CN117720417A

CN117720417A - Production method of electronic grade propylene glycol methyl ether acetate

Info

Publication number: CN117720417A
Application number: CN202311173294.3A
Authority: CN
Inventors: 孙津
Original assignee: Beijing Xingming Technology Co ltd
Current assignee: Beijing Xingming Technology Co ltd
Priority date: 2022-04-25
Filing date: 2022-04-25
Publication date: 2024-03-19
Also published as: CN114702385B; CN114702385A

Abstract

The invention provides a production method of electronic grade propylene glycol methyl ether acetate, which takes industrial grade propylene glycol methyl ether acetate as a feed to prepare the electronic grade propylene glycol methyl ether acetate, and specifically comprises the following steps in sequence: organic impurities and a small amount of water in the industrial grade propylene glycol methyl ether acetate are removed through a precise rectifying tower, large particles in the industrial grade propylene glycol methyl ether acetate are removed through a micro-filter (4), anions and/or cations in the industrial grade propylene glycol methyl ether acetate are removed through an anion and cation remover (6), most of water in the industrial grade propylene glycol methyl ether acetate is removed through a dehydration processor (2), and small particles in the industrial grade propylene glycol methyl ether acetate are removed through a nano-filter (12). The invention has the beneficial effects that: the production method of the ultra-clean propylene glycol methyl ether acetate has the advantages of short flow, low energy consumption, good separation effect, strong process continuity and high purity.

Description

Production method of electronic grade propylene glycol methyl ether acetate

Technical Field

The application is issued by China patent office on 25 th 04 th 2022, the application number is 2022104417973, and the invention creates a division of patent application with the name of a high-purity electronic-grade propylene glycol methyl ether acetate production method and device.

Background

With the rapid development of semiconductor and liquid crystal display technologies, the requirements for chemical reagents are increasing. In the integrated circuit and liquid crystal display processing process, the high-cleanness chemical reagent is mainly used for cleaning and etching the surfaces of chips, silicon circles and liquid crystal displays, the purity and cleanliness of the high-cleanness chemical reagent have great influence on the yield, the electrical property and the reliability, ultra-clean Propylene Glycol Methyl Ether Acetate (PGMEA) serving as an important electronic chemical is widely used for semiconductor and liquid crystal displays, along with the processing size of the integrated circuit and the liquid crystal display entering into the nanoera, the high-cleanness Propylene Glycol Methyl Ether Acetate (PGMEA) matched with the integrated circuit and the liquid crystal display has higher requirements, and the SEMI C12 standard formulated by the international semiconductor equipment and material organization needs to be met, wherein the metal cation content is less than 100ppt, the particle size is controlled below 0.2 mu m, and the particle number is negotiated with an electronic chemical demand enterprise.

The research reports of the domestic high-quality and high-degree reagents are not more, the retrievable data are more in the aspects of reports of basic technologies and patents, the international reagent process route belongs to industry confidentiality, and some basic technologies also apply for patent protection.

At present, the only technical patent of electronic grade Propylene Glycol Methyl Ether Acetate (PGMEA) in China realizes PGMEA purification by utilizing the azeotropic principle of water and PGMEA, and most of the PGMEA patents are the PGMEA recovered from electronic waste liquid, and the specific patent conditions are as follows:

application number: 202110336400.X; publication number: CN113072447a, applicant: new Zhongtian environmental protection stock limited company (Chongqing city, xinjiang district, huijun road No. 16); the inventors: chen Guoping, left-hand side, caesalpinia, he Ruiming, hu Jielu, a method for recovering PGMEA from electronic PGMEA waste solvent by a two-step method of thin film evaporation-rectification is proposed, which is essentially flash evaporation-rectification, the PGMEA product recovered by the method has no control means on metals and particles, cannot reach electronic grade PGMEA for recycling, and the evaporation and rectification are divided into two steps, so that the energy consumption is high.

Application number: 202011615015.0; publication number: CN112592276a, applicant: shenzhen environmental protection technology group Co., ltd; the inventors: the invention provides a method for recycling PGMEA waste liquid produced by a liquid crystal display array process by adopting a rectification (sedimentation dessolidation+rectification) method, wherein the reflux ratio is 1-3, the tower bottom temperature is 126-148 ℃, and the method can only obtain 95-98% pure PGMEA and cannot obtain electronic-grade PGMEA.

Application number: 202011615012.7; publication number: CN112608235a, applicant: shenzhen environmental protection technology group Co., ltd; the inventors: the invention provides a method for recycling PGMEA waste liquid produced by liquid crystal display array process production by adopting membrane separation water removal and rectification combined technology, wherein organic membranes are produced by Nanjing Tian membrane company, the water content after membrane separation is below 0.5%, and then the organic membranes enter a rectification tower, the reflux ratio is 1-3:1, the tower bottom temperature is 126-148 ℃, and the PGMEA with the purity of 95-98% is obtained, and the electronic grade PGMEA cannot be obtained.

Application number: 201810082616.6; authorization number: CN108299202B, applicant: fine chemical engineering and high molecular material research institute in the new technology industry development area of Zibo; the inventors: lv Lingjuan, du Zhenjiang, liu Ning and Naping Bai Peng, the invention provides that by adding extractant ethyl benzyl ether, azeotropy of water and PGMEA is destroyed, PGMEA is extracted from PGMEA water solution, the tower bottom liquid is subjected to reduced pressure rectification, the PGMEA product is obtained at the tower top, and the entrainer at the tower bottom can be recycled.

Application number: 201810082752.5; publication number: CN108299203a, applicant: fine chemical engineering and high molecular material research institute in the new technology industry development area of Zibo; the inventors: lv Lingjuan, du Zhenjiang, liu Ning, natant and Bai Peng, the invention proposes that by adding cyclohexane serving as an extractant, azeotropy of water and PGMEA is destroyed, PGMEA is extracted from an aqueous solution of PGMEA, a product of PGMEA is obtained from a tower bottom, tower top water and cyclohexane are condensed and layered, an entrainer can be recycled, water extraction is carried out, the patent is an intermittent process, continuity cannot be realized, the patent does not control particles and metal ions, and electronic-grade PGMEA cannot be obtained.

Application number: 201810082753.X; publication number: CN108129317a, applicant: fine chemical engineering and high molecular material research institute in the new technology industry development area of Zibo; the inventors: lv Lingjuan, du Zhenjiang, liu Ning and Naping Bai Peng, the invention provides a method for continuously recovering PGMEA from PGMEA/water solution by utilizing an azeotropic distillation method, wherein an entrainer cyclohexane and an aqueous solution of PGMEA are continuously added into a distillation tower, more than 99.9% of PGMEA is continuously extracted from the tower bottom, cyclohexane and water vapor are extracted from the tower top, the cyclohexane is separated after condensation, the upper cyclohexane is recycled, and the lower water is discharged from a device.

Application number: 201410547139.8; authorization number: CN104370742B, applicant: huizhou TCL environmental technologies limited; the inventors: wang Zhijun and Li Gongling, this patent proposes that PGMEA waste liquid containing impurities such as PGME (propylene glycol methyl ether), ketones, benzene, ethoxyesters, methoxyesters, water, solid resistors, electronic components and the like is filtered, the raw materials are settled, vacuum distillation and rectification are performed to obtain a product with a purity of more than 95% (up to 99%), and electronic-grade PGMEA cannot be reused.

