CN114539191B - Method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method - Google Patents
Method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method Download PDFInfo
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- CN114539191B CN114539191B CN202210287126.6A CN202210287126A CN114539191B CN 114539191 B CN114539191 B CN 114539191B CN 202210287126 A CN202210287126 A CN 202210287126A CN 114539191 B CN114539191 B CN 114539191B
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- C07—ORGANIC CHEMISTRY
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- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention discloses a method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method, belonging to the technical field of fine chemical engineering, comprising the following steps: maleic anhydride and 1, 4-butanediol are mixed according to the mole ratio of 1 (1-2), and the space velocity of liquid feeding is 1.0-2.5 h ‑1 The reaction is carried out under the action of hydrogen and a catalyst, the reaction pressure is 0.07-0.08 MPa, the reaction temperature is 200-240 ℃, wherein, H 2 The molar ratio of maleic anhydride to the mixture of maleic anhydride and 1, 4-butanediol is (10-25): 1; and then separating and purifying the product after the reaction.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method.
Background
Gamma-butyrolactone, also known as 4-hydroxybutyrolactone (GBL), has a structure of a compound containing a five-membered heterocyclic ring, is a colorless liquid, has an acetone-like smell, and has the characteristics of high boiling point and high dissolution capacity. The catalyst has the advantages of good reaction performance, high conductivity, good stability and safe use. Gamma-butyrolactone is used as an important organic solvent and is widely used in petroleum industry, medicine, synthetic fiber, synthetic resin, pesticide and other fields. As an important fine chemical and organic chemical raw material, the method is mainly used for synthesizing products such as pyrrolidone, N-methyl pyrrolidone, vinyl pyrrolidone and the like.
According to the classification of synthetic raw materials, the industrialized synthesis method of gamma-butyrolactone mainly comprises two methods of a maleic anhydride hydrogenation method and a 1, 4-butanediol dehydrogenation method. The 1, 4-butanediol dehydrogenation method generally adopts a gas phase dehydrogenation method, a Cu-based catalyst and byproduct hydrogen are usually exhausted or used as fuel at present, the use efficiency is low, and the production cost is high. When the maleic anhydride is hydrogenated to produce gamma-butyrolactone, tetrahydrofuran (THF) is co-produced, and the yield ratio of THF and gamma-butyrolactone can be regulated and controlled according to the requirement. However, maleic anhydride hydrogenation is gradually eliminated because of the problems of low catalyst productivity, short service life, unstable production device operation and the like. In order to overcome the defects of the two processes, the gamma-butyrolactone is prepared by coupling reaction, so that the maleic anhydride hydrogenation reaction and the 1, 4-butanediol dehydrogenation reaction are complementary in material and energy, and the same target product GBL is generated, thereby effectively improving the utilization rate of raw materials and reducing the production cost.
Disclosure of Invention
The invention aims to provide a method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method, which can effectively improve the raw material utilization rate and the target product yield.
Based on the above purpose, the invention adopts the following technical scheme: a method for preparing GBL by maleic anhydride hydrogenation and 1,4 butanediol dehydrogenation coupling method comprises the following steps: maleic anhydride and 1, 4-butanediol are mixed according to the mole ratio of 1 (1-2), and the space velocity of liquid feeding is 1.0-2.5 h -1 The reaction is carried out under the action of hydrogen and a catalyst, the reaction pressure is 0.07-0.08 MPa, the reaction temperature is 200-240 ℃, wherein, H 2 The mole ratio of maleic anhydride/1, 4-butanediol mixture is (10-25): 1, a step of; and then separating and purifying the product after the reaction. Wherein the structural molecular formula of maleic anhydride is
The reaction formula of maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling is
Further, the catalyst takes expanded graphite as a carrier, and RuO2 ruthenium oxide, sm2O3 samarium oxide and CuO are loaded on the carrier, wherein the dosage ratio of the expanded graphite to the metal oxide is (1-1.5): 1, cuO,RuO 2 And Sm 2 O 3 The molar ratio of (2) is 5: (0.5-4): (1-5).
