CN111097444A - Catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation, preparation method and application of catalyst and method for preparing gamma-butyrolactone - Google Patents
Catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation, preparation method and application of catalyst and method for preparing gamma-butyrolactone Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysts, and discloses a catalyst for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation, a preparation method and application thereof, and a method for preparing gamma-butyrolactone, wherein the catalyst comprises the following components in percentage by weight: 40-70 wt% of CuO, 15-40 wt% of ZnO and Al2O33‑10wt％、La2O32-8 wt% and MnO 1-5 wt%. The catalyst of the invention has higher activity and selectivity, the conversion rate of maleic anhydride is more than 99%, and the selectivity of gamma-butyrolactone is more than 96%.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation and a preparation method thereof, application of the catalyst for preparing the gamma-butyrolactone through the maleic anhydride gas-phase hydrogenation, and a method for preparing the gamma-butyrolactone through the maleic anhydride gas-phase hydrogenation.
Background
Gamma-butyrolactone is an important organic chemical product. As a solvent, most of low molecular polymers, partial high molecular polymers and resin can be dissolved, and the solvent is a high-safety, low-toxicity and environment-friendly solvent; as raw materials, can produce gamma-butyrolactam, N-methyl pyrrolidone and N-vinyl pyrrolidone, and can be used as intermediates of products such as herbicides, perfumes, medicines, dyes, etc.
At present, there are many methods for industrially synthesizing gamma-butyrolactone, one of which is a maleic anhydride hydrogenation method using maleic anhydride as a raw material, and the method has the advantages of simple process, low investment and the like. China is a big country for producing maleic anhydride, and gamma-butyrolactone is a product with high additional value in maleic anhydride deep-processed products.
The maleic anhydride hydrogenation method is also classified into a liquid-phase hydrogenation method and a gas-phase hydrogenation method, but the scale of domestic production equipment is low regardless of the method. The catalyst has the defects of short service life, low yield, unstable operation and the like, so the application of the catalyst in industry is restricted.
At present, a plurality of patents are provided for preparing gamma-butyrolactone by hydrogenating maleic anhydride. For example, in patent applications with publication numbers CN106955710A and CN101940927A, a liquid phase hydrogenation method is used, but the liquid phase hydrogenation method has high requirements for the performance of the catalyst, and has high reaction pressure, complex production process and difficult industrialization. Patent application publication No. CN1058400A discloses a method for preparing a catalyst suitable for preparing gamma-butyrolactone by gas-phase hydrogenation of maleic anhydride, but the selectivity of the catalyst to gamma-butyrolactone is low, namely about 85%.
Therefore, it is urgently needed to develop a catalyst with simple production process and high catalytic efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a catalyst for preparing gamma-butyrolactone through gas-phase catalytic hydrogenation of maleic anhydride, which has a simple production process and high catalytic efficiency, a preparation method and application thereof. The prepared catalyst has the characteristics of high catalyst activity and selectivity, catalytic reaction is carried out under normal pressure, and the raw material maleic anhydride does not need to be dissolved by a solvent, and has industrial application performance.
In order to achieve the above object, a first aspect of the present invention provides a catalyst for preparing γ -butyrolactone by gas-phase hydrogenation of maleic anhydride, which comprises, based on the total weight of the catalyst: 40-70 wt% of CuO, 15-40 wt% of ZnO and Al2O33-10wt％、La2O32-8 wt% and MnO 1-5 wt%.
A second aspect of the present invention provides a method for producing the above catalyst, comprising: and preparing the precursor solution of each component of the catalyst by a coprecipitation method to obtain the catalyst.
The third aspect of the invention provides the application of the catalyst in the reaction of preparing gamma-butyrolactone by gas-phase hydrogenation of maleic anhydride.
