CN113134336A - Method for removing arsenic and free chlorine in hydrochloric acid - Google Patents
Method for removing arsenic and free chlorine in hydrochloric acid Download PDFInfo
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- CN113134336A CN113134336A CN202110410696.5A CN202110410696A CN113134336A CN 113134336 A CN113134336 A CN 113134336A CN 202110410696 A CN202110410696 A CN 202110410696A CN 113134336 A CN113134336 A CN 113134336A
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- B01J20/26—Synthetic macromolecular compounds
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Abstract
The invention belongs to the field of chemical engineering, and particularly relates to a method for removing arsenic and free chlorine in hydrochloric acid; the invention adopts the principle that divalent tin salt is added into hydrochloric acid to react with impurities, and can simultaneously remove trivalent arsenide AsCl in the hydrochloric acid3And free chlorine to produce hydrochloric acid and high chlorineStannoic acid of boiling point; the invention uses low boiling point AsCl3Converting into As simple substance, converting free chlorine into stable stannic acid with high boiling point, and removing As and stannic acid by rectification to simultaneously remove trivalent arsenide AsCl in hydrochloric acid3And free chlorine. The invention can prevent arsenic element and metal ions from entering the products of the fraction along with small liquid drops in the distillation steam in the distillation process, and ensures that the products are not polluted by the metal ions. The method is an efficient impurity removal method for simultaneously removing two impurities in hydrochloric acid, the principle of the method is simple, the equipment requirement is not high, the content of single metal ions of the prepared product is below 1 mu g/L, and the high-purity hydrochloric acid meets the electronic grade requirement.
Description
Technical Field
The invention belongs to the field of chemical engineering, and particularly relates to a method for removing arsenic and free chlorine in hydrochloric acid.
Background
The ultra-pure reagent is one of essential key chemical raw materials in micro-machining manufacturing in the electronic field, and is mainly used for cleaning and etching chips. The ultra-high pure hydrochloric acid is a strong acid cleaning agent and is usually matched with nitric acid and hydrogen peroxide for use.
CN109678112A discloses a production process of high-purity hydrochloric acid, which comprises the steps of burning chlorine and hydrogen on a combustion table of a synthesis furnace to generate white hydrogen chloride gas, and absorbing the hydrogen chloride gas by water in a cooling tower to generate hydrochloric acid with the concentration of 31%; sodium sulfite solution is dripped from the top of the hydrochloric acid storage tank through a dripping tank and fully reacts with free chlorine; the treated hydrochloric acid solution enters a resin tower, and after the tower is filled with the acid solution, redundant iron is removed through adsorption, so that the high-purity hydrochloric acid meeting the production requirement is prepared. The process can effectively reduce the content of free chlorine and iron in the hydrochloric acid, so that the prepared high-purity hydrochloric acid meets the requirements of process conditions for preparing alkali by a membrane method, the service life of a subsequent reaction device is prolonged, the economic benefit of a company is increased, and the advantages are obvious.
CN203048587U discloses a high-purity hydrochloric acid apparatus for producing, including the one-level falling film absorber, hydrogen pipe and oxidation tube lead to the bottom of two unification hybrid furnaces respectively, the top of two unification hybrid furnaces passes through the pipeline and communicates with the one-level falling film absorber, the one-level falling film absorber loops through the pipe connection with second grade falling film absorber and tail gas absorption tower, be provided with the circulating pipe who communicates with the one-level falling film absorber in the lower part of one-level falling film absorber, the bottom of one-level falling film absorber passes through the pipeline and communicates with high-purity hydrochloric acid intermediate tank, still be connected with freezing water pipe on circulating pipe, still be connected with the bypass pipe on the pipeline between one-level falling film absorber and high-purity hydrochloric acid intermediate tank, high-concentration hydrochloric acid intermediate tank passes through bypass pipe and communicates with the one-level falling film absorber. The utility model discloses a production device to traditional high-purity hydrochloric acid improves, makes the production device of producing high-purity hydrochloric acid can produce two products of high-purity hydrochloric acid and high concentration hydrochloric acid.
