CN102716750A - Catalyst for constant-pressure gas-phase hydrogenation preparation of gamma-butyrolactone by maleic anhydride and preparation method thereof - Google Patents

Catalyst for constant-pressure gas-phase hydrogenation preparation of gamma-butyrolactone by maleic anhydride and preparation method thereof Download PDF

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Publication number
CN102716750A
CN102716750A CN201210222118XA CN201210222118A CN102716750A CN 102716750 A CN102716750 A CN 102716750A CN 201210222118X A CN201210222118X A CN 201210222118XA CN 201210222118 A CN201210222118 A CN 201210222118A CN 102716750 A CN102716750 A CN 102716750A
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catalyst
cis
gamma
butyrolacton
pressure gas
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冯先涛
李小虎
张之翔
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XI'AN CATALYST CHEMICAL CO Ltd
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XI'AN CATALYST CHEMICAL CO Ltd
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Abstract

The invention discloses a catalyst for constant-pressure gas-phase hydrogenation preparation of gamma-butyrolactone by maleic anhydride. The catalyst comprises the following components in percent by weight: 6-75% of CuO, 10-52% ZnO, and 15-42% of SiO2. The invention further discloses a preparation method of the catalyst, comprising the following steps of: adding silica sol into de-ionized water to prepare a solution; adding copper nitrate and zinc nitrate into the deionized water so as to prepare a nitrate solution with a concentration of 1 mol/L; adding the nitrate solution and a sodium carbonate solution with a mass concentration of 20% into a silica sol solution by using a double-dripping manner, stirring, and controlling a PH value of a solution system to be 7; ageing, washing, filtering, drying and roasting sediments after sedimentation; and finally, obtaining the catalyst to be prepared by sheeting and forming the roasted sediments, and crashing and sieving the formed sediments. The catalyst disclosed by the invention has a simple process and has the advantages of high activity, high selectivity, long service life, easiness for regeneration and the like.

Description

The cis-anhydride normal pressure gas phase hydrogenation prepares the Catalysts and its preparation method of gamma-butyrolacton
Technical field
The invention belongs to catalyst technical field, be specifically related to the Catalysts and its preparation method that a kind of cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton.
Background technology
Gamma-butyrolacton is that a kind of boiling point is high, dissolubility is strong, the solvent of electrical property and good stability, is widely used in fields such as petrochemical industry, medicine, dyestuff, agricultural chemicals and fine chemistry industry.In recent years, the gamma-butyrolacton large usage quantity in the pyrrolidinone compounds chemical products are produced especially.
The process route of synthetic gamma butyrolactone mainly contains 1,4-butanediol dehydrogenation method and maleic anhydride hydrogenation method at present.Along with the industrialization that n butane oxidation prepares the cis-butenedioic anhydride technology, the process route cost of maleic anhydride hydrogenation synthetic gamma butyrolactone reduces greatly, and the process route that makes the cis-anhydride normal pressure gas phase hydrogenation prepare gamma-butyrolacton causes that people pay close attention to widely and study.
The catalyst that the cis-anhydride normal pressure gas phase hydrogenation prepares the gamma-butyrolacton employing roughly can be divided into following three types: noble metal catalyst, Ni series catalysts and Cu series catalysts, wherein the Cu series catalysts is the focus of studying both at home and abroad.
U.S. Pat 5122495A discloses the catalyst that a kind of cis-butenedioic anhydride gas phase hydrogenation prepares gamma-butyrolacton.The constituent content of this catalyst (wt%) is respectively CuO 30%~65%, and ZnO 18%~50%, Al 2O 38%~22%.The 400g catalyst of in reactor, packing into, hydrogen acid anhydride mol ratio is under 230~280 conditions, and the cis-butenedioic anhydride conversion ratio is about 100%, and the selectivity of gamma-butyrolacton is about 85%~95%.But catalyst uses for the first time after 100~500 hours and need under 400 ℃~450 ℃ high temperature, regeneration just can continue to use, thereby has increased the difficulty of commercial Application.
U.S. Pat 3065243A discloses a kind of in the presence of the Cu-Cr catalyst; With cis-butenedioic anhydride, succinyl oxide, corresponding acid or ester is the method for raw material gas phase hydrogenation system gamma-butyrolacton; But cis-butenedioic anhydride conversion ratio and gamma-butyrolacton selectivity are quite low, and the Cu-Cr catalyst contains poisonous component Cr element etc.