The fourth aspect of the invention provides a method for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation, which comprises the following steps:
activating the catalyst, and then carrying out contact reaction on the activated catalyst, hydrogen and maleic anhydride to prepare gamma-butyrolactone;
wherein the molar ratio of the hydrogen to the maleic anhydride is 10-30: 1, the space velocity of maleic anhydride is 0.1hr-1-0.5 hr-1The temperature of the contact reaction is 200-300 ℃, and the pressure is 0.1-0.3 MPa.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst has higher activity and selectivity, the conversion rate of maleic anhydride is more than 99 percent, and the selectivity of gamma-butyrolactone is more than 96 percent;
(2) the catalytic reaction is carried out under normal pressure, the process flow is simple, the operation is convenient, and the investment is less;
(3) the raw material maleic anhydride is not required to be dissolved by a solvent, and can be directly fed, so that the production cost is reduced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The first aspect of the present invention provides a catalyst for preparing gamma-butyrolactone by gas-phase hydrogenation of maleic anhydride, which comprises the following components, by weight: 40-70 wt% of CuO, 15-40 wt% of ZnO and Al2O33-10wt％、La2O32-8 wt% and MnO 1-5 wt%.
According to the present invention, preferably, the catalyst comprises, based on the total weight of the catalyst: 50-60 wt% of CuO, 78-35 wt% of ZnO25 and Al2O37-9wt％、La2O34-6 wt% and MnO 1.5-2.5 wt%.
According to the present invention, preferably, the precursor of copper oxide is selected from at least one of soluble copper salts; further preferably at least one of copper nitrate, copper sulfate, copper chloride and copper acetate; more preferably copper nitrate.
According to the present invention, preferably, the precursor of zinc oxide is selected from at least one of soluble zinc salts; more preferably at least one of zinc nitrate, zinc sulfate, zinc chloride and zinc acetate; more preferably zinc nitrate.
According to the invention, preferably, the precursor of the alumina is selected from at least one of soluble aluminium salts; further preferably at least one of aluminum nitrate, aluminum sulfate, aluminum chloride and aluminum acetate; more preferably aluminum nitrate.
According to the present invention, preferably, the precursor of lanthanum oxide is selected from at least one of soluble lanthanum salts; further preferably lanthanum chloride and/or lanthanum nitrate; more preferably lanthanum nitrate.
According to the invention, preferably, the precursor of the manganese oxide is selected from at least one of soluble manganese salts; further preferably at least one of manganese chloride, manganese acetate and manganese nitrate; more preferably manganese nitrate.
A second aspect of the present invention provides a method for producing the above catalyst, comprising: and preparing the precursor solution of each component of the catalyst by a coprecipitation method to obtain the catalyst.
According to a preferred embodiment of the present invention, the preparation method comprises:
(1) uniformly mixing precursors of copper oxide, zinc oxide, aluminum oxide, lanthanum oxide and manganese oxide with water to obtain a mixed solution;
(2) adding an alkali solution and the mixed solution into a reaction kettle containing water for contact reaction to obtain a precipitate;
(3) and filtering, washing, drying and roasting the precipitate to obtain the catalyst.
According to the present invention, preferably, the step (2) comprises: adding the alkali solution and the mixed solution into a reaction kettle containing water in a split parallel flow mode for contact reaction to obtain a precipitate.
According to the invention, preferably, in the step (2), the temperature of the contact reaction is 40-90 ℃, the pH value of the reaction system is controlled to be 5-8, and the alkali solution is ammonia water and/or a sodium carbonate solution, preferably a sodium carbonate solution;
the drying and calcination in step (3) may be carried out under the process conditions common in the art, and in the present invention, it is preferable to: the drying temperature is 100-120 ℃, and the drying time is 10-20 h; the temperature of the calcination is 280-400 ℃, preferably 350-400 ℃, and the time is 2-6 hours.
In order to increase the strength and lubricity of the catalyst, preferably, the step (3) further comprises mixing the catalyst with graphite, and then tabletting; the graphite is used in an amount of 0.5 to 2 wt% based on the weight of the catalyst.
