CN114874069B - Method and device for preparing electronic grade ethylene glycol - Google Patents
Method and device for preparing electronic grade ethylene glycol Download PDFInfo
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- CN114874069B CN114874069B CN202111399928.8A CN202111399928A CN114874069B CN 114874069 B CN114874069 B CN 114874069B CN 202111399928 A CN202111399928 A CN 202111399928A CN 114874069 B CN114874069 B CN 114874069B
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 35
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000006227 byproduct Substances 0.000 claims abstract description 22
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 118
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000002994 raw material Substances 0.000 claims description 31
- 230000007062 hydrolysis Effects 0.000 claims description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 42
- 239000007788 liquid Substances 0.000 description 16
- 238000010992 reflux Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical industry, in particular to a method and a device for preparing electronic grade ethylene glycol. The method for preparing the electronic grade ethylene glycol is simple, fully utilizes byproducts generated in the process of preparing the ethylene carbonate by a cycloaddition process, greatly reduces the production cost, simultaneously reduces the influence of direct discharge of the byproducts on the environment, avoids the loss of materials, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method and a device for preparing electronic grade ethylene glycol.
Background
Ethylene carbonate (EC for short) is an organic solvent and an organic synthesis intermediate with excellent performance, has the advantages of high boiling point, low toxicity, low corrosiveness and the like, is widely applied to the fields of plastics, printing and dyeing, high polymer synthesis, gas separation, electrochemistry and the like, and has the earliest industrial preparation method of ethylene carbonate, namely a phosgene method, but has the defects of long process flow, low yield, high production cost, high toxicity, serious pollution and the like; the EC production by transesterification is limited to laboratory stage and is not suitable for large-scale industrial production.
CN107915708B discloses a method for producing ethylene carbonate by using ethylene oxide and carbon dioxide under the condition of high-temperature catalysis, which is a method for preparing ethylene carbonate (i.e. cycloaddition process) widely used in industry at present, which uses ethylene oxide and carbon dioxide as raw materials, has the advantages of low production cost, high conversion rate, high selectivity and the like, and not only accords with the concepts of green chemistry and atom economyCan also reduce CO in industrial tail gas 2 Greenhouse effect caused by emissions of (2); however, when preparing ethylene carbonate by cycloaddition, the formation of by-products, such as polyethylene glycol, ether, etc., is often accompanied by the boiling point of these by-products being lower than that of ethylene carbonate; therefore, the by-product is withdrawn from the top reflux portion of the rectifying column before the product ethylene carbonate is collected, and if the by-product is directly discharged into the environment, not only is the environment polluted, but also material loss is caused.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method and a device for preparing electronic grade ethylene glycol, which are used for preparing the electronic grade ethylene glycol by collecting byproducts generated by preparing ethylene carbonate by a cycloaddition process and a small part of residual ethylene carbonate which can not be extracted from the byproducts.
The technical scheme adopted by the invention is as follows:
in a first aspect, the present invention relates to a method for preparing electronic grade ethylene glycol, which uses a byproduct obtained by preparing ethylene carbonate by a cycloaddition process and ethylene carbonate remained in the byproduct as raw materials, and sequentially performs a high-temperature normal-pressure hydrolysis reaction and a high-temperature high-pressure hydrolysis reaction on the raw materials, so as to obtain the electronic grade ethylene glycol after the reaction.
The byproduct obtained by preparing ethylene carbonate by the cycloaddition process mainly comprises polyethylene glycol and ether, namely the polyethylene glycol and the ether and a small part of ethylene carbonate remained in the byproduct are taken as raw materials together, and after high-temperature normal-pressure hydrolysis reaction and high-temperature high-pressure hydrolysis reaction, all components (polyethylene glycol, ether and ethylene carbonate) in the raw materials can be hydrolyzed and converted into electronic grade ethylene glycol.
Preferably, the polyethylene glycol is diethylene glycol and the ether is ethylene oxide which is an unreacted starting material in the preparation of ethylene carbonate by a cycloaddition process.
