CN110963887A - Fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid - Google Patents
Fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid Download PDFInfo
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- CN110963887A CN110963887A CN201811157876.1A CN201811157876A CN110963887A CN 110963887 A CN110963887 A CN 110963887A CN 201811157876 A CN201811157876 A CN 201811157876A CN 110963887 A CN110963887 A CN 110963887A
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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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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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
- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
Abstract
A fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid comprises the following steps: (1) respectively adding the raw material 1, 6-adipic acid and the solvent into a mixing tank, and heating the mixing tank at the same time; (2) uniformly mixing the raw material liquid prepared in the step (1) with hydrogen by using a pump, and feeding the mixture into a fixed bed reactor filled with a supported ruthenium and rhodium catalyst at a certain airspeed for reduction reaction; (4) and (4) carrying out gas-liquid separation on the reactant obtained in the step (3) by a condenser to obtain a 1, 6-hexanediol product. The invention innovatively adopts supported ruthenium and rhodium catalysts, the catalyst carrier is alumina, and adipic acid is used as a raw material to continuously prepare 1, 6-hexanediol by using a fixed bed reactor. The reaction steps are simple, the conversion rate and the selectivity of the product are high, and the method has a good application prospect.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a reaction process for preparing 1, 6-hexanediol from 1, 6-adipic acid.
Background
1, 6-hexanediol is a solid at room temperature, melting point 42 ℃ and molecular weight 118.18. The 1, 6-hexanediol is mainly used for producing novel polyester, paint, adhesive, detergent, antifoaming agent, plasticizer and the like, is a newly-found important fine chemical raw material and is known as organic synthesized novel diamond. The polyester polyol prepared from 1, 6-hexanediol is used for modifying polyurethane elastomer, and the modified resin has excellent mechanical strength, heat resistance, water resistance and oxidation resistance. The 1, 6-hexanediol has a long carbon chain and relatively high flexibility, and can be used for preparing a novel polyester product with special performance; 1, 6-hexanediol is used for preparing a medical intermediate 1, 6-dibromohexane, so that indole hormone-inhibiting medicines with special curative effects on prostatitis can be synthesized; in addition, with the continuous improvement of living standard, the requirements of people on environment quality are higher and higher, and the demand of environment-friendly products is increased, so that the industry of the coating and the cross-linking agent develops towards the direction of environmental protection, no toxicity and no public hazard, and the 1, 6-hexanediol plays a greater role in preparing environment-friendly water-soluble resin coating, polyurethane cross-linking agent and the like.
At present, the industrial mature method for producing 1, 6-hexanediol mainly uses dimethyl adipate as a raw material to obtain a 1, 6-hexanediol product through hydrogenation reaction. Research institutions at home and abroad carry out a great deal of research on the preparation method of 1, 6-hexanediol, and there are two methods in general: one is to use dimethyl adipate to carry out hydrogenation reaction; another is direct reduction with adipic acid.
CN1011113128 discloses a method for preparing 1, 6-hexanediol by hydrogenation of 1, 6-dimethyl adipate, wherein the hydrogen-ester ratio is 50-150: 1, the load of a catalyst is 0.1-0.5 kg of ester/h, the catalyst is kg, the temperature is 150-300 ℃, the reaction pressure is 4-7 MPa, and Cu/ZnO/Al is adopted2O3The catalyst and the fixed bed reactor have the advantages that the conversion rate of 1, 6-dimethyl adipate is more than 99 percent, and the selectivity of 1, 6-hexanediol is more than 96 percent.
CN101138726 discloses a catalyst of 1, 6-hexanediol and a preparation method thereof, wherein the catalyst comprises 25-60% of CuO, 25-60% of ZnO and Al2O310-30%. The conversion rate of 1, 6-dimethyl adipate is more than 99 percent, and the 1, 6-adipic acid isThe selectivity to alcohol is greater than 96%.
CN101265158B discloses a method for preparing 1, 6-hexanediol, which comprises the steps of setting an esterification reaction tower to pre-esterify adipic acid and methanol by using a solid acid catalyst, rectifying the reactant, purifying and then carrying out hydrogenation reaction. The ratio of hydrogen to ester is 50-350: 1, the temperature is 150-250 ℃, the pressure is 2.5-10 MPa, the catalyst is 25-60% of CuO, 25-60% of ZnO and Al2O310-30%. The reaction product is purified to obtain the 1, 6-hexanediol with the purity of more than 99 percent.