Summary of the invention
Technical problem to be solved by this invention is to be to above-mentioned deficiency of the prior art; Provide a kind of and do not contained heavy metal harmful elements such as noble metal and Ba, Cr, and activity, selectivity, all good cis-anhydride normal pressure gas phase hydrogenation of life-span prepare the catalyst of gamma-butyrolacton.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is: a kind of cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton, it is characterized in that, said catalyst is made up of following component in percentage by weight: CuO 6%~75%; ZnO 10%~52%, SiO 215%~42%.
Above-mentioned a kind of cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton, it is characterized in that, is made up of following component in percentage by weight: CuO 31%~50%, and ZnO 25%~45%, SiO 220%~30%.
Above-mentioned a kind of cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton, it is characterized in that, is made up of following component in percentage by weight: CuO 40%, and ZnO 35%, SiO 225%.
The present invention also provides the simple cis-anhydride normal pressure gas phase hydrogenation of a kind of technology to prepare the Preparation of catalysts method of gamma-butyrolacton, it is characterized in that this method comprises the steps:
Step 1, Ludox is added deionized water for stirring obtain silicon sol solution after evenly; The mass ratio of said Ludox and deionized water is 1:10~521;
Step 2, copper nitrate and zinc nitrate added the nitrate solution that is mixed with 1mol/L in the deionized water; Sodium carbonate added to be mixed with mass concentration in the deionized water be 20% sodium carbonate liquor; The mass ratio of said copper nitrate and zinc nitrate is 1:0.15~12;
Step 3, adopt two modes that drip to join simultaneously described in the step 1 in the silicon sol solution nitrate solution described in the step 2 and sodium carbonate liquor; Mix; The pH value of control solution system is 7, after deposition finishes with sediment ageing 25min~35min; Said two time that drips is 20min~40min; Said temperature of precipitation is 60 ℃~70 ℃;
Step 4, with the sediment after the ageing in the step 3 through the distilled water washing and filtering; Behind the no nitrate anion of check filtrating; With the dry 8h~12h under 80 ℃~100 ℃ of the sediment behind the washing and filtering, afterwards again at 300 ℃~500 ℃ following roasting 3h~5h, then with the sediment compression molding after the roasting; Crush and screen, get the catalyst that the cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton.
Above-mentioned a kind of cis-anhydride normal pressure gas phase hydrogenation prepares the Preparation of catalysts method of gamma-butyrolacton, it is characterized in that, Ludox described in the step 1 is a JN-30 type Ludox, and said mixing time is 0.5h;
Above-mentioned a kind of cis-anhydride normal pressure gas phase hydrogenation prepares the Preparation of catalysts method of gamma-butyrolacton, it is characterized in that, the granularity of the said catalyst of step 4 kind is 40 orders~80 orders.
The present invention also provides a kind of cis-anhydride normal pressure gas phase hydrogenation to prepare the Application of Catalyst of gamma-butyrolacton; It is characterized in that; The condition that the cis-anhydride normal pressure gas phase hydrogenation prepares the catalytic reaction of gamma-butyrolacton is: reaction temperature is 250~300 ℃, and reaction pressure is 0.1MPa, and cis-butenedioic anhydride liquid air speed is 0.01h -1~0.5h -1, the mol ratio of hydrogen and cis-butenedioic anhydride is 15~100.
The present invention compared with prior art has the following advantages:
1, the catalyst of the present invention's preparation need not add noble metal and harmful heavy metal auxiliary agent, is green catalyst.
2, the catalyst of the present invention preparation have active high, selectivity is high, the life-span is long and regenerate advantage such as easy.
3, preparation method's technology of the present invention is simple, is fit to suitability for industrialized production.
Through embodiment, technical scheme of the present invention is done further detailed description below.
The specific embodiment
Embodiment 1
Present embodiment cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton, is made up of following component in percentage by weight: CuO 6%, and ZnO 52%, SiO 242%.
