CN108636440B - Catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and preparation method thereof - Google Patents
Catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and preparation method thereof Download PDFInfo
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- CN108636440B CN108636440B CN201810336749.1A CN201810336749A CN108636440B CN 108636440 B CN108636440 B CN 108636440B CN 201810336749 A CN201810336749 A CN 201810336749A CN 108636440 B CN108636440 B CN 108636440B
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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
- B01J29/00—Catalysts comprising molecular sieves
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention relates to a catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and a preparation method of 1, 3-propylene glycol, wherein the catalyst comprises a molecular sieve, and Pt, X and W loaded on the molecular sieve, wherein X is Mo and/or Co. The preparation method of the 1, 3-propylene glycol comprises the steps of introducing 10-60% by mass of glycerol aqueous solution into the presence of the catalyst at a reaction temperature of 130-200 ℃, introducing hydrogen to control the pressure to be 1-6 MPa and the space velocity to be 0.1-5 h‐1And reacting to generate the 1, 3-propylene glycol. The catalyst has high stability, is suitable for preparing 1, 3-propylene glycol by hydrogenating a glycerol aqueous solution, is used for preparing the 1, 3-propylene glycol by adopting the method, has the advantages of easily obtained raw materials, mild reaction conditions and high reaction temperature, only needs water as a solvent, has high generation rate of the 1, 3-propylene glycol, meets the requirements of green chemical industry, and has great market value and industrial application prospect.
Description
Technical Field
The invention relates to a catalyst for preparing 1, 3-propylene glycol by hydrogenation of a glycerol aqueous solution and a preparation method of the catalyst.
Background
The rapid expansion of biodiesel production capacity around the world causes an excess in the production of by-product glycerol. Thus making glycerol an extremely price attractive raw material.
1, 3-propanediol is an important chemical raw material, polyester fiber trimethylene terephthalate (PTT) synthesized by taking the 1, 3-propanediol as a monomer has the high performance of polyethylene terephthalate (PET) and the easy processability of polybutylene terephthalate (PBT), and has wide application prospect in the fields of producing plasticizers, detergents, preservatives, emulsifiers and the like.
At present, the preparation method of 1, 3-propylene glycol mainly comprises the following steps: ethylene oxide process, acrolein hydration process, microbial fermentation process, and glycerin hydrocatalytic conversion process. The ethylene oxide method and the acrolein hydration method both need two-step reaction to prepare the 1, 3-propylene glycol, and have the disadvantages of complicated reaction process, high equipment requirement and harsh operation conditions; the microbial fermentation method has low product concentration, complicated separation steps, short life of the biological enzyme and strict process requirements; therefore, the process of direct hydrocatalytic conversion using glycerol as a feedstock is the simplest.
Chinese patent CN96198050.8 discloses a method for producing 1, 3-propanediol by carbonylation and hydrogenation of ethylene oxide, and a method for producing 3-hydroxypropionaldehyde by reaction of synthesis gas and ethylene oxide in the presence of a catalyst, and a method for producing 1, 3-propanediol by reaction of 3-hydroxypropionaldehyde and hydrogen in the presence of a catalyst. Chinese patent CN93114516.3 discloses a technique for producing 1, 3-propanediol by acrylic acid hydration hydrogenation, firstly glycerol is dehydrated under the action of a catalyst to produce acrolein, the acrolein is hydrated to produce 3-hydroxypropionaldehyde, and the 3-hydroxypropionaldehyde is reacted with hydrogen under the action of the catalyst to produce 1, 3-propanediol. The two methods have the problems of complicated process, harsh reaction conditions and great environmental pollution.
The literature (appl. Microbiol. Biothechnol.1995,16,79-80) reports a process by which glycerol can be transformed into 1, 3-propanediol by strains of Citrobacter, Klebsiella and Clostridium. But the method has low production efficiency.
The solvents in Chinese patents 200810224899.X and 201010262066.X adopt a compound solvent 1, 3-dimethyl-2-imidazolidinone-water or alcohol-water mixture, and the solvent recovery is complex.
Chinese patent 200910237839.6 uses Pt, W, refractory oxide or its precursor, and the carrier includes ZrO2Or TiO2. However, the yield of 1, 3-propanediol did not exceed 6%.
Disclosure of Invention
The invention aims to provide a catalyst for preparing 1, 3-propylene glycol by hydrogenating a glycerol aqueous solution, and when the catalyst is used for preparing the 1, 3-propylene glycol, the reaction conditions are mild, the reaction is stable, and the solvent is only water.
It is another object of the present invention to provide a process for preparing the above catalyst.
It is a third object of the present invention to provide a process for producing 1, 3-propanediol, which produces 1, 3-propanediol at a high production rate, using the above-mentioned catalyst.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention aims to provide a catalyst for preparing 1, 3-propylene glycol by hydrogenating a glycerol aqueous solution, which comprises a molecular sieve and Pt, X and W loaded on the molecular sieve, wherein X is Mo and/or Co.
