阅读说明：本技术 一种电子级吡唑水溶液及其制备方法 (Electronic grade pyrazole aqueous solution and preparation method thereof ) 是由 胡硕真 张新胜 金家昱 王坦 郭江楠 程芸芸 高思捷 于 2020-08-08 设计创作，主要内容包括：本发明是一种电子级吡唑水溶液及其制备方法。该吡唑水溶液中Na～+、Mg～(2+)、K～+、Ca～(2+)、Cu～(2+)、Zn～(2+)、Ni～(2+)、Cr～(3+),Al～(3+)、Fe～(3+)等金属离子含量低于50 ppb,吡唑含量≥10%。本方法通过离子膜电解和离子交换树脂的组合工艺达到对吡唑水溶液的提纯,其中离子膜电解槽中加入离子交换树脂用以增强溶液的导电性和辅助脱除金属离子。阳极室吡唑原液中的一部分金属离子在电场力作用下由阳极室迁移到阴极室,还有一部分离子被电解槽内离子树脂吸附,最终在阳极室得到电子级吡唑水溶液。该电子级吡唑水溶液可用于超大规模集成电路或屏幕显示器等微电子工业所用化学清洗液的溶剂。(The invention relates to an electronic-grade pyrazole aqueous solution and a preparation method thereof. Na in the aqueous pyrazole solution + 、Mg 2+ 、K + 、Ca 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Cr 3+ ，Al 3+ 、Fe 3+ The content of the plasma metal ions is lower than 50 ppb, and the content of the pyrazole is more than or equal to 10 percent. The method achieves the purification of the pyrazole aqueous solution by the combined process of ion membrane electrolysis and ion exchange resin, wherein the ion exchange resin is added into an ion membrane electrolysis cell to enhance the conductivity of the solution and assist in removing metal ions. A part of metal ions in the pyrazole stock solution in the anode chamber are transferred from the anode chamber to the cathode chamber under the action of electric field force, and a part of ions are electrifiedAnd adsorbing by using ion resin in the electrolytic bath, and finally obtaining the electronic grade pyrazole aqueous solution in the anode chamber. The electronic grade pyrazole aqueous solution can be used as a solvent of chemical cleaning solution for microelectronic industries such as ultra-large scale integrated circuits or screen displays.)

1. An electronic grade pyrazole aqueous solution preparation device is characterized by comprising an ultrapure electrolytic tank (1), an anolyte storage tank (2), an anolyte circulating pump (3), a catholyte storage tank (4) and a catholyte circulating pump (5);

the ultrapure electrolytic cell (1) comprises an anode chamber (6), an anode plate (7), a cathode chamber (8), a cathode plate (9), a cation exchange membrane (10) and an ultrapure electrolytic cell clamp (19);

the anode chamber (6) is separated from the cathode chamber (8) by a cation exchange membrane (10);

cationic exchange resin (11) is respectively filled in the anode chamber (6) and the cathode chamber (8);

the anolyte storage tank (2) and the catholyte storage tank (4) are of a jacket type, and flowing hot water for heat preservation is arranged in the jacket;

the linings of the anolyte storage tank (2) and the catholyte storage tank (4), the plate frame materials of the anode chamber (6) and the cathode chamber (8), the anolyte circulating pump (3) and the catholyte circulating pump (5), and the materials of pipelines, pipes and valves are all fluorine-containing materials with the purity of 99.9-99.999 percent, such as PTFE or PFA or PVDF;

the bottom of the anode chamber (6) is provided with an anode chamber pyrazole aqueous solution inlet (12), and the top is provided with an anode chamber pyrazole aqueous solution outlet (13);

the bottom of the cathode chamber (8) is provided with a cathode chamber pyrazole aqueous solution inlet (14), and the top is provided with a cathode chamber pyrazole aqueous solution outlet (15);

the anode chamber pyrazole aqueous solution inlet (12), the anode chamber pyrazole aqueous solution outlet (13), the cathode chamber pyrazole aqueous solution inlet (14) and the cathode chamber pyrazole aqueous solution outlet (15) are respectively provided with a filter screen (16);

a solution outlet of the anolyte storage tank (2) is connected with an anode chamber pyrazole aqueous solution inlet (12) through an anolyte circulating pump (3) by a pipeline, and an anode chamber pyrazole aqueous solution outlet (13) is connected with a solution inlet of the anolyte storage tank (2); and a solution outlet of the catholyte storage tank (4) is connected with a cathode chamber pyrazole aqueous solution inlet (14) through a pipeline by a catholyte circulating pump (5), and a cathode chamber pyrazole aqueous solution outlet (15) is connected with a solution inlet of the catholyte storage tank (4).

