CN110845302A - Method for preparing ethylene glycol based on polyethylene carbonate - Google Patents

Method for preparing ethylene glycol based on polyethylene carbonate Download PDF

Info

Publication number
CN110845302A
CN110845302A CN201911210003.7A CN201911210003A CN110845302A CN 110845302 A CN110845302 A CN 110845302A CN 201911210003 A CN201911210003 A CN 201911210003A CN 110845302 A CN110845302 A CN 110845302A
Authority
CN
China
Prior art keywords
pec
ethylene glycol
carbonate
mixture
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911210003.7A
Other languages
Chinese (zh)
Inventor
王永杰
杨振声
沈国良
邹明旭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang University of Technology
Original Assignee
Shenyang University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenyang University of Technology filed Critical Shenyang University of Technology
Priority to CN201911210003.7A priority Critical patent/CN110845302A/en
Publication of CN110845302A publication Critical patent/CN110845302A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07C29/095—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 organic acids
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a preparation method of ethylene glycol, in particular to a method for preparing ethylene glycol based on polyethylene carbonate. Taking the PEC residual liquid as a raw material, then adding water and a catalyst for reaction to obtain ethylene glycol; the PEC raffinate comprises the following raw materials: the PEC is mainly used, and the PEC also comprises ethylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol or high polyalcohol and alcohol ether, 1, 4-dioxane, unreacted ethylene oxide, carbon dioxide, alkyl bromide compounds and ammonia substances. In the prior art, when ethylene carbonate is refined, because cyclic EC is a polymer monomer, PEC residual liquid with relatively high molecular weight is formed under the initiation action of thermal free radicals, but no good method for treating PEC kettle residue is provided at present. The method solves the problem that the kettle residue is difficult to treat, and can be used in industrial production for preparing ethylene glycol and plasticizer from PEC.