Application number: 201080068890.X; authorization number: CN103080067B, applicant: korean easy An Ai rich technologies limited; the inventors: zheng Xuantie, wen Zaixiong, ding Zhenpei, pei Enheng, jiang Dushun and Li Minggao, the patent provides a PGMEA (propylene glycol methyl ether acetate, boiling point 146 ℃) waste liquid recovery method produced by a semiconductor and display manufacturing process, and since MMP (3-methoxy methyl acrylate, boiling point 143 ℃) and cyclohexanone (boiling point 155 ℃) contained in waste liquid have small boiling point difference with the PGMEA, the waste liquid is not suitable to be removed by adopting a distillation method, and the C1-20 alkoxide compound is added to enable MMP and cyclohexanone to react and convert into substances with large boiling point difference with the PGMEA for removal.

Application number: 200510132392.8; authorization number: CN1987663B, applicant: new stock Co., ltd; the inventors: guo Guangliang and Dai Xing are prepared from PGMEA (propylene glycol methyl ether acetate) or its derivative and cyclohexanone or its derivative according to a certain proportion.

Application number: 95197185.9; authorization number: CN1074426C, applicant: kelarett finance (BVI) Inc.; the inventors: the invention provides a method for preparing a metal ion-containing photoresist, which comprises the steps of swelling deionized water, leaching the deionized water three times (back flushing for 25 min), carrying out acid treatment on the total sulfuric acid in a 6-bed layer of 10% sulfuric acid 32ml/min, removing acid from the deionized water at the same flow rate until the PH is unchanged, carrying out acetone dehydration in a 2-time bed layer, carrying out PGMEA (program product analysis) removal on the acetone in a 2-time bed layer volume total flow, circulating hot water (60 ℃) through a jacket in order to keep the temperature of a column bed at 55-60 ℃, enabling raw materials to contain 375ppb of sodium ions, enabling iron ions to pass through the treated resin (200g Amberlite,LRC718 chelate resin) at the flow rate of 35min in the bed layer, enabling sodium ions of the product to be less than 5ppb, enabling Fe ions to be less than 23ppb, and enabling the metal ion content of the photoresist to not reach the requirement of SIMI C12 (G4).

Disclosure of Invention

Aiming at the technical problems, the invention aims to provide the electronic grade propylene glycol methyl ether acetate production method which has the advantages of short flow, low energy consumption, good separation effect, strong process continuity, high purity and low impurity content.

1. The first aspect of the invention relates to an electronic grade propylene glycol monomethyl ether acetate production device, which is sequentially connected with a precise rectifying tower, a micro-filter, an anion-cation remover, a dehydration processor and a nanofiltration device in series according to the direction of feeding the industrial grade propylene glycol monomethyl ether into the electronic grade propylene glycol monomethyl ether discharge; the precise rectifying tower comprises a partition tower string for precise rectification;

the partition tower string for precision rectification comprises a partition tower with an upper partition and a partition tower with a middle partition which are connected in series according to the direction of feeding the industrial grade propylene glycol monomethyl ether into the discharging of the electronic grade propylene glycol monomethyl ether; the area ratio of the feeding side to the product extraction side of the dividing wall tower ranges from 1:9 to 9:1, and the theoretical plate number is 20-100.

Further, the apparatus comprises a micro filter membrane having a pore size of 0.2 μm or less and a pore size uniformity coefficient of 1.2 or less; preferably, the microfilter membrane has a pore size of 0.1 μm or 0.2 μm; further preferred are: the micro-filter membrane is at least one of polytetrafluoroethylene membrane, polyether sulfone membrane, polyvinylidene fluoride membrane, polyimide membrane and polyamide membrane;

The anion and cation remover comprises an ion exchange resin anion and cation remover or an ion exchange fiber anion and cation remover; the ion exchange resin anion and cation remover comprises ion exchange resin with aperture of 0.6mm or less and particle size uniformity coefficient of 1.1 or less; preferably, the ion exchange resin has a particle size of at least one of 0.3mm, 0.4mm, 0.5mm and 0.6mm, and the ion exchange resin has a particle size uniformity coefficient of at least one of 1.05, 1.06, 1.07 and 1.09; the ion exchange fiber anion-cation remover comprises ion exchange fibers with the aperture of 0.6mm or less; preferably, it is: the ion exchange resin comprises one or more of sulfonic acid-based styrene resin, carboxyl-based styrene resin, quaternary amine-based styrene resin, perfluorinated sulfonic acid resin and sulfonated polyether sulfone resin, and the ion exchange fiber comprises one or more of sulfonic acid-based styrene fiber, carboxyl-based styrene fiber, quaternary amine-based styrene fiber, perfluorinated sulfonic acid fiber and sulfonated polyether sulfone fiber.

Further, the apparatus includes at least one of a dividing wall column for dehydration treatment, a conventional rectifying column string for dehydration treatment, a membrane separation dehydration treatment, a dehydrating agent dehydration treatment, or an adsorption dehydration treatment;

The area ratio of the feeding side to the product extraction side of the dividing wall column for dehydration treatment ranges from 1:9 to 9:1, and the theoretical plate number of the dividing wall column is 55; the divided wall tower for the dehydration processor includes, but is not limited to, at least one of a divided wall tower of an intermediate divided wall, a divided wall tower of an upper divided wall, and a divided wall tower of a lower divided wall;

the conventional rectifying tower string for dehydration comprises a conventional rectifying tower for primary dehydration with at least one theoretical plate number of 60 and a conventional rectifying tower for secondary dehydration with at least one theoretical plate number of 70 which are connected in series according to the direction of feeding industrial grade propylene glycol methyl ether acetate into discharging of electronic grade propylene glycol methyl ether acetate; preferably, it is: the total number of the conventional rectifying towers for the primary dehydration treatment and the conventional rectifying towers for the secondary dehydration treatment is less than or equal to 6; further preferred are: the total number of the conventional rectifying towers for the primary dehydration treatment and the conventional rectifying towers for the secondary dehydration treatment is less than or equal to 3; still further preferred is: the total number of the conventional rectifying towers for the primary dehydration treatment and the conventional rectifying towers for the secondary dehydration treatment is 2;

the molecular sieve membrane of the membrane separation dehydration processor is at least one selected from a 3A molecular sieve membrane, a 4A molecular sieve membrane and a 5A molecular sieve membrane;

The dehydrating agent of the dehydrating agent dehydration processor is at least one of calcium hydride or calcium chloride;

the molecular sieve adsorbent of the adsorption dehydration processor is at least one selected from a 3A molecular sieve adsorbent, a 4A molecular sieve adsorbent and a 5A molecular sieve adsorbent; further preferred are: the molecular sieve adsorbent of the adsorption dehydration processor is a 3A molecular sieve adsorbent.

Further, the number of theoretical plates of the dividing wall column is 40-80;

the nanofiltration comprises a nanofiltration membrane with a pore diameter of 50nm or less and a pore diameter uniformity coefficient of 1.2 or less; preferably, the pore size of the nanofiltration membrane is 10nm, 20nm, 30nm or 50nm.