Specifically, the catalyst of the present invention can be prepared by the following technical scheme:
(1) weighing copper nitrate, zinc nitrate, aluminum nitrate, lanthanum nitrate and manganese nitrate solution according to the mass ratio of each component in the catalyst, and mixing and dissolving in deionized water to obtain a mixed solution;
(2) putting a proper amount of deionized water into a reaction kettle, adding a sodium carbonate solution and a mixed solution into the reaction kettle in a parallel flow manner at 40-90 ℃ to perform a contact reaction, continuously stirring, and controlling the pH value of the reaction to be 5-8; after the addition is finished, continuously stirring for 0.5-5 hours at the temperature to obtain a precipitate;
(3) filtering and washing the precipitate obtained in the step (2), drying at 100-120 ℃ for 10-20 hours, roasting at 280-400 ℃ for 2-6 hours to obtain the catalyst, then adding 0.5-2 wt% of graphite based on the weight of the catalyst, mixing, tabletting and forming.
The third aspect of the invention provides the application of the catalyst in the reaction of preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation.
The fourth aspect of the present invention provides a method for preparing gamma-butyrolactone by gas-phase hydrogenation of maleic anhydride, which comprises:
activating the catalyst, and then carrying out contact reaction on the activated catalyst, hydrogen and maleic anhydride to prepare gamma-butyrolactone;
wherein the molar ratio of the hydrogen to the maleic anhydride is 10-30: 1, the space velocity of maleic anhydride is 0.1hr-1-0.5 hr-1The temperature of the contact reaction is 200-300 ℃, and the pressure is 0.1-0.3 MPa.
In the present invention, the catalyst may be activated by conventional activation processes in the art, preferably by reducing the catalyst with a nitrogen-hydrogen mixture to activate the catalyst; wherein, the temperature of the reduction reaction is preferably 220-320 ℃, and the time is preferably 4-8 h.
The invention is further illustrated by the following examples.
The raw materials used in the following examples and comparative examples are commercially available; the amount of graphite added is based on the weight of the catalyst.
Example 1
Weighing copper nitrate (Cu (NO)3)2·3H2O)334.08g, zinc nitrate (Zn (NO)3)2·6H2O)219.34g, aluminum nitrate (Al (NO)3)3·6H2O)117.72g, lanthanum nitrate (La (NO)3)3·6H2O)26.58g and manganese nitrate (Mn (NO)3)2)20.18g was dissolved in 2000mL of deionized water; firstly, 200mL of deionized water is put into a reaction kettle, under the condition of continuous stirring, the mixed solution of copper-zinc-aluminum-lanthanum-manganese and sodium carbonate solution with the mass concentration of 12 wt% are added in a concurrent flow manner, and the reaction is controlledKeeping the pH value at 7.2, raising the temperature of the reaction solution to 65 ℃, continuing to preserve heat and stir for 2 hours after the charging is finished, filtering, washing, drying for 12 hours at 120 ℃, and then roasting for 4 hours at 350 ℃ in a muffle furnace to prepare the catalyst; then adding 1 wt% of graphite and tabletting to form the product. The catalyst contains 55 percent of CuO, 30 percent of ZnO and Al based on the total weight of the catalyst2O38％、La2O35％、MnO 2％。
After the catalyst was prepared, the catalyst activity was evaluated by the following method: in a stainless steel fixed bed reactor, the formed catalyst is reduced by a nitrogen-hydrogen mixture for 6 hours at the temperature of 270 ℃, and then is in contact reaction with hydrogen and maleic anhydride, wherein the reaction conditions are as follows: the reaction temperature is 240 ℃, the pressure is 0.1MPa, and the space velocity of the liquid (maleic anhydride) is 0.1hr-1The molar ratio of maleic anhydride to hydrogen is 1: and 15, condensing the reacted gas to obtain a liquid product. The conversion rate of maleic anhydride was determined to be 100% and the selectivity of gamma-butyrolactone was determined to be 99.7% (see table 1).
