CN103539765A - Method for preparing gamma-butyrolactone through maleic anhydride hydrogenation and ethanol dehydrogenation coupling - Google Patents
Method for preparing gamma-butyrolactone through maleic anhydride hydrogenation and ethanol dehydrogenation coupling Download PDFInfo
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- CN103539765A CN103539765A CN201310477249.7A CN201310477249A CN103539765A CN 103539765 A CN103539765 A CN 103539765A CN 201310477249 A CN201310477249 A CN 201310477249A CN 103539765 A CN103539765 A CN 103539765A
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- butyrolactone
- maleic anhydride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention relates to a method for preparing gamma-butyrolactone through maleic anhydride hydrogenation and ethanol dehydrogenation coupling, and belongs to the field of organic catalysis. According to the method, the two substances ethanol and maleic anhydride are mixed, and gamma-butyrolactone is prepared through maleic anhydride hydrogenation and ethanol dehydrogenation coupling reactions under conditions of normal vapor pressure and no additional hydrogen, and with a load-type copper-series catalyst. With maleic anhydride hydrogenation of the process, high gamma-butyrolactone yield can be obtained. Ethanol is subjected to a dehydrogenation reaction under the effect of the catalyst, such that acetaldehyde and ethyl acetate with high added values are produced. The method has the advantages of low reaction energy consumption, low production cost, high selectivity, and high yield.
Description
Technical field
The present invention relates to a kind of method of preparing gamma-butyrolactone, belong to organic catalysis field.
Background technology
Gamma-butyrolactone is a kind of pentacyclic heterogeneous ring compound that contains, and can dissolve various organic and mineral compound, is commonly used for solvent, extraction agent and absorption agent.Can there is the chemical reaction of a series of open loop and not open loop in good reactivity worth, can be used for the raw materials for production of Ciprofloxacin, piracetam, VITMAIN B1, Polyvinylpyrolidone (PVP) etc.
The conventional production methods of gamma-butyrolactone remains the Reppe method that adopts.This method is carried out in two steps: acetylene and formaldehyde reaction first generate BDO, and then BDO makes gamma-butyrolactone through catalytic dehydrogenation.But because Reppe method exists severe reaction conditions, need polystep reaction, using explosive acetylene and carcinogens formaldehyde is the shortcomings such as raw material.In recent years, along with the raising of maleic anhydride production ability and the decline of price, the production of gamma-butyrolactone turns to maleic anhydride hydrogenation method gradually.By maleic anhydride hydrogenation, prepare gamma-butyrolactone and mainly contain two kinds of methods: the one, the exploitation of cis-butenedioic anhydride gas phase hydrogenation Fa，You U.S. Standard Oil company.This method adopts Cu/Zn/Zr catalyzer, at 260-290 ℃, under 0.3-0.8 MPa condition, carries out cis-butenedioic anhydride gas-phase reaction.Feed stock conversion reaches 91%, and product gamma-butyrolactone selectivity reaches 89%.But the Zr component in catalyzer easily produces environmental pollution.The 2nd, cis-butenedioic anhydride By Liquid-phase Hydrogenation Process, this method be take gamma-butyrolactone as solvent, mixes through preheating, at 6～12 MPa, at 160～280 ℃, by the reactor hydrogenation of catalyzer is housed with recycle hydrogen.This liquid phase cracking process is favourable to strong exothermal reaction, but needs solvent, under mesohigh condition, carries out, and process is complicated, invests high.
We select carried copper catalyst series to carry out maleic anhydride hydrogenation and alcohol dehydrogenase coupling reaction, and by adjusting reaction parameter, maleic anhydride hydrogenation reaction can obtain higher gamma-butyrolactone yield.Under catalyst action, there is acetaldehyde and the ethyl acetate that dehydrogenation reaction generates high added value in ethanol.Reaction is carried out under the condition of ordinary-pressure gas-phase, the additional hydrogen of nothing, required little energy, and production cost is low, has highly selective and high yield.
Summary of the invention
The object of the invention is to propose a kind of method that new gas phase hydrogenation is prepared gamma-butyrolactone, adopt carried copper catalyst series catalysis maleic anhydride hydrogenation and alcohol dehydrogenase coupling reaction to prepare gamma-butyrolactone.
The said maleic anhydride hydrogenation of the present invention and alcohol dehydrogenase coupling reaction are prepared the method for gamma-butyrolactone, and reaction is in fixed-bed reactor, and ordinary-pressure gas-phase, carries out under the condition without additional hydrogen.
Used catalyst of the present invention can represent with following general formula: CuO/MO
x
MO wherein
xbe respectively Al
2o
3, ZrO
2, ZnO.
