WO2022127018A1 - 一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法 - Google Patents

一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法 Download PDF

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WO2022127018A1
WO2022127018A1 PCT/CN2021/094244 CN2021094244W WO2022127018A1 WO 2022127018 A1 WO2022127018 A1 WO 2022127018A1 CN 2021094244 W CN2021094244 W CN 2021094244W WO 2022127018 A1 WO2022127018 A1 WO 2022127018A1
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rectification
gas
adsorption
grade
tower
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French (fr)
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钟娅玲
汪兰海
钟雨明
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浙江天采云集科技股份有限公司
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Priority to JP2022506378A priority Critical patent/JP7523820B2/ja
Publication of WO2022127018A1 publication Critical patent/WO2022127018A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/195—Separation; Purification
    • C01B7/197—Separation; Purification by adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/195—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/195—Separation; Purification
    • C01B7/196—Separation; Purification by distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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  • the invention relates to the purification and purification of electronic-grade HF prepared by using industrial-grade high-concentration hydrogen fluoride (HF) as a raw material, and more particularly relates to a FTrPSA (full temperature range pressure swing adsorption) separation for the purification of industrial-grade high-concentration HF into electronic grade and purification methods.
  • HF high-concentration hydrogen fluoride
  • Hydrogen fluoride is the basic raw material of fluorine chemical industry, which can be used to manufacture organic fluorine, inorganic fluorine salts and other fields such as fluorine-containing catalysts, fluorosilicic acid, etc. Among them, HF is used in refrigerants, surfactants, fluorine rubber, fluorine coatings, There are more and more applications in organic fluorine fields such as fluorine-containing resins, fluorine-containing pesticides, high-purity fluorine resins, and pharmaceutical intermediates.
  • ultra-high-purity electronic-grade HF gas and liquid
  • IC integrated circuit
  • VLSI very large-scale integrated circuit
  • the industrial preparation and extraction of high-purity HF mainly use industrial-grade high-concentration HF as raw material and adopt distillation/rectification and membrane separation-based purification methods, including rectification, distillation, sub-boiling distillation, decompression Distillation, gas absorption, microfiltration, ultrafiltration and nanofiltration, and various combinations.
  • distillation point distillation point
  • solubility or molecular size between each component in the raw material (liquid/gas) and HF at different temperatures are used to separate the impurities in the raw material one by one.
  • the main impurity components in the raw material are fluorosilicic acid (H 2 SiF 6 ), water (H 2 O), chloride (mainly hydrogen chloride HCl), phosphide (P), metal oxide (MeO), metal ions and Solid particles (SS), etc.
  • Electronic grade HF products are divided into EL (general electronic grade), UP (ultra-pure), UPS (ultra-high purity), UPSS (ultra-high-purity), and the International Semiconductor Industry Association (SEMI) has also formulated the corresponding SEMI-C /S level standard, equivalent to UPS/UPSS level.
  • the commonly used UP electronic grade HF (liquid) indicators in China are: H 2 SiF 6 content less than 100ppm, chloride (Cl) less than 5ppm, P less than 1ppm, MeO/Me+ less than 10ppb, SS ( ⁇ 1 ⁇ m) less than 25 units (pieces)/ml, etc., among which MeO/Me+ impurities such as arsenic (As), magnesium (Mg), calcium (Ca), sodium (Na) and potassium (K), which are particularly water-soluble, must be removed clean, otherwise it has a significant impact on the performance of the semiconductor chip.
  • MeO/Me+ impurities such as arsenic (As), magnesium (Mg), calcium (Ca), sodium (Na) and potassium (K), which are particularly water-soluble, must be removed clean, otherwise it has a significant impact on the performance of the semiconductor chip.
  • the electronic-grade HF liquid used as a cleaning agent for semiconductor chips or wet etching its HF content is different grades such as 49%, and the rest are deionized water. Therefore, the industry usually adopts the fluorite method or the fluorosilicic acid method to prepare the rectification and membrane filtration of the anhydrous HF (AHF) production process to obtain a purified AHF gas with a purity of 99.9%, after absorption with deionized water, and then using Electronic-grade hydrofluoric acid is further purified by controlling spray density, gas-liquid ratio and membrane filtration to obtain electronic-grade HF liquid products.
  • AHF anhydrous HF
  • the adsorption method is used for the purification of HF, in which the adsorbent is mostly the fluoride of basic metal, and the chemical reaction of metal fluoride and HF at a lower temperature is used to selectively carry out chemical adsorption to form metal fluoride-HF.
  • the complex is decomposed at a higher temperature, so as to realize the desorption of HF from the adsorbent, and other impurities have no selectivity on the adsorbent, so as to realize the separation and purification of HF.
  • the applicable working conditions of this chemical adsorption method are mostly fluorination reactions to prepare chlorofluoroalkanes (CFC), hydrochlorofluoroalkanes (HCFC), hydrofluoroalkanes (HFC), sulfuryl fluoride (SO 2 F 2 ), etc.
  • CFC chlorofluoroalkanes
  • HCFC hydrochlorofluoroalkanes
  • HFC hydrofluoroalkanes
  • SO 2 F 2 sulfuryl fluoride
  • the adsorbent will also undergo chemical reaction with water and other impurity components, resulting in serious pulverization and failure of the adsorbent. Deep dehydration and impurity removal cannot be carried out effectively, and the most important thing is that the alkali metal or metal ions on the adsorbent are brought into the HF gas itself due to the chemical reaction with HF, which brings difficulties to the subsequent HF purification. Therefore, the chemical adsorption method can hardly be effectively applied to the preparation of AHF by the fluorite method or the fluorosilicic acid method.
  • Japan is one of the very few countries in the world that has the technology to prepare AHF with a purity of 99.9999% to 99.99999999% (6N to 12N).
