Production method of electronic-grade hydroquinone

Abstract

The invention relates to a production method of electronic-grade hydroquinone, which comprises the following steps: feeding industrial-grade hydroquinone from outside of a boundary area and a solvent into a stirring and heating mixer for stirring and mixing to obtain a hydroquinone solution, firstly feeding the hydroquinone solution into a micro-filter to remove particles of more than 0.2 mu m, and then feeding the hydroquinone solution into an ion remover to remove anions and cations in the hydroquinone; and then, continuously sending into a nanofilter to filter out particles with the particle size of more than 10nm, finally sending into a crystallizer to carry out crystallization treatment, and drying the obtained crystallized product to obtain the high-purity hydroquinone product meeting the SEMI C12 standard and above. Compared with the prior art, the method has the advantages of short flow, low energy consumption, good separation effect, strong process continuity, high purity and low impurity content, and can meet the production of high-purity hydroquinone with the requirement of G4 or above.

Description

Technical Field

[0001] This invention belongs to the field of electronic-grade hydroquinone technology, and relates to a method for producing electronic-grade hydroquinone using industrial-grade hydroquinone as raw material. Background Technology

[0002] With the rapid development of technologies in the semiconductor, power battery, pharmaceutical, and chemical industries, the requirements for high-purity chemical reagents are becoming increasingly stringent. Their purity and cleanliness have a significant impact on yield, electrical performance, and reliability. High-purity hydroquinone, as an important electronic chemical, is widely used in power batteries, pharmaceuticals, and semiconductor lithography. As integrated circuit processing dimensions enter the nanometer era, the lifespan requirements for power batteries are increasing, and health and life science standards for pharmaceuticals are becoming more stringent. This places even higher demands on the high-purity hydroquinone used in these applications, requiring it to meet the SEMI C12 standard set by the Semiconductor Equipment and Materials International (SEMI), with a metal cation content of less than 100 ppt.

[0003] There are few research reports on high-quality, high-purity reagents in China; the available information mostly focuses on basic technologies and patents. Internationally, high-purity reagent process routes are considered industry secrets, and many basic technologies are protected by patents.

[0004] For example, Chinese patent application CN202310338042.5 provides a method for producing hydroquinone, an electronic chemical, including a dissolution step, a microfiltration step, an anion and cation removal step, a flash evaporation separation step or a distillation separation step, a nanofiltration step, a crystallization step, and a drying step. Although this patent can obtain hydroquinone that meets the requirements of G4 and above for electronic chemicals, the overall process is complex, and steps such as flash evaporation or distillation separation are energy-intensive and involve side reactions. Summary of the Invention

[0005] The purpose of this invention is to provide a method for producing electronic-grade hydroquinone that has a short process, low energy consumption, good separation effect, strong process continuity, high purity, and low impurity content.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] In one aspect, the present invention provides a method for producing electronic-grade hydroquinone. Industrial-grade hydroquinone from outside the designated area and a solvent are fed into a stirred and heated mixer for stirring and mixing to obtain a hydroquinone solution. The solution is then fed into a microfilter to remove particles larger than 0.2 μm, followed by an ion remover to remove cations and anions from the hydroquinone. Next, it is fed into a nanofilter to remove particles larger than 10 nm, and finally into a crystallizer for crystallization. The resulting crystalline product is dried to obtain a high-purity hydroquinone product that meets or exceeds the SEMI C12 standard.

[0008] Furthermore, the solvent is one or a combination of several of the following: water, methanol, ethanol, n-propanol, isopropanol, acetone, methyl acetate, and ethyl acetate. The molar ratio of the solvent to hydroquinone is 1 to 15:1, and can be 1:1, 5:1, 10:1, 15:1, etc.

[0009] Furthermore, the microfiltration membrane used in the microfilter is one of the following: polytetrafluoroethylene membrane, polyethersulfone membrane, polyvinylidene fluoride membrane, polyimide membrane, and polyamide membrane, with a pore size of 0.1-0.5 μm.

[0010] Furthermore, the ion remover uses ion exchange resin or ion exchange fiber for ion removal treatment.

[0011] Furthermore, the ion exchange resin is one or more of sulfonated styrene resin, carboxylated styrene resin, quaternary ammonium styrene resin, perfluorosulfonic acid resin, and sulfonated polyethersulfone resin.

[0012] The ion exchange fiber is one or more of the following: sulfonated styrene fiber, carboxylated styrene fiber, quaternary ammonium styrene fiber, perfluorosulfonic acid fiber, and sulfonated polyethersulfone fiber.