The second aspect of the invention relates to a method for producing electronic grade propylene glycol methyl ether acetate, which takes industrial grade propylene glycol methyl ether acetate as a feed to prepare the electronic grade propylene glycol methyl ether acetate, and specifically comprises one or more of the following steps:

removing most of the water in the industrial grade propylene glycol methyl ether acetate;

removing large particles in the industrial grade propylene glycol methyl ether acetate;

removing tiny particles in the industrial grade propylene glycol methyl ether acetate;

the method also comprises the steps of removing organic impurities and a small part of water in the industrial grade propylene glycol methyl ether acetate, wherein:

Before or after the step of removing organic impurities and part of water in the industrial grade propylene glycol methyl ether acetate, the method further comprises the following steps: removing anions and/or cations in the industrial grade propylene glycol methyl ether acetate;

wherein, after removing organic impurities and a small amount of water in the industrial grade propylene glycol methyl ether acetate, removing most of water in the industrial grade propylene glycol methyl ether acetate when removing anions and/or cations in the industrial grade propylene glycol methyl ether acetate;

the anions and/or cations comprise mainly at least one of the four groups shown in table 1:

table 1. Grouping of anions and/or cations.

Wherein, after removing organic impurities and a part of water in the industrial grade propylene glycol methyl ether acetate, the concentration of anions in the propylene glycol methyl ether acetate is controlled to be 50ppb or less, and the single cation concentration is controlled to be 100ppt or less; removing large particles in the industrial grade propylene glycol methyl ether acetate refers to removing particles with the particle size of more than 0.2 mu m; removing tiny particles in the industrial grade propylene glycol methyl ether acetate refers to filtering out particles with the particle size of more than 50 nm; the propylene glycol methyl ether acetate raw material is industrial propylene glycol methyl ether acetate, the purity of the propylene glycol methyl ether acetate is more than 95% by mass, the water content is more than 500ppm, the metal ions are more than 500ppt, the anions are more than 500ppb, and the particles with the particle size of more than 0.2 μm (micrometer) are more than 1000 pieces/ml (milliliter). Other impurity components are not limited.

The industrial grade Propylene Glycol Methyl Ether Acetate (PGMEA) raw material has about 95 percent of the mass content of the Propylene Glycol Methyl Ether Acetate (PGMEA), and is mainly realized by rectification or a permeable membrane or a dehydrating agent through dehydration treatment, wherein the adopted rectification tower can be a conventional rectification tower or a partition wall tower, the permeable membrane is a hydrophilic membrane, and the dehydrating agent can be a molecular sieve, silica gel, calcium hydride, calcium chloride, magnesium sulfate and the like; the dehydrated large particles enter a micro-filter to remove part of Propylene Glycol Methyl Ether Acetate (PGMEA) and then enter an anion and cation removing device, and the process is realized through exchange resin or fiber; propylene Glycol Methyl Ether Acetate (PGMEA) after anion and cation removal enters a precise rectifying device, a conventional rectifying tower or a partition tower is adopted for multistage rectification, the number of the conventional rectifying tower can be halved by the partition tower, equipment is reduced, energy consumption is reduced, and the flow is shortened; propylene Glycol Methyl Ether Acetate (PGMEA) distilled from the rectifying tower or the partition tower enters the nanofiltration device, and enters a product barrel for sealing after fine particles are removed.

Further, the conditions for feeding technical grade propylene glycol methyl ether acetate are as follows: the feeding pressure is 0.3-0.8Mpa, and the feeding temperature is 40-150 ℃; preferably, it is: the feeding pressure is selected from any one of 0.3Mpa, 0.4Mpa, 0.5Mpa, 0.7Mpa and 0.8Mpa, and the feeding temperature is selected from any one of 40 ℃, 50 ℃, 60 ℃, 100 ℃, 110 ℃, 120 ℃, 140 ℃ and 150 ℃; it is further preferred that any one of the following sets of conditions is included: the feeding pressure is 0.8Mpa, and the feeding temperature is 150 ℃; the feeding pressure is 0.7Mpa, and the feeding temperature is 140 ℃; the feeding pressure is 0.3Mpa, and the feeding temperature is 40 ℃; the feeding pressure is 0.5Mpa, and the feeding temperature is 120 ℃; the feeding pressure is 0.3Mpa, and the feeding temperature is 50 ℃; the feeding pressure is 0.5Mpa, and the feeding temperature is 60 ℃; the feeding pressure is 0.5Mpa, and the feeding temperature is 110 ℃; the feed pressure was 0.4MPa and the feed temperature was 100 ℃.

Further, the method comprises the steps of removing organic impurities and a part of water in the industrial grade propylene glycol methyl ether acetate by adopting a precise rectifying tower, wherein the precise rectifying tower comprises a conventional rectifying tower string for precise rectification or a partition tower string for precise rectification, and the method comprises the following steps of:

the conventional rectifying tower string for precision rectification comprises at least two conventional rectifying towers with theoretical plates of 10-100, wherein the tower top pressure of the conventional rectifying towers is 200pa-0.5Mpa, the tower top temperature is 0-200 ℃, and the reflux ratio is 1-10; preferably, it is: the theoretical plate number is 40-80, the tower top pressure is 0.001-0.3 Mpa, the tower top temperature is 31-177 ℃, and the reflux ratio is 3-10;

it is further preferred that the conventional rectifying column string for precision rectification and its operating parameters include any one of four groups shown in table 2:

table 2. Grouping of conventional rectifying column trains and operating parameters for precision rectification.

Further, the method comprises the steps that the partition tower string for precision rectification comprises at least one partition tower for precision rectification, wherein the area ratio of a feeding side to a product extraction side is in the range of 1:9 to 9:1, the theoretical plate number of the partition tower for precision rectification is 20-100, the tower top pressure of the partition tower for precision rectification is 0.005Mpa-0.3Mpa, the tower top temperature is 43-177 ℃, and the reflux ratio is 1-10; preferably, it is: the area ratio of the feeding side to the product extraction side is in the range of 4:6 to 6:4, the theoretical plate number is 50-90, and the reflux ratio is 4-10; the partition tower string for precision rectification includes, but is not limited to, any one or more of a partition tower of an intermediate partition, a partition tower of an upper partition, and a partition tower of a lower partition; the partition column for precision rectification includes any one of the four groups shown in table 3:

TABLE 3 grouping of the column strings and operating parameters for precision rectification.

The method comprises the steps of carrying out a first treatment on the surface of the The bulkhead tower includes, but is not limited to, any one of a bulkhead tower of an intermediate bulkhead, a bulkhead tower of an upper bulkhead, and a bulkhead tower of a lower bulkhead;

further, the method adopts an anion and cation remover to remove anions and/or cations in the industrial propylene glycol methyl ether acetate, wherein:

the anion and cation remover comprises an ion exchange resin anion and cation remover or an ion exchange fiber anion and cation remover; the ion exchange resin anion and cation remover comprises ion exchange resin with aperture of 0.6mm or less and particle size uniformity coefficient of 1.1 or less; preferably, the particle size of the ion exchange resin is 0.3mm, 0.4mm, 0.5mm or 0.6mm, and the particle size uniformity coefficient of the ion exchange resin is at least one of 1.05, 1.06, 1.07, 1.08, 1.09 and 1.1; the ion exchange fiber anion-cation remover comprises ion exchange fibers with the aperture of 0.6mm or less; preferably, it is: the ion exchange resin comprises one or more of sulfonic acid-based styrene resin, carboxyl-based styrene resin, quaternary amine-based styrene resin, perfluorinated sulfonic acid resin and sulfonated polyether sulfone resin, and the ion exchange fiber comprises one or more of sulfonic acid-based styrene fiber, carboxyl-based styrene fiber, quaternary amine-based styrene fiber, perfluorinated sulfonic acid fiber and sulfonated polyether sulfone fiber.