CN102372604A discloses a method for preparing 1, 6-hexanediol by hydrogenation of 1, 6-dimethyl adipate, wherein the reaction time is 5-12 h, the conversion rate of 1, 6-dimethyl adipate is 60-99.9% by adopting a noble metal catalyst and a batch reaction kettle, and the selectivity of 1, 6-hexanediol is more than 70% under the conditions that the hydrogen-ester ratio is 50-200: 1, the temperature is 150-220 ℃, the reaction pressure is 3-5 MPa, the stirring speed is 500-1000 rpm.
CN104549254 discloses a catalyst for preparing 1, 6-hexanediol by reduction between adipic acids, wherein the active component of the catalyst is one of Ru, Re, In and Ir, the catalyst adopts active carbon as a carrier, the reduction is carried out by using a reaction kettle, water is used as a solvent, the reaction temperature is 80-300 ℃, and the reaction pressure is 3-10 Mpa, so that the 1, 6-hexanediol is obtained.
In the above patent, 1, 6-hexanediol is prepared by hydrogenation reaction using dimethyl adipate, and the reaction process involves two steps: one step is adipate esterification reaction, and dimethyl adipate is obtained by purification; one step is the hydrogenation reaction of dimethyl adipate to obtain 1, 6-hexanediol. The operation flow is increased, the reaction time is prolonged, and the reaction cost is increased. Most of the reaction processes for preparing hexanediol by direct reduction of adipic acid adopt batch reaction processes, and have low productivity and complex operation. The method adopts a supported ruthenium and rhodium catalyst, adopts alumina as a catalyst carrier, and takes adipic acid as a raw material to continuously prepare the 1, 6-hexanediol by using a fixed bed reactor.
Disclosure of Invention
The invention aims to simplify the preparation process of 1, 6-hexanediol and reduce the reaction cost.
The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid is characterized by comprising the following steps: the reaction process comprises the following steps: (1) respectively adding the raw material 1, 6-adipic acid and a solvent into a mixing tank according to a certain mass ratio, and heating the mixing tank at the same time; (2) uniformly mixing the raw material liquid prepared in the step (1) with hydrogen by using a pump, and feeding the mixture into a fixed bed reactor filled with a supported ruthenium and rhodium catalyst at a certain airspeed for reduction reaction; (4) and (4) carrying out gas-liquid separation on the reactant obtained in the step (3) by a condenser to obtain a 1, 6-hexanediol product.
The solvent in the invention can be methanol, ethanol and water.
The mass ratio of the 1, 6-adipic acid to the solvent is 1: 2-1: 4.
The heating temperature of the mixing tank is 30-50 ℃.
The reduction reaction is carried out at the reaction temperature of 185-245 ℃.
The reaction pressure is 1.5-5 Mpa.
The hydrogen acid ratio is 30: 1-120: 1, and the volume space velocity is 0.5-1.5 h-1。
The supported ruthenium and rhodium catalyst has active components including ruthenium and rhodium in 0.5-5 wt% and carrier Al2O3The content is 90-99.5%.
According to the reaction process disclosed by the invention, the conversion rate of the 1, 6-adipic acid is 90-99%, and the selectivity of the 1, 6-hexanediol is 90-96%.
The invention innovatively adopts supported ruthenium and rhodium catalysts, the catalyst carrier is alumina, and adipic acid is used as a raw material to continuously prepare 1, 6-hexanediol by using a fixed bed reactor. The reaction steps are simple, the conversion rate and the selectivity of the product are high, and the method has a good application prospect.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Respectively adding 1, 6-adipic acid and methanol into a mixing tank, wherein the mass ratio of the 1, 6-adipic acid to the methanol is 1:3, and the heating temperature of the mixing tank is 45 ℃. Using Rh/Al2O3The catalyst is subjected to reduction reaction, the Rh content is 0.5 percent, and the carrier Al2O3The content is 99.5 percent. (the specific reaction conditions are shown in Table 1.
