CN114470958A

CN114470958A - Production method and device of high-purity electronic grade methanol

Info

Publication number: CN114470958A
Application number: CN202210138887.5A
Authority: CN
Inventors: 孙津
Original assignee: Beijing Xingming Technology Co ltd
Current assignee: Beijing Xingming Technology Co ltd
Priority date: 2022-02-15
Filing date: 2022-02-15
Publication date: 2022-05-13

Abstract

The invention provides a method and a device for producing high-purity electronic grade methanol, which have the advantages of short flow, low energy consumption, good separation effect, strong process continuity, high purity and low impurity content, and can obtain a high-purity electronic grade methanol product meeting the standard of an electronic chemical product SEMI C12 (G4). Most of water in industrial-grade methanol is removed through a water removal device, the industrial-grade methanol enters a micro filter, particles with particle size of more than 0.2 mu m are removed, the industrial-grade methanol enters an anion and cation remover to remove most of anions and cations in the methanol, then the industrial-grade methanol enters a conventional rectifying tower or a partition rectifying tower, and the obtained product methanol is subjected to nanofiltration to remove particles with particle size of more than 10nm, so that a high-purity electronic-grade methanol product which meets the SEMI C12(G4) standard is obtained.

Description

Production method and device of high-purity electronic grade methanol

Technical Field

The invention belongs to the field of preparation of high-purity electronic chemical methanol required by manufacturing of semiconductor chips, display panels, solar cells and the like, and particularly relates to a method and a device for producing high-purity electronic grade methanol.

Background

With the rapid development of semiconductor technology, the demand for high purity chemical reagents is increasing. In the process of processing an integrated circuit, a high-purity high-cleanness chemical reagent is mainly used for cleaning and etching the surfaces of a chip and a silicon wafer, and the purity and the cleanliness of the chemical reagent have great influence on the yield, the electrical property and the reliability of the integrated circuit. High-purity ultra-clean methanol is widely used in cleaning, drying and the like in the processes of semiconductors, large-scale integrated circuit processing and the like as an important electronic chemical. As the processing size of integrated circuits enters the nanometer era, higher requirements are put on high-purity ultra-clean methanol matched with the integrated circuits, and the requirements need to reach the SEMI C12 standard established by the international semiconductor equipment and material organization, wherein the content of metal cations is less than 100ppt, the particle size is controlled below 0.2 mu m, and the number of particles is negotiated with enterprises needing electronic chemicals. At present, high-purity electronic grade methanol in China is usually prepared by purifying industrial grade methanol raw materials. The purity of the current production can only reach the standard of chromatographic GRADE and pesticide residue GRADE, can only reach the MOS GRADE in the application of semiconductor industry, and has a larger gap from the GRADE 5(G5) GRADE (SEMI 12 and above). Most of the raw materials are produced by adopting an intermittent process, the energy consumption is high, the flow is long, and large-scale industrial production cannot be realized. The domestic prior art conditions are as follows:

CN100384798C, this patent proposes a method for obtaining high purity alcohols by rectification and adsorption method using industrial grade alcohols as raw materials. The adsorbent is modified carbon fiber, the carbon fiber is soaked in 2-4mol/L oxidant (nitric acid, potassium permanganate, dichromate and perchlorate) aqueous solution at 20-60 ℃ in an acidic environment for 2-6h before use, washed by dilute hydrochloric acid or dilute sulfuric acid, washed by pure water to prepare acid radical-free ions, dried and dried at 80-250 ℃ for activation, and the high-purity alcohol (comprising methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, ethylene glycol and propylene glycol) reagent with ppb cation content can be obtained. This method can only obtain a ppb level reagent, and cannot obtain a reagent for semiconductors of G3 or higher.

CN101250088B and CN201190138Y, the contents of which are completely the same, the invention proposes that industrial-grade methanol is taken as a raw material, pretreated by 0.5-1% of ethylenediamine tetraacetic acid, filtered and then enters a rectifying tower, and finally, the product is obtained by nanofiltration through an anion and cation exchange device. The method can obtain single cation content below 1ppb, single anion content below 100ppb, and dust ion content above 0.5 micron below 5/ml. The invention can not obtain high-purity methanol for semiconductors above G3.

CN101570467B, the invention takes 99.5% methanol as raw material, and the methanol is jected to oxidation reaction for 2 to 4 hours by 0.5 to 1.0 percent of hydrogen peroxide or potassium permanganate (methanol) and 0.1 to 0.4 percent of sulfuric acid (methanol), the methanol is distilled out, 0.2 to 0.8 percent of calcium hydride (methanol) is added for reduction and rectification, the temperature of a tower kettle is 70 to 78 ℃, the temperature of the tower top is 64 to 67 ℃, the reflux ratio is 10: 4-5, filtering the distillate by using a 0.45 micron PVDF membrane to obtain the high-purity methanol with the purity of more than 99.9 percent. The method can obtain pesticide residue grade and elution grade chromatographic methanol, does not provide a control method for metal ions and particles, and cannot produce the methanol which meets the requirements of semiconductor G3 grade or above.

CN102701906A, the invention takes 98% industrial methanol as raw material, adds high-efficiency purifying agent (mixture of high-purity potassium carbonate and high-purity sodium sulfate) and high-efficiency dehydrating agent (mixture of magnesium chips and iodine) to be mixed evenly in turn, reacts, and then adopts a rectification method to collect the methanol under the protection of nitrogen. The method has no control means for metal ions and particles, and cannot produce methanol which meets the requirements of semiconductors and is above G3. The patent has withdrawn.

CN112159305A, the invention uses industrial methanol as raw material, and the methanol is obtained by adding oxidant (hydrogen peroxide, potassium dichromate, potassium permanganate, sodium hypochlorite) in sequence, reacting at 48-55 ℃ for 3-6h, then entering a first rectifying tower, adding reducing agent (sulfite, bisulfite) into distillate, reacting at 48-55 ℃ for 3-6h, then entering a second rectifying tower, adding dehydrating agent (magnesium chips) into distillate, and finally rectifying under the protection of nitrogen. The method has no control means for metal ions and particles, and cannot produce methanol which meets the semiconductor grade above G3.

CN102875326B, the invention takes industrial methanol with the water content of 4.5-5.5% as raw material, prepares high-purity anhydrous methanol by azeotropic distillation and adsorption separation method, the entrainer is ethyl acetate, the adsorption material is ATBS (2-acrylamide-2-methyl propane sulfonic acid, also called AMBS), the obtained metal ion is less than 0.005%, the purity is more than 99.95%, and meets the SEMIC-1 standard methanol product, the method has no control means for the particle, the metal ion can not meet the production requirement of the methanol with the G3 level for the semiconductor.

CN103304390A, the invention takes anisole, toluene or chlorobenzene as an extracting agent, and adopts an intermittent method to extract and separate a methanol and butanone mixture, wherein methanol, a methanol-butanone transition section, butanone and a butanone-extracting agent transition section are sequentially extracted from the tower top at different mass ratios of the extracting agent to the tower top distillate, different tower top temperatures and different reflux ratios. The method has no control method for particles and metal ions, and cannot produce electronic grade methanol. The patent has been withdrawn.

CN103304371A, the invention uses glycol, toluene, chlorobenzene, anisole or phenol as extractant, and adopts batch method to extract and separate the mixture of methanol and methyl acrylate, the mass ratio of different extractants to the overhead distillate, the temperature of the overhead, the reflux ratio are different, and the overhead sequentially extracts methanol, methanol-methyl acrylate transition section, methyl acrylate-extractant transition section. The method has no control method for particles and metal ions, and cannot produce electronic grade methanol. This patent has been rejected.

CN103319309A, amyl alcohol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol or N, N-Dimethylformamide (DMF) are used as extracting agents, a mixture of methanol and nitromethane is extracted and separated by a batch method, the mass ratio of different extracting agents to overhead distillate, the temperature of the overhead and the reflux ratio are different, and methanol, a methanol-nitromethane transition section, nitromethane and a nitromethane-extracting agent transition section are sequentially extracted from the overhead. The method has no control method for particles and metal ions, and cannot produce electronic grade methanol. The patent has been rejected.

CN103342626B, the invention takes 99% industrial grade methanol as raw material, and the raw material is sequentially pretreated, naturally cooled to 70 ℃, heated and distilled to extract 65 ℃ fraction; then removing impurities by adsorption of a silicon-aluminum molecular sieve; and finally, carrying out batch rectification to obtain the chromatographic grade methanol. The method has no control method for particles and metal ions, and cannot produce electronic grade methanol.

CN106890480A, the invention provides a method for removing ions in raw materials by sequentially passing through an ion exchange resin, a perfluorinated particulate impurity filter and a two-stage perfluorinated deionization purifier. The invention does not further describe the characteristics of the raw materials and the product index. The patent has withdrawn.

CN109627144A, the invention provides that G3 grade methanol can be obtained by using industrial grade methanol as a raw material through rectification, ultra-clean filtration and ultra-clean split charging, but the invention does not mention the control indexes of metal ions and particles.

CN110218146A, the invention uses industrial methanol or acetonitrile as raw material to produce high-purity reagent methanol or acetonitrile by falling film crystallization method. The method has no control means on particles and metal ions, and cannot produce electronic grade high-purity reagents.

CN110776400A, the invention takes industrial methanol as raw material, and the product is obtained through 8 steps of treatment. The method specifically comprises the following steps: adsorbing and filtering by using a multi-wall CNTS graphite adsorption column; removing ether by using an IM-5 type molecular sieve, and removing ester by using 732 type acidic cation exchange water; the modified 13x molecular sieve and LS-40 macroporous resin remove acid and alkali, and ultraviolet light removes aldehydes and partial oxidizing impurities; PF5A ion composite removed macromolecules; dehydrating by a polydimethylsiloxane membrane material to obtain LC-MS grade methanol. The method has long process flow, and the indexes of particles and metal ions can not meet the requirement of producing electronic grade methanol above G3.

Disclosure of Invention

Aiming at the technical problems, the invention provides the method and the device for producing the electronic grade high-purity methanol, which have the advantages of short flow, low energy consumption, good separation effect, strong process continuity, high purity and low impurity content.

A first aspect of the present invention relates to a high purity electronic grade methanol production plant, comprising:

a microfilter and an anion and cation remover group which are connected in series according to the direction of feeding industrial grade methanol to the discharge of high-purity electronic grade methanol; wherein the content of the first and second substances,

when the micro filter and the anion and cation remover group are connected in series with a dehydration processor or a precision rectifying tower in front of the micro filter and the anion and cation remover group, the micro filter and the anion and cation remover group are connected in series with the precision rectifying tower and a nano filter group or the dehydration processor and the nano filter group in back of the micro filter and the anion and cation remover group, and the dehydration processor or the precision rectifying tower cannot be arranged in front of and behind the micro filter and the anion and cation remover group at the same time;

when a dewatering processor or a precision rectifying tower is not connected in series before the micro filter and the anion and cation remover group, the precision rectifying tower and the nano filter group are connected in series after the micro filter and the anion and cation remover group;

the device further comprises: and the anion and cation remover, the precise rectifying tower and the nano filter group are connected in series according to the direction of feeding industrial grade methanol to discharging high-purity electronic grade methanol.

Further, the micro-filter and the anion and cation remover group comprise a micro-filter and an anion and cation remover which are connected in series in the direction from the industrial grade methanol to the high-purity electronic grade methanol; wherein the content of the first and second substances,

the microfilter comprises a microfilter membrane having a pore size of 0.2 μm or less and a pore size uniformity coefficient of 1.3 or less, preferably a microfilter membrane having a pore size of 0.1-0.2 μm; further preferred are: the microfilter membrane is at least one of a polytetrafluoroethylene membrane, a polyether sulfone membrane, a polyvinylidene fluoride membrane (PVDF), a polyimide membrane and a 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 the particle size of 0.6mm or less and the uniform coefficient of the particle size of 1.1 or less; preferably, the particle size of the ion exchange resin is at least one of 0.3mm, 0.4mm, 0.5mm and 0.6 mm; the ion exchange fiber anion and cation remover comprises ion exchange fibers with the particle size of 0.6mm or less and the uniform coefficient of the particle size of 1.1 or less; it is preferable that: the ion exchange resin comprises one or more of sulfonic styrene resin, carboxyl styrene resin, quaternary ammonium styrene resin, perfluorinated sulfonic acid resin and sulfonated polyether sulfone resin, and the ion exchange fiber comprises sulfonic styrene fiber, carboxyl styrene fiber, quaternary ammonium styrene fiber, perfluorinated sulfonic acid fiber and sulfonated polyether sulfone fiber.

Further, the dewatering processor comprises at least one of a partition tower for dewatering treatment, a conventional rectifying tower string for dewatering treatment, a membrane separation dewatering processor, a dewatering agent dewatering processor or an adsorption dewatering processor;

the area ratio of the feeding side to the product extraction side of the dividing wall tower for dehydration treatment ranges from 7:3 to 3:7, the number of theoretical plates is 80-100, the area ratio of the feeding side to the product extraction side is preferably 7:3 to 4:6, and the number of theoretical plates is 100, and the dividing wall tower for dehydration treatment comprises at least one of a dividing wall tower with a middle dividing wall, a dividing wall tower with an upper dividing wall and a dividing wall tower with a lower dividing wall;

the conventional rectifying tower string for dehydration treatment comprises at least one first-stage conventional rectifying tower for dehydration treatment with the theoretical plate number of 80 and at least one second-stage conventional rectifying tower for dehydration treatment with the theoretical plate number of 70 which are connected in series in the direction from industrial-grade methanol to high-purity electronic-grade methanol; it is preferable that: the total number of the conventional rectifying tower for the first-stage dehydration treatment and the conventional rectifying tower for the second-stage dehydration treatment is less than or equal to 6; further preferred are: the total number of the conventional rectifying tower for the first-stage dehydration treatment and the conventional rectifying tower for the second-stage dehydration treatment is less than or equal to 3; still further preferred are: the total number of the conventional rectifying tower for the first-stage dehydration treatment and the conventional rectifying tower for the second-stage dehydration treatment is less than or equal to 2;

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

the dehydrating agent of the dehydrating agent dehydrating processor is selected from at least one of calcium hydride or calcium chloride;

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

Further, the precision rectifying tower and the nano-filter group comprise a precision rectifying tower and a nano-filter which are connected in series in the direction of feeding industrial grade methanol to discharging high-purity electronic grade methanol;

the precise rectifying tower comprises a conventional rectifying tower string for precise rectification or a bulkhead tower string for precise rectification;

the conventional rectifying tower string for precise rectification comprises at least two conventional rectifying towers which are connected in series and used for precise rectification, wherein the number of theoretical plates is 20-100; it is preferable that: the number of the theoretical plates is 50-80;

the bulkhead column string for precision rectification comprises at least one bulkhead column for precision rectification, the area ratio of a feed side to a product extraction side ranges from 4:6 to 6:4, and the number of theoretical plates is 20-100; it is preferable that: the area ratio of the feeding side to the product extraction side ranges from 4:6 to 6:4, and the number of theoretical plates is 80-100; the dividing wall column for precision rectification includes, but is not limited to, any one of a dividing wall column with a middle dividing wall, a dividing wall column with an upper dividing wall and a dividing wall column with a lower dividing wall;

the nano filter comprises a nano filter membrane with the aperture of 50nm or less and the aperture uniformity coefficient of 1.25 or less; preferably, the pore size of the nanofilter membrane is 10nm, 20nm or 50 nm.

Further, a plurality of condensers are arranged at the top of the dividing wall tower for dehydration treatment or the dividing wall tower for precision rectification, or a plurality of reboilers are arranged in the towers of the dividing wall tower and the dividing wall tower, or a plurality of intermediate condensers or a plurality of intermediate reboilers are arranged in the towers of the dividing wall tower and the dividing wall tower; the combination of the condenser and the reboiler includes, but is not limited to, the following eight: two condensers and one reboiler; one condenser and one reboiler; a condenser and two reboilers; two condensers and two reboilers; no condenser or one reboiler; there are no condensers and two reboilers; two condensers have no reboiler and one condenser has no reboiler.

The second aspect of the invention relates to a method for producing high-purity electronic grade methanol, which takes industrial grade methanol as a feed to prepare the high-purity electronic grade methanol, and specifically comprises one or more of the following steps:

removing most of the water in the industrial grade methanol;

removing large particles from the industrial-grade methanol;

removing organic impurities and a small part of water in the industrial grade methanol,

removing micro particles in the industrial grade methanol;

wherein:

before or after the step of removing the organic impurities and a small part of water in the industrial-grade methanol, the method also comprises the following steps:

removing anions and/or cations in the industrial-grade methanol,

wherein, when anions and/or cations in the industrial-grade methanol are removed after the organic impurities and a small part of water in the industrial-grade methanol are removed, most of water in the industrial-grade methanol is removed.

Further to the foregoing, the anion and/or cation thereof comprises at least one of the following groups:

a first group: sodium ions, potassium ions, and boron ions;

second group: sodium ions, potassium ions, calcium ions, lead ions and boron ions;

third group: sodium ions, potassium ions, calcium ions and boron ions;

and a fourth group: sodium ions, potassium ions, calcium ions, lead ions, iron ions, copper ions, arsenic ions and boron ions.

As further improvement, adopt accurate rectifying column to remove organic impurity and a small part of water in the industrial grade methyl alcohol, accurate rectifying column includes that accurate rectification uses conventional rectifying column cluster or accurate rectification to use next door column cluster, wherein:

the conventional rectifying tower string for precise rectification comprises at least two conventional rectifying towers for precise rectification, wherein the number of theoretical plates of the conventional rectifying towers is 20-100; it is preferable that: the conventional rectifying tower for precise rectification has the following conditions: the number of theoretical plates is 50-80, the operating pressure is 100pa-1.5Mpa, the temperature at the top of the tower is-45-167 ℃, the reflux ratio is 1-10, and the temperature at the bottom of the tower is-40-250 ℃; it is further preferred to include any one of the following sets of conditions:

the first group comprises that the tower top pressure of a first-stage conventional rectifying tower is 0.6MPa, the tower top temperature is 119 ℃, the theoretical plate number is 50, the reflux ratio is 6, the tower top pressure of a second-stage conventional rectifying tower is 0.2MPa, the tower top temperature is 84 ℃, the theoretical plate number is 50, and the reflux ratio is 6;

the second group comprises that the tower top pressure of the first-stage conventional rectifying tower is 1.5MPa, the tower top temperature is 155 ℃, the theoretical plate number is 80, the reflux ratio is 2, the tower top pressure of the second-stage conventional rectifying tower is 0.8MPa, the tower top temperature is 130 ℃, the theoretical plate number is 70, the reflux ratio is 2, the tower top pressure of the third-stage conventional rectifying tower is 0.1MPa, the tower top temperature is 65 ℃, the theoretical plate number is 50, the reflux ratio is 8, the tower top pressure of the fourth-stage conventional rectifying tower is 0.04MPa, the tower top temperature is 44 ℃, the theoretical plate number is 50, and the reflux ratio is 8;

the third group comprises a first-stage conventional rectifying tower, a second-stage conventional rectifying tower, a third-stage conventional rectifying tower, a fourth-stage conventional rectifying tower, a fifth-stage conventional rectifying tower, a sixth-stage conventional rectifying tower, a fifth-stage conventional rectifying tower, a sixth-stage conventional rectifying tower, a fourth-rectifying tower, wherein the tower top pressure of the first-stage conventional rectifying tower is 0.1MPa, the tower top temperature is 64 ℃, the number of theoretical plates is 80, and the reflux ratio is 3;

the fourth group, the top pressure of the first stage conventional rectifying tower is 0.4MPa, the top temperature is 105 ℃, the number of theoretical plates is 80, and the reflux ratio is 6; the tower top pressure of the second-stage conventional rectifying tower is 0.1MPa, the tower top temperature is 65 ℃, the theoretical plate number is 70, the reflux ratio is 9, the tower top pressure of the third-stage conventional rectifying tower is 0.06MPa, the tower top temperature is 53 ℃, the theoretical plate number is 50, the reflux ratio is 8, the tower top pressure of the fourth-stage conventional rectifying tower is 0.02MPa, the tower top temperature is 30 ℃, the theoretical plate number is 50, and the reflux ratio is 10;

the bulkhead column string for precision rectification comprises at least one bulkhead column for precision rectification, the area ratio of a feed side to a product extraction side ranges from 4:6 to 6:4, and the number of theoretical plates is 20-100; it is preferable that: the conditions of the dividing wall column are as follows: the area ratio of the feed side to the product extraction side is 4:6 to 6:4, the number of theoretical plates is 80-100, the operating pressure is 500pa-0.4Mpa, the temperature at the top of the tower is-45-167 ℃, the temperature at the bottom of the tower is-40-250 ℃, and the reflux ratio is 2-10; it is further preferred to include any one of the following sets of conditions:

the first group, the pressure at the top of the tower is 0.02Mpa, the temperature at the top of the tower is 30 ℃, the area ratio of a feeding side to a product extraction side is 4:6, the number of theoretical plates is 80, and the reflux ratio is 10;

the second group, the top pressure of the first partition tower is 0.2MPa, the top temperature of the first partition tower is 84 ℃, the area ratio of the feeding side to the product extraction side is 5:5, the number of theoretical plates is 90, the reflux ratio is 6, the top pressure of the second partition tower is 0.06MPa, the top temperature of the second partition tower is 53 ℃, the area ratio of the two side surfaces is 5:5, the number of theoretical plates is 80, and the reflux ratio is 4;

in the third group, the top pressure of the first dividing wall tower is 0.08MPa, the top temperature is 60 ℃, the area ratio of the feeding side to the product extraction side is 5:5, the number of theoretical plates is 90, and the reflux ratio is 6; the tower top pressure of the second partition tower is 0.01MPa, the tower top temperature is 17 ℃, and the area ratio of two sides is 6: 4; theoretical plate number 80, reflux ratio 7;

fourthly, the top pressure of the first partition tower is 5kPa, the top temperature of the first partition tower is 5 ℃, the area ratio of the feeding side to the product extraction side is 4:6, the number of theoretical plates is 90, the reflux ratio is 7, the top pressure of the second partition tower is 500Pa, the top temperature of the second partition tower is-27 ℃, the area ratio of the feeding side to the product extraction side is 5:5, the number of theoretical plates is 80, and the reflux ratio is 8;

the dividing wall tower comprises any one of a dividing wall tower of a middle dividing wall, a dividing wall tower of an upper dividing wall and a dividing wall tower of a lower dividing wall;

and removing anions and/or cations in the industrial methanol by adopting an anion and cation remover, wherein:

the anion and cation remover comprises an ion exchange resin anion and cation remover or an ion exchange fiber anion and cation remover, and the ion exchange resin anion and cation remover comprises ion exchange resin with the particle size of 0.6mm or less and the uniform coefficient of the particle size of 1.1 or less; preferably, the particle size of the ion exchange resin is 0.3mm, 0.4mm, 0.5mm and 0.6 mm; the ion exchange fiber anion and cation remover comprises ion exchange fibers with the particle size of 0.6mm or less and the uniform coefficient of the particle size of 1.1 or less; it is preferable that: the ion exchange resin or ion exchange fiber is selected from one or more of sulfostyrene resin or fiber, carboxyl styrene resin or fiber, quaternary ammonium styrene resin or fiber, perfluorinated sulfonic acid resin or fiber, and sulfonated polyether sulfone resin or fiber.

As a further improvement, a dewatering processor is adopted to remove most of water in the industrial methanol, wherein:

the dehydration processor adopts any one or more of a partition tower for dehydration treatment or 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 feed side to the product extraction side of the dividing wall tower for dehydration treatment ranges from 4:6 to 7:3, the number of theoretical plates is 80-100, and the reflux ratio of the top of the tower is 1-10; it is preferable that: the area ratio of the feed side to the product extraction side is 7:3, the number of theoretical plates is 100, the pressure at the top of the tower is 0.4MPa, the temperature at the top of the tower is 105 ℃, and the reflux ratio is 5; the dividing wall tower for dehydration treatment includes but is not limited to any one of a dividing wall tower of a middle dividing wall, a dividing wall tower of an upper dividing wall and a dividing wall tower of a lower dividing wall;

the conventional rectifying tower string for dehydration treatment comprises a first-stage conventional rectifying tower for dehydration treatment with at least one theoretical plate number of 80 and a second-stage conventional rectifying tower for dehydration treatment with at least one theoretical plate number of 70 which are connected in series in the direction from industrial-grade methanol to high-purity electronic-grade methanol to be discharged, wherein the tower top pressure of the first-stage conventional rectifying tower for dehydration treatment is 2MPa, the tower top temperature is 167 ℃, and the reflux ratio is 1-10; the pressure at the top of the conventional rectifying tower for the second-stage dehydration treatment is 1MPa, the temperature at the top of the conventional rectifying tower is 138 ℃, and the reflux ratio is 1-10; it is preferable that: the total number of the conventional rectifying tower for the first-stage dehydration treatment and the conventional rectifying tower for the second-stage dehydration treatment is less than or equal to 6; further preferred are: the total number of the conventional rectifying tower for the first-stage dehydration treatment and the conventional rectifying tower for the second-stage dehydration treatment is less than or equal to 3; still further preferred are: the total number of the conventional rectifying tower for the first-stage dehydration treatment and the conventional rectifying tower for the second-stage dehydration treatment is less than or equal to 2;

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

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

In a further aspect of the foregoing process, the industrial grade methanol has a methanol purity of 95% or greater by mass, a water content of 500ppm or greater, metal ions of 500ppt or greater, anions of 500ppb or greater, and greater than 1000 particles/ml greater than 0.2 μm; it is preferable that: the composition of the technical grade methanol is referred to the indices of the feedstock in table 1.

The invention has the beneficial effects that: firstly, an electronic grade high-purity methanol generation device with short flow, low energy consumption, good separation effect, strong process continuity, high purity and low impurity content is provided, and secondly, a method for producing electronic grade high-purity methanol with low energy consumption, short flow and low investment is provided by utilizing multi-stage conventional rectifying tower or next-wall tower equipment; can meet the requirements of SEMI C12(G4) for producing methanol, which is the highest standard of electronic chemicals.

Drawings

FIG. 1: is a schematic diagram of the production method and the device of the electronic grade high-purity methanol.

FIG. 2: is a schematic diagram of a process and apparatus variation 1 for the production of electronic grade high purity methanol of the present invention.

FIG. 3: is a schematic diagram of a process and apparatus variation 2 for the production of electronic grade high purity methanol of the present invention.

FIG. 4: is a schematic diagram of a process and apparatus variation 3 for the production of electronic grade high purity methanol of the present invention.

FIG. 5: is a schematic diagram of a process and apparatus variant 4 for the production of electronic grade high purity methanol of the present invention.

FIG. 6: is a schematic diagram of a process and apparatus variation 5 for the production of electronic grade high purity methanol of the present invention.

FIG. 7 is a schematic view of: is a schematic diagram of a process and apparatus variation 6 for the production of electronic grade high purity methanol of the present invention.

FIG. 8: is a schematic diagram of a process and apparatus variation 7 for the production of electronic grade high purity methanol of the present invention.

FIG. 9: is a schematic diagram of a process and apparatus variation 8 for the production of electronic grade high purity methanol in accordance with the present invention.

FIG. 10: is a schematic diagram of the production process and apparatus of electronic grade high purity methanol of comparative example 5 of the present invention.

FIG. 11: is a schematic diagram of a possible form of the dividing wall column of the invention; wherein form a is a spacer wall; the form B is an upper partition wall; form C is the lower bulkhead.

Description of reference numerals:

1 technical grade methanol; 2, a dewatering processor; 3 dehydrating the methanol; 4a micro-filter; 5 micro-filtering the obtained product and then carrying out methanol; 6 anion and cation remover; 7 removing the anions and the cations and then using methanol; 8, a divided wall column; 9, methanol after first-stage rectification; 10 divided wall column; 11 methanol after second-stage rectification; 12 nano filter; 13 electronic grade high purity methanol product; 14 light component; 15 heavy component; 16 conventional rectifying tower, 17 conventional rectifying tower, 18 conventional rectifying tower and 19 conventional rectifying tower; 20, methanol after the three-stage rectifying tower; methanol after 21-stage rectification tower; 22 methanol after secondary dehydration.

Detailed Description

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

Interpretation of terms

The present invention can be classified into a dividing wall column for dehydration treatment, a dividing wall column for precision rectification, and the like according to the effect;

the conventional rectifying tower is also called as 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 effect;

"custom functionality" in "custom functional resin" refers to functionality that is customized in Chinesemet, Beijing.

The "area ratio of both sides of the dividing wall column" also referred to as "area ratio of the feed side and the product take-off side" means the ratio of the cross-sectional areas of both sides divided by the partition.

The invention also relates to the high-purity electronic grade methanol, the high-purity electronic chemical methanol and the ultra-pure methanol meeting SEMI C12(G4) standard.

"before" or "after" means the order of the individual units in series, in the direction of the industrial grade methanol feed to the high purity electronic grade methanol discharge.

The present invention is not particularly limited to "in series" and the prior art techniques that ensure the passage of methanol in each step are within the scope of the present invention, including direct and indirect connections.

Some embodiments of the invention include a microfilter and anion and cation remover bank in series with the direction of industrial grade methanol feed to high purity electronic grade methanol discharge; wherein the content of the first and second substances,

when the micro-filter and the anion and cation remover group are not connected with a dewatering processor or a precision rectifying tower in series before, the micro-filter and the anion and cation remover group are connected with the precision rectifying tower and the nano-filter group in series after or only connected with the precision rectifying tower in series.

In one embodiment, the apparatus shown in fig. 1 comprises a dehydration processor 2, a micro-filter 4, an anion and cation remover 6, a precision rectifying tower 8, a precision rectifying tower 10 and a nano-filter 12 connected in series in the direction from the industrial grade methanol 1 to the high purity electronic grade methanol 13, and in some embodiments, auxiliary equipment such as a pump and a heat exchanger corresponding to the dehydration processor, the micro-filter, the anion and cation remover and the precision rectifying tower. The device provided by the embodiment of the invention can provide an ultra-clean high-purity methanol production method with short flow, low energy consumption, good separation effect, strong process continuity, high purity and low impurity content, and can obtain a high-clean high-purity methanol product meeting the standard of electronic chemicals SEMI C12(G4) or above.

The water removal device 2 of the embodiment of the invention removes most of water in methanol, the micro filter 4 removes large particles in the methanol, the anion and cation remover 6 removes most of cations and anions in the methanol, the

precise rectifying towers

8 and 10 remove small parts of water, organic impurities and the like in the methanol, and the nano filter 12 removes tiny particles in methanol liquid, so that the contents of water, particles and other impurities in the methanol meet the requirements of the standard of an electronic chemical SEMI C12 (G4).

The following exemplary description applies to the apparatus of the present invention to prepare high purity methanol that satisfies the standard of the electrochemical chemical SEMI C12(G4) or higher.

With continued reference to fig. 1, industrial grade methanol (1) from outside the battery compartment enters a dehydration processor (2) to remove most of water, the dehydration processor can adopt four methods of dehydration by a conventional rectifying tower or a bulkhead rectifying tower, dehydration by a dehydrating agent, membrane separation dehydration and adsorption dehydration, the dehydrating agent can select calcium hydride, calcium chloride and the like, the membrane separation dehydration can adopt a 3A molecular sieve membrane, a 4A molecular sieve membrane, a 5A molecular sieve membrane and the like, and the adsorption dehydration can select a 3A molecular sieve adsorbent, a 5A molecular sieve adsorbent and the like; the dehydrated methanol (3) enters a micro-filter (4) to remove particles of more than 0.2 mu m (micron), and the micro-filter can adopt a polytetrafluoroethylene membrane, a polyether sulfone membrane, a polyvinylidene fluoride membrane (PVDF), a polyimide membrane, a polyamide membrane or other equivalent membranes with the aperture of 0.2 mu m (micron) or less and the aperture uniformity coefficient of 1.3 or less; after microfiltration, the methanol enters a cation and anion remover (6) to remove cations and anions in the methanol, wherein the cation and anion remover can adopt ion exchange resin or ion exchange fiber, the ion exchange resin adopts customized functional resin, and the ion exchange fiber adopts customized functional fiber and mainly comprises one or more of sulfonic styrene fiber carboxyl styrene fiber, quaternary ammonium styrene fiber, perfluorinated sulfonic acid fiber and sulfonated polyether sulfone fiber; removing the cationic and anionic methanol and feeding the methanol into precise rectifying towers (8) and (10), and increasing or reducing the number of the precise rectifying towers by 0-6 according to the requirements of actual raw materials and product standards, wherein the conventional rectifying towers or partition rectifying towers can be adopted, the number of the conventional rectifying towers can be greatly reduced under the condition that the same separation precision requirement is met by the partition rectifying towers, the 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 investment are greatly reduced, the area ratio of the two sides of the rectifying towers ranges from 4:6 to 6:4, and the form mainly comprises three types, namely a middle partition wall, an upper partition wall and a lower partition wall, but not limited to the three types; the methanol product obtained by precision rectification is filtered by nanofiltration to remove particles with the diameter of 20nm or more, the nanofiltration membrane can adopt a polytetrafluoroethylene membrane, a polyether sulfone membrane, a polyvinylidene fluoride (PVDF) membrane, a polyimide membrane, a polyamide membrane or other equivalent membranes with the pore diameter of 50nm or less, and finally the methanol product meeting the requirements of the SEMI12 standard is obtained.

When the micro filter and the anion and cation remover group are not connected with a dewatering device in series before, the micro filter and the anion and cation remover group are connected with the precision rectifying tower and the nano filter group in series after.

The following is an example of an apparatus for an electronic grade high purity methanol production plant.

The device of example 1, as shown in fig. 2, comprises a dividing wall tower (2), a micro-filter (4), an anion and cation remover (6), a dividing wall tower (10) and a nano-filter (12) which are connected in series from a feeding material (1) to a discharging material (13).

The device of embodiment 2, as shown in fig. 3, comprises a conventional rectifying tower (16), a conventional rectifying tower (17), a microfilter (4), an anion and cation remover (6), a conventional rectifying tower (18) and a conventional rectifying tower (19) which are connected in series from the feeding (1) to the discharging (13).

Example 3 of the apparatus, as shown in fig. 4, the apparatus comprises a water removal apparatus (2), a micro-filter (4), an anion and cation remover (6), a partition wall column (8), a partition wall column (10), and a nanofiltration apparatus (12) connected in series from a feed (1) to a discharge (13).

The device of example 4, as shown in fig. 5, comprises a dewatering device (2), a micro-filter (4), an anion and cation remover (6), a conventional rectifying tower (16), a conventional rectifying tower (17), a conventional rectifying tower (18), a conventional rectifying tower (19) and a nano-filter (12) which are connected in series from a feeding material (1) to a discharging material (13).

As shown in fig. 6, the apparatus of example 5 includes a microfilter (4), an anion and cation remover (6), a partition column (8), a partition column (10), and a nanofiltration device (12) connected in series in the direction from the feed (1) to the discharge (13).

As shown in fig. 7, the apparatus of example 6 includes a microfilter (4), an anion and cation remover (6), a conventional rectifying column (16), a conventional rectifying column (17), a conventional rectifying column (18), a conventional rectifying column (19), and a nanofilter (12) connected in series from a feed (1) to a discharge (13).

As shown in fig. 8, the apparatus of example 7 includes an anion and cation remover (6), a partition column (8), a partition column (10), and a nanofiltration device (12) connected in series in the direction from the feed (1) to the discharge (13).

In the embodiment 8 of the apparatus, as shown in fig. 9, the apparatus comprises an anion and cation remover (6), a conventional rectifying column (16), a conventional rectifying column (17), a conventional rectifying column (18), a conventional rectifying column (19) and a nanofiltration device (12) which are connected in series from the feeding (1) to the discharging (13).

The device 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 device (12) which are connected in series according to the direction from the feeding of industrial grade methanol 1 to the discharging of high-purity electronic grade methanol 13 as shown in figure 10.

In some embodiments of the present invention, the method for producing high purity electronic grade methanol using technical grade methanol as a feedstock comprises one or more of the following steps:

removing most of the water in the industrial grade methanol;

removing large particles from the industrial-grade methanol;

removing micro particles in the industrial grade methanol;

wherein:

before or after the step of removing organic impurities and a small part of water in the industrial-grade methanol, the method also comprises the following steps:

removing anions and/or cations in the industrial-grade methanol,

in the sub-step of removing anions and/or cations from the technical grade methanol, the anions and/or cations mainly comprise at least one group of:

a first group: sodium ions, potassium ions, and boron ions;

third group: sodium ions, potassium ions, calcium ions and boron ions;

and a fourth group: sodium ions, potassium ions, calcium ions, lead ions, iron ions, copper ions, arsenic ions, and boron ions;

The process of the invention is explained below with specific examples.

Method example 1

With continued reference to FIG. 2, the feed pressure was 0.6 MPa; the feeding temperature is 25 ℃; the dewatering device adopts a bulkhead tower (8), the bulkhead tower adopts an A form, the area ratio of the feeding side to the product discharging side is 7:3, the pressure at the top of the tower is 0.4MPa, the temperature at the top of the tower is 105 ℃, the number of theoretical plates is 100, and the reflux ratio is 5; the micro filter adopts a polytetrafluoroethylene membrane with the pore diameter uniformity coefficient of 1.15 and the diameter of 0.2 mu m; the ion exchange resin adopts sulfonic styrene functional resin with the uniform coefficient of 1.08 and the grain diameter of 0.4 mm; the dividing wall tower (10) adopts a B form, and the operating conditions are as follows: the pressure at the top of the tower is 0.02MPa, the temperature at the top of the tower is 30 ℃, the area ratio of two sides is 4:6, the number of theoretical plates is 80, and the reflux ratio is 10; the nanofilter used a polytetrafluoroethylene membrane with a pore size of 10nm and a uniformity coefficient of 1.2. High purity electronic grade methanol products were obtained above SEMI C12(G4) standard with product specifications as shown in table 1.

Method example 2

With continued reference to FIG. 3, the feed pressure was 0.4 MPa; the feeding temperature is 60 ℃; the dehydration is realized by two conventional rectifying towers, and the operation parameters are as follows: the pressure at the top of the conventional rectifying tower (16) is 2MPa, the temperature at the top of the conventional rectifying tower is 167 ℃, the number of theoretical plates is 80, and the reflux ratio is 4; the pressure at the top of the conventional rectifying tower (17) is 1MPa, the temperature at the top of the conventional rectifying tower is 138 ℃, the theoretical plate number is 70, and the reflux ratio is 4; the microfilter adopts a polyamide membrane with the diameter of 0.2 mu m and the uniform aperture coefficient of 1.1; the ion exchange resin adopts perfluorinated sulfonic acid resin with the particle size of 0.5mm and the uniformity coefficient of 1.05; two conventional rectifying towers are adopted in the rectifying process, the pressure at the top of the conventional rectifying tower (18) is 0.6MPa, the temperature at the top of the tower is 119 ℃, the number of theoretical plates is 50, and the reflux ratio is 6; the pressure at the top of the conventional rectifying tower (19) is 0.2MPa, the temperature at the top of the conventional rectifying tower is 84 ℃, the number of theoretical plates is 50, and the reflux ratio is 6; the nanofilter used a polyvinylidene fluoride membrane (PVDF) with a pore diameter of 10nm and a pore diameter uniformity coefficient of 1.2. High purity electronic grade methanol products were obtained above SEMI C12(G4) standard with product specifications as shown in table 1.

Method example 3 (preferred embodiment)

With continued reference to FIG. 4, the feed pressure was 0.3 MPa; the feeding temperature is 50 ℃; the dewatering processor adopts a 3A molecular sieve membrane; the micro filter adopts a polyvinylidene fluoride (PVDF) membrane with the pore diameter uniformity coefficient of 0.1 mu m and the pore diameter uniformity coefficient of 1.1; the ion exchange resin adopts carboxyl styrene functional resin with the grain diameter of 0.6mm and the uniform coefficient of 1.05; the dividing wall tower (8) adopts the form A, and the operating parameters are as follows: the pressure at the top of the tower is 0.2MPa, the temperature at the top of the tower is 84 ℃, the area ratio of two sides is 5:5, the number of theoretical plates is 90, and the reflux ratio is 6; the dividing wall tower (10) adopts the form A, and the operating parameters are as follows: the area ratio of two sides is 5:5, the number of theoretical plates is 80, the pressure at the top of the tower is 0.06MPa, the temperature at the top of the tower is 53 ℃, and the reflux ratio is 4; the nanofilter used a polyvinylidene fluoride membrane (PVDF) with a pore size of 20nm and a uniformity coefficient of 1.2. High purity electronic grade methanol products were obtained above SEMI C12(G4) standard with product specifications as shown in table 1.

Method example 4

With continued reference to FIG. 5, the feed pressure was 0.3 MPa; the feeding temperature is 50 ℃; the dehydration processor adopts 3A molecular sieve adsorbent; the microfilter adopts a polyethersulfone membrane with the diameter of 0.1 mu m and the uniform pore diameter coefficient of 1.3; the ion exchange resin adopts sulfonic styrene functional resin with the particle size of 0.3mm and the uniformity coefficient of 1.1; the operation parameters of the conventional rectifying tower for precise rectification are as follows: the pressure at the top of the conventional rectifying tower (16) is 1.5MPa, the temperature at the top of the rectifying tower is 155 ℃, the number of theoretical plates is 80, and the reflux ratio is 2; the pressure at the top of the conventional rectifying tower (17) is 0.8MPa, the temperature at the top of the conventional rectifying tower is 130 ℃, the number of theoretical plates is 70, and the reflux ratio is 2; the pressure at the top of the conventional rectifying tower (18) is 0.1MPa, the temperature at the top of the rectifying tower is 65 ℃, the reflux ratio is 8, and the number of theoretical plates is 50; the pressure at the top of the conventional rectifying tower (19) is 0.04MPa, the temperature at the top of the rectifying tower is 44 ℃, the number of theoretical plates is 50, and the reflux ratio is 8; the nanofilter adopts a polyether sulfone membrane with the aperture of 10nm and the aperture uniformity coefficient of 1.1. High purity electronic grade methanol products were obtained above SEMI C12(G4) standard with product specifications as shown in table 1.

Method example 5 (preferred embodiment)

With continued reference to FIG. 6, the feed pressure was 0.2 MPa; the feeding temperature is 40 ℃; the micro filter adopts a polyvinylidene fluoride (PVDF) membrane with the aperture of 0.2 mu m and the uniform coefficient of 1.15; the ion exchange resin adopts sulfostyrene resin with the particle size of 0.5mm and the uniform coefficient of the particle size of 1.07; the dividing wall tower (8) for precise rectification adopts the form A, and the operating parameters are as follows: the pressure at the top of the tower is 0.08MPa, the temperature at the top of the tower is 60 ℃, the area ratio of two sides is 5:5, the number of theoretical plates is 90, and the reflux ratio is 6; the dividing wall tower (10) adopts a B form, and the operating parameters are as follows: the area ratio of the two sides is 6:4, the number of theoretical plates is 80, the reflux ratio is 7, the pressure at the top of the tower is 0.01MPa, and the temperature at the top of the tower is 17 ℃. The nano filter adopts a polyimide membrane with the aperture of 10nm and the aperture uniformity coefficient of 1.2. High purity electronic grade methanol products were obtained above SEMI C12(G4) standard with product specifications as shown in table 1.

Method example 6

With continued reference to FIG. 7, the feed pressure was 0.2 MPa; the feeding temperature is 40 ℃; the microfilter adopts a polyamide membrane with the diameter of 0.2 mu m and the uniform pore diameter coefficient of 1.15; the ion exchange resin (6) adopts quaternary ammonium styrene resin with the particle size of 0.6mm and the uniform coefficient of particle size of 1.07; the operation parameters of the conventional rectifying tower for precise rectification are as follows: the pressure at the top of the conventional rectifying tower (16) is 0.1MPa, the temperature at the top of the rectifying tower is 64 ℃, the number of theoretical plates is 80, and the reflux ratio is 3; the pressure at the top of the conventional rectifying tower (17) is 0.01MPa, the temperature at the top of the conventional rectifying tower is 17 ℃, the number of theoretical plates is 70, and the reflux ratio is 3; the pressure at the top of the conventional rectifying tower (18) is 1kPa, the temperature at the top of the rectifying tower is-19 ℃, the theoretical plate number is 50, and the reflux ratio is 5; the overhead pressure of the conventional rectifying tower (19) is 100Pa, the overhead temperature is-45 ℃, the theoretical plate number is 50, and the reflux ratio is 5. The nano filter adopts a polyimide membrane with the aperture of 10nm and the uniform aperture coefficient of 1.25 to obtain a high-purity electronic grade methanol product which is higher than the SEMI C12(G4) standard, and the product index is shown in Table 1.

Method example 7

With continued reference to FIG. 8, the feed pressure was 0.2 MPa; the feeding temperature is 50 ℃; the ion exchange resin (6) adopts sulfonic styrene functional resin with the particle diameter of 0.5mm and the uniform coefficient of the particle diameter of 1.06; the dividing wall tower (8) adopts a B form, and the operating parameters are as follows: the pressure at the top of the tower is 5kPa, the temperature at the top of the tower is 5 ℃, the area ratio of two sides is 4:6, the number of theoretical plates is 90, and the reflux ratio is 7; the dividing wall tower (10) adopts a C type, and the operation parameters are as follows: the area ratio of two sides is 5:5, the number of theoretical plates is 80, the pressure at the top of the tower is 500Pa, the temperature at the top of the tower is-27 ℃, and the reflux ratio is 8; the nano filter adopts a polyimide film with the uniform aperture coefficient of 1.05 of 50 nm; high purity electronic grade methanol products were obtained above SEMI C12(G4) standard with product specifications as shown in table 1.

Method example 8 (preferred embodiment)

With continued reference to FIG. 9, the feed pressure was 0.2 MPa; the feeding temperature is 60 ℃; the ion exchange resin (6) adopts sulfonic styrene functional resin with the grain diameter of 0.4mm and the grain diameter uniformity coefficient of 1.05; the operation parameters of the conventional rectifying tower for precise rectification are as follows: the pressure at the top of the conventional rectifying tower (16) is 0.4MPa, the temperature at the top of the rectifying tower is 105 ℃, the number of theoretical plates is 80, and the reflux ratio is 6; the pressure at the top of the conventional rectifying tower (17) is 0.0.1MPa, the temperature at the top of the tower is 65 ℃, the number of theoretical plates is 70, and the reflux ratio is 9; the pressure at the top of the conventional rectifying tower (18) is 0.06MPa, the temperature at the top of the rectifying tower is 53 ℃, the number of theoretical plates is 50, and the reflux ratio is 8; the pressure at the top of the conventional rectifying tower (19) is 0.02MPa, the temperature at the top of the conventional rectifying tower is 30 ℃, the number of theoretical plates is 50, and the reflux ratio is 10. The nano filter (12) adopts a polytetrafluoroethylene membrane with the uniform coefficient of 50nm pore diameter of 1.05; high purity electronic grade methanol products were obtained above SEMI C12(G4) standard with product specifications as shown in table 1.

Comparative example 1

This comparative example is the same as example 1 in terms of raw materials and flow scheme, with reference to FIG. 2. The difference from example 1 is that the particle diameter uniformity coefficient of the ion exchange resin used was changed to 1.2. The other conditions were all the same. The product index is shown in Table 2. Sodium, potassium and boron do not meet SEMI C12(G4) requirements; sodium, potassium, calcium, lead and boron do not meet the G5 requirement.

Comparative example 2

This comparative example is the same as example 2, with reference to figure 3, for the same materials and procedure. The difference from example 2 was that the particle diameter of the ion exchange resin used was changed to 0.7mm, and the other conditions were all the same. The product index is shown in Table 2. Sodium, potassium, calcium and boron do not meet SEMI C12(G4) requirements; sodium, potassium, calcium, lead, iron, copper, arsenic and boron do not meet the G5 requirement.

Comparative example 3

This comparative example is the same as example 7, with reference to figure 8, for the same materials and procedure. The difference from example 7 is that the pore diameter uniformity coefficient of the nanofiltration membrane was changed to 1.3, and the others were the same. The product index is shown in Table 2. The particles failed to meet SEMI C12(G4) and G5 requirements.

Comparative example 4

This comparative example is the same as example 8, with reference to figure 9, for the same materials and procedure. The difference from example 8 is that the pore size of the nanofiltration membrane is changed to 100nm, and the rest is the same. The particles failed to meet SEMI C12(G4) and G5 requirements.

Comparative example 5

This comparative example, referring to FIG. 10, differs from example 8 in that the ion exchange resin and the rectification order are exchanged, other conditions are identical, and the product indexes are shown in Table 2. The water content did not meet SEMI C12(G4) requirements.

Test example 1

The content of the components in the electronic chemical methanol of the examples 1 to 8 and the comparative examples 1 to 5 was measured by the following measuring instruments: the cation adopts Agilent ICP-MS/MS8900, the anion adopts Switzerland 940 ion chromatography, the water content adopts a coulomb method card water analyzer of type 851, and the organic impurities adopt Agilent GC-MS gas chromatography. The results are shown in tables 1-2, where the feedstock in table 1 refers to technical grade methanol.

TABLE 1 composition of technical grade methanol and index of the product obtained after treatment according to the invention

TABLE 1 continuation of the table

TABLE 2 comparison of the product indices of the examples with those of the comparative examples

The above table is for illustrating the components contained in the methanol raw material, the content of the components is greatly related to the source, but the applicability of the invention is not limited, and the methanol product produced by the method of the invention can meet the standard requirements of SEMI C12(G4) or above.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. The utility model provides a high-purity electronic grade methanol production device which characterized in that: the device comprises:

a micro-filter and an anion-cation remover set which are connected in series according to the direction of feeding industrial grade methanol to the discharge direction of high-purity electronic grade methanol; wherein the content of the first and second substances,

2. The apparatus of claim 1, wherein: the microfilter and anion and cation remover group comprises a microfilter and an anion and cation remover which are connected in series in the direction from industrial grade methanol to high-purity electronic grade methanol; wherein the content of the first and second substances,

the microfilter comprises a microfilter membrane having a pore size of 0.2 μm or less and a pore size uniformity coefficient of 1.3 or less, preferably a microfilter membrane having a pore size of 0.1-0.2 μm;

further preferred are: the microfilter membrane is at least one of a polytetrafluoroethylene membrane, a polyether sulfone membrane, a polyvinylidene fluoride membrane (PVDF) polyimide membrane and a polyamide membrane;

3. The apparatus of claim 1, wherein: the dewatering processor comprises at least one of a partition tower for dewatering treatment, a conventional rectifying tower string for dewatering treatment, a membrane separation dewatering processor, a dewatering agent dewatering processor or an adsorption dewatering processor;

4. The apparatus of claim 1, wherein: the precise rectifying tower and the nano-filter group comprise a precise rectifying tower and a nano-filter which are connected in series according to the direction from industrial grade methanol to high-purity electronic grade methanol;

the bulkhead column string for precision rectification comprises at least one bulkhead column for precision rectification, wherein the area ratio of a feeding side to a product extraction side ranges from 4:6 to 6:4, and the number of theoretical plates is 20-100; it is preferable that: the area ratio of the feeding side to the product extraction side ranges from 4:6 to 6:4, and the number of theoretical plates is 80-100; the dividing wall column for precision rectification includes, but is not limited to, any one of a dividing wall column with a middle dividing wall, a dividing wall column with an upper dividing wall and a dividing wall column with a lower dividing wall;

the nano filter comprises a nano filter membrane with the pore diameter of 50nm or less and the uniform coefficient of the pore diameter of 1.25 or less; preferably, the pore size of the nanofilter membrane is 10nm, 20nm or 50 nm.

5. The apparatus of claim 1, wherein: arranging a plurality of condensers at the top of the dividing wall tower for dehydration treatment or the dividing wall tower for precision rectification, or arranging a plurality of reboilers in the towers of the dividing wall tower and the dividing wall tower, or arranging a plurality of intermediate condensers or a plurality of intermediate reboilers in the towers of the dividing wall tower and the dividing wall tower; the combination of the condenser and the reboiler includes, but is not limited to, the following eight: two condensers and one reboiler; one condenser and one reboiler; a condenser and two reboilers; two condensers and two reboilers; no condenser or one reboiler; there are no condensers and two reboilers; two condensers have no reboiler and one condenser has no reboiler.

6. A method for producing high-purity electronic grade methanol, which takes industrial grade methanol as a feed to prepare the high-purity electronic grade methanol, comprises one or more of the following steps:

removing most of the water in the industrial grade methanol;

removing large particles from the industrial-grade methanol;

removing organic impurities and a small part of water in the industrial grade methanol;

removing micro particles in the industrial grade methanol;

wherein:

removing anions and/or cations in the industrial-grade methanol,

7. The method of claim 6, wherein in the substep of removing anions and/or cations from the technical grade methanol, the anions and/or cations consist essentially of at least one of the group consisting of:

a first group: sodium ions, potassium ions, and boron ions;

third group: sodium ions, potassium ions, calcium ions and boron ions;

8. The method of claim 6, wherein: adopt accurate rectifying column to remove organic impurity and few subtotal water in the industrial grade methyl alcohol, accurate rectifying column includes that accurate rectification is with conventional rectifying column cluster or accurate rectification is with next door tower cluster, wherein:

the conventional rectifying tower string for precise rectification comprises at least two conventional rectifying towers for precise rectification, wherein the number of theoretical plates of the conventional rectifying towers is 20-100; it is preferable that: the conventional rectifying tower for precise rectification has the following conditions: the number of theoretical plates is 50-80, the operating pressure is 100pa-1.5Mpa, the reflux ratio is 1-10, the temperature at the top of the tower is-45-167 ℃, and the temperature at the bottom of the tower is-40-250 ℃; it is further preferred to include any one of the following sets of conditions:

the third group comprises a first-stage conventional rectifying tower with the tower top pressure of 0.1MPa, the tower top temperature of 64 ℃, the theoretical plate number of 80 and the reflux ratio of 3, a second-stage conventional rectifying tower with the tower top pressure of 0.01MPa, the tower top temperature of 17 ℃, the theoretical plate number of 70 and the reflux ratio of 3, a third-stage conventional rectifying tower with the tower top pressure of 1kPa, the tower top temperature of-19 ℃, the theoretical plate number of 50 and the reflux ratio of 5, a fourth-stage conventional rectifying tower with the tower top pressure of 100Pa, the tower top temperature of-45 ℃, the theoretical plate number of 50 and the reflux ratio of 5;

the bulkhead column string for precision rectification comprises at least one bulkhead column for precision rectification, wherein the area ratio of a feeding side to a product extraction side ranges from 4:6 to 6:4, and the number of theoretical plates is 20-100; it is preferable that: the conditions of the dividing wall column are as follows: the area ratio of the feed side to the product extraction side is 4:6 to 6:4, the number of theoretical plates is 80-100, the operating pressure is 500pa-0.4Mpa, the temperature at the top of the tower is-45-167 ℃, and the reflux ratio is 2-10; it is further preferred to include any one of the following sets of conditions:

in the third group, the top pressure of the first dividing wall tower is 0.08MPa, the top temperature is 60 ℃, the area ratio of the feeding side to the product extraction side is 5:5, the number of theoretical plates is 90, and the reflux ratio is 6; the tower top pressure of the second partition tower is 0.01MPa, the tower top temperature is 17 ℃, the area ratio of two sides is 6:4, the number of theoretical plates is 80, and the reflux ratio is 7;

9. The method of claim 1, wherein: and (2) adopting a dehydration processor to remove most of water in the industrial methanol, wherein:

the area ratio of the feed side to the product extraction side of the dividing wall tower for dehydration treatment ranges from 4:6 to 7:3, the number of theoretical plates is 80-100, and the reflux ratio of the tower top is 1-10; it is preferable that: the area ratio of the feed side to the product extraction side is 7:3, the number of theoretical plates is 100, the pressure at the top of the tower is 0.4MPa, the temperature at the top of the tower is 105 ℃, and the reflux ratio is 5; the dividing wall tower for dehydration treatment includes but is not limited to any one of a dividing wall tower of a middle dividing wall, a dividing wall tower of an upper dividing wall and a dividing wall tower of a lower dividing wall;

10. The method of claim 1, wherein: the methanol purity of the industrial grade methanol is more than 95% by mass, the water content is more than 500ppm, the metal ion is more than 500ppt, the anion is more than 500ppb, and the particle size larger than 0.2 μm is more than 1000/ml; it is preferable that: the composition of the technical grade methanol is referred to the indices of the feedstock in table 1.