Further, the catalyst is prepared by the following method:
(1) Cu (NO) 3 ) 2 ·3H 2 O、N 4 O 10 Ru、Sm(NO 3 ) 3 Dissolving Cu in water to obtain mixed salt solution 2+ 、Ru + 、Sm 3+ The molar ratio of (2) is 5: (0.5-4): (2-10), synchronously adding a sodium carbonate solution with the concentration of 1mol/L and expanded graphite powder into the mixed salt solution under the condition of intense stirring, performing coprecipitation reaction at the constant temperature of 70 ℃ in a water area, controlling the pH value of a reaction system to be 7.0-7.5, and stopping stirring after the dripping is finished; standing at 70deg.C for 30min, standing at room temperature for 20-30 hr, filtering, washing precipitate, drying at 150deg.C, and roasting at 350deg.C in an atmosphere furnace for 4 hr;
(2) And (3) reducing the roasted solid in a hydrogen-nitrogen mixed gas for 8 hours, wherein the reduction temperature is from room temperature to 300 ℃ at a speed of 5 ℃ per minute, and the gas flow is 50mL/min, so as to obtain the activated catalyst.
Preferably, the expanded graphite has an initial expansion temperature of 290-300 ℃ and a high initial expansion temperature with an expansion volume of more than or equal to 230 ml/g.
Preferably, the mole ratio of maleic anhydride to 1, 4-butanediol is 1:1.55.
Preferably, the liquid feed space velocity is 2.5h -1 。
(1) The invention prepares gamma-butyrolactone by coupling reaction, so that maleic anhydride hydrogenation reaction and 1, 4-butanediol dehydrogenation reaction are complementary in material and energy, hydrogen generated by 1, 4-butanediol dehydrogenation reaction can be reduced without emptying, hydrogen source can be directly provided for maleic anhydride hydrogenation reaction, the use amount of hydrogen is reduced, the same target product GBL is generated, and meanwhile, a small amount of hydrogen is additionally supplemented, so that the reaction is ensured to be full, the raw material utilization rate is effectively improved, and the production cost is reduced.
(2) The catalyst adopted by the invention takes the expanded graphite as a carrier, and ruthenium oxide RuO is loaded on the expanded graphite carrier 2 Sm oxide 2 O 3 And CuO, whichMiddle CuO, ruO 2 And Sm 2 O 3 The molar ratio of (2) is 5: (0.5-4): (1-5), especially RuO 2 、Sm 2 O 3 And the molar ratio of CuO is 5:4:1, the catalytic effect is optimal. Wherein, the expanded graphite is loose and porous, has good compression rebound resilience and adsorptivity, and is loaded with RuO 2 、Sm 2 O 3 After the CuO is added, the CuO is taken as an activation center, and RuO is taken as an activation center 2 And Sm 2 O 3 As an auxiliary agent, the selectivity of gamma-butyrolactone can be effectively improved.
The method of the invention has the advantages of convenient preparation, higher activity and selectivity of the catalyst, the maleic anhydride conversion rate is more than or equal to 99.5 percent, the 1, 4-butanediol conversion rate is more than or equal to 99.5 percent, and the yield of gamma-butyrolactone is more than or equal to 98.6 percent.
Detailed Description
The present invention will be described in further detail by way of the following specific examples, which are not intended to limit the scope of the present invention.
