CN111233655B - Method for preparing glutaric acid from aldopentose diacid - Google Patents
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- CN111233655B CN111233655B CN202010212305.4A CN202010212305A CN111233655B CN 111233655 B CN111233655 B CN 111233655B CN 202010212305 A CN202010212305 A CN 202010212305A CN 111233655 B CN111233655 B CN 111233655B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention provides a method for preparing glutaric acid from aldopentose diacid, which comprises the following steps: firstly, in aqueous solution, aldopentose diacid is on a catalyst A to obtain 2, 4-dihydroxy glutaric acid; in the second step, glutaric acid is further obtained on catalyst B. According to the invention, water is used as a reaction solvent, no extra halogen element is introduced, the used heterogeneous catalyst can be recycled, and the whole production process is relatively green.
Description
Technical Field
The invention belongs to the field of preparation of chemical raw materials, and particularly relates to a method for preparing glutaric acid from aldopentose diacid.
Background
Glutaric acid, commonly known as mucic acid, is an important chemical raw material and an organic intermediate, and plays an important role in various fields. In the field of polymers, the initiator can be used for synthesizing resin and rubber. In the field of organic synthesis, the method can be used for preparing dimethyl glutarate, dibutyl glutarate, glutaric anhydride and the like. In the field of medicine, glutaric acid and derivatives thereof peroxyglutaric acid can be used for sterilization, disinfection and the like. The adipic acid can be industrially recovered from byproducts of adipic acid production, but the process is excessively dependent on the production of the adipic acid, and a large amount of greenhouse gases such as nitrogen oxides and the like are generated in the production process, so that the environment is seriously polluted. Therefore, the development of a green glutaric acid production process has very important application value. Xylose, arabinose and other aldopentoses are constituent units of hemicellulose, which can be selectively oxidized to aldopentose diacid. Starting from a biomass raw material which is a renewable resource and is aldopentose diacid, a heterogeneous catalysis method is adopted, water is used as a solvent, and green and efficient glutaric acid production is not reported.
At present, only one patent (US20100317825a1) reports a process for producing glutaric acid from aldopentose diacid, but in the process, glacial acetic acid with strong corrosiveness is used as a solvent, and hydrobromic acid, hydroiodic acid and the like are used as catalysts for activating a C-O bond, so that the production cost is high, the requirement on the corrosion resistance of equipment is extremely high, and the environment pollution is inevitable in the production process.
Disclosure of Invention
The invention aims to provide a method for preparing glutaric acid from aldopentose diacid, and the method has the advantages of low production cost, greenness, sustainability and environmental friendliness in the reaction process.
The method for preparing glutaric acid from aldopentose diacid comprises the following steps:
1) reacting aldopentose diacid with hydrogen in aqueous solution in the presence of a catalyst A to obtain 2, 4-dihydroxyglutaric acid;
2) reacting the 2, 4-dihydroxyglutaric acid in step 1) in an aqueous solution in the presence of a catalyst B to obtain glutaric acid.
In step 1) of the above process, the aldopentose diacid may be selected from at least one of: xylaric acid (English name: Xylaric acid, CAS number: 10158-64-2), D-arabinonic acid (English name: D-Arabinoic acid, CAS number: 20869-04-9), L-arabinonic acid (English name: L-Arabinoic acid, CAS number: 608-54-8), and ribonic acid (English name: Ribaronic acid, CAS number: 33012-62-3).
In the step 1), the mass percentage of the aldopentose diacid in the aqueous solution can be 0.5-20%, specifically 1% or 5-10%;
in the above method step 1), the mass ratio of the aldopentose diacid to the catalyst a may be 1: 0.5-2, specifically 1: 0.5, 1: 0.67, 1:1 or 1: 2.
in the step 1), the reaction temperature of the first step reaction can be 120-180 ℃, specifically 120 ℃, 150 ℃ or 150-180 ℃;
the reaction time of the first step reaction can be 2-20 h, specifically 10h or 10-15 h;
the hydrogen partial pressure of the first step reaction can be 1 MPa-4 MPa, and specifically can be 1MPa, 2MPa or 2-3 MPa.