[0013] Furthermore, the nanofiltration membrane used in the nanofiltration device is a polytetrafluoroethylene membrane, polyethersulfone membrane, polyvinylidene fluoride membrane, polyimide membrane, or polyamide membrane with a pore size of 10-50 nm.

[0014] Furthermore, the crystallizer has two or more stages, with each stage having a crystallization temperature of 20-170℃.

[0015] Furthermore, the crystallizer is a suspension stirring crystallizer, a plate crystallizer, or a melt crystallizer.

[0016] Furthermore, the temperature of the dryer does not exceed 180°C.

[0017] In another aspect, the present invention provides an apparatus for producing electronic-grade hydroquinone, for carrying out the production method as described in any of the preceding claims, the apparatus comprising: sequentially connected components...

[0018] A stirring and heating mixer is used to prepare the hydroquinone solution;

[0019] Microfilters are used to perform microfiltration processes;

[0020] Anion and cation remover, used to perform ion removal process;

[0021] Nanofilters are used to perform nanofiltration processes;

[0022] A crystallizer is used to perform the crystallization process;

[0023] A dryer is used to perform the drying process.

[0024] While existing technologies such as CN202310338042.5 can produce hydroquinone products that meet the G4 and above requirements for electronic chemicals, the overall process is complex and cumbersome. Furthermore, current mainstream improvement approaches primarily involve adding processing steps to increase the purity of electronic chemicals. In contrast, this invention optimizes and improves the parameters of each process, eliminating cumbersome and energy-intensive distillation and separation steps. By directly using crystallization and subsequent drying processes in conjunction with pre-processing, it effectively removes impurities such as water and organic impurities. This results in a product with high purity, high process yield, and low impurity content. Moreover, due to the elimination of the flash distillation (distillation) separation process, the entire production method exhibits strong process continuity and has significant industrialization potential.

[0025] The hydroquinone raw material used in this invention is industrial-grade hydroquinone with a purity of over 99% by mass, a water content of over 500 ppm, a metal ion content of over 500 ppt, anion content of over 500 ppb, and more than 1000 particles larger than 0.2 μm / ml. The hydroquinone product produced using this patented method has a purity of over 99.9%, a water content of less than 100 ppm, a metal ion content of less than 100 ppt, anion content of less than 50 ppt, and less than 200 particles larger than 0.2 μm / ml, meeting the requirements of SEMI-C12(G4) and above. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the production process of electronic-grade high-purity hydroquinone according to the present invention;

[0027] Explanation of markings in the diagram:

[0028] 1-Industrial grade hydroquinone raw material; 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-Nanofilter; 10-Hydroquinone after nanofiltration; 11-Crystallizer; 12-Crystallization mother liquor; 13-Hydroquinone product after crystallization; 14-Dryer; 15-Electronic grade hydroquinone product. Detailed Implementation

[0029] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0030] Unless otherwise specified, the raw materials or processing techniques used in the following embodiments or examples are conventional commercially available raw materials or conventional processing techniques in the art.

[0031] In some embodiments, the present invention provides a method for producing electronic-grade hydroquinone, such as... Figure 1 As shown, industrial-grade hydroquinone raw material 1 from outside the boundary area and solvent 2 are heated and mixed in a stirring and heating mixer 3 to prepare hydroquinone solution 4. Then, it enters a microfilter 5 for microfiltration to remove particles larger than 0.2 μm. Next, the microfiltered hydroquinone 6 continues to enter an anion and cation remover 7 for full reaction to remove most of the anions and cations in the hydroquinone, resulting in deionized hydroquinone 8, which enters a nanofilter 9 to filter out particles larger than 10 nm. The resulting nanofiltered hydroquinone 10 is then sent to a crystallizer 11 for full crystallization. The resulting crystallization mother liquor 12 is discharged, and the crystallized hydroquinone product 13 is sent to a dryer 14 for drying to obtain electronic-grade hydroquinone product 15 for output.

[0032] The hydroquinone raw material of this invention is industrial grade hydroquinone with a hydroquinone purity of 99% or higher by mass, a water content of 500 ppm or higher, a metal ion content of 500 ppt or higher, an anion content of 500 ppb or higher, and more than 1000 particles larger than 0.2 μm (micrometers) per ml (milliliters).

[0033] In some specific embodiments, the solvent is one or a combination of several of the following: water, methanol, ethanol, n-propanol, isopropanol, acetone, methyl acetate, and ethyl acetate, and the molar ratio of the solvent to hydroquinone is 1 to 15:1.