Further to the foregoing, a dehydration processor is employed to remove a majority of the water from the industrial propylene glycol methyl ether acetate, wherein:

the dehydration processor adopts a partition tower for dehydration treatment or any one or more of a conventional rectifying tower string for dehydration treatment, a dehydrating agent dehydration processor, a membrane separation dehydration processor or an adsorption dehydration processor;

the area ratio of the feeding side to the product extraction side of the partition wall tower for dehydration treatment ranges from 1:9 to 9:1, the theoretical plate number of the partition wall tower is 55, the tower top pressure is 0.7Mpa, the tower top temperature is 216 ℃, and the tower top reflux ratio is 5; the divided wall tower for the dehydration processor includes, but is not limited to, at least one of a divided wall tower of an intermediate divided wall, a divided wall tower of an upper divided wall, and a divided wall tower of a lower divided wall;

the conventional rectifying tower string for dehydration comprises a first-stage conventional rectifying tower for dehydration with at least one theoretical plate number of 60 and a second-stage conventional rectifying tower for dehydration with at least one theoretical plate number of 70, which are connected in series according to the direction of feeding industrial-grade propylene glycol methyl ether acetate into discharging of electronic-grade propylene glycol methyl ether acetate, wherein the tower top pressure of the first-stage conventional rectifying tower and the second-stage conventional rectifying tower is 0.4MPa-0.6MPa, the tower top temperature is 190-209 ℃, and the reflux ratio is 4-5; preferably, it is: the total number of the conventional rectifying towers for the primary dehydration treatment and the conventional rectifying towers for the secondary dehydration treatment is less than or equal to 6; further preferred are: the total number of the conventional rectifying towers for the primary dehydration treatment and the conventional rectifying towers for the secondary dehydration treatment is less than or equal to 3; still further preferred is: the total number of the conventional rectifying towers for the primary dehydration treatment and the conventional rectifying towers for the secondary dehydration treatment is 2;

The molecular sieve membrane of the membrane separation dehydrator is at least one selected from a 3A molecular sieve membrane, a 4A molecular sieve membrane and a 5A molecular sieve membrane;

the dehydrating agent of the dehydrating agent dehydrator is at least one of calcium hydride or calcium chloride;

the molecular sieve adsorbent of the adsorption dehydrator is at least one selected from a 3A molecular sieve adsorbent, a 4A molecular sieve adsorbent and a 5A molecular sieve adsorbent.

Further, the purity of the industrial grade propylene glycol methyl ether acetate is above 95% by mass, the water content is above 500ppm, the metal ions are above 500ppt, the anions are above 500ppb, and the particles with the particle size of more than 0.2 μm (micrometer) are more than 1000 pieces/ml (milliliter); preferably, it is: the composition of the technical grade propylene glycol methyl ether acetate is referred to in the index of the raw materials in table 4.

The invention has the beneficial effects that: the invention provides a method and a device for producing ultra-clean Propylene Glycol Methyl Ether Acetate (PGMEA) with short flow, low energy consumption, good separation effect, strong process continuity, high purity and low impurity content, and the method and the device can obtain the high-clean Propylene Glycol Methyl Ether Acetate (PGMEA) product meeting the electronic chemical SEMI C12 (G4) standard. The industrial grade Propylene Glycol Methyl Ether Acetate (PGMEA) is subjected to dehydration treatment by a dehydration processor to remove most of water, enters a micro-filter to remove particles with the particle size of more than 0.2 mu m, enters an anion-cation remover to remove most of anions and cations in the Propylene Glycol Methyl Ether Acetate (PGMEA), then enters a conventional rectifying tower or a partition rectifying tower, and the obtained Propylene Glycol Methyl Ether Acetate (PGMEA) is subjected to nanofiltration to remove particles with the particle size of 10nm or more to obtain an electronic grade Propylene Glycol Methyl Ether Acetate (PGMEA) product which finally meets SEMI C12 (G4) standard or more.

Drawings

Fig. 1: the invention relates to a device schematic diagram of a production method of electronic grade propylene glycol methyl ether acetate.

Fig. 2: is a schematic diagram of a device variant 1 of the method for producing electronic grade propylene glycol methyl ether acetate.

Fig. 3: is a schematic diagram of a device variant 2 of the method for producing electronic grade propylene glycol methyl ether acetate.

Fig. 4: is a schematic diagram of device variant 3 of the method for producing electronic grade propylene glycol methyl ether acetate according to the present invention.

Fig. 5: is a schematic diagram of a variation 4 of the apparatus for the process for producing electronic grade propylene glycol methyl ether acetate of the present invention.

Fig. 6: is a schematic diagram of a variation 6 of the apparatus for producing electronic grade propylene glycol methyl ether acetate according to the present invention.

Fig. 7: is a schematic diagram of a variation 7 of the apparatus for the process for producing electronic grade propylene glycol methyl ether acetate of the present invention.

Fig. 8: is a schematic diagram of a variation 8 of the apparatus for the process for producing electronic grade propylene glycol methyl ether acetate of the present invention.

Fig. 9: is a schematic diagram of a variation 9 of the apparatus for producing electronic grade propylene glycol methyl ether acetate according to the present invention.

Fig. 10: is a schematic diagram of the apparatus of the method for producing electronic grade propylene glycol methyl ether acetate of comparative example 5 of the present invention.

Fig. 11: is a schematic diagram of a possible form of a divided wall column of the present invention; wherein the form a intermediate partition; form B is an upper partition wall; the C form is a lower partition wall.

Reference numerals illustrate:

1. technical grade propylene glycol methyl ether acetate; 2. a dehydrator; 3. propylene glycol methyl ether acetate after first dehydration; 4. a microfilter; 5. propylene glycol methyl ether acetate after microfiltration; 6. an anion and cation remover; 7. propylene glycol methyl ether acetate after ion removal; 8. a first-stage dividing wall column; 9. propylene glycol methyl ether acetate after first rectification; 10. a second-stage dividing wall column; 11. propylene glycol methyl ether acetate after second rectification; 12. a nanofiltration device; 13. an electronic grade propylene glycol methyl ether acetate product; 14. a light component; 15. a heavy component; 16. a first-stage conventional rectifying tower; 17. a second-stage conventional rectifying tower; 18. three-stage conventional rectifying towers; 19. four-stage conventional rectifying towers; 20. propylene glycol methyl ether acetate after third rectification; 21. propylene glycol methyl ether acetate after fourth rectification.

Detailed Description

The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention.

Interpretation of the terms

The divided wall column is also called a divided wall rectifying column, and can be classified into a divided wall column for dehydration treatment, a divided wall column for precision rectification, and the like according to the present invention;

the conventional rectifying tower is also called a rectifying tower, and can be divided into a conventional rectifying tower for dehydration treatment and a conventional rectifying tower for precision rectification according to the action of the invention;

the "area ratio of the two sides of the dividing wall column" is also referred to as the "area ratio of the feed side and the product extraction side", and refers to the area ratio of the two sides divided by the dividing wall.

