WO2022127019A1 - 一种含HF/HCl蚀刻尾气FTrPSA分离与回收循环再利用方法 - Google Patents

一种含HF/HCl蚀刻尾气FTrPSA分离与回收循环再利用方法 Download PDF

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WO2022127019A1
WO2022127019A1 PCT/CN2021/094254 CN2021094254W WO2022127019A1 WO 2022127019 A1 WO2022127019 A1 WO 2022127019A1 CN 2021094254 W CN2021094254 W CN 2021094254W WO 2022127019 A1 WO2022127019 A1 WO 2022127019A1
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gas
hcl
adsorption
tower
rectification
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French (fr)
Chinese (zh)
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钟娅玲
汪兰海
钟雨明
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Zhe Jinag Techairs Cloud Technologies Inc
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Zhe Jinag Techairs Cloud Technologies Inc
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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
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • C01B7/0706—Purification ; Separation of hydrogen chloride
    • C01B7/0712—Purification ; Separation of hydrogen chloride by distillation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • C01B7/0706—Purification ; Separation of hydrogen chloride
    • C01B7/0718—Purification ; Separation of hydrogen chloride 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
    • C01B7/196—Separation; Purification by distillation
    • 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

Definitions

  • the invention relates to the field of environmental protection of effective component recovery and recycling of etching tail gas in a semiconductor manufacturing process, and more particularly to a method for separating, recycling and recycling FTrPSA (full temperature range pressure swing adsorption) of etching tail gas containing HF/HCl .
  • FTrPSA full temperature range pressure swing adsorption
  • Etching on silicon-based (Si) or silicon carbide (SiC)-based wafers or epitaxial films is the most important step in chip manufacturing such as semiconductor integrated circuits (ICs).
  • ICs semiconductor integrated circuits
  • fluorine (F), chlorine-containing Plasma or conventional gas dry etching of (Cl) compounds is widely used in the semiconductor industry; for example, the production of usually integrated circuits (ICs) involves steps such as deposition, masking, etching and stripping in order to form and Connect circuit components like transistors, resistors, and capacitors.
  • Etching technology processing methods and devices such as reactive ion etching (RIE), electron cyclotron resonance (ECR), helical wave source (HWS) and inductively coupled plasma source (ICP), which have appeared successively, are adapted to the requirements of this high-resolution integrated circuit. And generated, such as the etching area is greater than 300mm, the etching line width is less than 0.1 ⁇ m and so on.
  • RIE reactive ion etching
  • ECR electron cyclotron resonance
  • HWS helical wave source
  • ICP inductively coupled plasma source
  • Etching is the process of selectively removing unwanted material from the surface of a silicon- or silicon-carbide-based wafer or epitaxial thin film ("wafer" for short), on a glue-coated wafer Duplicate mask graphics correctly.
  • Etching can also be divided into wet and dry methods. Among them, plasma etching in dry etching has become the main etching process.
  • the gases commonly used in dry etching are mainly fluorine-based gases and the introduction of Cl and Br-based mixed gases, such as hydrogen fluoride (HF), hydrogen chloride (HCl), carbon tetrafluoride (CF 4 ), sulfur hexafluoride (SF 6 ), nitrogen trifluoride (NF 3 ), carbon tetrachloride (CCl 4 ), etc., while hydrogen ( H 2 ), argon (Ar), oxygen (O 2 ), nitrogen (N 2 ), etc. are used as carrier gases to react with Si or SiC on the wafer surface in a low-pressure discharge plasma environment to generate HF in the gas phase.
  • HF hydrogen fluoride
  • HCl hydrogen chloride
  • CF 4 carbon tetrafluoride
  • SF 6 sulfur hexafluoride
  • NF 3 nitrogen trifluoride
  • CCl 4 carbon tetrachloride
  • the etching tail gas has the characteristics of flammable, explosive, toxic and corrosive dangerous chemical gas.
  • the treatment method should not only meet the atmospheric emission standards, but also be effective in technology and economy, and reduce production costs.
  • etching tail gas There are five main methods for industrially treating etching tail gas: water washing, acid-base neutralization, oxidative combustion, adsorption and plasma combustion.
  • the water washing method is aimed at the working conditions where the etching tail gas mainly contains extremely acidic and toxic impurities.
  • the acid components are absorbed to form liquids and the toxic impurities components are converted into non-toxic substances or precipitation (water slurry). emission.
  • this method is simple and easy to operate and widely used in industry, due to the limitation of absorption phase balance and conversion efficiency, and the extremely strong corrosiveness of the formed absorption liquid, many acidic impurity components still remain in the exhaust gas after absorption. It is difficult to fully meet the emission standards, and must be further diluted with air or treated by other methods such as combustion or adsorption, in order to meet the emission standards.
  • the water washing method can also use heated water vapor, which is more conducive to the conversion of harmful impurities into harmless oxides at higher temperatures, so that the purification efficiency of the water washing method becomes higher.
  • the main problem of the water washing method is that it consumes a lot of water, and produces secondary pollutants such as hydrofluoric acid, hydrochloric acid or fluorosilicic acid that are difficult to recover and are highly corrosive, resulting in a large investment in treatment equipment; at the same time, the water washing method forms Some high-fluorine or high-chlorine silicic acid and silicon or silica particle dust are easy to form slurry and block valves or pipes and other equipment, and decompose and corrode equipment under heat, resulting in leakage and other hazards; It has a certain effect in the working conditions that contain more water-soluble harmful impurity components or are prone to conversion reactions with water vapor.
