CN107915577B - Method for synthesizing ethylene glycol by hydrolyzing ethylene carbonate - Google Patents

Method for synthesizing ethylene glycol by hydrolyzing ethylene carbonate Download PDF

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CN107915577B
CN107915577B CN201610878296.6A CN201610878296A CN107915577B CN 107915577 B CN107915577 B CN 107915577B CN 201610878296 A CN201610878296 A CN 201610878296A CN 107915577 B CN107915577 B CN 107915577B
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ethylene carbonate
catalyst
apo
hydrolyzing
ethylene
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CN107915577A (en
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陈梁锋
何文军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12Preparation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/82Phosphates
    • B01J29/83Aluminophosphates [APO compounds]
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for synthesizing ethylene glycol by hydrolyzing ethylene carbonate, which mainly solves the problems of poor catalyst stability and easy loss of active components in the prior art. The invention adopts the steps of contacting ethylene carbonate and water with a catalyst under reaction conditions; the technical scheme that the catalyst is a phosphorus-aluminum-oxygen catalyst APO better solves the problem, and can be used in the industrial production of ethylene glycol prepared by hydrolyzing ethylene carbonate.

Description

Method for synthesizing ethylene glycol by hydrolyzing ethylene carbonate
Technical Field
The invention relates to a method for synthesizing 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 (US4524224, 1985), compounds of Mo and W (JP822106631, 1982; WO2009071651, 2009), quaternary ammonium salts and ion exchange resins (EP0133763, 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 strong alkali type ion exchange resin has good activity and selectivity when used for cyclic carbonate hydrolysis, but due to poor temperature resistance and swelling resistance, the activity is reduced rapidly in the catalytic reaction process (Yu FP, Cai H, He WJ, et al.J.appl.Polym.Sci.,2010,115: 2946-2954), which is the main reason for the failure of the catalyst to be industrialized.
Disclosure of Invention
The invention aims to solve the technical problems of poor catalyst stability and easy loss of active components in the prior art, and provides a novel method for synthesizing ethylene glycol by hydrolyzing ethylene carbonate. The method has the characteristics of high catalyst activity and selectivity and low loss of active components.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for synthesizing ethylene glycol by hydrolyzing ethylene carbonate comprises the steps of contacting ethylene carbonate and water with a catalyst under reaction conditions; the catalyst is a phosphorus-aluminum-oxygen catalyst APO.
In the technical scheme, the weight content of Al in the phosphorus-aluminum-oxygen APO is Al2O310-80%, preferably 20-60%, more preferably 30-50%; the content of P is as P2O5In an amount of 20 to 90%, preferably 40 to 80%, more preferably 50 to 70%.
In the technical scheme, the reaction temperature is 60-200 ℃, preferably 80-160 ℃, and more preferably 100-140 ℃.
In the technical scheme, the molar ratio of the water to the ethylene carbonate is (1-10): 1, preferably (1-8): 1, and more preferably (1-6): 1.
In the technical scheme, the weight ratio of the catalyst to the ethylene carbonate is (0.005-1): 1, preferably (0.01-0.5): 1, and more preferably (0.02-0.2): 1.
The aluminum-phosphorus oxide in the invention is a mixed oxide of aluminum oxide and phosphorus oxide. The preparation method is well known in the art and can be prepared by the following method: 1) aluminum nitrate (Al (NO) was added at room temperature3)3·9H2O) and diammonium hydrogen phosphate are dissolved in water, and then concentrated nitric acid is added to acidify the solution to obtain a solution A; 2) adding concentrated ammonia water into the solution A at room temperature to adjust the pH value to 8, filtering the formed precipitate, washing, drying and roasting to obtain the productAluminophospho APO. The drying temperature is 100-150 ℃, and the drying time is 5-24 hours. The roasting temperature is 550-650 ℃, and the roasting time is 1-24 hours. The adding amount of the concentrated nitric acid is 5-20% of the weight of the aluminum nitrate.
The catalyst used in the invention is phosphorus-aluminum-oxygen, compared with ion exchange resin, the catalyst has stable property and greatly improved heat resistance, and solves the problems of poor catalyst stability and easy loss of active components in the prior art. By adopting the method, at the reaction temperature of 120 ℃, the molar ratio of water to ethylene carbonate is 1.5:1, and 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 97.2 percent, the selectivity of the ethylene glycol is 99.6 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 ]
Preparation of aluminophosphateoxy APO: dissolving 58.8g of aluminum nitrate and 22.3g of diammonium hydrogen phosphate in 500ml of deionized water at room temperature, stirring for 1h, adding 10ml of concentrated nitric acid for acidification, continuously dropwise adding concentrated ammonia water to adjust the pH value to 8, filtering the formed precipitate, washing with deionized water for 3 times, drying at 120 ℃ overnight, drying and roasting at 500 ℃ to obtain aluminum oxide phosphate APO-1, and determining the weight content of Al in the APO-1 by ICP-AES (inductively coupled plasma-atomic emission spectrometry)2O340% by weight of P, the content of P being expressed as P2O5The amount was 60%.