The invention relates to an electronic grade propylene glycol methyl ether acetate, which is also called as an electronic grade propylene glycol methyl ether acetate, an electronic chemical propylene glycol methyl ether acetate and an ultrapure propylene glycol methyl ether acetate meeting SEMI C12 (G4) standard.

The process of the process is that the process is carried out according to the direction of feeding the industrial grade propylene glycol methyl ether acetate into the discharging of the electronic grade propylene glycol methyl ether acetate, and the devices are connected in series sequentially.

The invention is not particularly limited, and the prior art for ensuring the passing of propylene glycol methyl ether acetate in each step is within the selection range of the invention, including direct connection and indirect connection.

In some embodiments of the present invention, an electronic grade propylene glycol methyl ether acetate production apparatus, an anion and cation remover; wherein,

when the dehydration processor or the precise rectifying tower is connected in series according to the direction of feeding the industrial grade propylene glycol methyl ether acetate into the electronic grade propylene glycol methyl ether acetate before the anion and cation remover, the precise rectifying tower and the nanofiltration set or the dehydration processor and the nanofiltration set are connected in series after the anion and cation remover, and the front and rear of the anion and cation remover cannot be the dehydration processor or the precise rectifying tower at the same time;

when the dehydration processor and the precise rectifying tower are not connected in series according to the direction of feeding the industrial grade propylene glycol methyl ether acetate into the discharging of the electronic grade propylene glycol methyl ether acetate before the anion-cation remover, the precise rectifying tower and the nanofiltration set are connected in series or only the precise rectifying tower is connected in series after the anion-cation remover;

in one embodiment, the electronic grade propylene glycol methyl ether acetate production device shown in fig. 1 comprises a dehydration processor 2, a micro-filter 4, an anion and cation remover 6, a precise rectifying tower 8, a precise rectifying tower 10 and a nano-filter 12 which are connected in series in the direction from the feeding of the industrial grade propylene glycol methyl ether acetate 1 to the discharging of the electronic grade propylene glycol methyl ether acetate 13, and in some embodiments, the electronic grade propylene glycol methyl ether acetate production device further comprises auxiliary equipment such as pumps, heat exchangers and the like corresponding to the dehydration processor, the micro-filter, the anion and cation remover and the precise rectifying tower. The device provided by the embodiment of the invention can provide the ultra-clean propylene glycol methyl ether acetate production method with short flow, low energy consumption, good separation effect, strong process continuity, high purity and low impurity content, and the high-clean propylene glycol methyl ether acetate product meeting the electronic chemical SEMI C12 (G4) standard is obtained. According to the dehydration processor 2 provided by the embodiment of the invention, most of water in propylene glycol methyl ether acetate is removed, the micro-filter 4 is used for removing large particles in propylene glycol methyl ether acetate, the anion-cation remover 6 is used for removing most of cations and anions in propylene glycol methyl ether acetate, the precision rectifying towers 8 and 10 are used for removing small parts of water, organic impurities and the like in propylene glycol methyl ether acetate, and finally the nano-filter 12 is used for removing small particles in propylene glycol methyl ether acetate liquid, so that the water, particles and other impurity content in the propylene glycol methyl ether acetate meet the requirements above SEMI C12 (G4) standard of electronic chemicals. Finally, the production of propylene glycol methyl ether acetate meeting the highest standard requirement of electronic chemicals from industrial-grade propylene glycol methyl ether acetate is realized.

The following exemplary description applies the apparatus of the present invention to prepare a high clean propylene glycol methyl ether acetate product meeting the electronic chemical SEMI C12 (G4) standard or above.

With continued reference to fig. 1, the industrial grade propylene glycol methyl ether acetate 1 from outside the boundary zone enters a dehydration processor 2 to remove most of the water, the dehydration processor 2 can adopt four methods of conventional rectifying tower or partition tower dehydration, dehydrating agent dehydration, membrane separation dehydration and adsorption dehydration, the dehydrating agent is selected from calcium hydride and calcium chloride, the separation membrane is selected from 3A molecular sieve membrane, 4A molecular sieve membrane and 5A molecular sieve membrane, the adsorbent is selected from 3A molecular sieve adsorbent and 5A molecular sieve adsorbent, and in other embodiments, the dehydration can be performed by osmotic membrane evaporation, and the osmotic membrane is a hydrophilic membrane; the dehydrated propylene glycol methyl ether acetate 3 enters a micro-filter 4 to remove particles (large particles) with the particle diameter of more than 0.2 mu m, wherein the micro-filter can adopt a polytetrafluoroethylene membrane, a polyether sulfone membrane, a polyvinylidene fluoride membrane, a polyimide membrane and a polyamide membrane with the pore diameter of 0.2 mu m and the pore diameter uniformity coefficient of 1.2 or less; the mixture enters an anion and cation remover 6 after microfiltration to remove most anions and cations in propylene glycol methyl ether acetate, wherein the anion and cation remover 6 can adopt ion exchange resin or ion exchange fiber, for example, the ion exchange resin adopts customized functional resin, the ion exchange fiber adopts customized functional fiber, the particle size of the ion exchange resin and the ion exchange fiber is 0.6mm or less, the particle size uniformity coefficient is 1.1 or less, the ion exchange resin comprises one or more of sulfonic acid styrene resin, carboxyl styrene resin, quaternary amino styrene resin, perfluorinated sulfonic acid resin and sulfonated polyether sulfone resin, and the ion exchange fiber comprises one or more of sulfonic acid styrene fiber, carboxyl styrene fiber, quaternary amino styrene fiber, perfluorinated sulfonic acid fiber and sulfonated polyether sulfone fiber; the removed anionic and cationic propylene glycol methyl ether acetate 7 enters a precise rectifying tower (a multi-stage rectifying device), and the multi-stage rectification adopts a conventional rectifying tower or a partition tower, for example, the conventional rectifying tower 16, the conventional rectifying tower 17, the conventional rectifying tower 18, the conventional rectifying tower 19, or the partition tower 8 and the partition tower 10 can be adopted, and the number of the precise rectifying towers can be increased or reduced to 0-6 according to the actual raw materials and product standard requirements. In other embodiments of the present invention, the number of conventional rectifying towers can be greatly reduced under the condition of meeting the same separation precision requirement, the original two conventional rectifying towers can be reduced to one tower, the original 4 rectifying towers are reduced to two towers, the conventional 6 rectifying towers are reduced to 3 rectifying towers, the energy consumption and the investment are greatly reduced, the area ratio of two sides of the dividing wall tower ranges from 1:9 to 9:1, and referring to fig. 11, the dividing wall tower mainly comprises three types of middle dividing wall, upper dividing wall and lower dividing wall, but is not limited to the above three types; the propylene glycol methyl ether acetate product obtained by precise rectification is filtered by a nanofiltration membrane 12 to remove particles with the diameter of more than 50nm, the nanofiltration membrane is a nanofiltration membrane with the aperture of 50nm or less and the aperture uniformity coefficient of 1.2 or less, the nanofiltration membrane is selected from a polytetrafluoroethylene membrane, a polyether sulfone membrane, a polyvinylidene fluoride membrane (PVDF), a polyimide membrane or a polyamide membrane, and finally the electronic grade propylene glycol methyl ether acetate product 13 meeting the requirements of SEMI C12 (G4) standard is obtained and can enter a product barrel for sealing.

The following is an apparatus example of an electronic grade propylene glycol methyl ether acetate production apparatus.