In the step 2) of the method, the mass ratio of the catalyst B to the aldopentose diacid in the step 1) can be 0.5-4: 1, specifically, it may be 0.5: 1. 1.25: 1. 1.33:1, 2: 1 or 4: 1.
the reaction temperature of the second step reaction is 180-250 ℃, and specifically can be 200 ℃ or 180-210 DEG C
The reaction time of the second step reaction can be 2-20 h, specifically 10h, 15h or 10-20 h;
the hydrogen partial pressure of the second step reaction can be 1 MPa-4 MPa, and specifically can be 1MPa, 2MPa or 2-3 MPa.
In the above method, the catalyst a is a supported noble metal catalyst; the catalyst B is a catalyst formed by a supported noble metal catalyst and a supported metal oxide catalyst in a mechanical mixing mode.
The loading amount of the noble metal in the supported noble metal catalyst can be 0.5-5%, and specifically can be 1%.
The loading amount of the metal oxide in the supported metal oxide catalyst can be 2-20%, and specifically can be 10%;
in the catalyst B, the mass ratio of the supported noble metal catalyst to the supported metal oxide catalyst can be 1: 1-10, and specifically can be 1:4 or 1: 1.
The noble metal in the supported noble metal catalyst comprises at least one of Pd, Pt, Ru, Rh and Ir;
the metal oxide in the supported metal oxide catalyst comprises ReOx、MoOx、VOx、NbOxAnd WOxAt least one of;
the supported noble metal catalyst, the support of the supported metal oxide catalyst, comprises at least one of silica, zirconia, titania, and ceria.
Specifically, the supported noble metal catalyst can be TiO2Supported Pd catalyst (e.g. 1% Pd/TiO)2A catalyst); the supported metal oxide catalyst can be TiO2Loaded MoO3Catalyst (e.g. 10% MoO)3/TiO2A catalyst).
In the above method, the first-step reaction and the second-step reaction may be carried out in different reactors; the first-step reaction and the second-step reaction may also be carried out in the same reactor.
When the first-step reaction and the second-step reaction are carried out in the same reactor (i.e., one-pot method), the method for preparing glutaric acid from aldopentose diacid comprises the steps of: adding an aqueous solution of glutaric acid, a catalyst A and a catalyst B into a reaction vessel, and carrying out the first-step reaction and then the second-step reaction to obtain glutaric acid.
The reaction conditions of the one-pot process are as described above.
The invention has the following advantages:
according to the invention, water is used as a reaction solvent, no extra halogen element is introduced, the used heterogeneous catalyst can be recycled, and the whole production process is relatively green.
Drawings
FIG. 1 is a reaction scheme for the preparation of glutaric acid starting from aldopentose diacid according to the present invention.
Detailed Description
The present invention is described below with reference to specific embodiments, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the following examples, specific catalysts were prepared as follows:
1、TiO2preparation of Supported Pd catalyst
With 1% Pd/TiO2The preparation of the catalyst is illustrated by way of example and not by way of limitation.
560 mg of 10 wt% Pd (NH)3)4(NO3)2The aqueous solution was mixed with 20 mL of deionized water, and 2g of TiO was added2The support was stirred at room temperature for 8h, the solvent was evaporated to dryness on a rotary evaporator and then dried in an oven at 120 ℃ for 10 h. Calcining at 400 deg.C in air for 3 hr, and adding 20% H2+N2Reducing for 1 h at the temperature of 300 ℃ to obtain 1 percent Pd/TiO2A catalyst. The supported amount of Pd was 1% (mass%).
2、TiO2Loaded MoO3Preparation of the catalyst
At 10% MoO3/TiO2The preparation of the catalyst is illustrated by way of example and not by way of limitation.
368 mg ammonium heptamolybdate was mixed with 20 mL deionized water and 2g TiO was added2The support was stirred at room temperature for 8h, the solvent was evaporated to dryness on a rotary evaporator and then dried in an oven at 120 ℃ for 10 h. Roasting at 500 deg.C in air for 4h to obtain 10% MoO3/TiO2A catalyst. MoO3The loading amount of (B) was 10% (mass%).
