CN115367707A - Production method of ultra-pure electronic grade hydrogen chloride and electronic grade hydrochloric acid - Google Patents
Production method of ultra-pure electronic grade hydrogen chloride and electronic grade hydrochloric acid Download PDFInfo
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Abstract
The invention provides a method for producing ultra-pure electronic grade hydrogen chloride and electronic grade hydrochloric acid, which comprises the steps of filtering chlorine generated in the chlor-alkali industry at low temperature, circularly absorbing and drying concentrated sulfuric acid, and carrying out classified complexing adsorption to obtain high-purity chlorine, carrying out cryogenic filtration and multistage pressure swing adsorption on hydrogen generated in the chlor-alkali industry to obtain high-purity hydrogen, combusting the high-purity chlorine and the high-purity hydrogen in a synthesis tower to produce hydrogen chloride gas, feeding part of the synthesized hydrogen chloride into a rectifying tower for rectification and purification to obtain 9N electronic grade hydrogen chloride, carrying out cocurrent flow circulating absorption on the other part of the hydrogen chloride gas subjected to multistage condensation in an absorption tower to obtain an intermediate hydrochloric acid product, adding a free chlorine removal liquid into the intermediate product to remove free chlorine, heating the analysis tower to analyze the hydrogen chloride gas, carrying out defogging and filtering on the analyzed hydrogen chloride gas through a microporous membrane, thus obtaining the high-purity hydrogen chloride gas, and finally carrying out spray absorption in the synthesis tower to obtain the ultra-pure electronic grade hydrochloric acid with metal ions less than 10ppt.
Description
Technical Field
The invention belongs to the field of electronic chemicals, and particularly relates to a production method of ultra-pure electronic grade hydrogen chloride and electronic grade hydrochloric acid.
Background
The electronic grade hydrochloric acid is also called ultra-pure hydrochloric acid, belongs to ultra-pure high-purity reagents, is widely applied to the manufacturing industries of photovoltaics, panels and large-scale integrated circuits, is mainly used for high-temperature gas phase etching of silicon and gallium arsenide before epitaxial growth, sodium ion cleaning, surface chemical treatment of metals and the like, and is one of important reagents in the electronic industry.
Electronic chemicals in China are started late, the development of process research and industrial application of electronic-grade hydrochloric acid is slow, electronic-grade sulfuric acid produced in China is mainly a low-end product and can only meet the requirements of manufacturing procedures in the fields of photovoltaics, panels and the like, and electronic-grade hydrochloric acid for the semiconductor field is mainly imported, so that the development of key technology for producing high-end electronic-grade hydrochloric acid to realize localization is a necessary trend of development.
The industrial preparation of hydrochloric acid is usually carried out using Cl 2 At H 2 The HCl is generated by middle combustion and is dissolved in high-purity water to produce ultra-clean high-purity hydrochloric acid, and the HCl contains Fe 3+ And appears yellow. In recent years, the production of hydrochloric acid, cl, from hydrogen chloride, a by-product of the production of chlorinated organic compounds, has also been developed industrially 2 Reaction with ethylene to produce dichloroethane (CH) 3 CHCl 2 ) Then the ethyl Chloride (CH) is prepared by decomposition reaction 3 CH 2 Cl) and HCl. The preparation of the electronic grade hydrochloric acid comes from the purification of industrial HCl, and the method can comprise rectification, sub-boiling distillation and other methods. Wherein the sub-boiling distillation process comprises the following steps: distillation, filtration and washing, absorption, sub-boiling distillation and the like. Wherein the distillation process utilizes the difference of boiling points to realize HCl and H 2 Separation of O to thereby remove H 2 And metal impurity ions in the O, removing solid impurities in the distilled HCl by filtering, and absorbing the washed HCl by ultrapure water to form high-purity hydrochloric acid. The sub-boiling distillation method is to heat the industrial hydrochloric acid to a temperature about 5 to 20 ℃ lower than the boiling point, and because the industrial hydrochloric acid does not reach the boiling point, the gas phase balanced with the liquid phase does not consist of a large amount of steam particles any more, but is balanced with the liquid phase in a molecular state, so metal ions and solid particles are rarely or not mixed in the steam, and the distillation method is practicalThe content of metal ions in the liquid after condensation and reflux is low. But the yield of the isothermal diffusion method and the sub-boiling method is small, and the obtained hydrochloric acid has high purity, but is suitable for preparing high-purity hydrochloric acid in a small amount by experiments, and has no industrial use value. The distillation method has large yield, but the purity of the obtained hydrochloric acid is not high and the concentration is not too high. The rectification method is the mainstream technology for purifying hydrochloric acid at present, and although the yield is large, the equipment is relatively complex.
