CN112607707B - Separation and purification method for FTrPSA (fluorine-doped silica gel) refined from industrial high-concentration HF (hydrogen fluoride) into electronic grade - Google Patents
Separation and purification method for FTrPSA (fluorine-doped silica gel) refined from industrial high-concentration HF (hydrogen fluoride) into electronic grade Download PDFInfo
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Abstract
The invention discloses a separation and purification method of FTrPSA (fluorine-doped silica gel) refined from industrial high-concentration HF (hydrogen fluoride) into electronic grade, and relates to purification of electronic grade HF prepared from industrial high-concentration Hydrogen Fluoride (HF), wherein each component (HF is an effective component and H is an effective component) in industrial AHF (Hydrogen fluoride)2O、H2SO4、SO2、SiF4、NH3、CO2、H2SiF6And trace amounts of HCl, water-soluble Me + ions and SS particles as main impurity components) under different pressures and temperatures, and separating and purifying by adopting a cyclic operation of taking two sections of medium-temperature pressure swing adsorption processes as main processes and HF rectification/membrane separation coupling, so that adsorption and desorption are easy to match and balance in the medium-temperature pressure swing adsorption process, thereby realizing the preparation of electronic grade HF products. The invention solves the problem that AHF refining is subjected to phase equilibrium or short service life of adsorbent in the traditional separation processes of rectification, distillation, absorption or chemical adsorption and the like, and fills the blank of the technical field.
Description
Technical Field
The invention relates to purification of electronic grade Hydrogen Fluoride (HF) prepared by taking industrial grade high-concentration HF as a raw material, in particular to a separation and purification method of FTrPSA (full temperature range pressure swing adsorption) by refining industrial grade high-concentration HF into electronic grade.
Background
Hydrogen Fluoride (HF) is a basic raw material for fluorine chemical industry, and is used for producing organic fluorine, inorganic fluorine salt, and other fields such as fluorine-containing catalyst, fluorosilicic acid, etc., wherein HF is increasingly used in organic fluorine fields such as refrigerants, surfactants, fluororubbers, fluorine coatings, fluorine-containing resins, fluorine-containing pesticides, high-purity fluorine resins, pharmaceutical intermediates, etc. At present, with the development of the semiconductor industry, ultra-high purity electronic grade HF (gas and liquid) has been widely used in the cleaning, etching and chemical deposition processes of Integrated Circuits (ICs) and very large scale integrated circuits (VLSI) chips, is one of the key chemical materials in the manufacturing process of the microelectronics industry, and in addition, can also be used as an analytical reagent and for preparing high purity fluorine-containing chemicals and semiconductor materials.
At present, for the industrial preparation and extraction of high-purity HF, industrial high-concentration HF is mainly used as a raw material, and a purification method mainly comprising distillation/rectification and membrane separation is adopted, wherein the purification method comprises rectification, distillation, sub-boiling distillation, reduced pressure distillation, gas absorption, microfiltration, ultrafiltration, nanofiltration, various combinations and the like. In these conventional purification processes, the difference in volatility (boiling point) or solubility or molecular size between each component in the raw material (liquid/gas) and HF at different temperatures is utilized to separate and purify the impurities in the raw material one by one to obtain anhydrous HF (ahf) product with comparable purity. The main impurity component in the raw material is fluosilicic acid (H)2SiF6) Water (H)2O), chlorides (mainly hydrogen chloride HCl), phosphides (P), metal oxides (MeO), metal ions, solid particles (SS), and the like. Electronic grade HF products are classified into EL (general electronic grade), UP (ultra pure), UPs (ultra pure), UPSs (ultra high pure), and the semiconductor industry international association (SEMI) also sets out a corresponding SEMI-C/S grade standard, which is equivalent to UPs/UPSs grade. For example, the UP electronic grade HF (liquid) index commonly used in China is H2SiF6The content is less than 100ppm, the chloride (Cl) is less than 5ppm, the P is less than 1ppm, the MeO/Me + is less than 10ppb, the SS (more than or equal to 1 mu m) is less than 25 units (one)/milliliter, and the like, wherein the MeO/Me + is particularly water-soluble MeO/Me + impurities such As arsenic (As), magnesium (Mg), calcium (Ca), sodium (Na), potassium (K) and the like, and the impurities must be completely removed, otherwise, the impurities must be completely removedThe performance of the sheet has a significant impact. The HF content of the electronic grade HF liquid used as a semiconductor chip cleaning agent or wet etching liquid is different grades, such as 49 percent, and the rest is deionized