 30～55%.
2. the supported non-precious metal catalyst of a kind of synthetic aceticanhydride as claimed in claim 1 is characterized in that described carrier is active carbon, magnesia or carborundum.
3. the preparation method of the supported non-precious metal catalyst of a kind of synthetic aceticanhydride as claimed in claim 1 or 2, it is characterized in that Ni presoma, Sn presoma, Cr presoma being mixed with mixed solution by the catalyst composition, carrier is added the mixed solution dipping that contains catalyst precursor, left standstill 4～25 hours, in 80～130 ℃ of oven dry, at N
2In 400～800 ℃ of roastings 4～6 hours, can make required catalyst in the atmosphere;
Described Ni presoma is nickel nitrate, nickelous sulfate, nickel chloride or nickel acetate;
Described Sn presoma is stannic chloride, stannous chloride or nitric acid tin;
Described Cr presoma is chromic nitrate, chromium sulfate or chromium chloride.
4. the application of the supported non-precious metal catalyst of a kind of synthetic aceticanhydride as claimed in claim 1 or 2, the mol ratio that it is characterized in that reactant methyl acetate and auxiliary agent iodomethane is 4: 1～9: 1, the mol ratio of reactor feed gas carbon monoxide and hydrogen is 5: 1～12: 1, the mol ratio of methyl acetate and carbon monoxide is 1: 1～1: 4, be reflected on the fixed bed reactors and carry out, the reacting gas air speed is 900～1700h
-1, reaction temperature is 185～220 ℃, reaction pressure 4～8MPa, reaction time 4～22h.
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