CN1111167A - Catalyst for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation - Google Patents
Catalyst for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation Download PDFInfo
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- CN1111167A CN1111167A CN 94104447 CN94104447A CN1111167A CN 1111167 A CN1111167 A CN 1111167A CN 94104447 CN94104447 CN 94104447 CN 94104447 A CN94104447 A CN 94104447A CN 1111167 A CN1111167 A CN 1111167A
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Abstract
The said catalyst consists of CuO, ZnO, Al2O3 as matrix and the fourth component Pd or Pt painted on the surface of matrix. unreduced catalyst matrix is composed of: CuO 20-65 wt.%, ZnO 20-55 wt.%, Al2O3 5-30 wt.% and the ratio of fourth component to the matrix is 0.005-0.1 wt.% and the catalyst size is 5 mm in diameter and 5 mm in length. When used in the conditions of 280 deg.C, 1 atm and hydrogen-anhydride molar ratio of 40, the said catalyst as an excellent industrial one can result in a cis-butanedioie anhydride conversion rate of 100% and a Gamma butyrolactone selectivity of 92.7%.
Description
The present invention relates to a kind of catalyst, particularly Cu-series catalyst by the cis-butenedioic anhydride hydrogenation preparing gama-butalactone.
Gamma-butyrolacton is a kind of high boiling solvent, and dissolving power is strong, electrical property and good stability, and use and Administrative Security are easy, are used for fields such as fiber, resin, PETROLEUM PROCESSING.It is again main organic synthesis intermediate simultaneously, is used to produce N-methyl pyrrolidone, alpha-pyrrolidone, α-acetyl group butyrolactone etc., and since 1980, its demand constantly increases.With the cis-butenedioic anhydride is the route of raw material, by the industrialization that takes the lead in of E.I.Du Pont Company and Mitsubishi.The technological process of cis-butenedioic anhydride gas phase hydrogenation is: the cis-butenedioic anhydride steam mixes through preheating with hydrogen and enters the fixed bed reactors that catalyst is housed, and product obtains qualified gamma-butyrolacton through condensation, rectifying.The general Cu-series catalyst that adopts is reflected under 220-300 ℃, normal pressure or the low pressure and carries out.The disclosed catalyst of Chinese patent application " ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride " (publication number CN1058400A, 1992) is by Cu, ZnO, Al
2O
3Reach at least a the mixing in Ni, Ru, four kinds of elements of Ce, Zr.Catalyst consists of Cu 25%(weight), ZnO 30%, Al
2O
340%, Ni 4%, and Ce+Zr 1%, and catalyst grain size 20-40 order reacts on the stainless steel tube fixed bed reactors of the long 75mm of internal diameter 16mm, and hydrogen and cis-butenedioic anhydride mol ratio are 40:1,290 ℃ of reaction temperatures, cis-butenedioic anhydride air speed 40hr
-1Under the condition, cis-butenedioic anhydride conversion ratio 99.6%, gamma-butyrolacton selectivity 84.5%.Only disclosing catalyst grain size is the 20-40 order, and the catalyst situation and the relevant reaction result of commercial scale granularity is not provided as yet.The disclosed catalyst of Chinese patent " maleic anhydride hydrogenation changes into oxolane and the used coated catalysts of gamma-butyrolacton " (publication number CN1048172A, 1991) of American Oil Co.'s application adopts and apply the catalytic activity oxide on the outer surface of inert carrier (as silica, alumina).The catalytic activity oxide comprises the oxide mixture of Cu, Zn, Al, its active component adopts known intermediate processing preparation (or selecting commercially available catalyst), before calcining step, flood with one or more promoter element, or in settling step, add promoter element, the first-selected Cr element of its promoter element, make powdered activated component and be coated on the inert carrier, be reflected under 1-100 atmospheric pressure and the 200-400 ℃ temperature and carry out, product gamma-butyrolacton selectivity reaches as high as 91%.Though this catalyst is industrial granularity catalyst, this catalyst is owing to the adding of Cr element, and reaction effect is better, but the existence of Cr element easily causes environmental pollution, and is harmful to health.
The catalyst that the purpose of this invention is to provide the cis-butenedioic anhydride hydrogenation preparing gama-butalactone of a kind of high conversion that does not contain the Cr element, high selectivity with industrial application value.
Technical scheme of the present invention is that catalyst is with CuO, ZnO and Al
2O
3Be parent, the 4th kind of component is Pd or Pt, and the 4th kind of component is sprayed on the parent surface, and the composition percentage by weight of unreduced catalyst Precursors is: CuO 20-65%, ZnO 20-55%, Al
2O
35-30%, the weight ratio of the 4th component and parent is 0.005-0.1%.The granularity of catalyst is φ 5 * 5mm.
Conventional coprecipitation method is adopted in the preparation of its parent of catalyst provided by the invention, and each component ratio can be pressed percentage by weight and regulate, CuO 10-65%, best 20-65%, ZnO 10-60%, best 20-55%, Al
2O
35-30%.The 4th component is with Pd or Pt, Pd and Pt are the extremely close elements of catalytic property, the 4th component and catalyst Precursors weight ratio are 0.001-1%, be preferably 0.005-0.1%, adopt the method for spraying to be added on the catalyst Precursors surface, therefore the 4th component can make noble metal guarantee to give full play to catalytic action under the low condition of consumption in the catalyst surface enrichment like this.