An electronic grade hydrochloric acid production method disclosed in Chinese patent No. CN 109650340B is characterized in that industrial grade hydrochloric acid is used as a raw material, hydrochloric acid steam formed by heating through a reboiler enters a rectifying tower, a tower kettle of the rectifying tower is made of high borosilicate glass, the whole body of the rectifying tower is made of PVDF, before hydrochloric acid azeotrope is formed in the rectifying tower, gas-phase light components are obtained through repeated rectification, the gas-phase light components overflow from the top of the rectifying tower and enter an absorption tower made of PVDF through a pipeline made of PVDF, meanwhile, ultrapure water is used for absorbing the gas-phase light components to form a high-purity hydrochloric acid solution, the high-purity hydrochloric acid solution flows out from the bottom of the absorption tower and sequentially flows back into the absorption tower through an absorption tank and a circulating pump, and is repeatedly absorbed until the concentration of the high-purity hydrochloric acid solution in the absorption tank reaches more than 37%, and a high-purity electronic grade hydrochloric acid finished product is obtained. The production method takes industrial hydrochloric acid as a raw material, and the hydrochloric acid steam obtained by evaporation is rectified, so that the energy consumption is high, the yield is low, and the produced electronic grade hydrochloric acid cannot meet the requirement of a semiconductor on the demand of ultra-high-purity electronic grade hydrochloric acid, and is not suitable for industrial mass production. The Chinese patent with the patent number CN 113307228A discloses an electronic grade hydrochloric acid production method, which uses industrial hydrogen chloride as a raw material, adopts a reducing agent to remove free chlorine in hydrogen chloride gas, and obtains the electronic grade hydrochloric acid by condensing, demisting and circularly absorbing the dechlorinated hydrogen chloride gas with water. According to the production method, stannous chloride is used for removing free chlorine, gas is condensed, demisted and absorbed to obtain electronic-grade hydrochloric acid, stannous oxide impurities are introduced in the process, and the electronic-grade hydrochloric acid obtained by condensing, demisting and absorbing industrial hydrogen chloride gas cannot meet the requirement of the ultrahigh-purity electronic-grade hydrochloric acid for semiconductors.
The Chinese patent with the patent number CN 109761196A discloses an electronic grade hydrochloric acid production method, wherein activated carbon or resin is adopted to adsorb and remove chlorine, the concentration of Fe2+ ions in the activated carbon is more than 5ppm, and in addition, a graphite falling film absorption tower is adopted as an absorption tower, so that a large amount of impurities are brought in after absorption, the product purity is not high, and the ultrahigh-purity electronic grade hydrochloric acid for semiconductors cannot be met.
Disclosure of Invention
The invention aims to provide a method for preparing electronic grade hydrochloric acid for the semiconductor industry, which has the advantages of low production cost, simple and easily-controlled process and stable product quality, and breaks through the key technology of controlling the content of metal ion impurities in the production process of the electronic grade hydrochloric acid by using chlorine and hydrogen which are byproducts of the chlor-alkali industry as raw materials. The brief process flow of the invention is shown in the attached figure 1:
in order to achieve the purpose, the invention adopts the following method:
a production method of electronic grade hydrogen chloride and electronic grade hydrochloric acid comprises the following production steps:
(1) Filtering industrial chlorine gas by adopting a molecular sieve and filtering at low temperature to obtain pure chlorine gas;
(2) Carrying out deep cooling on industrial hydrogen at-75 to-90 ℃, and then filtering and adsorbing to obtain high-purity hydrogen;
(3) Introducing high-purity hydrogen sprayed in the vertical direction from the bottom of the synthesis tower into purified chlorine gas through a spray gun to generate hydrogen chloride gas in the synthesis tower, and cooling the jacket of the synthesis tower by adopting pure water;
(4) Cooling the hydrogen chloride gas produced by the synthesis tower to 40-50 ℃ after cooling and heat exchange, and circularly absorbing the cooled hydrogen chloride gas by hydrochloric acid mother liquor in a parallel flow manner in an absorption tower to obtain a hydrochloric acid intermediate product;
(5) The hydrochloric acid intermediate product is sent to an intermediate storage tank, and free chlorine is circularly removed by adding a free chlorine removing agent;
(6) The hydrochloric acid intermediate product without free chlorine enters an analytical tower, and the analyzed hydrogen chloride gas is filtered to obtain pure hydrogen chloride gas;
(7) Circularly absorbing the hydrogen chloride gas in an absorption tower, and continuously supplementing ultrapure water to the bottom of the absorption tower to obtain the electronic grade hydrochloric acid.
In the step (1), the purity of the industrial chlorine is 98.5-99.0%, and the liquid carrying amount is 0.07-0.09%;
the molecular sieve is a CaA, naX or SBA-15 molecular sieve, and is obtained by soaking the molecular sieve in an electronic grade hydrochloric acid solution for 0.5-10h and then drying, wherein the mass concentration of the hydrochloric acid solution is 20-36%; or the CaA, naX or SBA-15 molecular sieve is synthesized in an acid environment, the acid is hydrochloric acid, and the mass concentration of the hydrochloric acid is 20-36%.
The temperature in the filtering process is 0-20 ℃;
the water content of the pure chlorine is lower than 0.001%, and the metal ions are lower than 0.0002%.
The preparation method of the SBA-15 molecular sieve comprises the steps of adding a P123 template into an HCl solution with the mass concentration of 20-36%, and stirring at 45 ℃ until the P123 is completely dissolved to obtain a clear and transparent solution; then weighing tetraethyl silicate, adding the tetraethyl silicate into the solution, heating the oil bath to 55 ℃, stirring, standing and aging; transferring the obtained sample into a crystallization kettle with a polytetrafluoroethylene lining, and crystallizing for 20 hours at 110 ℃; and (3) carrying out suction filtration on the crystallized solid by using absolute ethyl alcohol and deionized water, washing, drying for 10 hours at 80 ℃ in a constant-temperature drying oven, and finally calcining for 4 hours at 500 ℃ to obtain the white powdery spherical SBA-15 mesoporous molecular sieve. The mass/volume ratio of the P123 template agent, the tetraethyl silicate and the 20-36% HCl solution is 1:2.5-5:1-5.
