CN109052325A - A kind of electron level hydrogen fluoride preparation section - Google Patents

A kind of electron level hydrogen fluoride preparation section Download PDF

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Publication number
CN109052325A
CN109052325A CN201811207361.8A CN201811207361A CN109052325A CN 109052325 A CN109052325 A CN 109052325A CN 201811207361 A CN201811207361 A CN 201811207361A CN 109052325 A CN109052325 A CN 109052325A
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liquid
hydrogen fluoride
gas
tower
condensation
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CN109052325B (en
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杨松
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Chongqing Chemical Research Institute Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0003—Condensation of vapours; Recovering volatile solvents by condensation by using heat-exchange surfaces for indirect contact between gases or vapours and the cooling medium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0033—Other features
    • B01D5/0036—Multiple-effect condensation; Fractional condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0033—Other features
    • B01D5/0054—General arrangements, e.g. flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
    • B01D5/0063—Reflux condensation
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

The present invention relates to technical field of fluorine chemical industry, and in particular to a kind of electron level hydrogen fluoride preparation section.It is characterized in that: including rising cyclic oxidation reaction process, recirculating fluidized bed rectification working process, washing absorption condensation procedure.

Description

A kind of electron level hydrogen fluoride preparation section
Technical field
The present invention relates to technical field of fluorine chemical industry, and in particular to a kind of electron level hydrogen fluoride preparation section.
Background technique
Electron level hydrogen fluoride, for industries such as photovoltaic, integrated circuits, is these rows primarily as cleaning agent and etchant One of crucial auxiliary material of industry, since performance of the arsenic impurities to electronic device seriously affects, the removing of arsenic is fluorination The key technology of hydrogen purification, the method generallyd use is that trivalent arsenic is oxidized to higher boiling pentavalent arsenic compound using oxidant, Volatilization gender gap is recycled to be distilled exclusion.(Patent No. CN201110276860.4, patent name are Chinese invention patent A method of preparing electronic-stage hydrofluoric acid) disclose a kind of method for preparing electronic-stage hydrofluoric acid, comprising the following steps: (1) The gasification of technical grade anhydrous HF raw material: primary industry grade HF is gasified at 35 DEG C；(2) after fluorine gas oxidation and de- light component will gasify HF and fluorine gas be continuously passed through fluorine gas oxidation reactor, be equipped on fluorine gas oxidation reactor adjust reaction mass temperature cooling The top on absorption tower is constantly squeezed into HF on the absorption tower of heat exchanger and built-in filler by circulating pump, makes the fluorine that unreacted is complete The circulation HF counter current contacting that gas and absorption tower flow down；The dosage of fluorine gas is 1-2g/kgHF, and the temperature control of fluorine gas oxidation reaction exists 0-20 DEG C, the pressure of equipment is normal pressure, and the internal circulating load of pump is 10 times for feeding HF mass；(3) high boiling rectifying by top oxygen HF after changing de- light component enters high boiling rectifying column, and the temperature of high boiling the top of the distillation column HF is controlled at 20 DEG C, high boiling rectifying column Reflux ratio is 1-3；(4) HF and fresh electronic grade high-purity water of the water washing and rectification after high boiling rectifying squeeze into water washing and rectification respectively In the tower reactor of tower, water washing and rectification tower is set as two sections, is below washing section, is above rectifying section；In washing section, in tower reactor heater Under the action of, hydrofluoric acid gasifies, and the hydrofluoric acid of reflux and the high purity water being newly added uniformly are distributed by liquid distribution trough On filler, the hydrofluoric acid vapor counter current contacting risen with tower reactor washs the impurity in HF, and tower reactor draws the dense of liquid The temperature of degree control liquid in 70-80%, water washing and rectification tower tower bottom constant temperature reboiler is 48-65 DEG C；Hydrogen fluorine after washing Acid enters rectifying section, and overhead condenser is entered after rectification and purification, and after condensation, partial reflux, reflux ratio is controlled in 2-4, tower Operating pressure be 110kPa, the product of overhead extraction is the anhydrous HF for meeting electronic grade product quality requirement；Wherein: anhydrous The electronic grade product hydrofluoric acid of various concentration is made in HF after being only absorbed by the water.Chinese invention patent (Patent No. CN 201310052553.7 patent name is a kind of preparation method of electronic-stage hydrofluoric acid) disclose a kind of electronic-stage hydrofluoric acid Preparation method, characterized in that anhydrous hydrogen fluoride for industrial use liquid and pure water are passed through in rectifying column, form the hydrogen fluorine of the first concentration Acid；Then hydrogenperoxide steam generator is added, aoxidizes arsenic therein, silicon impurities, then carry out rectifying；The hydrogen fluoride gas that rectifying is obtained It is condensed into hydrogen fluoride liquid, carries out first time filtering, and with absorbing pure water at the hydrofluoric acid of the second concentration, then carry out second of mistake Filter, obtains electronic-stage hydrofluoric acid product；By tail gas absorbing pure water, industrial stage hydrofluoric acid is made.Preparation process of the present invention is simple, Additional impurities are not introduced, the electronic-stage hydrofluoric acid of preparation reaches semiconductor equipment and material international standard SEMI-C7 standard, yield It is high, at low cost, electronic-stage hydrofluoric acid can not only have been prepared using a production process but also the pure stage hydrofluoric acid of analysis can be prepared.
