CN103044367A - Production method of gamma-butyrolactone - Google Patents
Production method of gamma-butyrolactone Download PDFInfo
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- CN103044367A CN103044367A CN2011103132776A CN201110313277A CN103044367A CN 103044367 A CN103044367 A CN 103044367A CN 2011103132776 A CN2011103132776 A CN 2011103132776A CN 201110313277 A CN201110313277 A CN 201110313277A CN 103044367 A CN103044367 A CN 103044367A
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Abstract
The invention relates to a method for producing gamma-butyrolactone through dehydrogenation of 1,4-butanediol. A catalyst is composed of CuO-ZnO-Al2O3 and assistant K and/or Li impregnated on the surface of CuO-ZnO-Al2O3; the catalyst comprises 37-52% of CuO, 40-55% of ZnO, 7-9.5% of Al2O3 and a proper mixture ratio of assistant K and/or Li; and the catalyst is free of Cr. When the catalyst is used under the conditions that the reaction temperature is 230-250 DEG C, the reaction pressure is 0-0.4 MPa, the feeding airspeed is 1.0-2.5 h<-1> and the hydrogen/alcohol mol ratio is 3-10, the conversion rate of 1,4-butanediol can be up to 98%, and the selectivity of gamma-butyrolactone can be up to 99% or above.
Description
Technical field
The invention relates to the BDO method that gas-phase dehydrogenation is produced gamma-butyrolactone in the presence of catalyzer.
Background technology
Gamma-butyrolactone (γ-Butyrolactone is called for short γ-BL or GBL) is called and is that GBL, molecular formula are C
4H
6O
2Himself structure is a kind of compound that contains 5-membered heterocycles, and gamma-butyrolactone is a kind of colourless liquid, and the smell of similar acetone is arranged, and has high boiling point and high dissolving power, can be preferably water-soluble, methyl alcohol, ethanol, acetone, ether and benzene.Its reactivity worth is good, and specific conductivity is high, and good stability uses safety.As a kind of important organic solvent, gamma-butyrolactone is widely used in many aspects such as petroleum industry, medicine, synthon, synthetic resins, agricultural chemicals.As a kind of important fine chemistry industry and Organic Chemicals, be mainly used in the products such as synthesis of pyrrolidine ketone, N-Methyl pyrrolidone, vinyl pyrrolidone, and many new purposes are constantly under development.
From M.B.Chanlatoft in 1884 at first lactonized synthetic gamma-butyrolactone with the 4 hydroxybutyric acid molecule after, people had carried out a large amount of deep researchs to the synthetic and production technology of gamma-butyrolactone, existing different Technology
Route carries out industrial production, and the raw material classification according to synthetic mainly contains following three kinds of methods: furfural method, cis-butenedioic anhydride (MA) hydrogenation method and BDO (BDO) dehydriding.Furfural method process is complicated, and cost is higher, has lost the market competitiveness, and this method is eliminated at present, and maleic anhydride hydrogenation method raw material is easy to get, and cost is low, but acidity is relatively high in the crude product, and this brings certain impact for the separation of product and the quality of end product.1, the by product of 4-butanediol dehydrogenation method mainly is tetrahydrofuran (THF) (THF) and a small amount of butanols (BOL), and component is simple, and product is easily separated, synthetic gamma-butyrolactone quality better can satisfy as pharmaceutical raw material and the battery electrolyte high request to the gamma-butyrolactone quality.