water. Therefore, in industry, a fluorite method or a fluorosilicic acid method is usually adopted to prepare Anhydrous HF (AHF) in a production process, fine AHF gas with the purity of 99.9% is obtained after rectification and membrane filtration, and after the fine AHF gas is absorbed by deionized water, electronic-grade hydrofluoric acid is further purified by methods of controlling spray density, gas-liquid ratio, membrane filtration and the like to obtain an electronic-grade HF liquid product. However, due to other impurities in the rectification process such as sulfuric acid (H) due to water and HF and from the fluorite or fluorosilicate process itself2SO4) Sulfur dioxide (SO)2) Hydrogen chloride (HCl), silicon tetrafluoride (SiF)4) Ammonia (NH)3) And carbon dioxide (CO)2) The impurities and HF cannot be completely separated due to the limitations of the miscibility and the phase balance of the rectification separation, so that the obtained refined AHF gas still contains more impurity components and is brought into subsequent processes of deionized water absorption, spraying density and gas-liquid ratio control, membrane filtration and the like, and the removal of trace or trace impurity components through the subsequent purification is very difficult. Therefore, the method is very important for regulating and controlling the purity of the fine AHF product obtained in the production process of preparing the AHF by the fluorite method or the fluosilicic acid method. Therefore, industrial grade HF or AHF feed gas with the content of 95-99% is directly rectified, distilled, sub-distilled or specially rectified, the rectifying or distilling cost is very high due to too low impurity concentration, and although the boiling point difference between the impurity component and HF is large, the mass transfer distribution of other impurity components in water is affected by water, so that the rectifying or distilling is more seriously limited by phase balance, and the purifying depth far reaches the electronic grade requirement.
HF purification has been reported to be carried out by an adsorption method in which the adsorbent is mostly a fluoride of an alkali metal, selective chemisorption is carried out by a chemical reaction between a metal fluoride and HF at a relatively low temperature to form a metal fluoride-HF complex, and a decomposition reaction of the complex is carried out at a relatively high temperature to thereby effect desorption of HF from the adsorbent and to prevent other impurities from being present on the adsorbentSelectivity is realized, thereby realizing the separation and purification of HF. The chemical adsorption method is suitable for preparing chlorofluoroalkane (CFC), Hydrochlorofluorocarbon (HCFC), Hydrochlorofluorocarbon (HFC) and sulfuryl fluoride (SO) by fluorination reaction2F2) In the case of products, the selective adsorption, separation and recovery of HF by the reaction gas mixture generated by the reaction have good effect, but the loss rate of the adsorbent is high. For the catalyst containing water or sulfuric acid or SiF4In the crude HF or the refined HF obtained by the fluorite method or the fluorosilicic acid method, the adsorbent undergoes chemical reaction with impurity components such as water, so that the adsorbent is seriously pulverized and deactivated, and thus deep dehydration and impurity removal cannot be effectively performed. Therefore, the chemical adsorption method can hardly be effectively applied to the preparation of AHF by the fluorite method or the fluorosilicic acid method. This is one of the main reasons why only low-grade electronic-grade AHF products can be produced currently in our country, and is one of the important reasons why japan has restricted export of electronic-grade AHF to korea due to its technical advantages in the trade dispute of electronic-grade semiconductor chemicals that occurred in two countries in korea in 2019, and japan is a very small number of countries that internationally possess technology for producing AHF having a purity of 99.9999% to 99.99999999% (6N to 12N).
Disclosure of Invention
The invention aims to: in view of the above problems, the present invention provides a separation and purification method of FTrPSA (Full Temperature Swing Adsorption) for refining industrial grade high concentration HF into electronic grade, wherein FTrPSA is a method based on PSA and coupled with various separation technologies, and uses each component (HF is effective component and H is H) in industrial grade AHF (gas)2O、H2SO4、SO2、SiF4、NH3、CO2、H2SiF6And trace amounts of HCl, water-soluble Me + ions and SS particles as main impurity components) under different pressures and temperatures, and adopting the method of adopting the difference of adsorption/rectification/membrane separation coefficients and physicochemical propertiesThe two-section medium temperature pressure swing adsorption process is mainly coupled with HF rectification/membrane separation, so that the adsorption and desorption in the medium temperature pressure swing adsorption process are easy to match and balance for separation and purification through cyclic operation, and the preparation of electronic grade HF products is realized.