The method for soaking the SBA-15 molecular sieve in the hydrochloric acid solution comprises the following steps of taking 500g of the SBA-15 molecular sieve with the aperture of 6-13nm SSA 2 Soaking in electronic grade HCl solution with mass concentration of 20-36% for 5 hr, and drying at 80 deg.C.
The 5A molecular sieve is also called CaA molecular sieve, belonging to the pore canal cation of Ca 2+ The LTA type molecular sieve has the composition of 0.75 CaO.0.25 Na 2 O·A1 2 O 3 ·2SiO 2 ·4.5H 2 O, the method for soaking by hydrochloric acid solution is that the model is XFF2111113-61-4, 500g, the diameter: soaking 3-5mm in 20-36 wt% electronic grade HCl solution for 5 hr, and drying at 80 deg.C.
The NaX molecular sieve is prepared by mixing sodium aluminate and silica sol in a mass ratio of 1:12, adding a sodium hydroxide solution to adjust the pH value to 11, sealing and uniformly stirring, and aging for 2 days to obtain the NaX molecular sieve with the particle size of 20-40 nm. Then soaking the NaX molecular sieve in an electronic grade HCl solution with the mass concentration of 20-36% for 5 hours, and drying at 80 ℃.
In the step (2), the purity of the industrial hydrogen is 99.5 percent, and the liquid carrying amount is 0.07-0.09 percent;
the hydrogen filter group used for filtering is a 0.1-0.01 mu m filter pore membrane for multi-stage filtration;
or multi-stage gradient filtration is carried out by adopting a filter pore membrane with the diameter of 0.1-0.01 mu m;
the multistage pressure swing adsorption comprises a multistage pressure swing adsorption bed consisting of any one or more of activated carbon, 5A zeolite, nano-silica, metal Organic Frameworks (MOFs) and manganese oxide octahedral molecular sieve OMS-2, and the pressure swing adsorption is carried out within the pressure range of 0.5-9 atm.
The MOFs is a synthesis method of a metal-organic framework material which takes 4,6-di (1H-1,2,4-triazol-1-yl) isophthalic acid as a ligand and transition metal cobalt as a metal center. The chemical general formula is C24H12Co2N12O9, and the preparation method thereof is referred to 2021104022279.
Manganese oxide octahedral molecular sieve OMS-2 is in MPEG solution and KMnO 4 Adding maleic acid (KMnO) 4 The mass ratio of maleic acid to maleic acid is 4: 1) And aging for 10h after uniformly stirring, filtering the precipitate, washing with water, drying, and sintering at 300 ℃ for 1h to obtain the OMS-2 material.
In the preferred scheme, the multistage pressure swing adsorption comprises a three-stage pressure swing adsorption bed consisting of any one or more of activated carbon, 5A zeolite, nano-silica, metal Organic Frameworks (MOFs) and manganese oxide octahedral molecular sieve OMS-2, and the pressure swing adsorption is carried out within the pressure range of 0.5-9 atm.
For example, active, 5A zeolite and nano silicon dioxide carbon are sequentially adopted as three-stage pressure swing adsorption beds, and pressure swing adsorption is respectively carried out under 0.5atm, 7.5atm and 1.2 atm.
Or the metal organic frameworks MOFs, the metal organic frameworks MOFs and the metal organic frameworks MOFs are used as three-stage pressure swing adsorption beds, and the pressure swing adsorption beds are respectively carried out under 1.6atm, 5.5atm and 7.8 atm.
Or performing pressure swing adsorption on MOFs, manganese oxide octahedral molecular sieve OMS-2 and manganese oxide octahedral molecular sieve OMS-2 as three-stage pressure swing adsorption beds at 9.0atm, 4.3atm and 8.2atm, respectively.
The above pressure swing adsorption conditions achieve technical effects in a variety of ways, achieving hydrogen gas with water content below 0.0001% and metal ions below 0.00001%.
The spray gun in the step (3) is of a three-layer sleeve structure, circulating water is introduced to the outermost layer of the spray gun, hydrogen is introduced to the middle interlayer of the spray gun, and chlorine is introduced to the inner layer of the spray gun; by circulating water
The temperature is controlled to be 40-55 ℃. The middle interlayer is filled with hydrogen and the inner layer is filled with chlorine to converge in the horizontal direction. The synthetic tower is a two-in-one graphite synthetic tower.
The hydrogen chloride gas and the hydrochloric acid mother liquor cooled to 40-50 ℃ in the step (4) enter from the top of the absorption tower, are circularly absorbed in parallel flow in the absorption tower, and are added with ultrapure water through the bottom of the absorption tower to stabilize the concentration of the hydrochloric acid in the hydrochloric acid intermediate product to be 32-36%;
the hydrochloric acid mother liquor enters in a spraying mode, and the aperture of a spray head is less than 0.01mm in the spraying process;
the mass concentration of the hydrochloric acid mother liquor is 32-34%.