2. The electronic grade pyrazole aqueous solution preparation device according to claim 1, wherein the cathode plate (9) is a titanium electrode, a platinum electrode or a titanium iridium alloy electrode with the purity of 99.9-99.999%, and the anode plate (7) is a platinum electrode or a titanium electrode with the purity of 99.9-99.999%; the distance between the cathode plate (9) and the anode plate (7) is 0.5-3.0 cm.

3. The apparatus for preparing electronic grade pyrazole aqueous solution according to claim 1, wherein the cation exchange resin (11) is acid, alkali, and high temperature resistant 001 x 7 type resin, 2800H type resin, or 1500H type resin, and has a particle size of (0.315-1.25 mm) or more than 95%, or (0.45-1.25 mm) or more than 95%, or (0.71-1.25 mm) or more than 95%, and a wet bulk density of 650-850 kg/m³；

The cationic exchange resin (11) is filled in the cathode chamber (8) with the density of 70-95% of the wet bulk density, and is filled in the anode chamber (6) with the density of 80-97% of the wet bulk density.

4. The method for preparing the electronic-grade pyrazole aqueous solution by using the electronic-grade pyrazole aqueous solution preparation device as claimed in claim 1, comprising the following steps of:

A. respectively adding specified amounts of cationic exchange resin (11) into an anode chamber (6) and a cathode chamber (8), respectively adding ultrapure hydrochloric acid aqueous solution for washing into an anode liquid storage tank (2) and a cathode liquid storage tank (4), respectively starting an anode liquid circulating pump (3) and a cathode liquid circulating pump (5), circularly washing each component in an ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then washing with ultrapure water for 6-10 times until the washing liquid is neutral and the content of each metal ion is lower than 5 ppb;

B. adding 10-30% pyrazole aqueous solution raw materials into an anolyte storage tank (2) and a catholyte storage tank (4) at the same time, respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5), and switching on a power supply between a cathode plate and an anode plate to start electrolysis after the pyrazole aqueous solution in the whole device circularly flows to reach a specific temperature;

C. continuously pumping and circulating, continuously reducing metal ions in the pyrazole aqueous solution in the anode chamber (6) and the anolyte storage tank (2) to finally obtain an electronic-grade pyrazole aqueous solution, and then pumping the pyrazole aqueous solution in the anode chamber (6) and the anolyte storage tank (2) to a product storage tank through a product outlet (17) to obtain an electronic-grade pyrazole aqueous solution product with the mass concentration of 10-30%; meanwhile, the pyrazole aqueous solution in the cathode chamber (8) and the catholyte storage tank (4) is pumped out through an outlet (18) and can be sold as industrial chemicals;

D. and (3) adding an ultra-pure hydrochloric acid aqueous solution into the anode chamber (6) and the cathode chamber (8), soaking for 5-8 hours for regenerating the cationic resin (11), then fully washing the electronic grade pyrazole aqueous solution preparation device by adopting ultra-pure water, and transferring to the operation step B after the requirements of the step A are met.

5. The method for preparing the electronic grade pyrazole aqueous solution according to claim 4, wherein the pyrazole aqueous solution in the step B is prepared from an industrial grade pyrazole product or a pharmaceutical grade pyrazole product by adding water to dissolve the pyrazole aqueous solution to obtain the pyrazole aqueous solution with the required concentration.

6. The method for preparing the electronic-grade pyrazole aqueous solution according to claim 4, wherein in the step B, the voltage of the cathode and anode plates is 15-50V, and the flow rate of the solution in the anode chamber (6) and the cathode chamber (8) is 0.5-2.0 m/min through pumping of the anolyte circulating pump (3) and the catholyte circulating pump (5).

