Preparation process of electronic-grade ATMP

Abstract

The invention discloses a preparation process of electronic-grade ATMP, and belongs to the technical field of water treatment. The process aims at solving the problems that the content of impurities such as Cl <-> and Fe in an existing ATMP product is high, and the electronic-grade application requirement is difficult to meet. The process combining ion exchange treatment and recrystallization purification is adopted, firstly, metal ions of an industrial-grade ATMP raw material are preliminarily removed through ion exchange resin, then concentration crystallization and recrystallization are sequentially conducted, and finally the high-purity ATMP product is obtained through blending. By means of the process, the electronic-grade ATMP with the key indexes that the Cl <-> content is smaller than or equal to 100 ppm and the Fe content is smaller than or equal to 1 ppm can be stably produced, the product purity is high, the process operation is simple, the cost is low, and the process is suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of water treatment, and particularly relates to a preparation process of electronic-grade ATMP. BACKGROUND

[0002] ATMP, aminotrimethylenephosphonic acid, is generally synthesized by taking ammonium chloride, formaldehyde, hydrochloric acid and phosphorous acid as raw materials in one step, and is an important organic phosphonic acid water treatment agent. Due to its excellent chelation, scale inhibition and corrosion inhibition performance, it is widely used in the field of industrial water treatment. In the circulating cooling water system, it can effectively chelate hardness ions such as calcium and magnesium in water, prevent the formation of scale layers such as calcium carbonate and calcium sulfate, and inhibit the corrosion of metal surfaces; in the boiler water system, it can prevent the formation of scale on the inner wall of the boiler through chelation, and has corrosion inhibition effect on carbon steel, copper and other metal materials; in the reverse osmosis (RO) system, it can be used in combination with scale inhibitors to inhibit the deposition of calcium carbonate, barium sulfate and other insoluble salts on the surface of the reverse osmosis membrane; in the oilfield water injection system, it can chelate calcium, magnesium, iron and other ions in water to prevent the formation of scale in the formation, and inhibit the corrosion of metal pipelines; in industrial cleaning, it can be used as a corrosion inhibitor for cleaning agents to prevent metal equipment from being corroded during cleaning; in the sewage treatment process, it can chelate heavy metal ions (such as iron, copper, zinc, etc.) in sewage to reduce their pollution to the environment; in the papermaking process, it can prevent the formation of scale in the white water system during papermaking, and inhibit the corrosion of metal equipment.

[0003] The active component of ATMP on the market is generally 50%, the chloride content is less than 2% in terms of chlorine, and the iron ion is less than 20 ppm. Electronic-grade ATMP is an acidic liquid with strong metal ion chelation capacity, which can improve the grinding efficiency and improve the smoothness in the processes such as grinding, polishing and etching in semiconductor processing; when used in the etching process of display panels and PCB boards, it can effectively reduce burr generation and improve the smoothness of the copper foil surface. The active component (calculated as ATMP) of electronic-grade ATMP is ≥50%, the metal ion content in ATMP is very low, especially the iron ion needs to be reduced to below 1 ppm, and the chloride ion needs to be reduced to below 100 ppm, which belongs to a new type of biological chemical product and special fine chemical product. The high purity of the product can be used in special fields, such as electronic product cleaning agent in the electronic industry, metal chelating agent in the textile printing and dyeing industry, and metal surface treatment agent, etc.

[0004] The existing ATMP product has many impurities, especially the indicators such as Cl - , Fe 2+ / 3+ are difficult to meet the requirements of electronic and high-end cosmetics fields. The existing purification methods such as solvent method have high cost, and ion exchange method has the disadvantage of complex operation.

[0005] Based on this, the application provides a preparation process of electronic-grade ATMP. Summary of the Invention

[0006] The purpose of this invention is to provide a preparation process for electronic-grade ATMP. This invention is a simple, low-cost, and stable method for the cyclic crystallization purification of ATMP, capable of producing ultra-high purity ATMP. This invention purifies existing ATMP products to meet the ion standards for preparing electronic-grade ATMP, providing a method for the stable production of Cl... - A low-cost method for obtaining electronic-grade ATMP aqueous solutions with ≤100 ppm and Fe≤1 ppm.