The components of the free chlorine remover in the step (5) comprise 1-25% of SEMI C12 grade electronic grade hydrogen peroxide, 5-25% of electronic grade hydrochloric acid with metal ions lower than 20ppt, and the balance of ultrapure water with the resistivity higher than 18.2M omega cm; the free chlorine removing agent is pumped in at the flow rate of 5ml/min-10 ml/min.
The low-temperature filtration temperature in the step (6) is-10 to 10 ℃, the size of a micropore in the filtration process of the microporous membrane is less than 0.05 mu m, and the aperture of the microporous membrane filtration membrane is preferably 3nm; the grade of hydrogen chloride gas after low-temperature filtration and microporous membrane filtration is more than 6N.
And (7) continuously supplementing ultrapure water from the bottom of the absorption tower in the circulating absorption process of the high-purity hydrogen chloride gas in the absorption tower to obtain the electronic grade hydrochloric acid with the mass concentration of 32-34% and the metal ions lower than 10ppt.
And performing circulating filtration on the obtained electronic-grade hydrochloric acid with the mass concentration of 32-34% and the metal ion content of less than 10ppt by adopting a PTFE (polytetrafluoroethylene) microporous adsorption film to obtain the electronic-grade hydrochloric acid with the metal ion content of less than 10ppt.
In the device, except for the hydrogen chloride synthesis tower, one or two of stainless steel lining PTFE, HDPE and PFA are adopted in other devices.
The invention adopts a one-step synthesis and two-step absorption method, firstly, chlorine and hydrogen are purified to more than 5N, then the chlorine and the hydrogen are combusted into hydrogen chloride gas, one part of the hydrogen chloride gas is rectified to obtain high-purity hydrogen chloride (9N), the other part of the hydrogen chloride gas is absorbed, analyzed, purified and absorbed to obtain SEMI C12 grade electronic grade hydrochloric acid, and metal ions are lower than 10ppt. The main innovation points are as follows:
by purifying the raw material gas, the purity of the synthesized hydrogen chloride is greatly improved, the water content in the synthesized hydrogen chloride is reduced, the corrosion of the synthesis gas to a synthesis tower is reduced, and the introduction of metal ions is reduced.
The design innovation of the hydrogen chloride synthetic tower is that hydrogen chloride is horizontally sprayed from a spray gun at the middle lower part of the synthetic tower, hydrogen is vertically sprayed upwards from the bottom of the tower, a hydrogen chloride spray gun adopts a three-layer sleeve structure, circulating water is led to the outermost layer of the spray gun, hydrogen is led to a middle interlayer, chlorine is led to the inner layer, and the chlorine is blown away and uniformly distributed by the hydrogen in the middle layer of the spray gun, so that the reaction degree of the chlorine and the hydrogen can be greatly improved, and on the other hand, the outer layer cooling water of the spray gun continuously cools the spray gun, so that the corrosion degree of the spray gun is reduced, and metal ions are brought in.
Molecular sieve and adsorbent
Adding SEMI C12 grade electronic grade hydrogen peroxide into the primary product electronic grade hydrochloric acid after primary absorption of hydrogen chloride to remove free chlorine in the electronic grade hydrochloric acid; the hydrogen peroxide in the electronic grade hydrochloric acid in slight excess is decomposed in the analysis and secondary absorption of the electronic grade hydrochloric acid, and no new impurity is introduced in the whole free chlorine removal process.
The concentration of metal ions in the electronic-grade hydrochloric acid is purified by adopting primary absorption, analysis, gas purification and absorption gradient, the concentration is finally within 10ppt, the granularity in the electronic-grade hydrochloric acid is removed by adopting a 10nm microporous membrane for filtration, and the product meets the SEMI C12 grade.
By process innovation, 9N-grade electronic grade hydrogen chloride gas and SEMI C12-grade electronic grade hydrochloric acid can be simultaneously prepared, and equipment investment and energy consumption are saved while high-quality products are guaranteed.
Drawings
FIG. 1 is a flow chart of the production process of electronic grade hydrogen chloride and electronic grade hydrochloric acid.
Detailed Description
In this example, chlorine gas having a purity of 98.5% and a liquid carrying amount of 0.09% and hydrogen gas having a purity of 98.5% and a liquid carrying amount of 0.08% were by-produced in the chlor-alkali industry as raw materials.
The tower filter is internally provided with three stages of PFA wire mesh cylindrical stacked layers with equivalent rate of 0.1 μm filter holes.
The filter group was a filter with a filter pore membrane disposed in three stages of 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, and 0.01 μm filters in this order, and gradient filtration was performed.
The spray gun is of a three-layer sleeve structure, circulating water is introduced to the outermost layer of the spray gun, hydrogen is introduced to the middle interlayer, and chlorine is introduced to the inner layer. The middle interlayer is filled with hydrogen and the inner layer is filled with chlorine to converge in the horizontal direction. The synthetic tower is a two-in-one graphite synthetic tower.
The aperture of the microporous membrane filter membrane is 3nm.