Preferably, the mass of the X is 0.1-5% of the total mass of the catalyst.
More preferably, the mass of the X is 0.1-3% of the total mass of the catalyst.
Preferably, the mass of the Pt is 0.1-5% of the total mass of the catalyst.
More preferably, the mass of the Pt is 1-3% of the total mass of the catalyst.
Preferably, the mass of W is 5-20% of the total mass of the catalyst.
More preferably, the mass of W is 10-15% of the total mass of the catalyst.
Preferably, when X is Mo and Co, the mass ratio of Mo to Co is 3-5: 1.
Preferably, the mass percentage of Pt, X and W is 2: 0.5-2.5: 9-11, and more preferably 2: 1-2.5: 9-11.
The invention also aims to provide a preparation method of the catalyst for preparing 1, 3-propylene glycol by hydrogenating the glycerol aqueous solution, which comprises the following steps:
(1) dipping an ammonium metatungstate aqueous solution into a molecular sieve, keeping the temperature of the molecular sieve at 90-100 ℃ for 15-25 hours, then drying the molecular sieve at 105-115 ℃, and roasting the molecular sieve at 650-750 ℃ for 2-4 hours;
(2) soaking the intermediate product prepared in the step (1) in a mixed solution of chloroplatinic acid and molybdenum nitrate, or a mixed solution of chloroplatinic acid and cobalt nitrate, or a mixed solution of chloroplatinic acid, molybdenum nitrate and cobalt nitrate, aging for 8-10 hours, drying, and roasting at 400-500 ℃ for 2-4 hours to prepare the catalyst.
Preferably, the roasting temperature of the step (2) is 450-500 ℃.
The third purpose of the invention is to provide a preparation method of 1, 3-propylene glycol, which comprises the steps of introducing hydrogen into a glycerol aqueous solution with the mass percentage concentration of 10-60% in the presence of a catalyst at the reaction temperature of 130-200 ℃ to control the pressure to be 1-6 MPa, and reacting to generate the 1, 3-propylene glycol, wherein the catalyst is the catalyst.
Preferably, the space velocity of the glycerol aqueous solution is 0.1-0.5 h-1。
Preferably, the reactor is a fluidized bed or a fixed bed.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the catalyst has high stability, is suitable for preparing 1, 3-propylene glycol by hydrogenating a glycerol aqueous solution, is used for preparing the 1, 3-propylene glycol by adopting the method, has the advantages of easily obtained raw materials, mild reaction conditions and high reaction temperature, only needs water as a solvent, has high generation rate of the 1, 3-propylene glycol, meets the requirements of green chemical industry, and has great market value and industrial application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these embodiments are provided to illustrate the basic principles, essential features and advantages of the present invention, and the present invention is not limited by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Example 1
The catalyst is Pt/Mo/W-molecular sieve, and the mass percentage of the metal is Pt: mo: w is 2: 1: 10. the preparation method of the catalyst comprises the steps of 1) dipping the required amount of ammonium metatungstate aqueous solution into the molecular sieve, keeping the temperature at 90 ℃ for 20 hours, drying the molecular sieve at 110 ℃, and roasting the molecular sieve at 700 ℃ for 3 hours to obtain a tungsten-molecular sieve composite oxide carrier; 2) mixing chloroplatinic acid and molybdenum nitrate with required amount with a carrier, soaking for 9 hours, drying at 110 ℃, and roasting at 400 ℃ for 3 hours to obtain the catalyst A.
Example 2
The catalyst is Pt/Mo/W-molecular sieve, and the mass percentage of the metal is Pt: mo: w is 2: 1: 10. the preparation procedure was the same as in example 1 except that the calcination temperature in the second step was changed to 500 ℃ to obtain catalyst B.
Example 3
The catalyst is Pt/Mo/W-molecular sieve, and the mass percentage of the metal is Pt: mo: w is 2: 2: 10. the procedure was the same as in example 1 to obtain catalyst C.
Example 4
The catalyst is Pt/Mo/W-molecular sieve, and the mass percentage of the metal is Pt: mo: w is 2:5: 10. the preparation procedure was the same as in example 1 to obtain catalyst D.
Example 5
The catalyst is Pt/Co/W-molecular sieve, and the mass percentage of metals is Pt: co: w is 2: 0.5: 10. the procedure was the same as in example 1 to obtain catalyst E.
Example 6
The catalyst is Pt/Co/W-molecular sieve, and the mass percentage of metals is Pt: co: w is 2: 1: 10. the procedure was the same as in example 1 to obtain catalyst F.
Example 7
The catalyst is Pt/Co/W-molecular sieve, and the mass percentage of metals is Pt: co: w is 2: 2: 10. the procedure was the same as in example 1 to obtain catalyst G.
Example 8
The catalyst is Pt/Mo/Co/W-molecular sieve, and the mass percentage of the metal is Pt: mo: co: w is 2: 2: 0.5: 10. The procedure was the same as in example 1 to obtain catalyst H.