Table 1 example 1 reaction conditions and results
| Reaction temperature/. degree.C | Space velocity/h-1 | Hydrogen to acid ratio | pressure/MPa | X/% | S/% |
| 185 | 0.6 | 30:1 | 4.5 | 90.42 | 97.79 |
| 195 | 0.5 | 50:1 | 4 | 91.05 | 97.48 |
| 215 | 1.3 | 120:1 | 1.5 | 93.84 | 96.26 |
| 235 | 0.8 | 40:1 | 5 | 95.45 | 94.76 |
| 225 | 1.0 | 60:1 | 2 | 94.15 | 93.65 |
| 245 | 1.5 | 100:1 | 3 | 97.85 | 92.23 |
Note:X1, 6-adipic acid conversion;S，1, 6-hexanediol selectivity.
Example 2
Respectively adding 1, 6-adipic acid and water into a mixing tank, wherein the mass ratio of the 1, 6-adipic acid to the water is 1:4, and the heating temperature of the mixing tank is 50 ℃. Using Rh/Ru/Al2O3The catalyst is subjected to reduction reaction, and the carrier Al contains 1.5 percent of Rh and 2.5 percent of Ru2O3The content was 95%. (the specific reaction conditions are shown in Table 2.
Table 2 example 2 reaction conditions and results
| Reaction temperature/. degree.C | Space velocity/h-1 | Hydrogen to ester ratio | pressure/MPa | X/% | S/% |
| 190 | 0.6 | 70:1 | 5 | 91.55 | 96.79 |
| 245 | 0.5 | 35:1 | 4.5 | 94.65 | 95.78 |
| 205 | 1.3 | 120:1 | 3 | 92.94 | 96.26 |
| 215 | 0.8 | 80:1 | 5 | 94.45 | 94.76 |
| 225 | 1.0 | 60:1 | 2 | 95.85 | 94.35 |
| 235 | 1.5 | 90:1 | 1.5 | 95.85 | 91.23 |
Note:X1, 6-adipic acid conversion;S，1, 6-hexanediol selectivity.
Example 3
Respectively adding 1, 6-adipic acid and ethanol into a mixing tank, wherein the mass ratio of the 1, 6-adipic acid to the ethanol is 1:2, and the heating temperature of the mixing tank is 35 ℃. Using Ru/Al2O3The catalyst is subjected to reduction reaction, and the content of Ru is 5 percent of that of carrier Al2O3The content was 95%. (the specific reaction conditions are shown in Table 3.
Table 3 example 3 reaction conditions and results
| Reaction temperature/. degree.C | Space velocity/h-1 | Hydrogen to ester ratio | pressure/MPa | X/% | S/% |
| 195 | 0.8 | 120:1 | 5 | 95.46 | 93.79 |
| 230 | 0.6 | 40:1 | 4 | 96.66 | 95.78 |
| 205 | 1.5 | 110:1 | 3 | 91.84 | 96.26 |
| 215 | 0.9 | 80:1 | 4.5 | 94.45 | 96.76 |
| 245 | 1.2 | 60:1 | 2 | 91.45 | 94.35 |
| 235 | 1.4 | 90:1 | 3.5 | 93.95 | 92.15 |
Note:X1, 6-adipic acid conversion;S，1, 6-hexanediol selectivity.
Example 4
Respectively adding 1, 6-adipic acid and water into a mixing tank, wherein the mass ratio of the 1, 6-adipic acid to the water is 1:3.5, and the heating temperature of the mixing tank is 45 ℃. Using Rh/Ru/Al2O3The catalyst is subjected to reduction reaction, and the carrier Al contains 3.5 percent of Rh and 1.5 percent of Ru2O3The content was 95%. (the specific reaction conditions are shown in Table 4.
Table 4 example 4 reaction conditions and results
| Reaction temperature/. degree.C | Space velocity/h-1 | Hydrogen to ester ratio | pressure/MPa | X/% | S/% |
| 190 | 0.6 | 70:1 | 4 | 93.46 | 96.79 |
| 245 | 0.5 | 60:1 | 4 | 96.66 | 95.68 |
| 205 | 1.3 | 120:1 | 3 | 95.74 | 94.34 |
| 200 | 0.8 | 90:1 | 4.5 | 94.68 | 95.78 |
| 215 | 1.0 | 55:1 | 2 | 93.85 | 90.55 |
| 240 | 1.5 | 95:1 | 1.5 | 97.95 | 91.25 |
Note:X1, 6-adipic acid conversion;S，1, 6-hexanediol selectivity.