Catalyst composition discussion Performance test
Example 1-1
(1) Preparation of the catalyst: cu (NO) 3 ) 2 ·3H 2 O、N 4 O 10 Ru、Sm(NO 3 ) 3 Dissolving Cu in water to obtain mixed salt solution 2+ 、Ru + 、Sm 3+ The molar ratio of (2) is 5:4:2, synchronously adding a sodium carbonate solution with the concentration of 1mol/L and expanded graphite powder into the mixed salt solution under the condition of intense stirring, performing coprecipitation reaction under the constant-temperature water area at 70 ℃, controlling the pH value of a reaction system to be 7.0-7.5, and stopping stirring after the dripping is finished; standing at 70deg.C for 30min, standing at room temperature for 20-30 hr, filtering, washing precipitate, drying at 150deg.C, and roasting at 350deg.C in an atmosphere furnace for 4 hr;
(2) Reducing the roasted solid in a hydrogen-nitrogen mixed gas for 8 hours, wherein the reduction temperature is from room temperature to 300 ℃ at a speed of 5 ℃ per minute, the gas flow is 50mL/min, and an activated catalyst is obtained, the catalyst takes expanded graphite with an initial expansion temperature of 290-300 ℃ and a high initial expansion temperature, the expansion volume of which is more than or equal to 230mL/g, as a carrier, and RuO2 ruthenium oxide, sm2O3 samarium oxide and CuO are loaded on the carrier, wherein the catalyst comprises a catalyst body, a catalyst body and a catalyst body, wherein the catalyst body comprises a catalyst body and a catalyst body, and the catalyst body comprises a catalyst body, wherein the catalyst body comprises a catalyst body and a catalyst body, and the catalyst body comprises a catalystThe mass ratio of the expanded graphite to the metal oxide is 1:1, cuO, ruO 2 And Sm 2 O 3 The molar ratio of (2) is 5:4:1.
(3) Synthesis of GBL: the method comprises the following steps: maleic anhydride and 1, 4-butanediol are mixed according to the mol ratio of 1:1.55, and the space velocity of liquid feeding is 1.5h -1 The reaction is carried out under the action of hydrogen and a catalyst, the reaction pressure is 0.07-0.08 MPa, the reaction temperature is 200 ℃, wherein, H 2 The molar ratio of maleic anhydride/1, 4-butanediol mixture to maleic anhydride was 20:1, a step of; and then separating and purifying the product after the reaction.
Examples 1-2, examples 1-3 and examples 1-4 differ from example 1-1 in that CuO, ruO 2 And Sm 2 O 3 The molar ratio of (2) is different and the specific parameters are shown in Table 1.
Comparative example 1 preparation of CuO and RuO by coprecipitation reaction 2 And Sm 2 O 3 Catalyst, no carrier
(1) Preparation of the catalyst: cu (NO) 3 ) 2 ·3H 2 O、N 4 O 10 Ru、Sm(NO 3 ) 3 Dissolving Cu in water to obtain mixed salt solution 2+ 、Ru + 、Sm 3+ The molar ratio of (2) is 5:4:2, the concentration of copper nitrate in the mixed solution is 0.81mol/L.
(2) Synchronously dripping the mixed solution prepared in the step (1) and 1mol/L sodium carbonate solution with the same volume into a reaction container with a certain amount of distilled water, performing coprecipitation reaction at a constant temperature of 70 ℃, stirring in the reaction process, controlling the pH of a reaction system to be 7.0-7.5, and stopping stirring after the dripping of the mixed solution is finished; standing the reaction mixture at 70 ℃ for 30min, and standing at room temperature for 20h; the reaction mixture after standing was then filtered to obtain a precipitate.
(3) Drying the precipitate, and roasting at 350 ℃ for 4 hours to obtain the catalyst.
TABLE 1 catalytic performance results for catalysts of different compositions
As can be seen from Table 1, in example 1, cuO: ruO 2 :Sm 2 O 3 When the catalyst is used for catalyzing maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling to prepare gamma-butyrolactone, the conversion rate of maleic anhydride and 1, 4-butanediol is highest, and the gamma-butyrolactone yield is highest. The porous expanded graphite is used as a carrier in the catalyst, so that the catalyst has good compression rebound resilience and adsorptivity, and components in the catalyst can be effectively dispersed on the surface of the expanded graphite and in pore channels of the expanded graphite, so that the specific surface area and the number of active sites of the catalyst are improved, the catalytic efficiency is high, and the selectivity is good.