Catalyst grain size of the present invention is the commercial scale catalyst of φ 5 * 5mm, needs reduction before using.Reaction condition is reaction temperature 200-350 ℃, is preferably in 250-300 ℃, the reaction pressure normal pressure, and hydrogen acid anhydride mol ratio is 5: 1-200: 1, the cis-butenedioic anhydride conversion ratio can reach 100%, and the gamma-butyrolacton selectivity can reach more than 90%.Catalyst provided by the invention has commercial scale, and does not contain the harmful Cr element of contaminated environment, and cis-butenedioic anhydride conversion ratio that obtains and gamma-butyrolacton selectivity are all very high.
Embodiment 1:
Be reflected in the fixed bed reactors and carry out, reactor is φ 32 * 3 * 650 stainless steel tubes, and interior filling φ 5 * 5mm cylindrical catalyst 50ml, catalyst Precursors form percentage by weight and be: CuO 65%, ZnO 20%, Al
2O
315%, Pd and catalyst Precursors weight ratio are: 0.005%, and catalyst reduces in nitrogen and hydrogen mixture earlier, cis-butenedioic anhydride steam and hydrogen are mixed into catalytic bed, in 280 ℃ of reaction temperatures, normal pressure, hydrogen acid anhydride mol ratio is under 40 conditions, cis-butenedioic anhydride conversion ratio 100%, gamma-butyrolacton selectivity 90.3%.
Embodiment 2:
Reaction unit, catalyst grain size and consumption are with embodiment 1, and it is CuO 30%, ZnO 55%, Al that catalyst Precursors is formed percentage by weight
2O
315%, Pd and catalyst Precursors weight ratio are 0.05%, and 290 ℃ of reaction temperatures, hydrogen acid anhydride mol ratio are 40, cis-butenedioic anhydride conversion ratio 100%, gamma-butyrolacton selectivity 91.5%.
Embodiment 3:
Reaction unit, catalyst grain size and consumption are with embodiment 1, and catalyst Precursors is formed percentage by weight CuO 40%, ZnO 40%, Al
2O
320%, Pd and catalyst Precursors weight ratio are 0.01%, and 280 ℃ of reaction temperatures, hydrogen acid anhydride mol ratio are 40, cis-butenedioic anhydride conversion ratio 100%, gamma-butyrolacton selectivity 92.7%.
Embodiment 4:
With the Pt element substitution Pd element of the 4th component among the embodiment 1-3, all the other compositions and weight ratio are constant.
Claims (2)
1, a kind of catalyst that is used for the cis-butenedioic anhydride hydrogenation preparing gama-butalactone is by CuO, ZnO, Al
2O
3Form with the 4th component metals element, it is characterized in that with CuO, ZnO and Al
2O
3Be parent, the 4th kind of component is Pd or Pt, and the 4th kind of component is sprayed on the parent surface, and the composition percentage by weight of unreduced catalyst Precursors is:
CuO 20-65%；
ZnO 20-55%；
Al
2O
35-30%，
The weight ratio of the 4th component and parent is 0.005-0.1%.
2, catalyst according to claim 1, the granularity that it is characterized in that catalyst is φ 5 * 5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104447A CN1044866C (en) | 1994-05-05 | 1994-05-05 | Catalyst for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104447A CN1044866C (en) | 1994-05-05 | 1994-05-05 | Catalyst for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1111167A true CN1111167A (en) | 1995-11-08 |
| CN1044866C CN1044866C (en) | 1999-09-01 |
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ID=5031588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94104447A Expired - Fee Related CN1044866C (en) | 1994-05-05 | 1994-05-05 | Catalyst for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1095400C (en) * | 1999-12-08 | 2002-12-04 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone from cis-aldehyde by ordinary-pressure gas-phase hydrogenation and its use |
| WO2003104214A3 (en) * | 2002-06-11 | 2004-03-18 | Basf Ag | Two-stage method for producing butandiol in two reactors |
| CN103539765A (en) * | 2013-10-14 | 2014-01-29 | 江苏大学 | Method for preparing gamma-butyrolactone through maleic anhydride hydrogenation and ethanol dehydrogenation coupling |
Families Citing this family (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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001282A (en) * | 1973-02-12 | 1977-01-04 | General Electric Company | Process for producing gamma-butyrolactone |
| JPS5524107A (en) * | 1978-08-09 | 1980-02-21 | Asahi Chem Ind Co Ltd | Preparation of lactone |
| JPS61246173A (en) * | 1985-04-23 | 1986-11-01 | Idemitsu Petrochem Co Ltd | Productionof gamma-butyrolactone |
-
1994
- 1994-05-05 CN CN94104447A patent/CN1044866C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095400C (en) * | 1999-12-08 | 2002-12-04 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone from cis-aldehyde by ordinary-pressure gas-phase hydrogenation and its use |
| 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 |
| WO2003104214A3 (en) * | 2002-06-11 | 2004-03-18 | Basf Ag | Two-stage method for producing butandiol in two reactors |
| CN103539765A (en) * | 2013-10-14 | 2014-01-29 | 江苏大学 | Method for preparing gamma-butyrolactone through maleic anhydride hydrogenation and ethanol dehydrogenation coupling |
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| Publication number | Publication date |
|---|---|
| CN1044866C (en) | 1999-09-01 |
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Granted publication date: 19990901 |