1,4-butanediol dehydrogenation catalyst system therefor processed is take the Cu-Cr series catalysts as main, adopt Cu-Cr-Mn and/or Ba catalyzer such as United States Patent (USP) 5210229, add Alkali-Metal Na or K modification, although reduced the acidity of catalyzer, reduced dehydration reaction, but reduced the activity of catalyzer, need to improve temperature of reaction and compensate (being increased to 270 ℃ from 230 ℃), as at 230 ℃, H
2/ alcohol (mole)=4:1, pressure 4kg/cm
2(table), weight space velocity 3.0h
-1The time, BDO transformation efficiency 91.39%, gamma-butyrolactone selectivity 98.98%, tetrahydrofuran (THF) selectivity 0.14% improves temperature to 270 ℃, more than three then be respectively 99.49%, 97.93% and 0.17%.Such as the clear 61-246173(1986 of Japanese Patent), adopt the Cu-Cr-Zn catalyzer, it forms Cu:Cr:Zn=35:68:38, when 228 ℃ of temperature of reaction, gamma-butyrolactone content is 98.2wt% in the product, Japanese Patent JP03,232, the Cu-Cr-Ba catalyzer is adopted, wherein Cu:Cr:Ba=47:42:6 in 874 (1991), in the time of 230 ℃, BDO transformation efficiency 96.1mol%, gamma-butyrolactone selectivity 95.1 mol%.That adopts the Cu-Cr series catalysts also has: EP523774A, CN1173492, CN1194268, CN1169428, CN1220186A.Although contain the yield that the Cr catalyzer can improve gamma-butyrolactone, the Cr element in the catalyzer can cause environmental pollution, and is harmful to HUMAN HEALTH, so people are developing the catalyzer that does not contain Cr always, the Cu/SiO that adopts pickling process to prepare such as US6093677
2-CaO catalyzer, gas-phase dehydrogenation, at temperature of reaction 190-230 ℃, pressure 1-2bar, air speed 0.5-7.5kg/kgCu.h, BDO transformation efficiency are greater than 99%, and the gamma-butyrolactone selectivity is greater than 97%.Also just like catalyzer such as Cu-Zn, Pt, Pd, wherein take the Cu-Zn catalyzer as main, difference is to have added different auxiliary agents to improve the reactivity worth of catalyzer in concrete preparation process.Such as CN1111168, catalyst system therefor is comprised of Cu-Zn-Al oxide matrix and spraying Pd or Pt thereon, under temperature of reaction 190-290 ℃, reaction pressure normal pressure, hydrogen alcohol mol ratio 1-6 condition, use this catalyzer, 1,4-butyleneglycol transformation efficiency can reach 100%, and the gamma-butyrolactone selectivity can reach 97%.CN1304795 adopts the Cu-Zn-Al catalyzer, and auxiliary agent is at least a among two kinds of BaO, the Pd, and at temperature of reaction 200-260 ℃, reaction pressure is less than 0.05MPa, liquid hourly space velocity 0.1-1.2h
-1, the BDO transformation efficiency can reach 100%, and the gamma-butyrolactone selectivity is greater than 96%.CN1562473 adopts CuO-ZnO-Ce
2O
3Catalyzer, Ce
2O
3Content is 2-3%, and at temperature of reaction 210-260 ℃, reaction pressure is less than 0.05MPa, liquid hourly space velocity 0.1-0.7h
-1, the BDO transformation efficiency is greater than 98%, and the gamma-butyrolactone selectivity is greater than 95%.
CN99113276.9 discloses a kind of preparation method of copper containing catalyst, cupric oxide 10%～90% in the catalyzer that obtains, the oxide compound that helps catalyst component is 0%～50%, aluminum oxide is 5%～40%, comprise simultaneously 0.1%～4.0% alkalimetal oxide, this catalyzer can be used for hydrogenation or the dehydrogenation reaction of organic reaction, the described wide range of this patent, when the catalyzer that embodiment obtains is used for gamma-butyrolactone production, result of use is unsatisfactory, be mainly manifested in BDO and more dehydration reaction occur and generate tetrahydrofuran (THF), make the selectivity variation of gamma-butyrolactone.
Summary of the invention
Not enough for prior art, the invention provides a kind of production method of gamma-butyrolactone, adopt the suitable catalyzer that forms, lower temperature of reaction, higher liquid hourly space velocity, moderate hydrogen/alcohol than and near under the condition of normal pressure, the transformation efficiency of BDO dehydrogenation can reach more than 98%, the selectivity of gamma-butyrolactone can reach more than 99%, the resultant of reaction component is simple, and product is easily separated, the gamma-butyrolactone quality better of producing.