CN202785640U discloses a purification device of ultra-high purity hydrochloric acid, including preheater and the elevated tank that is linked together with the storage tank, the preheater includes inner tube and the outer tube of cover setting around the inner tube, the discharge gate of elevated tank is connected with the feed inlet of outer tube, the discharge gate of outer tube is linked together with the stills, the bottom of stills is provided with the discharge gate of high boiling point thing, communicating packed column and retort are set gradually in the upper portion of stills, the discharge gate at retort top is connected with the feed inlet of inner tube, the discharge gate of inner tube is connected with the condenser, the discharge gate of condenser is connected with the feed inlet of blending tank, the discharge gate of blending tank is connected with the finished product jar, the feed inlet of blending tank sets up the low end at the blending tank, the discharge gate height of blending tank is greater than the feed inlet height of blending tank. The device not only reduces the occupied space, but also has stable and reliable product quality.
Arsenic element in hydrochloric acid is trivalent AsCl3And trivalent H3AsO3However, AsCl3And the boiling point of the solution is relatively close to that of 28-32% hydrochloric acid solution, and trivalent arsenic ions are difficult to remove by a common rectification method. In addition, the prior art methods for removing free chlorine in hydrochloric acid adopt activated carbon, exchange resin, molecular sieve and the like, and the methods have the defect of insufficient removal of free chlorine.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for removing arsenic and free chlorine from hydrochloric acid.
A method for removing arsenic and free chlorine in hydrochloric acid comprises the following specific scheme:
1) adding 1000-1500 parts by mass of industrial-grade hydrochloric acid into a reaction kettle, slowly dripping 5-20 parts by mass of a divalent tin salt solution with the mass percent content of 4% -10% into the reaction kettle, controlling the temperature to be 40-60 ℃, controlling the addition to be completed within 30-60min, and stirring and mixing for 20-40min to obtain raw material hydrochloric acid;
2) placing raw material hydrochloric acid into a distillation kettle, slowly heating, controlling the temperature to be 80-120 ℃ for distillation, simultaneously starting cooling water, and collecting fractions to obtain electronic grade hydrochloric acid; it is characterized in that a hydrochloric acid steam filter membrane is arranged at a steam outlet of the distillation kettle.
The hydrochloric acid steam filter membrane is a metal ion adsorption filter membrane, and the preparation method comprises the following steps:
pouring 10-25 parts of polysulfone resin, 1-5 parts of benzophenone, 1-5 parts of additive, 60-80 parts of solvent and 0.5-5 parts of pore-forming agent into a preparation kettle according to the mass parts, heating to 50-80 ℃, stirring for 60-120min, and dispersing for 30-60min by using ultrasonic waves to obtain spinning solution; then spinning to obtain a hollow fiber membrane; then vertically irradiating the hollow fiber membrane by using an electron beam with the energy of 5-10MeV and the irradiation dose of 800-1500kGy, immersing the hollow fiber membrane in a sodium iminodiacetate solution with the mass percent of 1-8% after irradiation treatment, adding 1-4 parts of 2- (propyl-2-alkenoylamino) acetic acid, 0.1-0.5 part of vinylpyridine, 0.1-0.5 part of 3- (2-carboxyvinyl) phenylboronic acid and 2-4 parts of benzoyl peroxide, controlling the temperature for 20-60min, keeping for 25-75min for grafting modification, washing the fiber membrane with clear water after the grafting modification is finished, then soaking the membrane in 10-40% glycerol water solution for 24-72h, taking out the membrane, washing with pure water, and drying to obtain the metal ion adsorption filter membrane.
Benzophenone abstracts hydrogen on polysulfone chain to generate polysulfone chain free radical, then carries out free radical copolymerization with 2- (propyl-2-alkenoylamino) acetic acid, vinylpyridine and 3- (2-carboxyvinyl) phenylboronic acid,
the additive is mesoporous silicon dioxide or bentonite or activated clay.
The solvent is N-methyl pyrrolidone or dimethyl sulfoxide.
The pore-foaming agent is polyethylene glycol 1000 or povidone K30.
The content of the industrial grade hydrochloric acid is 28-32% by mass.
The stannous salt is stannous chloride or stannous sulfate.
The reaction kettle and the distillation kettle are graphite reaction kettles.
