阅读说明：本技术 一种环保再利用的电子级四甲基氢氧化铵生产制备工艺 (Production and preparation process of environment-friendly recycled electronic-grade tetramethyl ammonium hydroxide ) 是由 季中伟 马立军 乔正收 李玉芬 刘庆五 张勇 王金城 于 2021-09-17 设计创作，主要内容包括：本发明公开了一种环保再利用的电子级四甲基氢氧化铵生产制备工艺,依次包括如下步骤：废料预处理步骤；交换材料预处理步骤；交换材料转型处理步骤；废料交换除杂处理步骤；杂质吸附处理步骤；硫酸四甲基铵溶液处理步骤；硫酸四甲基铵溶液分解处理步骤和四甲基铵溶液过滤处理步骤。该环保再利用的电子级四甲基氢氧化铵生产制备工艺,首先通过加热使得交换材料热涨将内部的杂质进行排出,之后采用酸、碱、酸依次清洗对交换材料进行清洁,最后通过超纯水将杂质和其他的残留物进行冲洗,这种方式能够使得装置在使用的时候更加的稳定,防止交换材料中的杂质影响到成品的质量。(The invention discloses an environment-friendly recycled production and preparation process of electronic-grade tetramethyl ammonium hydroxide, which sequentially comprises the following steps: a waste pretreatment step; pretreatment of exchange materials; a step of transformation treatment of the exchange material; waste exchange and impurity removal treatment; an impurity adsorption treatment step; treating tetramethyl ammonium sulfate solution; a decomposition treatment step of a tetramethylammonium sulfate solution and a filtration treatment step of the tetramethylammonium solution. This electronic grade tetramethyl ammonium hydroxide production preparation technology that environmental protection was recycled makes exchange material heat rise through the heating at first and discharges inside impurity, later adopts acid, alkali, sour to wash in proper order and cleans exchange material, washes impurity and other residues through ultrapure water at last, and this kind of mode can make the device more stable when using, prevents that impurity in the exchange material from influencing finished product quality.)

1. An environment-friendly and reusable preparation process for producing electronic-grade tetramethyl ammonium hydroxide is characterized by sequentially comprising the following steps:

(1) a waste pretreatment step: firstly, adding the waste liquid into a sedimentation tank to precipitate large-particle impurities, metal particle substances and the like in the waste material, carrying out rough filtration through a filtration system, and waiting for standby after the filtration is finished;

(2) exchange material pretreatment: adding the exchange material into a cleaning pool to heat, then repeatedly performing immersion cleaning and washing until cleaning is performed until immersion cleaning liquid is clear and the foam amount is small, then adding the cleaned exchange material into an acid pool to clean, then adding the cleaned exchange material into an alkali pool to clean, adding the cleaned exchange material into the acid pool again to clean after the alkali pool is cleaned, and washing acid-base residues on the surface through ultrapure water after the cleaning is completed to wait for later use;

(3) exchange material transformation treatment: adsorbing the cleaned exchange material in the step (2) by tetramethylammonium ions in the waste liquid in the adsorption step (1) to make the exchange material become a tetramethylammonium type;

(4) waste exchange and impurity removal treatment: washing the surface of the exchange material subjected to adsorption in the step (3) by using ultrapure water, and removing impurities such as photoresist, precipitate and the like;

(5) impurity adsorption treatment: filtering the precipitate washed in the step (4) by an ultrafiltration material to prevent the direct discharge of sewage from polluting and damaging the environment;

(6) treating a tetramethylammonium sulfate solution: eluting the exchange material adsorbed in the step (4) by sulfuric acid to obtain a tetramethylammonium sulfate solution;

(7) decomposing and treating the tetramethylammonium sulfate solution: adding an inactive metal into the tetramethylammonium sulfate solution obtained in the step (6), and heating to generate sulfur dioxide, sulfate precipitates and a tetramethylammonium hydroxide solution;

(8) filtering the tetramethylammonium solution: and (4) filtering the reactant in the step (7) to obtain a crude product of the tetramethylammonium hydroxide, and then, concentrating and purifying by using an exchange material again to finally obtain a pure finished product.