  • the acid-base neutralization method is aimed at the acidic characteristics of the etching tail gas.
  • an alkaline solution such as calcium hydroxide
  • the fluoride ion or HF in it is formed into calcium fluoride (CaF 2 , namely artificial fluorite) or high fluorine/high Calcium chlorosilicate is removed by precipitation or slurry, and the unabsorbed gas is added to other alkaline solutions to further remove the acidic impurities, so that the residual acidic impurities in the tail gas meet the emission standards.
  • the well-known British company EDWARDS invented a chemical neutralization method and device - gas reactor column (GRC, gasreactorcolumn), the principle of which is to use chemical neutralization method to treat exhaust gas; the device
  • the column tube is filled with an appropriate mixture of inorganic small particles.
  • the tail gas undergoes a neutralization reaction through the column tube.
  • the gas reactor column is a dry chemical reaction, which can be directly connected to the vacuum system. Connected, the exhaust gas undergoes a sufficient chemical reaction through the alkaline or metal alkaline substances in the column tube, some are converted into inert substances, and some are adsorbed by the chemical reaction, which greatly reduces the harmful exhaust gas discharged.
  • the replacement frequency of the gas column is relatively high, and sometimes there is incomplete adsorption or penetration of harmful components caused by the deactivation of the reaction column, resulting in secondary pollution.
  • the acid-base neutralization method or chemical neutralization method is still limited by the equilibrium of absorption or chemical adsorption. To completely make the exhaust emission meet the standard, multi-stage or multi-column neutralization reactions are required, and the cost is relatively high.
  • the oxidative combustion method utilizes the flammability of etching exhaust gas containing more flammable components, such as H 2 , silane, silicon tetrafluoride, and organic matter (VOC), etc., under sufficient temperature and time, pass air Or the oxygen-containing compound gas is incinerated in contact with flammable components, so that oxides can be generated, and then the oxidized product is cooled by heat exchange until it is condensed and discharged, and the remaining residual gas is washed with an alkaline solution to remove the acid in the exhaust gas. .
  • flammable components such as H 2 , silane, silicon tetrafluoride, and organic matter (VOC), etc.
  • the etching tail gas contains more non-flammable HF, HCl and other acid gases, this method is not suitable for processing the etching tail gas, especially the tail gas contains specific photoresist, such as polymethyl methyl (PMMA), etc., generally It is difficult to be cleaned in the cleaning process, and a small amount of photoresist remaining in the etching exhaust gas cannot be treated by burning (it will form dioxins or oxazoles), and other physical methods can only be used. At present, the oxidative combustion method is only suitable for the treatment of exhaust gas produced in some chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • the adsorption method is to achieve selective separation and purification according to the physical or chemical adsorption force between the etching tail gas components and the selected specific adsorbent; commonly used aluminum oxide, activated carbon or molecular sieves are highly polar HF. , HCl, H 2 O, SiF 4 , SiH 4 , CO 2 and VOC have obvious adsorption effect. However, due to the strong adsorption force, the regeneration of the adsorbent will be quite difficult, the service life will be short and the cost will rise. It is worth noting that the adsorbents used for the adsorption of HF are relatively special. Most of these adsorbents are fluorides of alkaline metals.
  • the chemical reaction between metal fluorides and HF at lower temperatures is used to selectively carry out chemical adsorption, forming
  • the metal fluoride-HF 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, thus realizing the desorption of HF. Separation and purification.
  • the applicable working conditions of this chemical adsorption method are mostly fluorination reaction to prepare chlorofluoroalkanes (CFC), hydrochlorofluoroalkanes (HCFC), hydrofluoroalkanes (HFC), sulfuryl fluoride (SO 2 F 2 ), etc.
  • the selective adsorption, separation and recovery of HF by the reaction mixture produced by the reaction is relatively good, but the loss rate of the adsorbent is large.
  • the adsorbent will also undergo chemical reaction or co-adsorption phenomenon with impurity components such as water, resulting in pulverization or supersaturated adsorption of the adsorbent, which cannot be effectively treated and Purification; in addition, selective adsorption using metal getter or membrane separation system is more effective for the removal of some impurities, but the effect on etching tail gas is not obvious and the cost is high.
  • One of the biggest problems of the adsorption method is that it is more suitable for the low concentration of adsorbate (impurity) components in the etching tail gas. Increase, the operating cost also increases, the desorption effect is poor.
  • Plasma purification method is currently a popular treatment method, especially for fluorinated exhaust gas, including etching exhaust gas, hydrogen fluoride preparation exhaust gas and other HF-containing exhaust gas.
  • Plasma purification is the use of plasma-enhanced decomposition (destruction) to directly transform harmful components. This transformation is completed in a high-density plasma region obtained by glow discharge or other discharge forms. There are a large number of active particles in the etchant, and these particles can destroy the toxic and refractory substances in the etching exhaust.
  • this method is a very promising exhaust gas treatment method, such as pulsed corona plasma chemical treatment (PPCP, pulsed corona Induced plasma) for nitrogen oxides (NO X ), sulfur dioxide (SO 2 ), Mercury (Hg) vapor and volatile organic compounds (VOCs) have better treatment effect.
