CN1026321C - Ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride - Google Patents
Ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride Download PDFInfo
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- CN1026321C CN1026321C CN 91107478 CN91107478A CN1026321C CN 1026321 C CN1026321 C CN 1026321C CN 91107478 CN91107478 CN 91107478 CN 91107478 A CN91107478 A CN 91107478A CN 1026321 C CN1026321 C CN 1026321C
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- cis
- anhydride
- butyrolactone
- maleic anhydride
- gamma
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Abstract
The present invention relates to a method for synthesizing gamma-butyrolactone by the ordinary-pressure gas-phase hydrogenation of maleic anhydride. Maleic anhydride, or succinic anhydride or the mixture of the maleic anhydride or succinic anhydride is used as raw materials in gas-phase sampling. Catalytic hydrogenation is carried out on a catalyst at normal pressure, wherein the catalyst is the mixture of Cu, ZnO, Al2O3, and at least one element of the four elements of Ni, Ru, Ce and Zr. The reaction temperature is from 200 to 350 DEG C., and the molar ratio of hydrogen to maleic anhydride is from 5: 1 to 200: 1. According to the present invention, the single pass conversion rate of maleic anhydride approaches to 100%, and the selectivity of gamma-butyrolactone and tetrahydrofuran can reach 95%. The present invention has the advantages of simple process flow, convenient operation, little investment and easy popularization and application.
Description
The invention belongs to chemical technology field, particularly a kind of method of gas phase hydrogenation synthetic gamma butyrolactone.
Gamma-butyrolactone (γ-Butyrolactone) is a kind of stable compound, its fusing point-44 ℃, and 204 ℃ of boiling points, purposes is very extensive.At first, it is an excellent solvent, energy dissolved epoxy, polyacrylonitrile, polyvinyl chloride and multipolymer, Mierocrystalline cellulose superpolymer and other superpolymer.It can also be as the swelling agent of cellulose acetate and the electrolytic solution of electrical condenser.As chemical intermediate, it can make N-Methyl pyrrolidone, alpha-pyrrolidone, Polyvinylpyrolidone (PVP), ethanoyl gamma-butyrolactone and α-Tetralone an intermediate of Sertraline etc.With cis-butenedioic anhydride (Maleic anhydride) is that raw material system gamma-butyrolactone can coproduced tetrahydro furan (Tetrahydrofuran), tetrahydrofuran (THF) is a kind of lower boiling (66 ℃) solvent of excellent property, can dissolve nearly all superpolymer except that polyethylene, polypropylene, fluorine resin.
The patent of relevant maleic anhydride hydrogenation system gamma-butyrolactone is a lot of in the world at present, in the former patent, high-pressure liquid phase method has accounted for consequence, an example of high-pressure liquid phase method is United States Patent (USP) U.S.Pat.No 2,772,291, in the presence of the Ni-Cr-Co catalyzer, cis-butenedioic anhydride under high pressure generates gamma-butyrolactone, tetrahydrofuran (THF), 1, the mixture of multiple materials such as 4-butyleneglycol.The liquid phase reaction patent of making raw material system gamma-butyrolactone with cis-butenedioic anhydride has afterwards been improved catalyzer, as United States Patent (USP) U.S.Pat..No 3,312,718, its succinyl oxide almost can absolutely be converted into gamma-butyrolactone, is hydrogenation catalyst with Ni, and tungstosilicic acid is a promotor.In addition, U.S.Pat.No 3,113, and 139 have introduced with Pa and make catalyzer, obtain gamma-butyrolactone from succinyl oxide in the presence of liquid phase and certain solvent, but catalyst life lacks, and productive rate is low.
At present industrialized is that raw material system gamma-butyrolactone all is a liquid phase method with cis-butenedioic anhydride, succinyl oxide.Because catalyzed reaction is carried out under condition of high voltage, so complex process, invests also bigger.As the gas phase hydrogenation method that replaces it, can under low pressure carry out, U.S.Pat.No 3,065, and 243 have introduced low-pressure vapor phase system gamma-butyrolactone in the presence of chromite.The work afterwards of this field comprises various catalyzer, as different combinations such as Cr, Cu, Zn, or utilizes some traditional hydrogenation catalysts to comprise Rn, Rh etc., because activity of such catalysts is poor under condition of normal pressure, therefore the application of industrial value is not arranged so far.
The object of the present invention is to provide a kind of cis-butenedioic anhydride per pass conversion height, product selectivity is good, operating procedure is simple, thereby can realize the method for the ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride of suitability for industrialized production.
According to the present invention, the raw material cis-butenedioic anhydride need not be dissolved in the gamma-butyrolactone, direct gas phase sample introduction, under condition of normal pressure on catalyzer shortening.The catalyzer that uses by Cu, ZnO, Al
2O
3With Ni, Ru, Ce, at least a composition in four kinds of elements of Zr, during reaction, temperature of reaction changes between 200 ℃ and 350 ℃.Be preferably between 250-300 ℃.The hydrogen stoichiometry that enters reactor is excessive, and the ratio of general hydrogen mole number and cis-butenedioic anhydride mole number can be at 5: 1 to 200: 1, and the cis-butenedioic anhydride air speed is at 10-70hr
-1Between, unstripped gas and catalytic bed are preferably in variation in the smaller scope duration of contact, and as between 2 seconds to 10 seconds, because duration of contact, long by product can increase, as propyl alcohol, butanols, and it is insufficient to cross short reaction duration of contact, and transformation efficiency is low.Vapor-phase reactant is by behind the catalyzer, the per pass conversion of cis-butenedioic anhydride or succinyl oxide or their mixture is near 100%, the selectivity of gamma-butyrolactone and tetrahydrofuran (THF) reaches 95%, gas-phase product can obtain containing the thick product of gamma-butyrolactone and tetrahydrofuran (THF) after water-cooled, salt are cold, thick product can obtain gamma-butyrolactone and tetrahydrofuran (THF) through rectifying again.
