A method for removing arsenic elements from electronic-grade hydrochloric acid

Abstract

The present invention relates to a method for removing arsenic elements from electronic-grade hydrochloric acid; in the present invention, industrial-grade hydrochloric acid is separated by distillation to produce gaseous hydrogen chloride, which sequentially passes through an activated carbon adsorption tower, an acid-resistant molecular sieve adsorption tower, and a zirconia adsorption tower, and then enters a temporary storage tank containing high-purity water after adsorption; the hydrogen chloride in the temporary storage tank is formulated into hydrochloric acid with a mass concentration of 28-32% and enters a distillation column, and the gaseous hydrogen chloride after distillation enters a blending tank; the gaseous hydrogen chloride in the blending tank is formulated into hydrochloric acid with a mass concentration of 36-37% and enters a finished product tank, and the hydrochloric acid in the finished product tank is obtained as electronic-grade hydrochloric acid through multi-stage filtration; the acid-resistant molecular sieve adsorption tower of the present invention uses a modified Y-type molecular sieve, which is prepared by reacting Γ-glycidoxypropyltrimethoxysilane, Y-type molecular sieve, aminotrimethylenephosphonic acid, and bis-(2-methylallyl)cyclooctane-1,5-diene ruthenium; the electronic-grade hydrochloric acid prepared by the present invention has low impurity content and high arsenic element removal rate.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic-grade hydrochloric acid, and in particular to a method for removing arsenic elements from electronic-grade hydrochloric acid. Background Art

[0002] Arsenic elements in hydrochloric acid exist in the forms of trivalent AsCl3 and trivalent H3AsO3. However, the boiling points of AsCl3 and 28-32% hydrochloric acid solution are relatively close, and it is difficult to remove trivalent arsenic ions by ordinary rectification methods.

[0003] The adsorption method uses an adsorbent to attract impurity elements to remove impurity ions, and can effectively adsorb impurity ions from gas or liquid. Adsorbents include kaolinite, lignin, carbon nanotubes, graphene, metal oxides, silica gel, etc. However, in order to effectively remove arsenic elements in hydrochloric acid, it is difficult to achieve the best separation effect with only one adsorbent.

[0004] Chinese Patent CN108609584A: discloses a production process of electronic-grade hydrochloric acid, which relates to the technical field of chemical engineering. The production process of electronic-grade hydrochloric acid provided by the present invention includes: placing industrial-grade hydrochloric acid in a reaction kettle, adding hydrazine hydrate thereto, and stirring and mixing until the reaction is complete; introducing all the reacted materials into a deacidification tower, maintaining a negative pressure in the deacidification tower, and introducing air into the deacidification tower to perform bubbling stirring and blowing desorption on the solution to obtain escape gas and bottom liquid of the tower; compressing the escape gas desorbed in the deacidification tower with a compressor; introducing the compressed escape gas into an acid washing tower for acid washing to obtain electronic-grade hydrochloric acid, and returning the non-condensable gas to the bottom of the deacidification tower for bubbling circulation, and maintaining a negative pressure in the acid washing tower.

[0005] Chinese Patent CN117585644A: relates to the technical field of high-purity hydrochloric acid, and specifically discloses a preparation method of electronic-grade hydrochloric acid. A preparation method of electronic-grade hydrochloric acid includes the following specific steps: S1: passing industrial-grade hydrochloric acid through primary filtration and pretreatment in sequence to obtain primary hydrochloric acid; S2: transporting the primary hydrochloric acid to a rectification tower to obtain gaseous hydrogen chloride, then dehydrating the gaseous hydrogen chloride with concentrated sulfuric acid and performing demisting treatment in sequence to reduce the moisture in the gaseous hydrogen chloride, and then performing condensation treatment to obtain a hydrochloric acid semi-finished product; S3: circulating and absorbing the hydrogen chloride tail gas of the hydrochloric acid semi-finished product with ultrapure water, and finally performing secondary filtration and impurity removal and purification to obtain electronic-grade hydrochloric acid; using a reducing agent to pretreat the industrial-grade hydrochloric acid in the pretreatment.