The production method of gamma-butyrolactone of the present invention comprises following content: take BDO as raw material, carry out dehydrogenation reaction and produce gamma-butyrolactone, catalyzer uses the CuO-ZnO-Al that contains K element and/or Li element auxiliary agent
2O
3Catalyzer, catalyzer forms and comprises by weight: CuO 37%～52%, and ZnO 40%～55%, Al
2O
37%～9.5%; Be preferably CuO 42%～50%, ZnO 42%～50%, Al
2O
37%～9.5%; The mol ratio of auxiliary agent K element and/or Li element and Al element is 0.10～0.25, is preferably 0.15～0.22.Reaction pressure (gauge pressure) 0～0.4MPa; 220～270 ℃ of temperature of reaction, preferred 230～250 ℃; Liquid feeding volume space velocity 0.5～3.5h
-1, preferred 1.0～2.5h
-1Charging H
2/ BDO mol ratio 3:1～10:1.
Do not contain Cr in the catalyzer that uses in the inventive method.
In the prior art, the reaction for gamma-butyrolactone is produced in the BDO dehydrogenation although Cu-Cr series catalysts reactivity worth is better, can work the mischief to environmental and human health impacts, the Cu/SiO of pickling process preparation
2The catalyzer price is expensive, and the main precious metal that adds is to improve activity in the Cu-Zn composite oxide catalysts, and the liquid hourly space velocity of simultaneous reactions is lower.Although the Cu-Zn-Al composite oxide catalysts has application in other reaction, but existing Cu-Zn-Al composite oxide catalysts, or contain the Cu-Zn-Al composite oxide catalysts of auxiliary agent, be used for 1, when the 4-butanediol dehydrogenation was produced the gamma-butyrolactone reaction, its reactivity worth all needed further to improve.The present invention finds by research, adopts the suitable Cu-Zn-Al composite oxide catalysts that forms, and auxiliary agent K and/or the Li of simultaneously load Optimum Contents not only can improve the activity of catalyzer, can also improve selectivity of catalyst.Catalyzer of the present invention does not contain the chromium component of BDO dehydrogenation reaction custom catalysts, has avoided problem of environmental pollution.
Specific embodiments
The catalyzer that the inventive method is used is with CuO-ZnO-Al
2O
3Precursor catalyst is precursor, and further dip loading K and/or Li element obtain final catalyzer.CuO-ZnO-Al
2O
3Precursor catalyst, to adopt conventional coprecipitation method preparation, the nitrate that is about to copper, zinc is made the aqueous solution, finish coprecipitation reaction with basic solution yellow soda ash or sodium bicarbonate, the subcarbonate that generates filters washing after aging, add aluminium hydroxide, again drying, roll, granulation, calcining, these processes of moulding, make the cylindrical precursor catalyst of Φ 5 * 4～5mm.Above-mentioned CuO-ZnO-Al
2O
3Detailed process and the condition of precursor catalyst preparation are well known to those skilled in the art.
Next step will prepare finished catalyst, the nitrate of K and/or Li is made the aqueous solution, usually be made into as required the aqueous solution of different concns, make the aqueous solution of 1.0-1.2mol/L among the present invention, with this precursor catalyst of making more than solution impregnation, and at 80-100 ℃ of lower reflux 2-6 hour, the catalyzer behind the dipping is dry, and namely obtain finished catalyst in 380-590 ℃ of lower roasting.
The above catalyzer that makes is used for 1, the 4-butanediol Dehydrogenation For Producing Butyrolactone, the cylindrical catalyst particle that is about to certain volume is contained in the stainless steel tubular type reactor, reaction is carried out front need and first catalyzer is carried out conventional reduction processing, make the copper of oxidation state become reduction-state, with pump alcohol is delivered into reactor after the reduction.Because reaction in order to improve the material gasification effect, prevents the butyleneglycol coking for the gas-phase dehydrogenation reaction, also need to pass into hydrogen or nitrogen in the reaction process, because of the good heat conductivity of hydrogen, and the fine metallic reducing attitude of keeping catalyst surface of energy, so select hydrogen among the present invention.
Reaction product is after the cooling of the gas-liquid separator of reactor outlet, and gas can loop back reactor, also can emptying, and product liquid forms with gas chromatographic analysis after collecting.
Embodiment 1
By the method described in the embodiment, be prepared into catalyst A, B, C, D, the E of the inventive method use of following composition.The reactivity worth of catalyzer is seen embodiment 2-6, and wherein transformation efficiency and selectivity are calculated with molar weight.