2. The production and preparation process of the environmentally-friendly recycled electronic-grade tetramethylammonium hydroxide according to claim 1, characterized in that: and (3) adopting cation exchange resin as the exchange material in the step (2).

3. The production and preparation process of the environmentally-friendly recycled electronic-grade tetramethylammonium hydroxide according to claim 1, characterized in that: the cleaning acid in the step (2) is hydrochloric acid, phosphoric acid and methanesulfonic acid, the cleaning alkali is sodium hydroxide solution, and the heating temperature is 50-60 ℃.

4. The production and preparation process of the environmentally-friendly recycled electronic-grade tetramethylammonium hydroxide according to claim 1, characterized in that: and (3) adopting YHMBR-1 as ultrafiltration equipment in the step (5).

5. The production and preparation process of the environmentally-friendly recycled electronic-grade tetramethylammonium hydroxide according to claim 1, characterized in that: the inert metal adopted in the step (7) is Cu or Ag, and the heating temperature is 40-60 ℃.

Technical Field

The invention relates to the technical field of tetramethylammonium hydroxide, in particular to an environment-friendly and reusable preparation process for electronic-grade tetramethylammonium hydroxide.

Background

Tetramethyl ammonium hydroxide is a colorless crystal, is very easy to absorb moisture, has certain ammonia smell, has strong basicity, and can quickly absorb carbon dioxide in air. The main application is as follows: in the analysis aspect, tetramethylammonium hydroxide was used as a polarographic reagent. In the aspect of product purification, the catalyst is used as an ash-free alkali for precipitating a plurality of metal elements. The organic silicon chip is commonly used as brightening agent, cleaning agent, etching agent and the like for the surface of a computer silicon chip in the production of organic silicon chips. In the printing of circuit boards and the manufacturing of microscope lenses, the silicon-silicon. The tetramethyl hydroxide has the advantages that: it has strong basicity and is stable at temperatures not exceeding the decomposition point. After the catalysis is finished, the catalyst is easy to remove, and no residue is left. No pollution to organic silicon products. Hence also called "temporary catalysts", are useful in the analysis of polarographic reagents for precipitating ash-free hydrides of many elements.

But the technique for producing tetramethyl ammonium hydroxide on the market at present is relatively imperfect, people's demand has been satisfied, often handle through anion membrane electrolysis when carrying out recovery processing to tetramethyl ammonium hydroxide's waste material among the prior art, this kind of mode not only can cause the equipment investment height, the working cost is big, and adopt cation exchange material to carry out abundant cleanness and processing before exchanging at present on the market, cause the later stage can appear impurity when carrying out the transformation and exchanging, thereby make the great reduction of finished product quality, lead to its unable application in the middle of the operating mode of reality. Therefore, an environment-friendly and reusable preparation process for producing electronic-grade tetramethylammonium hydroxide is provided, so as to solve the problems.

Disclosure of Invention

The invention aims to provide an environment-friendly and reusable electronic-grade tetramethylammonium hydroxide production and preparation process, which aims to solve the problems that the existing technology for producing tetramethylammonium hydroxide on the market in the background technology is relatively incomplete and cannot meet the requirements of people, the waste of tetramethylammonium hydroxide in the prior art is usually treated by anion membrane electrolysis when being recycled, the method not only causes high equipment investment and high operating cost, but also causes impurities to appear in the later transformation and exchange process because cation exchange materials adopted on the market are not sufficiently cleaned and treated before the exchange, thereby greatly reducing the quality of finished products and causing the finished products to be incapable of being applied to actual working conditions.