[0006] Chinese Patent CN109761196A: A method for producing electronic-grade hydrochloric acid is provided, which successively includes the following steps: 1. The synthesized hydrogen chloride gas enters an adsorption tower to remove free chlorine; 2. Using reagent-grade hydrochloric acid solvent, it enters the washing tower from the upper inlet of the washing tower to wash the adsorbed hydrogen chloride gas to remove soluble impurities; 3. The washed hydrogen chloride gas is condensed by the first-stage and second-stage condensers and enters a demister to remove the water mist therein, obtaining high-purity hydrogen chloride gas; 4. The high-purity hydrogen chloride is absorbed by the first-stage and second-stage falling film absorbers and a tail gas absorption tower, and then passes through a hydrochloric acid cooler to obtain the finished product; 5. Ultra-pure water is used as the absorption water; 6. The finished product obtained in step 4 enters a finished product storage tank, and then passes through ultrafiltration to remove particulate impurities to obtain electronic-grade hydrochloric acid.

[0007] For the electronic-grade hydrochloric acid prepared by the above patent and the prior art, the free chlorine, arsenic element and other impurities still need to be further reduced. Summary of the Invention

[0008] In order to solve the above problems, the present invention provides a method for removing arsenic element in electronic-grade hydrochloric acid, and its operation steps are as follows:

[0009] S1: The industrial-grade hydrochloric acid with a mass concentration of 25-30% is separated by rectification to generate gaseous hydrogen chloride. The gaseous hydrogen chloride enters and successively passes through an activated carbon adsorption tower, an acid-resistant molecular sieve adsorption tower, and a zirconia adsorption tower. The adsorbed gaseous hydrogen chloride enters a temporary storage tank containing high-purity water;

[0010] S2: The hydrogen chloride entering the temporary storage tank is formulated into hydrochloric acid with a mass concentration of 28-32% and enters a rectification tower for rectification. The rectified gaseous hydrogen chloride enters a formulation tank;

[0011] S3: The gaseous hydrogen chloride entering the formulation tank is formulated into hydrochloric acid with a mass concentration of 36-37% and enters a finished product tank. The hydrochloric acid in the finished product tank passes through multi-stage filtration to obtain electronic-grade hydrochloric acid.

[0012] The adsorption temperature in S1 is 25-35°C, and the adsorption time is 10-60 min.

[0013] The rectification temperature in S2 is 105-120°C.

[0014] The acid-resistant molecular sieve adsorption tower uses a modified Y-type molecular sieve, and its preparation method is as follows:

[0015] A1: 2-5 parts of Γ-glycidoxypropyltrimethoxysilane, 100-150 parts of Y-type molecular sieve, and 1000-1300 parts of solvent are stirred and mixed at room temperature;

[0016] A2: Add 9 - 18 parts of aminotrimethylenephosphonic acid and 0.003 - 0.03 parts of bis-(2 - methylallyl)cycloocta - 1,5 - dieneruthenium; adjust the pH to 9 with triethylamine, react, filter, wash with water until neutral, and dry to obtain modified Y - type molecular sieve.

[0017] The solvent of A1 is DMF.

[0018] The stirring time of A1 is 90 - 120 min.

[0019] The reaction temperature of A2 is 80 - 90 °C and the reaction time is 24 - 48 hours.

[0020] The preparation method of zirconia particles in the zirconia adsorption tower is as follows:

[0021] Add 10 - 16 parts of high - purity ZrCl4 into the reaction kettle, introduce 10 - 32 parts of oxygen and 10 - 32 parts of hydrogen and heat for reaction to obtain zirconia particles.

[0022] The heating reaction temperature is 300 - 700 °C and the reaction time is 2 - 6 h.

[0023] The diameter of the zirconia particles is 6 - 10 microns, the specific surface area is 320 - 400 m 2 / g, and the porosity is 0.12 - 0.20 cm 3 / g.

[0024] Reaction mechanism

[0025] Γ - glycidoxypropyltrimethoxysilane undergoes a condensation reaction with the hydroxyl groups on the surface of Y - type molecular sieve to form epoxy - functionalized Y - type molecular sieve. This step is crucial because it provides active sites for the subsequent ring - opening reaction.

[0026] The epoxy - functionalized Y - type molecular sieve then undergoes a ring - opening reaction with the amino group of aminotrimethylenephosphate to form stable chemical bonds. This process enables the effective grafting of trimethylenephosphate onto the molecular sieve surface.

[0027] Bis-(2 - methylallyl)cycloocta - 1,5 - dieneruthenium undergoes an amino - allyl addition reaction with aminotrimethylenephosphate, further stabilizing the structure on the molecular sieve surface and introducing a ruthenocene complex. This modified Y - type molecular sieve has stronger adsorption capacity and selectivity.