Maleic anhydride hydrogenation and alcohol dehydrogenase preparation of coupling gamma-butyrolactone, comprise the following steps:
(1), according to the composition requirement of catalyzer, Cu salt is made into the certain density aqueous solution (mass concentration: 10%～45%), add carrier to flood and make the CuO/ Al that CuO content is respectively 5%-20% (mass percent)
2o
3catalyzer, CuO content is the CuO/ZrO of 10% (mass percent)
2catalyzer and CuO content are the CuO/ ZnO catalyst of 10% (mass percent).Sample dried overnight at 120 ℃ after dipping, 400～500 ℃ of roasting 3～4 h, by sample compressing tablet, catalyst Precursors is made in screening.
(2) catalyzer is first used H
2-N
2(10:90, V/V, 250 ml/min) gas mixture carries out reduction activation, under 0.1 MPa pressure, and with 1.5 ℃/min temperature programming to 200 ℃, then with 1.0 ℃/min temperature programming to 280 ℃, while H
2volume fraction slowly brings up to 30%, at 280 ℃ of constant temperature, reduces 3 h.
(3) cis-butenedioic anhydride is dissolved in to ethanol and is mixed with cis-butenedioic anhydride/alcohol mixeding liquid (10:90, W/W), after vaporization, enter and in the fixed-bed reactor that are mounted with reducing catalyst, carry out gas phase coupling reaction.In this reaction process, maleic anhydride hydrogenation reaction generates gamma-butyrolactone, and Dehydrogenating reaction of alcohol mainly generates acetaldehyde and ethyl acetate.
Wherein the Cu salt described in step (1) is Cu (NO
3)
23H
2o.
Wherein the carrier described in step (1) is: Al
2o
3, ZrO
2or ZnO.
Wherein the middle cis-butenedioic anhydride/alcohol mixeding liquid of step (3) is transported in the vaporizing chamber of above-mentioned fixed-bed reactor with the speed of 5 ml/min, passes into N
2flow rate is 80 ml/min, after 350 ℃ of vaporizations, enters reactor; Temperature of reaction 240-300 ℃.
One of distinguishing feature of the present invention is that the activity of catalyzer is higher.For example, cis-butenedioic anhydride is dissolved in to ethanol and makes cis-butenedioic anhydride/alcohol mixeding liquid (10:90, W/W), use catalyzer of the present invention, liquid phase air speed 0.2 h
-1, at normal pressure, under 270～300 ℃ of reaction conditionss, the transformation efficiency of cis-butenedioic anhydride approaches 100%, and the yield of gamma-butyrolactone is higher than 95%.
Another distinguishing feature of the present invention is that acetaldehyde and the ethyl acetate that dehydrogenation reaction generates high added value occurs ethanol under catalyst action.In reaction process, have hydrogen compensation and heat compensation, make reaction be easy to control, institute's energy requirement reduces, and production cost reduces.
embodiment:
Below in conjunction with concrete embodiment, the present invention will be further described:
embodiment 1
CuO/Al
2o
3(5:95, W/W) catalyzer is prepared by equi-volume process: first measure carrier A l
2o
3dipping volume.According to the composition requirement of catalyzer, take the raw material Cu (NO of respective amount
3)
23H
2o and Al
2o
3incipient impregnation.Sample is dry 12 h at 120 ℃, and 400 ℃ of roasting 3 h, make catalyst Precursors.Catalyst Precursors is at 12 MPa lower sheetings, and the particle that is sieved into 20～40 order sizes is standby.
Adopt fixed-bed reactor, loaded catalyst 5 ml, raw material is cis-butenedioic anhydride/ethanolic soln (10:90, W/W), enters stainless steel tube shape reactor (long 20 cm, internal diameter 0.8cm) reaction after gasification.Before active testing, catalyzer is first used H
2-N
2(10:90, V/V, 250 ml/min) gas mixture carries out reduction activation, under 0.1 MPa pressure, and with 1.5 ℃/min temperature programming to 200 ℃, with 1.0 ℃/min temperature programming to 280 ℃, H simultaneously
2volume fraction slowly brings up to 30%, at 280 ℃ of constant temperature, reduces 3 h.The method can be reduced to zerovalent copper by the cupric in catalyzer more thoroughly.