  • FTrPSA full temperature range pressure swing adsorption
  • purification method for refining industrial grade high concentration HF into electronic grade
  • full temperature range pressure swing adsorption full name in English
  • FTrPSA Full Temperature Range-Pressure Swing Adsorption
  • PSA pressure swing adsorption
  • H 2 O, H 2 SO 4 , SO 2 , SiF 4 , NH 3 , CO 2 , H 2 SiF 6 and a small amount of HCl, water-soluble Me+ ions and SS particles are the main impurity components) itself in
  • the two-stage medium-temperature pressure swing adsorption process is mainly coupled with HF rectification/membrane separation, so that the adsorption process in the medium-temperature pressure swing adsorption process is adopted. Separation and purification are carried out with the cycle operation that is easy to match and balance with desorption, so as to realize the preparation of electronic grade HF products.
  • An industrial-grade high-concentration HF is refined into an electronic-grade FTrPSA separation and purification method.
  • the raw material gas comes from the industrial-grade high-concentration hydrogen fluoride (HF) gas produced in the production process of preparing anhydrous hydrogen fluoride (AHF) by the fluorite method or the fluorosilicic acid method.
  • HF high-concentration hydrogen fluoride
  • AHF hydrous hydrogen fluoride
  • the first stage PSA (1 # PSA) enters at the bottom of the adsorption tower, the operating pressure of 1 # PSA is 0.2-0.3 MPa, the operating temperature is 50-80 °C, and the non-adsorption phase gas flowing out from the top of the adsorption tower in the adsorption step is refined HF gas, after the condensed non-condensable gas is precisely filtered and absorbed by deionized water, a HF aqueous solution with a concentration of 40-49% is obtained as a general electronic EL grade hydrofluoric acid product for export, and after condensation, it forms
  • the refined HF liquid enters the next process—membrane separation, and the desorption gas flowing out from the bottom of the 1 # PSA adsorption tower in the desorption step is pressurized and exchanged with cold and heat from the adsorption tower of the second stage PSA (2 # PSA).
  • the operating pressure of the 2 # PSA adsorption tower is 0.2 ⁇ 0.3MPa, and the operating temperature is 50 ⁇ 80 °C, and the non-adsorption phase intermediate gas flowing out from the top of the 2 # PSA adsorption tower in the adsorption step is mixed with the raw material gas and returned To 1 # PSA adsorption tower, and the desorption gas flowing out from the bottom of 2 # PSA adsorption tower is concentrated gas, enters subsequent ammonia decarburization process, and further recovers effective components;
  • HF rectification, purified HF liquid from membrane separation operation enters the rectification tower of HF rectification operation, the rectification tower of this operation adopts upper and lower two sections of rectification to form, purifies rectified HF liquid or rectifies from lower section
  • the top of the rectification or from the bottom of the upper rectification, the light component impurity gas distilled from the top of the upper rectification tower is returned to the subsequent tail gas absorption process, or is distilled from the bottom of the upper rectification or from the top of the lower rectification.
  • the non-condensable gas formed by the condensation of the product is AHF gas, the purity is greater than or equal to 99.99%, and it is directly used as the product gas of electronic UP or UPS grade AHF.
  • Ammonia decarburization the concentrated gas from the medium temperature pressure swing adsorption process, after being pressurized to normal pressure or slightly positive pressure, enters the rectification distillate from ammonia water, sulfuric acid and the lower section of the HF rectification process and is condensed
  • the formed liquid is mixed in proportion as the ammonia water decarbonization absorption tower as the absorbent, and the mixed solution of ammonium bicarbonate and ammonium bifluoride formed at the bottom of the absorption tower is output, and is directly used as the return material or pre-production in the production process of AHF prepared by the fluorosilicic acid method. Mix the reaction mass.
  • the medium membrane separation system in step (2) uses a microfiltration membrane or an ultrafiltration membrane as a membrane component.
  • the tail gas absorption process and the light component impurity gas distilled from the top of the rectification tower of the HF rectification process is mixed with the non-condensable gas from the top of the ammonia decarburization absorption tower and enters the tail gas with sulfuric acid as the absorbent.
  • the absorption tower forms a fluorosilicic acid solution from the bottom of the absorption tower, which is output as a raw material and can be directly returned to the raw material liquid for the production of anhydrous hydrogen fluoride AHF by the fluorosilicic acid method.
  • the non-condensable gas flowing out from the top of the absorption tower is used as The exhaust gas is discharged directly.
  • the adsorption tower in the described medium temperature pressure swing adsorption process is filled with active aluminum oxide, silica gel and molecular sieve, and in the adsorbent composition filled in the 1 # PSA adsorption tower, aluminum oxide: silica gel: molecular sieve The weight ratio is (4-6): (2-4): (1-3); in the adsorbent composition loaded in the 2 # PSA adsorption tower, aluminum oxide: silica gel: molecular sieve weight ratio is (3-5 ):(1-3):(3-5).
  • the loading quantity and distribution of the three adsorbents depend on the concentration of HF in the feed gas and the content of impurity components, and the loading quantity distribution of the adsorbents in the second-stage PSA adsorption tower is not the same.
  • the tail gas is absorbed, and the light component impurity gas distilled from the top of the rectification tower of the HF rectification process is mixed with the non-condensable gas from the top of the ammonia decarburization absorption tower and enters the tail gas absorption tower with sulfuric acid as the absorbent,
  • the fluorosilicic acid solution is formed from the bottom of the absorption tower, which is output as a raw material and can be directly returned to the raw material liquid of the production process of preparing AHF by the fluorosilicic acid method, and the non-condensable gas flowing out from the top of the absorption tower is directly discharged as exhaust gas.
  • the refined HF liquid inlet end of the HF rectification process is set at the bottom of the upper section or the top of the lower section, depending on the raw material gas including H 2 O, H 2 SO 4 , SO 2 , SiF 4 , NH 3 , The content of the main impurity components of CO 2 , H 2 SiF 6 .
  • the non-condensable gas formed at the bottom of the upper section of the rectification of the HF rectification process or from the top distillate of the lower section of the rectification after condensation is AHF gas, the purity is greater than or equal to 99.99%, and is further condensed to form AHF.
  • the fluorine exchange resin After the liquid, it enters the fluorine exchange resin to further remove Me+ to form UPSS electronic grade AHF liquid, which can be arbitrarily mixed with deionized water to form HF solution to meet the needs of various concentrations of HF solutions in the semiconductor industry.