7. The method for preparing an electronic grade pyrazole aqueous solution according to claim 4, wherein the electrolysis temperature in the step B is 25-50 ℃.

8. The method for preparing the electronic-grade pyrazole aqueous solution according to claim 4, wherein the content of various metal ions in the electronic-grade pyrazole aqueous solution product obtained in the step C is less than 50 ppb, and the mass percentage of pyrazole is more than or equal to 10%.

9. The method of claim 4, wherein the ultra-pure hydrochloric acid in steps A and D has a purity of 99.9-99.999% and a concentration of 10-30%.

Technical Field

The invention relates to the field of preparation of electronic-grade reagents, in particular to an electronic-grade pyrazole aqueous solution and a preparation method thereof.

Background

Pyrazole is a colorless or white acicular or prismatic crystalline organic cyclic compound, is commonly used as a halogen-containing solvent, a stabilizer of lubricating oil, a chelating agent or an organic synthesis intermediate, and plays an important role in research and development of medicines and pesticides.

The electronic grade pyrazole aqueous solution is an ultra-clean high-purity reagent, and can be used as a cleaning agent for cleaning silicon wafers, substrates and the like in the microelectronic industry such as the integrated circuit and electronic element processing field due to the strong metal ion chelating effect. The key of the ultra-clean high-purity reagent is to control the amount of metal ions contained in the reagent and the content of dust particles in the reagent, and for integrated circuits with small line width, a few metal ions or dust can be enough to scrap the whole circuit. The metal ion content of the pyrazole sold in the market at present is high, so that the pyrazole cannot meet the requirements of the silicon wafer cleaning industry, and the research on the purification preparation process at home and abroad is less. Therefore, it is important to develop a technology capable of reducing the content of metal impurity ions in an aqueous pyrazole solution and to prepare an electronic-grade aqueous pyrazole solution.

Disclosure of Invention

In order to prepare the electronic-grade pyrazole aqueous solution, the invention provides a mode of combining ion membrane electrolysis and cation exchange resin, and the electronic-grade pyrazole aqueous solution is prepared at low cost. The specific embodiment is as follows:

an electronic grade pyrazole aqueous solution preparation device is characterized by comprising an ultrapure electrolytic tank (1), an anolyte storage tank (2), an anolyte circulating pump (3), a catholyte storage tank (4) and a catholyte circulating pump (5);

the ultrapure electrolytic cell (1) comprises an anode chamber (6), an anode plate (7), a cathode chamber (8), a cathode plate (9), a cation exchange membrane (10) and an ultrapure electrolytic cell clamp (19);

the anode chamber (6) is separated from the cathode chamber (8) by a cation exchange membrane (10);

cationic exchange resin (11) is respectively filled in the anode chamber (6) and the cathode chamber (8);

the anolyte storage tank (2) and the catholyte storage tank (4) are of a jacket type, and flowing hot water for heat preservation is arranged in the jacket;

the linings of the anolyte storage tank (2) and the catholyte storage tank (4), the plate frame materials of the anode chamber (6) and the cathode chamber (8), the anolyte circulating pump (3) and the catholyte circulating pump (5), and the materials of pipelines, pipes and valves are all fluorine-containing materials with the purity of 99.9-99.999 percent, such as PTFE or PFA or PVDF;

the bottom of the anode chamber (6) is provided with an anode chamber pyrazole aqueous solution inlet (12), and the top is provided with an anode chamber pyrazole aqueous solution outlet (13);

the bottom of the cathode chamber (8) is provided with a cathode chamber pyrazole aqueous solution inlet (14), and the top is provided with a cathode chamber pyrazole aqueous solution outlet (15);

the anode chamber pyrazole aqueous solution inlet (12), the anode chamber pyrazole aqueous solution outlet (13), the cathode chamber pyrazole aqueous solution inlet (14) and the cathode chamber pyrazole aqueous solution outlet (15) are respectively provided with a filter screen (16);

a solution outlet of the anolyte storage tank (2) is connected with an anode chamber pyrazole aqueous solution inlet (12) through an anolyte circulating pump (3) by a pipeline, and an anode chamber pyrazole aqueous solution outlet (13) is connected with a solution inlet of the anolyte storage tank (2); a solution outlet of the catholyte storage tank (4) is connected with a cathode chamber pyrazole aqueous solution inlet (14) through a catholyte circulating pump (5) by a pipeline, and a cathode chamber pyrazole aqueous solution outlet (15) is connected with a solution inlet of the catholyte storage tank (4);

the cathode plate (9) is a titanium electrode, a platinum electrode or a titanium iridium alloy electrode with the purity of 99.9-99.999%, and the anode plate (7) is a platinum electrode or a titanium electrode with the purity of 99.9-99.999%; the distance between the cathode plate (9) and the anode plate (7) is 0.5-3.0 cm.