The inventor selects to use a high-temperature normal-pressure hydrolysis reaction and a high-temperature high-pressure hydrolysis reaction in combination for improving the hydrolysis conversion rate of raw materials, namely, the raw materials sequentially pass through the high-temperature normal-pressure hydrolysis reaction and the high-temperature high-pressure hydrolysis reaction, wherein the high-temperature normal-pressure hydrolysis reaction mainly aims at the hydrolysis conversion of a small part of ethylene carbonate remained in byproducts, and the ethylene carbonate can be hydrolyzed and converted into ethylene glycol in the high-temperature normal-pressure hydrolysis reaction;
in addition, the reason why the present inventors have found in many cases that the degree of hydrolysis of ethylene carbonate is closely related to the pressure in the reaction by using a high-temperature normal-pressure hydrolysis reaction is that, when the pressure in the reaction is too high, the carbon dioxide produced by hydrolysis of ethylene carbonate is at a critical concentration in the reaction solution, and the forward progress of the hydrolysis reaction is suppressed, thereby lowering the conversion rate of ethylene carbonate, leading to incomplete conversion of ethylene carbonate and loss of a part of the raw materials.
Meanwhile, the present inventors have also found that the byproduct obtained by preparing ethylene carbonate by cycloaddition process, for example, polyethylene glycol, cannot be completely converted only by high temperature and normal pressure hydrolysis, and thus, it is also necessary to combine high temperature and high pressure hydrolysis after the high temperature and normal pressure hydrolysis, and the polyethylene glycol can be completely hydrolyzed only in the high temperature and high pressure hydrolysis.
Further, the high-temperature normal-pressure hydrolysis reaction is carried out at a reaction temperature of 105-120 ℃ for 4-6 hours, the mass ratio of water to raw materials is 0.8-1:2-2.4, and the mass ratio of catalyst to raw materials is 0.001-0.002:1, so that the raw materials are hydrolyzed to generate ethylene glycol.
Preferably, the reaction temperature of the high-temperature normal-pressure hydrolysis reaction is 110 ℃, the reaction time is 5 hours, the mass ratio of water to raw materials is 1:2, and the mass ratio of the catalyst to the raw materials is 0.0015:1.
Further, the high-temperature high-pressure hydrolysis reaction is that the reaction temperature is 110-120 ℃, the reaction time is 2-4 hours, and under the condition that the reaction pressure is 1.0-1.5 Mpa, the raw materials which are not completely hydrolyzed after the high-temperature normal-pressure hydrolysis reaction are continuously hydrolyzed under the action of a catalyst to generate ethylene glycol. Further, the catalyst is 0.1% -0.2% of the total feeding amount, preferably 0.15%.
Preferably, the high-temperature high-pressure hydrolysis reaction is carried out at a reaction temperature of 120 ℃, a reaction time of 3 hours and a reaction pressure of 1.3Mpa.
Further, the high-temperature normal-pressure hydrolysis reaction and/or the high-temperature high-pressure hydrolysis reaction process further comprise a catalyst, wherein the catalyst is at least one selected from potassium carbonate, potassium hydroxide, sodium carbonate and sodium hydroxide.
Further, the method also comprises vacuum rectification, and the hydrolysate obtained after the high-temperature normal-pressure hydrolysis reaction and the high-temperature high-pressure hydrolysis reaction are subjected to vacuum rectification extraction to obtain the electronic grade ethylene glycol.
In a second aspect, the invention relates to a device for preparing electronic grade ethylene glycol, which comprises a high-temperature normal-pressure hydrolysis reaction kettle and a high-temperature normal-pressure hydrolysis reaction kettle which are sequentially connected in series, wherein an outlet of the high-temperature normal-pressure hydrolysis reaction kettle is communicated with an inlet of the high-temperature normal-pressure hydrolysis reaction kettle, and an outlet of the high-temperature normal-pressure hydrolysis reaction kettle is communicated with a decompression rectifying tower.
Further, the temperature in the high-temperature normal-pressure hydrolysis reaction kettle is 105-120 ℃, the temperature in the high-temperature normal-pressure hydrolysis reaction kettle is 110-120 ℃, the pressure in the kettle is 1.0-1.5 Mpa, the pressure at the top of the vacuum rectification tower is-0.08 Mpa, and the reflux ratio is 2-3.
Further, the temperature of the reboiler in the vacuum rectification tower is 150 ℃.
Further, the electronic grade ethylene glycol is extracted from the side of the vacuum rectifying tower, and the liquid extracted from the top of the vacuum rectifying tower and the liquid in the tower kettle are refluxed to the high-temperature normal-pressure hydrolysis reaction kettle or the high-temperature high-pressure hydrolysis reaction kettle.