Device example 1 an electronic grade propylene glycol methyl ether acetate production device as shown in figure 2 comprises a dehydration processor 2, a micro-filter 4, an anion and cation remover 6, a precise rectifying tower 10 and a nano-filter 12 which are connected in series in the direction from the feeding of the industrial grade propylene glycol methyl ether acetate 1 to the discharging of the electronic grade propylene glycol methyl ether acetate 13; in a particularly preferred embodiment, the dehydration processor 2 adopts a first-stage dividing wall column 8, the dividing wall column adopts a form A, the area ratio of the feeding side to the discharging side of the product is 7:3, and the theoretical plate number is 55; the micro-filter 4 adopts a polytetrafluoroethylene film with the aperture of 0.2 mu m and the aperture uniformity coefficient of 1.15; the anion and cation remover 6 adopts sulfonic styrene functional resin with the particle diameter of 0.4mm and the particle diameter uniformity coefficient of 1.08; the two-stage partition tower 10 adopts a mode A, the area ratio of two sides is 4:6, and the theoretical plate number is 50; the nanofiltration membrane 12 was a polytetrafluoroethylene membrane having a pore size of 10nm and a uniformity coefficient of 1.2.

Device example 2 an electronic grade propylene glycol methyl ether acetate production device as shown in fig. 3 comprises a rectifying tower 16, a rectifying tower 17, a microfilter 4, an anion and cation remover 6, a rectifying tower 18, a rectifying tower 19 and a nanofiltration 12 which are connected in series in the direction from the feeding of the industrial grade propylene glycol methyl ether acetate 1 to the discharging of the electronic grade propylene glycol methyl ether acetate 13, wherein in a specific preferred embodiment, the dehydration processor 2 comprises a primary conventional rectifying tower 16 and a secondary conventional rectifying tower 17, and the theoretical plate number of the primary conventional rectifying tower 16 is 60; the theoretical plate number 70 of the second-stage conventional rectifying tower 17, the micro-filter 4 adopts a vinylidene fluoride film with the aperture of 0.2 mu m and the aperture uniformity coefficient of 1.1, the anion and cation remover 6 adopts carboxyl styrene functional resin with the particle size of 0.5mm and the particle size uniformity coefficient of 1.05, and the theoretical plate number 50 of the rectifying tower 18; the theoretical plate number of the rectifying tower 19 is 50, and the nanofiltration 12 is a polyvinylidene fluoride membrane with the aperture of 20nm and the aperture uniformity coefficient of 1.15.

Device example 3 an electronic grade propylene glycol methyl ether acetate production device as shown in fig. 4, wherein the device is connected in series with a first-stage separation wall tower 8, a second-stage separation wall tower 10, a micro-filter 4, an anion and cation remover 6, a dehydration processor 2 and a nano-filter 12 according to the direction of feeding the industrial grade propylene glycol methyl ether acetate into the electronic grade propylene glycol methyl ether acetate discharge, in a specific preferred embodiment, the separation wall tower 8 adopts a B form, the area ratio of two sides of the first-stage separation wall tower 8 is 5:5, the theoretical plate number is 80, the second-stage separation wall tower 10 adopts an A form, the area ratio of two sides of the separation wall tower 10 is 5:5, and the theoretical plate number is 90; the microfilter 4 is a polyvinylidene fluoride membrane with a pore diameter of 0.1 μm and a pore diameter uniformity coefficient of 1.1, the anion and cation remover 6 is a carboxystyrene functional resin with a particle diameter of 0.6mm and a uniformity coefficient of 1.05, and the nanofilter 12 is a polyvinylidene fluoride membrane with a pore diameter of 20nm and a pore diameter uniformity coefficient of 1.15.

Device example 4 an electronic grade propylene glycol methyl ether acetate production device as shown in fig. 5 comprises a first-stage conventional rectifying tower 16, a second-stage conventional rectifying tower 17, a third-stage conventional rectifying tower 18, a fourth-stage conventional rectifying tower 19, a micro-filter 4, an anion and cation remover 6, a dehydration processor 2 and a nano-filter 12 which are connected in series according to the direction of feeding the industrial grade propylene glycol methyl ether acetate into the electronic grade propylene glycol methyl ether acetate discharge, and in a particularly preferred embodiment, the theoretical plate number 80 of the first-stage conventional rectifying tower 16; the theoretical plate number of the second-stage conventional rectifying tower 17 is 70; the theoretical plate number of the three-stage conventional rectifying tower 18 is 50; the theoretical plate number of the four-stage conventional rectifying tower 19 is 50; the micro-filter 4 is a polytetrafluoroethylene membrane with the aperture of 0.2 mu m and the aperture uniformity coefficient of 1.2, the anion and cation remover 6 is 0.3mm particle size, the sulfonate styrene functional resin with the particle size uniformity coefficient of 1.1, the dehydration processor 2 adopts a 4A molecular sieve membrane, and the nano-filter 12 is a polytetrafluoroethylene membrane with the aperture of 10nm and the aperture uniformity coefficient of 1.1.

Device example 5 an electronic grade propylene glycol methyl ether acetate production device as shown in figure 6 comprises a micro-filter 4, an anion and cation remover 6, a first-stage separation wall tower 8, a second-stage separation wall tower 10 and a nano-filter 12 which are connected in series in the direction of feeding the industrial grade propylene glycol methyl ether acetate into the discharge of the electronic grade propylene glycol methyl ether acetate, wherein in a specific preferred embodiment, the micro-filter 4 is a polyvinylidene fluoride membrane with 0.1 mu m aperture and 1.15 aperture uniformity coefficient, the anion and cation remover 6 adopts sulfonic styrene resin with 0.5mm particle size and 1.07 particle size uniformity coefficient, the separation wall tower 8 adopts a C form, the area ratio of two sides of the separation wall tower 8 is 5:5, and the theoretical plate number is 90; the partition tower 10 adopts a B type, the area ratio of two sides of the partition tower 10 is 6:4, the theoretical plate number is 80, and the nanofiltration 12 is a polyimide film with the aperture of 30nm and the aperture uniformity coefficient of 1.1.

Device example 6 an electronic grade propylene glycol methyl ether acetate production device as shown in fig. 7 comprises a microfilter 4, an anion and cation remover 6, a rectifying tower 16, a rectifying tower 17, a rectifying tower 18, a rectifying tower 19 and a nanofiltration 12 which are connected in series according to the direction of feeding the industrial grade propylene glycol methyl ether acetate 1 to discharging the electronic grade propylene glycol methyl ether acetate 13, and in a particularly preferred embodiment, the microfilter 4 is a polyimide film with 0.2 μm aperture and aperture uniformity coefficient of 1.05; the anion and cation remover 6 is quaternary amino styrene functional resin with the particle size of 0.6mm and the particle size uniformity coefficient of 1.05, and the theoretical plate number of the primary rectifying tower 16 is 90; theoretical plate number 60 of the second-stage conventional rectifying tower 17; the theoretical plate number of the three-stage conventional rectifying tower 18 is 50; the theoretical plate number 40 of the four-stage conventional rectifying tower 19, the nanofiltration 12 is a polyimide film with the aperture of 10nm and the aperture uniformity coefficient of 1.2.