The material of the cationic exchange resin (11) is 001 x 7 type which is resistant to acid and alkali corrosion and high temperatureThe resin or 2800H type resin or 1500H type resin has a particle size of (0.315-1.25 mm) or more than 95%, or (0.45-1.25 mm) or more than 95%, or (0.71-1.25 mm) or more than 95%, and wet bulk density of 650-850 kg/m³；

The cationic exchange resin (11) is filled in the cathode chamber (8) with the density of 70-95% of the wet bulk density, and is filled in the anode chamber (6) with the density of 80-97% of the wet bulk density.

The method for preparing the electronic-grade pyrazole aqueous solution by using the electronic-grade pyrazole aqueous solution preparation device comprises the following steps of:

A. respectively adding specified amounts of cationic exchange resin (11) into an anode chamber (6) and a cathode chamber (8), respectively adding ultrapure hydrochloric acid aqueous solution for washing into an anode liquid storage tank (2) and a cathode liquid storage tank (4), respectively starting an anode liquid circulating pump (3) and a cathode liquid circulating pump (5), circularly washing each component in an ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then washing with ultrapure water for 6-10 times until the washing liquid is neutral and the content of each metal ion is lower than 5 ppb;

B. adding 10-30% pyrazole aqueous solution raw materials into an anolyte storage tank (2) and a catholyte storage tank (4) at the same time, respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5), and switching on a power supply between a cathode plate and an anode plate to start electrolysis after the pyrazole aqueous solution in the whole device circularly flows to reach a specific temperature;

C. continuously pumping and circulating, continuously reducing metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) to finally obtain an electronic grade pyrazole aqueous solution, and then pumping the pyrazole aqueous solution in the anode chamber (6) and the anolyte storage tank (2) to a product storage tank through a product outlet (17) to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 10-30%; meanwhile, the pyrazole aqueous solution in the cathode chamber (8) and the catholyte storage tank (4) is pumped out through an outlet (18) and can be sold as industrial chemicals;

D. and (3) adding an ultra-pure hydrochloric acid aqueous solution into the anode chamber (6) and the cathode chamber (8), soaking for 5-8 hours for regenerating the cationic resin (11), then fully washing the electronic grade pyrazole aqueous solution preparation device by adopting ultra-pure water, and transferring to the operation step B after the requirements of the step A are met.

And B, the raw material of the pyrazole aqueous solution in the step B is an industrial-grade pyrazole product or a medical-grade pyrazole product, and the pyrazole aqueous solution with the required concentration is obtained after the pyrazole aqueous solution is dissolved by adding water.

And in the step B, the voltage of the cathode and anode plates is 15-50V, and the flow velocity of the solution in the anode chamber (6) and the cathode chamber (8) is 0.5-2.0 m/min through pumping of the anolyte circulating pump (3) and the catholyte circulating pump (5).

And the electrolysis temperature in the step B is 25-50 ℃.

And D, the content of various metal ions in the electronic grade pyrazole aqueous solution product obtained in the step C is lower than 50 ppb, and the mass percentage content of pyrazole is more than or equal to 10%.

The purity of the ultra-pure hydrochloric acid aqueous solution in the steps A and D is 99.9-99.999%, and the concentration is 10-30%.

Compared with the prior art, the method for preparing the electronic grade pyrazole aqueous solution by combining the ionic membrane electrolysis and the cation exchange resin has the following outstanding effects and advantages:

(1) in the process of solution circulation and electrolysis, a part of metal ions in the solution in the anode chamber are driven by electric field force to migrate from the anode chamber to the cathode chamber through the middle cation exchange membrane (9), and the other part of metal ions exchange with hydrogen ions on the cation type resin (11) and are adsorbed on the cation type resin (11); under the combined action of the driving of an electrolytic electric field of an ionic membrane electrolysis method and the adsorption action of cation exchange resin, the concentration of metal ions in the pyrazole aqueous solution is greatly reduced.