Example 1
A production method of electronic grade hydrogen chloride and electronic grade hydrochloric acid comprises the following production steps:
(1) Filtering industrial chlorine gas by an SBA-15 molecular sieve, cooling the industrial chlorine gas to 10 ℃ by a cooler, and then deeply filtering the industrial chlorine gas by a tower filter to obtain pure chlorine gas with the water content of less than 0.001% and the metal ions of less than 0.0002%;
the preparation method of the SBA-15 molecular sieve comprises the steps of adding a P123 template into an HCl solution with the mass concentration of 20-36%, and stirring at 45 ℃ until the P123 is completely dissolved to obtain a clear and transparent solution; then weighing tetraethyl silicate, adding the tetraethyl silicate into the solution, heating the oil bath to 55 ℃, stirring, standing and aging; transferring the obtained sample into a crystallization kettle with a polytetrafluoroethylene lining, and crystallizing for 20 hours at 110 ℃; and (3) carrying out suction filtration on the crystallized solid by using absolute ethyl alcohol and deionized water, washing, drying for 10 hours at 80 ℃ in a constant-temperature drying oven, and finally calcining for 4 hours at 500 ℃ to obtain the white powdery spherical SBA-15 mesoporous molecular sieve. The mass/volume ratio of the P123 template agent, the tetraethyl silicate and the 20-36% HCl solution is 1:3:4.
(2) The hydrogen generated in the chlor-alkali industry is subjected to deep cooling at the temperature of-75 ℃, then is subjected to deep filtration by a filter set and multi-stage pressure swing adsorption to obtain high-purity hydrogen, and the hydrogen with the water content lower than 0.0001% and the metal ions lower than 0.00001% is obtained;
the multistage pressure swing adsorption process adopts active, 5A zeolite and nano silicon dioxide carbon as three-stage pressure swing adsorption beds in sequence, and pressure swing adsorption is carried out under 0.5atm, 7.5atm and 1.2atm respectively.
(3) Introducing purified chlorine gas from the bottom of a synthesis tower through a spray gun, and introducing hydrogen sprayed in the vertical direction into a two-in-one graphite synthesis tower through the spray gun to generate hydrogen chloride gas, wherein the spray gun and the synthesis tower are both provided with jackets, the jackets are cooled by pure water, the temperature of circulating water is controlled to be 55 ℃, and the liquid level of a tower kettle of the synthesis tower is kept at 20mm;
(4) The hydrogen chloride gas produced by the synthesis tower is subjected to multistage cooling to 50 ℃ through heat exchange of a tower top cooler and a gas guide pipe jacket, the hydrogen chloride gas is subjected to parallel flow circulation absorption in an absorption tower by 32% hydrochloric acid mother liquor, the hydrogen chloride gas and hydrochloric acid solution enter from the tower top, three hydrochloric acid spherical nozzles are arranged at the top of the absorption tower, the three nozzles are uniformly distributed on the top cover of the absorption tower and mutually form an included angle of 60 degrees, and the size of a small hole on each nozzle is 0.01mm;
(5) Adding ultrapure water to stabilize the concentration to 33% through the bottom of an absorption tower to obtain a hydrochloric acid intermediate product, adding a free chlorine removal agent to the hydrochloric acid intermediate product to circularly remove free chlorine, wherein the free chlorine removal liquid comprises 10% of SEMI C12 grade electronic grade hydrogen peroxide, 25% of electronic grade hydrochloric acid with metal ions lower than 20ppt, and the balance of ultrapure water with the resistivity higher than 18.2M omega cm, based on the total weight of the free chlorine removal liquid;
(6) The hydrochloric acid intermediate product without free chlorine enters an analytical tower, and the analyzed hydrogen chloride gas is filtered at low temperature of 15 ℃ and through a microporous membrane to obtain pure hydrogen chloride gas;
(7) Circularly absorbing hydrogen chloride gas in an absorption tower, and continuously supplementing ultrapure water to the bottom of the absorption tower to obtain electronic grade hydrochloric acid with the mass concentration of 32% and metal ions of 24 ppt;
(8) And (3) circularly filtering the electronic-grade hydrochloric acid reaching the finished product storage tank through a PTFE microporous adsorption membrane to finally obtain the electronic-grade hydrochloric acid with metal ions lower than 10ppt.
Example 2
The method and the steps are the same as example 1, only the molecular sieve in the step (1) is the CaA molecular sieve, and the CaA molecular sieve belongs to the pore canal, and the cation is Ca 2+ The LTA type molecular sieve has the composition of 0.75 CaO.0.25 Na 2 O·A1 2 O 3 ·2SiO 2 ·4.5H 2 O, soaking a product with a hydrochloric acid solution, wherein the product is prepared by mixing a mixture of a product with a market model of XFF2111113-61-4, 500g, diameter: soaking 3-5mm in 20-36% HCl solution for 5 hr, and drying at 80 deg.C.
The metal ion of the final electronic grade hydrochloric acid is less than 16ppt.
Example 3
The method and the steps are the same as the example 1, only the molecular sieve in the step (1) is the SBA-15 molecular sieve, and the method for soaking the SBA-15 molecular sieve in the hydrochloric acid solution comprises the following steps of mixing 500g of the molecular sieve purchased from Jiangsu Xiancheng nano material science and technology company Limited, the model number of the molecular sieve is 500g, and the pore diameter is 6-13nm SSA 2 The product is obtained by soaking the raw materials in HCl solution with the mass concentration of 20-36% for 5h and then drying the raw materials at 80 ℃. The metal ion of the final electronic grade hydrochloric acid is less than 10ppt.