Example 1 two-pot two-step Process for the preparation of glutaric acid from aldopentose diacid in aqueous solution
This is illustrated by way of example and not limitation with respect to xylaric acid.
The first step of reaction:
in a 50mL autoclave, 0.2g of 2% Pd/TiO was added2The method comprises the following steps of sealing a reaction kettle by using a catalyst and 15mL of 2 mass percent aqueous solution of xylaric acid, filling 2MPa hydrogen into the reaction kettle after washing for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 150 ℃, and stirring and reacting for 10 hours at the rotating speed of 600 rpm. After the reaction is finished, cooling to room temperature in ice water bath, carrying out vacuum filtration, wherein the filtrate is 2, 4-dihydroxy glutaric acid, and the yield is 97%.
The second step of reaction:
in a 50mL autoclave, 0.2g of 10% MoO was added3/TiO20.05g of 1% Pd/TiO2And (3) sealing the reaction kettle by using the catalyst and the 2, 4-dihydroxy glutaric acid aqueous solution obtained in the first step, filling 2MPa hydrogen into the reaction kettle after washing for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting for 15 hours at the rotating speed of 600 rpm. After the reaction was completed, the reaction mixture was cooled to room temperature in an ice-water bath, and then vacuum filtered to obtain glutaric acid with a yield of 93% (based on xylaric acid).
Example 2 two-pot two-step Process for the preparation of glutaric acid from aldopentose diacid in aqueous solution
This is illustrated by way of example and not limitation with respect to D-arabinonic acid.
The first step of reaction:
in a 50mL autoclave, 0.2g of 2% Pd/TiO was added2Catalyst and 15mL of 2 mass percent of D-ArabiaThe method comprises the following steps of filling 2MPa hydrogen into a saccharic acid aqueous solution after a reaction kettle is sealed and washed with 2MPa hydrogen for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 150 ℃, and stirring and reacting for 10 hours at the rotating speed of 600 rpm. After the reaction is finished, cooling to room temperature in ice water bath, carrying out vacuum filtration, wherein the filtrate is 2, 4-dihydroxy glutaric acid, and the yield is 94%.
The second step of reaction:
in a 50mL autoclave, 0.2g of 10% MoO was added3/TiO20.05g of 1% Pd/TiO2And (3) sealing the reaction kettle by using the catalyst and the 2, 4-dihydroxy glutaric acid aqueous solution obtained in the first step, filling 2MPa hydrogen into the reaction kettle after washing for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting for 15 hours at the rotating speed of 600 rpm. After the reaction is finished, cooling to room temperature in an ice-water bath, and carrying out vacuum filtration to obtain glutaric acid with the yield of 91% (based on D-arabic acid).
Example 3 one-pot two-step preparation of glutaric acid from aldopentose diacid in aqueous solution
This is illustrated by way of example and not limitation with respect to xylaric acid.
In a 50mL autoclave, 0.2g of 10% MoO was added3/TiO20.2g of 1% Pd/TiO2The method comprises the following steps of (1) sealing a reaction kettle by using a catalyst and 15mL of 2 mass percent aqueous solution of xylaric acid, filling 2MPa hydrogen into the reaction kettle after washing for three times, heating the reaction kettle on a heating furnace to the reaction temperature of 150 ℃, and stirring and reacting for 15 hours at the rotating speed of 600 rpm; then the temperature is increased to 200 ℃, and the reaction is continued for 15 h. After the reaction was completed, the reaction mixture was cooled to room temperature in an ice-water bath, and then vacuum filtered to obtain glutaric acid with a yield of 91% (based on xylaric acid).
Example 4 one-pot two-step preparation of glutaric acid from aldopentose diacid in aqueous solution
This is illustrated by way of example and not limitation with respect to D-arabinonic acid.