(2) Cation exchange resin is added into the electrolytic cell, and the conductivity of the pyrazole aqueous solution which is not conductive originally is greatly increased by means of the conductivity of the cation exchange resin, so that the efficiency of the electrolytic cell is obviously improved.

(3) The process provided by the method is simple to operate and low in cost.

Drawings

FIG. 1 is a schematic view of a plate-and-frame type ionic membrane electrolytic circulation device

FIG. 2 is a schematic view of the inside of a plate and frame type electrolytic cell;

the parts in the figure illustrate:

1-ultrapure electrolytic tank, 2-anolyte storage tank, 3-anolyte circulating pump, 4-catholyte storage tank, 5-catholyte circulating pump, 6-anode chamber, 7-anode plate, 8-cathode chamber, 9-cathode plate, 10-cation exchange membrane, 11-cation exchange resin, 12-anode chamber pyrazole aqueous solution inlet, 13-anode chamber pyrazole aqueous solution outlet, 14-cathode chamber pyrazole aqueous solution inlet, 15-cathode chamber pyrazole aqueous solution outlet, 16-filter screen, 17-anolyte storage tank product outlet, 18-catholyte storage tank outlet, 19-ultrapure electrolytic tank clamp

Detailed Description

The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.

Example 1

In the used ultra-pure electrolytic tank (1), a cathode plate (9) is a titanium electrode (with the purity of 99.99 percent), and an anode plate (7) is a platinum electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 0.8 cm. The cationic exchange resin (11) used in the anode chamber (6) and the cathode chamber (8) is 001 x 7 type cationic exchange resin, the particle size range is that the particle size is (0.315-1.25 mm) is not less than 95 percent, and the wet bulk density is 800 kg/m³The cathode chamber (8) is packed at a density of 80% of its wet bulk density, and the anode chamber (6) is packed at a density of 85% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 10% is obtained by dissolving the industrial grade pyrazole product in water.

First, prescribed amounts of 001 x 7 type cationic exchange resin (11) were added to the anode chamber (6) and cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.9%, concentration 10%) was added to the anolyte tank (2) and catholyte tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.

Adding a 10% pyrazole aqueous solution raw material into an anolyte storage tank (2) and a catholyte storage tank (4) at the same time, and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of solutions in an anode chamber (6) and a cathode chamber (8) to be 1.0 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 25 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 20V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 10%, wherein the specific content of each metal ion is shown in table 1.

After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.

Pyrazole products treated by a combination of ion-exchange resin and membrane electrolysis processes, wherein Na is present⁺、Mg²⁺、K⁺、Ca²⁺、Cu²⁺、Zn²⁺、Ni²⁺、Cr³⁺、Al³⁺、Fe³⁺The total content is less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 10 percent, thereby achieving the standard of the electronic grade pyrazole cation impurity content.

Example 2

The cathode plate (9) of the used ultra-pure electrolytic tank (1) is a platinum electrode (with the purity of 99.99 percent), and the anode plate (7) is a titanium electrode (with the purity of 99.99 percent); a cathode plate (9) and an anodeThe distance between the plates (7) was 1.0 cm. The cationic exchange resin (11) used in the anode chamber (6) and the cathode chamber (8) is 2800H type cationic exchange resin, the particle size range is that the particle size is (0.315-1.25 mm) is not less than 95%, and the wet bulk density is 810 kg/m³The cathode chamber (8) was packed at a density of 81% of its wet bulk density, and the anode chamber (6) was packed at a density of 87% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 10% is obtained by dissolving the industrial grade pyrazole product in water.

First, a prescribed amount of 2800H type cationic exchange resin (11) was added to the anode chamber (6) and the cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.99%, concentration 20%) was added to the anolyte tank (2) and the catholyte tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.