Example 2
A catalyst for vapor phase hydrogenation of maleic anhydride to γ -butyrolactone was prepared according to the method of example 1, except that (1) copper nitrate (Cu (NO) was adjusted3)2·3H2O), zinc nitrate (Zn (NO)3)2·6H2O), aluminum nitrate (Al (NO)3)3·6H2O), lanthanum nitrate (La (NO)3)3·6H2O) and manganese nitrate (Mn (NO)3)2) So that the prepared catalyst contained 50% of CuO, 34.5% of ZnO and Al2O37％、La2O36 percent and MnO 2.5 percent, based on the total weight of the catalyst. (2) The copper-zinc-silicon-lanthanum-manganese mixed solution and a sodium carbonate solution with the mass concentration of 12 wt% are added in parallel, the reaction pH value is controlled to be 6.5, the temperature of the reaction solution is increased to 85 ℃, and other preparation methods, process parameters and material using amounts are the same as those in example 1.
After the catalyst was obtained, the catalyst evaluation method was the same as in example 1. The conversion rate of maleic anhydride was determined to be 100% and the selectivity of gamma-butyrolactone was determined to be 99.0% (see table 1).
Example 3
A catalyst for vapor phase hydrogenation of maleic anhydride to γ -butyrolactone was prepared according to the method of example 1, except that (1) copper nitrate (Cu (NO) was adjusted3)2·3H2O), zinc nitrate (Zn (NO)3)2·6H2O), aluminum nitrate (Al (NO)3)3·6H2O), lanthanum nitrate (La (NO)3)3·6H2O) and manganese nitrate (Mn (NO)3)2) So that the catalyst prepared contains CuO 60%, ZnO 25.5%, and Al2O39％、La2O34% and MnO 1.5%, based on the total weight of the catalyst. (2) The copper-zinc-silicon-lanthanum-manganese mixed solution and a sodium carbonate solution with the mass concentration of 12 wt% are added in parallel, the reaction pH value is controlled to be 7.8, the temperature of the reaction solution is increased to 60 ℃, and other preparation methods, process parameters and material using amounts are the same as those in example 1.
After the catalyst was obtained, the catalyst evaluation method was the same as in example 1. The conversion rate of maleic anhydride was determined to be 100% and the selectivity of gamma-butyrolactone 98.6% (see table 1).
Example 4
Weighing copper nitrate (Cu (NO)3)2·3H2O)267.26g, zinc nitrate (Zn (NO)3)2·6H2O) 292.43g, aluminum nitrate (Al (NO)3)3·6H2O)88.31g, lanthanum nitrate (La (NO)3)3·6H2O)37.21g and manganese nitrate (Mn (NO)3)2)30.27g, the other preparation methods and process parameters and the amount of the substances are the same as in example 1. The catalyst contains CuO 44%, ZnO 40% and Al based on the total weight of the catalyst2O36％、La2O37％、MnO 3％。
After the catalyst was obtained, the catalyst evaluation method was the same as in example 1. The conversion rate of maleic anhydride was found to be 99.5% and the selectivity of gamma-butyrolactone 97.1% (see table 1).
Example 5
Weighing copper nitrate (Cu (NO)3)2·3H2O)419.13g, zinc nitrate(Zn(NO3)2·6H2O) 146.22g, aluminum nitrate (Al (NO)3)3·6H2O)58.86g, lanthanum nitrate (La (NO)3)3·6H2O)15.95g and manganese nitrate (Mn (NO)3)2)40.37g, the other preparation methods and process parameters and the amount of the substances are the same as in example 1. The catalyst contains 69 percent of CuO, 20 percent of ZnO and Al based on the total weight of the catalyst2O34％、La2O33％、MnO 4％。
After the catalyst was obtained, the catalyst evaluation method was the same as in example 1. The conversion rate of maleic anhydride was determined to be 100% and the selectivity of gamma-butyrolactone 96.2% (see table 1).