The catalyzer that the present invention uses is a kind of uniform mixture, is 100% in the gross weight of catalyzer, and the content range of each component is: Cu0.2-50%.Generally between 1-40%.ZnO：10-60%。Ni, Ru, Ce, one or more total amount of Zr: between 0.01-10%.Generally at 0.1-5%.Al
2O
3: between 1-40%.Catalyzer needs reduction activation in nitrogen atmosphere before use.Ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride, it requires catalyzer that good transformation efficiency and selectivity are arranged under normal pressure, also good stability will be arranged, and our catalyzer has reached this requirement basically.
Because the catalyzed reaction among the present invention is carried out under condition of normal pressure, so technical process is simple, and is easy to operate, less investment, instant effect is easy to apply.The cis-butenedioic anhydride per pass conversion is near 100%, and the selectivity of product is good, and thick product is easily separated, the product purity height.It is raw material that the present invention makes with the cis-butenedioic anhydride, and the normal pressure gas phase hydrogenation method of producing gamma-butyrolactone has realized the target of suitability for industrialized production.
Example 1: be reflected on the atmospheric fixed bed reactor and carry out, reaction tubes is by internal diameter 16mm, the stainless steel tube of long 75mm is made, temperature of reaction is measured by nickel chromium-nickel silicon thermocouple, by temperature controller (error ± 1 ℃) temperature control, with the 20-40 purpose catalyzer reactor flat-temperature zone of packing into, reduction after 8 hours under nitrogen atmosphere, cis-anhydride normal pressure gas phase sample introduction.Catalyzer consists of Cu25%(weight), ZnO30%, Al
2O
340%, Ni4%, Ce+Zr1%.At cis-butenedioic anhydride air speed 40hr
-1, hydrogen and cis-butenedioic anhydride mol ratio are 40: 1, under 290 ℃ of conditions of temperature of reaction, and cis-butenedioic anhydride transformation efficiency 99.6%, gamma-butyrolactone selectivity 84.5%, tetrahydrofuran (THF) selectivity 12.1%.
Example 2: with the reaction unit of example 1, catalyzer consists of Cu40%, ZnO30%, Al
2O
329.7%, Ce+Zr0.3%.At cis-butenedioic anhydride air speed 45hr
-1, hydrogen and cis-butenedioic anhydride mol ratio 40: 1, under 280 ℃ of conditions of temperature of reaction, cis-butenedioic anhydride transformation efficiency 99.5%, gamma-butyrolactone selectivity 85,1%, tetrahydrofuran (THF) selectivity 11.8%.
Example 3: with the reaction unit of example 1, catalyzer consists of Cu40%, ZnO40%, Al
2O
319.5%, Ru0.5%.At cis-butenedioic anhydride air speed 50hr
-1, hydrogen and cis-butenedioic anhydride mol ratio 50: 1, under 270 ℃ of conditions of temperature of reaction, cis-butenedioic anhydride transformation efficiency 99.9%, gamma-butyrolactone selectivity 82.9%, tetrahydrofuran (THF) selectivity 13.6%.
Claims (1)
- A kind of method of maleic anhydride hydrogenation synthetic gamma butyrolactone, cis-butenedioic anhydride be direct gas phase sample introduction under condition of normal pressure, and shortening on catalyzer is characterized in that catalyzer is by Cu, ZnO, Al 2O 3And Ni, Ru, Ce, one or more uniform mixing in four kinds of elements of Zr form, and the content of each component is in weight percent, Cu: 1-40%; ZnO: 10-60%; Ni, Ru, Ce, Zr gross weight: 0.1-5%; Al 2O 3: 1-40%, temperature of reaction is 250-300 ℃, the hydrogen mole number that enters reactor is 5 with the ratio of cis-butenedioic anhydride mole number: 1-50: 1, the cis-butenedioic anhydride air speed is 10-50hr -1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107478 CN1026321C (en) | 1991-08-28 | 1991-08-28 | Ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107478 CN1026321C (en) | 1991-08-28 | 1991-08-28 | Ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1058400A CN1058400A (en) | 1992-02-05 |
| CN1026321C true CN1026321C (en) | 1994-10-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91107478 Expired - Fee Related CN1026321C (en) | 1991-08-28 | 1991-08-28 | Ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1273320B (en) * | 1994-02-22 | 1997-07-08 | Alusuisse Italia Spa | PROCEDURE FOR THE PRODUCTION OF RANGE-BUTYROLACTONE |
| CN1044338C (en) * | 1994-06-23 | 1999-07-28 | 化学工业部北京化工研究院 | Catalyst for preparing cyanopyridine by ammoxidation of alkyl-pyridine and its application |
| US5637735A (en) * | 1994-08-10 | 1997-06-10 | China Petrochemical Corporation | Process for the preparation of gamma-butyrolactone |
| CN1094789C (en) * | 2000-08-14 | 2002-11-27 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone by dehydrogenation of 1,4-butanediol and its application |
| CN1094790C (en) * | 2000-12-26 | 2002-11-27 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone and its preparing method |
| CN112742394A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Method for preparing gamma-butyrolactone by maleic anhydride liquid-phase hydrogenation |
| CN113332999B (en) * | 2021-06-03 | 2022-09-13 | 上海贯新科技有限公司 | Novel catalyst for preparing succinic anhydride and 1, 4-butanediol by maleic anhydride hydrogenation |
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1991
- 1991-08-28 CN CN 91107478 patent/CN1026321C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| Publication number | Publication date |
|---|---|
| CN1058400A (en) | 1992-02-05 |
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