Adding a 10% pyrazole aqueous solution raw material into an anolyte storage tank (2) and a catholyte storage tank (4) at the same time, and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of solutions in an anode chamber (6) and a cathode chamber (8) to be 1.2 m/min. The feed amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 30 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 25V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 10%, wherein the specific content of each metal ion is shown in table 1.

After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.

Pyrazole products treated by a combination of ion-exchange resin and membrane electrolysis processes, wherein Na is present⁺、Mg²⁺、K⁺、Ca²⁺、Cu²⁺、Zn²⁺、Ni²⁺、Cr³⁺、Al³⁺、Fe³⁺The total content is less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 10 percent, thereby achieving the standard of the electronic grade pyrazole cation impurity content.

Example 3

The cathode plate (9) of the used ultra-pure electrolytic tank (1) is a titanium iridium alloy electrode (with the purity of 99.99 percent), and the anode plate (7) is a platinum electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 1.5 cm. The cationic exchange resin (11) used in the anode chamber (6) and the cathode chamber (8) is 2800H type cationic exchange resin, the particle size range is that the particle size is (0.45-1.25 mm) is not less than 95%, and the wet bulk density is 780 kg/m³The cathode chamber (8) was packed at a density of 84% of its wet bulk density, and the anode chamber (6) was packed at a density of 89% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 20 percent is obtained by dissolving the industrial grade pyrazole product in water.

First, a prescribed amount of 2800H type cationic exchange resin (11) was added to the anode chamber (6) and the cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.99%, concentration 20%) was added to the anolyte tank (2) and the catholyte tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.

And (3) simultaneously adding a pyrazole aqueous solution raw material with the concentration of 20% into an anolyte storage tank (2) and a catholyte storage tank (4), and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of the solutions in the anode chamber (6) and the cathode chamber (8) to be 1.4 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 35 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 30V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 20%, wherein the specific content of each metal ion is shown in table 1.

After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.

Pyrazole products treated by a combination of ion-exchange resin and membrane electrolysis processes, wherein Na is present⁺、Mg²⁺、K⁺、Ca²⁺、Cu²⁺、Zn²⁺、Ni²⁺、Cr³⁺、Al³⁺、Fe³⁺Are all less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 20 percent, thereby reaching the standard of the electronic grade pyrazole cation impurity content.

Example 4

In the used ultra-pure electrolytic tank (1), a cathode plate (9) is a titanium electrode (with the purity of 99.99 percent), and an anode plate (7) is a platinum electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 2.2 cm. The cationic exchange resin (11) used in the anode chamber (6) and the cathode chamber (8) is 001 x 7 type cationic exchange resin, the particle size range is that the particle size is (0.45-1.25 mm) is not less than 95%, and the wet bulk density is 750 kg/m³The cathode chamber (8) is packed at a density of 90% of its wet bulk density, and the anode chamber (6) is packed at a density of 93% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 30% is obtained by dissolving the industrial grade pyrazole product in water.

First, prescribed amounts of 001 x 7 type cationic exchange resin (11) were added to the anode chamber (6) and cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.99%, concentration 30%) was added to the anolyte tank (2) and catholyte tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.

And (3) simultaneously adding a pyrazole aqueous solution raw material with the concentration of 30% into an anolyte storage tank (2) and a catholyte storage tank (4), and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of the solutions in the anode chamber (6) and the cathode chamber (8) to be 1.0 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 40 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 35V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 30%, wherein the specific content of each metal ion is shown in table 1.

After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.

Pyrazole products treated by a combination of ion-exchange resin and membrane electrolysis processes, wherein Na is present⁺、Mg²⁺、K⁺、Ca²⁺、Cu²⁺、Zn²⁺、Ni²⁺、Cr³⁺、Al³⁺、Fe³⁺Are all less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 30 percent, thereby reaching the standard of the electronic grade pyrazole cation impurity content.

Example 5

In the used ultra-pure electrolytic tank (1), a cathode plate (9) is a titanium electrode (with the purity of 99.99 percent), and an anode plate (7) is a titanium electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 1.8 cm. Cationic exchange resins (11) used in the anode compartment (6) and cathode compartment (8)Is 1500H type cationic exchange resin with particle size of 0.71-1.25 mm or more than 95% and wet bulk density of 680 kg/m³The cathode chamber (8) was packed at a density of 93% of its wet bulk density, and the anode chamber (6) was packed at a density of 95% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 30% is obtained by dissolving the industrial grade pyrazole product in water.