[0028] Technical effects

[0029] A method for removing arsenic element from electronic - grade hydrochloric acid according to the present invention has the following remarkable effects compared with the prior art:

[0030] 1. Zirconia is a weakly acidic oxide with stable chemical properties and sufficient stability in acidic solutions, having good adsorption effects on both arsenic(Ⅲ) and arsenic(Ⅴ); the present invention uses zirconia particles, combined with activated carbon and acid-resistant molecular sieves, to remove arsenic elements in hydrochloric acid;

[0031] 2. The present invention can effectively remove most of the free chlorine, arsenic elements and other impurities in industrial-grade hydrochloric acid through an activated carbon adsorption tower, an acid-resistant molecular sieve adsorption tower, and a zirconia adsorption tower; in order to prevent impurities brought by the adsorbent in the adsorption tower from entering the product, the adsorbed hydrogen chloride is further absorbed with high-purity water to prepare hydrochloric acid with a concentration of 28 - 32%, and the impurities brought by the adsorption tower are dissolved in high-purity water, and further rectified to obtain high-purity hydrogen chloride;

[0032] 3. Impurities in industrial hydrochloric acid can be effectively removed through rectification. Combining the technology of using activated carbon, molecular sieves and zirconia to adsorb arsenic impurities in hydrochloric acid, mesoporous zirconia, as an adsorbent, can effectively remove arsenic impurities in further hydrochloric acid;

[0033] 4. The combination of trimethylenetriphosphate and ruthenocene complex in the present invention greatly improves the adsorption capacity of Y-type molecular sieve for arsenic elements. This is because trimethylenetriphosphate has multiple functional groups that can form stable complexes with arsenic elements, and the introduction of ruthenocene complex further enhances this stability.

[0034] The modified Y-type molecular sieve can not only efficiently remove arsenic elements in electronic-grade hydrochloric acid, but also maintain the high purity of hydrochloric acid. This is because no other impurity ions are introduced during the whole process, which is crucial for the production of electronic-grade products.

[0035] The continuous and stable production capacity of this technology is also one of its important advantages. The electronic-grade hydrochloric acid treated by this method can meet strict industrial standards, while ensuring the stability of production efficiency and product quality.

[0036] In summary, the ruthenocene complex-modified Y-type molecular sieve shows excellent performance and technical effects in removing arsenic elements in electronic-grade hydrochloric acid. It can not only effectively transform and fix arsenic elements, but also maintain the high purity of hydrochloric acid and the continuity of production, which is of great significance for the production of electronic-grade products. Specific Embodiments

[0037] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with examples and comparative examples:

[0038] Refer to Q / GR101 - 2024 electronic-grade hydrochloric acid for testing.

[0039] Example 1

[0040] A method for removing arsenic element from electronic-grade hydrochloric acid, and its operation steps are as follows:

[0041] S1: The industrial-grade hydrochloric acid with a mass concentration of 25% is separated by rectification to produce gaseous hydrogen chloride. The gaseous hydrogen chloride enters and passes through an activated carbon adsorption tower, an acid-resistant molecular sieve adsorption tower, and a zirconia adsorption tower in sequence. The adsorbed gaseous hydrogen chloride enters a temporary storage tank containing high-purity water;

[0042] S2: The hydrogen chloride entering the temporary storage tank is formulated into hydrochloric acid with a mass concentration of 28% and enters a rectification tower for rectification. The rectified gaseous hydrogen chloride enters a formulation tank;

[0043] S3: The gaseous hydrogen chloride entering the formulation tank is formulated into hydrochloric acid with a mass concentration of 36% and enters a finished product tank. The hydrochloric acid in the finished product tank is obtained as electronic-grade hydrochloric acid through multi-stage filtration.

[0044] The adsorption temperature in S1 is 25°C, and the adsorption time is 10 min.

[0045] The rectification temperature in S2 is 105°C.

[0046] The acid-resistant molecular sieve adsorption tower uses a modified Y-type molecular sieve, and its preparation method is as follows:

[0047] A1: 2 g of Γ-glycidoxypropyltrimethoxysilane, 100 g of Y-type molecular sieve, and 1000 g of solvent are stirred and mixed at room temperature;

[0048] A2: 9 g of aminotrimethylene phosphonic acid and 0.003 g of bis-(2-methylallyl)cyclooct-1,5-diene ruthenium are added; the pH is adjusted to 9 with triethylamine, and the reaction is carried out. After filtration, washing with water until neutral, and drying, a modified Y-type molecular sieve is obtained.

[0049] The solvent in A1 is DMF.

[0050] The stirring time in A1 is 90 min.