Under normal pressure, by cis-butenedioic anhydride/alcohol mixeding liquid (10:90, W/W), the speed with 5 ml/min is transported in the vaporizing chamber of above-mentioned fixed-bed reactor, after 350 ℃ of vaporizations, enters reactor.Keep N
2flow rate is 80 ml/min, temperature of reaction 240,260, and 280,300 ℃, serial sampling 1 h at given temperature, product is collected in water-bath condensation.Gas chromatograph for product (marker method) is analyzed.Test result is in Table 1.
embodiment 2
CuO/Al
2o
3(10:90, W/W) catalyzer is prepared by equi-volume process: first measure carrier A l
2o
3dipping volume.According to the composition requirement of catalyzer, take the raw material Cu (NO of respective amount
3)
23H
2o and Al
2o
3incipient impregnation.Sample is dry 12 h at 120 ℃, and 500 ℃ of roasting 4 h, make catalyst Precursors.Catalyst Precursors is at 12 MPa lower sheetings, and the particle that is sieved into 20～40 order sizes is standby.
Adopt the method identical with example 1 to carry out reduction activation and the active testing of catalyzer.Product is collected in water-bath condensation.Adopt the gas chromatography identical with example 1 to carry out the detection of product, test result is in Table 1.
embodiment 3
CuO/Al
2o
3(20:80, W/W) catalyzer is prepared by equi-volume process: first measure carrier A l
2o
3dipping volume.According to the composition requirement of catalyzer, take the raw material Cu (NO of respective amount
3)
23H
2o and Al
2o
3incipient impregnation.Sample is dry 12 h at 120 ℃, and 450 ℃ of roasting 3 h, make catalyst Precursors.Catalyst Precursors is at 12 MPa lower sheetings, and the particle that is sieved into 20～40 order sizes is standby.
Adopt the method identical with example 1 to carry out reduction activation and the active testing of catalyzer.Product is collected in water-bath condensation.Adopt the gas chromatography identical with example 1 to carry out the detection of product, test result is in Table 1.
embodiment 4
CuO/ZrO
2(10:90, W/W) catalyzer is prepared by equi-volume process: first measure carrier ZrO
2dipping volume.According to the composition requirement of catalyzer, take the raw material Cu (NO of respective amount
3)
23H
2o and ZrO
2incipient impregnation.Sample is dry 12 h at 120 ℃, and 450 ℃ of roasting 3 h, make catalyst Precursors.Catalyst Precursors is at 12 MPa lower sheetings, and the particle that is sieved into 20～40 order sizes is standby.
Adopt the method identical with example 1 to carry out reduction activation and the active testing of catalyzer.Product is collected in water-bath condensation.Adopt the gas chromatography identical with example 1 to carry out the detection of product, test result is in Table 1.
embodiment 5
CuO/ZnO(10:90, W/W) catalyzer prepared by equi-volume process: the dipping volume of first measuring carrier ZnO.According to the composition requirement of catalyzer, take the raw material Cu (NO of respective amount
3)
23H
2o and ZnO incipient impregnation.Sample is dry 12 h at 120 ℃, and 450 ℃ of roasting 3 h, make catalyst Precursors.Catalyst Precursors is at 12 MPa lower sheetings, and the particle that is sieved into 20～40 order sizes is standby.
Adopt the method identical with example 1 to carry out reduction activation and the active testing of catalyzer.Product is collected in water-bath condensation.Adopt the gas chromatography identical with example 1 to carry out the detection of product, test result is in Table 1.
Table 1. active testing analytical table
Note:
(1) MA-cis-butenedioic anhydride, DS-diethyl succinate, GBL-gamma-butyrolactone, ET-ethanol,
AD-acetaldehyde, EA-ethyl acetate.
(2) hydrogen cancellation ratio (%)=(amounts of hydrogen of amounts of hydrogen/maleic anhydride hydrogenation consumption that ethanol is taken off) * 100%
(3) heat compensation rate (%)=(maleic anhydride hydrogenation is emitted heat/alcohol dehydrogenase and absorbed heat) * 100%.
Claims (4)
1. a method for maleic anhydride hydrogenation and alcohol dehydrogenase preparation of coupling gamma-butyrolactone, according to following step, carry out:
(1), according to the composition requirement of catalyzer, it is 10%～45% the aqueous solution that Cu salt is made into mass concentration, adds carrier to flood and makes the CuO/ Al that CuO content is respectively mass percent 5%-20%
2o
3catalyzer, CuO content is the CuO/ZrO of mass percent 10%
2catalyzer and CuO content are the CuO/ ZnO catalyst of mass percent 10%; Sample dried overnight at 120 ℃ after dipping, 400～500 ℃ of roasting 3～4 h, by sample compressing tablet, catalyst Precursors is made in screening;
(2) catalyzer is first used volume ratio 10:90, the H of 250 ml/min
2-N
2gas mixture carries out reduction activation, under 0.1 MPa pressure, and with 1.5 ℃/min temperature programming to 200 ℃, with 1.0 ℃/min temperature programming to 280 ℃, H simultaneously
2volume fraction slowly brings up to 30%, at 280 ℃ of constant temperature, reduces 3 h;
(3) cis-butenedioic anhydride is dissolved in to 10:90, the ethanol of W/W is mixed with cis-butenedioic anhydride/alcohol mixeding liquid, after vaporization, enters and in the fixed-bed reactor that are mounted with reducing catalyst, carries out gas phase coupling reaction; In this reaction process, maleic anhydride hydrogenation reaction generates gamma-butyrolactone, and Dehydrogenating reaction of alcohol mainly generates acetaldehyde and ethyl acetate.