The invention adopts the principle that divalent tin salt is added into hydrochloric acid to react with impurities, and can simultaneously remove trivalent arsenide AsCl in the hydrochloric acid3And free chlorine, and the impurity removal principle is as follows:
2AsCl3+3SnCl2=2As+3SnCl4
Cl2+ SnCl2=SnCl4
the stannic chloride generated by the reaction is easy to be fully hydrolyzed in hydrochloric acid solution to generate hydrochloric acid and stannic acid (SnO2.2H2O) with high boiling point; the invention uses low boiling point AsCl3Converting into As simple substance, converting free chlorine into stable stannic acid with high boiling point, and removing As and stannic acid by rectification to simultaneously remove trivalent arsenide AsCl in hydrochloric acid3And free chlorine.
The hydrochloric acid steam filter membrane is arranged at the steam outlet of the distillation kettle, and is a metal ion adsorption filter membrane, so that arsenic elements and metal ions can be prevented from entering a distillate product along with small drops in distillation steam in the distillation process, and the product is prevented from being polluted by the metal ions. The method is an efficient impurity removal method for simultaneously removing two impurities in hydrochloric acid, the principle of the method is simple, the equipment requirement is not high, and the prepared high-purity hydrochloric acid has the metal ion content below 1 mu g/L and meets the electronic grade requirement.
Detailed Description
The invention is further illustrated by the following specific examples:
the contents of arsenic salt and metal ions (mainly tin) in the hydrochloric acid before and after treatment were measured by an atomic absorption spectrophotometer method. The measurement of free chlorine was carried out according to the method of "accurate measurement of free chlorine content in high-purity hydrochloric acid" in Majinxiang et al.
Example 1
A method for removing arsenic and free chlorine in hydrochloric acid comprises the following specific scheme:
1) adding 1000kg of industrial grade hydrochloric acid into a reaction kettle, slowly dripping 5kg of divalent tin salt solution with the mass percentage content of 4% into the reaction kettle, controlling the temperature to be 40 ℃, controlling the adding to be finished within 30min, and then stirring and mixing for 20min to obtain raw material hydrochloric acid;
2) putting raw material hydrochloric acid into a distillation kettle, slowly heating, controlling the temperature to be 80 ℃ for distillation, simultaneously starting cooling water, and collecting fractions to obtain electronic grade hydrochloric acid; it is characterized in that a hydrochloric acid steam filter membrane is arranged at a steam outlet of the distillation kettle.
The hydrochloric acid steam filter membrane is a metal ion adsorption filter membrane, and the preparation method comprises the following steps:
pouring 10kg of polysulfone resin, 1kg of benzophenone, 1kg of additive, 60kg of solvent and 0.5kg of pore-forming agent into a preparation kettle, heating to 50 ℃, stirring for 60min, and dispersing for 30min by using ultrasonic waves to obtain spinning solution; then spinning to obtain a hollow fiber membrane; then vertically irradiating the hollow fiber membrane by using an electron beam with energy of 5-MeV and irradiation dose of 800kGy, immersing the hollow fiber membrane in a sodium iminodiacetate solution with the mass percent of 1% after irradiation treatment, adding 1kg of 2- (propyl-2-enamino) acetic acid, 0.1kg of vinylpyridine, 0.1kg of 3- (2-carboxyvinyl) phenylboronic acid and 2kg of benzoyl peroxide, controlling the temperature for 20min, keeping for 25min for grafting modification, washing the fiber membrane by using clear water after the grafting modification is completed, then soaking the fiber membrane in a glycerol aqueous solution with the mass percent of 10% for 24h, taking out the fiber membrane, washing the fiber membrane by using pure water, and drying the washed fiber membrane to obtain the metal ion adsorption filter membrane.
The additive is mesoporous silicon dioxide or bentonite or activated clay.
The solvent is N-methyl pyrrolidone or dimethyl sulfoxide.
The pore-foaming agent is polyethylene glycol 1000 or povidone K30.
The industrial grade hydrochloric acid accounts for 28 percent by mass.
The stannous salt is stannous chloride or stannous sulfate.
The reaction kettle and the distillation kettle are graphite reaction kettles.