The Preparation of catalysts method that present embodiment cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton may further comprise the steps:
Step 1, JN-30 type Ludox is added deionized water for stirring obtain silicon sol solution after evenly; The mass ratio of said JN-30 type Ludox and deionized water is 1:10; Said mixing time is 0.5h;
Step 2, copper nitrate and zinc nitrate added the nitrate solution that is mixed with 1mol/L in the deionized water; Sodium carbonate added to be mixed with mass concentration in the deionized water be 20% sodium carbonate liquor; The mass ratio of said copper nitrate and zinc nitrate is 1:12;
Step 3, adopt two modes that drip to join simultaneously described in the step 1 in the silicon sol solution nitrate solution described in the step 2 and sodium carbonate liquor, mix, the pH value of control solution system is 7, after deposition finishes with sediment ageing 25min; Said pair of dropping time is 30min; Said precipitation temperature is 70 ℃;
Step 4, with the sediment after the ageing in the step 3 through the distilled water washing and filtering; Behind the no nitrate anion of check filtrating; With the dry 8h under 100 ℃ of the sediment behind the washing and filtering, afterwards again at 300 ℃ of following roasting 5h, then with the sediment compression molding after the roasting; Crush and screen, get the catalyst that the cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton; The granularity of said catalyst is 40 orders~80 orders.
Getting the catalyst 30g that makes in the present embodiment and pack in the fixed bed reactors, is 250 ℃ in reaction temperature, and reaction pressure is 0.1MPa, and cis-butenedioic anhydride liquid air speed is 0.01h -1, hydrogen and cis-butenedioic anhydride mol ratio are that the cis-butenedioic anhydride conversion ratio is near 100% under 100 the condition, the gamma-butyrolacton selectivity is 98.6%.
Embodiment 2
Present embodiment cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton and is made up of following component in percentage by weight: CuO 75%, and ZnO 10%, SiO 215%.
The present embodiment preparation method is with embodiment 1.
Getting the catalyst 30g that makes in the present embodiment and pack in the fixed bed reactors, is 300 ℃ in reaction temperature, and reaction pressure is 0.1MPa, and cis-butenedioic anhydride liquid air speed is 0.5h -1, hydrogen and cis-butenedioic anhydride mol ratio are that the cis-butenedioic anhydride conversion ratio is near 100% under 15 the condition, the gamma-butyrolacton selectivity is 97.8%.
Embodiment 3
Present embodiment cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton and is made up of following component in percentage by weight: CuO 31%, and ZnO 45%, SiO 224%.
The Preparation of catalysts method that present embodiment cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton may further comprise the steps:
Step 1, JN-30 type Ludox is added deionized water for stirring obtain silicon sol solution after evenly; The mass ratio of said JN-30 type Ludox and deionized water is 1:521; Said mixing time is 0.5h;
Step 2, copper nitrate and zinc nitrate added the nitrate solution that is mixed with 1mol/L in the deionized water; Sodium carbonate added to be mixed with mass concentration in the deionized water be 20% sodium carbonate liquor; The mass ratio of said copper nitrate and zinc nitrate is 1:0.15;
Step 3, adopt two modes that drip to join simultaneously described in the step 1 in the silicon sol solution nitrate solution described in the step 2 and sodium carbonate liquor, mix, the pH value of control solution system is 7, after deposition finishes with sediment ageing 35min; Said pair of dropping time is 40min; Said precipitation temperature is 60 ℃;
Step 4, with the sediment after the ageing in the step 3 through the distilled water washing and filtering; Behind the no nitrate anion of check filtrating; With the dry 12h under 80 ℃ of the sediment behind the washing and filtering, afterwards again at 500 ℃ of following roasting 3h, then with the sediment compression molding after the roasting; Crush and screen, get the catalyst that the cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton; The granularity of said catalyst is 40 orders~80 orders.
Getting the catalyst 30g that makes in the present embodiment and pack in the fixed bed reactors, is 275 ℃ in reaction temperature, and reaction pressure is 0.1MPa, and cis-butenedioic anhydride liquid air speed is 0.1h -1, hydrogen and cis-butenedioic anhydride mol ratio are that the cis-butenedioic anhydride conversion ratio is near 100% under 50 the condition, the gamma-butyrolacton selectivity is 92.5%.
Embodiment 4
Present embodiment cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton and is made up of following component in percentage by weight: CuO 50%, and ZnO 20%, SiO 230%.
The present embodiment preparation method is with embodiment 3.
Getting the catalyst 30g that makes in the present embodiment and pack in the fixed bed reactors, is 270 ℃ in reaction temperature, and reaction pressure is 0.1MPa, and cis-butenedioic anhydride liquid air speed is 0.12h -1, hydrogen and cis-butenedioic anhydride mol ratio are that the cis-butenedioic anhydride conversion ratio is near 100% under 50 the condition, the gamma-butyrolacton selectivity is 93.7%.