Compared with the prior art, the invention has the following advantages:
the invention provides a method and a device for preparing electronic grade ethylene glycol, which are characterized in that byproducts generated by preparing ethylene carbonate by a cycloaddition process and a small part of residual ethylene carbonate in the byproducts are taken as raw materials together, and the raw materials are subjected to high-temperature normal-pressure hydrolysis reaction and high-temperature high-pressure hydrolysis reaction in sequence, and then subjected to reduced-pressure rectification extraction to obtain the electronic grade ethylene glycol. The method for preparing the electronic grade ethylene glycol is simple, fully utilizes byproducts generated in the process of preparing the ethylene carbonate by a cycloaddition process, greatly reduces the production cost, simultaneously reduces the pollution caused by direct discharge of the byproducts to the environment, avoids the loss of materials, and is suitable for industrial production.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for preparing electronic grade ethylene glycol according to the present invention.
In the figure: 1. high-temperature normal-pressure hydrolysis reaction kettle; 2. a high-temperature high-pressure hydrolysis reaction kettle; 3. and (5) a decompression rectifying tower.
Detailed Description
The following description of the embodiments of the present invention will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Example 1
High-temperature normal-pressure hydrolysis: placing raw materials containing 10g of ethylene carbonate, 10g of diethylene glycol and 10g of ethylene oxide into a 100ml high-temperature normal-pressure hydrolysis reaction kettle 1 containing 15g of water, adding 0.045g of potassium carbonate, and reacting for 4 hours at 105 ℃;
high temperature and high pressure hydrolysis: introducing the first-stage product subjected to the high-temperature normal-pressure hydrolysis reaction into a high-temperature high-pressure hydrolysis reaction kettle 2 containing 15g of water and 0.045g of potassium hydroxide, and reacting for 2 hours at 120 ℃ under the pressure condition of 1.3 Mpa;
and (3) vacuum rectification: and (3) introducing the secondary product after the high-temperature high-pressure hydrolysis reaction into a vacuum rectifying tower 3, setting the tower top pressure of the vacuum rectifying tower 3 to be-0.08 Mpa, setting the reflux ratio to be 2, extracting electronic grade ethylene glycol from the tower side of the vacuum rectifying tower 3 at the temperature of a reboiler in the tower of 150 ℃, and refluxing the tower top extracted liquid and the tower bottom liquid to the high-temperature normal-pressure hydrolysis reaction kettle 1 or the high-temperature high-pressure hydrolysis reaction kettle 2. The reaction parameters are shown in Table 1, and the test results are shown in Table 2.
Example 2
High-temperature normal-pressure hydrolysis: placing raw materials containing 10g of ethylene carbonate, 10g of diethylene glycol and 10g of ethylene oxide into a 100ml high-temperature normal-pressure hydrolysis reaction kettle 1 containing 15g of water, adding 0.045g of potassium carbonate, and reacting for 6 hours at 120 ℃;
high temperature and high pressure hydrolysis: introducing the first-stage product subjected to the high-temperature normal-pressure hydrolysis reaction into a high-temperature high-pressure hydrolysis reaction kettle 2 containing 15g of water and 0.045g of potassium hydroxide, and reacting for 4 hours at 110 ℃ under the pressure condition of 1.0 Mpa;
and (3) vacuum rectification: and (3) introducing the secondary product after the high-temperature high-pressure hydrolysis reaction into a vacuum rectifying tower 3, setting the tower top pressure of the vacuum rectifying tower 3 to be-0.08 Mpa, setting the reflux ratio to be 2.5, extracting electronic grade ethylene glycol from the tower side of the vacuum rectifying tower 3 at the temperature of a reboiler in the tower of 150 ℃, and refluxing the tower top extracted liquid and the tower bottom liquid to the high-temperature normal-pressure hydrolysis reaction kettle 1 or the high-temperature high-pressure hydrolysis reaction kettle 2. The reaction parameters are shown in Table 1, and the test results are shown in Table 2.