The technical scheme adopted by the invention is as follows:
a raw material gas is from industrial grade high-concentration Hydrogen Fluoride (HF) gas generated in the production process of preparing Anhydrous Hydrogen Fluoride (AHF) by a fluorite method or a fluosilicic acid method, and mainly contains HF with the concentration of 95-99% (v/v) and sulfuric acid (H/v)2SO4) Water (H)2O), sulfur dioxide (SO)2) Silicon tetrafluoride (SiF)4) Ammonia (NH)3) Fluosilicic acid (H)2SiF6) Carbon dioxide (CO)2) Chloride (calculated by HCl), metal ions (Me +) and fine particles (SS) impurity components, wherein Me + mainly comprises water-soluble sodium (Na), magnesium (Mg), calcium (Ca) and arsenic (As) ions, the diameter of the SS particles is more than 1 micrometer (mum), the temperature is 20-60 ℃, and the pressure is normal pressure or micro-positive pressure; the method comprises the following steps:
(1) medium temperature pressure swing adsorption, wherein a feed gas is subjected to heat exchange to 50-80 ℃, is pressurized to 0.2-0.3 MPa, and then enters a medium temperature pressure swing adsorption process consisting of two sections of Pressure Swing Adsorption (PSA), each section of pressure swing adsorption consists of at least more than 2 adsorption towers, at least 1 adsorption tower is in an adsorption step, the other adsorption towers are in desorption steps of different stages including pressure reduction reverse discharge or vacuumizing, pressure boosting or final charging, and the feed gas is desorbed from a first section of PSA (1)#PSA) bottom entry of the adsorption column, 1#The operating pressure of PSA is 0.2-0.3 MPa, the operating temperature is 50-80 ℃, the non-adsorption phase gas flowing out from the top of the adsorption tower in the adsorption step is fine HF gas, the condensed non-condensable gas is subjected to precision filtration and is absorbed by deionized water to obtain a 40-49% HF aqueous solution which is used as a general electronic EL-grade hydrofluoric acid product for output, and the fine HF liquid formed after condensation enters the next process, namely membrane separation, and is desorbed from the step 1#Desorbed gas flowing out from the bottom of the PSA adsorption tower is pressurized and subjected to heat and heat exchange, and then the desorbed gas flows out from the second section of PSA (2)#PSA) at the bottom of the adsorption column, 2#The operating pressure of the PSA adsorption tower is 0.2-0.3 MPa, the operating temperature is 50-80 ℃, and the PSA adsorption tower is in the adsorption step 2#The intermediate gas of the non-adsorption phase flowing out from the top of the PSA adsorption tower is mixed with the feed gas and returned to the gas mixing tank 1#PSA adsorption column, from 2#The desorbed gas flowing out of the bottom of the PSA adsorption tower is concentrated gas, and enters the subsequent ammonia decarburization process to further recover effective components;
(2) membrane separation, wherein the fine HF liquid which is formed by condensation from a medium-temperature pressure swing adsorption process is pressurized to 1.0-1.6 MPa and at the temperature of 50-80 ℃, enters an inorganic ceramic membrane or stainless steel membrane separation system which is formed by a first stage or a second stage, the membrane aperture is smaller than 1 micron, purified fine HF liquid flows out from one side of a permeation membrane, wherein the content of SS particles with the diameter larger than 1 micron is smaller than 25 (one) unit/milliliter (Ea/ml), enters the next process, namely HF rectification, SS particle concentrated solution is enriched on one side which does not permeate the membrane, SS particles are removed after cooling and sedimentation, the liquid returns to the membrane separation system after being heated and pressurized, and effective components are further recovered;
(3) HF rectification, wherein purified and refined HF liquid from a membrane separation process enters a rectification tower of an HF rectification process, the rectification tower of the process is composed of an upper section of rectification and a lower section of rectification, the purified and refined HF liquid enters from the top of the lower section of rectification or from the bottom of the upper section of rectification, light component impurity gas distilled from the top of the upper section of rectification returns to a subsequent tail gas absorption process, or noncondensable gas formed by condensing the bottom of the upper section of rectification or the top distillate of the lower section of rectification is AHF gas, the purity is more than or equal to 99.99 percent, the noncondensable gas is directly used as product gas of electronic UP or UPS grade AHF, the liquid formed by condensation is used as reflux of the upper section or the lower section of rectification, a bottom fluid containing a small amount of heavy component impurity components distilled from the bottom of the lower section of rectification, the noncondensable gas formed by condensation returns to a medium temperature pressure swing adsorption process, and effective components are further recovered, the liquid formed after condensation is used as an absorbent to enter the next procedure, namely ammonia water decarburization;
(4) ammonia water decarbonization, wherein concentrated gas from a medium-temperature pressure swing adsorption process is pressurized to normal pressure or micro-positive pressure, enters a liquid formed by condensation of ammonia water, sulfuric acid and a rectification distillate from the lower section of an HF rectification process, is mixed in proportion to be used as an ammonia water decarbonization absorption tower of an absorbent, and a mixed solution of ammonium bicarbonate and ammonium bifluoride formed from the bottom of the absorption tower is output and directly used as a return material or a premixed reaction material in the production process of preparing AHF by a fluorosilicic acid method.