Example 4
The method and the steps are the same as the example 1, only the molecular sieve in the step (1) is a NaX molecular sieve, and the NaX molecular sieve is prepared by mixing sodium aluminate and silica sol in a mass ratio of 1:12, adding a sodium hydroxide solution to adjust the pH value to 11, sealing and uniformly stirring, and aging for 2 days to obtain the NaX molecular sieve with the particle size of 20-40 nm. Then soaking the NaX molecular sieve in an HCl solution with the mass concentration of 20-36% for 5 hours, and drying at 80 ℃. The metal ion of the final electronic grade hydrochloric acid is less than 14ppt.
Example 5
The method and the steps are the same as the example 1, and only in the step (2), the multi-pressure swing adsorption mode is that the metal organic frameworks MOFs, the metal organic frameworks MOFs and the metal organic frameworks MOFs are used as three-stage pressure swing adsorption beds, and the pressure swing adsorption is respectively carried out under 1.6atm, 5.5atm and 7.8 atm. The metal ion of the final electronic grade hydrochloric acid is less than 15ppt.
Example 6
The method and the steps are the same as the example 1, only in the step (2), the multi-pressure swing adsorption mode is that the metal organic frameworks MOFs, the manganese oxide octahedral molecular sieve OMS-2 and the manganese oxide octahedral molecular sieve OMS-2 are used as three-stage pressure swing adsorption beds, and the pressure swing adsorption is respectively carried out under 1.0atm, 4.3atm and 8.2 atm. The metal ion of the final electronic grade hydrochloric acid is less than 17ppt.
Example 7
The method and the steps are the same as the example 1, only in the step (2), the multi-pressure swing adsorption mode is that nano-silica, manganese oxide octahedral molecular sieve OMS-2 and nano-silica are used as three-stage pressure swing adsorption beds, and pressure swing adsorption is carried out under 1.5atm, 4.5atm and 6.0atm respectively. The metal ion of the final electronic grade hydrochloric acid is less than 12ppt.
Example 8
The method and the steps are the same as the example 1, and the multi-pressure swing adsorption mode in the step (2) is to use nano-silica, MOFs (metal organic frameworks) and 5A zeolite as three-stage pressure swing adsorption beds and respectively carry out pressure swing adsorption under the pressure swing adsorption conditions of 5.5atm, 4.5atm and 9.0 atm. The metal ion of the final electronic grade hydrochloric acid is less than 10ppt.
Example 9
The chlorine with the purity of 98.5 percent, the liquid content of 0.07 percent, the chlorine with the purity of 99.5 percent and the liquid content of 0.08 percent are taken as raw materials, the chlorine is filtered by a molecular sieve and filtered at low temperature to obtain pure chlorine, the industrial chlorine is filtered by an SBA-15 molecular sieve synthesized in a hydrochloric acid environment, the temperature of a cooler is reduced to 10 ℃, and then the industrial chlorine is filtered by a filter tower and deeply filtered by a filter to obtain the pure chlorine with the water content of less than 0.001 percent and the metal ions of less than 0.0002 percent; the hydrogen is deeply filtered by a filter group with the lowest aperture of 0.03 mu m and is subjected to multi-stage pressure swing adsorption after being deeply chilled at the temperature of-85 ℃ to obtain high-purity hydrogen, and the hydrogen with the water content of less than 0.0001 percent and the metal ions of less than 0.00001 percent is obtained; introducing purified chlorine gas from the bottom of a synthesis tower through a spray gun, and introducing hydrogen sprayed in the vertical direction into a two-in-one graphite synthesis tower through the spray gun to generate hydrogen chloride gas, wherein the spray gun and the synthesis tower are both provided with jackets, the temperature of circulating water is controlled at 50 ℃, and the liquid level of a tower kettle of the synthesis tower is kept at 15mm; the hydrogen chloride gas produced by the synthesis tower is subjected to multistage cooling to 45 ℃ through heat exchange of a tower top cooler and a gas guide pipe jacket, the hydrogen chloride gas is subjected to parallel flow circulation absorption in an absorption tower by 32% hydrochloric acid mother liquor, the hydrogen chloride gas and hydrochloric acid solution enter from the tower top, three hydrochloric acid spherical nozzles are arranged at the top of the absorption tower, the three nozzles are uniformly distributed on the top cover of the absorption tower and mutually form an included angle of 60 degrees, and the size of a small hole on each nozzle is less than 0.01mm; adding ultrapure water to stabilize the concentration to 34% through the bottom of an absorption tower to obtain a hydrochloric acid intermediate product, adding a free chlorine removal agent to the hydrochloric acid intermediate product to circularly remove free chlorine, wherein the components of the free chlorine removal liquid comprise SEMI C12 grade electronic grade hydrogen peroxide accounting for 20% of the total weight of the free chlorine removal liquid, electronic grade hydrochloric acid with 20% of metal ions lower than 20ppt, and the balance of ultrapure water with the resistivity higher than 18.2M omega cm; the hydrochloric acid intermediate product without free chlorine enters an analytical tower, and the analyzed hydrogen chloride gas is filtered at low temperature of 10 ℃ and through a microporous membrane to obtain pure hydrogen chloride gas, wherein the grade of the hydrogen chloride gas is more than 6N; circularly absorbing hydrogen chloride gas in an absorption tower, and continuously supplementing ultrapure water to the bottom of the absorption tower to obtain electronic grade hydrochloric acid with the mass concentration of 32% and metal ions of 18 ppt; the electronic-grade hydrochloric acid reaching the finished product storage tank is subjected to circulating filtration through a PTFE microporous adsorption membrane, except for a hydrogen chloride synthesis tower, other equipment adopts one or two of stainless steel lined PTFE, HDPE and PFA, and finally the electronic-grade hydrochloric acid with metal ions of 15ppt is obtained.