  • the high-concentration HF gas produced in the process of preparing AHF by the traditional fluorite method or the fluorosilicic acid method is used as the raw material to prepare the EL/UP/UPS and even the UPSS electronic grade AHF gas or liquid required by the semiconductor industry. , solves the problem that AHF refining is subject to the traditional separation process of rectification, distillation, absorption or chemical adsorption, or the problem of short service life of the adsorbent, and fills the gap in this technical field;
  • the present invention utilizes the differences in the adsorption/condensation/rectification/membrane separation coefficients and physicochemical properties of each component in the raw material gas (HF is an effective component, and the rest are impurity components) itself at different pressures and temperatures,
  • the two-stage medium temperature pressure swing adsorption process is mainly combined with condensation, membrane separation and HF rectification, so that the adsorption and desorption in the medium temperature pressure swing adsorption process can be easily matched and balanced for separation and purification, so as to realize the depth of HF Dehydration and impurity removal;
  • the present invention overcomes the adsorption in the existing chemical adsorption method due to the adsorption of HF and the adsorbent at a low temperature due to a chemical (Aohe) reaction and a decomposition reaction at a high temperature for desorption.
  • a chemical reaction for crude HF or refined HF obtained by the fluorite method or fluorosilicic acid method containing water or sulfuric acid or SiF, the existing adsorbent in chemical adsorption is due to impurities such as water and other components.
  • a chemical reaction also occurs, resulting in serious pulverization and failure of the adsorbent, so that the deep dehydration and impurity removal cannot be carried out effectively.
  • the present invention avoids the occurrence of problems such as poor rectification effect caused by the simple rectification process including the large fluctuation of the temperature in the middle of the rectifying tower, the temperature at the bottom of the tower not meeting the requirements, and the large fluctuation of the HF concentration in the AHF refining process, because
  • two-stage PSA is used to first remove most of the main heavy component impurities, so that the concentration of HF entering the HF rectification process fluctuates less, and the upper and lower two-stage rectification methods are used to realize deep dehydration in the preparation of AHF products. With impurity removal, electronic grade AHF products can be obtained, and 40-49% concentration of HF aqueous solution can also be obtained;
  • the materials of the medium temperature pressure swing adsorption and HF rectification process are returned to the front-end condensation or ammonia decarburization and other processes to further recover HF, so that the AHF product yield exceeds 90%. %, and achieved the exhaust emission standard through the exhaust gas absorption process.
  • Embodiment 1 is a schematic flowchart of Embodiment 1 of the present invention.
  • FIG. 2 is a schematic flowchart of Embodiment 2 of the present invention.
  • Concentration hydrogen fluoride (HF) gas which contains 98% (v/v) HF, 1% water (H 2 O), and other impurities, including sulfur dioxide (SO 2 ), silicon tetrafluoride (SiF 4 ), ammonia (NH 3 ), fluorosilicic acid (H 2 SiF 6 ), carbon dioxide (CO 2 ), chloride (calculated as HCl) in a total of 0.9 to 1.0%, sodium (Na), magnesium (Mg), calcium
  • concentration of metal ions (Me+) dominated by (Ca) and arsenic (As) ions is trace ppm level, the fine particles (dss ⁇ 1 ⁇ m) are greater than 100, the temperature is 20-30°C, and the pressure is normal pressure; specific implementation steps include:
  • the raw material gas is subjected to cold and heat exchange to 60 ⁇ 70 °C and pressurized to 0.2 ⁇ 0.3MPa by the induced draft fan, and then enters the medium temperature pressure swing adsorption process composed of two stages of pressure swing adsorption (PSA), Among them, the first stage PSA (1 # PSA) has three adsorption towers, one adsorption tower is adsorbed, and the other two adsorption towers are respectively depressurized and vacuumed, and the desorption steps of raw material gas pressure and final charging are carried out.
  • PSA pressure swing adsorption
  • the non-adsorption phase gas flowing out from the top of the adsorption tower in the adsorption step is refined HF gas, which is condensed After the non-condensable gas is precisely filtered and absorbed by deionized water, a HF aqueous solution with a concentration of 49% is obtained as a general electronic EL grade hydrofluoric acid product for export, and the refined HF liquid formed after condensation enters the next process.
  • the operating pressure of the PSA adsorption tower is 0.2 ⁇ 0.3MPa, and the operating temperature is 60 ⁇ 70°C.
  • the non-adsorption phase intermediate gas flowing out from the top of the 2 # PSA adsorption tower in the adsorption state is mixed with the raw gas and returned to the 1 # PSA adsorption tower, and the stripping gas flowing out from the bottom of the 2 # PSA adsorption tower is a concentrated gas, enters the subsequent ammonia decarburization process, and further reclaims the effective component;
  • the refined HF liquid from the medium-temperature pressure swing adsorption process and formed by condensation is pressurized to 1.6MPa, and the temperature is 60-70°C, and then enters the separation system by a primary inorganic ceramic membrane, and the membrane pore size is 0.2 ⁇ 0.4 micron, the membrane material is zirconia, titania and alumina composite membrane, the content of zirconia and titania exceeds that of alumina, and the corrosion-resistant tetrafluoroethylene is used as the anti-corrosion sealing material to form a multi-channel internal pressure membrane module,
  • the purified refined HF liquid flows out from one side of the permeable membrane, and the content of SS particles with a diameter greater than 1 ⁇ m is less than 25 (units/ml (Ea/ml), and enters the next process—HF rectification.