Comparative example 1
Weighing copper nitrate (Cu (NO)3)2·3H2O)334.08g, zinc nitrate (Zn (NO)3)2·6H2O)219.34g and aluminum nitrate (Al (NO)3)3·6H2O)117.72g was dissolved in 2000mL deionized water; firstly, putting 200mL of deionized water into a reaction kettle, adding a copper-zinc-aluminum mixed solution and a sodium carbonate solution with the mass concentration of 12 wt% in a concurrent flow manner under the condition of continuous stirring, controlling the pH value of the reaction to be 7.2, simultaneously raising the temperature of the reaction solution to 65 ℃, continuing to keep the temperature and stir for 2 hours after the addition is finished, filtering, washing, drying for 12 hours at 120 ℃, and then roasting for 4 hours at 350 ℃ in a muffle furnace to prepare the catalyst; then adding 1 wt% of graphite and tabletting to form the product. The catalyst contains CuO 59.14%, ZnO 32.26%, and Al based on the total weight of the catalyst2O38.60％。
After the catalyst was obtained, the catalyst evaluation method was the same as in example 1. The conversion rate of maleic anhydride was determined to be 100% and the selectivity of gamma-butyrolactone 92.8% (see table 1).
Comparative example 2
Weighing copper nitrate (Cu (NO)3)2·3H2O)334.08g, zinc nitrate (Zn (NO)3)2·6H2O)219.34g, aluminum nitrate (Al (NO)3)3·6H2O)117.72g and manganese nitrate (Mn (NO)3)2)70.63g was mixed in 2000mL deionized waterPerforming the following steps; firstly, putting 200mL of deionized water into a reaction kettle, adding a copper-zinc-aluminum-manganese mixed solution and a sodium carbonate solution with the mass concentration of 12 wt% in a concurrent flow manner under the condition of continuous stirring, controlling the pH value of the reaction to be 7.2, simultaneously raising the temperature of the reaction solution to 65 ℃, continuing to keep the temperature and stir for 2 hours after the addition is finished, filtering, washing, drying for 12 hours at 120 ℃, and then roasting for 4 hours at 350 ℃ in a muffle furnace to obtain a catalyst; then adding 1 wt% of graphite and tabletting to form the product. The catalyst contains 55 percent of CuO, 30 percent of ZnO and Al based on the total weight of the catalyst2O38％、MnO 7％。
After the catalyst was obtained, the catalyst evaluation method was the same as in example 1. The conversion rate of maleic anhydride was determined to be 100% and the selectivity of gamma-butyrolactone 94.6% (see table 1).
Comparative example 3
Weighing copper nitrate (Cu (NO)3)2·3H2O)334.08g, zinc nitrate (Zn (NO)3)2·6H2O)219.34g, aluminum nitrate (Al (NO)3)3·6H2O)117.72g and lanthanum nitrate (La (NO)3)3·6H2O)37.21g was dissolved in 2000mL deionized water; firstly, putting 200mL of deionized water into a reaction kettle, adding a copper-zinc-aluminum-lanthanum mixed solution and a sodium carbonate solution with the mass concentration of 12 wt% in a concurrent flow manner under the condition of continuous stirring, controlling the pH value of the reaction to be 7.2, simultaneously raising the temperature of the reaction solution to 65 ℃, continuing to keep the temperature and stir for 2 hours after the addition is finished, filtering, washing, drying for 12 hours at 120 ℃, and then roasting for 4 hours at 350 ℃ in a muffle furnace to prepare the catalyst; then adding 1 wt% of graphite and tabletting to form the product. The catalyst contains 55 percent of CuO, 30 percent of ZnO and Al based on the total weight of the catalyst2O38％、La2O37％。
After the catalyst was obtained, the catalyst evaluation method was the same as in example 1. The conversion rate of maleic anhydride was found to be 99.3% and the selectivity of gamma-butyrolactone was found to be 95.2% (see table 1).