Embodiment 5
Present embodiment cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton and is made up of following component in percentage by weight: CuO 55%, and ZnO 25%, SiO 220%.
The Preparation of catalysts method that present embodiment cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton may further comprise the steps:
Step 1, JN-30 type Ludox is added deionized water for stirring obtain silicon sol solution after evenly; The mass ratio of said JN-30 type Ludox and deionized water is 1:200; Said mixing time is 0.5h;
Step 2, copper nitrate and zinc nitrate added the nitrate solution that is mixed with 1mol/L in the deionized water; Sodium carbonate added to be mixed with mass concentration in the deionized water be 20% sodium carbonate liquor; The mass ratio of said copper nitrate and zinc nitrate is 1:5;
Step 3, adopt two modes that drip to join simultaneously described in the step 1 in the silicon sol solution nitrate solution described in the step 2 and sodium carbonate liquor, mix, the pH value of control solution system is 7, after deposition finishes with sediment ageing 30min; Said pair of dropping time is 20min; Said precipitation temperature is 65 ℃;
Step 4, with the sediment after the ageing in the step 3 through the distilled water washing and filtering; Behind the no nitrate anion of check filtrating; With the dry 10h under 90 ℃ of the sediment behind the washing and filtering, afterwards again at 400 ℃ of following roasting 4h, then with the sediment compression molding after the roasting; Crush and screen, get the catalyst that the cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton; The granularity of said catalyst is 40 orders~80 orders.
Getting the catalyst 30g that makes in the present embodiment and pack in the fixed bed reactors, is 275 ℃ in reaction temperature, and reaction pressure is 0.1MPa, and cis-butenedioic anhydride liquid air speed is 0.15h -1, hydrogen and cis-butenedioic anhydride mol ratio are that the cis-butenedioic anhydride conversion ratio is near 100% under 50 the condition, the gamma-butyrolacton selectivity is 95.6%.
Embodiment 6
Present embodiment cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton and is made up of following component in percentage by weight: CuO 40%, and ZnO 35%, SiO 225%.
The present embodiment preparation method is with embodiment 5.
Getting the catalyst 30g that makes in the present embodiment and pack in the fixed bed reactors, is 270 ℃ in reaction temperature, and reaction pressure is 0.1MPa, and cis-butenedioic anhydride liquid air speed is 0. 2h -1, hydrogen and cis-butenedioic anhydride mol ratio are that the cis-butenedioic anhydride conversion ratio is near 100% under 50 the condition, the gamma-butyrolacton selectivity is 97.5%.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any restriction, every technical spirit changes any simple modification, change and the equivalence that above embodiment did according to the present invention, all still belongs in the protection domain of technical scheme of the present invention.

Claims (7)

1. a cis-anhydride normal pressure gas phase hydrogenation prepares the catalyst of gamma-butyrolacton, it is characterized in that be made up of following component in percentage by weight: CuO 6%~75%, and ZnO 10%~52%, SiO 215%~42%.
2. a kind of cis-anhydride normal pressure gas phase hydrogenation according to claim 1 prepares the catalyst of gamma-butyrolacton, it is characterized in that, is made up of following component in percentage by weight: CuO 31%~50%, and ZnO 25%~45%, SiO 220%~30%.
3. a kind of cis-anhydride normal pressure gas phase hydrogenation according to claim 1 prepares the catalyst of gamma-butyrolacton, it is characterized in that, is made up of following component in percentage by weight: CuO 40%, and ZnO 35%, SiO 225%.
4. method for preparing like claim 1,2 or 3 said catalyst is characterized in that this method may further comprise the steps:
Step 1, Ludox is added deionized water for stirring obtain silicon sol solution after evenly; The mass ratio of said Ludox and deionized water is 1:10~521;
Step 2, copper nitrate and zinc nitrate added the nitrate solution that is mixed with 1mol/L in the deionized water; Sodium carbonate added to be mixed with mass concentration in the deionized water be 20% sodium carbonate liquor; The mass ratio of said copper nitrate and zinc nitrate is 1:0.15~12;
Step 3, adopt two modes that drip to join simultaneously described in the step 1 in the silicon sol solution nitrate solution described in the step 2 and sodium carbonate liquor; Mix; The pH value of control solution system is 7, after deposition finishes with sediment ageing 25min~35min; Said two time that drips is 20min~40min; Said temperature of precipitation is 60 ℃~70 ℃;
Step 4, with the sediment after the ageing in the step 3 through the distilled water washing and filtering; Behind the no nitrate anion of check filtrating; With the dry 8h~12h under 80 ℃~100 ℃ of the sediment behind the washing and filtering, afterwards again at 300 ℃~500 ℃ following roasting 3h~5h, then with the sediment compression molding after the roasting; Crush and screen, get the catalyst that the cis-anhydride normal pressure gas phase hydrogenation prepares gamma-butyrolacton.