Example 10
The chlorine with the purity of 99.5 percent, the liquid content of 0.05 percent, the chlorine with the purity of 99.8 percent and the liquid content of 0.07 percent are taken as raw materials, the chlorine is filtered by a molecular sieve and filtered at low temperature to obtain pure chlorine, the industrial chlorine is filtered by an SBA-15 molecular sieve synthesized in a hydrochloric acid environment, the temperature of a cooler is reduced to 0 ℃, and then the industrial chlorine is filtered by a filter tower and deeply filtered by a filter to obtain the pure chlorine with the water content of less than 0.001 percent and the metal ions of less than 0.0002 percent; deeply filtering the hydrogen at-90 ℃ by a filter group with the lowest pore diameter of 0.03 mu m, and performing multi-stage pressure swing adsorption to obtain high-purity hydrogen, wherein the water content of the hydrogen is lower than 0.0001%, and the metal ions of the hydrogen are lower than 0.00001%; introducing purified chlorine gas from the bottom of a synthesis tower through a spray gun, and introducing hydrogen sprayed in the vertical direction into a two-in-one graphite synthesis tower through the spray gun to generate hydrogen chloride gas, wherein the spray gun and the synthesis tower are both provided with jackets, the jackets are cooled by pure water, the temperature of circulating water is controlled at 40 ℃, and the liquid level of a tower kettle of the synthesis tower is kept at 20mm; the hydrogen chloride gas produced by the synthesis tower is subjected to multistage cooling to 40 ℃ through heat exchange of a tower top cooler and a gas guide pipe jacket, the hydrogen chloride gas is subjected to parallel flow circulation absorption in an absorption tower by 32% hydrochloric acid mother liquor, the hydrogen chloride gas and hydrochloric acid solution enter from the tower top, three hydrochloric acid spherical nozzles are arranged at the top of the absorption tower, the three nozzles are uniformly distributed on the top cover of the absorption tower and mutually form an included angle of 60 degrees, and the size of a small hole on each nozzle is less than 0.01mm; adding ultrapure water to stabilize the concentration to 36% through the bottom of the absorption tower to obtain a hydrochloric acid intermediate product, adding a free chlorine removal agent to circularly remove free chlorine after the hydrochloric acid intermediate product is put into an intermediate storage tank, wherein the free chlorine removal liquid comprises 5% of SEMI C12 grade electronic grade hydrogen peroxide, 25% of electronic grade hydrochloric acid with metal ions lower than 20ppt and the balance of ultrapure water with the resistivity higher than 18.2M omega cm; the hydrochloric acid intermediate product without free chlorine enters an analytical tower, and the analyzed hydrogen chloride gas is filtered at low temperature of 5 ℃ and through a microporous membrane to obtain pure hydrogen chloride gas, wherein the grade of the hydrogen chloride gas is more than 6N; circularly absorbing the hydrogen chloride gas in an absorption tower, and continuously supplementing ultrapure water into the bottom of the absorption tower to obtain electronic grade hydrochloric acid with the mass concentration of-34% and metal ions of 15 ppt; the electronic-grade hydrochloric acid reaching the finished product storage tank is subjected to circulating filtration through a PTFE microporous adsorption membrane, except for a hydrogen chloride synthesis tower, other equipment adopts one or two of stainless steel lined PTFE, HDPE and PFA, and finally the electronic-grade hydrochloric acid with metal ions lower than 10ppt is obtained.
Claims (9)
1. The production method of the electronic grade hydrogen chloride and the electronic grade hydrochloric acid is characterized by comprising the following production steps:
(1) Filtering industrial chlorine gas by adopting a molecular sieve and filtering at low temperature to obtain pure chlorine gas;
(2) Carrying out deep cooling on industrial hydrogen at-75 to-90 ℃, and then filtering and adsorbing to obtain high-purity hydrogen;
(3) Introducing high-purity hydrogen sprayed in the vertical direction from the bottom of the synthesis tower into purified chlorine gas through a spray gun to generate hydrogen chloride gas in the synthesis tower, and cooling the jacket of the synthesis tower by adopting pure water;
(4) One part of hydrogen chloride gas produced by the synthesis tower enters a rectifying tower for rectification and purification to obtain 9N electronic grade hydrogen chloride, the other part of hydrogen chloride gas is cooled to 40-50 ℃ after cooling and heat exchange, and the cooled hydrogen chloride gas is subjected to parallel flow circulation absorption in an absorption tower by hydrochloric acid mother liquor to obtain a hydrochloric acid intermediate product;
(5) The hydrochloric acid intermediate product is sent to an intermediate storage tank, and free chlorine is circularly removed by adding a free chlorine removing agent;
(6) The hydrochloric acid intermediate product without free chlorine enters an analytical tower, and the analyzed hydrogen chloride gas is filtered to obtain pure hydrogen chloride gas;
(7) Circularly absorbing the hydrogen chloride gas in an absorption tower, and continuously supplementing ultrapure water to the bottom of the absorption tower to obtain the electronic grade hydrochloric acid.