[0007] The objective of this invention can be achieved through the following technical solutions: A fabrication process for electronic-grade ATMP, comprising the following steps: (1) Weigh a certain amount of conventional ATMP product with 50% active component, pass it through an ion exchange column packed with 1000 mm ion exchange resin, and collect the ATMP product after resin treatment. (2) The resin-treated ATMP product is heated and concentrated at 100℃-130℃ until the active component is 75%-90%, then crystallized and filtered. The filter residue is quickly rinsed twice with a small amount of high-purity water. (3) Add high-purity water to the filter residue, adjust the active component to between 75% and 90%, heat until completely dissolved, allow to crystallize naturally or recrystallize by water cooling, rinse the filter residue twice with a small amount of high-purity water, and precisely adjust the filter residue with high-purity water to an activity of (50.0±0.5)%, then test the key indicators: Cl - Content ≤100 ppm, Fe content ≤1 ppm; (4) If Cl is detected - If the Fe content exceeds the standard, the unqualified product will be used as the raw material for the next purification and will directly enter step (2).

[0008] In the above technical solution, the ion exchange resin used in step (1) is preferably a strong acid cation exchange resin. By using the ion exchange resin, some impurity ion content is removed, which reduces the difficulty of further reducing the ion content in the subsequent process.

[0009] In the above technical solution, the ion exchange resin used in step (1) is further preferably a sulfonic acid group –SO3H type strong acid cation exchange resin.

[0010] In the above technical solution, step (2) concentration and crystallization can remove the ion content dissolved in water in the mother liquor. Moreover, low-temperature (15℃-30℃) rapid rinsing can effectively wash away the mother liquor impurities attached to the surface without dissolving a large amount of the target product.

[0011] In the above technical solution, step (3) uses high-purity water recrystallization, which can further reduce the content of water-soluble impurity ions in ATMP to basically meet the target ion requirements.

[0012] In the above technical solution, step (4) refines the endpoint control to 50.0 ± 0.5%, and sets high-standard technical performance indicators, which are far superior to those of conventional industrial-grade ATMP (Cl). - (Potentially several thousand ppm, Fe possibly above 10 ppm), meeting the requirements for electronic-grade chemicals.

[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The preparation process of electronic-grade ATMP provided by this invention is relatively simple, has a high safety factor, and a short production cycle. It can effectively reduce the content of various ions in ATMP and can be mass-produced.

[0014] 2. This invention uses the combined action of ion exchange and recrystallization to obtain granular crystals with uniform particle size and smooth surface. This method only involves one ion exchange, which effectively extends the resin life and avoids the low yield and long cycle caused by multiple recrystallizations.

[0015] 3. Through this process, even when using 50% raw materials from different batches with slight quality fluctuations, it is possible to stably produce products with various indicators falling within a narrow high-standard range, proving the reproducibility and industrial value of the process. Detailed Implementation

[0016] The technical solution and effects of the present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0017] The active ingredient used in this invention is 50% of the conventional ATMP product Cl. - Content: 1500 ppm, Fe content: 10 ppm.

[0018] The ion exchange resin used in this invention is the 001x7 model 732 cation exchange resin. Example 1

[0019] A fabrication process for electronic-grade ATMP, comprising the following steps: (1) Weigh 1000g of conventional ATMP product with 50% active ingredient, heat and concentrate the product at 100-130℃ until the active ingredient is 85%, then crystallize and filter. (2) The filter residue is dissolved in high-purity water and recrystallized twice. After filtration, the filter residue is adjusted with high-purity water to the detection index of 50% of active component. (3) If the indicators do not meet the requirements, repeat step (2); (4) Precisely adjust the activity to 50.2% using high-purity water, and then test the key indicators: Cl - Content 285 ppm, Fe content 2 ppm. Example 2

[0020] A fabrication process for electronic-grade ATMP, comprising the following steps: (1) Weigh 1000g of a conventional ATMP product with 50% active ingredient; (2) Pass the product from (1) through a pre-treated ion exchange resin column (column height 1500 mm, resin height 1000 mm) at a flow rate of 10 BV / H, repeat the column pass twice, and collect the treated ATMP product. (3) The treated ATMP product was precisely mixed with high-purity water to an activity of 50.2%, and then the key indicators were tested: Cl - Content 850 ppm, Fe content 6.5 ppm. Example 3