[0034] In some specific embodiments, the microfiltration membrane used in the microfilter is one of the following: polytetrafluoroethylene membrane, polyethersulfone membrane, polyvinylidene fluoride membrane, polyimide membrane, and polyamide membrane with a pore size of 0.1-0.5 μm.

[0035] In some specific embodiments, the ion remover uses ion exchange resin or ion exchange fiber for ion removal treatment.

[0036] In a more specific embodiment, the ion exchange resin is one or more of sulfonated styrene resin, carboxylated styrene resin, quaternary ammonium styrene resin, perfluorosulfonic acid resin, and sulfonated polyethersulfone resin;

[0037] The ion exchange fiber is one or more of the following: sulfonated styrene fiber, carboxylated styrene fiber, quaternary ammonium styrene fiber, perfluorosulfonic acid fiber, and sulfonated polyethersulfone fiber.

[0038] In some specific embodiments, the nanofiltration membrane used in the nanofiltration device is a polytetrafluoroethylene membrane, polyethersulfone membrane, polyvinylidene fluoride membrane, polyimide membrane, or polyamide membrane with a pore size of 10-50 nm.

[0039] In some specific embodiments, the crystallizer has two or more stages, and the crystallization temperature of each stage is 20-170°C.

[0040] In some specific embodiments, the crystallizer is a suspension stirring crystallizer, a plate crystallizer, or a melt crystallizer.

[0041] In some specific embodiments, the temperature of the dryer does not exceed 180°C.

[0042] Each of the above implementation methods can be implemented individually, or in any combination of two or more.

[0043] The above implementation methods will be described in more detail below with reference to specific embodiments.

[0044] Example 1

[0045] In such Figure 1 Based on the existing process flow, the specific process parameters in this embodiment are set as follows:

[0046] The solvent ethanol and hydroquinone were fed into a stirring and mixing heater (3) at a molar ratio of 2.3:1 and heated to 68°C. After being mixed evenly, the mixture entered a microfilter. The microfilter used a polytetrafluoroethylene membrane with a pore size of 0.2 μm and a uniformity coefficient of 1.3. The ion exchange resin was a mixture of sulfonated styrene resin and quaternary ammonium styrene resin with a particle size of 0.6 mm and a uniformity coefficient of 1.05, mixed in a volume ratio of 1:1. The nanofilter used a polytetrafluoroethylene membrane with a pore size of 20 nm and a uniformity coefficient of 1.15. The crystallizer used a 4-stage crystallization process with crystallization temperatures of 30°C, 100°C, 160°C, and 165°C, respectively. The operating conditions of the dryer were 110°C, 60 kPa, and 1.8 h. A high-purity hydroquinone product with a purity higher than the SEMI C12 (G4) standard was obtained. The product indicators are shown in Table 2.

[0047] Example 2

[0048] In such Figure 1 Based on the existing process flow, the specific process parameters in this embodiment are set as follows:

[0049] Solvent isopropanol and hydroquinone were fed in a molar ratio of 2.8:1 into a stirred mixer and heated to 70°C. The mixture was then fed into a microfilter using a polyimide membrane with a pore size of 0.4 μm and a uniformity coefficient of 1.20. The ion exchange resin was a mixture of perfluorosulfonic acid resin and quaternary ammonium styrene resin, with a particle size of 0.3 mm and a uniformity coefficient of 1.25, compounded in a volume ratio of 2:3. A nanofiltration unit used a polyimide membrane with a pore size of 15 nm and a uniformity coefficient of 1.25. A three-stage crystallizer was used, with crystallization temperatures of 20°C, 120°C, and 167°C, respectively. The product was dried at 120°C, 100 kPa, for 1 hour. High-purity hydroquinone products exceeding the SEMIC 12 (G4) standard were obtained. Product specifications are shown in Table 2.

[0050] Example 3

[0051] In such Figure 1 Based on the existing process flow, the specific process parameters in this embodiment are set as follows:

[0052] Ethyl acetate and hydroquinone were fed in a 5.5:1 molar ratio into a stirred mixer and heated to 48°C. The mixture was then fed into a microfilter using a polyamide membrane with a 0.2 μm pore size and a uniformity coefficient of 1.3. The ion exchange resin was a mixture of sulfonated styrene resin and quaternary ammonium styrene resin, with a particle size of 0.5 mm and a uniformity coefficient of 1.1, compounded in a 2:1 volume ratio. A nanofiltration unit used a polyvinylidene fluoride (PVDF) membrane with a 25 nm pore size and a uniformity coefficient of 1.15. A three-stage crystallizer was used, with crystallization temperatures of 10°C, 90°C, and 166°C, respectively. The product was dried at 125°C, 90 kPa, for 45 min. High-purity hydroquinone exceeding the SEMI C12 (G4) standard was obtained. Product specifications are shown in Table 2.