Example 2
A method for removing arsenic and free chlorine in hydrochloric acid comprises the following specific scheme:
1) adding 1200kg of industrial grade hydrochloric acid into a reaction kettle, slowly dripping 12kg of bivalent tin salt solution with the mass percentage content of 8% into the reaction kettle, controlling the temperature to be 50 ℃, controlling the adding to be finished within 40min, and then stirring and mixing for 30min to obtain raw material hydrochloric acid;
2) putting raw material hydrochloric acid into a distillation kettle, slowly heating, controlling the temperature to be 100 ℃ for distillation, simultaneously starting cooling water, and collecting fractions to obtain electronic grade hydrochloric acid; it is characterized in that a hydrochloric acid steam filter membrane is arranged at a steam outlet of the distillation kettle.
The hydrochloric acid steam filter membrane is a metal ion adsorption filter membrane, and the preparation method comprises the following steps:
pouring 17kg of polysulfone resin, 3kg of benzophenone, 3kg of additive, 67kg of solvent and 3kg of pore-forming agent into a preparation kettle, heating to 70 ℃, stirring for 90min, and dispersing for 50min by using ultrasonic waves to obtain spinning solution; then spinning to obtain a hollow fiber membrane; then vertically irradiating the hollow fiber membrane by using an electron beam with energy of 7MeV and irradiation dose of 900kGy, immersing the hollow fiber membrane in a sodium iminodiacetate solution with the mass percent of 5 percent after irradiation treatment, adding 2kg of 2- (propyl-2-enamino) acetic acid, 0.3kg of vinylpyridine, 0.3kg of 3- (2-carboxyvinyl) phenylboronic acid and 3kg of benzoyl peroxide, controlling the temperature for 40min, keeping for 65min for grafting modification, washing the fiber membrane by using clear water after the grafting modification is completed, then soaking the fiber membrane in a glycerol aqueous solution with the mass percent of 30 percent for 62h, taking out the fiber membrane, washing the fiber membrane by using pure water, and drying the washed fiber membrane to obtain the metal ion adsorption filter membrane.
The additive is mesoporous silicon dioxide.
The solvent is N-methyl pyrrolidone.
The pore-foaming agent is polyethylene glycol 1000.
The industrial grade hydrochloric acid accounts for 30 percent by mass.
The stannous salt is stannous chloride.
The reaction kettle and the distillation kettle are graphite reaction kettles.
Example 3
A method for removing arsenic and free chlorine in hydrochloric acid comprises the following specific scheme:
1) adding 1200kg of industrial grade hydrochloric acid into a reaction kettle, slowly dripping 12kg of bivalent tin salt solution with the mass percentage content of 8% into the reaction kettle, controlling the temperature to be 50 ℃, controlling the adding to be finished within 40min, and then stirring and mixing for 30min to obtain raw material hydrochloric acid;
2) putting raw material hydrochloric acid into a distillation kettle, slowly heating, controlling the temperature to be 100 ℃ for distillation, simultaneously starting cooling water, and collecting fractions to obtain electronic grade hydrochloric acid; it is characterized in that a hydrochloric acid steam filter membrane is arranged at a steam outlet of the distillation kettle.
The hydrochloric acid steam filter membrane is a metal ion adsorption filter membrane, and the preparation method comprises the following steps:
pouring 25kg of polysulfone resin, 5kg of benzophenone, 5kg of additive, 80kg of solvent and 5kg of pore-forming agent into a preparation kettle, heating to 80 ℃, stirring for 120min, and dispersing for 60min by using ultrasonic waves to obtain spinning solution; then spinning to obtain a hollow fiber membrane; then vertically irradiating the hollow fiber membrane by using an electron beam with the energy of 10MeV and the irradiation dose of 1500kGy, immersing the hollow fiber membrane in 8 mass percent of sodium iminodiacetate solution after irradiation treatment, adding 4kg of 2- (propyl-2-enamino) acetic acid, 0.5kg of vinylpyridine, 0.5kg of 3- (2-carboxyvinyl) phenylboronic acid and 4kg of benzoyl peroxide, controlling the temperature for 60min, keeping for 75min for grafting modification, washing the fiber membrane by using clear water after the grafting modification is finished, then soaking the fiber membrane in 40 mass percent of glycerol aqueous solution for 72h, taking out the fiber membrane, washing the fiber membrane by using pure water, and drying the fiber membrane to obtain the metal ion adsorption filter membrane.