[ example 2 ]
The procedure for the preparation of aluminophosphate APO was the same as in example 1, except that 14.7g and 33.5g of aluminum nitrate and 33.5g of diammonium phosphate were used, respectively, to obtain aluminophosphate APO-2, and the weight content of Al in APO-2 was determined by ICP-AES as Al2O3Calculated as 10%, the weight content of P is calculated as P2O5The calculated value is 90%.
[ example 3 ]
The procedure for the preparation of Aluminoaluminophosphate APO was the same as in example 1, except that 36.8g of aluminum nitrate and 36.8g of diammonium phosphate were used27.9g of aluminumoxy APO-3, and the weight content of Al in the APO-3 was determined by ICP-AES as Al2O3Calculated as 25%, the weight content of P is calculated as P2O5The content was found to be 75%.
[ example 4 ]
The procedure for the preparation of aluminophosphate APO was the same as in example 1, except that 73.5g and 18.6g of aluminum nitrate and 18.6g of diammonium hydrogen phosphate were used, respectively, to obtain aluminophosphate APO-4, and the weight content of Al in APO-4 was determined by ICP-AES as Al2O3Calculated as 50%, the weight content of P is calculated as P2O5Calculated as 50%.
[ example 5 ]
The procedure for the preparation of aluminophosphate APO was the same as in example 1, except that 95.6g and 13.0g of aluminum nitrate and 13.0g of diammonium hydrogen phosphate were used, respectively, to obtain aluminophosphate APO-5, and the weight content of Al in APO-5 was determined by ICP-AES as Al2O3Calculated as 65%, the weight content of P is calculated as P2O5The weight is 35%.
[ example 6 ]
The procedure for the preparation of aluminophosphate APO was the same as in example 1, except that 117.6g and 7.4g of aluminum nitrate and diammonium hydrogen phosphate were used, respectively, to obtain aluminophosphate APO-6, and the weight content of Al in APO-6 was determined by ICP-AES as Al2O3Calculated as 80%, the weight content of P is calculated as P2O5Calculated as 20%.
[ example 7 ]
The catalyst APO-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 NAPO-1 were placed in a 100 ml autoclave (molar ratio of water to ethylene carbonate: 1, weight ratio of catalyst to ethylene carbonate: 0.05: 1) and reacted at 120 ℃ for 2 hours. After the reaction was complete, the autoclave was cooled to room temperature and vented. And (3) performing gas chromatography analysis on the liquid-phase product to obtain that the conversion rate of the ethylene carbonate is 97.2%, the selectivity of the ethylene glycol is 99.6%, and the balance is the polyethylene glycol.
[ examples 8 to 12 ]
The catalysts APO-2 to APO-6 prepared in the examples 2 to 6 are used in the reaction for preparing ethylene glycol by hydrolyzing ethylene carbonate, the reaction conditions are the same as those in the example 7, and the obtained reaction results are shown in Table 1.
TABLE 1
Figure BDA0001126120800000041
[ example 13 ]
The same as [ example 7 ] except that the reaction temperature was 140 ℃. The conversion of ethylene carbonate obtained was 99.1%, the selectivity for ethylene glycol was 98.5%, and the selectivity for polyethylene glycol was 1.5%.
[ example 14 ]
The same as [ example 7 ] except that the reaction temperature was 160 ℃. The conversion of ethylene carbonate obtained was 99.5%, the selectivity for ethylene glycol was 97.0%, and the selectivity for polyethylene glycol was 3.0%.
[ example 15 ]
The same as [ example 7 ] except that the reaction temperature was 100 ℃. The conversion of ethylene carbonate obtained was 61.3%, the selectivity for ethylene glycol was 99.4% and the selectivity for polyethylene glycol was 0.6%.
[ example 16 ]
The same as in example 7 except that the mass of deionized water was 27.0 grams (molar ratio of water to ethylene carbonate was 3: 1). The conversion rate of the obtained ethylene carbonate is 98.6%, the selectivity of the ethylene glycol is 99.4%, and the selectivity of the polyethylene glycol is 0.6%.
[ example 17 ]
The same as in example 7 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 99.8%, the selectivity of the ethylene glycol is 99.5%, and the selectivity of the polyethylene glycol is 0.5%.
[ example 18 ]
The same as in example 7 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 71.6%, the selectivity of the ethylene glycol is 99.1%, and the selectivity of the polyethylene glycol is 0.9%.
[ example 19 ]
The same as in example 7 except that the amount of catalyst was 8.8g (the ratio of catalyst to ethylene carbonate was 0.2: 1). The conversion rate of the obtained ethylene carbonate is 99.9%, the selectivity of the ethylene glycol is 97.9%, and the selectivity of the polyethylene glycol is 2.1%.
[ example 20 ]
The same as in example 7 except that the mass of the catalyst was 17.6g (the mass ratio of the catalyst to the ethylene carbonate was 0.4: 1). The conversion rate of the obtained ethylene carbonate is 99.9%, the selectivity of the ethylene glycol is 96.3%, and the selectivity of the polyethylene glycol is 3.7%.
[ example 21 ]
The catalyst after the reaction was isolated and used for 5 times under the same reaction conditions as in example 18, without significant decrease in activity. The reaction results are shown in Table 2.
TABLE 2
Figure BDA0001126120800000061

Claims (5)

1. A method for synthesizing ethylene glycol by hydrolyzing ethylene carbonate comprises the steps of contacting ethylene carbonate and water with a catalyst under reaction conditions; the catalyst is a phosphorus-aluminum-oxygen catalyst APO, and the weight content of Al in the phosphorus-aluminum-oxygen APO is Al2O3Calculated as 20-60%, the content of P is calculated as P2O540-80% of the total; the phosphorus aluminum oxygen APO is a mixed oxide of aluminum oxide and phosphorus oxide;
wherein the reaction temperature is 80-160 ℃.
2. The method for synthesizing ethylene glycol by hydrolyzing ethylene carbonate according to claim 1, wherein the weight content of Al in the phosphorus aluminum oxide (APO) is Al2O330-50% of P, and the content of P is P2O5Calculated as 50-70%.
3. The method for synthesizing the ethylene glycol by hydrolyzing the ethylene carbonate according to claim 1, wherein the molar ratio of the water to the ethylene carbonate is (1-10): 1, and the weight ratio of the catalyst to the ethylene carbonate is (0.005-1): 1.
4. The method for synthesizing the ethylene glycol by hydrolyzing the ethylene carbonate according to claim 3, wherein the molar ratio of the water to the ethylene carbonate is (1-8): 1, and the weight ratio of the catalyst to the ethylene carbonate is (0.01-0.5): 1.
5. The method for synthesizing the ethylene glycol by hydrolyzing the ethylene carbonate according to claim 4, wherein the reaction temperature is 100-140 ℃, the molar ratio of the water to the ethylene carbonate is (1-6): 1, and the weight ratio of the catalyst to the ethylene carbonate is (0.02-0.2): 1.
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Publication number Priority date Publication date Assignee Title
US4400559A (en) * 1982-06-14 1983-08-23 The Halcon Sd Group, Inc. Process for preparing ethylene glycol
CN1274418C (en) * 2000-03-31 2006-09-13 意大利博雷加德有限公司 Phosphorous-aluminium-mixed oxide catalyst, process for its preparation and use thereof
TW200503997A (en) * 2002-12-20 2005-02-01 Shell Int Research Process for the preparation of alkylene glycol
CN100406419C (en) * 2006-05-26 2008-07-30 华东理工大学 Method for preparing dibasic alcohol
CN101121642A (en) * 2006-08-10 2008-02-13 中国科学院过程工程研究所 Catalytic method used for cyclic carbonates hydrolysis
CN102491876A (en) * 2011-11-11 2012-06-13 中国科学院过程工程研究所 Method for preparing vicinal diol by solid base catalyst

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