In order to achieve the purpose, the invention provides the following technical scheme: an environment-friendly and reusable preparation process for producing electronic-grade tetramethyl ammonium hydroxide sequentially comprises the following steps:

(1) a waste pretreatment step: firstly, adding the waste liquid into a sedimentation tank to precipitate large-particle impurities, metal particle substances and the like in the waste material, carrying out rough filtration through a filtration system, and waiting for standby after the filtration is finished;

(2) exchange material pretreatment: adding the exchange material into a cleaning pool to heat, then repeatedly performing immersion cleaning and washing until cleaning is performed until immersion cleaning liquid is clear and the foam amount is small, then adding the cleaned exchange material into an acid pool to clean, then adding the cleaned exchange material into an alkali pool to clean, adding the cleaned exchange material into the acid pool again to clean after the alkali pool is cleaned, and washing acid-base residues on the surface through ultrapure water after the cleaning is completed to wait for later use;

(3) exchange material transformation treatment: adsorbing the cleaned exchange material in the step (2) by tetramethylammonium ions in the waste liquid in the adsorption step (1) to make the exchange material become a tetramethylammonium type;

(4) waste exchange and impurity removal treatment: washing the surface of the exchange material subjected to adsorption in the step (3) by using ultrapure water, and removing impurities such as photoresist, precipitate and the like;

(5) impurity adsorption treatment: filtering the precipitate washed in the step (4) by an ultrafiltration material to prevent the direct discharge of sewage from polluting and damaging the environment;

(6) treating a tetramethylammonium sulfate solution: eluting the exchange material adsorbed in the step (4) by sulfuric acid to obtain a tetramethylammonium sulfate solution;

(7) decomposing and treating the tetramethylammonium sulfate solution: adding an inactive metal into the tetramethylammonium sulfate solution obtained in the step (6), and heating to generate sulfur dioxide, sulfate precipitates and a tetramethylammonium hydroxide solution;

(8) filtering the tetramethylammonium solution: and (4) filtering the reactant in the step (7) to obtain a crude product of the tetramethylammonium hydroxide, and then, concentrating and purifying by using an exchange material again to finally obtain a pure finished product.

Preferably, the exchange material in step (2) is cation exchange resin.

Preferably, hydrochloric acid, phosphoric acid and methanesulfonic acid are used as the cleaning acid in the step (2), a sodium hydroxide solution is used as the cleaning alkali, and the heating temperature is 50-60 ℃.

Preferably, the ultrafiltration device in the step (5) adopts YHMBR-1.

Preferably, the inert metal used in the step (7) is Cu or Ag, and the heating temperature is 40-60 ℃.

Compared with the prior art, the invention has the beneficial effects that: the production and preparation process of the environment-friendly recycled electronic-grade tetramethyl ammonium hydroxide comprises the following steps:

(1) firstly, the exchange material is heated to expand, so that impurities in the exchange material are discharged, then the exchange material is cleaned by sequentially cleaning acid, alkali and acid, and finally the impurities and other residues are washed by ultrapure water, so that the device is more stable in use, and the impurities in the exchange material are prevented from influencing the quality of a finished product;

(2) by using the inactive metal to separate the sulfate and the tetramethylammonium hydroxide solution, the method can reduce the recycling cost, and can ensure that the finished product can be more economically recovered, thereby ensuring that the product can be distinguished on the market;

(3) the cleaned impurities are filtered through the ultrafiltration equipment, so that the residual substances and the impurities are prevented from being discharged together with water, the environmental pollution is caused, the ecological environment is destroyed, and the production process is more environment-friendly and stable.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example one

The invention provides a technical scheme that: an environment-friendly and reusable preparation process for producing electronic-grade tetramethyl ammonium hydroxide sequentially comprises the following steps:

(1) a waste pretreatment step: firstly, adding the waste liquid into a sedimentation tank to precipitate large-particle impurities, metal particle substances and the like in the waste material, carrying out rough filtration through a filtration system, and waiting for standby after the filtration is finished;