Description

Method for preparing ethylene glycol based on polyethylene carbonate
Technical Field
The invention relates to a preparation method of ethylene glycol, in particular to a method for preparing ethylene glycol based on polyethylene carbonate.
Background
In the prior art, polyethylene carbonate (PEC) adopts Lewis acid salt as a catalyst to carry out ring-opening polymerization on Ethylene Carbonate (EC), and a polymerization product PEC is used for replacing a traditional liquefier EC to liquefy corn straws. The prior art should be much lower than us, wherein aliphatic ethylene carbonate is introduced into the chemical structure of the new liquefied product, and the biodegradation rate of the PEC product is improved by about 30% compared with that of the ethylene carbonate liquefied corn straw, but the current demand cannot be met.
The residual liquid of the aliphatic PEC used at present is mainly PEC, and also comprises residual EC, ethylene glycol, diethylene glycol, triethylene glycol or high polyalcohol and alcohol ether, 1, 4-dioxane, unreacted ethylene oxide, carbon dioxide, alkyl bromide compounds, ammonia substances and the like, and if the residual liquid cannot be treated in time, the residual liquid brings great harm to the environment.
At present, the minimum amount of the PEC kettle residues in the whole country is estimated to be 3-4 million tons, and the PEC kettle residues are calculated according to the condition that the PEC kettle residues left after EC distillation in the northeast region are 0.8-1.5 million tons and the PEC kettle treatment cost is 2 million yuan per ton and 8 million yuan per ton. Therefore, a method for solving the problem of still residue in the preparation of ethylene glycol is urgently needed.
Disclosure of Invention
The purpose of the invention is as follows:
the invention aims to solve the technical problems of more residual liquid, low biodegradation rate and high residual liquid treatment cost in the process of preparing ethylene glycol by EC in the prior art, and provides a method for preparing ethylene glycol based on poly (ethylene carbonate).
The technical scheme is as follows:
a method for preparing ethylene glycol based on poly (ethylene carbonate) comprises the steps of taking PEC residual liquid as a raw material, then adding water and a catalyst for reaction, and obtaining ethylene glycol after the reaction; the PEC raffinate comprises the following raw materials: the PEC is mainly used, and the PEC also comprises ethylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol or high polyalcohol and alcohol ether, 1, 4-dioxane, unreacted ethylene oxide, carbon dioxide, alkyl bromide compounds and ammonia substances.
Further, the reaction conditions are that the reaction temperature is 80-160 ℃, the reaction time is 2-8 hours, the mass ratio of water to the PEC residual liquid is (0.4-1): 1, and the mass ratio of the catalyst to the PEC residual liquid is (0.005-1): 1.
Further, the catalyst is PEC raffinate which comprises PEC as a main component, ethylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol or high polyalcohol and alcohol ether, 1, 4-dioxane, unreacted ethylene oxide, carbon dioxide, bromine alkyl compound and ammonia.
Further, the catalyst comprises a mixture A, a mixture B and an auxiliary agent C, wherein the mixture A, the mixture B, the auxiliary agent C = (0-1), the mixture (1-3) and the mixture (0-2) are mixed according to the mass ratio; wherein the compound A and the auxiliary C cannot be zero at the same time.
Further, mixture a in the catalyst comprises: the method comprises the steps of taking mixed acid consisting of dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid, matching castor oil and oleic acid as raw materials, neutralizing with 30% sodium hydroxide aqueous solution at 65-85 ℃, carrying out saponification reaction for 1-3 hours, adding a transparent agent (comprising sodium methoxide or sodium ethoxide aqueous solution, and carrying out micronization and nanocrystallization on the crystal grain size of a catalyst under the action of the sodium methoxide or sodium ethoxide aqueous solution, so that the transparency of a catalyst product is greatly improved), and uniformly stirring to obtain a mixture A.