  • the SS concentrate is enriched on the side, the SS particles are removed after cooling and sedimentation, and the liquid is heated and pressurized and returned to the membrane
  • the rectification tower of this operation adopts upper and lower two sections of rectification to form, and purified rectified HF liquid is rectified from lower section Entering from the top, the operating temperature of the upper rectifying tower is 18-30 °C, and the light component impurity gas distilled from the top of the upper rectifying tower mainly includes low-boiling impurity components such as SO 2 and SiF 4 , and is returned to the subsequent tail gas
  • the non-condensable gas formed by the condensation of the bottom distillate from the upper rectification is AHF gas with a purity greater than or equal to 99.99%, which is directly used as the product gas of electronic UP or UPS grade AHF, and the liquid formed after condensation , as the reflux of the upper section rectification, the operating temperature of the lower section rectification is 20 ⁇ 100 °C, and the bottoms fluid containing a small amount of heavy component
  • the concentrated gas from the medium temperature pressure swing adsorption process is pressurized to 0.03 ⁇ 0.2MPa by the induced draft fan, then enters the rectification distillate from ammonia water, sulfuric acid and the lower section of the HF rectification process and is condensed
  • the liquid formed is mixed in the ratio of 5:3:2 to the ammonia decarburization absorption tower as the absorbent, and the mixed solution of ammonium bicarbonate and ammonium bifluoride formed at the bottom of the absorption tower is output, which is directly used as the preparation of AHF by the fluorosilicic acid method in the production process.
  • the returned material or premixed reaction material, and the non-condensable gas flowing out from the top of the ammonia decarburization absorption tower enters the subsequent tail gas absorption process;
  • tail gas absorption from the light component impurity gas that the upper section rectifying tower top of HF rectifying operation distills, mixes with the non-condensable gas from the ammonia decarburization absorption tower top and enters the tail gas absorption tower that takes sulfuric acid as absorbent,
  • the fluorosilicic acid solution is formed from the bottom of the absorption tower, which is output as a raw material and can be directly returned to the raw material liquid of the production process of preparing AHF by the fluorosilicic acid method, and the non-condensable gas flowing out from the top of the absorption tower is directly discharged as exhaust gas.