Further, the middle membrane separation system in the step (2) takes a micro-filtration membrane or an ultrafiltration membrane as a membrane component.
And further, the tail gas absorption process is also included, light component impurity gas distilled from the top of the upper-stage rectifying tower in the HF rectifying process and non-condensable gas from the top of the ammonia water decarburization absorption tower are mixed and enter a tail gas absorption tower which takes sulfuric acid as an absorbent, a fluosilicic acid solution is formed from the bottom of the absorption tower and is output as a raw material, the raw material solution can be directly returned to the raw material liquid in the production process of preparing Anhydrous Hydrogen Fluoride (AHF) by a fluosilicic acid method for recycling, and the non-condensable gas flowing out from the top of the absorption tower is directly discharged as exhaust gas.
Further, active aluminum oxide, silica gel and molecular sieve are filled in the adsorption tower in the medium-temperature pressure swing adsorption procedure, 1#The weight ratio of aluminum oxide to silica gel to molecular sieve in the adsorbent composition filled in the PSA adsorption tower is (4-6) to (2-4) to (1-3); 2#The weight ratio of the aluminum oxide to the silica gel to the molecular sieve in the adsorbent composition filled in the PSA adsorption tower is (3-5) to (1-3) to (3-5).
Wherein, the filling quantity and distribution of the three adsorbents depend on the HF concentration of the raw material gas and the content of the impurity components, and the filling quantity distribution of the adsorbents in the two-stage PSA adsorption tower is not the same.
Further, tail gas absorption, namely mixing light component impurity gas distilled from the top of the upper-stage rectifying tower in the HF rectifying process with non-condensable gas from the top of the ammonia water decarburization absorption tower, feeding the mixture into a tail gas absorption tower using sulfuric acid as an absorbent, forming fluosilicic acid solution from the bottom of the absorption tower, outputting the fluosilicic acid solution as a raw material, directly returning the raw material solution in the production process of preparing AHF by a fluosilicic acid method for recycling, and directly discharging the non-condensable gas flowing out from the top of the absorption tower as an exhaust gas.
Further, the saidThe refined HF liquid inlet end of the HF rectification process is arranged at the bottom of the upper section or at the top of the lower section, depending on the feed gas containing H2O、H2SO4、SO2、SiF4、NH3、CO2、H2SiF6The content of main impurity components.
Further, the noncondensable gas formed by condensing the distillate at the bottom of the upper-stage rectification or at the top of the lower-stage rectification in the HF rectification process is AHF gas, the purity of the noncondensable gas is more than or equal to 99.99%, the noncondensable gas enters fluorine exchange resin after being further condensed to form AHF liquid, Me + is further removed, UPSS electronic-grade AHF liquid is formed, and the noncondensable gas can be randomly mixed with deionized water to form HF solution, so that the requirements of the HF solution with various concentrations in the semiconductor industry are met.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention prepares the EL/UP/UPS and UPSS electronic grade AHF gas or liquid required by the semiconductor industry by taking high-concentration HF gas produced in the production process of preparing AHF by the traditional fluorite method or fluosilicic acid method as a raw material, solves the problem that AHF refining is limited by the traditional separation processes of rectification, distillation, absorption or chemical absorption and the like and has phase balance or short service life of an adsorbent, and fills the blank of the technical field;
2) the invention uses the difference of adsorption/condensation/rectification/membrane separation coefficient and physicochemical property of each component (HF is effective component, the rest is impurity component) in the feed gas under different pressure and temperature, adopts two sections of medium temperature pressure swing adsorption process as main and condensation, membrane separation and HF rectification coupling, so that the adsorption and desorption in the medium temperature pressure swing adsorption process are easy to match and balance for cyclic operation to separate and purify, thereby realizing deep dehydration and impurity removal of HF;
3) the invention overcomes the problem of large adsorbent loss rate in the frequent cyclic operation process of adsorption and desorption caused by the prior chemical adsorption method that HF and the adsorbent are subjected to chemical (chelating) reaction at low temperature for adsorption and then are subjected to decomposition reaction at high temperature for desorption, and simultaneously, the invention can treat the adsorbent containing water or sulfuric acid or SiF4Crude H obtained by fluorite method or fluorosilicic acid methodF or refined HF, the adsorbent in the existing chemical adsorption can also undergo chemical reaction with impurity components such as water, so that the adsorbent is seriously pulverized and failed, and can not be effectively subjected to deep dehydration and impurity removal;