Further, B in the strong base type composite metal nano soap is selected from sodium methoxide, sodium ethoxide, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate or at least one selected from sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
Further, the auxiliary agent C is PEC residual liquid, the PEC residual liquid comprises PEC as a main component, Ethylene Carbonate (EC), ethylene glycol, diethylene glycol, triethylene glycol or high polyalcohol and alcohol ether, 1, 4-dioxane, unreacted ethylene oxide, carbon dioxide, alkyl bromide and ammonia substances.
Further, adding the mixture A into a solution B with the mass ratio of 30-40%, mixing at 65-85 ℃ according to the mass ratio of 1: 1 of the mixture A and the mixture B, and performing pre-saponification for 0.5-2.5 hours to obtain a mixture; and adding 10 mass percent of an auxiliary agent C and a proper amount of water into the mixture A and the mixture B, and reacting for 8-30 hours at the temperature of 20-50 ℃ to obtain the strong base type composite metal nano soap.
The advantages and effects are as follows:
according to the method, the composite metal nano soap catalyst is adopted, and the high-strength C12-C18 carbon chain nano material is doped into the soap base material, so that the temperature resistance of the composite metal nano soap is enhanced, and the compatibility of the composite metal nano soap with chain-like polyethylene carbonate is enhanced. The phase transfer catalyst helps the chain-like polyethylene carbonate reactant to transfer from one phase to another phase capable of reacting, thereby accelerating the reaction rate of a heterogeneous system. The PEC conversion rate can approach 100% by adopting the method, the selectivity of the ethylene glycol can reach 99%, the catalytic effect is extremely obvious, and the excellent technical effect is obtained.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples. It is to be noted that the following examples are only for the purpose of further illustrating the present invention and should not be construed as limiting the scope of the present invention.
Hydrolysis of esters is an important chemical reaction, and is widely applied to various fields of petrochemical production, wherein hydrolysis of cyclic Ethylene Carbonate (EC), chain polyethylene carbonate (PEC), chain polypropylene carbonate and the like is more important as a basic position.
Hydrolysis of PEC is EO with CO2An important step for preparing Ethylene Glycol (EG) by hydrating the obtained kettle residual PEC. 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,the EC route first utilizes CO discharged from ethylene oxidation to EO2EC is generated from raw materials and EO under the action of a catalyst, and then the EC obtained by rectification and separation can be sold as a valuable commodity, the obtained PEC residue is difficult to treat, so that the EC is difficult to continuously produce, and the accumulated large amount of PEC causes harm to the environment. The PEC is used as a raw material to catalyze and hydrolyze to generate EG, the process water ratio is close to the stoichiometric ratio of 1, and the method is an industrialization direction for preparing valuable commercial EG by treating the residual PEC in the future.
Currently, methods for preparing ethylene glycol from EC are well known to those skilled in the art. Generally, the kettle residue (mainly PEC) contains chain-shaped polyethylene carbonate, cyclic ethylene carbonate EC, ethylene glycol, diethylene glycol, triethylene glycol or high polyalcohol and alcohol ether, 1, 4-dioxane and unreacted ethylene oxide, carbon dioxide, bromine alkyl compound and ammonia, so that the difficulty of the kettle residue treatment is greatly increased due to uncertainty of residual liquid components.
Hydrolysis of PEC is EO with CO2An important step of preparing EG by catalyzing, synthesizing and producing EC and hydrating the obtained kettle residual PEC. 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 from raw materials and EO under the action of a catalyst, and then the EC obtained by rectification and separation can be sold as a valuable commodity, the obtained PEC residue is difficult to treat, so that the EC is difficult to continuously produce, and the accumulated large amount of PEC causes harm to the environment. The PEC is used as a raw material to catalyze and hydrolyze to generate EG, the water ratio of the process is close to the stoichiometric ratio of 1, and the PEC is a valuable commodity E prepared by processing kettle residues in the futureG industrialization direction.