  • the raw material gas is a high-concentration HF gas from the fluorite method to prepare AHF production process, wherein, there is no NH 3 or CO 2 impurity components, and the ammonia decarbonization process can be omitted, That is, the concentrated gas from the medium temperature pressure swing adsorption process is returned to the condensation process in the production process of AHF produced by the fluorite method, and the effective components are further recovered.
  • the ratio of the adsorbent combination loaded in the 1 # PSA adsorption tower of the described medium temperature pressure swing adsorption process is, aluminum oxide: silica gel: molecular sieve is 5: 3: 2, 2 #
  • the combined ratio of adsorbents loaded in the PSA adsorption tower is 4:2:4.

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  • Inorganic Chemistry (AREA)
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Abstract

本发明公开了一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法，涉及以工业级高浓度氟化氢(HF)为原料制备电子级HF的净化提纯，利用工业级AHF(气体)中各组分(HF为有效组分，H 2O、H 2SO 4、SO 2、SiF 4、NH 3、CO 2、H 2SiF 6及微量的HCl、水溶性Me+离子及SS颗粒为主要杂质组分)本身在不同压力与温度下的吸附/精馏/膜分离系数及物理化学性质的差异性，采取以两段中温变压吸附工序为主与HF精馏/膜分离耦合，使得中温变压吸附过程中吸附与解吸易于匹配和平衡的循环操作来进行分离与净化，从而实现电子级HF产品的制取。本发明解决了AHF精制受制于传统精馏、蒸馏、吸收或化学吸附等分离过程的相平衡或吸附剂使用寿命短的问题，填补了该技术领域的空白。

Description

一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法 技术领域
本发明涉及以工业级高浓度氟化氢(HF)为原料制备电子级HF的净化提纯，更具体的说是涉及一种工业级高浓度HF精制为电子级的FTrPSA(全温程变压吸附)分离与提纯方法。
背景技术
氟化氢(HF)是氟化工的基本原料，可用来制造有机氟、无机氟盐及其它诸如含氟催化剂、氟硅酸等领域，其中，HF在制冷剂、表面活性剂、氟橡胶、氟涂料、含氟树脂、含氟农药、高纯度氟树脂、医药中间体等有机氟领域的应用越来越多。目前，随着半导体产业的发展，超高纯度的电子级HF(气体与液体)已广泛应用于集成电路(IC)和超大规模集成电路(VLSI)芯片的清洗、蚀刻及化学沉积制程，是微电子行业制作过程中的关键性基础化工材料之一，此外，还可用作为分析试剂和制备高纯度的含氟化学品及半导体材料。
目前，工业上对于高纯度的HF制备与提取主要是以工业级高浓度的HF为原料并采用蒸馏/精馏及膜分离为主的提纯方法，包括精馏、蒸馏、亚沸蒸馏、减压蒸馏、气体吸收、微滤、超滤及纳滤，以及各种组合等。在这些传统的提纯工艺中，利用原料(液/气)中各组分与HF之间在不同的温度下的挥发度(沸点)或溶解度或分子大小的差异，将原料中杂质一一分离与净化脱除，得到纯度相当的无水HF(AHF)产品。原料中主要杂质组分为氟硅酸(H 2SiF 6)、水(H 2O)、氯化物(以氯化氢HCl为主)、磷化物(P)、金属氧化物(MeO)、金属离子及固体颗粒(SS)等。电子级的HF产品分为EL(一般电子级)、UP(超纯)、UPS(超高纯)、UPSS(超高高纯)，国际半导体行业协会(SEMI)也制定了相应的SEMI-C/S级标准，相当于UPS/UPSS级。比如，国内普遍应用的UP电子级HF(液体)指标为，H 2SiF 6含量小于100ppm、氯化物(Cl)小于5ppm、P小于1ppm、MeO/Me+小于10ppb、SS(≥1μm)小于25单位(个)/毫升，等等，其中MeO/Me+尤为水溶性的砷(As)、镁(Mg)、钙(Ca)、钠(Na)和钾(K)等MeO/Me+杂质，必须脱除干净，否则对半导体芯片的性能产生重大影响。而作为半导体芯片清洗剂或湿法蚀刻的电子级HF液体，其HF含量为不同等级比如49％，其余均为去离子水。因此，工业上通常是采用萤石法或氟硅酸法制备无水HF(AHF)生产过程的精馏和膜过滤后得到纯度为99.9％精AHF气体，用去离子水进行吸收后，再采用控制喷淋密度、气液比及膜过滤等方法使电子级氢氟酸进一步纯化得到电子级HF液体产品。然而，由于精馏过程中的因水和HF以及来自萤石法或氟硅酸法工艺本身产生的其它杂 质诸如硫酸(H 2SO 4)、二氧化硫(SO 2)、氯化氢(HCl)、四氟化硅(SiF 4)、氨(NH 3)及二氧化碳(CO 2)等互溶性，以及精馏分离受到的相平衡限制而无法将这些杂质与HF完全分离掉，进而所得到的精AHF气体中仍含有较多的杂质组分，并带入了后续的去离子水吸收、控制喷淋密度与气液比、膜过滤等工艺中，要通过这些后续的纯化除去微量或痕量的杂质组分也是非常困难的。正因如此，对从萤石法或氟硅酸法制备AHF生产过程中获得的精AHF产品的纯度的调控至关重要。因而，对95～99％含量的工业级HF或AHF原料气直接进行精馏、蒸馏、亚蒸馏或特殊精馏，由于杂质浓度太低，精馏或蒸馏的成本非常高，虽然杂质组分与HF之间的沸点相差较大，但由于水分会影响其它各杂质组分在水中的传质分配，导致精馏或蒸馏受制于相平衡的限制更加严重，纯化深度远远达不到电子级要求。