(2) exchange material pretreatment: adding an exchange material into a cleaning pool to heat, then repeatedly performing immersion cleaning and washing until cleaning liquid is clear and the amount of foam is small, then adding the cleaned exchange material into an acid pool to clean, then adding the cleaned exchange material into an alkali pool to clean, adding the cleaned exchange material into the acid pool again to clean after the alkali pool is cleaned, and washing acid-base residues on the surface through ultrapure water after the cleaning is completed for later use, wherein the exchange material adopts cation exchange resin, the cleaning acid adopts hydrochloric acid, the cleaning alkali adopts sodium hydroxide solution, and the heating temperature is 50 ℃;

(3) exchange material transformation treatment: adsorbing the cleaned exchange material in the step (2) by tetramethylammonium ions in the waste liquid in the adsorption step (1) to make the exchange material become a tetramethylammonium type;

(4) waste exchange and impurity removal treatment: washing the surface of the exchange material subjected to adsorption in the step (3) by using ultrapure water, and removing impurities such as photoresist, precipitate and the like;

(5) impurity adsorption treatment: filtering the precipitate washed in the step (4) by using an ultrafiltration material to prevent the direct discharge of sewage from polluting and damaging the environment, wherein YHMBR-1 is adopted as ultrafiltration equipment;

(6) treating a tetramethylammonium sulfate solution: eluting the exchange material adsorbed in the step (4) by sulfuric acid to obtain a tetramethylammonium sulfate solution;

(7) decomposing and treating the tetramethylammonium sulfate solution: adding an inactive metal into the tetramethylammonium sulfate solution obtained in the step (6), and heating to generate sulfur dioxide, sulfate precipitates and a tetramethylammonium hydroxide solution, wherein the inactive metal is Cu, and the heating temperature is 40 ℃;

(8) filtering the tetramethylammonium solution: and (4) filtering the reactant in the step (7) to obtain a crude product of the tetramethylammonium hydroxide, and then, concentrating and purifying by using an exchange material again to finally obtain a pure finished product.

Example two

The invention provides a technical scheme that: an environment-friendly and reusable preparation process for producing electronic-grade tetramethyl ammonium hydroxide sequentially comprises the following steps:

(1) a waste pretreatment step: firstly, adding the waste liquid into a sedimentation tank to precipitate large-particle impurities, metal particle substances and the like in the waste material, carrying out rough filtration through a filtration system, and waiting for standby after the filtration is finished;

(2) exchange material pretreatment: adding an exchange material into a cleaning pool to heat, then repeatedly performing immersion cleaning and washing until cleaning liquid is clear and the amount of foam is small, then adding the cleaned exchange material into an acid pool to clean, then adding the cleaned exchange material into an alkali pool to clean, adding the cleaned exchange material into the acid pool again to clean after the alkali pool is cleaned, and washing acid-base residues on the surface through ultrapure water after the cleaning is completed for later use, wherein the exchange material adopts cation exchange resin, the cleaning acid adopts phosphoric acid, the cleaning alkali adopts sodium hydroxide solution, and the heating temperature is 52 ℃;

(3) exchange material transformation treatment: adsorbing the cleaned exchange material in the step (2) by tetramethylammonium ions in the waste liquid in the adsorption step (1) to make the exchange material become a tetramethylammonium type;

(4) waste exchange and impurity removal treatment: washing the surface of the exchange material subjected to adsorption in the step (3) by using ultrapure water, and removing impurities such as photoresist, precipitate and the like;

(5) impurity adsorption treatment: filtering the precipitate washed in the step (4) by using an ultrafiltration material to prevent the direct discharge of sewage from polluting and damaging the environment, wherein YHMBR-1 is adopted as ultrafiltration equipment;

(6) treating a tetramethylammonium sulfate solution: eluting the exchange material adsorbed in the step (4) by sulfuric acid to obtain a tetramethylammonium sulfate solution;

(7) decomposing and treating the tetramethylammonium sulfate solution: adding an inactive metal into the tetramethylammonium sulfate solution obtained in the step (6), and heating to generate sulfur dioxide, sulfate precipitates and a tetramethylammonium hydroxide solution, wherein the inactive metal is Ag, and the heating temperature is 45 ℃;

(8) filtering the tetramethylammonium solution: and (4) filtering the reactant in the step (7) to obtain a crude product of the tetramethylammonium hydroxide, and then, concentrating and purifying by using an exchange material again to finally obtain a pure finished product.