Comparative example 1
The catalyst is Pt/W-molecular sieve, and the mass percentage of metals is Pt: mo: w is 2: 0: 10. the procedure was the same as in example 1 to obtain catalyst L.
Evaluation of catalyst:
the reaction is carried out on a fixed bed reactor, 10g of catalyst is added into 30 percent glycerol aqueous solution, the reaction temperature is 160 ℃, the hydrogen pressure is 4MPa, and the airspeed of the glycerol aqueous solution is 0.3h-1。
The results of the experiments are given in table 1, wherein the glycerol conversion and the selectivity data of the main products (calculated from the gas chromatography measurements) are given. By comparison, it is found that the addition of Mo and Co can improve the conversion of glycerin and the yield of 1, 3-propanediol, and the effect of Mo is superior to that of Co. The effect of adding Mo and Co simultaneously is better than that of adding Mo and Co independently.
TABLE 1
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (8)
1. A preparation method of 1, 3-propylene glycol is characterized by comprising the following steps: introducing hydrogen into a glycerol aqueous solution with the mass percentage concentration of 10-60% at the reaction temperature of 130-160 ℃ in the presence of a catalyst to control the pressure to be 1-6 MPa, and reacting to generate the 1, 3-propylene glycol, wherein the catalyst comprises a molecular sieve and also comprises Pt, X and W loaded on the molecular sieve, wherein the mass ratio of the Pt, the X and the W is 2: 1-2.5: 9-11, or the mass ratio of the Pt, the X and the W is 2:5: 9-11, and the X is Mo, Co, or Mo and Co;
the preparation method of the catalyst comprises the following steps:
(1) dipping an ammonium metatungstate aqueous solution into a molecular sieve, keeping the temperature of the molecular sieve at 90-100 ℃ for 15-25 hours, then drying the molecular sieve at 105-115 ℃, and roasting the molecular sieve at 650-750 ℃ for 2-4 hours;
(2) soaking the intermediate product prepared in the step (1) in a mixed solution of chloroplatinic acid and molybdenum nitrate, or a mixed solution of chloroplatinic acid and cobalt nitrate, or a mixed solution of chloroplatinic acid, molybdenum nitrate and cobalt nitrate, aging for 8-10 hours, drying, and roasting at 400-500 ℃ for 2-4 hours to prepare the catalyst.
2. The process for producing 1, 3-propanediol according to claim 1, characterized in that: the mass of the X is 0.1-5% of the total mass of the catalyst.
3. The process for producing 1, 3-propanediol according to claim 2, characterized in that: the mass of the X is 0.1-3% of the total mass of the catalyst.
4. The process for producing 1, 3-propanediol according to claim 1, characterized in that: the mass of the Pt is 0.1-5% of the total mass of the catalyst.
5. The process for producing 1, 3-propanediol according to claim 4, characterized in that: the mass of the Pt is 1-3% of the total mass of the catalyst.
6. The process for producing 1, 3-propanediol according to claim 1, characterized in that: the mass of W is 5-20% of the total mass of the catalyst.
7. The process for producing 1, 3-propanediol according to claim 6, characterized in that: the mass of W is 10-15% of the total mass of the catalyst.
8. The process for producing 1, 3-propanediol according to claim 1, characterized in that: when the X is Mo and Co, the mass ratio of the Mo to the Co is 3-5: 1.
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| CN201810336749.1A CN108636440B (en) | 2018-04-16 | 2018-04-16 | Catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and preparation method thereof |
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| CN113429260B (en) * | 2021-05-24 | 2023-04-07 | 中科合成油技术股份有限公司 | Method for preparing propylene glycol by catalytic hydrogenolysis of glycerol |
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| CN106552623A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of load type double-metal component catalyst and preparation method thereof and hydrogenolysis of glycerin reaction method |
| CN106824191A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院大连化学物理研究所 | Application of the bimetallic catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols |
| CN106883098A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | Application of the multiple active components catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols |
| CN107096564A (en) * | 2017-06-05 | 2017-08-29 | 扬州大学 | The supporting Pts of SAPO 34 and WOx a kind of catalyst and preparation method thereof |
| CN107159300A (en) * | 2017-06-27 | 2017-09-15 | 太原理工大学 | A kind of support type mesoporous molecular sieve catalyst and its preparation method and application |
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| US8629310B2 (en) * | 2012-03-09 | 2014-01-14 | Phillips 66 Company | Transportation fuels from biomass oxygenates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106552623A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of load type double-metal component catalyst and preparation method thereof and hydrogenolysis of glycerin reaction method |
| CN106824191A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院大连化学物理研究所 | Application of the bimetallic catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols |
| CN106883098A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | Application of the multiple active components catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols |
| CN107096564A (en) * | 2017-06-05 | 2017-08-29 | 扬州大学 | The supporting Pts of SAPO 34 and WOx a kind of catalyst and preparation method thereof |
| CN107159300A (en) * | 2017-06-27 | 2017-09-15 | 太原理工大学 | A kind of support type mesoporous molecular sieve catalyst and its preparation method and application |
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