Example 3
High-temperature normal-pressure hydrolysis: placing raw materials containing 10g of ethylene carbonate, 10g of diethylene glycol and 10g of ethylene oxide into a 100ml high-temperature normal-pressure hydrolysis reaction kettle 1 containing 15g of water, adding 0.045g of potassium carbonate, and reacting for 5 hours at 110 ℃;
high temperature and high pressure hydrolysis: introducing the first-stage product subjected to the high-temperature normal-pressure hydrolysis reaction into a high-temperature high-pressure hydrolysis reaction kettle 2 containing 15g of water and 0.045g of potassium hydroxide, and reacting for 3 hours at 120 ℃ under the pressure condition of 1.5 Mpa;
and (3) vacuum rectification: and (3) introducing the secondary product after the high-temperature high-pressure hydrolysis reaction into a vacuum rectifying tower 3, setting the tower top pressure of the vacuum rectifying tower 3 to be-0.08 Mpa, setting the reflux ratio to be 3, extracting electronic grade ethylene glycol from the tower side of the vacuum rectifying tower 3 at the temperature of a reboiler in the tower of 150 ℃, and refluxing the tower top extracted liquid and the tower bottom liquid to the high-temperature normal-pressure hydrolysis reaction kettle 1 or the high-temperature high-pressure hydrolysis reaction kettle 2. The reaction parameters are shown in Table 1, and the test results are shown in Table 2.
Comparative example 1
High-temperature normal-pressure hydrolysis: placing raw materials containing 10g of ethylene carbonate, 10g of diethylene glycol and 10g of ethylene oxide into a 100ml high-temperature normal-pressure hydrolysis reaction kettle 1 containing 15g of water, adding 0.045g of potassium carbonate, and reacting for 4 hours at 105 ℃;
and (3) vacuum rectification: and (3) introducing the product obtained after the high-temperature normal-pressure hydrolysis reaction into a vacuum rectifying tower 3, setting the tower top pressure of the vacuum rectifying tower 3 to be-0.08 Mpa, setting the reflux ratio to be 2, extracting electronic grade ethylene glycol from the tower side of the vacuum rectifying tower 3 at the tower inner reboiler temperature of 150 ℃, and refluxing the tower top extracted liquid and the tower bottom liquid to the high-temperature normal-pressure hydrolysis reaction kettle 1 or the high-temperature high-pressure hydrolysis reaction kettle 2. The reaction parameters are shown in Table 1, and the test results are shown in Table 2.
Comparative example 2
High-temperature normal-pressure hydrolysis: placing raw materials containing 10g of ethylene carbonate, 10g of diethylene glycol and 10g of ethylene oxide into a 100ml high-temperature normal-pressure hydrolysis reaction kettle 1 containing 15g of water, adding 0.045g of potassium carbonate, and reacting for 6 hours at 105 ℃;
and (3) vacuum rectification: and (3) introducing the product obtained after the high-temperature normal-pressure hydrolysis reaction into a vacuum rectifying tower 3, setting the tower top pressure of the vacuum rectifying tower 3 to be-0.08 Mpa, setting the reflux ratio to be 2, extracting electronic grade ethylene glycol from the tower side of the vacuum rectifying tower 3 at the tower inner reboiler temperature of 150 ℃, and refluxing the tower top extracted liquid and the tower bottom liquid to the high-temperature normal-pressure hydrolysis reaction kettle 1 or the high-temperature high-pressure hydrolysis reaction kettle 2. The reaction parameters are shown in Table 1, and the test results are shown in Table 2.
Comparative example 3
High temperature and high pressure hydrolysis: placing a raw material containing 10g of ethylene carbonate, 10g of diethylene glycol and 10g of ethylene oxide into a high-temperature high-pressure hydrolysis reaction kettle 2 containing 15g of water and 0.045g of potassium hydroxide, and reacting for 2 hours at 120 ℃ under the pressure condition of 1.3 Mpa;
and (3) vacuum rectification: and (3) introducing the secondary product after the high-temperature high-pressure hydrolysis reaction into a vacuum rectifying tower 3, setting the tower top pressure of the vacuum rectifying tower 3 to be-0.08 Mpa, setting the reflux ratio to be 2, extracting electronic grade ethylene glycol from the tower side of the vacuum rectifying tower 3 at the temperature of a reboiler in the tower of 150 ℃, and refluxing the tower top extracted liquid and the tower bottom liquid to the high-temperature normal-pressure hydrolysis reaction kettle 1 or the high-temperature high-pressure hydrolysis reaction kettle 2. The reaction parameters are shown in Table 1, and the test results are shown in Table 2.