Table 1 catalyzer forms (chemical analysis data)
| Form wt% | CuO | ZnO | Al 2O 3 | The K/Al mol ratio | The Li/Al mol ratio |
| A | 45.5 | 46.1 | 7.4 | 0.17 | / |
| B | 45.6 | 45.0 | 8.2 | 0.20 | / |
| C | 46.5 | 42.9 | 9.1 | 0.11 | 0.08 |
| D | 44.8 | 46.3 | 8.5 | / | 0.17 |
| E | 45.7 | 45.5 | 8.4 | / | 0.21 |
Embodiment 2
B catalyzer 20ml with the dilution of 20ml porcelain ring, is encased in the fixed-bed reactor the high about 1.7m of reactor, internal diameter 25mm, built-in Thermal couple casing pipe, reactor have 6 sections heating by electric cookers, corresponding 6 thermocouple temperature controls, catalyzer is contained in the 4th section, its complementary space of reactor is all used the porcelain ring filling, adopts the upper feeding mode, and 1 to 3 section on top is as raw material 1, then the gasification section of 4-butyleneglycol enters catalyst layer with raw material preheating and gasification.
Reaction procatalyst hydrogen reducing, amounts of hydrogen is 10L/hr, and reduction temperature is 200 ℃, and the recovery time is 8-10 hour, and reduction is reacted 240 ℃ of temperature after finishing by the part that cooks noodle; Volume space velocity 1.5h during feeding liquid
-1H
2/ pure mol ratio 5:1, BDO transformation efficiency 98.5%; Gamma-butyrolactone selectivity 99.4%.
Embodiment 3
Reaction unit is identical, and catalyst levels and reductive condition are identical with embodiment 2, selects C catalyzer in the table 1, reacts 250 ℃ of temperature by the part that cooks noodle; Feeding liquid hourly space velocity 1.8h
-1H
2/ pure mol ratio 3:1; BDO transformation efficiency 98.9%, gamma-butyrolactone, gamma-butyrolactone selectivity 99.5%.
Embodiment 4
Reaction unit is identical, and catalyst levels and reductive condition are identical with embodiment 2, selects E catalyzer in the table 1, reacts 235 ℃ of temperature by the part that cooks noodle; Feeding liquid hourly space velocity 2.0h
-1H
2/ pure mol ratio 7:1; BDO transformation efficiency 97.3%, gamma-butyrolactone selectivity 99.6%.
Embodiment 5
Select A catalyzer in the table 1, other condition is with embodiment 2, and reaction result is BDO transformation efficiency 98.0%, gamma-butyrolactone selectivity 99.6%.
Embodiment 6
Select D catalyzer in the table 1, other condition is with embodiment 2, and reaction result is BDO transformation efficiency 97.8%, gamma-butyrolactone selectivity 99.1%.
Comparative example 1
Press the CuO-ZnO-Al of CN99113276.9 preparation
2O
3-base metal catalysts A(consists of CuO45.4%; ZnO35.1%; Al
2O
318.3%; K
2O 1.2%) and E(consist of CuO45.3%; ZnO35.0%; Al
2O
318.2%; Cs
2O1.5%), according to the reaction conditions of embodiment 2, the reaction result when using catalyst A is BDO transformation efficiency 97.2%, gamma-butyrolactone selectivity 94.2%., the reaction result when using catalyzer E is BDO transformation efficiency 97.6%, gamma-butyrolactone selectivity 95.5%.Can find out low about 5 percentage points of gamma-butyrolactone selectivity ratios the inventive method.
Claims (10)
1. the production method of a gamma-butyrolactone take BDO as raw material, is carried out dehydrogenation reaction and is produced gamma-butyrolactone, and it is characterized in that: catalyzer uses the CuO-ZnO-Al that contains K element and/or Li element auxiliary agent
2O
3Catalyzer, catalyzer forms and comprises by weight: CuO 37%～52%, and ZnO 40%～55%, Al
2O
37%～9.5%, the mol ratio of auxiliary agent K element and/or Li element and Al element is 0.10～0.25.
2. in accordance with the method for claim 1, it is characterized in that: the reaction pressure of dehydrogenation reaction is 0～0.4MPa, 220～270 ℃ of temperature of reaction, liquid feeding volume space velocity 0.5～3.5h
-1, charging H
2/ BDO mol ratio 3:1～10:1.