The PEC residual liquid is the residual PEC of the kettle, contains alkyl bromide compounds and ammonia substances, and can only be treated as hazardous chemical wastes if not treated, so that the great resource waste is caused.
Example 1
Heating castor oil under the action of alkali to generate sodium ricinoleate, separating glycerin, adding acid to acidify to generate ricinoleic acid soap which is white paste A; the concrete preparation method of the mixture A is that mixed acid consisting of dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid is matched with castor oil and oleic acid as raw materials, the raw materials are neutralized and saponified with 30% sodium hydroxide aqueous solution at 85 ℃ for 1 hour, then a transparent agent is added, and the mixture A is obtained after even stirring.
Adding the mixture A into 30-40% NaOH solution, and pre-saponifying for 0.5-2.5 hours at 60-75 ℃ according to a mass ratio of 1: 1 to obtain a phase transfer catalyst (A + B); adding auxiliary PEC residual liquid into the phase transfer catalyst to prepare the composite metal nano soap catalyst.
At 1.5M3Adding 400kg of water and 600kg of PEC (polyethylene glycol terephthalate) residue into a reaction kettle, adding 20kg of composite metal nano soap catalyst, stirring and reacting for 4 hours at the reaction temperature of 120-140 ℃, adding equivalent sulfuric acid to neutralize to be neutral, cooling to 50-70 ℃, and discharging to obtain 1000kg of product containing 93% of ethylene glycol.
And (3) rectifying and separating a product containing 93% of ethylene glycol: 1000kg of a product of 93% ethylene glycol was added to 1.5M3In the reboiler (2), the pressure reduction separation is carried out by a rectifying tower with 15-18 theoretical plates to obtain 800 kg of 99.6% ethylene glycol.
Example 2
Transformation of EC raffinate: due to the uncertainty of the components of the PEC raffinate, in the presence of a relatively large amount of PEC (such as PEC content greater than 85%), 30-40% NaOH and Na solutions are added2CO3Adding auxiliary PEC residual liquid at 60-75 ℃ according to a mass ratio of 1: 1And (3) reacting for 0.5-2.5 hours according to the mass ratio to obtain the phase transfer catalyst (B + auxiliary agent C, namely sodium alkoxide).
At 1.5M3Adding 400kg of water and 600kg of PEC (polyethylene glycol terephthalate) residue into a reaction kettle, adding 20kg of a phase transfer sodium alkoxide catalyst, stirring and reacting for 4 hours at the reaction temperature of 120-140 ℃, adding equivalent sulfuric acid to neutralize to be neutral, cooling to 50-70 ℃, and discharging to obtain 1000kg of product containing 96% of ethylene glycol; and (3) rectifying and separating a product of 96% ethylene glycol: 1000kg of a product of 96% ethylene glycol are added to 1.5M3In the reboiler (2), the pressure reduction separation is carried out by a rectifying tower with 15-18 theoretical plates to obtain 800 kg of 99.7% ethylene glycol.
Example 3
And (3) transforming PEC raffinate: due to the uncertainty of the composition of the PEC raffinate, in a solution containing a relatively large amount of PEC (e.g., greater than 75% PEC), 30-40% KOH and K are added2CO3Adding auxiliary PEC residual liquid, and reacting for 0.5-2.5 hours at the temperature of 60-75 ℃ according to the mass ratio of 1: 1 to obtain the phase transfer catalyst (B + auxiliary C).
At 1.5M3Adding 400kg of water and 600kg of PEC (polyethylene glycol) residue in a reaction kettle, adding 20kg of phase transfer catalyst, stirring and reacting for 4 hours at the reaction temperature of 120-140 ℃, adding equivalent sulfuric acid to neutralize to be neutral, cooling to 50-70 ℃, and discharging to obtain 1000kg of product containing 97% of ethylene glycol; and (3) rectifying and separating a product of 97% ethylene glycol: 1000kg of a product of 97% ethylene glycol was added to 1.5M3In the reboiler (2), the pressure reduction separation is carried out by a rectifying tower with 15-18 theoretical plates to obtain 800 kg of 99.8% ethylene glycol.
Example 4