(II) Hydrogen usage tests of examples 2-1 to 2-3
A method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method comprises the following steps:
maleic Anhydride (MA) and 1, 4-Butanediol (BDO) according to the mol ratio of 1:1.55 and the space velocity of liquid feeding of 1.5h -1 The reaction is carried out under the action of hydrogen and a catalyst (the catalyst prepared in example 1) at a reaction pressure of 0.07-0.08 MPa and a reaction temperature of 200 ℃, wherein in the different examples H 2 The molar ratio to MA/BDO is shown in Table 2; and then separating and purifying the product after the reaction.
TABLE 2 influence of different Hydrogen usage on the experimental results
Examples | H 2 Molar ratio to MA/BDO | Maleic anhydride conversion (%) | 1, 4-butanediolConversion (%) | GBL yield (%) |
Example 1-1 | 25 | 100 | 99.9 | 99.1 |
Example 2-1 | 20 | 99.9 | 99.9 | 99.1 |
Example 2-2 | 15 | 99.5 | 99.9 | 98.8 |
Examples 2 to 3 | 10 | 98.8 | 99.9 | 98.6 |
As can be seen from the experimental results of Table 2, when H 2 When the mole ratio of MA/BDO is 25:1, the conversion rate of maleic anhydride and 1, 4-butanediol is highest, and the yield of gamma-butyrolactone is highest, but the overall change is not great, because the maleic anhydride hydrogenation reaction and the 1, 4-butanediol dehydrogenation reaction are complemented in terms of materials and energy, the requirement for hydrogen is greatly reduced, only a small amount of hydrogen is needed to be supplemented, and the smooth progress of the maleic anhydride hydrogenation reaction is stimulated.
(III) experiment of the amounts of maleic anhydride and 1, 4-butanediol used in examples 3-1 and 3-2
A method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method comprises the following steps:
the molar ratio of Maleic Anhydride (MA) to 1, 4-Butanediol (BDO) is shown in Table 3, the space velocity of the liquid feed is 1.5h -1 Is reacted under the action of hydrogen and catalyst (the catalyst prepared in example 1-1) at 0.07-0.08 MPa and 200 deg.C and H 2 The molar ratio of MA to BDO is 20:1; and then separating and purifying the product after the reaction.
TABLE 3 influence of the molar ratios of different maleic anhydride to 1, 4-butanediol on the experimental results
Examples | Molar ratio of MA to BDO | Maleic anhydride conversion (%) | Conversion of 1, 4-butanediol (%) | GBL yield (%) |
Example 1-1 | 1:1.55 | 100 | 99.9 | 99.1 |
Example 3-1 | 1:1 | 99.5 | 99.9 | 98 |
Example 3-2 | 1:2 | 99.8 | 99.9 | 99.1 |
As can be seen from the experimental results in Table 3, when the molar ratio of MA to BDO is 1:1.55, i.e. 1-4 butanediol is slightly excessive, the conversion of MA and BDO is highest, and the yield of gamma-butyrolactone is also highest. When the ratio is less than 1:1.55, the dehydrogenation amount of the 1, 4-butanediol is less than the hydrogenation amount of the maleic anhydride, the reaction of preparing GBL by hydrogenating the maleic anhydride is incomplete, and the yield of GBL is reduced. When the dehydrogenation amount of the 1, 4-butanediol is larger than that of the maleic anhydride, and a large amount of hydrogen is discharged, so that resource waste is caused.
(IV) liquid feed space velocity experiment of examples 4-1 to 4-3
A method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method comprises the following steps:
maleic Anhydride (MA) and 1, 4-Butanediol (BDO) were reacted at a molar ratio of 1:1.55 and liquid feed space velocity as shown in Table 4 using the catalyst prepared in example 1 at a reaction pressure of 0.07 to 0.08MPa and a reaction temperature of 200℃wherein H 2 The molar ratio of MA to BDO is 20:1; and then separating and purifying the product after the reaction.