In a 50mL autoclave, 0.2g of 10% MoO was added3/TiO20.2g of 1% Pd/TiO2The method comprises the following steps of (1) sealing a reaction kettle by using a catalyst and 15mL of an aqueous solution of arabinonic acid with the mass percentage of 2%, filling 2MPa hydrogen into the reaction kettle after washing for three times, filling the 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 150 ℃, and stirring and reacting for 15 hours at the rotating speed of 600 rpm; then the temperature is increased to 200 ℃, and the reaction is continued for 15 h. After the reaction is finished, cooling to room temperature in an ice-water bath, and carrying out vacuum filtration to obtain glutaric acid with the yield of 89% (based on D-arabic acid).
Claims (6)
1. A process for the preparation of glutaric acid from aldopentose diacid comprising the steps of:
1) reacting aldopentose diacid with hydrogen in aqueous solution in the presence of a catalyst A in a first step to obtain 2, 4-dihydroxyglutaric acid;
2) in the presence of a catalyst B, carrying out a second-step reaction on the 2, 4-dihydroxy glutaric acid obtained in the step 1) in an aqueous solution to obtain glutaric acid;
the catalyst A is a supported noble metal catalyst;
the catalyst B is a catalyst formed by a supported noble metal catalyst and a supported metal oxide catalyst in a mechanical mixing mode;
the noble metal in the supported noble metal catalyst comprises at least one of Pd, Pt, Ru, Rh and Ir;
the metal oxide in the supported metal oxide catalyst comprises ReOx、MoOx、VOx、NbOxAnd WOxAt least one of;
the supported noble metal catalyst, the support of the supported metal oxide catalyst, comprises at least one of silica, zirconia, titania, and ceria;
the loading amount of the noble metal in the supported noble metal catalyst is 0.5 to 5 percent;
the loading amount of the metal oxide in the supported metal oxide catalyst is 2-20%;
in the catalyst B, the mass ratio of the supported noble metal catalyst to the supported metal oxide catalyst is 1: 1-10;
the aldopentose diacid is selected from at least one of the following: xylaric acid, D-arabinedioic acid, L-arabinedioic acid, and ribosylic acid.
2. A process for the preparation of glutaric acid from aldopentose diacid comprising the steps of: adding an aqueous solution of glutaric acid, a catalyst A and a catalyst B into a reaction vessel, and carrying out the first-step reaction and then the second-step reaction to obtain glutaric acid;
the catalyst A is a supported noble metal catalyst;
the catalyst B is a catalyst formed by a supported noble metal catalyst and a supported metal oxide catalyst in a mechanical mixing mode;
the noble metal in the supported noble metal catalyst comprises at least one of Pd, Pt, Ru, Rh and Ir;
the metal oxide in the supported metal oxide catalyst comprises ReOx、MoOx、VOx、NbOxAnd WOxAt least one of;
the supported noble metal catalyst, the support of the supported metal oxide catalyst, comprises at least one of silica, zirconia, titania, and ceria;
the loading amount of the noble metal in the supported noble metal catalyst is 0.5 to 5 percent;
the loading amount of the metal oxide in the supported metal oxide catalyst is 2-20%;
in the catalyst B, the mass ratio of the supported noble metal catalyst to the supported metal oxide catalyst is 1: 1-10;
the aldopentose diacid is selected from at least one of the following: xylaric acid, D-arabinedioic acid, L-arabinedioic acid, and ribosylic acid.
3. The method according to claim 1 or 2, characterized in that: the mass percentage of the aldopentose diacid in the aqueous solution is 0.5-20%;
the mass ratio of the aldopentose diacid to the catalyst A is 1: 0.5 to 2.
4. The method according to claim 1 or 2, characterized in that: the reaction temperature of the first step reaction is 120-180 ℃; the reaction time is 2-20 h;
the hydrogen partial pressure of the first step reaction is 1 MPa-4 MPa.
5. The method according to claim 1 or 2, characterized in that: the mass ratio of the catalyst B to the aldopentose diacid is 0.5-4: 1.
6. the method according to claim 1 or 2, characterized in that: the reaction temperature of the second step is 180-250 ℃, and the reaction time is 2-20 h;
the hydrogen partial pressure of the second step reaction is 1 MPa-4 MPa.
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