And (3) transforming PEC raffinate: due to the uncertainty of the components of the PEC raffinate, in a solution containing a relatively large amount of PEC (such as PEC content greater than 65%), 30-40% of solution K is added2CO3Adding auxiliary PEC raffinate, and reacting for 0.5-2.5 hours at 60-75 ℃ according to the mass ratio of 1: 1 to obtain the phase transfer catalyst (B + auxiliary C).
At 1.5M3Adding 400kg of water and 600kg of PEC (polyethylene glycol terephthalate) residue into a reaction kettle, adding 25kg of phase transfer catalyst, stirring and reacting for 5 hours at the reaction temperature of 120-140 ℃, and adding equivalent sulfuric acidNeutralizing to be neutral, cooling to 50-70 ℃, discharging to obtain 1000kg of product containing 98% of glycol.
And (3) rectifying and separating products of 98% ethylene glycol: 1000kg of a product of 98% ethylene glycol was added to 1.5M3In the reboiler (2), decompression separation is carried out by a rectifying tower with 15-18 theoretical plates to obtain 790 kg of 99.9% ethylene glycol.
Example 4 substantially eliminates alkyl bromide and ammonia species from the PEC raffinate, saving subsequent hazardous chemical disposal costs and substantially achieving maximum conversion.
Example 5
And (3) transforming PEC raffinate: due to the uncertainty of the components of the PEC raffinate, in a PEC containing relatively large amount (such as PEC content more than 55%), 30-40% of Na solution is added2CO3Adding auxiliary PEC residual liquid, and reacting for 0.5-2.5 hours at the temperature of 60-75 ℃ according to the mass ratio of 1: 1 to obtain 25kg of phase transfer catalyst (B + auxiliary C).
At 1.5M3Adding 400kg of water and 600kg of PEC (polyethylene glycol) residue into a reaction kettle, adding 25kg of phase transfer catalyst (solution B + auxiliary agent C), stirring and reacting for 6 hours at the reaction temperature of 120-140 ℃, adding equivalent sulfuric acid to neutralize to be neutral, cooling to 50-70 ℃, and discharging to obtain 1000kg of product containing 92% of ethylene glycol; and (3) rectifying and separating a product of 92% ethylene glycol: 1000kg of a product of 92% ethylene glycol was added to 1.5M3In the reboiler (3), the pressure reduction separation is carried out by a rectifying tower with 15-18 theoretical plates to obtain 810 kg of 99.5% ethylene glycol.
Example 6
Adding PEC raffinate into rectifying still, vacuum rectifying to obtain EC, refining EC with PEC raffinate to obtain still residue containing PEC, diethylene glycol, triethylene glycol, polyalcohol and alcohol ether, alkyl bromide and ammonia, and adding B (such as 10kg of 30-40% solution K) into PEC with relatively large amount (such as PEC content greater than 95%)2CO3) Adding 10kg of auxiliary agent triethylene glycol, and reacting for 0.5-2.5 hours at the temperature of 60-75 ℃ according to the mass ratio of 1: 1 to obtain a phase transfer triethylene glycol potassium catalyst (solution B + auxiliary agent B, 20 kg); at 1.5M3400kg of water, 600kg of PEC (such as PE) remaining in the reactorThe content of C is more than 95%), adding 20k of phase transfer triethylene glycol potassium catalyst, stirring and reacting for 6 hours at the reaction temperature of 120-140 ℃, adding equivalent sulfuric acid for neutralization to neutrality, cooling to 50-70 ℃, and discharging to obtain 1000kg of product containing 92% of ethylene glycol; and (3) rectifying and separating a product of 92% ethylene glycol: 1000kg of a product of 92% ethylene glycol was added to 1.5M3In the reboiler (2), the pressure reduction separation is carried out by a rectifying tower with 15-18 theoretical plates to obtain 800 kg of 99.5% ethylene glycol.
Example 7
Transformation of EC raffinate: due to the uncertainty of the PEC raffinate composition, in a PEC raffinate containing a relatively large amount (e.g., greater than 85% PEC content), a 10% sodium carbonate solution was added to the adjuvant PEC raffinate and reacted at 60 ℃ for 2.5 hours at a 1: 2 mass ratio to give a phase transfer catalyst (B + adjuvant C).
At 1.5M3Adding 400kg of water and 600kg of PEC (polyethylene glycol terephthalate) residue into a reaction kettle, adding 10kg of phase transfer catalyst, stirring and reacting for 4 hours at the reaction temperature of 120-140 ℃, adding equivalent sulfuric acid to neutralize to be neutral, cooling to 50-70 ℃, and discharging to obtain 1000kg of product containing 90% of ethylene glycol; and (3) rectifying and separating a product of 90% ethylene glycol: 1000kg of a product of 90% ethylene glycol are added to 1.5M3In the reboiler (2), the pressure reduction separation is carried out by a rectifying tower with 15-18 theoretical plates to obtain 750 kg of 99.5% ethylene glycol.