Device example 7, as shown in fig. 8, the device comprises an anion and cation remover 6, a partition tower 8, a partition tower 10 and a nanofiltration 12 which are connected in series in the direction from the feeding of the industrial grade propylene glycol methyl ether acetate 1 to the discharging of the electronic grade propylene glycol methyl ether acetate 13, wherein in a specific preferred embodiment, the anion and cation remover 6 is sulfonic styrene functional resin with the particle size of 0.5mm and the particle size uniformity coefficient of 1.06, the partition tower 8 adopts the form of B, the area ratio of two sides is 4:6, and the theoretical plate number is 90; the partition tower 10 adopts a B form, the area ratio of two sides is 5:5, the theoretical plate number is 80, and the nanofiltration 12 is a polyimide film with the aperture of 50nm and the aperture uniformity coefficient of 1.05.

Device example 8 an electronic grade propylene glycol methyl ether acetate production device as shown in fig. 9 comprises an anion and cation remover 6, a rectifying tower 16, a rectifying tower 17, a rectifying tower 18, a rectifying tower 19 and a nanofiltration 12 which are connected in series in the direction from the feeding of the industrial grade propylene glycol methyl ether acetate 1 to the discharging of the electronic grade propylene glycol methyl ether acetate 13, wherein in a specific preferred embodiment, the anion and cation remover 6 is sulfonic styrene functional resin with the particle size of 0.4mm and the particle size uniformity coefficient of 1.09, and the theoretical plate number of the first-stage conventional rectifying tower 16 is 80; the theoretical plate number of the second-stage conventional rectifying tower 17 is 70; the theoretical plate number of the three-stage conventional rectifying tower 18 is 50; the theoretical plate number of the four-stage conventional rectifying tower 19 is 50, and the nanofiltration 12 is a polytetrafluoroethylene membrane with a pore diameter of 50nm and a pore diameter uniformity coefficient of 1.05.

Device comparative example 1 an electronic grade propylene glycol methyl ether acetate production device as shown in fig. 10 comprises a rectifying tower 16, a rectifying tower 17, a rectifying tower 18, a rectifying tower 19, an anion and cation remover 6 and a nanofiltration 12 which are connected in series in the direction from the feeding of the industrial grade propylene glycol methyl ether acetate 1 to the discharging of the electronic grade propylene glycol methyl ether acetate 13, wherein the anion and cation remover 6 is sulfonic styrene functional resin with the particle size of 0.4mm and the particle size uniformity coefficient of 1.09, and the theoretical plate number of the first-stage conventional rectifying tower 16 is 80; the theoretical plate number of the second-stage conventional rectifying tower 17 is 70; the theoretical plate number of the three-stage conventional rectifying tower 18 is 50; the theoretical plate number of the four-stage conventional rectifying tower 19 is 50, and the nanofiltration 12 is a polytetrafluoroethylene membrane with a pore diameter of 50nm and a pore diameter uniformity coefficient of 1.05.

In some embodiments of the present invention, the method for producing electronic grade propylene glycol methyl ether acetate comprises the steps of using industrial grade propylene glycol methyl ether acetate as a feed to produce electronic grade propylene glycol methyl ether acetate, comprising one or more of the following steps:

removing most of water in the industrial grade propylene glycol methyl ether acetate;

removing organic impurities and a part of water in the industrial grade propylene glycol methyl ether acetate;

also comprises the steps of removing organic impurities and a small part of water in the industrial grade propylene glycol methyl ether acetate, wherein:

before or after the step of removing organic impurities and a part of water in the industrial grade propylene glycol methyl ether acetate, the method also comprises the following steps: removing anions and/or cations in the industrial grade propylene glycol methyl ether acetate;

wherein, when removing anions and/or cations in the industrial grade propylene glycol methyl ether acetate after removing organic impurities and a part of water in the industrial grade propylene glycol methyl ether acetate, removing most of water in the industrial grade propylene glycol methyl ether acetate.

The method for removing anions and/or cations in the industrial grade propylene glycol methyl ether acetate mainly comprises at least one of four groups shown in the table 1:

table 1. Grouping of anions and/or cations.

The following are examples of processes for the production of electronic grade propylene glycol methyl ether acetate.

Example 1

With continued reference to fig. 2, the parameters corresponding to the various components in the apparatus are shown in table 4,

table 4. Parameters corresponding to the components in the apparatus of example 1.

Obtaining the SEMI C12 (G4) standard and the high-purity Propylene Glycol Methyl Ether Acetate (PGMEA) product with the product index shown in Table 12.

Example 2

With continued reference to fig. 3, the device parameters are shown in table 5,

table 5. Parameters corresponding to the components in the apparatus of example 2.

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Example 3 (preferred embodiment)

With continued reference to fig. 4, the device parameters are shown in table 6,

table 6. Parameters corresponding to the components in the apparatus of example 3.

Obtaining the high-purity propylene glycol methyl ether acetate product with SEMI C12 (G4) standard and above, and the product index is shown in Table 12.

Example 4 (preferred embodiment)

With continued reference to fig. 5, the device parameters are shown in table 7,

table 7. Parameters corresponding to the components in the apparatus of example 4.

Example 5

With continued reference to fig. 6, the device parameters are shown in table 8,

table 8. Parameters corresponding to the components in the apparatus of example 5.

Obtaining the SEMI C12 (G4) standard and the high-purity Propylene Glycol Methyl Ether Acetate (PGMEA) product with the product index shown in Table 13.

Example 6

With continued reference to fig. 7, the device parameters are shown in table 9,

table 9. Parameters corresponding to the components in the device of example 6.

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Example 7

With continued reference to fig. 8, the device parameters are shown in table 10,

table 10. Parameters corresponding to the components in the device of example 7.

Example 8

With continued reference to fig. 9, the device parameters are shown in table 11,

table 11. Parameters corresponding to the components in the apparatus of example 8.

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Comparative example 1

The comparative example is the same as the raw materials and the flow of the example 1, and with continued reference to fig. 2, and is different from the example 1 in that the particle size uniformity coefficient of the resin in the anion and cation remover is 1.2, the product index is shown in table 14, and sodium ions, calcium ions and boron ions cannot meet the requirements of SEMI C12 (G4); sodium ion, iron ion, copper ion, lead ion, calcium ion, potassium ion, boron ion and silicon ion cannot meet the G5 requirement.

Comparative example 2

The comparative example is the same as the raw materials and the flow of the example 1, and is continued to refer to fig. 3, and is different from the example 2 in that the particle size of the ion exchange resin adopted is changed to 0.7mm, the product indexes are shown in table 14, and sodium ions, calcium ions, potassium ions and boron ions cannot meet the requirements of SEMI C12 (G4); sodium ion, iron ion, lead ion, potassium ion, calcium ion, titanium ion, silicon ion, nickel ion, copper ion, arsenic ion, tin ion and boron ion cannot meet the G5 requirement.

Comparative example 3

The comparative example, which is identical to the raw materials and the flow path of example 1 and is different from example 7 in that the pore size uniformity coefficient of the nanofiltration is 1.25, the product index is shown in table 14, and the propylene glycol methyl ether acetate particles prepared in the comparative example can meet SEMI C12 (G4) but cannot meet G5 requirements.

Comparative example 4

The comparative example is the same as the raw materials and the flow of example 8, and with continued reference to fig. 9, and differs from example 8 in that the pore diameter of the nanofiltration is 100nm, the product index is shown in table 14, and the propylene glycol methyl ether acetate particles prepared in the comparative example can meet the SEMI C12 (G4) requirement, but cannot meet the G5 requirement.