[0051] The reaction temperature in A2 is 80°C, and the reaction time is 24 hours.

[0052] The preparation method of the zirconia particles in the zirconia adsorption tower is as follows:

[0053] 10 g of high-purity ZrCl4 is added to a reaction kettle, 10 g of oxygen and 10 g of hydrogen are introduced, and the reaction is carried out under heating to obtain zirconia particles.

[0054] The heating reaction temperature is 300°C, and the reaction time is 2 h.

[0055] The diameter of the zirconia particles is 6 microns, and the specific surface area is 320 m 2 / g, porosity 0.12 cm 3 / g.

[0056] Example 2

[0057] A method for removing arsenic element from electronic grade hydrochloric acid, the operation steps of which are as follows:

[0058] S1: The industrial grade hydrochloric acid with a mass concentration of 28% is separated by rectification to produce gaseous hydrogen chloride. The gaseous hydrogen chloride enters and successively passes through an activated carbon adsorption tower, an acid-resistant molecular sieve adsorption tower, and a zirconia adsorption tower. The adsorbed gaseous hydrogen chloride enters a temporary storage tank containing high-purity water;

[0059] S2: The hydrogen chloride entering the temporary storage tank is formulated into hydrochloric acid with a mass concentration of 30% and enters a rectification tower for rectification. The rectified gaseous hydrogen chloride enters a formulation tank;

[0060] S3: The gaseous hydrogen chloride entering the formulation tank is formulated into hydrochloric acid with a mass concentration of 36% and enters a finished product tank. The hydrochloric acid in the finished product tank is obtained as electronic grade hydrochloric acid through multi-stage filtration.

[0061] The adsorption temperature in S1 is 28 °C, and the adsorption time is 30 min.

[0062] The rectification temperature in S2 is 110 °C.

[0063] The acid-resistant molecular sieve adsorption tower uses a modified Y-type molecular sieve, and its preparation method is as follows:

[0064] A1: 3 g of Γ-glycidoxypropyltrimethoxysilane, 110 g of Y-type molecular sieve, and 1100 g of solvent are stirred and mixed at room temperature;

[0065] A2: Add 12 g of aminotrimethylene phosphonic acid and 0.01 g of bis-(2-methylallyl)cycloocta-1,5-diene ruthenium; adjust the pH to 9 with triethylamine, react, filter, wash with water until neutral, and dry to obtain the modified Y-type molecular sieve.

[0066] The solvent in A1 is DMF.

[0067] The stirring time in A1 is 100 min.

[0068] The reaction temperature in A2 is 85 °C, and the reaction time is 30 hours.

[0069] The preparation method of the zirconia particles in the zirconia adsorption tower is as follows:

[0070] Add 12 g of high-purity ZrCl4 to a reaction kettle, introduce 16 g of oxygen and 16 g of hydrogen and heat to react to obtain zirconia particles.

[0071] The heating reaction temperature is 400 °C and the reaction time is 3 h.

[0072] The diameter of the zirconia particles is 7 μm, the specific surface area is 360 m 2 / g, and the porosity is 0.16 cm 3 / g.

[0073] Example 3

[0074] A method for removing arsenic element from electronic-grade hydrochloric acid, and its operation steps are as follows:

[0075] S1: The industrial-grade hydrochloric acid with a mass concentration of 28% is separated by rectification to produce gaseous hydrogen chloride. The gaseous hydrogen chloride enters and passes through an activated carbon adsorption tower, an acid-resistant molecular sieve adsorption tower, and a zirconia adsorption tower in sequence. The adsorbed gaseous hydrogen chloride enters a temporary storage tank containing high-purity water;

[0076] S2: The hydrogen chloride entering the temporary storage tank is formulated into hydrochloric acid with a mass concentration of 30% and enters a rectification tower for rectification. The rectified gaseous hydrogen chloride enters a formulation tank;

[0077] S3: The gaseous hydrogen chloride entering the formulation tank is formulated into hydrochloric acid with a mass concentration of 37% and enters a finished product tank. The hydrochloric acid in the finished product tank is obtained as electronic-grade hydrochloric acid through multi-stage filtration.

[0078] The adsorption temperature in S1 is 32 °C and the adsorption time is 50 min.

[0079] The rectification temperature in S2 is 115 °C.