2. the method for a kind of maleic anhydride hydrogenation according to claim 1 and alcohol dehydrogenase preparation of coupling gamma-butyrolactone, is characterized in that wherein the Cu salt described in step (1) is Cu (NO
3)
23H
2o.
3. the method for a kind of maleic anhydride hydrogenation according to claim 1 and alcohol dehydrogenase preparation of coupling gamma-butyrolactone, is characterized in that wherein the carrier described in step (1) is: Al
2o
3, ZrO
2or ZnO.
4. the method for a kind of maleic anhydride hydrogenation according to claim 1 and alcohol dehydrogenase preparation of coupling gamma-butyrolactone, it is characterized in that cis-butenedioic anhydride/alcohol mixeding liquid in step (3) is wherein transported in the vaporizing chamber of above-mentioned fixed-bed reactor with the speed of 5 ml/min, passes into N
2flow rate is 80 ml/min, after 350 ℃ of vaporizations, enters reactor; Temperature of reaction 240-300 ℃.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880787A (en) * | 2014-03-12 | 2014-06-25 | 江苏大学 | Method for preparing gamma-butyrrolactone and acetone through coupling reaction |
| CN112517013A (en) * | 2020-12-23 | 2021-03-19 | 中科合成油技术有限公司 | Cu-based catalyst and method for preparing gamma-valerolactone and delta-cyclopentanolactone by using same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111167A (en) * | 1994-05-05 | 1995-11-08 | 化学工业部北京化工研究院 | Catalyst for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation |
| US5478952A (en) * | 1995-03-03 | 1995-12-26 | E. I. Du Pont De Nemours And Company | Ru,Re/carbon catalyst for hydrogenation in aqueous solution |
| RO110338B1 (en) * | 1994-12-05 | 1995-12-29 | Sc Chimcomplex Sa | Preparation process of gamma-butyrolactone through maleic anhydride hydrogenation |
| CN101343211A (en) * | 2008-08-21 | 2009-01-14 | 四川德莱投资有限公司 | Method for preparing BDO or succinic diester with by-product from maleic anhydride |
-
2013
- 2013-10-14 CN CN201310477249.7A patent/CN103539765A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111167A (en) * | 1994-05-05 | 1995-11-08 | 化学工业部北京化工研究院 | Catalyst for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation |
| RO110338B1 (en) * | 1994-12-05 | 1995-12-29 | Sc Chimcomplex Sa | Preparation process of gamma-butyrolactone through maleic anhydride hydrogenation |
| US5478952A (en) * | 1995-03-03 | 1995-12-26 | E. I. Du Pont De Nemours And Company | Ru,Re/carbon catalyst for hydrogenation in aqueous solution |
| CN101343211A (en) * | 2008-08-21 | 2009-01-14 | 四川德莱投资有限公司 | Method for preparing BDO or succinic diester with by-product from maleic anhydride |
Non-Patent Citations (1)
| Title |
|---|
| DEZHI GAO等: "Coupling reaction between ethanol dehydrogenation and maleic anhydride hydrogenation catalyzed by Cu/Al2O3, Cu/ZrO2, and Cu/ZnO catalysts", 《CHEMICAL ENGINEERING JOURNAL》, vol. 233, 30 August 2013 (2013-08-30) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880787A (en) * | 2014-03-12 | 2014-06-25 | 江苏大学 | Method for preparing gamma-butyrrolactone and acetone through coupling reaction |
| CN103880787B (en) * | 2014-03-12 | 2016-08-24 | 江苏大学 | A kind of coupled reaction prepares the method for gamma-butyrolacton and acetone |
| CN112517013A (en) * | 2020-12-23 | 2021-03-19 | 中科合成油技术有限公司 | Cu-based catalyst and method for preparing gamma-valerolactone and delta-cyclopentanolactone by using same |
| CN112517013B (en) * | 2020-12-23 | 2023-07-28 | 中科合成油技术股份有限公司 | Cu-based catalyst and method for preparing gamma-valerolactone and delta-cyclopentalactone by using same |
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