Example 5
Respectively adding 1, 6-adipic acid and methanol into a mixing tank, wherein the mass ratio of the 1, 6-adipic acid to the methanol is 1:3.5, and the heating temperature of the mixing tank is 40 ℃. Using Rh/Al2O3The catalyst is subjected to reduction reaction, the Rh content is 4.5 percent, and the carrier Al2O3The content was 95.5%. (the specific reaction conditions are shown in Table 5.
Table 5 example 5 reaction conditions and results
| Reaction temperature/. degree.C | Space velocity/h-1 | Hydrogen to ester ratio | pressure/MPa | X/% | S/% |
| 195 | 0.6 | 70:1 | 4 | 95.46 | 94.78 |
| 235 | 0.5 | 60:1 | 5 | 93.76 | 95.98 |
| 205 | 1.3 | 120:1 | 3 | 92.87 | 96.56 |
| 200 | 0.8 | 90:1 | 4.5 | 94.55 | 95.96 |
| 220 | 1.0 | 55:1 | 2 | 93.56 | 90.25 |
| 230 | 1.5 | 95:1 | 1.5 | 93.75 | 95.95 |
Note:X1, 6-adipic acid conversion;S，1, 6-hexanediol selectivity.
Example 6
Respectively adding 1, 6-adipic acid and methanol into a mixing tank, wherein the mass ratio of the 1, 6-adipic acid to the methanol is 1:5, and the heating temperature of the mixing tank is 50 ℃. Using Ru/Al2O3The catalyst is subjected to reduction reaction, the content of Ru is 5 percent, and the carrier Al2O3The content was 95%. (the specific reaction conditions are shown in Table 6.
Table 6 example 6 reaction conditions and results
| Reaction temperature/. degree.C | Space velocity/h-1 | Hydrogen to ester ratio | pressure/MPa | X/% | S/% |
| 195 | 0.6 | 80:1 | 5 | 95.46 | 94.78 |
| 235 | 0.5 | 30:1 | 4.5 | 95.76 | 96.98 |
| 205 | 1.3 | 120:1 | 3 | 95.87 | 96.57 |
| 200 | 0.8 | 130:1 | 5 | 94.55 | 95.85 |
| 220 | 1.0 | 60:1 | 4 | 96.56 | 90.28 |
| 230 | 1.5 | 90:1 | 2 | 97.75 | 93.95 |
Note:X1, 6-adipic acid conversion;S，1, 6-hexanediol selectivity.
Example 7
1, 6-adipic acid and methanol are respectively added into a mixing tank, the mass ratio of the 1, 6-adipic acid to the methanol is 1:5, and the heating temperature of the mixing tank is 50 ℃. Using Ru/Al2O3The catalyst is subjected to reduction reaction, the content of Ru is 3 percent, and the carrier Al2O3The content was 97%. The reaction temperature is 235 ℃ and the space velocity is 0.7h-1The pressure is 5MPa, after the reaction is carried out for 300 hours,Xcan be kept at 94.86%,Scan be maintained at 95.23 percent, and the shape of the catalyst is kept intact.
Example 8
1, 6-adipic acid and methanol are respectively added into a mixing tank, the mass ratio of the 1, 6-adipic acid to water is 1:5, and the heating temperature of the mixing tank is 50 ℃. Using Ru/Rh/Al2O3The catalyst is subjected to reduction reaction, the content of Ru is 3 percent, the content of Rh is 4.5 percent, and the carrier Al2O3The content was 92.5%. The reaction temperature is 205 ℃ and the space velocity is 1h-1Reacting for 2.5 hours under the pressure of 4MPa,Xcan reach the content of 93.86 percent,Scan be maintained at 96.23%.
Comparative example 1
1, 6-adipic acid and water are respectively added into a mixing tank, the mass ratio of the 1, 6-adipic acid to the water is 1:4, and the heating temperature of the mixing tank is 50 ℃. The reduction reaction is carried out by utilizing a Ru/active carbon catalyst, the content of Ru is 5 percent, and the content of active carbon of a carrier is 95 percent. The reaction temperature is 235 ℃ and the space velocity is 0.7h-1The pressure is 5MPa, after the reaction is carried out for 300 hours,Xcan be kept at 65.46%,Scan be maintained at 75.23%.
Comparative example 2
Respectively adding 1, 6-adipic acid and methanol into a reaction kettle, wherein the mass ratio of the 1, 6-adipic acid to water is 1:5, and adding 5% of Ru/Rh/Al2O3Catalyst, 3% of Ru, 4.5% of Rh, carrier Al2O3The content was 92.5%. The reaction temperature is 205 ℃ and the reaction pressure is 6 MPa. After the reaction is carried out for 8 hours,Xcan reach the content of 91.06 percent,Scan be maintained at 90.23%.
From the above examples, it can be seen that the reaction process for preparing 1, 6-hexanediol from 1, 6-adipic acid prepared by the invention has the advantages of simple process steps, low production cost and high reaction performance.
Claims (10)
1. A fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid is characterized in that: the reaction process comprises the following steps: (1) respectively adding the raw material 1, 6-adipic acid and the solvent into a mixing tank, and heating the mixing tank at the same time; (2) uniformly mixing the raw material liquid prepared in the step (1) with hydrogen by using a pump, and feeding the mixture into a fixed bed reactor filled with a supported ruthenium and rhodium catalyst at a certain airspeed for reduction reaction; (4) and (4) condensing the reactant obtained in the step (3) and carrying out gas-liquid separation to obtain the 1, 6-hexanediol product.
2. The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid according to claim 1, characterized in that the solvent is methanol, ethanol or water.
3. The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid according to claim 1, wherein the mass ratio of 1, 6-adipic acid to the solvent is 1:2 to 1: 4.
4. The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid according to claim 1, wherein the heating temperature of the mixing tank is 30-50 ℃.
5. The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid according to claim 1, wherein the reduction reaction temperature is 185-245 ℃, the hydrogen-acid ratio is 30: 1-120: 1, the reaction pressure is 1.5-5 MPa, and the volume space velocity is 0.5-1.5 h-1。
6. The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid according to claim 1, wherein the reduction reaction temperature is 185-245 ℃.
7. The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid according to claim 1, wherein the hydrogen-acid ratio of the reduction reaction is 30: 1-120: 1, and the volume space velocity is 0.5-1.5 h-1。
8. The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid according to claim 1, wherein the reduction reaction pressure is 1.5-5 Mpa.
9. The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid according to claim 1, wherein the catalyst comprises ruthenium as an active component, rhodium in an amount of 0.5 to 5%, and carrier Al2O3The content is 90-99.5%.
10. The fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid according to claim 1, wherein the conversion rate of 1, 6-adipic acid is 90-99%, and the selectivity of 1, 6-hexanediol is 90-96%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07165644A (en) * | 1993-10-22 | 1995-06-27 | Mitsubishi Chem Corp | Production of 1,4-butanediol and/or tetrahydrofuran |
| CN1374884A (en) * | 1999-09-21 | 2002-10-16 | 旭化成株式会社 | Catalysts for hydrogenation of carboxylic acid |
| CN1391549A (en) * | 1999-11-05 | 2003-01-15 | 旭化成株式会社 | Process for the preparation of diol mixtures |
| CN104549254A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing 1,6-hexanediol through direct reduction of adipic acid |
-
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- 2018-09-30 CN CN201811157876.1A patent/CN110963887B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07165644A (en) * | 1993-10-22 | 1995-06-27 | Mitsubishi Chem Corp | Production of 1,4-butanediol and/or tetrahydrofuran |
| CN1374884A (en) * | 1999-09-21 | 2002-10-16 | 旭化成株式会社 | Catalysts for hydrogenation of carboxylic acid |
| CN1391549A (en) * | 1999-11-05 | 2003-01-15 | 旭化成株式会社 | Process for the preparation of diol mixtures |
| CN104549254A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing 1,6-hexanediol through direct reduction of adipic acid |
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