EXAMPLE III

The invention provides a technical scheme that: an environment-friendly and reusable preparation process for producing electronic-grade tetramethyl ammonium hydroxide sequentially comprises the following steps:

(1) a waste pretreatment step: firstly, adding the waste liquid into a sedimentation tank to precipitate large-particle impurities, metal particle substances and the like in the waste material, carrying out rough filtration through a filtration system, and waiting for standby after the filtration is finished;

(2) exchange material pretreatment: adding an exchange material into a cleaning pool to heat, then repeatedly performing immersion cleaning and washing until cleaning liquid is clear and the amount of foam is small, then adding the cleaned exchange material into an acid pool to clean, then adding the cleaned exchange material into an alkali pool to clean, adding the cleaned exchange material into the acid pool again to clean after the alkali pool is cleaned, and washing acid-base residues on the surface through ultrapure water after the cleaning is completed for later use, wherein the exchange material adopts cation exchange resin, the cleaning acid adopts methanesulfonic acid, the cleaning alkali adopts sodium hydroxide solution, and the heating temperature is 55 ℃;

(3) exchange material transformation treatment: adsorbing the cleaned exchange material in the step (2) by tetramethylammonium ions in the waste liquid in the adsorption step (1) to make the exchange material become a tetramethylammonium type;

(4) waste exchange and impurity removal treatment: washing the surface of the exchange material subjected to adsorption in the step (3) by using ultrapure water, and removing impurities such as photoresist, precipitate and the like;

(5) impurity adsorption treatment: filtering the precipitate washed in the step (4) by using an ultrafiltration material to prevent the direct discharge of sewage from polluting and damaging the environment, wherein YHMBR-1 is adopted as ultrafiltration equipment;

(6) treating a tetramethylammonium sulfate solution: eluting the exchange material adsorbed in the step (4) by sulfuric acid to obtain a tetramethylammonium sulfate solution;

(7) decomposing and treating the tetramethylammonium sulfate solution: adding an inactive metal into the tetramethylammonium sulfate solution obtained in the step (6), and heating to generate sulfur dioxide, sulfate precipitates and a tetramethylammonium hydroxide solution, wherein the inactive metal is Cu, and the heating temperature is 55 ℃;

(8) filtering the tetramethylammonium solution: and (4) filtering the reactant in the step (7) to obtain a crude product of the tetramethylammonium hydroxide, and then, concentrating and purifying by using an exchange material again to finally obtain a pure finished product.

Example four

The invention provides a technical scheme that: an environment-friendly and reusable preparation process for producing electronic-grade tetramethyl ammonium hydroxide sequentially comprises the following steps:

(1) a waste pretreatment step: firstly, adding the waste liquid into a sedimentation tank to precipitate large-particle impurities, metal particle substances and the like in the waste material, carrying out rough filtration through a filtration system, and waiting for standby after the filtration is finished;

(2) exchange material pretreatment: adding an exchange material into a cleaning pool to heat, then repeatedly performing immersion cleaning and washing until cleaning liquid is clear and the foam amount is small, then adding the cleaned exchange material into an acid pool to clean, then adding the cleaned exchange material into an alkali pool to clean, adding the cleaned exchange material into the acid pool again to clean after the alkali pool is cleaned, and washing acid-base residues on the surface through ultrapure water after the cleaning is completed for later use, wherein the exchange material adopts cation exchange resin, the cleaning acid adopts hydrochloric acid, the cleaning alkali adopts sodium hydroxide solution, and the heating temperature is 58 ℃;