Comparative example 4
High temperature and high pressure hydrolysis: placing a raw material containing 10g of ethylene carbonate, 10g of diethylene glycol and 10g of ethylene oxide into a high-temperature high-pressure hydrolysis reaction kettle 2 containing 15g of water and 0.045g of potassium hydroxide, and reacting for 4 hours at 120 ℃ under the pressure condition of 1.3 Mpa;
and (3) vacuum rectification: and (3) introducing the secondary product after the high-temperature high-pressure hydrolysis reaction into a vacuum rectifying tower 3, setting the tower top pressure of the vacuum rectifying tower 3 to be-0.08 Mpa, setting the reflux ratio to be 2, extracting electronic grade ethylene glycol from the tower side of the vacuum rectifying tower 3 at the temperature of a reboiler in the tower of 150 ℃, and refluxing the tower top extracted liquid and the tower bottom liquid to the high-temperature normal-pressure hydrolysis reaction kettle 1 or the high-temperature high-pressure hydrolysis reaction kettle 2. The reaction parameters are shown in Table 1, and the test results are shown in Table 2.
Comparative example 5
High-temperature normal-pressure hydrolysis: placing raw materials containing 10g of ethylene carbonate, 10g of diethylene glycol and 10g of ethylene oxide into a 100ml high-temperature normal-pressure hydrolysis reaction kettle 1 containing 15g of water, adding 0.045g of potassium carbonate, and reacting for 5 hours at 110 ℃;
high temperature and high pressure hydrolysis: introducing the first-stage product subjected to the high-temperature normal-pressure hydrolysis reaction into a high-temperature high-pressure hydrolysis reaction kettle 2 containing 15g of water and 0.045g of potassium hydroxide, and reacting for 3 hours at 120 ℃ under the pressure condition of 1.5 Mpa; the product was collected. The reaction parameters are shown in Table 1, and the test results are shown in Table 2.
TABLE 1
TABLE 2
The invention adopts the combination of high-temperature normal-pressure hydrolysis reaction and high-temperature high-pressure hydrolysis reaction, wherein the reaction temperature of the high-temperature normal-pressure hydrolysis reaction is 105-120 ℃, the reaction time is 4-6 hours, the reaction temperature of the high-temperature high-pressure hydrolysis reaction is 110-120 ℃, the reaction time is 2-4 hours, the reaction pressure is 1.0-1.5 Mpa, the data of the embodiment 1-3 show that the conversion rate of ethylene carbonate in the raw materials can reach 99.9%, the conversion rate of diethylene glycol can reach 99.8%, the conversion rate of epoxy diethyl ether reaches 100%, meanwhile, the content of the obtained electronic grade ethylene glycol can reach 99.9% after decompression rectification extraction, the acidity is less than or equal to 0.001%, the ash content is less than or equal to 0.001%, meanwhile, iron ions and chloride ions are not detected, and the moisture content in the embodiment 3 is as low as 120ppm.
Both comparative examples 1 and 2 only involved high temperature normal pressure hydrolysis, and the raw materials were subjected to high temperature normal pressure hydrolysis and then directly subjected to vacuum distillation extraction, and it can be seen from the data of comparative examples 1 and 2 that, in the case of only high temperature normal pressure hydrolysis, although the conversion rate of ethylene carbonate and epoxy ether was considerable, the conversion rate of diethylene glycol was only 60% -65%, and the content of electronic grade ethylene glycol finally obtained was only about 95% due to incomplete conversion of diethylene glycol, and it was found that the by-products produced by the cycloaddition process method were not completely converted by the high temperature normal pressure hydrolysis alone, resulting in waste of materials.
Again, as can be seen from the data of comparative examples 3 and 4, both comparative examples 3 and 4 are the cases involving only high temperature and high pressure hydrolysis reaction, i.e., the raw materials are directly subjected to reduced pressure rectification extraction after high temperature and high pressure hydrolysis reaction, and as can be seen from the analysis data, although diethylene glycol and ethylene oxide can be more completely hydrolyzed in the high temperature and high pressure hydrolysis reaction, the conversion rate of ethylene carbonate in the high temperature and high pressure hydrolysis reaction is only about 65%, because in the high pressure environment, the concentration of carbon dioxide generated by hydrolysis of ethylene carbonate in the reaction liquid reaches the critical concentration, the forward progress of the hydrolysis reaction is inhibited, the conversion rate of ethylene carbonate is reduced, and the ethylene carbonate cannot be completely converted.