[0053] Example 4

[0054] In such Figure 1 Based on the existing process flow, the specific process parameters in this embodiment are set as follows:

[0055] The solvent butyl acetate and hydroquinone were fed in a molar ratio of 4.2:1 into a stirred mixer and heated to 65°C. After mixing, the mixture entered a microfilter using a polyimide membrane with a pore size of 0.1 μm and a uniformity coefficient of 1.45. The ion exchange resin was a mixture of perfluorosulfonic acid resin and quaternary ammonium styrene resin with a particle size of 0.6 mm and a uniformity coefficient of 1.05, mixed at a volume ratio of 5:2. The nanofilter used a polyvinylidene fluoride (PVDF) membrane with a pore size of 10 nm and a uniformity coefficient of 1.3. The crystallizer employed a three-stage crystallization process with crystallization temperatures of 20°C, 140°C, and 168°C, respectively. The dryer operated at 105°C, 70 kPa, for 2 hours. A high-purity hydroquinone product exceeding the SEMI C12 (G4) standard was obtained. Product specifications are shown in Table 2.

[0056] Example 5

[0057] In such Figure 1 Based on the existing process flow, the specific process parameters in this embodiment are set as follows:

[0058] Acetic acid and hydroquinone were fed in a 7.5:1 molar ratio into a stirred mixer and heated to 65°C. The mixture was then fed into a microfilter using a polyimide membrane with a 0.1 μm pore size and a uniformity coefficient of 1.45. The ion exchange resin was a mixture of styrene phosphate resin and quaternary ammonium styrene resin, with a particle size of 0.5 mm and a uniformity coefficient of 1.15, mixed at a volume ratio of 1:3. A nanofiltration membrane with a 40 nm pore size and a uniformity coefficient of 1.1 was used. A four-stage crystallizer was employed, with crystallization temperatures of 25°C, 75°C, 115°C, and 166°C, respectively. The product was dried at 130°C, 100 kPa, for 20 min. High-purity hydroquinone exceeding the SEMI C12 (G4) standard was obtained. Product specifications are shown in Table 2.

[0059] Example 6

[0060] In such Figure 1 Based on the existing process flow, the specific process parameters in this embodiment are set as follows:

[0061] The solvent water and hydroquinone were fed in a molar ratio of 13.2:1 into a stirred mixer and heated to 60°C. The mixture then entered a microfilter using a polyimide membrane with a pore size of 0.1 μm and a uniformity coefficient of 1.45. The ion exchange resin was a mixture of perfluorosulfonic acid resin and quaternary ammonium styrene resin with a particle size of 0.4 mm and a uniformity coefficient of 1.25, mixed at a volume ratio of 2:3. A nanofiltration unit used a polytetrafluoroethylene membrane with a pore size of 50 nm and a uniformity coefficient of 1.05. A two-stage crystallizer was used, with crystallization temperatures of 50°C and 167°C, respectively. The product was then dried at 85°C, 50 kPa, for 3 hours. High-purity hydroquinone products exceeding the SEMI C12 (G4) standard were obtained. Product specifications are shown in Table 2.

[0062] Comparative Example 1

[0063] This comparative example uses the same raw materials and process as Example 1, the difference being that the particle size uniformity coefficient of the ion exchange resin used in the ion exchange remover is changed to 1.4. Product specifications are shown in Table 3. Sodium and potassium do not meet the SEMI C12 (G4) requirements; sodium, iron, calcium, potassium, zinc, arsenic, cobalt, boron, silicon, and lead do not meet the SEMI C12 (G5) requirements.

[0064] Comparative Example 2

[0065] This comparative example uses the same raw materials and process as Example 1, the difference being that the ion exchange resin particle size used in the ion exchange remover is changed to 0.7 mm. Product specifications are shown in Table 3. Sodium, potassium, aluminum, boron, and silicon do not meet the SEMI C12 (G4) requirements; sodium, iron, copper, calcium, lead, potassium, boron, silicon, magnesium, zinc, arsenic, aluminum, silver, tin, and cobalt do not meet the G5 requirements.

[0066] Comparative Example 3

[0067] The feed and operating conditions for this comparative example are exactly the same as in Example 1, except that the crystallizer is changed from a two-stage to a single-stage process, and the drying temperature is adjusted to 150°C. Product specifications are shown in Table 3. The product purity does not meet the requirements of SEMI C12(G4).