有报道采用吸附法进行HF精制，其中，吸附剂多为碱性金属的氟化物，利用金属氟化物与HF在较低温度下发生化学反应而选择性地进行化学吸附，形成金属氟化物-HF的络合物，在较高的温度下再进行络合物的分解反应，从而实现HF从吸附剂上脱附，其它杂质在吸附剂上没有选择性，从而实现HF的分离与净化。这种化学吸附法适用的工况，大多为氟化反应制备氟氯烷烃(CFC)、含氢氯氟烷烃(HCFC)、含氢氟烷烃(HFC)、硫酰氟(SO 2F 2)等产品的场合，反应所产生的反应混合气对HF的选择性吸附、分离及回收，效果比较好，但吸附剂损失率大。而对含有水或硫酸或SiF 4等的萤石法或氟硅酸法得到的粗HF或精HF，吸附剂因与水等杂质组分也会发生化学反应导致吸附剂粉化与失效严重而无法有效地进行深度脱水除杂，尤其重要的是，吸附剂上的碱性金属或金属离子因与HF发生化学反应而带入到HF气体本身中，为后续的HF纯化带来了困难。因此，化学吸附法几乎无法对萤石法或氟硅酸法制备AHF过程中有效地应用。这也是为什么我国目前只能生产低等级的电子级AHF产品的主要原因之一，也是2019年韩日两国发生的电子级半导体化学品贸易争端中日本以其技术优势而限制出口电子级AHF给韩国的一个重要原因之一，日本是国际上拥有制备纯度为99.9999％～99.99999999％(6N～12N)AHF技术的极少数国家。
发明内容
本发明的目的在于：针对上述存在的问题，本发明提供一种工业级高浓度HF精制为电子级的FTrPSA(全温程变压吸附)分离与提纯方法，全温程变压吸附(英文全称：Full Temperature Range-Pressure Swing Adsorption，简称：FTrPSA)是一种以变压吸附(PSA)为基础并可与各种分离技术相耦合的方法，利用工业级AHF(气体)中各组分(HF为有效组分，H 2O、H 2SO 4、SO 2、SiF 4、NH 3、CO 2、H 2SiF 6及微量的HCl、水溶性Me+离子及SS颗粒为主要杂质组分)本身在不同压力与温度下的吸附/精馏/膜分离系数及物理化学性质的差异性，采取以两段中温变压吸附工序为主与HF精馏/膜分离耦合，使得中温变压吸附过程中 吸附与解吸易于匹配和平衡的循环操作来进行分离与净化，从而实现电子级HF产品的制取。
本发明采用的技术方案如下：
一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法，原料气来自萤石法或氟硅酸法制备无水氟化氢(AHF)生产过程中产生的工业级高浓度氟化氢(HF)气体，主要含有浓度为95～99％(v/v)的HF，以及硫酸(H 2SO 4)、水(H 2O)，二氧化硫(SO 2)、四氟化硅(SiF 4)、氨(NH 3)、氟硅酸(H 2SiF 6)、二氧化碳(CO 2)、氯化物(以HCl计)、金属离子(Me+)及微细颗粒(SS)杂质组分，其中，Me+以水溶性的钠(Na)、镁(Mg)、钙(Ca)、砷(As)离子为主，SS颗粒直径大于1微米(μm)，温度为20～60℃，压力为常压或微正压；包括如下步骤：
(1)中温变压吸附，原料气经冷热交换至50～80℃并经增压至0.2～0.3MPa后，进入由两段变压吸附(PSA)组成的中温变压吸附工序，每段变压吸附至少2个以上的吸附塔组成，并且至少1个吸附塔处于吸附步骤，其余吸附塔处于包括降压逆放或抽真空、升压或终充的不同阶段的解吸步骤，原料气从第一段PSA(1 #PSA)吸附塔底进入，1 #PSA的操作压力为0.2～0.3MPa，操作温度为50～80℃，从处于吸附步骤的吸附塔顶部流出的非吸附相气体为精HF气体，经冷凝后的不凝气体经精密过滤并经去离子水吸收后，得到浓度为40～49％的HF水溶液作为一般性的电子EL级氢氟酸产品外输，而经冷凝后形成的精HF液体进入下一个工序—膜分离，从处于解吸步骤的1 #PSA吸附塔底流出的解吸气，经增压与冷热交换后从第二段PSA(2 #PSA)的吸附塔底进入，2 #PSA吸附塔的操作压力为0.2～0.3MPa，操作温度为50～80℃，从处于吸附步骤的2 #PSA吸附塔顶流出的非吸附相的中间气体，与原料气混合返回至1 #PSA吸附塔，而从2 #PSA吸附塔底流出的解吸气为浓缩气体，进入后续的氨水脱碳工序，进一步回收有效组分；
(2)膜分离，来自中温变压吸附工序并经冷凝形成的精HF液体，经过增压至1.0～1.6MPa，温度为50～80℃，进入由一级或二级构成的无机陶瓷膜或不锈钢膜分离系统，膜孔径小于1微米，从透过膜的一侧流出净化精HF液体，其中直径大于1μm的SS颗粒含量小于25(个)单位/毫升(Ea/ml)，进入下一个工序—HF精馏，未透过膜的一侧富集SS颗粒浓缩液，并冷却、沉降后脱除SS颗粒，液体经加热加压后返回膜分离系统，进一步回收有效组分；
(3)HF精馏，来自膜分离工序的净化精HF液体，进入HF精馏工序的精馏塔，本工序的精馏塔采用上下两段精馏组成，净化精HF液体或从下段精馏的顶部或从上段精馏的底部进入，从上段精馏塔顶馏出的轻组分杂质气体，返回至后续的尾气吸收工序，或从上段精馏的底部或从下段精馏的顶部馏出物经冷凝后所形成的不凝气体为AHF气体，纯度大于等 于99.99％，直接作为电子UP或UPS级AHF的产品气，经冷凝后所形成的液体，作为上段或下段精馏的回流，从下段精馏的底部馏出的含少量重组分杂质组分的塔底物流体，经冷凝后所形成的不凝气体，返回至中温变压吸附工序，进一步回收有效组分，经冷凝后所形成的液体，作为吸收剂进入下一个工序—氨水脱碳；
(4)氨水脱碳，来自中温变压吸附工序的浓缩气体，经过增压至常压或微正压后，进入由氨水、硫酸及来自HF精馏工序下段精馏馏出物并经冷凝后形成的液体，按比例混合作为为吸收剂的氨水脱碳吸收塔，从吸收塔底形成的碳酸氢铵及氟化氢铵混合溶液输出，直接作为氟硅酸法制备AHF生产过程中的返料或预混合反应物料。
进一步的，步骤(2)的中膜分离系统以微滤膜或超滤膜为膜组件。
进一步的，还包括尾气吸收工序，来自HF精馏工序的上段精馏塔顶馏出的轻组分杂质气体，与来自氨水脱碳吸收塔顶的不凝气体混合进入以硫酸为吸收剂的尾气吸收塔，从吸收塔底形成氟硅酸溶液，作为原料输出，可直接返回至氟硅酸法制备无水氟化氢AHF生产过程的原料液循环使用，而从吸收塔顶流出的不凝气体，作为排放气直接排放。
进一步的，所述的中温变压吸附工序中的吸附塔中装填有活性三氧化二铝、硅胶与分子筛，1 #PSA吸附塔中所装填的吸附剂组合物中三氧化二铝:硅胶:分子筛重量比为(4-6):(2-4):(1-3)；2 #PSA吸附塔中所装填的吸附剂组合物中三氧化二铝:硅胶:分子筛重量比为(3-5):(1-3):(3-5)。
其中，三种吸附剂的装填数量及分布取决于原料气HF浓度的大小与杂质组分含量的大小，并且在二段PSA吸附塔中的吸附剂装填数量分布也不经相同。
进一步的，尾气吸收，来自HF精馏工序的上段精馏塔顶馏出的轻组分杂质气体，与来自氨水脱碳吸收塔顶的不凝气体混合进入以硫酸为吸收剂的尾气吸收塔，从吸收塔底形成氟硅酸溶液，作为原料输出，可直接返回至氟硅酸法制备AHF生产过程的原料液循环使用，而从吸收塔顶流出的不凝气体，作为排放气直接排放。
更进一步的，所述的HF精馏工序的精HF液体进口端，设置在上段底部或下段顶部，取决于原料气中包括H 2O、H 2SO 4、SO 2、SiF 4、NH 3、CO 2、H 2SiF 6主要杂质组分含量的大小。