TABLE 4 influence of the molar ratios of different maleic anhydride to 1, 4-butanediol on the experimental results
Examples | Space velocity/h of liquid feed -1 | Maleic anhydride conversion (%) | 1-4 butanediol conversion (%) | GBL yield (%) |
Example 4-1 | 1.0 | 100 | 99.9 | 99.2 |
Example 1-1 | 1.5 | 100 | 99.9 | 99.1 |
Example 4-2 | 2.0 | 99 | 99.8 | 99.0 |
Examples 4 to 3 | 2.5 | 98 | 99.5 | 98.9 |
As can be seen from the experimental results in Table 4, when the space velocity of the liquid feed was 1.0h -1 The conversion rate of MA and BDO is highest, and the yield of gamma-butyrolactone is also highest. But at a smaller space velocity, the same throughput is requiredThe amount of catalyst required is large, and the reactor volume is large, so that the space velocity of liquid feed is selected to be 1.5h from the aspect of economic adaptability -1 As the optimal liquid feed space velocity.
Claims (5)
1. A method for preparing GBL by maleic anhydride hydrogenation and 1,4 butanediol dehydrogenation coupling method, which is characterized by comprising the following steps: maleic anhydride and 1, 4-butanediol are mixed according to the mole ratio of 1 (1-2), and the space velocity of liquid feeding is 1.0-2.5 h -1 The reaction is carried out under the action of hydrogen and a catalyst, the reaction pressure is 0.07-0.08 MPa, the reaction temperature is 200-240 ℃, wherein, H 2 The molar ratio of maleic anhydride to the mixture of maleic anhydride and 1, 4-butanediol is (10-25): 1; then separating and purifying the product after the reaction; the catalyst takes expanded graphite as a carrier, and RuO is loaded on the carrier 2 、Sm 2 O 3 And CuO, wherein the mass ratio of the expanded graphite to the metal oxide is (1 to 1.5): 1, cuO, ruO 2 And Sm 2 O 3 The molar ratio of (2) is 5: (0.5-4): (1-5).
2. The method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method according to claim 1, wherein the catalyst is prepared by the following steps:
(1) Cu (NO) 3 ) 2 •3H 2 O、N 4 O 10 Ru、Sm(NO 3 ) 3 Dissolving Cu in water to obtain mixed salt solution 2+ 、Ru + 、Sm 3+ The molar ratio of (2) is 5: (0.5-4): (2-10), synchronously adding a sodium carbonate solution with the concentration of 1mol/L and expanded graphite powder into the mixed salt solution under the condition of intense stirring, performing coprecipitation reaction at the constant temperature of 70 ℃ in a water area, controlling the pH value of a reaction system to be 7.0-7.5, and stopping stirring after the dripping is finished; standing at 70deg.C for 30min, standing at room temperature for 20-30 hr, filtering, washing precipitate, drying at 150deg.C, and roasting at 350deg.C in nitrogen atmosphere furnace for 4 hr;
(2) And (3) reducing the roasted solid in a hydrogen-nitrogen mixed gas for 8 hours, wherein the reduction temperature is from room temperature to 300 ℃ at a speed of 5 ℃ per minute, and the gas flow is 50mL/min, so as to obtain the activated catalyst.
3. The method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method according to claim 1 or 2, wherein the expanded graphite is expanded graphite with an initial expansion temperature of 290-300 ℃ and a high initial expansion temperature, wherein the expansion volume of the expanded graphite is more than or equal to 230 ml/g.
4. The method for preparing GBL by coupling maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation according to claim 1, wherein the mole ratio of maleic anhydride to 1, 4-butanediol is 1:1.55.
5. The method for preparing GBL by coupling maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation according to claim 1, wherein the liquid feeding space velocity is 2.5h -1 。
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CN1562474A (en) * | 2004-03-16 | 2005-01-12 | 中国科学院山西煤炭化学研究所 | Coupled method of preparing catalyst of gamma-butyolactone and usage |
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CN1562474A (en) * | 2004-03-16 | 2005-01-12 | 中国科学院山西煤炭化学研究所 | Coupled method of preparing catalyst of gamma-butyolactone and usage |
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 |
WO2021115813A1 (en) * | 2019-12-10 | 2021-06-17 | Basf Se | Process for producing 1,4-butanediol, gamma-butyrolactone and tetrahydrofuran in the gas phase while avoiding polymeric deposits |
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