2. The method for producing electronic grade hydrogen chloride and electronic grade hydrochloric acid according to claim 1, wherein the purity of the industrial chlorine gas in the step (1) is 98.5-99.0%, and the liquid carrying amount is 0.07-0.09%;
the molecular sieve is a CaA, naX or SBA-15 molecular sieve, and is obtained by soaking the molecular sieve in a hydrochloric acid solution for 0.5-10h and then drying, wherein the mass concentration of the hydrochloric acid solution is 20-36%;
the temperature in the filtering process is 0-20 ℃;
the water content of the pure chlorine is lower than 0.001%, and the metal ions are lower than 0.0002%.
3. The method for producing electronic-grade hydrogen chloride and electronic-grade hydrochloric acid according to claim 1, wherein the purity of the industrial hydrogen in the step (2) is 99.5%, and the liquid carrying amount is 0.07-0.09%;
the hydrogen filter group used for filtering is a 0.1-0.05 mu m filter pore membrane for multi-stage filtration;
or multi-stage gradient filtration is carried out by adopting a filter pore membrane with 0.1-0.05 mu m;
the multistage pressure swing adsorption comprises a multistage pressure swing adsorption bed consisting of any one or more of activated carbon, 5A zeolite, nano-silica, metal Organic Frameworks (MOFs) and manganese oxide octahedral molecular sieve OMS-2, and the pressure swing adsorption is carried out within the pressure range of 0.5-9 atm.
4. The method for producing electronic grade hydrogen chloride and electronic grade hydrochloric acid according to claim 1, wherein the spray gun in the step (3) is of a three-layer sleeve structure, the outermost layer of the spray gun is filled with circulating water, the middle interlayer is filled with hydrogen, and the inner layer is filled with chlorine; the temperature of circulating water is controlled to be 40-55 ℃.
5. The method for producing electronic-grade hydrogen chloride and electronic-grade hydrochloric acid according to claim 1, wherein the hydrogen chloride gas cooled to 40-50 ℃ in step (4) and the hydrochloric acid mother liquor enter the absorption tower from the top thereof, are circularly absorbed in the absorption tower in parallel flow, and ultrapure water is added from the bottom of the absorption tower to stabilize the hydrochloric acid concentration in the hydrochloric acid intermediate product to 34-36%, wherein the content of metal ions in the electronic-grade hydrochloric acid is less than 30ppt
The hydrochloric acid mother liquor enters in a spraying mode, and the aperture of a spray head is less than 0.01mm in the spraying process;
the mass concentration of the hydrochloric acid mother liquor is 32-34%.
6. The method for producing electronic grade hydrogen chloride and electronic grade hydrochloric acid according to claim 1, wherein the free chlorine removing agent in the step (5) comprises SEMI C12 grade electronic grade hydrogen peroxide 1-25%, electronic grade hydrochloric acid with metal ions less than 20ppt 5-25%, and ultrapure water with resistivity greater than 18.2M Ω cm in balance; the free chlorine removing agent is pumped in at the flow rate of 5ml/min-10 ml/min.
7. The method for producing electronic grade hydrogen chloride and electronic grade hydrochloric acid according to claim 1, wherein the low temperature filtration temperature in the step (6) is-10 to 10 ℃, the size of the micropores in the microporous membrane filtration process is less than 0.05 μm, and the pore size of the microporous membrane filtration membrane is preferably 3nm.
8. The method for producing electronic-grade hydrogen chloride and electronic-grade hydrochloric acid according to claim 7, wherein ultrapure water is continuously fed from the bottom of the absorption tower during the circulating absorption process of the high-purity hydrogen chloride gas in the absorption tower in the step (7), so as to obtain electronic-grade hydrochloric acid with the mass concentration of 32% -34% and the metal ion content of less than 10ppt.
9. The production method of electronic-grade hydrogen chloride and electronic-grade hydrochloric acid according to claim 8, wherein the obtained electronic-grade hydrochloric acid with the mass concentration of 32-34% and the metal ion content of less than 10ppt is subjected to circulating filtration by using a PTFE microporous adsorption membrane to obtain the electronic-grade hydrochloric acid with the metal ion content of less than 10ppt.
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| CN1644487A (en) * | 2004-12-21 | 2005-07-27 | 上海氯碱化工股份有限公司 | Apparatus and method for preparing high-purity hydrochloric acid by low-temperature evaporation |
| CN201857259U (en) * | 2011-03-02 | 2011-06-08 | 特变电工新疆硅业有限公司 | Lamp cap for synthetic furnace of hydrogen chloride |
| CN111675195A (en) * | 2020-06-06 | 2020-09-18 | 江苏慧发企业管理有限公司 | Energy-saving environment-friendly process flow for synthesizing hydrochloric acid |
| CN113501498A (en) * | 2021-08-19 | 2021-10-15 | 成都国化环保科技有限公司 | Hydrochloric acid purification system and process |
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| CN201857259U (en) * | 2011-03-02 | 2011-06-08 | 特变电工新疆硅业有限公司 | Lamp cap for synthetic furnace of hydrogen chloride |
| CN111675195A (en) * | 2020-06-06 | 2020-09-18 | 江苏慧发企业管理有限公司 | Energy-saving environment-friendly process flow for synthesizing hydrochloric acid |
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