[0080] The acid-resistant molecular sieve adsorption tower uses a modified Y-type molecular sieve, and its preparation method is as follows:

[0081] A1: 4 g of Γ-glycidoxypropyltrimethoxysilane, 140 g of Y-type molecular sieve, and 1200 g of solvent are stirred and mixed at room temperature;

[0082] A2: 16 g of aminotrimethylene phosphonic acid and 0.02 g of bis-(2-methylallyl)cycloocta-1,5-diene ruthenium are added; the pH is adjusted to 9 with triethylamine, reacted, filtered, washed with water until neutral, and dried to obtain the modified Y-type molecular sieve.

[0083] The solvent in A1 is DMF.

[0084] The stirring time in A1 is 110 min.

[0085] The reaction temperature in A2 is 85 °C and the reaction time is 40 hours.

[0086] The preparation method of the zirconia particles in the zirconia adsorption tower is as follows:

[0087] Add 14 g of high-purity ZrCl4 into a reaction kettle, introduce 28 g of oxygen and 28 g of hydrogen, and heat them for reaction to obtain zirconia particles.

[0088] The temperature of the heating reaction is 600 °C, and the reaction time is 5 h.

[0089] The diameter of the zirconia particles is 9 microns, the specific surface area is 380 m 2 / g, and the porosity is 0.18 cm 3 / g.

[0090] Example 4

[0091] A method for removing arsenic elements from electronic-grade hydrochloric acid, and its operation steps are as follows:

[0092] S1: For industrial-grade hydrochloric acid with a mass concentration of 30%, through rectification separation, gaseous hydrogen chloride is generated. The gaseous hydrogen chloride enters and passes through an activated carbon adsorption tower, an acid-resistant molecular sieve adsorption tower, and a zirconia adsorption tower in sequence. The adsorbed gaseous hydrogen chloride enters a temporary storage tank containing high-purity water;

[0093] S2: The hydrogen chloride entering the temporary storage tank is formulated into hydrochloric acid with a mass concentration of 32% and enters a rectification tower for rectification. The rectified gaseous hydrogen chloride enters a formulation tank;

[0094] S3: The gaseous hydrogen chloride entering the formulation tank is formulated into hydrochloric acid with a mass concentration of 37% and enters a finished product tank. The hydrochloric acid in the finished product tank is obtained as electronic-grade hydrochloric acid through multi-stage filtration.

[0095] The adsorption temperature in S1 is 35 °C, and the adsorption time is 60 min.

[0096] The rectification temperature in S2 is 120 °C.

[0097] The acid-resistant molecular sieve adsorption tower uses a modified Y-type molecular sieve, and its preparation method is as follows:

[0098] A1: Mix 5 g of Γ-glycidoxypropyltrimethoxysilane, 150 g of Y-type molecular sieve, and 1300 g of solvent under stirring at room temperature;

[0099] A2: Add 18 g of aminotrimethylene phosphonic acid and 0.03 g of bis-(2-methylallyl)cyclooct-1,5-diene ruthenium; adjust the pH to 9 with triethylamine, react, filter, wash with water until neutral, and dry to obtain the modified Y-type molecular sieve.

[0100] The solvent in A1 is DMF.

[0101] The stirring time in A1 is 120 min.

[0102] The reaction temperature of A2 is 90 °C and the reaction time is 48 hours.

[0103] The preparation method of zirconia particles in the zirconia adsorption tower is as follows:

[0104] Add 16 g of high-purity ZrCl4 into a reaction kettle, introduce 32 g of oxygen and 32 g of hydrogen, and heat and react to obtain zirconia particles.

[0105] The heating reaction temperature is 700 °C and the reaction time is 6 h.

[0106] The diameter of the zirconia particles is 10 microns, the specific surface area is 400 m 2 / g, and the porosity is 0.20 cm 3 / g.

[0107] Comparative Example 1

[0108] Do not modify the Y-type molecular sieve, and the others are the same as in Example 1.

[0109] Comparative Example 2

[0110] Do not add aminotrimethylene phosphonic acid, and the others are the same as in Example 1.

[0111] Comparative Example 3

[0112] Do not add bis-(2-methylallyl)cycloocta-1,5-diene ruthenium, and the others are the same as in Example 1.