The additive is bentonite.
The solvent is dimethyl sulfoxide.
The pore-foaming agent is povidone K30.
The industrial grade hydrochloric acid accounts for 32 percent by mass.
The stannous salt is stannous sulfate.
The reaction kettle and the distillation kettle are graphite reaction kettles.
The quality test results of the hydrochloric acid prepared in the above examples are shown in the following table:
| free chlorine (mg/L) | Arsenic salt (mu g/L) | Content of individual Metal ions (μ g/L) | |
| Before treatment | 8.15 | 16.2 | 17.6 |
| Example 1 | 0.27 | 0.20 | 0.23 |
| Example 2 | 0.24 | 0.27 | 0.17 |
| Example 3 | 0.19 | 0.27 | 0.20 |
Comparative example 1
A method for removing arsenic and free chlorine in hydrochloric acid comprises the following specific scheme:
1) adding 1000kg of industrial grade hydrochloric acid into a reaction kettle, slowly dripping 5kg of divalent tin salt solution with the mass percentage content of 4% into the reaction kettle, controlling the temperature to be 40 ℃, controlling the adding to be finished within 30min, and then stirring and mixing for 20min to obtain raw material hydrochloric acid;
2) putting the raw material hydrochloric acid into a distillation kettle, slowly heating, controlling the temperature to be 80 ℃ for distillation, simultaneously starting cooling water, and collecting fractions to obtain the electronic grade hydrochloric acid.
The industrial grade hydrochloric acid accounts for 28 percent by mass.
The stannous salt is stannous chloride or stannous sulfate.
The reaction kettle and the distillation kettle are graphite reaction kettles.
Comparative example 2
A method for removing arsenic and free chlorine in hydrochloric acid comprises the following specific scheme:
1) adding 1000kg of industrial grade hydrochloric acid into a reaction kettle, slowly dripping 5kg of divalent tin salt solution with the mass percentage content of 4% into the reaction kettle, controlling the temperature to be 40 ℃, controlling the adding to be finished within 30min, and then stirring and mixing for 20min to obtain raw material hydrochloric acid;
2) putting raw material hydrochloric acid into a distillation kettle, slowly heating, controlling the temperature to be 80 ℃ for distillation, simultaneously starting cooling water, and collecting fractions to obtain electronic grade hydrochloric acid; it is characterized in that a hydrochloric acid steam filter membrane is arranged at a steam outlet of the distillation kettle.
The hydrochloric acid steam filter membrane is a metal ion adsorption filter membrane, and the preparation method comprises the following steps:
pouring 10kg of polysulfone resin, 1kg of benzophenone, 1kg of additive, 60kg of solvent and 0.5kg of pore-foaming agent into a preparation kettle, heating to 50 ℃, stirring for 60min, and dispersing for 30min by using ultrasonic waves to obtain spinning solution; then spinning to obtain a hollow fiber membrane; and vertically irradiating the hollow fiber membrane by using an electron beam with the energy of 5MeV and the irradiation dose of 800kGy, immersing the hollow fiber membrane in a glycerol aqueous solution with the mass percentage of 10% for 24 hours after irradiation treatment, taking out the hollow fiber membrane, washing the hollow fiber membrane by using pure water, and drying the hollow fiber membrane to obtain the metal ion adsorption filter membrane.
The additive is mesoporous silicon dioxide or bentonite or activated clay.
The solvent is N-methyl pyrrolidone or dimethyl sulfoxide.
The pore-foaming agent is polyethylene glycol 1000 or povidone K30.
The industrial grade hydrochloric acid accounts for 28 percent by mass.
The stannous salt is stannous chloride or stannous sulfate.
The reaction kettle and the distillation kettle are graphite reaction kettles.