Example 8
Transformation of EC raffinate: due to the uncertainty of the composition of the PEC raffinate, sodium methoxide or sodium ethoxide was added to the auxiliary PEC raffinate in a relatively large amount of PEC (e.g., PEC content greater than 85%) and reacted at 75 ℃ for 0.5 hour at a mass ratio of 3: 1 to obtain a phase transfer catalyst (B + auxiliary C).
At 1.5M3Adding 400kg of water and 600kg of PEC (polyethylene glycol terephthalate) residue into a reaction kettle, adding 20kg of a phase transfer sodium alkoxide catalyst, stirring and reacting for 4 hours at the reaction temperature of 120-140 ℃, adding equivalent sulfuric acid to neutralize to be neutral, cooling to 50-70 ℃, and discharging to obtain 1000kg of product containing 96% of ethylene glycol; and (3) rectifying and separating a product of 96% ethylene glycol: 1000kg of a product of 96% ethylene glycol are added to 1.5M3In the reboiler of (2), by the number of theoretical plates 15Decompression separation is carried out on 18 rectifying towers to obtain 790 kg of 99.7% ethylene glycol.
Example 9
The concrete preparation method of the mixture A is that mixed acid consisting of dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid is matched with castor oil and oleic acid as raw materials, the raw materials are neutralized and saponified with 30% sodium hydroxide aqueous solution at 85 ℃ for 1 hour, then a transparent agent is added, and the mixture A is obtained after even stirring.
Adding one or more of sodium hydroxide, sodium methoxide or sodium carbonate into the mixture A, and pre-saponifying for 2.5 hours at the temperature of 60-75 ℃ according to the mass ratio of 1: 1 of the mixture A to the mixture B to obtain a phase transfer catalyst (A + B);
at 1.5M3Adding 400kg of water and 600kg of PEC (polyethylene glycol terephthalate) residue into a reaction kettle, adding 20kg of phase transfer catalyst, stirring and reacting for 2 hours at the reaction temperature of 80 ℃, adding equivalent sulfuric acid to neutralize to be neutral, cooling to 50-70 ℃, and discharging to obtain 1000kg of product containing 91% of glycol.
Product rectification separation of ethylene glycol with 91% content: 1000kg of a 91% glycol product was added to 1.5M3In the reboiler (2), the pressure reduction separation is carried out by a rectifying tower with 15-18 theoretical plates to obtain 760 kg of 99.6 percent ethylene glycol.
Example 10
The concrete preparation method of the mixture A is that mixed acid consisting of dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid is matched with castor oil and oleic acid as raw materials, the raw materials are neutralized and saponified with 30% sodium hydroxide aqueous solution at 85 ℃ for 1 hour, then a transparent agent is added, and the mixture A is obtained after even stirring.
Adding one or more of sodium hydroxide, sodium methoxide or sodium carbonate into the mixture A, and pre-saponifying at 75 ℃ for 0.5 hour according to the mass ratio of 1: 3 to obtain a phase transfer catalyst (A + B);
at 1.5M3Adding 400kg of water and 600kg of PEC (polyethylene glycol terephthalate) residue into a reaction kettle, adding 20kg of phase transfer catalyst, stirring and reacting for 8 hours at the reaction temperature of 160 ℃, adding equivalent sulfuric acid to neutralize to be neutral, cooling to 50-70 ℃, and discharging to obtain 1000kg of product containing 96% of ethylene glycol.
And (3) rectifying and separating the product with the content of 96% of ethylene glycol: 1000kg of a 96% glycol product was added to 1.5M3In the reboiler (2), decompression separation is carried out by a rectifying tower with 15-18 theoretical plates to obtain 790 kg of 99.6% ethylene glycol.
The method for preparing the ethylene glycol has the advantages that 500 ten thousand yuan is estimated to be invested by the Liaoning Hongkong chemical engineering Limited company and harmless treatment is carried out. The method can increase the benefit of 2 million yuan per ton of ethylene glycol by calculating about 0.8 ton of ethylene glycol per ton of kettle residue, and can increase the benefit of 10 million yuan per ton of ethylene glycol by 4500 yuan per ton at present.