4) the invention avoids the problems of large fluctuation of the middle temperature of the rectifying tower, incapability of meeting the requirements of the tower bottom temperature, poor rectifying effect caused by large fluctuation of HF concentration and the like in the pure rectifying process of the AHF refining process, because the invention firstly adopts two-stage PSA to remove most of main heavy component impurities, so that the fluctuation of the HF concentration entering the HF rectifying process is small, and adopts an upper and lower two-stage rectifying mode to realize deep dehydration and impurity removal of the AHF product preparation, obtain an electronic grade AHF product and simultaneously obtain an HF aqueous solution with the concentration of 40-49%;
5) when the electronic grade AHF product is obtained, the HF is further recovered by the processes of returning the materials in the medium-temperature pressure swing adsorption and HF rectification processes to the front end of condensation or ammonia water decarburization and the like, so that the yield of the AHF product exceeds 90%, and the tail gas emission reaches the standard through the tail gas absorption process.
Drawings
FIG. 1 is a schematic flow chart of example 1 of the present invention;
fig. 2 is a schematic flow chart of embodiment 2 of the present invention.
Detailed Description
The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
As shown in figure 1, a separation and purification method of FTrPSA for refining industrial grade high concentration HF into electronic grade, the raw material gas comes from industrial grade high concentration Hydrogen Fluoride (HF) gas generated in the production process of preparing Anhydrous Hydrogen Fluoride (AHF) by fluorite method and fluorosilicic acid method, wherein,containing HF at a concentration of 98% (v/v), containing water (H)2O) content of 1%, and other impurities including sulfur dioxide (SO)2) Silicon tetrafluoride (SiF)4) Ammonia (NH)3) Fluosilicic acid (H)2SiF6) Carbon dioxide (CO)2) The total content of chlorides (calculated by HCl) is 0.9-1.0%, the concentration of metal ions (Me +) taking sodium (Na), magnesium (Mg), calcium (Ca) and arsenic (As) ions As main components is in a trace ppm level, the concentration of fine particles (dss is more than or equal to 1 mu m) is more than 100, the temperature is 20-30 ℃, and the pressure is normal pressure; the specific implementation steps comprise:
(1) performing medium-temperature pressure swing adsorption, wherein a feed gas is subjected to cold heat exchange to 60-70 ℃, is pressurized to 0.2-0.3 MPa by an induced draft fan, and then enters a medium-temperature pressure swing adsorption process consisting of two sections of Pressure Swing Adsorption (PSA), wherein the first section of PSA (1)#PSA) comprises 3 adsorption towers, 1 adsorption tower for adsorption, and another 2 adsorption towers for respectively performing pressure reduction and vacuum pumping, and raw material gas pressurization and final charging, wherein the raw material gas is discharged from 1 adsorption tower#PSA adsorption column bottoms, 1#The operating pressure of PSA is 0.2-0.3 MPa, the operating temperature is 60-70 ℃, the non-adsorption phase gas flowing out from the top of the adsorption tower in the adsorption step is fine HF gas, the condensed non-condensable gas is subjected to precision filtration and is absorbed by deionized water to obtain HF aqueous solution with the concentration of 49 percent, the HF aqueous solution is used as a general electronic EL-grade hydrofluoric acid product for output, the fine HF liquid formed after condensation enters the next process, namely membrane separation, and the pure HF liquid is separated from the adsorption tower 1 in the desorption step#Desorbed gas flowing out from the bottom of the PSA adsorption tower is pressurized and subjected to heat and heat exchange, and then the desorbed gas flows out from the second section of PSA (2)#PSA) at the bottom of the adsorption column, 2#PSA is composed of 3 adsorption towers, wherein 1 adsorption tower is always in adsorption state, the other 2 adsorption towers are respectively in desorption state of depressurization and vacuum pumping, and fine HF gas pressurization and final charging, the adsorption and desorption are operated circularly, 2#The operating pressure of the PSA adsorption tower is 0.2-0.3 MPa, the operating temperature is 60-70 ℃, and the PSA adsorption tower is in an adsorption state of 2#The intermediate gas of the non-adsorption phase flowing out from the top of the PSA adsorption tower is mixed with the feed gas and returned to the gas mixing tank 1#PSA adsorption column, from 2#The desorbed gas flowing out from the bottom of the PSA adsorption tower is concentrated gas, enters the subsequent ammonia water decarburization process, and is further recovered effectivelyPreparing components;