Comparative example 3
A method for removing arsenic and free chlorine in hydrochloric acid comprises the following specific scheme:
1) adding 1000kg of industrial grade hydrochloric acid into a reaction kettle, slowly dripping 5kg of divalent tin salt solution with the mass percentage content of 4% into the reaction kettle, controlling the temperature to be 40 ℃, controlling the adding to be finished within 30min, and then stirring and mixing for 20min to obtain raw material hydrochloric acid;
2) putting raw material hydrochloric acid into a distillation kettle, slowly heating, controlling the temperature to be 80 ℃ for distillation, simultaneously starting cooling water, and collecting fractions to obtain electronic grade hydrochloric acid; it is characterized in that a hydrochloric acid steam filter membrane is arranged at a steam outlet of the distillation kettle.
The hydrochloric acid steam filter membrane is a metal ion adsorption filter membrane, and the preparation method comprises the following steps:
pouring 10kg of polysulfone resin, 1kg of benzophenone, 1kg of additive, 60kg of solvent and 0.5kg of pore-forming agent into a preparation kettle, heating to 50 ℃, stirring for 60min, and dispersing for 30min by using ultrasonic waves to obtain spinning solution; then spinning to obtain a hollow fiber membrane; then vertically irradiating the hollow fiber membrane by using an electron beam with energy of 5-MeV and irradiation dose of 800kGy, immersing the hollow fiber membrane in a sodium iminodiacetate solution with the mass percent of 1% after irradiation treatment, adding 0.1kg of vinylpyridine, 0.1kg of 3- (2-carboxyvinyl) phenylboronic acid and 2kg of benzoyl peroxide, controlling the temperature for 20min, keeping for 25min for grafting modification, washing the fiber membrane by using clear water after the grafting modification is finished, then soaking in a glycerol aqueous solution with the mass percent of 10% for 24h, taking out, washing by using pure water, and drying to obtain the metal ion adsorption filter membrane.
The additive is mesoporous silicon dioxide or bentonite or activated clay.
The solvent is N-methyl pyrrolidone or dimethyl sulfoxide.
The pore-foaming agent is polyethylene glycol 1000 or povidone K30.
The industrial grade hydrochloric acid accounts for 28 percent by mass.
The stannous salt is stannous chloride or stannous sulfate.
The reaction kettle and the distillation kettle are graphite reaction kettles.
The quality test results of the hydrochloric acid prepared in the above examples are shown in the following table:
comparative example 4
A method for removing arsenic and free chlorine in hydrochloric acid comprises the following specific scheme:
1) adding 1000kg of industrial grade hydrochloric acid into a reaction kettle, slowly dripping 5kg of divalent tin salt solution with the mass percentage content of 4% into the reaction kettle, controlling the temperature to be 40 ℃, controlling the adding to be finished within 30min, and then stirring and mixing for 20min to obtain raw material hydrochloric acid;
2) putting raw material hydrochloric acid into a distillation kettle, slowly heating, controlling the temperature to be 80 ℃ for distillation, simultaneously starting cooling water, and collecting fractions to obtain electronic grade hydrochloric acid; it is characterized in that a hydrochloric acid steam filter membrane is arranged at a steam outlet of the distillation kettle.
The hydrochloric acid steam filter membrane is a metal ion adsorption filter membrane, and the preparation method comprises the following steps:
pouring 10kg of polysulfone resin, 1kg of benzophenone, 1kg of additive, 60kg of solvent and 0.5kg of pore-forming agent into a preparation kettle, heating to 50 ℃, stirring for 60min, and dispersing for 30min by using ultrasonic waves to obtain spinning solution; then spinning to obtain a hollow fiber membrane; then vertically irradiating the hollow fiber membrane by using an electron beam with energy of 5-MeV and irradiation dose of 800kGy, immersing the hollow fiber membrane in a sodium iminodiacetate solution with the mass percent of 1% after irradiation treatment, adding 1kg of 2- (propyl-2-enamino) acetic acid, 0.1kg of vinylpyridine and 2kg of benzoyl peroxide, controlling the temperature for 20min, keeping for 25min for grafting modification, washing the fiber membrane by using clear water after the grafting modification is finished, then soaking in a glycerol aqueous solution with the mass percent of 10% for 24h, taking out, washing by using pure water, and drying to obtain the metal ion adsorption filter membrane.