  • PPCP pulsed corona plasma chemical treatment
  • NO X nitrogen oxides
  • SO 2 sulfur dioxide
  • SO 2 sulfur dioxide
  • Hg Mercury
  • VOCs volatile organic compounds
  • the removal of NO X and SO 2 is the oxidation reaction of strong free radicals generated by pulsed corona with them, and in the presence of additives such as ammonia (NH 3 ) and H 2 O, it is converted into sulfuric acid Salts and nitrates; VOCs are removed by the excitation, decomposition and ionization of high-energy electrons generated by pulsed corona, and finally CO 2 and CO with simple structure are generated; for fluorinated exhaust gas, hydrogen or hydrogen-containing compounds are added to Such as H 2 , NH 3 or methane (CH 4 ), under plasma conditions, components such as fluorides that are difficult to dissolve in water or difficult to decompose are decomposed, and the generated hydrogen ions (H+) and fluoride ions (F-) or chlorine ions are decomposed.
  • additives such as ammonia (NH 3 ) and H 2 O
  • VOCs are removed by the excitation, decomposition and ionization of high-energy electrons generated by pulsed cor
  • the ions (Cl+) form HF and HCl, which are then washed with water to purify the fluorinated tail gas.
  • the plasma treatment effect of etching tail gas with relatively high content of HF, HCl, etc. is general, and the cost is expensive, so it is only suitable for small-scale tail gas treatment.
  • the object of the present invention is to: provide a kind of HF/HCl etching tail gas FTrPSA (full temperature range pressure swing adsorption) separation and recovery recycling method, and obtain high - purity HF from the dry etching tail gas containing HF/HCl/H , HCl or H 2 and return to the etching process for recycling.
  • FTrPSA full temperature range pressure swing adsorption
  • Full temperature range pressure swing adsorption (full name: Full Temperature Range-Pressure Swing Adsorption, referred to as: FTrPSA) is a method based on pressure swing adsorption (PSA) and can be coupled with various separation technologies. The difference in the absorption/adsorption/rectification and physical and chemical properties of each component (HF/HCl is the effective component, and the rest are impurity components) at different pressures and temperatures.
  • the main and spray absorption, HF rectification/HCl refining (rectification) and condensation are coupled, so that the adsorption and desorption are easy to match and balance the cycle operation in the medium temperature pressure swing adsorption process for separation and purification, so as to achieve HF/HCl recovery and Return to the etching process for recycling.
  • the technical scheme adopted in the present invention is: a method for separating and recycling FTrPSA containing HF/HCl etching tail gas.
  • H 2 Hydrogen
  • active components hydrogen fluoride (HF) and hydrogen chloride (HCl)
  • HCl hydrogen chloride
  • H 2 O water
  • SiF 4 silicon tetrafluoride
  • SiCl 4 silicon tetrachloride
  • silane SiH 4
  • methane CH 4
  • CO carbon dioxide
  • VOCs volatile organic compounds
  • Me+ metal ions
  • fine solids and aerosol particles Part of the impurity components of high fluorosilicic acid/high chlorosilane, the temperature is normal temperature (20-25 °C), and the pressure is normal pressure or slightly positive pressure.
  • Pretreatment control the temperature of the raw material gas to be normal temperature (20-25°C) and the pressure to be 0.2-0.3MPa, and send it to the pretreatment unit to remove dust, particles, oil mist, VOCs, high fluorosilane/acid and High chlorosilane, the purified raw gas formed by pretreatment enters the chlorosilane/HCl spray absorption process, wherein the pretreatment unit includes a dust collector, a particle removal filter, a degreasing mist trap and an activated carbon adsorber;
  • Chlorosilane/HCl spray absorption the chlorosilane/HCl spray absorption process adopts the spray absorption tower of chlorosilane and HCl mixed liquid as the absorbent as the reactor, and the purified raw gas from the pretreatment process is subjected to cold and heat exchange After reaching 50 ⁇ 80°C, it enters from the bottom of the spray absorption tower and conducts reverse mass transfer exchange with the absorbent, wherein the absorption liquid enriched with chlorosilane/HCl flows out from the bottom of the spray absorption tower, and enters the subsequent multi-stage evaporation/ Compression/condensation process, meanwhile, the output of a small amount of residual particles, high-chlorosilane, high-fluorosilane/acid impurities from the bottom of the tower is processed for environmental protection, and the non-condensable gas enriched with HF and low-boiling point components flows out from the top of the spray absorption tower 1 , enter the medium temperature pressure swing adsorption process;
  • the medium temperature pressure swing adsorption process is composed of two stages of pressure swing adsorption, each stage of pressure swing adsorption is composed of more than 2 adsorption towers, and at least one adsorption tower is in the adsorption step, and the rest of the adsorption towers are in the desorption process.
  • the non-condensable gas 1 from the chlorosilane/HCl spray absorption process enters from the bottom of the first-stage PSA (1#PSA) adsorption tower, and the operating pressure of 1#PSA is 0.2 ⁇ 0.3MPa, and the operating temperature is 50 ⁇ 80 °C, Among them, the non-adsorption phase gas flowing out from the top of the adsorption tower in the adsorption step is crude HF gas, and the condensed non-condensable gas 2 is subjected to precision filtration and deionized water absorption to obtain an HF aqueous solution with a concentration of 40%.
  • the non-condensable gas 3 formed after water absorption is output as a hydrogen-rich gas, or used as a fuel gas, or as a raw material gas for pressure swing adsorption hydrogen extraction, and the crude HF liquid formed after condensation is finely filtered to enter the next process.
  • HF rectification the desorption gas flowing out from the bottom of the 1#PSA adsorption tower in the desorption step enters from the bottom of the adsorption tower of the second stage PSA (2#PSA) after pressurization and cold and heat exchange, and the 2#PSA adsorption
  • the operating pressure of the tower is 0.2 to 0.3 MPa, and the operating temperature is 50 to 80 °C.