(2) membrane separation, namely pressurizing fine HF liquid which is formed by condensation from a medium-temperature pressure swing adsorption process to 1.6MPa at the temperature of 60-70 ℃, entering a primary inorganic ceramic membrane separation system, wherein the membrane aperture is 0.2-0.4 micron, the membrane layer material is a zirconium oxide, titanium oxide and aluminum oxide composite membrane, the content of zirconium oxide and titanium oxide exceeds that of aluminum oxide, corrosion-resistant tetrafluoroethylene is used as an anti-corrosion sealing material to form a multi-channel internal-pressure type membrane assembly, purified fine HF liquid flows out from one side of a permeable membrane, the content of SS particles with the diameter of more than 1 mu m is less than 25 units/milliliter (Ea/ml), entering the next process, namely HF, gathering SS concentrated liquid on one side which does not penetrate through the membrane, removing the SS particles after cooling and sedimentation, returning the liquid to the membrane separation system after heating and pressurizing, and further recovering effective components;
(3) HF rectification, wherein purified and refined HF liquid from a membrane separation process enters a rectification tower of an HF rectification process, the rectification tower of the process is composed of an upper section and a lower section of rectification, the purified and refined HF liquid enters from the top of the lower section of rectification, the operating temperature of the upper section of rectification tower is 18-30 ℃, and light component impurity gas distilled from the top of the upper section of rectification tower mainly comprises SO2、SiF4The method comprises the following steps of waiting for low-boiling point impurity components, returning to a subsequent tail gas absorption process, condensing bottom distillate of upper-stage rectification to form noncondensable gas AHF gas with the purity of more than or equal to 99.99%, directly using the noncondensable gas as product gas of electronic UP or UPS grade AHF, condensing the liquid to form liquid serving as reflux of the upper-stage rectification, controlling the operating temperature of the lower-stage rectification to be 20-100 ℃, condensing the noncondensable gas formed by condensation of the noncondensable gas of a small amount of heavy component impurity components distilled from the bottom of the lower-stage rectification, returning to a medium-temperature pressure swing adsorption process, further recovering effective components, condensing the liquid to form liquid serving as an absorbent, and entering a subsequent ammonia water decarburization process, wherein the operating pressure of HF rectification is 0.03-0.2 MPa;
(4) ammonia water decarburization, wherein concentrated gas from a medium-temperature pressure swing adsorption process is pressurized to 0.03-0.2 MPa by an induced draft fan, enters an ammonia water decarburization absorption tower which is formed by condensing ammonia water, sulfuric acid and distillate from the lower stage of an HF rectification process, is mixed according to the proportion of 5:3:2 and is used as an absorbent, a mixed solution of ammonium bicarbonate and ammonium bifluoride formed at the bottom of the absorption tower is output and directly used as a return material or a premixed reaction material in the production process of preparing AHF by a fluosilicic acid method, and non-condensable gas flowing out from the top of the ammonia water decarburization absorption tower enters a subsequent tail gas absorption process;
(5) and (2) tail gas absorption, wherein light component impurity gas distilled from the top of an upper rectifying tower in an HF (hydrogen fluoride) rectifying process and non-condensable gas from the top of an ammonia water decarburization absorption tower are mixed and enter a tail gas absorption tower using sulfuric acid as an absorbent, a fluosilicic acid solution is formed from the bottom of the absorption tower and is output as a raw material, the raw material solution can be directly returned to a fluosilicic acid method for preparing a raw material liquid in an AHF (advanced high performance fluorine) production process for recycling, and the non-condensable gas flowing out from the top of the absorption tower is directly discharged as a discharge gas.
Example 2
As shown in FIG. 2, based on example 1, the raw material gas was a high-concentration HF gas from a production process of AHF by fluorite method, in which NH was not present3Or CO2The impurity components can save the ammonia water decarburization process, namely, the concentrated gas from the medium-temperature pressure swing adsorption process returns to the condensation process in the production process of preparing AHF by the fluorite method, and effective components are further recovered.