进一步的，所述的HF精馏工序的上段精馏的底部或从下段精馏的顶部馏出物经冷凝后所形成的不凝气体为AHF气体，纯度大于等于99.99％，经过进一步冷凝形成AHF液体后，进入氟交换树脂，进一步脱除Me+，形成UPSS电子级AHF液体，并可与去离子水任意调配形成HF溶液，满足半导体行业各种浓度的HF溶液的需求。
与现有的技术相比本发明的有益效果是：
1)本发明将由传统的萤石法或氟硅酸法制备AHF生产过程中所产出的高浓度HF气体为原料制备成半导体行业所需的EL/UP/UPS乃至UPSS电子级AHF气体或液体，解决了AHF精制受制于传统精馏、蒸馏、吸收或化学吸附等分离过程的相平衡或吸附剂使用寿命短的问题，填补了该技术领域的空白；
2)本发明利用原料气中各组分(HF为有效组分，其余为杂质组分)本身在不同压力与温度下的吸附/冷凝/精馏/膜分离系数及物理化学性质的差异性，采取以两段中温变压吸附工序为主与冷凝、膜分离及HF精馏耦合，使得中温变压吸附过程中吸附与解吸易于匹配和平衡的循环操作来进行分离与净化，从而实现HF的深度脱水与除杂；
3)本发明克服了现有化学吸附法因HF与吸附剂在低温下发生化学(敖合)反应进行吸附而在高温下发生分解反应进行解吸所导致的吸附与解吸频繁循环操作过程中的吸附剂损失率大的问题，同时，对含有水或硫酸或SiF 4的萤石法或氟硅酸法得到的粗HF或精HF，现有的化学吸附中的吸附剂因与水等杂质组分也会发生化学反应导致吸附剂粉化与失效严重而无法有效地进行深度脱水除杂，本发明采用的是中温变压的物理吸附，可以避免这种现象，吸附剂使用寿命长；
4)本发明避免了AHF精制过程中单纯精馏过程包括精馏塔中部温度出现较大波动、塔底温度达不到要求、HF浓度波动较大导致的精馏效果差等问题的出现，因为本发明是先采用二段PSA将主要的重组分杂质先脱除大部分，使得进入HF精馏工序的HF浓度波动较小，并且采用上下二段精馏方式，从中实现AHF产品制备的深度脱水与除杂，获得电子级AHF产品，同时也可获得40～49％浓度的HF水溶液；
5)本发明在获得电子级AHF产品生产的同时，通过中温变压吸附与HF精馏工序的物料返回至前端的冷凝或氨水脱碳等工艺，进一步回收HF，使得AHF产品收率超过了90％，并通过尾气吸收工序实现了尾气排放的达标。
附图说明
图1为本发明实施例1流程示意图；
图2为本发明实施例2流程示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明，即所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。
实施例1
如图1所示，一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法，原料气来自萤石法及氟硅酸法制备无水氟化氢(AHF)生产过程中产生的工业级高浓度氟化氢(HF)气体，其中，含有浓度为98％(v/v)的HF，含水(H 2O)量为1％，其余的杂质，包括二氧化硫(SO 2)、四氟化硅(SiF 4)、氨(NH 3)、氟硅酸(H 2SiF 6)、二氧化碳(CO 2)、氯化物(以HCl计)总计为0.9～1.0％，钠(Na)、镁(Mg)、钙(Ca)、砷(As)离子为主的金属离子(Me+)浓度为痕量的ppm级，微细颗粒(dss≥1μm)大于100，温度为20～30℃，压力为常压；具体实施步骤包括：
(1)中温变压吸附，原料气经冷热交换至60～70℃并经引风机增压至0.2～0.3MPa后，进入由两段变压吸附(PSA)组成的中温变压吸附工序，其中，第一段PSA(1 #PSA)吸附塔为3个，1个吸附塔吸附，另外2个吸附塔分别进行降压与抽真空、原料气充压与终充的解吸步骤，原料气从1 #PSA吸附塔底进入，1 #PSA的操作压力为0.2～0.3MPa，操作温度为60～70℃，从处于吸附步骤的吸附塔顶部流出的非吸附相气体为精HF气体，经冷凝后的不凝气体经精密过滤并经去离子水吸收后，得到浓度为49％的HF水溶液作为一般性的电子EL级氢氟酸产品外输，而经冷凝后形成的精HF液体进入下一个工序—膜分离，从处于解吸步骤的1 #PSA吸附塔底流出的解吸气，经增压与冷热交换后从第二段PSA(2 #PSA)的吸附塔底进入，2 #PSA是由3个吸附塔组成，其中，1个吸附塔始终处于吸附状态，另外2个吸附塔分别处于降压与抽真空、精HF气体充压与终充的解吸状态，吸附与解吸循环操作，2 #PSA吸附塔的操作压力为0.2～0.3MPa，操作温度为60～70℃，从处于吸附状态的2 #PSA吸附塔顶流出的非吸附相的中间气体，与原料气混合返回至1 #PSA吸附塔，而从2 #PSA吸附塔底流出的解吸气为浓缩气体，进入后续的氨水脱碳工序，进一步回收有效组分；
(2)膜分离，来自中温变压吸附工序并经冷凝形成的精HF液体，经过增压至1.6MPa，温度为60～70℃，进入由一级无机陶瓷膜分离系统，膜孔径为0.2～0.4微米，膜层材料为氧化锆、氧化钛及氧化铝复合膜，氧化锆与氧化钛含量超过氧化铝，以耐腐蚀的四氟乙烯为防腐密封材料，形成多通道内压式的膜组件，从透过膜的一侧流出净化精HF液体，其中直径大于1μm的SS颗粒含量小于25(个)单位/毫升(Ea/ml)，进入下一个工序—HF精馏，未透过膜的一侧富集SS浓缩液，经冷却、沉降后脱除SS颗粒，液体经加热加压后返回膜分离系统，进一步回收有效组分；
(3)HF精馏，来自膜分离工序的净化精HF液体，进入HF精馏工序的精馏塔，本工序的精馏塔采用上下两段精馏组成，净化精HF液体从下段精馏的顶部进入，上段精馏塔的操作温度为18～30℃，从上段精馏塔顶馏出的轻组分杂质气体，主要包括SO 2、SiF 4等低沸点杂质组分，返回至后续的尾气吸收工序，从上段精馏的底部馏出物经冷凝后所形成的不凝气体 为AHF气体，纯度大于等于99.99％，直接作为电子UP或UPS级AHF的产品气，经冷凝后所形成的液体，作为上段精馏的回流，下段精馏的操作温度为20～100℃，从下段精馏的底部馏出的含少量重组分杂质组分的塔底物流体，经冷凝后所形成的不凝气体，返回至中温变压吸附工序，进一步回收有效组分，经冷凝后所形成的液体，作为吸收剂进入后续的氨水脱碳工序，HF精馏的操作压力为0.03～0.2Mpa；
(4)氨水脱碳，自中温变压吸附工序的浓缩气体，经过引风机增压至0.03～0.2MPa后，进入由氨水、硫酸及来自HF精馏工序下段精馏馏出物并经冷凝后形成的液体，按5:3:2的比例混合作为吸收剂的氨水脱碳吸收塔，从吸收塔底形成的碳酸氢铵及氟化氢铵混合溶液输出，直接作为氟硅酸法制备AHF生产过程中的返料或预混合反应物料，而从氨水脱碳吸收塔顶流出的不凝气体，进入后续的尾气吸收工序；