The additive is mesoporous silicon dioxide or bentonite or activated clay.
The solvent is N-methyl pyrrolidone or dimethyl sulfoxide.
The pore-foaming agent is polyethylene glycol 1000 or povidone K30.
The industrial grade hydrochloric acid accounts for 28 percent by mass.
The stannous salt is stannous chloride or stannous sulfate.
The reaction kettle and the distillation kettle are graphite reaction kettles. A
| Free chlorine (mg/L) | Arsenic salt (mu g/L) | Content of individual Metal ions (μ g/L) | |
| Comparative example 1 | 0.8 | 0.51 | 0.67 |
| Comparative example 2 | 0.9 | 0.29 | 0.38 |
| Comparative example 3 | 0.7 | 0.13 | 0.19 |
| Comparative example 3 | 0.7 | 0.15 | 0.27 |
Claims (8)
1. A method for removing arsenic and free chlorine in hydrochloric acid comprises the following specific scheme:
1) adding 1000-1500 parts by mass of industrial-grade hydrochloric acid into a reaction kettle, slowly dripping 5-20 parts by mass of 4-10% divalent tin salt solution into the reaction kettle, controlling the temperature to be 40-60 ℃, controlling the addition to be completed within 30-60min, and stirring and mixing for 20-40min to obtain raw material hydrochloric acid;
2) placing raw material hydrochloric acid into a distillation kettle, slowly heating, controlling the temperature to be 80-120 ℃ for distillation, simultaneously starting cooling water, and collecting fractions to obtain electronic grade hydrochloric acid; it is characterized in that a hydrochloric acid steam filter membrane is arranged at a steam outlet of the distillation kettle.
2. The method for removing arsenic and free chlorine from hydrochloric acid as claimed in claim 1, wherein: the hydrochloric acid steam filter membrane is a metal ion adsorption filter membrane, and the preparation method comprises the following steps:
pouring 10-25 parts of polysulfone resin, 1-5 parts of benzophenone, 1-5 parts of additive, 60-80 parts of solvent and 0.5-5 parts of pore-forming agent into a preparation kettle according to the mass parts, heating to 50-80 ℃, stirring for 60-120min, and dispersing for 30-60min by using ultrasonic waves to obtain spinning solution; then spinning to obtain a hollow fiber membrane; then vertically irradiating the hollow fiber membrane by using an electron beam with the energy of 5-10MeV and the irradiation dose of 800-1500kGy, immersing the hollow fiber membrane in a sodium iminodiacetate solution with the mass percent of 1-8% after irradiation treatment, adding 1-4 parts of 2- (propyl-2-alkenoylamino) acetic acid, 0.1-0.5 part of vinylpyridine, 0.1-0.5 part of 3- (2-carboxyvinyl) phenylboronic acid and 2-4 parts of benzoyl peroxide, controlling the temperature for 20-60min, keeping for 25-75min for grafting modification, washing the fiber membrane with clear water after the grafting modification is finished, then soaking the membrane in 10-40% glycerol water solution for 24-72h, taking out the membrane, washing with pure water, and drying to obtain the metal ion adsorption filter membrane.
3. The method for removing arsenic and free chlorine from hydrochloric acid as claimed in claim 2, wherein: the additive is mesoporous silicon dioxide or bentonite or activated clay.
4. The method for removing arsenic and free chlorine from hydrochloric acid as claimed in claim 2, wherein: the solvent is N-methyl pyrrolidone or dimethyl sulfoxide.
5. The method for removing arsenic and free chlorine from hydrochloric acid as claimed in claim 2, wherein: the pore-foaming agent is polyethylene glycol 1000 or povidone K30.
6. The method for removing arsenic and free chlorine from hydrochloric acid as claimed in claim 1, wherein: the content of the industrial grade hydrochloric acid is 28-32% by mass.
7. The method for removing arsenic and free chlorine from hydrochloric acid as claimed in claim 1, wherein: the stannous salt is stannous chloride or stannous sulfate.
8. The method for removing arsenic and free chlorine from hydrochloric acid as claimed in claim 1, wherein: the reaction kettle and the distillation kettle are graphite reaction kettles.
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