  • the non-adsorption phase intermediate gas flowing out from the top of the 2#PSA adsorption tower in the adsorption step is different from the non-adsorption phase from the chlorosilane/HCl spray absorption process.
  • the condensed gas 1 is mixed and returned to the 1#PSA adsorption tower, and the effective components HF and HCl are further recovered, and the desorbed gas flowing out from the bottom of the 2#PSA adsorption tower is concentrated gas, which is returned to the chlorosilane/HCl spray absorption process for further recovery. active ingredient;
  • the HF rectification process comprises a rectifying tower formed by two upper and lower sections of rectification, and the rectified HF liquid obtained after the condensation of the thick HF gas from the medium temperature pressure swing adsorption process enters the rectification in the HF rectification process Tower, the rectified HF liquid enters from the top of the lower rectification tower or from the bottom of the upper rectification tower, wherein, the light component impurity gas distilled from the top of the upper rectification tower is returned to the subsequent tail gas absorption process, from the upper rectification tower.
  • the non-condensable gas 4 formed at the bottom of the distillation column or the top distillate from the lower section of the distillation column after condensation is anhydrous HF (AHF) gas, the purity is greater than or equal to 99.99%, directly used as electronic grade HF product gas, returned to dry It is recycled in the etching process.
  • AHF hydrous HF
  • the liquid formed after condensation is used as the reflux of the upper or lower rectification, and the bottoms liquid containing a small amount of heavy component impurity components distilled from the bottom of the lower rectification is formed after condensation.
  • the non-condensable gas 5 a part enters the multi-stage evaporation/compression/condensation process, and the other part enters the tail gas absorption process, and the liquid formed after the condensation returns to the chlorosilane/HCl spray absorption process as an absorbent and is recycled;
  • the absorption liquid from chlorosilane/HCl spray absorption process enters multi-stage evaporation, then enters condenser, therefrom obtains the thick HCl gas of gas phase and the bottom of heavy component tower from HF rectification process
  • the non-condensable gas 5 obtained after the fluid is condensed is mixed, and the thick HCl liquid formed after the condensation enters the HCl refining process, and the crude chlorosilane liquid flows out from the condenser, and enters the subsequent shallow cooling rectification process in the chlorosilane.
  • the non-condensable gas 6 flowing out of the condenser is returned to the medium temperature pressure swing adsorption process after the cold and heat exchange, and the effective components HF and HCl are further recovered;
  • the HCl refining process includes a HCl rectifying column and a vacuum rectifying column, the operating pressure of the HCl rectifying column is 0.3 ⁇ 0.6MPa, the operating temperature is 50 ⁇ 80 °C, and the operating pressure of the vacuum rectifying column is -0.08 ⁇ -0.1MPa, the operating temperature is 60 ⁇ 120°C, among which, the HCl product gas with a purity of more than 99.99% flows out from the top of the HCl rectification tower, a part is returned to the dry etching process for recycling, and the other part is liquefied as chlorosilane/
  • the absorbent of the HCl spray absorption process is recycled, and the effluent from the bottom of the HCl rectification column enters the vacuum rectification column, and the top gas flowing out from the top of the vacuum rectification column is a non-condensable gas 7, and a part enters the subsequent tail gas absorption process,
  • the other part is returned to the medium temperature pressure swing
  • the step of shallow cooling rectification in chlorosilane includes a rectifying column, a crude chlorosilane liquid from a multi-stage evaporation/compression/condensation process, and/or a vacuum column bottom from the HCl refining process
  • the shallow cooling rectification process in the chlorosilane that the heavy component fluid enters, the operating temperature is -35 ⁇ 10 °C, and the operating pressure is 0.6 ⁇ 2.0MPa, wherein, the non-condensable gas 8 flowing out from the top of the rectifying tower is cooled and heated After the exchange, it is returned to the medium temperature pressure swing adsorption process, and the chlorosilane liquid flows out from the bottom of the rectifying tower.
  • a part of it is mixed with HCl to form a mixed solution and returned to the chlorosilane/HCl spray absorption process as an absorbent for recycling, and the other part is mixed with sulfuric acid. Used as an absorbent in the exhaust gas
  • the tail gas absorption process adopts the tail gas absorption tower as the reactor of the chlorosilane liquid and the fresh sulfuric acid mixed solution from the shallow cooling rectification process in the chlorosilane as the absorbent, and the upper stage rectification tower from the HF rectification process
  • the light component impurity gas distilled from the top, the heavy components from the bottom of the lower stage rectification column of the HF rectification process, and the condensed non-condensable gas 5 and the non-condensable gas 7 from the HCl refining process are mixed and then enter the tail gas absorption tower.
  • the fluorosilicic acid solution is formed from the bottom of the absorption tower, and the raw material liquid of the AHF production process prepared by the defluorosilicic acid method is output as a raw material for recycling, and the non-condensable gas 9 flowing out from the top of the absorption tower is directly discharged as an exhaust gas.
  • the purified raw material gas directly enters the medium temperature pressure swing adsorption process, and the crude HF gas flowing out from the top of the 1# PSA tower is not condensed after condensation.
  • Gas 2 the HF aqueous solution with a concentration of 40% is obtained by precision filtration and deionized water absorption, and the non-condensable gas 3 formed after water absorption is output as hydrogen-rich gas, or used as fuel gas, or as pressure swing adsorption.
  • the raw gas of hydrogen, and the crude HF liquid formed by condensation enter HF rectification after precision filtration.