Table 1 comparative catalyst Performance table
| Catalyst and process for preparing same | Maleic anhydride conversion (%) | Gamma-butyrolactone Selectivity (%) |
| Example 1 | 100 | 99.7 |
| Example 2 | 100 | 99.0 |
| Example 3 | 100 | 98.6 |
| Example 4 | 99.5 | 97.1 |
| Example 5 | 100 | 96.2 |
| Comparative example 1 | 100 | 92.8 |
| Comparative example 2 | 100 | 94.6 |
| Comparative example 3 | 99.3 | 95.2 |
As can be seen from Table 1, the catalyst for preparing gamma-butyrolactone by gas-phase catalytic hydrogenation of maleic anhydride containing Cu-Zn-Al-La-Mn elements has high activity and selectivity.
As can be seen from example 1 and comparative example 1, in comparative example 1, because the auxiliary elements La and Mn described in the present invention are not introduced, the selectivity of gamma-butyrolactone is significantly reduced to 92.8% under the same reaction conditions as those of the present invention.
The catalyst of comparative example 2 was prepared without adding La element, and other elements had poor catalytic performance as in example 1, and under the same reaction conditions as in example 1, the conversion of maleic anhydride was 100%, the selectivity of γ -butyrolactone was 94.6%, whereas the conversion of maleic anhydride was 100% and the selectivity of γ -butyrolactone was 99.7% in example 1.
In the catalyst of comparative example 3, no Mn element was added during the preparation of the catalyst, and the other elements had poor catalytic performance as in example 1, and under the same reaction conditions as in example 1, the conversion of maleic anhydride was 99.3%, the selectivity of γ -butyrolactone was 95.2%, whereas the conversion of maleic anhydride was 100% in example 1, and the selectivity of γ -butyrolactone was 99.7%.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A catalyst for preparing gamma-butyrolactone by gas-phase hydrogenation of maleic anhydride is characterized in that the catalyst comprises the following components by weight: 40-70 wt% of CuO, 15-40 wt% of ZnO and Al2O33-10wt％、La2O32-8 wt% and MnO 1-5 wt%.
2. The catalyst of claim 1, wherein the catalyst comprises, based on the total weight of the catalyst: CuO50-60 wt%, ZnO25-35 wt%, Al2O37-9wt％、La2O34-6 wt% and MnO 1.5-2.5 wt%.
3. The catalyst of claim 1, wherein,
the precursor of the copper oxide is selected from at least one of soluble copper salts; preferably at least one of copper nitrate, copper sulfate, copper chloride and copper acetate; more preferably copper nitrate;
the precursor of the zinc oxide is selected from at least one of soluble zinc salts; preferably at least one of zinc nitrate, zinc sulfate, zinc chloride and zinc acetate; further preferably zinc nitrate;
the precursor of the alumina is selected from at least one of soluble aluminum salt; preferably at least one of aluminum nitrate, aluminum sulfate, aluminum chloride and aluminum acetate; further preferably aluminum nitrate;
the precursor of lanthanum oxide is selected from at least one of soluble lanthanum salts; preferably lanthanum chloride and/or lanthanum nitrate; further preferred is lanthanum nitrate;
the precursor of the manganese oxide is selected from at least one of soluble manganese salts; preferably at least one of manganese chloride, manganese acetate and manganese nitrate; more preferably, manganese nitrate.
4. A method for preparing the catalyst according to any one of claims 1 to 3, characterized in that the method comprises: and preparing the precursor solution of each component of the catalyst by a coprecipitation method to obtain the catalyst.
5. The production method according to claim 4, wherein the production method comprises:
(1) uniformly mixing precursors of copper oxide, zinc oxide, aluminum oxide, lanthanum oxide and manganese oxide with water to obtain a mixed solution;
(2) adding an alkali solution and the mixed solution into a reaction kettle containing water for contact reaction to obtain a precipitate;
(3) and filtering, washing, drying and roasting the precipitate to obtain the catalyst.
6. The production method according to claim 5, wherein the step (2) includes: adding the alkali solution and the mixed solution into a reaction kettle containing water in a split parallel flow mode for contact reaction to obtain a precipitate.