3. according to claim 1 or 2 described methods, it is characterized in that: temperature of reaction is 230～250 ℃.
4. according to claim 1,2 or 3 described methods, it is characterized in that: the liquid feeding volume space velocity is 1.0～2.5h
-1
5. it is characterized in that in accordance with the method for claim 1: catalyzer is with CuO-ZnO-Al
2The O precursor catalyst is precursor, and further dip loading K and/or Li element obtain final catalyzer.
6. it is characterized in that in accordance with the method for claim 5: CuO-ZnO-Al
2The O precursor catalyst adopts conventional coprecipitation method preparation, soon the nitrate of copper, the nitrate of zinc are made the aqueous solution, finish coprecipitation reaction with basic solution yellow soda ash or sodium bicarbonate, the subcarbonate that generates filters washing after aging, add aluminium hydroxide, again drying, roll, granulation, calcining, these processes of moulding, make precursor catalyst.
7. it is characterized in that in accordance with the method for claim 5: CuO-ZnO-Al
2The method that the O precursor catalyst prepares final catalyzer is, the nitrate of K and/or Li is made the aqueous solution, and the concentration of solution is 1.0-1.2mol/L, with this solution impregnation CuO-ZnO-Al
2O
3Precursor catalyst, and at 80-100 ℃ of lower reflux 2-6 hour, the catalyzer behind the dipping is dry, and namely obtain finished catalyst in 380-590 ℃ of lower roasting.
8. it is characterized in that in accordance with the method for claim 1: the mol ratio of auxiliary agent K element and/or Li element and Al element is 0.15～0.22.
9. according to claim 1 or 8 described methods, it is characterized in that: the catalyzer composition is included as CuO 42%～50% by weight, and ZnO 42%～50%, Al
2O
37%～9.5%.
10. it is characterized in that in accordance with the method for claim 1: catalyzer does not contain Cr.
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|---|---|---|---|---|
| CN103877981A (en) * | 2014-01-07 | 2014-06-25 | 濮阳迈奇科技有限公司 | Catalyst for preparing gamma-butyrolactone by gaseous phase dehydrogenation of 1, 4-butanediol under normal pressure and preparation method thereof |
| CN104549399B (en) * | 2013-10-23 | 2017-02-15 | 中国石油化工股份有限公司 | Shell catalyst for 1, 4-butanediol vapor-phase dehydrogenation and application of shell catalyst |
| CN112742432A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for preparing gamma-butyrolactone by maleic anhydride hydrogenation |
| CN112756004A (en) * | 2019-11-04 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone by maleic anhydride hydrogenation and preparation method and application thereof |
| US11260374B2 (en) | 2017-11-14 | 2022-03-01 | China Petroleum & Chemical Corporation | Cu-based catalyst, its preparation process and use thereof |
| CN115779957A (en) * | 2022-12-10 | 2023-03-14 | 南通嘉烝工程技术有限公司 | Catalyst for preparing gamma-butyrolactone by 1, 4-butanediol low-pressure dehydrogenation and application thereof |
| US12060319B2 (en) | 2017-11-14 | 2024-08-13 | China Petroleum & Chemical Corporation | Preparation process for Cu-based catalyst and use thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991016132A1 (en) * | 1990-04-16 | 1991-10-31 | Isp Investments Inc. | Process of vapor phase catalytic hydrogenation of maleic anhydride to gamma-butyrolactone in high conversion and high selectivity using an activated catalyst |
| CN1111168A (en) * | 1994-05-05 | 1995-11-08 | 化学工业部北京化工研究院 | Catalyst for preparing gamma-butyrolactone from 1,4-butanediol by dehydrogenation |
| JP2639463B2 (en) * | 1989-03-08 | 1997-08-13 | 東燃株式会社 | Method for producing 1,4-butanediol and tetrahydrofuran |
| CN1289638A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing Cu-contained catalyst |