  • the bottom of the adsorption tower of the second stage PSA (2#PSA) enters, and the non-adsorption phase intermediate gas flowing out from the top of the 2#PSA adsorption tower in the adsorption step is directly returned to the 1#PSA adsorption tower to further recover the effective components, while
  • the desorbed gas flowing out from the bottom of the 2#PSA adsorption tower is concentrated gas, and the non-condensable gas 1 formed by the newly installed condenser is mixed with the crude HF gas of the medium temperature pressure swing adsorption process to recover the effective component HF , and the liquid formed from the newly installed condenser directly enters the HCl refining process to recover HCl, wherein the heavy components flowing out from the HCl refining process are directly discharged after treatment, thus eliminating the need for chlorosilane/HCl spraying Absorption, multi-stage evaporation/compression/condensation and rectification of medium-shallow chlorosilane.
  • the purified raw material gas from the pretreatment process enters the chlorosilane/HCl spray absorption process after being exchanged with cold and heat to 80-160 °C, and is sprayed from the top of the absorption tower.
  • the outflowing non-condensable gas 1 and the non-condensable gas 2 formed after condensation enter the medium-temperature pressure swing adsorption process composed of two-stage PSA, and the condensed liquid formed after condensation directly enters the HCl refining process, from the spray absorption tower.
  • the absorbing liquid flowing out from the bottom enters the multi-stage evaporation/compression/condensation process.
  • the purified raw material gas from the pretreatment process enters the chlorosilane/HCl spray absorption process after being exchanged with cold and heat to 80-160° C.
  • the operating pressure of 1#PSA is 0.2 ⁇ 0.3MPa, and the operating temperature is 50 ⁇ 80°C.
  • the non-adsorption phase gas flowing out from the top of the adsorption tower in the adsorption step is the intermediate gas and enters the second stage (2#PSA) for adsorption
  • the non-adsorbed phase gas flowing out from the top of the adsorption tower in the adsorption step is crude HF gas, and the condensed non-condensable gas 3 is subjected to precision filtration and deionized water absorption to obtain a concentration of 40% HF aqueous solution for export.
  • the non-condensable gas 4 formed by water absorption is output as hydrogen-rich gas, or used as fuel gas, or as the raw material gas for pressure swing adsorption hydrogen extraction, and the crude HF liquid formed after condensation, after precision filtration, enters HF
  • the stripping gas flowing out from the bottom of the 1#PSA adsorption tower in the desorption step and the concentrated gas flowing out from the bottom of the 2#PSA adsorption tower are respectively returned to the chlorosilane/HCl spray absorption process to further recover the effective components, without
  • the condensed liquid formed by the condensation of the condensed gas 1 directly enters the HCl refining process, and the absorption liquid flowing out from the bottom of the spray absorption tower enters the multi-stage evaporation/compression/condensation process.
  • the purified raw material gas obtained from the raw material gas through the pretreatment process directly enters the medium temperature pressure swing adsorption process composed of a section of PSA, wherein a section of PSA is composed of 2.
  • adsorption tower It consists of more than one adsorption tower, one adsorption tower is in the adsorption step, and the other adsorption towers are in the desorption step including different stages of decompression and reverse discharge or vacuuming, boosting or final charging, and the operating pressure of the adsorption tower is 0.2 ⁇ 0.3MPa , the operating temperature is 70-90 °C, the purified raw gas enters from the bottom of the PSA adsorption tower, and the non-adsorption phase gas flowing out from the top of the adsorption tower in the adsorption step is adsorption waste gas, which is used as fuel gas, or as pressure swing adsorption for hydrogen extraction.
  • the outflowing heavy component fluid is directly purified by HCl, thereby obtaining HCl product gas, which is returned to the dry etching process for recycling, thus eliminating the need for chlorosilane/HCl spray absorption, multi-stage evaporation/compression/condensation, medium-shallow Cold chlorosilane rectification process, this working condition is also suitable for the separation and recycling of low-concentration HF/HCl acidic exhaust gas after etching tail gas treated by traditional water-washing absorption method.
  • Acid export treatment the washed non-condensable gas 2 is used as fuel gas or as the raw material gas for pressure swing adsorption hydrogen extraction, and the condensate formed after condensation enters the HF rectification process, and the non-condensable gas flows out from the HF rectification process.
  • the HF product gas flowing out from the HF rectification process is returned to the dry etching process for recycling, and the heavy component fluid flowing out from the bottom of the HF rectification tower is directly purified by HCl to obtain HCl products
  • the gas is returned to the dry etching process for recycling, thus eliminating the need for chlorosilane/HCl spray absorption, multi-stage evaporation/compression/condensation, medium-shallow chlorosilane rectification and medium-temperature pressure swing adsorption processes. It is suitable for the separation and recycling of high-concentration HF/HCl generated after plasma cleaning.
  • the raw material gas for pressure swing adsorption and hydrogen extraction is the non-condensable gas or adsorption waste gas generated after washing, wherein the non-condensable gas or adsorption waste gas first enters the drying tower to remove the moisture therein.
  • the present invention realizes the separation and recovery of HF and HCl from the HF/HCl-containing dry etching tail gas, and returns to the etching process for recycling, which greatly reduces the cost of etching gas raw materials and the cost of environmental protection treatment of tail gas, and solves the problem of existing
  • the technology only meets the standard emission and cannot realize the comprehensive utilization of exhaust gas, which fills the gap in this technical field;
  • the present invention utilizes the difference in adsorption/absorption/rectification and condensation coefficients and physical and chemical properties of each component in the raw gas (HF/HCl is an effective component, and the rest are impurity components) at different pressures and temperatures.