Firstly, prescribed amounts of 1500H type cationic exchange resin (11) are added to an anode chamber (6) and a cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.99%, concentration 20%) is added to an anode liquid storage tank (2) and a cathode liquid storage tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.

And (3) simultaneously adding a pyrazole aqueous solution raw material with the concentration of 30% into an anolyte storage tank (2) and a catholyte storage tank (4), and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of the solutions in the anode chamber (6) and the cathode chamber (8) to be 0.7 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 45 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 40V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 30%, wherein the specific content of each metal ion is shown in table 1.

After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.

Pyrazole products treated by a combined process of ion-exchange resin and membrane electrolysis, processes for their preparation and their useIn Na⁺、Mg²⁺、K⁺、Ca²⁺、Cu²⁺、Zn²⁺、Ni²⁺、Cr³⁺、Al³⁺、Fe³⁺Are all less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 30 percent, thereby reaching the standard of the electronic grade pyrazole cation impurity content.

Control group 1

The cathode plate (9) of the used ultra-pure electrolytic tank (1) is a titanium iridium alloy electrode (with the purity of 99.99 percent), and the anode plate (7) is a platinum electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 1.5 cm. The anode chamber (6) and the cathode chamber (8) are free of cation exchange resin. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 20 percent is obtained by dissolving the industrial grade pyrazole product in water.

Ultrapure water for washing is added into the anode liquid storage tank (2) and the cathode liquid storage tank (4) respectively. And starting the anolyte circulating pump (3) and the catholyte circulating pump (5) to circularly wash each part in the ultrapure electrolytic tank (1) so as to meet the purification requirement.

And (3) simultaneously adding a pyrazole aqueous solution raw material with the concentration of 20% into an anolyte storage tank (2) and a catholyte storage tank (4), and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of the solutions in the anode chamber (6) and the cathode chamber (8) to be 1.4 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 35 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 30V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain a pyrazole aqueous solution product with the mass concentration of 20%, wherein the specific content of each metal ion is shown in table 1.

Control group 2

The raw material of the used pyrazole aqueous solution is an industrial grade pyrazole product which is dissolved by adding water,to obtain a pyrazole aqueous solution with the mass concentration of 20%. The cation exchange resin is 2800H type cation exchange resin, the particle size range is that the particle size is more than or equal to 95% (0.45-1.25 mm), and the wet bulk density is 780 kg/m³. The ion exchange resin column was packed at a density of 84% of its wet bulk density. The cation exchange resin is washed by ultrapure hydrochloric acid (purity 99.9%, concentration 10%), and then washed by ultrapure water to meet the purification requirements. A 20% aqueous pyrazole solution was slowly added to the ion exchange column and controlled to flow through the resin at a 1-fold bed volume flow rate. When the pyrazole outflow concentration is close to 20%, the product starts to be collected, and the specific content of each metal ion in the product is shown in the table 1.

TABLE 1 Metal ion content scale (ppb) in the electronic grade pyrazole aqueous solution products of the examples

	Pyrazole concentration	Na +	Mg 2+	K +	Ca 2+	Cu 2+	Zn2+	Ni2+	Cr3+	Al3+	Fe3+
												Example 1	10%	8.2	10.5	0	15.6	12.3	5.6	19.6	13.6	35.0	46.2
Example 2	10%	0	3.5	0	6.5	8.5	0	15.6	13.6	30.2	35.6
												Example 3	20%	10.2	6.5	0	12.5	13.4	10.2	15.6	13.6	40.2	38
Example 4	30%	15.2	15.5	3.2	12.5	13.4	10.2	25.6	13.6	39.8	47.5
												Example 5	30%	20.3	16.3	5.8	20.5	16.7	10.2	25.6	27.6	46.3	47.5
Control group 1	20%	340.3	243.6	354.6	208.4	108.5	132.8	284.7	103.6	463.5	485.8
												Control group 2	20%	89.6	69.3	79.5	56.9	45.8	42.6	54.7	43.8	49.2	43.2