Comparative example 5

Comparative example 5 provides a method for producing electronic grade propylene glycol methyl ether acetate, as shown in fig. 10, which is different from example 8 in that an anion and cation removal step is placed after a rectification step, other parameters are the same as those of example 8, product indexes are shown in table 14, and the water content of propylene glycol methyl ether acetate produced in the comparative example cannot meet the requirements of SEMI C12 (G4).

Comparative example 6

This comparative example was identical to example 3 in terms of raw materials and flow, with continued reference to FIG. 4, and was different from example 3 in that the form of the divided wall column (8) was changed from B to A, and otherwise identical. The product index is shown in Table 2 (follow-up). Purity meets SEMI C12 (G4) requirements but fails to meet G5 requirements.

Comparative example 7

This comparative example was identical to example 3 in terms of raw materials and flow, with continued reference to FIG. 4, and was different from example 3 in that the form of the divided wall column (10) was changed from A to B, and otherwise identical. The product index is shown in Table 2 (follow-up). Purity meets SEMI C12 (G4) requirements but fails to meet G5 requirements.

Comparative example 8

This comparative example was identical to example 3 in terms of the raw materials and the flow path, with continued reference to FIG. 4, and was different from example 3 in that the type of the divided wall column (8) was changed from B to C, and the type of the divided wall column (10) was changed from A to C, and otherwise identical. The product index is shown in Table 2. The purity cannot meet the requirements of SEMI C12 (G4) and G5.

Test example 1

The content of the components in propylene glycol methyl ether acetate of the electronic chemicals of examples 1 to 8 and comparative examples 1 to 5 was detected by the following measuring instrument: the cation adopts Agilent ICP-MS/MS8900, the anion adopts Switzerland Wanton 940 ion chromatography, the water content adopts 851 coulomb method card type water analyzer, and the organic impurity adopts Agilent GC-MS gas chromatography. The results are shown in tables 12-15, with the raw materials in Table 12 referring to technical grade propylene glycol methyl ether acetate.

Table 12. Results of measuring the contents of the components in propylene glycol methyl ether acetate, electronic chemicals of examples 1 to 4.

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TABLE 13 detection results of the contents of the components in propylene glycol methyl ether acetate as an electronic chemical in examples 5 to 8.

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Table 14. Results of measuring the contents of the components in propylene glycol methyl ether acetate as an electronic chemical in comparative examples 1 to 5.

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Table 15. Results of measuring the contents of the components in propylene glycol methyl ether acetate as an electronic chemical in comparative examples 1 to 5.

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The above table is for explaining the great relation between the component content and the source of the components contained in the propylene glycol methyl ether acetate raw material, but the applicability of the invention is not limited, and the propylene glycol methyl ether acetate product produced by the method of the invention can meet the standard requirements of SEMI C12 (G4).

While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims

1. A production method of electronic grade propylene glycol methyl ether acetate is characterized in that: the method takes industrial grade propylene glycol methyl ether acetate as a feed to prepare high-purity electronic grade propylene glycol methyl ether acetate, and specifically comprises one or more of the following steps:

table 1. Grouping of anions and/or cations.

2. The method of claim 1, wherein: removing organic impurities and a small part of water in the industrial grade propylene glycol methyl ether acetate by adopting a precise rectifying tower, wherein the precise rectifying tower comprises a conventional rectifying tower string for precise rectification or a partition tower string for precise rectification, and the method comprises the following steps of:

3. The method of claim 1, wherein: the partition wall tower string for precision rectification comprises at least one partition wall tower for precision rectification, wherein the area ratio of a feeding side to a product extraction side is in the range of 1:9 to 9:1, the theoretical plate number is 20-100, the tower top pressure of the partition wall tower for precision rectification is 0.005-0.3 Mpa, the tower top temperature is 43-177 ℃, and the reflux ratio is 1-10; preferably, it is: the area ratio of the feeding side to the product extraction side is in the range of 4:6 to 6:4, the theoretical plate number is 50-90, and the reflux ratio is 4-10; the partition tower string for precision rectification includes, but is not limited to, any one or more of a partition tower of an intermediate partition, a partition tower of an upper partition, and a partition tower of a lower partition; the partition column for precision rectification includes any one of the four groups shown in table 3:

4. The method of claim 1, wherein: and adopting an anion and cation remover to remove anions and/or cations in the industrial propylene glycol methyl ether acetate, wherein:

the anion and cation remover comprises an ion exchange resin anion and cation remover or an ion exchange fiber anion and cation remover; the ion exchange resin anion and cation remover comprises ion exchange resin with aperture of 0.6mm and particle size uniformity coefficient of 1.1 or below; preferably, the particle diameter of the ion exchange resin is 0.3mm, 0.4mm or 0.5mm, and the particle diameter uniformity coefficient of the ion exchange resin is at least one of 1.06, 1.07, 1.08, 1.09 and 1.1; the ion exchange fiber anion-cation remover comprises ion exchange fibers with the aperture of less than 0.6 mm; preferably, it is: the ion exchange resin comprises one or more of sulfonic acid-based styrene resin, quaternary amine-based styrene resin, perfluorinated sulfonic acid resin and sulfonated polyether sulfone resin, and the ion exchange fiber comprises one or more of sulfonic acid-based styrene fiber, quaternary amine-based styrene fiber, perfluorinated sulfonic acid fiber and sulfonated polyether sulfone fiber.

5. The method of claim 1, wherein: removing most of the water in the industrial propylene glycol methyl ether acetate by adopting a dehydration processor, wherein:

the conventional rectifying tower string for dehydration comprises a first-stage conventional rectifying tower for dehydration with at least one theoretical plate number of 60 and a second-stage conventional rectifying tower for dehydration with at least one theoretical plate number of 70, which are connected in series according to the direction of feeding industrial-grade propylene glycol methyl ether acetate into high-purity electronic-grade propylene glycol methyl ether acetate for discharge, wherein the tower top pressure of the first-stage conventional rectifying tower and the second-stage conventional rectifying tower is 0.4MPa-0.6MPa, the tower top temperature is 190-209 ℃, and the reflux ratio is 4-5; preferably, it is: the total number of the conventional rectifying towers for the primary dehydration treatment and the conventional rectifying towers for the secondary dehydration treatment is less than or equal to 6; further preferred are: the total number of the conventional rectifying towers for the primary dehydration treatment and the conventional rectifying towers for the secondary dehydration treatment is less than or equal to 3; still further preferred is: the total number of the conventional rectifying towers for the primary dehydration treatment and the conventional rectifying towers for the secondary dehydration treatment is 2;

The molecular sieve membrane of the membrane separation dehydrator is at least one selected from a 4A molecular sieve membrane and a 5A molecular sieve membrane;

the molecular sieve adsorbent of the adsorption dehydrator is at least one selected from a 4A molecular sieve adsorbent and a 5A molecular sieve adsorbent.

6. The method of claim 1, wherein: the purity of the industrial grade propylene glycol methyl ether acetate is above 95% by mass, the water content is above 500ppm, the metal ions are above 500ppt, the anions are above 500ppb, and the particles with the particle size of more than 0.2 μm are more than 1000 particles/ml; preferably, it is: the composition of the technical grade propylene glycol methyl ether acetate is shown in the index of the raw materials in table 4:

table 4. Composition of technical grade propylene glycol methyl ether acetate.