(5)尾气吸收，来自HF精馏工序的上段精馏塔顶馏出的轻组分杂质气体，与来自氨水脱碳吸收塔顶的不凝气体混合进入以硫酸为吸收剂的尾气吸收塔，从吸收塔底形成氟硅酸溶液，作为原料输出，可直接返回至氟硅酸法制备AHF生产过程的原料液循环使用，而从吸收塔顶流出的不凝气体，作为排放气直接排放。
实施例2
如图2所示，在实施例1基础上，原料气是来自萤石法制备AHF生产过程的高浓度HF气体，其中，无NH 3或CO 2杂质组分，可省去氨水脱碳工序，即，来自中温变压吸附工序的浓缩气体，返回至萤石法制备AHF生产过程中的冷凝工序，进一步回收有效组分。
实施例3
在实施例1与2基础上，所述的中温变压吸附工序的1 #PSA吸附塔中所装填的吸附剂组合比例为，三氧化二铝:硅胶:分子筛为5:3:2，2 #PSA吸附塔中所装填的吸附剂组合比例为4:2:4。
以上所述实施例仅表达了本申请的具体实施方式，其描述较为具体和详细，但并不能因此而理解为对本申请保护范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请技术方案构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。

Claims (6)

  1. 一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法，其特征在于，包括如下步骤：
    (1)中温变压吸附，原料气经冷热交换至50～80℃并经增压至0.2～0.3MPa后，进入由两段变压吸附PSA组成的中温变压吸附工序，每段变压吸附至少由2个以上的吸附塔组成，并且至少1个吸附塔处于吸附步骤，其余吸附塔处于包括降压逆放或抽真空、升压或终充的不同阶段的解吸步骤，原料气从1 #PSA吸附塔底进入，1 #PSA的操作压力为0.2～0.3MPa，操作温度为50～80℃，从处于吸附步骤的吸附塔顶部流出的非吸附相气体为精HF气体，经冷凝后的不凝气体经精密过滤并经去离子水吸收后，得到浓度为40～49％的HF水溶液作为一般性的电子EL级氢氟酸产品外输，而经冷凝后形成的精HF液体进入下一个工序—膜分离，从处于解吸步骤的1 #PSA吸附塔底流出的解吸气，经增压与冷热交换后从2 #PSA的吸附塔底进入，2 #PSA吸附塔的操作压力为0.2～0.3MPa，操作温度为50～80℃，从处于吸附步骤的2 #PSA吸附塔顶流出的非吸附相的中间气体，与原料气混合返回至1 #PSA吸附塔，而从2 #PSA吸附塔底流出的解吸气为浓缩气体，进入后续的氨水脱碳工序，进一步回收有效组分；
    (2)膜分离，来自中温变压吸附工序并经冷凝形成的精HF液体，经过增压至1.0～1.6MPa，温度为50～80℃，进入由一级或二级构成的无机陶瓷膜或不锈钢膜分离系统，膜孔径小于1微米，从透过膜的一侧流出净化精HF液体，其中直径大于1μm的SS颗粒含量小于25Ea/ml，进入下一个工序—HF精馏，未透过膜的一侧富集SS颗粒浓缩液，并冷却、沉降后脱除SS颗粒，液体经加热加压后返回膜分离系统，进一步回收有效组分；
    (3)HF精馏，来自膜分离工序的净化精HF液体，进入HF精馏工序的精馏塔，本工序的精馏塔采用上下两段精馏组成，净化精HF液体或从下段精馏的顶部或从上段精馏的底部进入，从上段精馏塔顶馏出的轻组分杂质气体，返回至后续的尾气吸收工序，或从上段精馏的底部或从下段精馏的顶部馏出物经冷凝后所形成的不凝气体为AHF气体，纯度大于等于99.99％，直接作为电子UP或UPS级AHF的产品气，经冷凝后所形成的液体，作为上段或下段精馏的回流，从下段精馏的底部馏出的含少量重组分杂质组分的塔底物流体，经冷凝后所形成的不凝气体，返回至中温变压吸附工序，进一步回收有效组分，经冷凝后所形成的液体，作为吸收剂进入下一个工序—氨水脱碳；
    (4)氨水脱碳，来自中温变压吸附工序的浓缩气体，经过增压至常压或微正压后，进入由氨水、硫酸及来自HF精馏工序下段精馏馏出物并经冷凝后形成的液体，混合作为为吸 收剂的氨水脱碳吸收塔，从吸收塔底形成的碳酸氢铵及氟化氢铵混合溶液输出，直接作为氟硅酸法制备无水氟化氢AHF生产过程中的返料或预混合反应物料。
  2. 如权利要求1所述的一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法，其特征在于，步骤(1)所述的原料气来自萤石法或氟硅酸法制备无水氟化氢AHF生产过程中产生的工业级高浓度氟化氢气体，含有浓度为95～99％(v/v)的HF，以及硫酸(H 2SO 4)、水(H 2O)，二氧化硫(SO 2)、四氟化硅(SiF 4)、氨(NH 3)、氟硅酸(H 2SiF 6)、二氧化碳(CO 2)、氯化物(以HCl计)、金属离子(Me+)及微细颗粒(SS)杂质组分，其中，Me+包括水溶性的钠(Na)、镁(Mg)、钙(Ca)、砷(As)离子，SS颗粒直径大于1μm，温度为20～60℃，压力为常压或微正压。
  3. 如权利要求1所述的一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法，其特征在于，步骤(2)的中膜分离系统以微滤膜或超滤膜为膜组件。
  4. 如权利要求1所述的一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法，其特征在于，还包括尾气吸收工序，来自HF精馏工序的上段精馏塔顶馏出的轻组分杂质气体，与来自氨水脱碳吸收塔顶的不凝气体混合进入以硫酸为吸收剂的尾气吸收塔，从吸收塔底形成氟硅酸溶液，作为原料输出，可直接返回至氟硅酸法制备无水氟化氢AHF生产过程的原料液循环使用，而从吸收塔顶流出的不凝气体，作为排放气直接排放。
  5. 如权利要求1所述的一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法，其特征在于，所述的中温变压吸附工序中的吸附塔中装填有活性三氧化二铝、硅胶与分子筛，1 #PSA吸附塔中所装填的吸附剂组合物中三氧化二铝:硅胶:分子筛重量比为(4-6):(2-4):(1-3)；2 #PSA吸附塔中所装填的吸附剂组合物中三氧化二铝:硅胶:分子筛重量比为(3-5):(1-3):(3-5)。
  6. 如权利要求1所述的一种工业级高浓度HF精制为电子级的FTrPSA分离与提纯方法，其特征在于，所述的HF精馏工序的上段精馏的底部或从下段精馏的顶部馏出物经冷凝后所形成的不凝气体为AHF气体，纯度大于等于99.99％，经过进一步冷凝形成AHF液体后，进入氟交换树脂，进一步脱除Me+，形成UPSS电子级AHF液体，并可与去离子水任意调配形成HF溶液，满足半导体行业各种浓度的HF溶液的需求。
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