| CN1298759A (en) * | 1999-12-08 | 2001-06-13 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone by gas-phase normal-pressure hydrogenation of maleic anhydride and its use |
| CN1304795A (en) * | 2000-08-14 | 2001-07-25 | 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 |
| CN1890231A (en) * | 2003-12-09 | 2007-01-03 | 巴斯福股份公司 | Method for the production of defined mixtures of THF BDO and GBL by gas phase hydrogenation |
| CN101676277A (en) * | 2008-09-19 | 2010-03-24 | 于网林 | Butyrolactone synthesizing technology |
-
2011
- 2011-10-17 CN CN201110313277.6A patent/CN103044367B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2639463B2 (en) * | 1989-03-08 | 1997-08-13 | 東燃株式会社 | Method for producing 1,4-butanediol and tetrahydrofuran |
| WO1991016132A1 (en) * | 1990-04-16 | 1991-10-31 | Isp Investments Inc. | Process of vapor phase catalytic hydrogenation of maleic anhydride to gamma-butyrolactone in high conversion and high selectivity using an activated catalyst |
| CN1111168A (en) * | 1994-05-05 | 1995-11-08 | 化学工业部北京化工研究院 | Catalyst for preparing gamma-butyrolactone from 1,4-butanediol by dehydrogenation |
| CN1289638A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing Cu-contained catalyst |
| CN1298759A (en) * | 1999-12-08 | 2001-06-13 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone by gas-phase normal-pressure hydrogenation of maleic anhydride and its use |
| CN1304795A (en) * | 2000-08-14 | 2001-07-25 | 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 |
| CN1890231A (en) * | 2003-12-09 | 2007-01-03 | 巴斯福股份公司 | Method for the production of defined mixtures of THF BDO and GBL by gas phase hydrogenation |
| CN101676277A (en) * | 2008-09-19 | 2010-03-24 | 于网林 | Butyrolactone synthesizing technology |
Non-Patent Citations (6)
| Title |
|---|
| ICHIKAWA N ET AL: "Dehydrogenative cyclization of 1, 4-butanediol over copper-based catalyst", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 212, no. 1, 31 December 2004 (2004-12-31), XP002467416, DOI: doi:10.1016/j.molcata.2003.10.028 * |
| SATO S ET AL: "《Dehydrogenation of 1, 3-butanediol over Cu-based catalyst》", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 272, no. 1, 31 December 2007 (2007-12-31) * |
| 孙党莉 ET AL: "《1, 4-丁二醇脱氢制 γ-丁内酯的研究》", 《天然气化工》, vol. 1, no. 1, 31 December 2005 (2005-12-31) * |
| 陈学刚 ET AL: "Cu/ZnO/Al2O3 催化剂上 1, 4-丁二醇脱氢合成 γ-丁内酯", 《催化学报》, vol. 21, no. 3, 31 December 2000 (2000-12-31) * |
| 韦贵朋 ET AL: "1, 4-丁二醇脱氢合成 γ-丁内酯催化剂研究", 《河南化工》, vol. 23, no. 5, 31 December 2006 (2006-12-31) * |
| 马宁 ET AL: "合成 γ-丁内酯工艺对比研究", 《河南化工》, vol. 24, no. 8, 31 December 2007 (2007-12-31) * |
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| CN104549399B (en) * | 2013-10-23 | 2017-02-15 | 中国石油化工股份有限公司 | Shell catalyst for 1, 4-butanediol vapor-phase dehydrogenation and application of shell catalyst |
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| CN112742432A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for preparing gamma-butyrolactone by maleic anhydride hydrogenation |
| CN112742432B (en) * | 2019-10-30 | 2022-09-20 | 中国石油化工股份有限公司 | Method for preparing gamma-butyrolactone by maleic anhydride hydrogenation |
| CN112756004A (en) * | 2019-11-04 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing gamma-butyrolactone by maleic anhydride hydrogenation and preparation method and application thereof |
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| CN115779957A (en) * | 2022-12-10 | 2023-03-14 | 南通嘉烝工程技术有限公司 | Catalyst for preparing gamma-butyrolactone by 1, 4-butanediol low-pressure dehydrogenation and application thereof |
| CN115779957B (en) * | 2022-12-10 | 2024-03-19 | 南通格瑞凯泰工程技术有限公司 | Catalyst for preparing gamma-butyrolactone by low-pressure dehydrogenation of 1, 4-butanediol and application thereof |
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