  • the two-stage medium temperature pressure swing adsorption process is mainly combined with chlorosilane spray absorption, HF rectification, HCl refining (rectification), chlorosilane rectification and evaporation/compression/condensation.
  • the adsorption and desorption are easy to match and balance the cycle operation for separation and purification, so as to realize the separation and purification of HF/HCl and other impurity components, and return to the dry etching process for recycling;
  • the present invention overcomes the existing chemical adsorption method due to HF and adsorbent at low temperature chemical (Ao combination) reaction to carry out adsorption and decomposition reaction at high temperature to carry out desorption caused by the adsorption and desorption frequent cycle operation process.
  • the high loss rate of the adsorbent and the chemical reaction of the adsorbent with impurity components such as water will lead to serious pulverization and failure of the adsorbent, so that the adsorption and separation cannot be effectively carried out. It is easy to use the two polarities of HF and HCl for adsorption.
  • the present invention can effectively simplify the process under different raw material gas working conditions, and realize the recycling and reuse of HF/HCl, thus, the etching tail gas can be treated with the traditional water washing method or plasma method for the purpose of environmental protection, It will effectively recover HF/HCl and return it to the etching process or dry cleaning process for recycling, which solves the defect that the traditional treatment method cannot be recycled, and also meets the emission requirements;
  • the present invention can recover HF/HCl from the etching tail gas for recycling and reuse, and can also obtain valuable electronic-grade H2 products by adding PSA for hydrogen extraction, and can return to the dry etching process for recycling, or as a The source of hydrogen used in other semiconductor processes.
  • the process carrier gas is argon or nitrogen or mixed with hydrogen
  • electronic-grade argon can be obtained by adjusting PSA for hydrogen extraction or argon or nitrogen extraction, or by adding low-temperature adsorption. Nitrogen and other products.
  • Embodiment 1 is a schematic flowchart of Embodiment 1 of the present invention.
  • Embodiment 2 is a schematic flow chart of Embodiment 2 of the present invention.
  • Embodiment 3 is a schematic flowchart of Embodiment 3 of the present invention.
  • Embodiment 4 is a schematic flow chart of Embodiment 4 of the present invention.
  • Embodiment 5 is a schematic flowchart of Embodiment 5 of the present invention.
  • Embodiment 6 is a schematic flowchart of Embodiment 6 of the present invention.
  • FIG. 7 is a schematic flowchart of Embodiment 7 of the present invention.
  • normal temperature refers to 20-25 °C
  • normal pressure is one atmosphere.
  • a method for separating and recycling FTrPSA containing HF/HCl etching tail gas 83% (v/v), effective components hydrogen fluoride (HF) 9% and hydrogen chloride (HCl) 5%, and a small amount of water (H 2 O), silicon tetrafluoride (SiF 4 ), silicon tetrachloride ( SiCl 4 ), silane (SiH 4 ), methane (CH 4 ), carbon monoxide (CO), carbon dioxide (CO 2 ), and trace or trace amounts of volatile organic compounds (VOCs), metal ions (Me+), fine solids and gases Sol particles (SS), some impurity components of perfluorosilicic acid/perchlorosilane, normal temperature and pressure.
  • the feed gas is pressurized and then sent to a pretreatment unit consisting of a dust collector, a particle removal filter, a degreasing mist trap and an activated carbon adsorber, under the operating conditions of 0.2-0.3MPa pressure and normal temperature
  • a pretreatment unit consisting of a dust collector, a particle removal filter, a degreasing mist trap and an activated carbon adsorber, under the operating conditions of 0.2-0.3MPa pressure and normal temperature
  • dust, particles (SS), oil mist, VOCs, high fluorosilane/acid and high chlorosilane are successively removed, and the formed purified raw gas enters the next process—chlorosilane/HCl spray absorption;
  • Chlorosilane/HCl spray absorption the purified raw material gas from the pretreatment process, after cold and heat exchange to 50 ⁇ 80 °C, enters from the bottom of the spray absorption tower, using chlorosilane and HCl (1:1 ⁇ 1.4 )
  • the mixed liquid is used as an absorbent, and it is sprayed down from the top of the spray absorption tower to carry out reverse mass transfer exchange with the purified raw material gas, and the absorption liquid enriched with chlorosilane/HCl flows out from the bottom of the spray absorption tower, and enters the subsequent multi-stage evaporation.
  • the output of a small amount of residual particles, high-chlorosilane, high-fluorosilane/acid impurities from the bottom of the tower is processed for environmental protection, and the non-condensable gas enriched with HF and low-boiling point components flows out from the top of the spray absorption tower 1. Go directly to the next process—medium temperature pressure swing adsorption;
  • the non-condensable gas 1 from the chlorosilane/HCl spray absorption process enters the medium temperature pressure swing adsorption process composed of two stages of pressure swing adsorption (PSA), and the first and second stages of pressure swing adsorption (1#PSA, 2#PSA) are composed of 3 adsorption towers, 1 adsorption tower is in the adsorption step, and the other 2 adsorption towers are in different stages of desorption including decompression and reverse discharge or vacuuming, boosting or final charging Step
  • the non-condensable gas 1 enters from the bottom of 1#PSA adsorption tower, the operating pressure of 1#PSA is 0.2 ⁇ 0.3MPa, 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: Crude HF gas, the condensed non-condensable gas 2, the HF aqueous solution with a concentration
  • the operating pressure of the 2#PSA adsorption tower is 0.2 ⁇ 0.3MPa, and the operating temperature is 50 ⁇ 80°C, and flows out from the top of the 2#PSA adsorption tower in the adsorption step.