[0068] The content of components in hydroquinone, an electronic chemical produced in Examples 1-6 and Comparative Examples 1-5, was determined using the following instruments: PerkinElmer ICP-OES / Avio 550MAX for raw material cations, Agilent ICP-MS / MS 8900 for product cations, Metrohm 940 ion chromatograph for both raw materials and products, a Coulomb 851 cassette water analyzer for water content in both raw materials and products, Agilent GC-MS for organic impurities in both raw materials and products, and a RION-KS-42AF particle size analyzer. The results are shown in Tables 1-3. The raw materials mentioned in Table 1 refer to industrial-grade hydroquinone.

[0069] Table 1. Hydroquinone raw material specifications

[0070]

[0071] Table 2 Product indicators obtained from Examples 1 to 4

[0072]

[0073]

[0074] Table 3 shows the product indicators obtained after processing in Examples 5 and 6.

[0075]

[0076]

[0077] Table 4 shows the product indicators obtained after processing using Comparative Examples 1 to 3.

[0078]

[0079]

[0080] The table above is for illustrating the components contained in hydroquinone raw materials and does not limit the applicability of this invention. Hydroquinone products produced by the method of this patented invention can meet the SEMI C12 (G4) and above standard requirements.

[0081] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for producing electronic-grade hydroquinone, characterized in that, Industrial-grade hydroquinone and solvent from outside the designated area are fed into a stirred and heated mixer for mixing to obtain a hydroquinone solution. The solution is then first sent to a microfilter to remove particles larger than 0.2 μm, followed by an ion remover to remove cations and anions from the hydroquinone. Next, it is sent to a nanofilter to remove particles larger than 10 nm, and finally sent to a crystallizer for crystallization. The resulting crystallized product is dried to obtain a high-purity hydroquinone product that meets or exceeds the SEMI C12 standard.

2. The method for producing electronic-grade hydroquinone according to claim 1, characterized in that, The solvent is one or a combination of several of the following: water, methanol, ethanol, n-propanol, isopropanol, acetone, methyl acetate, and ethyl acetate. The molar ratio of the solvent to hydroquinone is 1 to 15:

1.

3. The method for producing electronic-grade hydroquinone according to claim 1, characterized in that, The microfiltration membrane used in the microfilter is one of the following: polytetrafluoroethylene membrane, polyethersulfone membrane, polyvinylidene fluoride membrane, polyimide membrane, or polyamide membrane, with a pore size of 0.1-0.5 μm.

4. The method for producing electronic-grade hydroquinone according to claim 1, characterized in that, The ion remover uses ion exchange resin or ion exchange fiber for ion removal treatment.

5. The method for producing electronic-grade hydroquinone according to claim 4, characterized in that, The ion exchange resin is one or more of sulfonated styrene resin, carboxylated styrene resin, quaternary ammonium styrene resin, perfluorosulfonic acid resin, and sulfonated polyethersulfone resin. The ion exchange fiber is one or more of the following: sulfonated styrene fiber, carboxylated styrene fiber, quaternary ammonium styrene fiber, perfluorosulfonic acid fiber, and sulfonated polyethersulfone fiber.

6. The method for producing electronic-grade hydroquinone according to claim 1, characterized in that, The nanofiltration membrane used in the nanofiltration device is a polytetrafluoroethylene membrane, polyethersulfone membrane, polyvinylidene fluoride membrane, polyimide membrane, or polyamide membrane with a pore size of 10-50 nm.

7. The method for producing electronic-grade hydroquinone according to claim 1, characterized in that, The crystallizer has two or more stages, and the crystallization temperature of each stage is 20-170℃.

8. The method for producing electronic-grade hydroquinone according to claim 1, characterized in that, The crystallizer is a suspension stirring crystallizer, a plate crystallizer, or a melt crystallizer.

9. The method for producing electronic-grade hydroquinone according to claim 1, characterized in that, The temperature of the dryer does not exceed 180°C.

10. An apparatus for producing electronic-grade hydroquinone, used for implementing the production method as described in any one of claims 1-9, characterized in that, The production apparatus comprises, in sequence, the following: A stirring and heating mixer is used to prepare the hydroquinone solution; Microfilters are used to perform microfiltration processes; Anion and cation remover, used to perform ion removal process; Nanofilters are used to perform nanofiltration processes; A crystallizer is used to perform the crystallization process; A dryer is used to perform the drying process.

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