[0021] A fabrication process for electronic-grade ATMP, comprising the following steps: (1) Weigh 1000g of conventional ATMP product with 50% active component and pass it through a pre-treated ion exchange resin column (column height 1500 mm, resin height 1000 mm) at a flow rate of 10 BV / H to collect the treated ATMP product. (2) Heat and concentrate the product at 100-130℃ until the active component is 85%, crystallize and filter, and rinse the filter residue twice with a small amount of high-purity water. (3) After the filter residue is dissolved in high-purity water, it is recrystallized once, filtered, and the filter residue is rinsed twice with a small amount of high-purity water. (4) Collect the recrystallized filter residue, precisely adjust it with high-purity water to an activity of 50.2%, and then test the key indicators: Cl - The content was 78 ppm, and the Fe content was 0.55 ppm.

[0022] This invention organically combines ion exchange adsorption and recrystallization of ATMP, resulting in a synergistic effect. This achieves a reduction in Cl in ATMP. - The Fe and other ion properties meet the requirements of electronic-grade ATMP. As can be seen from Examples 1 and 2, it is difficult to achieve Fe and Cl- ionization using ion exchange resin alone. -Reducing the content of various ions to the target value is difficult, and repeated use of ATMP due to its strong acidity is detrimental to the resin's lifespan. Recrystallization alone can also effectively reduce the content of various ions, but reaching the target value may require multiple recrystallizations, resulting in a long process cycle, low yield, and hindering industrial production. However, combining the two methods resulted in a qualitative leap in the indicators (Fe < 1 ppm, Cl < 1 ppm). - <100 ppm), such an improvement is unpredictable to those skilled in the art. This invention provides a clear, controllable, and stable process route for the production of electronic-grade ATMP, solving the bottleneck problem in the prior art.

[0023] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A fabrication process for electronic-grade ATMP, characterized in that, Includes the following steps: (1) Industrial-grade ATMP raw material was subjected to ion exchange treatment to obtain a preliminarily purified ATMP solution; (2) The ATMP solution obtained in step (1) is concentrated and crystallized to obtain ATMP crystals and mother liquor I. After separation, the ATMP crystals are rinsed. (3) Dissolve the ATMP crystals after rinsing in step (2) in high-purity water and recrystallize them to obtain high-purity ATMP crystals and mother liquor II. After separation, rinse the high-purity ATMP crystals. (4) The high-purity ATMP crystals rinsed in step (3) are mixed with high-purity water to form an aqueous solution with an active component concentration of (50.0±0.5)%, thereby obtaining electronic-grade ATMP products. In the aforementioned electronic-grade ATMP product, Cl - Content ≤100 ppm, Fe content ≤1 ppm.

2. The preparation process according to claim 1, characterized in that, In step (1), the concentration of the active component of the industrial-grade ATMP raw material is 50%.

3. The preparation process according to claim 1, characterized in that, In step (1), the ion exchange resin used in the ion exchange treatment is preferably a strong acidic cation exchange resin.

4. The preparation process according to claim 1, characterized in that, In step (2), the product is heated and concentrated at 100℃-130℃ until the active component is 75%-90%.

5. The preparation process according to claim 1, characterized in that, In steps (2) and (3), the rinsing is performed using high-purity water for rapid rinsing.

6. The preparation process according to claim 5, characterized in that, The rapid rinsing is performed 1-3 times.

7. The preparation process according to claim 1, characterized in that, In step (3), the recrystallization is either natural cooling crystallization or water cooling crystallization.

8. The preparation process according to claim 1, characterized in that, In step (3), after dissolving the ATMP crystals, the concentration of the active component of ATMP in the high-purity water is adjusted to 75%-90%.

9. The preparation process according to claim 1, characterized in that, It also includes step (5): detecting the Cl of the product obtained in step (4). - If any of the indicators, such as Fe content, does not meet the requirements, the unqualified product will be returned to step (2) as raw material for re-purification.