  • the intermediate gas of the non-adsorption phase is mixed with the non-condensable gas 1 from the chlorosilane/HCl spray absorption process and returned to the 1#PSA adsorption tower to further recover the effective components HF and HCl, and flow out from the bottom of the 2#PSA adsorption tower
  • the desorbed gas is concentrated gas, which is returned to the chlorosilane/HCl spray absorption process to further recover the effective components.
  • the liquid formed after condensation is used as the reflux of the upper rectification.
  • the liquid formed after condensation is returned to the chlorosilane/HCl spray absorption process as an absorbent for recycling.
  • the absorption liquid from chlorosilane/HCl spray absorption process enters multi-stage evaporation, then enters condenser, therefrom obtains the thick HCl gas of gas phase and the bottom of heavy component tower from HF rectification process
  • the fluid is mixed with the non-condensable gas 5 obtained after condensation, and the thick HCl liquid formed after condensation enters the next process—HCl refining, flows out the thick chlorosilane liquid from the condenser, and enters the subsequent chlorosilane.
  • Distillation the non-condensable gas 6 flowing out from the condenser is returned to the medium temperature pressure swing adsorption process after the cold and heat exchange, and the effective components HF and HCl are further recovered.
  • the crude HCl liquid from the multi-stage evaporation/compression/condensation process enters the HCl refining process composed of an HCl rectifying column and a vacuum rectifying column, wherein the HCl rectifying column operating pressure is 0.3 ⁇ 0.6MPa , The operating temperature is 50 ⁇ 80°C, the operating pressure of the vacuum rectifying tower is -0.08 ⁇ -0.1MPa, the operating temperature is 60 ⁇ 120°C, and the HCl product gas with a purity greater than 99.99% flows out from the top of the HCl rectifying tower, and a part is returned to It is recycled in the dry etching process, and part of it is liquefied and recycled as the absorbent in the chlorosilane/HCl spray absorption process.
  • the top gas non-condensable gas 7
  • a part enters the subsequent tail gas absorption process, and a part returns to the medium temperature pressure swing adsorption process, and the heavy component that flows out from the bottom of the vacuum rectification tower, a part returns to the multi-stage evaporation/compression/condensation process, and a part enters
  • the next step is the shallow cooling rectification step of chlorosilane.
  • the chlorosilane liquid flows out from the bottom of the tower, and a part forms a mixed solution with HCl in an appropriate ratio (1:1 ⁇ 1.4) as an absorbent and returns to the chlorosilane/HCl spray absorption process for recycling, and a part is mixed with sulfuric acid as the next process— Used as an absorbent for exhaust gas absorption.
  • Tail gas absorption the light fraction impurity gas distilled from the top of the rectifying tower of the upper section of the HF rectifying process is not condensed with the heavy components flowing out from the bottom of the rectifying tower of the lower section of the HF rectifying process and condensed
  • the gas 5 and a part of the non-condensable gas 7 from the HCl purification process are mixed and then enter the tail gas absorption tower using the chlorosilane liquid from the chlorosilane rectification process in the shallow cooling process and the fresh sulfuric acid mixture as the absorbent, and form fluorine from the bottom of the absorption tower.
  • the silicic acid solution is output as the raw material for the production of AHF by the defluorosilicic acid method, and the raw material liquid is recycled for use, and the non-condensable gas 9 flowing out from the top of the absorption tower is directly discharged as the exhaust gas.
  • the purified raw material gas directly enters the medium temperature pressure swing adsorption process, and flows out from the top of the 1#PSA tower.
  • Crude HF gas, the condensed non-condensable gas 2, the HF aqueous solution with a concentration of 40% is obtained through precision filtration and deionized water absorption, and the non-condensable gas 3 formed after water absorption is hydrogen-rich gas output as fuel
  • the crude HF liquid formed after condensation is subjected to precision filtration and then enters the HF rectification.
  • the desorption gas flowing out from the bottom of the 1#PSA adsorption tower in the desorption step is pressurized to 0.2-0.3MPa and then reduced from 2
  • the bottom of the adsorption tower of #PSA enters, and the intermediate gas of non-adsorption phase flowing out from the top of the 2#PSA adsorption tower in the adsorption step is directly returned to the 1#PSA adsorption tower to further recover the effective components, and from the bottom of the 2#PSA adsorption tower
  • the desorbed gas flowing out is concentrated gas, and the non-condensable gas 1 formed by the newly installed condenser is mixed with the crude HF gas of the medium-temperature pressure swing adsorption process to recover the effective component HF, and the effective component HF is recovered from the newly installed condenser.
  • the liquid formed after the condenser directly enters the HCl refining process to recover HCl, wherein the heavy components flowing out from the HCl refining process are directly discharged after treatment, thus eliminating the need for chlorosilane/HCl spray absorption, multi-stage evaporation/compression / Condensation and rectification of chlorosilanes with medium and shallow cooling.
  • the purified feed gas from the pretreatment process is cooled and heat exchanged to 80-160 After °C, it enters the chlorosilane/HCl spray absorption process, the non-condensable gas 1 flowing out from the top of the spray absorption tower, and the non-condensable gas 2 formed after condensation, then enter the medium-temperature pressure swing adsorption process composed of two stages of PSA.
  • the condensed liquid formed after condensation directly enters the HCl refining process, and the absorption liquid flowing out from the bottom of the spray absorption tower enters the multi-stage evaporation/compression/condensation process.