[0113] Mg / µg / L Al / µg / L Zn / µg / L Ca / µg / L Mn / µg / L Fe / µg / L As / µg / L Example 1 0.007 0.007 0.007 0.009 0.008 0.009 0.006 Example 2 0.006 0.006 0.006 0.008 0.007 0.008 0.005 Example 3 0.006 0.005 0.005 0.007 0.006 0.007 0.003 Example 4 0.005 0.005 0.004 0.006 0.006 0.007 0.002 Comparative Example 1 0.29 0.28 0.27 0.30 0.32 0.31 0.26 Comparative Example 2 0.17 0.16 0.16 0.18 0.21 0.20 0.16 Comparative Example 3 0.15 0.14 0.15 0.16 0.19 0.17 0.14

[0114] Through the data analysis of the above examples and comparative examples, the electronic-grade hydrochloric acid prepared by the present invention has low impurity content and high arsenic element removal rate. The contents of metal impurity elements in the hydrochloric acid prepared in the above examples and comparative examples were obtained by testing with Agilent ICP-MS8900. The test working parameters are as follows: power 1.5 KW, gas pressure 0.7 Mpa, hydrogen 0.05 Mpa, helium 0.05 Mpa, carrier gas flow rate 0.75 L / min, compensation gas flow rate 0.41 L / min, sampling depth 8 mm, and ultrapure water is Millipore water. The tuning mode is conventional. After putting the injection pipeline into the tuning solution and stabilizing for 15S, the signal value cps of the mass number 7Li element is greater than 4000. The test method is the standard addition method.

[0115] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments of equivalent changes within the scope of the technical solution of the present invention by using the technical content disclosed above. However, as long as it does not depart from the content of the technical solution of the present invention, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for removing arsenic from electronic grade hydrochloric acid, the operating steps of which are: S1: Industrial-grade hydrochloric acid with a mass concentration of 25-30% is separated by distillation to produce gaseous hydrogen chloride, which passes through an activated carbon adsorption tower, an acid-resistant molecular sieve adsorption tower, and a zirconium oxide adsorption tower in sequence. The adsorbed gaseous hydrogen chloride enters a temporary storage tank containing high-purity water; S2: The hydrogen chloride entering the temporary storage tank is adjusted to hydrochloric acid with a mass concentration of 28-32% and enters the distillation tower for distillation. The gaseous hydrogen chloride after distillation enters the adjustment tank; S3: The gaseous hydrogen chloride entering the preparation tank is prepared into hydrochloric acid with a mass concentration of 36-37% and enters the finished product tank. The hydrochloric acid in the finished product tank is filtered through multiple stages to obtain electronic grade hydrochloric acid; The acid-resistant molecular sieve adsorption tower adopts a modified Y-type molecular sieve, and its preparation method is as follows: A1: 2-5 parts of Γ-glycidoxypropyltrimethoxysilane, 100-150 parts of Y-type molecular sieves, and 1000-1300 parts of solvents are stirred and mixed at room temperature; A2: add 9-18 parts of aminotri(methylene)phosphoric acid and 0.003-0.03 parts of bis-(2-methylallyl)cyclooctane-1,5-dieneruthenium; The pH value is adjusted to 9 with triethylamine, reacted, filtered, washed with water until neutral, and dried to obtain a modified Y-type molecular sieve.

2. A method for removing arsenic from electronic grade hydrochloric acid according to claim 1, characterized in that: The adsorption temperature of S1 is 25-35°C, and the adsorption time is 10-60min.

3. The method for removing arsenic from electronic grade hydrochloric acid according to claim 1, characterized in that: The distillation temperature of S2 is 105-120°C.

4. The method for removing arsenic from electronic grade hydrochloric acid according to claim 1, characterized in that: The solvent of A1 is DMF.

5. The method for removing arsenic from electronic grade hydrochloric acid according to claim 1, characterized in that: The stirring time of A1 is 90-120 min.

6. The method for removing arsenic from electronic grade hydrochloric acid according to claim 1, characterized in that: The reaction temperature of A2 is 80-90°C, and the reaction time is 24-48 hours.

7. The method for removing arsenic from electronic grade hydrochloric acid according to claim 1, characterized in that: The preparation method of the zirconium oxide particles in the zirconium oxide adsorption tower is as follows: 10-16 parts of high-purity ZrCl4 are added into a reaction kettle, and 10-32 parts of oxygen and 10-32 parts of hydrogen are introduced and heated for reaction to obtain zirconium oxide particles.

8. The method for removing arsenic from electronic grade hydrochloric acid according to claim 7, characterized in that: The heating reaction temperature is 300-700°C, and the reaction time is 2-6h.

9. The method for removing arsenic from electronic grade hydrochloric acid according to claim 7, characterized in that: The diameter of the zirconium oxide particles is 6-10 microns, the specific surface area is 320-400m2 / g, and the porosity is 0.12-0.20cm3 / g.