(3) exchange material transformation treatment: adsorbing the cleaned exchange material in the step (2) by tetramethylammonium ions in the waste liquid in the adsorption step (1) to make the exchange material become a tetramethylammonium type;

(4) waste exchange and impurity removal treatment: washing the surface of the exchange material subjected to adsorption in the step (3) by using ultrapure water, and removing impurities such as photoresist, precipitate and the like;

(5) impurity adsorption treatment: filtering the precipitate washed in the step (4) by using an ultrafiltration material to prevent the direct discharge of sewage from polluting and damaging the environment, wherein YHMBR-1 is adopted as ultrafiltration equipment;

(6) treating a tetramethylammonium sulfate solution: eluting the exchange material adsorbed in the step (4) by sulfuric acid to obtain a tetramethylammonium sulfate solution;

(7) decomposing and treating the tetramethylammonium sulfate solution: adding an inactive metal into the tetramethylammonium sulfate solution obtained in the step (6), and heating to generate sulfur dioxide, sulfate precipitates and a tetramethylammonium hydroxide solution, wherein the inactive metal is Ag, and the heating temperature is 53 ℃;

(8) filtering the tetramethylammonium solution: and (4) filtering the reactant in the step (7) to obtain a crude product of the tetramethylammonium hydroxide, and then, concentrating and purifying by using an exchange material again to finally obtain a pure finished product.

EXAMPLE five

The invention provides a technical scheme that: an environment-friendly and reusable preparation process for producing electronic-grade tetramethyl ammonium hydroxide sequentially comprises the following steps:

(1) a waste pretreatment step: firstly, adding the waste liquid into a sedimentation tank to precipitate large-particle impurities, metal particle substances and the like in the waste material, carrying out rough filtration through a filtration system, and waiting for standby after the filtration is finished;

(2) exchange material pretreatment: adding an exchange material into a cleaning pool to heat, then repeatedly performing immersion cleaning and washing until cleaning liquid is clear and the amount of foam is small, then adding the cleaned exchange material into an acid pool to clean, then adding the cleaned exchange material into an alkali pool to clean, adding the cleaned exchange material into the acid pool again to clean after the alkali pool is cleaned, and washing acid-base residues on the surface through ultrapure water after the cleaning is completed for later use, wherein the exchange material adopts cation exchange resin, the cleaning acid adopts hydrochloric acid, the cleaning alkali adopts sodium hydroxide solution, and the heating temperature is 60 ℃;

(3) exchange material transformation treatment: adsorbing the cleaned exchange material in the step (2) by tetramethylammonium ions in the waste liquid in the adsorption step (1) to make the exchange material become a tetramethylammonium type;

(4) waste exchange and impurity removal treatment: washing the surface of the exchange material subjected to adsorption in the step (3) by using ultrapure water, and removing impurities such as photoresist, precipitate and the like;

(5) impurity adsorption treatment: filtering the precipitate washed in the step (4) by using an ultrafiltration material to prevent the direct discharge of sewage from polluting and damaging the environment, wherein YHMBR-1 is adopted as ultrafiltration equipment;

(6) treating a tetramethylammonium sulfate solution: eluting the exchange material adsorbed in the step (4) by sulfuric acid to obtain a tetramethylammonium sulfate solution;

(7) decomposing and treating the tetramethylammonium sulfate solution: adding an inactive metal into the tetramethylammonium sulfate solution obtained in the step (6), and heating to generate sulfur dioxide, sulfate precipitates and a tetramethylammonium hydroxide solution, wherein the inactive metal is Ag, and the heating temperature is 60 ℃;

(8) filtering the tetramethylammonium solution: and (4) filtering the reactant in the step (7) to obtain a crude product of the tetramethylammonium hydroxide, and then, concentrating and purifying by using an exchange material again to finally obtain a pure finished product.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.