5. method according to claim 4 is characterized in that, Ludox described in the step 1 is a JN-30 type Ludox, and the time of said stirring is 0.5h.
6. method according to claim 4 is characterized in that, the granularity of catalyst described in the step 4 is 40 orders~80 orders.
7. one kind like claim 1,2 or 3 said Application of Catalyst, and it is characterized in that the condition that the cis-anhydride normal pressure gas phase hydrogenation prepares the catalytic reaction of gamma-butyrolacton is: reaction temperature is 250~300 ℃, and reaction pressure is 0.1MPa, and cis-butenedioic anhydride liquid air speed is 0.01h -1~0.5h -1, hydrogen and cis-butenedioic anhydride mol ratio are 15~100.
CN201210222118XA 2012-06-29 2012-06-29 Catalyst for constant-pressure gas-phase hydrogenation preparation of gamma-butyrolactone by maleic anhydride and preparation method thereof Pending CN102716750A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1108253A (en) * 1993-08-10 1995-09-13 阿克佐诺贝尔公司 Process for producing gamma-butyrolactone
JP2002371075A (en) * 2001-06-14 2002-12-26 Chisso Corp Method for producing lactone
DE10133054A1 (en) * 2001-07-07 2003-01-16 Basf Ag Catalyst for the gas phase hydrogenation of dicarboxylic acids comprises copper oxide, palladium and/or a palladium compound and an oxide support
CN1479650A (en) * 2000-12-11 2004-03-03 巴斯福股份公司 Catalyst coating for hydrogenation of maleic anhyride and related compounds to give gamma-butyrolactone, tetrahyarofuran and derivatives thereof
CN1646514A (en) * 2002-04-30 2005-07-27 巴斯福股份公司 Method for producing gamma-butyrolactone
CN101307042A (en) * 2007-05-18 2008-11-19 中国石油化工股份有限公司 Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone
CN101704805A (en) * 2009-10-30 2010-05-12 江苏工业学院 Method for preparing gamma-butyrolactone through catalytic hydrogenation of dimethyl succinate
CN101947455A (en) * 2010-09-10 2011-01-19 南京化工职业技术学院 Gamma-butyrolactone catalyst prepared by hydrogenation of maleic anhydride and dehydrogenation coupling of 1,4-butanediol, preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1108253A (en) * 1993-08-10 1995-09-13 阿克佐诺贝尔公司 Process for producing gamma-butyrolactone
CN1479650A (en) * 2000-12-11 2004-03-03 巴斯福股份公司 Catalyst coating for hydrogenation of maleic anhyride and related compounds to give gamma-butyrolactone, tetrahyarofuran and derivatives thereof
JP2002371075A (en) * 2001-06-14 2002-12-26 Chisso Corp Method for producing lactone
DE10133054A1 (en) * 2001-07-07 2003-01-16 Basf Ag Catalyst for the gas phase hydrogenation of dicarboxylic acids comprises copper oxide, palladium and/or a palladium compound and an oxide support
CN1646514A (en) * 2002-04-30 2005-07-27 巴斯福股份公司 Method for producing gamma-butyrolactone
CN101307042A (en) * 2007-05-18 2008-11-19 中国石油化工股份有限公司 Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone
CN101704805A (en) * 2009-10-30 2010-05-12 江苏工业学院 Method for preparing gamma-butyrolactone through catalytic hydrogenation of dimethyl succinate
CN101947455A (en) * 2010-09-10 2011-01-19 南京化工职业技术学院 Gamma-butyrolactone catalyst prepared by hydrogenation of maleic anhydride and dehydrogenation coupling of 1,4-butanediol, preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李东光: "《实用燃料添加剂配方手册》", 29 February 2012, 化学工业出版社 *

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