  • the purified raw material gas from the pretreatment process is cooled and heat exchanged to 80-160 °C after Entering the chlorosilane/HCl spray absorption process, the non-condensable gas 1 flowing out from the top of the spray absorption tower, and the non-condensable gas 2 formed after condensation, then enter the medium-temperature pressure swing adsorption process composed of two-stage PSA, in which the non-condensable gas 2 is formed.
  • the condensed gas 2 enters from the bottom of the 1#PSA adsorption tower after being cooled to 50 ⁇ 80°C.
  • the operating pressure of 1#PSA is 0.2 ⁇ 0.3MPa, and the operating temperature is 50 ⁇ 80°C.
  • the gas flowing out from the top of the adsorption tower in the adsorption step The non-adsorbed phase gas is the intermediate gas and enters the bottom of the 2#PSA adsorption tower.
  • the non-adsorbed phase gas flowing out from the top of the adsorption tower in the adsorption step is the crude HF gas.
  • the condensed non-condensable gas 3 is precisely filtered and deionized.
  • the HF aqueous solution with a concentration of 40% is obtained by water absorption, and the non-condensable gas 4 formed after the water absorption is output as a hydrogen-rich gas, which is used as fuel gas, and the crude HF liquid formed by condensation enters HF after precision filtration.
  • the stripping gas flowing out from the bottom of the 1#PSA adsorption tower in the desorption step and the concentrated gas flowing out from the bottom of the 2#PSA adsorption tower are respectively returned to the chlorosilane/HCl spray absorption process to further recover the effective components, without
  • the condensed liquid formed by the condensation of the condensed gas 1 directly enters the HCl refining process, and the absorption liquid flowing out from the bottom of the spray absorption tower enters the multi-stage evaporation/compression/condensation process.
  • the total concentration of HF and HCl in the raw material gas does not exceed 3% and the H2 content exceeds 90%.
  • the purified raw material gas obtained through the pretreatment process directly enters the first stage of PSA.
  • the medium temperature pressure swing adsorption process composed of, wherein, a PSA is composed of 4 adsorption towers, one adsorption tower is in the adsorption step, and the remaining adsorption towers are in different stages of desorption including decompression and reverse discharge or vacuuming, boosting or final charging.
  • the operating pressure of the adsorption tower is 0.2 ⁇ 0.3MPa
  • the operating temperature is 70 ⁇ 90 °C
  • the purified feed gas enters from the bottom of the PSA adsorption tower
  • the non-adsorption phase gas flowing out from the top of the adsorption tower in the adsorption step is the adsorption waste gas, which is used as the adsorption waste gas.
  • the concentrated gas flowing out from the bottom of the adsorption tower in the desorption step the condensed non-condensable gas 1, mixed with the purified raw material gas and returned to the medium-temperature pressure swing adsorption process to further recover the effective components, and the condensed condensed liquid , and then enter the HF rectification process, the non-condensable gas 2 flowing out from the HF rectification process enters the tail gas absorption process for processing, the HF product gas flowing out from the HF rectification process is returned to the dry etching process for recycling, and the HF rectification process is recycled.
  • the heavy component fluid flowing out from the bottom of the tower is directly purified by HCl, thereby obtaining HCl product gas, which is returned to the dry etching process for recycling, thus eliminating the need for chlorosilane/HCl spray absorption, multi-stage evaporation/compression/condensation, Medium-shallow cold chlorosilane rectification process.
  • This working condition is also suitable for the separation, recovery and reuse of the acidic exhaust gas containing low-concentration HF/HCl after the traditional water-washing absorption method is used to treat the etching tail gas.
  • the purified raw material gas after the pretreatment process is condensed to form a non-condensable Gas 1 is eluted with water to remove a small amount of residual acidic components to produce dilute acid for export treatment.
  • the non-condensable gas 2 washed with water is used as fuel gas.
  • the non-condensable gas 3 flowing out of the distillation process enters the tail gas absorption process for processing, the HF product gas flowing out from the HF rectification process is returned to the dry etching process for recycling, and the heavy component fluid flowing out from the bottom of the HF rectification tower directly enters the HCl refining process , the HCl product gas is thus obtained, and returned to the dry etching process for recycling, thereby eliminating the need for chlorosilane/HCl spray absorption, multi-stage evaporation/compression/condensation, medium-shallow cold chlorosilane rectification and medium-temperature pressure swing adsorption. process.
  • This working condition is also suitable for the separation and recycling of high-concentration HF/HCl generated after plasma cleaning.
  • the non-condensable gas or adsorption waste gas generated after water washing is used as fuel gas, and is converted into the raw material gas for pressure swing adsorption hydrogen extraction , wherein, the non-condensable gas or adsorption waste gas first enters the drying tower, removes the moisture and a small amount of fluorine-containing and chlorine-containing acidic components, and then enters the adsorption purification to remove impurities including silane, phosphine, and metal ions.
  • the hydrogen-rich purified methane hydrogen gas is pressurized to 2.6-3.0 MPa, exchanged cold and heat to normal temperature, and then enters the pressure swing adsorption hydrogen extraction process composed of 5 adsorption towers, and flows out from the top of the adsorption tower.
  • Ultra-pure hydrogen enters the hydrogen purification process consisting of metal getters, so as to obtain H2 product gas that meets the electronic-grade hydrogen standard, and returns to the dry etching process for recycling.
  • the desorbed gas flowing from the bottom of the adsorption tower is rich in methane. gas, which is then used as fuel gas.

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