Claims (8)

1. A method for preparing ethylene glycol based on polyethylene carbonate is characterized in that: taking the PEC residual liquid as a raw material, then adding water and a catalyst for reaction to obtain ethylene glycol; the PEC raffinate comprises the following raw materials: the PEC is mainly used, and the PEC also comprises ethylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol or high polyalcohol and alcohol ether, 1, 4-dioxane, unreacted ethylene oxide, carbon dioxide, alkyl bromide compounds and ammonia substances.
2. The method for preparing ethylene glycol based on the polyethylene carbonate according to claim 1, wherein: the reaction conditions are that the reaction temperature is 80-160 ℃, the reaction time is 2-8 hours, the mass ratio of water to the PEC residual liquid is (0.4-1): 1, and the mass ratio of the catalyst to the PEC residual liquid is (0.005-1): 1.
3. The method for preparing ethylene glycol based on the polyethylene carbonate according to claim 1, wherein: the catalyst is PEC raffinate which comprises PEC as a main component, ethylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol or high polyalcohol and alcohol ether, 1, 4-dioxane, unreacted ethylene oxide, carbon dioxide, alkyl bromide compound and ammonia.
4. The process for preparing ethylene glycol based on poly (ethylene carbonate) according to claim 1 or 2, characterized in that: the catalyst comprises a mixture A, a mixture B and an auxiliary agent C, wherein the mixture A is mixed with the mixture B, the auxiliary agent C is not= (0-1) to (1-3) to (0-2) according to the mass ratio; wherein the compound A and the auxiliary C cannot be zero at the same time.
5. The method for preparing ethylene glycol based on the polyethylene carbonate according to claim 4, wherein: mixture a in the catalyst comprises: the method comprises the steps of taking mixed acid consisting of dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid, matching castor oil and oleic acid as raw materials, neutralizing with 30% sodium hydroxide aqueous solution at 65-85 ℃, carrying out saponification reaction for 1-3 hours, adding a transparent agent (comprising sodium methoxide or sodium ethoxide aqueous solution, and carrying out micronization and nanocrystallization on the crystal grain size of a catalyst under the action of the sodium methoxide or sodium ethoxide aqueous solution, so that the transparency of a catalyst product is greatly improved), and uniformly stirring to obtain a mixture A.
6. The method for preparing ethylene glycol based on the polyethylene carbonate according to claim 4, wherein: b in the strong base type composite metal nano soap is selected from sodium methoxide, sodium ethoxide, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate or at least one of sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
7. The method for preparing ethylene glycol based on the polyethylene carbonate according to claim 4, wherein: the auxiliary agent C is PEC residual liquid, the PEC residual liquid comprises PEC as a main component, Ethylene Carbonate (EC), ethylene glycol, diethylene glycol, triethylene glycol or high polyalcohol and alcohol ether, 1, 4-dioxane, unreacted ethylene oxide, carbon dioxide, bromine alkyl compound and ammonia.
8. The method for preparing ethylene glycol based on the polyethylene carbonate according to claim 4, wherein: adding the mixture A into a solution B with the mass ratio of 30-40%, mixing the mixture A and the solution B at 65-85 ℃ according to the mass ratio of 1: 1, and pre-saponifying for 0.5-2.5 hours to obtain a mixture; and adding 10 mass percent of an auxiliary agent C and a proper amount of water into the mixture A and the mixture B, and reacting for 8-30 hours at the temperature of 20-50 ℃ to obtain the strong base type composite metal nano soap.
CN201911210003.7A 2019-12-02 2019-12-02 Method for preparing ethylene glycol based on polyethylene carbonate Pending CN110845302A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911210003.7A CN110845302A (en) 2019-12-02 2019-12-02 Method for preparing ethylene glycol based on polyethylene carbonate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911210003.7A CN110845302A (en) 2019-12-02 2019-12-02 Method for preparing ethylene glycol based on polyethylene carbonate