The prior art 1 is distinguished using fluorine gas as the impurity in oxidizing hydrogen fluoride, and with the method for washing rectifying Remove high-boiling components such as HAsF6、MAsF6、H2SO4、H2O、H2SiF6、H3PO4Deng and volatile components SO2、SiF4、PF3、POF3、 AsF5、SF6、PF5Deng, the problem of remaining unsolved, has, first, fluorine gas has severe toxicity, elevated chemical activity and strong oxidizing property, it is existing Conveying machinery such as circulating pump is difficult to solve sealing problem, leakage occurs, serious safety accident easily occurs；Second, by rectifying and washing It is incorporated into and completes not meeting technical specification in a rectifying column；The prior art 2 indicates the arsenic impurities in hydrogen fluoride to electronics device The performance of part seriously affects, and the removing of arsenic is the key technology of hydrogen fluoride purification, and the method that the prior art generallys use is to make Trivalent arsenic is oxidized to higher boiling pentavalent arsenic compound with oxidant, recycles the process of distillation to be excluded, oxidant The problem of generally selecting potassium permanganate, hydrogen peroxide, potassium bichromate etc., remaining unsolved has, first, it is subsequent to introduce other impurities increase The difficulty and cost of processing；Second, the time of oxidation is longer, generally all reach 6~48 hours, energy consumption is higher.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of electron level hydrogen fluoride preparation section, features It is: including rising cyclic oxidation reaction process, recirculating fluidized bed rectification working process, washing absorption condensation procedure.
Process one, rising cyclic oxidation reaction process, rising recirculation reactor keep normal pressure state, are stored in catch box Anhydrous hydrogen fluoride rises through the heating and gasifying for the comb that boils is sent into oxidizing reactor, and 30~31 DEG C of heating temperature, since boiling is arranged It is in fluidized state after hydrogen fluoride gasification in pipe, is bubbled rising as gas-liquid mixed stream and enters oxidizing reactor, hydrogen fluoride gas-liquid After mixing flows through liquid barrier, liquid phase part loses kinetic energy because of the obstruction of liquid barrier and is enriched to oxidizing reactor in the effect of gravity Bottom, gas phase portion rises full of oxidizing reactor top and mixes abundant mass transfer with fluorine gas, due to the vaporizing volume bulbs of pressure Driving and gravity effect, gas-liquid mixed stream enter descending liquid comb condensation, descending liquid comb condensation temperature be 9~10 DEG C, fluorination Hydrogen is condensed into liquid again, and fluorine gas is because lower separate in separating tank with hydrogen fluoride condensate liquid of boiling point returns in oxidizing reactor Portion, condensate liquid are pooled in circulating storage groove through descending liquid comb, and circulating storage groove is connected to by the comb that flows back with catch box, partially fluorinated Hydrogen-cooled lime set enters catch box through reflux comb, and phegma flow is drawn flow ratio, that is, reflux ratio with intermediate products and is designed as 0.2~0.25, due to the effect that transpiration recycles, hydrogen fluoride constantly repeats gasification transpiration and rises, the dirty two-phase circulation of condensation liquefaction Change procedure, mixes with fluorine gas to quickly complete oxidation reaction and form condensate liquid at once again through fluorine gas and is enriched to circulation in gas phase stage In storage tank, after running a period of time, the hydrogen fluoride condensate liquid concentration in circulating storage groove through peroxidating is higher and higher, rear conduct up to standard Intermediate products, which are drawn, is sent into the rectifying of recirculating fluidized bed destilling tower.
Process two, recirculating fluidized bed rectification working process, the hydrogen fluoride liquid after oxidation processes are distilled from design in recirculating fluidized bed Feed liquid port in the middle part of tower body enters, and injects cloth liquid disk, injects 9~10 DEG C of temperature, hydrogen fluoride liquid is after cloth liquid disk is uniformly distributed Constant temperature reboiler is dripped, constant temperature reboiler includes heat exchange tube assemblies and wing plate, and constant temperature reboiler heating temperature is 30 DEG C, hydrogen fluoride Upflowing vapor is formed by gasifying when drop flows to level-one grade wing plate under, enters multistage rotary filter press condenser I across cloth liquid disk, It is 20~21 DEG C of cooling waters that the multistage design of rotary filter press condenser I, which has collet and is passed through temperature, the drop warp that upflowing vapor carries Cyclonic separation forms continuous liquid film, upflowing vapor and the abundant mass transfer of dirty liquid film on multistage I stack shell wall of rotary filter press condenser Enter the multistage rotary filter press condenser II outside recirculating fluidized bed distillation column body, multistage II same design of rotary filter press condenser afterwards Having collet and being passed through temperature is 19.5 ± 0.5 DEG C of cooling waters, and the volatile components hydrogen fluoride content of upflowing vapor constantly mentions at this time Height, the hydrogen fluoride liquid purity condensed out through multistage rotary filter press condenser II are continuously improved and draw from bottom, multistage spinning liquid The design of II bottom of separation condenser has U-shaped fluid-tight component and return pipe, and partially fluorinated hydrogen liquid, which is returned to cloth liquid disk, becomes phegma, Reflux ratio is designed as 0.2~0.25, the phegma that multistage rotary filter press condenser I condenses out in recirculating fluidized bed distillation column body Also again through cloth liquid disk downstream to constant temperature reboiler, then the difficult volatile component HAsF of tower bottom enrichment6、MAsF6Content is increasingly Height, to realize heavy constituent HAsF6、MAsF6Removing, from multistage rotary filter press condenser II discharge fixed gas as tail Pneumatic transmission enters washing absorption condensation tower assembly processing.
Process three, washing absorption condensation procedure, tail gas are imported through air induction conduit, and exhaust temperature is 19~21 DEG C at this time, main Will group be divided into hydrogen fluoride, tail gas flows up through filler and cloth liquid screen in washing absorption tower body, herein with spray pipe fitting sow Hydrofluoric acid condensate liquid mass-and heat-transfer, enter the inlet exhaust gas of condensing tower, the tail of condensing tower through exhaust manifolds through cooling tail gas Gas import and condensation tower body are designed using Venturi tube principle, it is therefore an objective to keep tail gas laggard through the lesser inlet exhaust gas compression of diameter Enter the condensation tower body diffusion being relatively large in diameter, drop is made to be evenly distributed in tail gas, so that the condensation efficiency in condensation tube sheet is improved, Tail gas is discharged after condensation tube sheet completes heat exchange through liquid removing device and exhaust port, the control of exhaust port temperature 9~ 10 DEG C, the hydrofluoric acid condensate liquid that washing absorption tower condenses out collects through filler flows through collector tube recycling along washing absorption tower body wall Into circulation storage tank, the hydrofluoric acid condensate liquid that condensing tower condenses out is recovered in circulation storage tank through condensate outlet, circulating pump Component will recycle the hydrofluoric acid condensate liquid in storage tank and return to spray pipe fitting washing condensation tail gas, due to washing absorption tower, condensing tower Bottom be connected to circulation storage tank, the cleaning solution of washing absorption tower and the condensate liquid of condensing tower, which are pooled to, to be recycled in storage tank, cold Lime set returns to washing absorption tower persistently cooling washing tail gas through circulation pump assembly conveying, then the absorbing pure water in circulation storage tank Hydrofluoric acid concentration is higher and higher, can obtain the industrial hydrofluoric acid of various concentration as needed.