Example 3
In addition to examples 1 and 2, 1 of the medium temperature pressure swing adsorption process#The adsorbent combination ratio of the alumina to the silica gel to the molecular sieve in the PSA adsorption tower is 5:3:2, 2#The adsorbent combination ratio filled in the PSA adsorption tower is 4:2: 4.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (6)
1. A separation and purification method of FTrPSA refined from industrial grade high-concentration HF into electronic grade is characterized by comprising the following steps:
(1) medium temperature pressure swing adsorption, wherein a feed gas is subjected to heat exchange to 50-80 ℃, is pressurized to 0.2-0.3 MPa, and then enters a medium temperature pressure swing adsorption process consisting of two sections of pressure swing adsorption PSA, each section of pressure swing adsorption at least consists of more than 2 adsorption towers, at least 1 adsorption tower is in an adsorption step, the other adsorption towers are in desorption steps of different stages including pressure reduction reverse release or vacuumizing, pressure boosting or final charging, and the feed gas is desorbed from 1#PSA adsorption column bottoms, 1#The operating pressure of PSA is 0.2-0.3 MPa, the operating temperature is 50-80 ℃, the non-adsorption phase gas flowing out from the top of the adsorption tower in the adsorption step is fine HF gas, the condensed non-condensable gas is subjected to precision filtration and is absorbed by deionized water to obtain a 40-49% HF aqueous solution which is used as a general electronic EL-grade hydrofluoric acid product for output, and the fine HF liquid formed after condensation enters the next process, namely membrane separation, and is desorbed from the step 1#Desorbed gas flowing out from the bottom of the PSA adsorption tower is pressurized and subjected to heat and heat exchange and then flows out from the 2#Adsorption column bottom entry of PSA, 2#The operating pressure of the PSA adsorption tower is 0.2-0.3 MPa, the operating temperature is 50-80 ℃, and the PSA adsorption tower is in the adsorption step 2#The intermediate gas of the non-adsorption phase flowing out from the top of the PSA adsorption tower is mixed with the feed gas and returned to the gas mixing tank 1#PSA adsorption column, from 2#The desorbed gas flowing out of the bottom of the PSA adsorption tower is concentrated gas, and enters the subsequent ammonia decarburization process to further recover effective components;
(2) membrane separation, wherein the fine HF liquid which is formed by condensation from a medium-temperature pressure swing adsorption process is pressurized to 1.0-1.6 MPa and at the temperature of 50-80 ℃, enters an inorganic ceramic membrane or stainless steel membrane separation system which is formed by a first stage or a second stage, the membrane aperture is smaller than 1 micron, purified fine HF liquid flows out from one side of a permeable membrane, the content of SS particles with the diameter larger than 1 micron is smaller than 25 Ea/ml, the purified fine HF liquid enters the next process, namely HF rectification, SS particle concentrated liquid is enriched on one side which does not permeate the membrane, the SS particles are removed after cooling and sedimentation, the liquid is heated and pressurized and then returns to the membrane separation system, and effective components are further recovered;
(3) HF rectification, wherein purified and refined HF liquid from a membrane separation process enters a rectification tower of an HF rectification process, the rectification tower of the process is composed of an upper section of rectification and a lower section of rectification, the purified and refined HF liquid enters from the top of the lower section of rectification or from the bottom of the upper section of rectification, light component impurity gas distilled from the top of the upper section of rectification returns to a subsequent tail gas absorption process, or noncondensable gas formed by condensing the bottom of the upper section of rectification or the top distillate of the lower section of rectification is AHF gas, the purity is more than or equal to 99.99 percent, the noncondensable gas is directly used as product gas of electronic UP or UPS grade AHF, the liquid formed by condensation is used as reflux of the upper section or the lower section of rectification, a bottom fluid containing a small amount of heavy component impurity components distilled from the bottom of the lower section of rectification, the noncondensable gas formed by condensation returns to a medium temperature pressure swing adsorption process, and effective components are further recovered, the liquid formed after condensation is used as an absorbent to enter the next procedure, namely ammonia water decarburization;
(4) ammonia water decarbonization, wherein concentrated gas from a medium-temperature pressure swing adsorption process is pressurized to normal pressure or micro-positive pressure, enters a liquid formed by condensation of ammonia water, sulfuric acid and a rectification distillate from the lower section of an HF rectification process, is mixed to form an ammonia water decarbonization absorption tower serving as an absorbent, and a mixed solution of ammonium bicarbonate and ammonium bifluoride formed from the bottom of the absorption tower is output and directly used as a return material or a premixed reaction material in the production process of preparing anhydrous hydrogen fluoride AHF by a fluorosilicic acid method.