Publications (1)

Publication Number Publication Date
CN110845302A true CN110845302A (en) 2020-02-28

Family

ID=69606932

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911210003.7A Pending CN110845302A (en) 2019-12-02 2019-12-02 Method for preparing ethylene glycol based on polyethylene carbonate

Country Status (1)

Country Link
CN (1) CN110845302A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114874069A (en) * 2021-11-24 2022-08-09 惠州市宙邦化工有限公司 Method and device for preparing electronic-grade ethylene glycol

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241630A (en) * 2001-02-21 2002-08-28 Matsushita Electric Ind Co Ltd Colored resin composition and method for recovering non-biodegradable colorant
JP2003221436A (en) * 2002-01-31 2003-08-05 Mitsubishi Chemicals Corp Method for manufacturing polyester
CN108658766A (en) * 2018-06-27 2018-10-16 铜陵金泰化工股份有限公司 A kind of device and method of coproduction ethylene glycol and dimethyl carbonate
CN110105174A (en) * 2019-05-22 2019-08-09 山东石大胜华化工集团股份有限公司 A method of ethylene glycol is produced using ethylene carbonate and methanol as raw material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241630A (en) * 2001-02-21 2002-08-28 Matsushita Electric Ind Co Ltd Colored resin composition and method for recovering non-biodegradable colorant
JP2003221436A (en) * 2002-01-31 2003-08-05 Mitsubishi Chemicals Corp Method for manufacturing polyester
CN108658766A (en) * 2018-06-27 2018-10-16 铜陵金泰化工股份有限公司 A kind of device and method of coproduction ethylene glycol and dimethyl carbonate
CN110105174A (en) * 2019-05-22 2019-08-09 山东石大胜华化工集团股份有限公司 A method of ethylene glycol is produced using ethylene carbonate and methanol as raw material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
朱伟光等: "固体碱低温催化碳酸乙烯酯水解合成乙二醇" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114874069A (en) * 2021-11-24 2022-08-09 惠州市宙邦化工有限公司 Method and device for preparing electronic-grade ethylene glycol
CN114874069B (en) * 2021-11-24 2024-03-22 惠州市宙邦化工有限公司 Method and device for preparing electronic grade ethylene glycol

Similar Documents

Publication Publication Date Title
CN102229586B (en) Preparation method for alpha-acetyl-gamma-butyrolactone
CN105344341B (en) A kind of preparation method of solid catalyst for Synthesis of dimethyl carbonate
CN101928389B (en) Method for preparing glycidol ether terminated propenol polyoxyethylene ether
CN107311868B (en) Method for preparing p-tert-butyl methyl benzoate
CN107814939B (en) Method for synthesizing poly (ethylene glycol methyl phosphonate) by metal oxide catalysis
CN110845302A (en) Method for preparing ethylene glycol based on polyethylene carbonate
CN101704711A (en) Method for preparing 1,2-diol compound by using catalytic hydration of epoxide
CN104119309B (en) A kind of environmentally friendly catalyzer is for the synthesis of the method for 6-caprolactone
CN109160880B (en) Preparation method of ethyl benzoate
CN112341335A (en) Synthesis method of methyl salicylate
CN101704730A (en) Ring opening etherification reaction method in two-step approach for synthesizing glycidol ether
CN101704803B (en) Method for preparing cylohexanediol diglycidyl ether
CN101544587B (en) Preparation method of alpha, alpha'-bis(tert-butyl peroxy) diisopropylbenzene
CN113548957B (en) Production method of tertiary carbonic acid
CN106076304B (en) Transesterification supported titanium2The preparation method of catalyst
CN112174801B (en) Method for coproducing glycolic acid and 1,1,1, 2-tetrafluoroethane by one-pot method
GB2023601A (en) A process for Hydrolyzing Alkylene Oxides to Alkylene Glycols
CN112624915A (en) Method for preparing 2, 5-dihydroxyterephthalic acid (DHTA)
CN106905127B (en) Method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone
CN101492348A (en) Method for producing 1-adamantane ethanol
CN108715580A (en) A kind of industrialized preparing process of 2- nitryl-4-thiamphenicol benzoic acids
CN110862296A (en) Method for separating reaction product in chloromethane production process
CN108715581A (en) A kind of preparation method of 2- nitryl-4-thiamphenicol benzoic acids
CN104311512B (en) A kind of clean method for preparing of 1,2-epoxy butane
CN108299638B (en) Synthesis method of allyl alcohol polyoxyethylene ether carboxylic glycidyl ester

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination