A production method of electronic chemical hydroquinone

Abstract

The present invention discloses a production method of hydroquinone, an electronic chemical, comprising a dissolving step, a microfiltration step, an anion and cation removal step, a flash separation step or a distillation separation step, a nanofiltration step, a crystallization step and a drying step. The dissolving step is to dissolve industrial-grade hydroquinone with a reagent to obtain a hydroquinone solution; the flash separation step is to separate the components of the hydroquinone solution after the nanofiltration step through a flash tank; the distillation separation step is to separate the components of the hydroquinone solution before the nanofiltration step through a first distillation tower and a second distillation tower; the crystallization step is to crystallize the hydroquinone solution after the flash separation step or the hydroquinone solution after nanofiltration through a crystallizer; the drying step is to dry the hydroquinone product after the crystallization step; and a heating step is also included. The product is a high-purity electronic-grade hydroquinone with high purity and low impurity content, which can meet the requirements of SEMIC12 (G4), the highest standard for electronic chemicals, and above.

Description

Technical Field

[0001] The present invention belongs to the technical field of electronic chemical preparation, and relates to high-purity electronic chemical hydroquinone in the fields of semiconductors, display panels, solar energy, power batteries, medicine, chemical industry, etc., and specifically relates to a production method of electronic chemical hydroquinone. Background Art

[0002] Hydroquinone, also known as hydroquinone, is an organic compound formed by the replacement of two para-hydrogens of benzene by hydroxyl groups. Its chemical formula is C 6 H 6 O 2 It is a white crystalline powder, mainly used to prepare black and white developers, anthraquinone dyes, azo dyes, rubber antioxidants, stabilizers and antioxidants. Electronic grade catechol is mainly used as an additive for lithium battery electrolytes.

[0003] High-purity electronic-grade hydroquinone is usually purified from industrial-grade hydroquinone raw materials. For example, Chinese patent application CN216472987 U discloses an electronic-grade catechol production device, which processes industrial-grade catechol through melt crystallization, distillation, and ion exchange to improve the purity of catechol. However, the finished particles cannot meet the requirements of SEMI C12 (G4) and SEMI C12 (G5).

[0004] The applicant's Chinese patent application CN114870420A discloses a high-purity electronic grade isopropyl alcohol production device, including: industrial grade isopropyl alcohol is subjected to microfiltration, anion and cation removal, dehydration treatment or precision distillation tower, nanofiltration, and the microfiltration and anion and cation removal cannot be dehydrated or distilled at the same time before and after; when there is no dehydration treatment and distillation before microfiltration and anion and cation removal, distillation and nanofiltration or only distillation are performed after microfiltration and anion and cation removal; when microfiltration and anion and cation removal only include anion and cation removal and the dehydration treatment or distillation before it, anion and cation removal Then nanofiltration; when microfiltration and anion and cation removal only include anion and cation removal and there is no dehydration and distillation in series before, the anion and cation removal is followed by a distillation tower and nanofiltration. The process device and physical parameters of this patent can obtain electronic-grade products of isopropanol, but due to the fact that the process parameters of different chemical products, especially different isomers of hydroquinone, have a greater impact on the purification results, the applicant has tested that it cannot be directly used for the preparation of electronic-grade products of crystalline powder chemical products. This application provides a preparation method for electronic-grade products directly used for hydroquinone. Summary of the invention

[0005] In view of the above problems, the present invention provides a method for producing hydroquinone, an electronic chemical. The production method of the present invention has a short process, low energy consumption, good separation effect, strong process continuity, and the obtained product has high purity and low impurity content, and can meet the requirements of the highest electronic chemical standard SEMI C12 (G4) and above. High-purity hydroquinone.

[0006] To achieve the above-mentioned purpose of the invention, the present invention provides the following technical scheme: a method for producing hydroquinone, an electronic chemical, comprising the following steps: dissolving industrial-grade hydroquinone to obtain a hydroquinone solution; removing particles with a particle size of 0.2 μm or more; removing anions and cations in the hydroquinone solution; removing organic impurities and solvents in the hydroquinone solution; removing particles with a particle size of 10 nm or more; and crystallization and drying steps.

[0007] Furthermore, a microfilter is used to remove particles with a particle size of 0.2 μm or more, wherein the microfiltration membrane is selected from a polytetrafluoroethylene membrane, a polyethersulfone membrane, a polyvinylidene fluoride membrane (PVDF), a polyimide membrane and a polyamide membrane with a pore size of 0.1-0.5 μm, and a pore size uniformity coefficient of 1.1-1.4;

[0008] Further, the anions and cations in the hydroquinone solution are removed by using an ion exchange resin and / or ion exchange fiber with a particle size of 0.3-0.6 mm, which is one or more of sulfonic acid styrene resin or fiber, carboxyl styrene resin or fiber, quaternary amino styrene resin or fiber, perfluorosulfonic acid resin or fiber, sulfonated polyethersulfone resin or fiber, and the pore size uniformity coefficient is 1.1-1.3;

[0009] Furthermore, a nanofilter is used to remove particles with a particle size of more than 10 nm, and the nanofilter membrane is selected from one of polytetrafluoroethylene membrane, polyethersulfone membrane, polyvinylidene fluoride membrane (PVDF), polyimide membrane or polyamide membrane with a pore size of 10-50 nm, and the pore size uniformity coefficient is 1.1-1.4.

[0010] Furthermore, the microfilter uses a polytetrafluoroethylene membrane with a pore size of 0.2 μm and a uniformity coefficient of 1.25; the microfilter uses a polyimide membrane with a pore size of 0.4 μm and a uniformity coefficient of 1.15;

[0011] The ion exchange resin used was a mixed resin with a particle size of 0.6 mm, a uniformity coefficient of 1.1, and a volume ratio of sulfonic acid styrene to quaternary amino styrene of 2:1; the ion exchange resin used was a mixed resin with a particle size of 0.3 mm, a uniformity coefficient of 1.3, and a volume ratio of perfluorosulfonic acid to quaternary amino styrene of 3:2;

[0012] The nanofilter uses a polytetrafluoroethylene membrane with a pore size of 20 nm and a uniformity coefficient of 1.2; the nanofilter uses a polyimide membrane with a pore size of 10 nm and a uniformity coefficient of 1.25.

[0013] The preparation method of the electronic chemical hydroquinone can remove metal impurities, non-metallic impurities and organic impurities in the industrial-grade hydroquinone, and the metal impurities, non-metallic impurities and organic impurities include at least one of the following: the first type, lead, aluminum, potassium, tungsten, gallium, germanium, silicon and organic impurities; the second type, lead, aluminum, potassium, gallium, germanium, silicon and organic impurities; the third type, lead, aluminum, potassium, tungsten, gallium, silicon and organic impurities; the fourth type, aluminum, potassium, tungsten, gallium, germanium, silicon and organic impurities.

[0014] The preparation method of the electronic chemical hydroquinone of the present invention has a significant effect on removing lead, aluminum, potassium, tungsten, gallium, germanium, silicon metal impurities, non-metallic impurities and other organic impurities, and can meet the highest standards of electronic chemicals.

[0015] Furthermore, the solvent used to dissolve industrial-grade hydroquinone is one or more of water, methanol, ethanol, n-propanol, isopropanol, acetone, methyl acetate, and ethyl acetate.

[0016] Furthermore, the crystallizer is of level 0-3, and the crystallization temperature is 20-170° C. The drying temperature of the dryer is 90-130° C.

[0017] The crystallizer can be a suspension stirring crystallizer, a plate crystallizer or a melt crystallizer, one or a combination of several, specifically: one-stage suspension stirring crystallization; one-stage plate crystallization; one-stage falling film crystallization; suspension stirring crystallization and plate crystallization in sequence; suspension stirring and falling film crystallization in sequence; two-stage plate crystallization in sequence; two-stage falling film crystallization in sequence; suspension stirring crystallization, plate crystallization and falling film crystallization in sequence; suspension stirring, two-stage plate crystallization in sequence, suspension stirring, two-stage falling film crystallization combination in sequence; but not limited to the above.

[0018] The preparation method removes metal impurities and non-metal impurities in the industrial-grade hydroquinone, and the metal impurities and non-metal impurities include at least one of the following: a first type, sodium, iron, calcium and potassium; a second type, sodium, iron, copper, calcium, potassium, zinc, arsenic, silver, cobalt, boron, silicon and lead; a third type, sodium, iron, copper, calcium, lead, potassium, boron and silicon; a fourth type, sodium, iron, copper, calcium, lead, potassium, boron, silicon, magnesium, zinc, arsenic, aluminum, silver, tin and cobalt. The contents of metal impurities and non-metal impurities in the industrial-grade hydroquinone are shown in Table 1.

[0019] The beneficial effects of the present invention are:

[0020] First, the industrial product hydroquinone is dissolved into a solution, and then sent to a microfilter to remove large particles (particles larger than 0.2 μm) in the hydroquinone solution, and then enters the anion and cation removal device. This process removes anions and cations through ion exchange resins or ion exchange fibers; then enters the separator, which removes organic impurities and solvents in the hydroquinone. The hydroquinone product distilled from the separator enters the nanofiltration device, removes fine particles (particles larger than 10 nm), and then crystallizes and purifies, and finally obtains the product after drying. This product is high-purity, low-impurity electronic-grade hydroquinone, which can meet the highest standard of electronic chemicals SEMI C12 (G4) and above requirements for high-purity hydroquinone.

[0021] Secondly, the separator of the present invention is one of a flash tank, a conventional distillation tower and a next-door distillation tower. Under the condition of meeting the same separation degree, the next-door tower can greatly reduce the number of conventional distillation towers, which can be reduced from the original 2 distillation towers to 1, the original 4 distillation towers to 2, and 6 conventional distillation towers to 3 next-door towers, which can greatly reduce energy consumption and investment and shorten the process.

[0022] Thirdly, the product indicators obtained by the preparation method and the preparation device of the present invention, such as extremely low contents of metal impurities such as lead, aluminum, potassium, tungsten, gallium, germanium, non-metallic impurities such as silicon, and organic impurities, meet the highest standard of electronic chemicals SEMI C12 (G4) and above requirements; and can be used to process industrial products such as hydroquinone with high contents of metal impurities such as lead, aluminum, potassium, tungsten, gallium, germanium, non-metallic impurities such as silicon, and organic impurities. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic diagram of an embodiment of the production method and production device of the electronic chemical hydroquinone of the present invention.

[0024] Figure 2 It is a schematic diagram of Example 2 of the production method and production device of the electronic chemical hydroquinone of the present invention.

[0025] Figure 3 It is a schematic diagram of Example 3 of the production method and production device of the electronic chemical hydroquinone of the present invention.

[0026] Figure 4 It is a schematic diagram of Example 4 of the production method and production device of the electronic chemical hydroquinone of the present invention.

[0027] Figure 5 It is a schematic diagram of Example 5 of the production method and production device of the electronic chemical hydroquinone of the present invention.

[0028] Figure 6 It is a schematic diagram of Example 6 of the production method and production device of the electronic chemical hydroquinone of the present invention.

[0029] Figure 7 It is a schematic diagram of Example 7 of the production method and production device of the electronic chemical hydroquinone of the present invention.

[0030] Figure 8 It is a schematic diagram of Example 8 of the production method and production device of the electronic chemical hydroquinone of the present invention.

[0031] Fig. 9 There are several forms of the bulkhead tower, A is the middle bulkhead, B is the upper bulkhead, and C is the lower bulkhead.

[0032] Description of reference numerals:

[0033] 1 industrial grade hydroquinone, 2 solvent, 3 stirring and heating mixer, 4 hydroquinone solution, 5 microfilter, 6 hydroquinone after microfiltration, 7 anion and cation remover, 8 hydroquinone after deionization, 9 primary separator, 10 light component, 11 heavy component, 12 hydroquinone after primary separation, 13 nanofilter, 14 hydroquinone after nanofiltration, 15 crystallizer, 17 hydroquinone product after crystallization, 18 dryer, 19 electronic grade hydroquinone product, 20 secondary separator, 21 hydroquinone after secondary separation, 24 tertiary separator DETAILED DESCRIPTION

[0034] The following examples further illustrate the content of the present invention, but should not be construed as limiting the present invention. Without departing from the spirit and substance of the present invention, modifications or substitutions made to the methods, steps or conditions of the present invention all fall within the scope of the present invention.

[0035] Example 1

[0036] like Figure 1 As shown, from the feed to the discharge, the process includes a mixer, a microfilter, an anion and cation remover, a nanofilter, a distillation tower with a dividing wall, a crystallizer and a dryer connected in series in sequence. The distillation tower with a dividing wall is in the form of a middle dividing wall.

[0037] The industrial-grade hydroquinone and solvent used in the present invention enter a stirring and heating mixer (3) to obtain a hydroquinone solution, and then enter a microfilter (5) to remove particles larger than 0.2 μm (micrometer). The microfilter can be a polytetrafluoroethylene membrane, a polyethersulfone membrane, a polyvinylidene fluoride membrane (PVDF), a polyimide membrane, a polyamide membrane or other membranes with the same pore size, with a pore size of 0.1-0.5 μm.

[0038] After microfiltration, the product enters an anion and cation remover (7), which is used to remove anions and cations in hydroquinone. The anion and cation remover can use ion exchange resin or ion exchange fiber, wherein the ion exchange resin uses a customized functional resin, and the ion exchange fiber uses a customized functional fiber, including one or more of sulfonic acid styrene resin or fiber, carboxyl styrene resin or fiber, quaternary amino styrene resin or fiber, perfluorosulfonic acid resin or fiber, and sulfonated polyethersulfone resin or fiber;

[0039] After the anions and cations are removed, the hydroquinone solution enters the nanofilter (13), which is used to filter out particles larger than 10 nm (nanometers). The membrane of the nanofilter (13) can be a polytetrafluoroethylene membrane with a pore size of 10-50 nm, a polyethersulfone membrane, a polyvinylidene fluoride membrane (PVDF), a polyimide membrane, a polyamide membrane or other membranes with the same pore size;

[0040] After nanofiltration, the product enters a separator (9). The number of separators can be increased by 0-6 according to the raw material and product standard requirements. The area ratio of the two sides of the distillation tower is in the range of 2:8 to 8:2. The forms mainly include the middle distillation tower, the upper distillation tower, and the lower distillation tower, but are not limited to the above three types. The hydroquinone obtained by the separator enters a crystallizer (15). The crystallizer can be 0-3 levels according to the needs. The crystallizer can be a suspension stirring crystallizer, a plate crystallizer, or a melting crystallizer. One or a combination of several. The product (17) obtained after crystallization passes through a dryer (18) to obtain a hydroquinone product that meets the SIMI C12 (G4) standard requirements.

[0041] The hydroquinone raw material of the present invention is industrial-grade hydroquinone, the mass content of hydroquinone is above 98%, the water content is above 500ppm, the metal ion is above 500ppt, the anion is above 500ppb, the particle size is greater than 0.2μm (micrometer), and the particle size is greater than 1000 / mL.

[0042] Example 2

[0043] like Figure 2 As shown, from feed to discharge, the process includes a mixer, a microfilter, an anion and cation remover, a nanofilter, a flash tank, a crystallizer and a dryer which are connected in series in sequence.

[0044] The solvent ethanol and hydroquinone enter the stirring and mixing heater (3) at a molar ratio of 2.5:1, and are heated to 70°C before entering the microfilter, which uses a polytetrafluoroethylene membrane with a pore size of 0.2μm and a uniformity coefficient of 1.25; the ion exchange resin uses a mixed resin with a particle size of 0.6mm, a uniformity coefficient of 1.1, and a volume ratio of sulfonate styrene and quaternary amino styrene of 2:1; the nanofilter uses a polytetrafluoroethylene membrane with a pore size of 20nm and a uniformity coefficient of 1.2; the separator (9) uses a flash tank with a pressure of 20kPa and a temperature of 130°C; the crystallizer (15) uses a two-stage plate crystallization, and the crystallization temperatures are 160°C and 165°C respectively; the dryer temperature, pressure and drying time are 100°C, 70kPa and 1.8h respectively. A high-purity hydroquinone product higher than the SEMI C12 (G4) standard is obtained, and the product indicators are shown in Table 2.

[0045] Example 3

[0046] like Figure 3 As shown, from feed to discharge, it includes a mixer, a microfilter, an anion and cation remover, a distillation tower, a nanofilter, a crystallizer and a dryer which are connected in series in sequence.

[0047] The solvent isopropanol and hydroquinone enter the stirring and mixing heater (3) at a molar ratio of 3:1, and are heated to 75°C and then enter the microfilter. The microfilter uses a polyimide membrane with a pore size of 0.4 μm and a uniformity coefficient of 1.15; the ion exchange resin uses a mixed resin with a particle size of 0.3 mm, a uniformity coefficient of 1.3, and a volume ratio of perfluorosulfonic acid and quaternary aminostyrene of 3:2; the separators (9) (20) use conventional distillation towers, wherein the separator (9) is the first distillation tower and the separator (20) is the second distillation tower. The distillation tower has a top pressure of 10 kPa, a top temperature of 114°C, a theoretical plate number of 11, and a reflux ratio of 1.2 for the first distillation tower; a top pressure of 1 kPa, a top temperature of 155°C, a theoretical plate number of 8, and a reflux ratio of 1 for the second distillation tower; the nanofilter (13) uses a polyimide membrane with a pore size of 10 nm and a uniformity coefficient of 1.25; the crystallizer (15) uses a 1-stage plate crystallization with a crystallization temperature of 167°C; the temperature, pressure, and drying time of the dryer are 110°C, 100 kPa, and 1.5 h, respectively. A high-purity hydroquinone product higher than the SEMI C12 (G4) standard is obtained, and the product indicators are shown in Table 2.

[0048] Example 4

[0049] like Figure 4 As shown, from the feed to the discharge, it includes a mixer, a microfilter, an anion and cation remover, a nanofilter, a distillation tower, a crystallizer and a dryer connected in series. The distillation tower has a middle distillation wall (type A), a condenser and a reboiler.

[0050] The solvent ethyl acetate and hydroquinone enter the stirring and mixing heater (3) at a molar ratio of 6:1, are heated to 50°C and then enter the microfilter, the microfilter adopts a polyamide membrane with a pore size of 0.2μm and a uniformity coefficient of 1.35; the ion exchange resin adopts a mixed resin with a particle size of 0.5mm, a uniformity coefficient of 1.12, and a volume ratio of sulfonic acid styrene resin and quaternary amino styrene of 3:1; the nanofilter (13) adopts a polyvinylidene fluoride (PVDF) membrane with a pore size of 30nm and a uniformity coefficient of 1.1; the separator (9) adopts a bulkhead tower type A form, with a two-side area ratio of 6:4, a tower top pressure of 3kPa, a tower top temperature of 81°C, a theoretical plate number of 18, and a reflux ratio of 1.5; the crystallizer (15) adopts a first-stage falling film crystallization, and the crystallization temperature is 166°C; the dryer is 130°C, 100kPa, 30min. The obtained product is a high-purity hydroquinone product that exceeds the SEMI C12 (G4) standard. The product indicators are shown in Table 3.

[0051] Example 5

[0052] like Figure 5 As shown, from feed to discharge, it includes a mixer, a microfilter, an anion and cation remover, a nanofilter, a crystallizer and a dryer which are connected in series in sequence.

[0053] The solvent butyl acetate and hydroquinone enter the stirring and mixing heater (3) at a molar ratio of 4.5:1, and enter the microfilter after being heated to 65°C. The microfilter adopts a polyimide membrane with a pore size of 0.1μm and a uniformity coefficient of 1.4; the ion exchange resin adopts a mixed resin with a particle size of 0.6mm, a uniformity coefficient of 1.08, and a volume ratio of 4:1 between perfluorosulfonic acid resin and quaternary aminostyrene; the nanofilter (13) adopts a polyvinylidene fluoride (PVDF) membrane with a pore size of 10nm and a uniformity coefficient of 1.25; the crystallizer (15) adopts a three-stage crystallization, which is: suspension stirring, two-stage plate crystallization, and the crystallization temperatures are 20°C, 140°C, and 168°C respectively; the dryer is 100°C, 80kPa, and 3h. A high-purity hydroquinone product higher than the SEMI C12 (G4) standard is obtained, and the product indicators are shown in Table 3.

[0054] Example 6

[0055] like Figure 6 As shown, from feed to discharge, it includes a mixer, anion and cation remover, a nanofilter, a conventional distillation tower, a crystallizer and a dryer which are connected in series in sequence.

[0056] The solvent acetic acid and hydroquinone enter the stirring and mixing heater (3) at a molar ratio of 8:1, and are heated to 70°C before entering the ion exchange resin; the ion exchange resin uses a particle size of 0.5 mm and a uniformity coefficient of 1.18, and a phosphate-based styrene resin and a quaternary amino styrene resin are mixed at a volume ratio of 3:1; the nanofilter uses a polyamide membrane with a pore size of 50 nm and a uniformity coefficient of 1.05; the separator (9) uses a flash tank with a pressure of 100 kPa and a temperature of 180°C; the crystallizer (15) uses a first-stage falling film crystallization with a crystallization temperature of 166°C; the dryer is 120°C, 90 kPa, and 40 minutes. A high-purity hydroquinone product higher than the SEMI C12 (G4) standard is obtained, and the product indicators are shown in Table 3.

[0057] Example 7

[0058] like Figure 7 As shown, from feed to discharge, it includes a mixer, anion and cation remover, a conventional distillation tower, a nanofilter, a crystallizer and a dryer which are connected in series in sequence.

[0059] Solvent water and hydroquinone enter the stirring and mixing heater (3) at a molar ratio of 14:1, and are heated to 65°C before entering the ion exchange resin; the ion exchange resin uses a mixed resin with a particle size of 0.4 mm and a uniformity coefficient of 1.27, and a volume ratio of 3:2 between perfluorosulfonic acid resin and quaternary aminostyrene; the separator (9) uses a flash tank with a pressure of 400 kPa and a temperature of 205°C; the nanofilter uses a polytetrafluoroethylene membrane with a pore size of 50 nm and a uniformity coefficient of 1.06; the crystallizer (15) uses a 1-stage plate crystallization with a crystallization temperature of 167°C; the dryer is 90°C, 50 kPa, and 2h. A high-purity hydroquinone product higher than the SEMI C12 (G4) standard is obtained, and the product indicators are shown in Table 3.

[0060] Example 8

[0061] like Figure 8 As shown, from the feed to the discharge, three distillation towers are used, including a mixer, a microfilter, an anion and cation remover, a nanofilter, and a separator connected in series. The first-stage distillation tower adopts a C-type distillation tower (lower distillation wall), a condenser, two reboilers, a condenser, and a reboiler. The second-stage distillation tower adopts an A-type (middle distillation wall), and the third-stage distillation tower adopts a B-type (upper distillation wall), two condensers, and a reboiler.

[0062] Solvent water and hydroquinone enter the stirring and mixing heater (3) at a molar ratio of 10:1, are heated to 90°C and then enter the microfilter, the microfilter uses a polyvinylidene fluoride (PVDF) membrane with a pore size of 0.5 μm and a uniformity coefficient of 1.1; the ion exchange resin uses a mixed resin with a particle size of 0.4 mm, a uniformity coefficient of 1.25, and a volume ratio of carboxyl styrene and primary amino styrene of 2:1; the nanofilter uses a polytetrafluoroethylene membrane with a pore size of 10 nm and a uniformity coefficient of 1.4; the separator (9) uses a bulkhead tower C type. The area ratio of the two sides is 4:6, the tower top pressure is 50 kPa, the tower top temperature is 146°C, the theoretical plate number is 18, and the reflux ratio is 1.5; the separator (20) adopts the type A of the dividing wall tower, the area ratio of the two sides is 5:5, the tower top pressure is 5 kPa, the tower top temperature is 189.8°C, the theoretical plate number is 12, and the reflux ratio is 2; the separator (24) adopts the type B of the dividing wall tower, the area ratio of the two sides is 6:4, the tower top pressure is 1 kPa, the tower top temperature is 154.5°C, the theoretical plate number is 10, and the reflux ratio is 2; a high-purity hydroquinone product higher than the SEMI C12 (G4) standard is obtained, and the product indicators are shown in Table 3.

[0063] Comparative Example 1

[0064] The raw materials and process are the same as in Example 3. Figure 4 The difference from Example 3 is that the particle size uniformity coefficient of the ion exchange resin used in the anion and cation remover is changed to 1.4. The product indicators are shown in Table 4. Sodium, iron, calcium and potassium cannot meet the requirements of SEMI C12 (G4); sodium, iron, copper, calcium, potassium, zinc, arsenic, silver, cobalt, boron, silicon and lead cannot meet the requirements of SEMI C12 (G5).

[0065] Comparative Example 2

[0066] The raw materials and process are the same as in Example 3. Figure 4 , the difference from Example 3 is that the particle size of the ion exchange resin used in the anion and cation remover is changed to 0.7 mm. The product indicators are shown in Table 4. Sodium, iron, copper, calcium, lead, potassium, boron and silicon cannot meet the requirements of SEMIC12 (G4); sodium, iron, copper, calcium, lead, potassium, boron, silicon, magnesium, zinc, arsenic, aluminum, silver, tin and cobalt cannot meet the requirements of G5.

[0067] Comparative Example 3

[0068] The raw materials and process are the same as in Example 7. Figure 8 , which is different from Example 7 in that the nanofilter pore size uniformity coefficient is changed to 1.5. Product specifications are shown in Table 4. The particles cannot meet the requirements of SEMI C12 (G4) and SEMI C12 (G5).

[0069] Comparative Example 4

[0070] The raw materials and process are the same as in Example 7. Figure 8 , which is different from Example 7 in that the pore size of the nanofilter is changed to 100 nm. Product specifications are shown in Table 4. The particles cannot meet the requirements of SEMI C12 (G4) and SEMI C12 (G5).

[0071] Comparative Example 5

[0072] The raw materials and operating conditions are the same as those in Example 6. Figure 7 , which is different from Example 6 in that the crystallizer is changed from three-stage to two-stage, and the product indicators are shown in Table 4. The product purity cannot meet the SEMI C12 (G4) requirements.

[0073] Comparative Example 6

[0074] The preparation process of electronic chemical hydroquinone is as follows: industrial-grade hydroquinone enters a melt crystallizer, and the discharge end pipe of the industrial-grade hydroquinone feed pipeline is connected to the feed end of the melt crystallizer; a melt crystallization residual liquid tank and a melt crystallization finished product tank, and the feed end pipes of the melt crystallization residual liquid tank and the melt crystallization finished product tank are connected to the discharge end of the melt crystallizer; a hydroquinone quartz distillation tower, the feed end of the hydroquinone quartz distillation tower is connected to the discharge end pipe of the melt crystallization residual liquid tank, and the discharge end is connected to the feed end pipe of the melt crystallizer, and a hydroquinone tower top condenser is arranged on the hydroquinone quartz distillation tower; an ion exchange column, an ion exchange resin layer is provided in the ion exchange column, the feed end of the ion exchange column is connected to the discharge end pipe of the melt crystallization finished product tank, and the waste liquid discharge end of the ion exchange column is connected to the feed end pipe of the hydroquinone quartz distillation tower; an industrial-grade hydroquinone discharge pipeline, and the feed end of the industrial-grade hydroquinone discharge pipeline is connected to the discharge end pipe of the ion exchange column. The product indicators are shown in Table 4. The particles cannot meet the requirements of SEMI C12 (G4) and SEMI C12 (G5).

[0075] Test example

[0076] The components in the electronic chemical hydroquinone obtained in Examples 2-8 and Comparative Examples 1-5 were tested for content, and the testing instruments were: PerkinElmer ICP-OES / Avio550MAX for raw material cations, Agilent ICP-MS / MS8900 for product cations, Swiss Metrohm 940 ion chromatograph for raw material and product anions, 851 Coulometric Karl Fischer water analyzer for raw material and product water content, Agilent GC-MS gas chromatograph for raw material and product organic impurities, and RION-KS-42AF for particle size analyzer. The results are shown in Tables 2-4, and the raw materials in Table 1 are industrial grade hydroquinone.

[0077] Table 1 Industrial hydroquinone raw material indicators

[0078]

[0079] Table 2 Product indicators obtained in Example 2 and Example 3 of the present invention

[0080]

[0081]

[0082] Table 3 Product indicators obtained in Examples 4-8 of the present invention

[0083]

[0084]

[0085] Table 4 Comparison of product indicators obtained from comparative examples 1-5

[0086]

[0087]

[0088] Table 5 Some indicators of products obtained by the preparation method and preparation device of the present invention

[0089]

[0090] In summary, the preparation method of the present invention obtains a high-purity electronic-grade hydroquinone with high product purity and low impurity content, which can meet the requirements of the highest electronic chemical standard SEMI C12 (G4) and above. The distillation tower next door used in the present invention can greatly reduce the number of conventional distillation towers, from the original 2 distillation towers to 1, the original 4 distillation towers to 2, and 6 conventional distillation towers to 3 distillation towers next door, which can greatly reduce energy consumption and investment and shorten the process.

[0091] Although the present invention has been described in detail above by general description, specific implementation methods and experiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A method for producing hydroquinone as an electronic chemical, comprising a dissolving step, a microfiltration step, an anion and cation removal step, a flash separation step or a distillation separation step, a nanofiltration step, a crystallization step and a drying step, wherein: The production method comprises any of the following steps: The first step sequentially includes a dissolution step, a microfiltration step, an anion and cation removal step, a nanofiltration step, a rectification and separation step, a crystallization step and a drying step; The second step sequentially includes a dissolution step, a microfiltration step, an anion and cation removal step, a nanofiltration step, a flash separation step, a crystallization step and a drying step; The third step sequentially includes a dissolution step, a microfiltration step, an anion and cation removal step, a rectification separation step, a nanofiltration step, a crystallization step and a drying step; The fourth step sequentially includes a dissolution step, a microfiltration step, an anion and cation removal step, a nanofiltration step, a rectification and separation step, a crystallization step, and a drying step; The fifth step sequentially includes a dissolution step, a microfiltration step, an anion and cation removal step, a nanofiltration step, a crystallization step and a drying step; The sixth step sequentially includes a dissolution step, anion and cation removal step, a nanofiltration step, a rectification and separation step, a crystallization step, and a drying step; The seventh step sequentially includes a dissolution step, a microfiltration step, an anion and cation removal step, a nanofiltration step, and a distillation separation step; The dissolving step is to dissolve industrial-grade hydroquinone with a reagent to obtain a hydroquinone solution, wherein the reagent is selected from one or more of ethanol and isopropanol; The flash separation step is to separate the components of the hydroquinone solution after the nanofiltration step through a flash tank, and the pressure of the flash separation step is 20 kPa and the temperature is 130° C. The distillation separation step is to separate the components of the hydroquinone solution through a first distillation tower and a second distillation tower, wherein the first distillation tower has a top pressure of 10 kPa, a top temperature of 114°C, a theoretical plate number of 11, and a reflux ratio of 1.2, and the second distillation tower has a top pressure of 1 kPa, a top temperature of 155°C, a theoretical plate number of 8, and a reflux ratio of 1; The crystallization step is to crystallize the hydroquinone solution through a crystallizer, the crystallizer adopts one or more of a first-stage plate crystallizer and a second-stage plate crystallizer, and the temperature of the crystallization step is 160-167° C.; The drying step is to dry the hydroquinone product at a temperature of 90-110° C., a pressure of 70-100 KPa, and a time of 1.5-1.8 hours; The method further comprises a heating step of heating the hydroquinone solution after the dissolving step to 70-75°C.

2. The production method according to claim 1, characterized in that The microfiltration step removes particles with a particle size of 0.2 μm or more, and the microfiltration membrane used is selected from a polytetrafluoroethylene membrane, a polyethersulfone membrane, a polyvinylidene fluoride membrane, a polyimide membrane and a polyamide membrane with a pore size of 0.1-0.5 μm, and the pore size uniformity coefficient is 1.1-1.4; The anion and cation removal step of each process uses an ion exchange resin and / or ion exchange fiber with a particle size of 0.3-0.6 mm to remove anions and cations in the hydroquinone solution, wherein the ion exchange resin and / or ion exchange fiber is one or more of sulfonic acid styrene resin or fiber, carboxyl styrene resin or fiber, quaternary amino styrene resin or fiber, perfluorosulfonic acid resin or fiber, sulfonated polyethersulfone resin or fiber, and has a pore size uniformity coefficient of 1.1-1.3; The nanofiltration step of each process uses a nanofilter for removing particles with a particle size of 10 nm or more, and the nanofilter membrane is selected from a polytetrafluoroethylene membrane, a polyethersulfone membrane, a polyvinylidene fluoride membrane, a polyimide membrane or a polyamide membrane with a pore size of 10-50 nm, and the pore size uniformity coefficient is 1.1-1.

4.

3. The production method according to claim 2, characterized in that: The microfilter uses a polytetrafluoroethylene membrane with a pore size of 0.2 μm and a uniformity coefficient of 1.25; the microfilter uses a polyimide membrane with a pore size of 0.4 μm and a uniformity coefficient of 1.15; The ion exchange resin in each step is a mixed resin with a particle size of 0.6 mm, a uniformity coefficient of 1.1, and a volume ratio of sulfonic acid styrene to quaternary amino styrene of 2:1, or a mixed resin with a particle size of 0.3 mm, a uniformity coefficient of 1.3, and a volume ratio of perfluorosulfonic acid to quaternary amino styrene of 3:2; The nanofilter uses a polytetrafluoroethylene membrane with a pore size of 20 nm and a uniformity coefficient of 1.2, and the nanofilter uses a polyimide membrane with a pore size of 10 nm and a uniformity coefficient of 1.

25.

4. The production method according to claim 3, characterized in that: The contents of various impurities in the electronic chemical hydroquinone are shown in the following table:

5. The production method according to claim 1, characterized in that: The contents of various impurities in the industrial grade hydroquinone are shown in the following table:

Images