Finally, as can be seen from the analysis of the data of comparative example 5, if the raw materials are subjected to high-temperature normal-pressure hydrolysis and high-temperature high-pressure hydrolysis in sequence, the raw materials are directly tested without being subjected to reduced-pressure rectification extraction, and the conversion rates of ethylene carbonate, diethylene glycol and ethylene oxide are not basically affected, but the electronic grade ethylene glycol which is a hydrolysis product cannot be completely separated from water without being subjected to reduced-pressure rectification extraction, so that the moisture content in the product is too high, and the moisture (such as distillation) can be removed by other means without being subjected to reduced-pressure rectification, however, the water removal temperature is too high under the condition of not reduced pressure, the energy consumption is serious, and the method is not suitable for industrial production.
The invention has been further described with reference to specific embodiments, but it should be understood that the detailed description is not to be construed as limiting the spirit and scope of the invention, but rather as providing those skilled in the art with the benefit of this disclosure with the benefit of their various modifications to the described embodiments.
Claims (5)
1. A method for preparing electronic grade ethylene glycol is characterized in that a byproduct obtained by preparing ethylene carbonate through a cycloaddition process and ethylene carbonate remained in the byproduct are taken as raw materials together, and high-temperature normal-pressure hydrolysis reaction and high-temperature high-pressure hydrolysis reaction are sequentially carried out, so that the electronic grade ethylene glycol is obtained after the reaction;
the by-products include polyethylene glycol and ethers; the pressure of the high-temperature high-pressure hydrolysis reaction is 1.0-1.5 Mpa.
2. The method for preparing electronic grade ethylene glycol according to claim 1, wherein the reaction temperature of the high-temperature normal-pressure hydrolysis reaction is 105-120 ℃, the reaction time is 4-6 hours, and the mass ratio of water to raw materials is 0.8-1:2-2.4.
3. The method for preparing electronic grade ethylene glycol according to claim 2, wherein the reaction temperature of the high temperature high pressure hydrolysis reaction is 110 to 120 ℃ and the reaction time is 2 to 4 hours.
4. The method for preparing electronic grade ethylene glycol according to claim 1, wherein the high temperature and normal pressure hydrolysis reaction and/or the high temperature and high pressure hydrolysis reaction process further comprises a catalyst, wherein the catalyst is at least one selected from potassium carbonate, potassium hydroxide, sodium carbonate and sodium hydroxide.
5. The method for preparing electronic grade ethylene glycol according to claim 1, further comprising vacuum rectification, wherein the hydrolysis products obtained after the high temperature normal pressure hydrolysis reaction and the high temperature high pressure hydrolysis reaction are subjected to vacuum rectification in sequence, and thus the electronic grade ethylene glycol is obtained.
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| CN202111399928.8A CN114874069B (en) | 2021-11-24 | 2021-11-24 | Method and device for preparing electronic grade ethylene glycol |
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| CN202111399928.8A CN114874069B (en) | 2021-11-24 | 2021-11-24 | Method and device for preparing electronic grade ethylene glycol |
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| CN114874069B true CN114874069B (en) | 2024-03-22 |
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| CN1309112A (en) * | 2000-02-17 | 2001-08-22 | 三菱化学株式会社 | Method for preparing alkylene diol |
| CN101861294A (en) * | 2007-11-14 | 2010-10-13 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycol |
| CN102060657A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Method for preparing dibasic alcohol |
| CN102603477A (en) * | 2012-02-29 | 2012-07-25 | 南京工业大学 | Method for preparing ethylene glycol by ethylene carbonate method |
| CN103209945A (en) * | 2010-11-29 | 2013-07-17 | 国际壳牌研究有限公司 | Process for preparation of ethylene glycol |
| CN110845302A (en) * | 2019-12-02 | 2020-02-28 | 沈阳工业大学 | Method for preparing ethylene glycol based on polyethylene carbonate |
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| CN1309112A (en) * | 2000-02-17 | 2001-08-22 | 三菱化学株式会社 | Method for preparing alkylene diol |
| CN101861294A (en) * | 2007-11-14 | 2010-10-13 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycol |
| CN102060657A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Method for preparing dibasic alcohol |
| CN103209945A (en) * | 2010-11-29 | 2013-07-17 | 国际壳牌研究有限公司 | Process for preparation of ethylene glycol |
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