CN107915575B - Method for preparing ethylene glycol by hydrolyzing ethylene carbonate - Google Patents
Method for preparing ethylene glycol by hydrolyzing ethylene carbonate Download PDFInfo
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- CN107915575B CN107915575B CN201610877515.9A CN201610877515A CN107915575B CN 107915575 B CN107915575 B CN 107915575B CN 201610877515 A CN201610877515 A CN 201610877515A CN 107915575 B CN107915575 B CN 107915575B
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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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a method for preparing ethylene glycol by hydrolyzing ethylene carbonate, which mainly solves the problems of difficult catalyst separation, low activity and low stability in the prior art. The invention adopts the steps of contacting ethylene carbonate and water with a catalyst under reaction conditions; the catalyst comprises the following components in parts by weight: a) 1-40 parts of heteropoly acid; (2) 60-99 parts of a carrier; the carrier is SiO2A material after contact with the zirconate; the zirconate is Zr (OC)aHb)4The technical scheme that a is an integer of 1-6 and b is an integer of 3-13 better solves the problem and can be used in industrial production of ethylene glycol prepared by hydrolysis of ethylene carbonate.
Description
Technical Field
The invention relates to a method for preparing ethylene glycol by hydrolyzing ethylene carbonate.
Background
Hydrolysis of esters is an important chemical reaction and is widely applied to various fields of petrochemical production, wherein hydrolysis of cyclic carbonates such as Ethylene Carbonate (EC), propylene carbonate and the like is a very important basic position.
Hydrolysis of EC is an important step in the production of Ethylene Glycol (EG) from Ethylene Oxide (EO) catalytic hydration in a two-step process. EG is an important organic chemical raw material and is mainly used for producing polyester fibers, antifreezing agents, unsaturated polyester resins, nonionic surfactants, ethanolamine, explosives and the like. The production technology of EG is mainly divided into petrochemical route and non-petrochemical route. In the petrochemical route, an EO direct hydration method and an EO catalytic hydration method exist, the direct hydration method can ensure higher EG yield only by requiring higher water ratio (more than 20), and the energy consumption in the process of EG purification is higher. EO catalyzed hydration processes in turn include direct catalyzed hydration processes and EC routes. The direct catalytic hydration process has a relatively low water ratio (around 5), but still requires evaporation to remove a large amount of water, whereas the EC route first utilizes the CO emitted from ethylene oxidation to make EO2EC is generated by raw materials and EO under the action of a catalyst, then EG is generated by catalytic hydrolysis by taking EC as an intermediate product, the water ratio in the process is close to the stoichiometric ratio of 1, and the method is the industrialization direction of preparing EG from EO in the future.
The catalysts currently used for the hydrolysis of cyclic carbonates are mainly: alkali (earth) metal (bi) carbonates (US 4524224, 1985), compounds of Mo and W (JP 822106631, 1982; WO2009071651, 2009), quaternary ammonium salts and ion exchange resins (EP 0133763, 1989; US6080897, 2000; US20090156867, 2009) and the like. However, these catalytic systems have problems of difficulty in separating the catalyst, low activity, low stability, and the like.
The heteropoly acid has high catalytic activity and is not easy to inactivate, so the heteropoly acid is widely applied to acid-catalyzed reaction. Supporting the heteropolyacid on the support can increase the surface area thereof and provide a suitable pore structure, and can facilitate the separation of the heteropolyacid catalyst. However, the biggest problem of the supported heteropolyacid catalyst is that the active component heteropolyacid of the catalyst is easy to dissolve out, thereby causing the reduction of the catalytic activity (CN 101293210A).
Disclosure of Invention
The invention aims to solve the technical problems of difficult catalyst separation, low activity and low stability in the prior art, and provides a novel method for preparing ethylene glycol by hydrolyzing ethylene carbonate. The method has the advantages of easy separation, high activity and good stability.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing ethylene glycol by hydrolyzing ethylene carbonate comprises the steps of contacting ethylene carbonate and water with a catalyst under reaction conditions;
the catalyst comprises the following components in parts by weight: a) 1-40 parts of heteropoly acid; (2) 60-99 parts of a carrier;
the carrier is SiO2A material after contact with the zirconate; the zirconate is Zr (OC)aHb)4Wherein a is an integer of 1 to 6, and b is an integer of 3 to 13.
In the above technical scheme, SiO2The contact conditions with the zirconate ester include: the temperature is 70-140 ℃, and preferably 90-120 ℃; the time is 2 to 40 hours, preferably 5 to 20 hours; zirconate and SiO2The weight ratio of (A) to (B) is 0.05 to 2, preferably 0.1 to 1.
In the above technical scheme, SiO2Selected from porous SiO2SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or diatomite; preference is given toPorous SiO2SBA-15, MCM-41, MCF or HMS.
In the above technical scheme, SiO2The specific surface area of (A) is 100-1500 m2Per gram, preferably 200 to 1000 m2Per gram.
In the technical scheme, the amount of the heteropoly acid is 1-30 parts by weight, and the amount of the carrier is 70-99 parts by weight.
In the above technical scheme, the reaction conditions include: the reaction temperature is 60-180 ℃, and preferably 80-160 ℃; the molar ratio of water to ethylene carbonate is (1-8) to 1, preferably (1-10) to 1; the weight ratio of the catalyst to the ethylene carbonate is (0.005-1): 1, preferably (0.01-0.5): 1.
In the above technical scheme, the heteropoly acid is one selected from phosphotungstic acid, silicotungstic acid, germanotungstic acid, arsenotungstic acid, phosphomolybdic acid, silicomolybdic acid, germanomolybdic acid or arsenomolybdic acid with a Keggin structure.
The preparation method of the catalyst comprises the following steps:
preparation of the carrier: adding SiO into a flask2Toluene and zirconates, in N2Refluxing under protection for a period of time, washing the obtained solid product with solvent, vacuum drying, and adding N2And protecting storage to obtain the carrier.
Loading of heteropoly acid: and dissolving heteropoly acid in a solvent, adding the carrier, stirring and refluxing for a period of time, washing the obtained solid product with the solvent, and drying overnight to obtain the catalyst.
Wherein, SiO is generated in the preparation process of the carrier2: toluene: the mass ratio of zirconate is 1 (5-20) to 0.1-2, the reflux time is 4-20 hours, the solvent for washing the product can be at least one of benzene, toluene, xylene, ethylbenzene and cumene, and the vacuum drying temperature is 60-150 ℃; in the process of loading the heteropoly acid, the heteropoly acid: solvent: the carrier is prepared from (20-100) to (1-10) by mass, the refluxing time is 5-25 hours, the solvent for washing the product can be at least one of acetonitrile, acrylonitrile and benzonitrile, and the drying temperature is 80-200 DEG C
The method of the invention adopts a load type heteropoly acid catalyst, because of SiO2The surface of (A) is modified by zirconate to obtain SiO2The zirconium acid ester has tighter combination with the heteropoly acid, plays a role of 'chemical glue', reduces the possibility of dissolution of the heteropoly acid and improves the stability of the catalyst. By adopting the method, at the reaction temperature of 100 ℃, the molar ratio of water to ethylene carbonate is 1.5: 1, the weight ratio of the catalyst to the ethylene carbonate is 0.05: under the condition of 1, the conversion rate of the ethylene carbonate is 99.8 percent, the selectivity of the ethylene glycol is 98.5 percent, and after the catalyst is repeatedly used for 5 times, the activity is reduced by less than 5 percent, thereby obtaining better technical effect.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
33.0 g of porous SiO was placed in a 500 ml three-neck flask2(Degussa, Aerosil 200, specific surface area 210 m2Per g), 270 ml of toluene, 15 ml of N-butyl zirconate are then added, in N2The reaction is refluxed for 16 h at 105 ℃ under protection. After the reaction was complete, the product was washed 4 times with toluene, dried under vacuum and then treated with N2Protected storage, labeled as ZS-1 carrier.
3.8 g of phosphotungstic acid with a Keggin structure is dissolved in 150 ml of acetonitrile, 7.5 g of ZS-1 carrier is added, stirring and refluxing are carried out for 15 h at the temperature of 80 ℃, a reaction mixture is filtered, after being washed for 4 times by acetonitrile, the mixture is dried at the temperature of 110 ℃ overnight, and the obtained catalyst is marked as HZS-1.
[ examples 2 to 9 ]
Zirconate treatment of SiO2The procedure was as in example 1, except that SiO was used2Kind of (3), kind of zirconate, zirconate and SiO2The weight ratio, treatment temperature and treatment time are different, and the carriers ZS-2-ZS-9 are obtained, as shown in Table 1.
TABLE 1
[ examples 10 to 17 ]
The heteropolyacid loading manner was the same as in example 1, except that the carriers used were ZS-2 to ZS-9, and the types and amounts of the heteropolyacids used were different, to obtain catalysts HZS-2 to HZS-9, as shown in table 2.
TABLE 2
Comparative example 1
SiO used2The supported phosphotungstic acid is Aerosil 200, but is not treated by zirconate, and the specific preparation process is as follows: 2.3 g of phosphotungstic acid with Keggin structure was dissolved in 150 ml of acetonitrile, and then 7.5 g of Aerosil 200 was added thereto, and after stirring and drying at 70 ℃, the resulting catalyst was dried overnight at 110 ℃, and the obtained catalyst was labeled as HZS-1C.
[ example 18 ]
The novel supported heteropolyacid catalyst HZS-1 prepared in example 1 was used in the reaction for preparing ethylene glycol by hydrolyzing ethylene carbonate. 44.0 g of ethylene carbonate, 13.5 g of deionized water and 2.2 g of catalyst were placed in a 100 ml autoclave (molar ratio of water to ethylene carbonate: 1, mass ratio of catalyst to ethylene carbonate: 0.05: 1) and reacted at 100 ℃ for 2 hours. After the reaction was complete, the autoclave was cooled to room temperature and vented. And (3) taking the liquid-phase product for gas chromatography analysis, and measuring that the conversion rate of the ethylene carbonate is 99.8%, the selectivity of the ethylene glycol is 98.5%, and the rest product is polyethylene glycol.
Comparative example 2
The catalyst activity test conditions were the same as in example 18 except that HZS-1C was used as the catalyst, giving a conversion of 93.4% for ethylene carbonate, 98.1% for ethylene glycol and 1.9% for polyethylene glycol.
[ examples 19 to 26 ]
The catalyst activity test conditions were the same as in example 18 except that HZS-2 to HZS-9 were used as catalysts, and the results were as shown in Table 3.
TABLE 3
[ example 27 ]
The same as [ example 18 ] except that the reaction temperature was 120 ℃. The conversion of ethylene carbonate obtained was 99.5%, the selectivity for ethylene glycol was 98.0% and the selectivity for polyethylene glycol was 2.0%.
[ example 28 ]
The same as [ example 18 ] except that the reaction temperature was 140 ℃. The conversion of ethylene carbonate obtained was 99.9%, the selectivity for ethylene glycol was 97.5% and the selectivity for polyethylene glycol was 2.5%.
[ example 29 ]
The same as [ example 18 ] except that the reaction temperature was 80 ℃. The conversion of ethylene carbonate obtained was 64.3%, the selectivity to ethylene glycol was 99.2% and the selectivity to polyethylene glycol was 0.8%.
[ example 30 ]
The same as in example 18 except that the mass of the deionized water was 27.0 g (molar ratio of water to ethylene carbonate was 3: 1). The conversion rate of the obtained ethylene carbonate is 99.8%, the selectivity of the ethylene glycol is 99.1%, and the selectivity of the polyethylene glycol is 0.9%.
[ example 31 ]
The same as in example 18 except that the mass of deionized water was 72.0 grams (water to ethylene carbonate molar ratio was 8: 1). The conversion rate of the obtained ethylene carbonate is 99.9%, the selectivity of the ethylene glycol is 99.4%, and the selectivity of the polyethylene glycol is 0.6%.
[ example 32 ]
The same as in example 18 except that the amount of catalyst used was 1.1 g (the ratio of catalyst to ethylene carbonate was 0.025: 1). The conversion rate of the obtained ethylene carbonate is 63.5%, the selectivity of the ethylene glycol is 99.3%, and the selectivity of the polyethylene glycol is 0.7%.
[ example 33 ]
The same as in example 18 except that the amount of catalyst was 8.8 g (the ratio of catalyst to ethylene carbonate was 0.2: 1). The conversion rate of the obtained ethylene carbonate is 99.7%, the selectivity of the ethylene glycol is 98.2%, and the selectivity of the polyethylene glycol is 1.8%.
[ example 34 ]
The same as in example 18 except that the mass of the catalyst was 17.6 g (the mass ratio of the catalyst to the ethylene carbonate was 0.4: 1). The conversion rate of the obtained ethylene carbonate is 99.8%, the selectivity of the ethylene glycol is 95.1%, and the selectivity of the polyethylene glycol is 4.9%.
[ example 35 ]
The catalyst after the reaction was used repeatedly for 5 times under the same reaction conditions [ example 18 ], and the activity was not significantly decreased. The reaction results are shown in Table 4.
TABLE 4
Comparative example 3
The catalyst after the reaction was completed in comparative example 2 was applied mechanically for 5 times under the same reaction conditions, and the activity was significantly decreased. The reaction results are shown in Table 5.
TABLE 5
Claims (8)
1. A method for preparing ethylene glycol by hydrolyzing ethylene carbonate comprises the steps of contacting ethylene carbonate and water with a catalyst under reaction conditions; in the method for preparing ethylene glycol by hydrolyzing ethylene carbonate, the weight ratio of a catalyst to ethylene carbonate is (0.05-0.2): 1;
the catalyst comprises the following components in parts by weight: (1) 16.3-31.9 parts of heteropoly acid; (2) 68.1-83.7 parts of a carrier;
the heteropoly acid is one of phosphotungstic acid, silicotungstic acid, germanium tungstic acid, arsenic tungstic acid, phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid or arsenic molybdic acid with a Keggin structure;
the carrier is SiO2A material after contact with the zirconate; the zirconate esterIs Zr (OC)aHb)4Wherein a is an integer of 1 to 6, and b is an integer of 3 to 13;
zirconate and SiO2The weight ratio of (A) to (B) is 0.25 to 2.
2. The method for preparing ethylene glycol by hydrolyzing ethylene carbonate according to claim 1, wherein SiO is SiO2The contact conditions with zirconate were: the temperature is 70-140 ℃, and the time is 2-40 hours.
3. The method for preparing ethylene glycol by hydrolyzing ethylene carbonate according to claim 2, wherein SiO is SiO2The contact conditions with zirconate were: the temperature is 90-120 ℃, the time is 5-20 hours, and the zirconate and the SiO2The weight ratio of (A) to (B) is 0.25 to 1.
4. The method for preparing ethylene glycol by hydrolyzing ethylene carbonate according to claim 1, wherein SiO is SiO2Selected from porous SiO2Aerosil 200, SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or diatomaceous earth.
5. The method for preparing ethylene glycol by hydrolyzing ethylene carbonate according to claim 4, wherein SiO is SiO2Selected from porous SiO2Aerosil 200, SBA-15, MCM-41, MCF or HMS.
6. The method for preparing ethylene glycol by hydrolyzing ethylene carbonate according to claim 1, wherein SiO is SiO2The specific surface area of (A) is 100-1500 m2Per gram.
7. The method for preparing ethylene glycol by hydrolyzing ethylene carbonate according to claim 6, wherein SiO is SiO2The specific surface area of (A) is 200-1000 m2Per gram.
8. The method for preparing ethylene glycol by hydrolyzing ethylene carbonate according to claim 1, wherein the reaction conditions are as follows: the reaction temperature is 60-180 ℃, and the molar ratio of water to ethylene carbonate is (1-10): 1.
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