7. The production method according to claim 5 or 6,
in the step (2), the temperature of the contact reaction is 40-90 ℃, the pH value of a reaction system is controlled to be 5-8, and the alkali solution is ammonia water and/or sodium carbonate solution;
in the step (3), the drying temperature is 100-120 ℃, and the time is 10-20 h; the roasting temperature is 280-400 ℃ and the roasting time is 2-6 hours.
8. The production method according to claim 5 or 6, wherein the step (3) further comprises mixing the catalyst with graphite, followed by tableting; the graphite is used in an amount of 0.5 to 2 wt% based on the weight of the catalyst.
9. Use of a catalyst according to any one of claims 1 to 3 in the gas phase hydrogenation of maleic anhydride to gamma-butyrolactone.
10. A method for preparing gamma-butyrolactone by maleic anhydride gas-phase hydrogenation is characterized by comprising the following steps:
activating the catalyst of any one of claims 1 to 3, and then carrying out contact reaction with hydrogen and maleic anhydride to prepare gamma-butyrolactone;
wherein the molar ratio of the hydrogen to the maleic anhydride is 10-30: 1, the space velocity of maleic anhydride is 0.1hr-1-0.5hr-1The temperature of the contact reaction is 200-300 ℃, and the pressure is 0.1-0.3 MPa.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4965378A (en) * | 1987-12-23 | 1990-10-23 | The Standard Oil Company | Vapor-phase hydrogenation of maleic anhydride to tetrahydrofuran and gamma-butyrolactone |
| CN103566940A (en) * | 2012-08-01 | 2014-02-12 | 江苏理文化工有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation and preparation method and application thereof |
| CN103566939A (en) * | 2012-08-01 | 2014-02-12 | 江苏理文化工有限公司 | Catalyst for preparing gamma-butyrolactone through normal-pressure gas-phase hydrogenation of maleic anhydride and preparation method and application thereof |
| CN104399484A (en) * | 2014-10-20 | 2015-03-11 | 中科合成油淮南催化剂有限公司 | Catalyst for [gamma]-butyrolactone preparation through dimethyl maleate hydrogenation, and preparation method thereof |
| CN106861703A (en) * | 2017-02-28 | 2017-06-20 | 山西大学 | A kind of catalyst and its preparation method and application for cis-butenedioic anhydride liquid-phase hydrogenatin synthesis gamma butyrolactone |
| CN106914246A (en) * | 2017-02-28 | 2017-07-04 | 山西大学 | The supported nickel catalyst and preparation method and application of cis-butenedioic anhydride liquid-phase hydrogenatin synthesis gamma butyrolactone |
-
2018
- 2018-10-25 CN CN201811251016.4A patent/CN111097444A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4965378A (en) * | 1987-12-23 | 1990-10-23 | The Standard Oil Company | Vapor-phase hydrogenation of maleic anhydride to tetrahydrofuran and gamma-butyrolactone |
| CN103566940A (en) * | 2012-08-01 | 2014-02-12 | 江苏理文化工有限公司 | Catalyst for preparing gamma-butyrolactone through maleic anhydride gas-phase hydrogenation and preparation method and application thereof |
| CN103566939A (en) * | 2012-08-01 | 2014-02-12 | 江苏理文化工有限公司 | Catalyst for preparing gamma-butyrolactone through normal-pressure gas-phase hydrogenation of maleic anhydride and preparation method and application thereof |
| CN104399484A (en) * | 2014-10-20 | 2015-03-11 | 中科合成油淮南催化剂有限公司 | Catalyst for [gamma]-butyrolactone preparation through dimethyl maleate hydrogenation, and preparation method thereof |
| CN106861703A (en) * | 2017-02-28 | 2017-06-20 | 山西大学 | A kind of catalyst and its preparation method and application for cis-butenedioic anhydride liquid-phase hydrogenatin synthesis gamma butyrolactone |
| CN106914246A (en) * | 2017-02-28 | 2017-07-04 | 山西大学 | The supported nickel catalyst and preparation method and application of cis-butenedioic anhydride liquid-phase hydrogenatin synthesis gamma butyrolactone |
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