2. The method for separating and purifying FTrPSA as claimed in claim 1, wherein the raw material gas in step (1) is derived from industrial-grade high-concentration hydrogen fluoride gas generated in the production process of preparing anhydrous hydrogen fluoride AHF by fluorite method or fluorosilicic acid method, and contains HF with concentration of 95-99% (v/v) and sulfuric acid (H)2SO4) Water (H)2O), sulfur dioxide (SO)2) Silicon tetrafluoride (SiF)4) Ammonia (NH)3) Fluosilicic acid (H)2SiF6) Carbon dioxide (CO)2) Hydrochloric acid (HCl), metal ions (Me +) and fine particles (SS) impurity components, wherein Me + comprises water-soluble sodium (Na), magnesium (Mg) and calcium(Ca) and arsenic (As) ions, wherein the diameter of SS particles is more than 1 mu m, the temperature is 20-60 ℃, and the pressure is normal pressure or micro-positive pressure.
3. The method for separating and purifying FTrPSA from industrial-grade high-concentration HF purified into electronic-grade FTrPSA as claimed in claim 1, wherein the middle membrane separation system in step (2) uses microfiltration membrane or ultrafiltration membrane as membrane component.
4. The separation and purification method of FTrPSA of industrial grade high concentration HF refined into electronic grade, according to claim 1, characterized in that, it further comprises a tail gas absorption process, wherein the light component impurity gas from the top of the upper rectification tower of the HF rectification process is mixed with the non-condensable gas from the top of the ammonia water decarburization absorption tower, and then enters the tail gas absorption tower using sulfuric acid as absorbent, and the fluosilicic acid solution is formed from the bottom of the absorption tower and is output as raw material, and can be directly returned to the raw material liquid of the process of preparing anhydrous hydrogen fluoride AHF by fluosilicic acid method for recycling, while the non-condensable gas from the top of the absorption tower is directly discharged as exhaust gas.
5. The method for separating and purifying FTrPSA in the refining of industrial grade high-concentration HF into electronic grade according to claim 1, wherein the adsorption tower in the medium temperature pressure swing adsorption process is filled with active alumina, silica gel and molecular sieve, 1#The weight ratio of aluminum oxide to silica gel to molecular sieve in the adsorbent composition filled in the PSA adsorption tower is (4-6) to (2-4) to (1-3); 2#The weight ratio of aluminum oxide to silica gel to molecular sieve in the adsorbent composition filled in the PSA adsorption tower is (3-5) to (1-3) to (3-5).
6. The method for separating and purifying FTrPSA of industrial grade high concentration HF refined into electronic grade according to claim 1, characterized in that the non-condensable gas formed by condensing the distillate at the bottom of the upper stage rectification or the top of the lower stage rectification in the HF rectification process is AHF gas with purity of 99.99% or more, and after further condensation to form AHF liquid, the AHF liquid enters fluorine exchange resin to further remove Me + to form UPSS electronic grade AHF liquid, and can be arbitrarily mixed with deionized water to form HF solution, thus meeting the requirements of HF solutions of various concentrations in semiconductor industry.
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| PCT/CN2021/094244 WO2022127018A1 (en) | 2020-12-16 | 2021-05-18 | Ftrpsa separation and purification method for refinement of electronic-grade hf from industrial-grade high-concentration hf |
| JP2022506378A JP2023524919A (en) | 2020-12-16 | 2021-05-18 | Separation and purification method for refining industrial-level high-concentration HF to electronic-level FTrPSA |
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| CN112607707B (en) * | 2020-12-16 | 2022-05-20 | 浙江天采云集科技股份有限公司 | Separation and purification method for FTrPSA (fluorine-doped silica gel) refined from industrial high-concentration HF (hydrogen fluoride) into electronic grade |
| CN113735063B (en) * | 2021-09-26 | 2023-04-18 | 金宏气体股份有限公司 | Purification device and purification process for 9N electronic grade HF |
| CN115385772A (en) * | 2022-07-04 | 2022-11-25 | 中船(邯郸)派瑞特种气体股份有限公司 | Purification method of electronic-grade monofluoromethane |
| CN115160105A (en) * | 2022-07-08 | 2022-10-11 | 苏州金宏气体股份有限公司 | Method and device for purifying hexafluoro-1,3-butadiene by using eddy current technology |
| CN115650173A (en) * | 2022-11-02 | 2023-01-31 | 屈发全 | Preparation method for producing electronic-grade hydrochloric acid by using byproduct HCL of R134A device |
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