Inventors have found that the international standard SEMI-C7 of semiconductor equipment and material structure ultra-clean and high pure chemical reagent, right Metal impurities require to be lower than 10ppb, due to the doped chemical that arsenic is semiconductor fabrication, to arsenic impurities in hydrofluoric acid standard Content requirement is particularly stringent.Existing method arsenic removal generallys use oxidant and the fluorination arsenic oxidation of volatile trivalent is generated higher boiling five The metal salt or complex compound of valence arsenic, then removed with the method for rectifying.This case is generated high using arsenic impurities in fluorine gas oxidation hydrogen fluoride Boil object HAsF6、MAsF6(metal salt or complex compound of pentavalent arsenic) recycles high-boiling components HAsF6、MAsF6With HF and other components Volatilization gender gap, take multiple equilibrium process, multi-component mixture isolated pure electron level hydrogen fluoride.The work of rectifying Skill process is all using phegma and to rise gas, forms gas-liquid counter current contact, the difficult volatilization group in uprising gas in a distillation column Divide constantly condensation, while it constantly receives the volatile components for gasifying out in the phegma flowed from the top down again, therefore at it In uphill process, wherein the content of volatile components is continuously improved, and higher volatile group from the available purity in the top of tower Divide product, in its downflow processes, volatile components therein constantly gasify another aspect phegma, while it is constantly received again The difficult volatile component condensed out in upflowing vapor, so wherein the content of difficult volatile component is continuously improved, it can in the bottom of tower To obtain the higher difficult volatile component product of purity.The aborning tail gas main component of hydrogen fluoride rectifying is HF steam, and there are also easily Volatile component SO2、SiF4、PF3、POF3、AsF5、SF6、PF5Deng this partial tail gas can use pure water condensing recovery system completely Standby industry stage hydrofluoric acid.
Inventors have found that can be good at solving to be easy leakage as oxidant using fluorine gas using the principle of transpiration circulation It causes casualties and encounters the problem of serious safeties accidents such as explosion occur for hydrogen, be specifically just stored in catch box Anhydrous hydrogen fluoride rises through the heating and gasifying for the comb that boils is sent into oxidizing reactor, and 30~31 DEG C of heating temperature, since boiling is arranged It is in fluidized state after hydrogen fluoride gasification in pipe, is bubbled rising as gas-liquid mixed stream and enters oxidizing reactor, oxidizing reactor Interior design has gas-liquid separator, and gas-liquid separator includes liquid barrier, separating tank, after hydrogen fluoride gas-liquid mixed flows through liquid barrier, liquid Mutually part loses kinetic energy because of the obstruction of liquid barrier and is enriched to oxidizing reactor bottom in the effect of gravity, and gas phase portion rising is filled Full oxidizing reactor top simultaneously mixes abundant mass transfer with fluorine gas, due to the driving of the vaporizing volume bulbs of pressure and the effect of gravity, Gas-liquid mixed stream enters the condensation of descending liquid comb, and descending liquid comb condensation temperature is 9~10 DEG C, and hydrogen fluoride is condensed into liquid again, Fluorine gas is because lower separate in separating tank with hydrogen fluoride condensate liquid of boiling point returns to oxidizing reactor top, and condensate liquid is through descending liquid comb It is pooled in circulating storage groove, circulating storage groove is connected to by the comb that flows back with catch box, and partially fluorinated hydrogen-cooled lime set is through the comb that flows back Into catch box, phegma flow and intermediate products draw flow ratio, that is, reflux ratio and are designed as 0.2~0.25.Circulating storage groove bottom Portion's design has sedimentation basin, for collecting the complex compound particle of precipitating.Due to the effect of transpiration circulation, hydrogen fluoride constantly repeats to gasify Transpiration rises, and condensation liquefaction flows down two-phase circulation change process, mixes with fluorine gas through fluorine gas in gas phase stage and quickly completes oxidation Reaction forms condensate liquid at once again and is enriched in circulating storage groove, after running a period of time, through the fluorination of peroxidating in circulating storage groove Hydrogen-cooled lime set concentration is higher and higher, draws after up to standard as intermediate products.
Inventors have found that the energy handled in prior art plate column or packed tower can be overcome using recirculating fluidized bed rectifying Power is small, and mass-transfer efficiency is low, and pressure drop is big, the small disadvantage of operating flexibility.Recirculating fluidized bed distillation column body is divided into two sections, and top is Rectifying section, lower part are stripping section, and rectifying section design has multistage rotary filter press condenser I, multistage rotary filter press condenser II, stripping Section design has constant temperature reboiler, and the hydrogen fluoride liquid after oxidation processes enters from feed liquid of the design in the middle part of recirculating fluidized bed distillation column body Mouth enters, and injects cloth liquid disk, injects 9~10 DEG C of temperature, and hydrogen fluoride liquid drips constant temperature reboiler after cloth liquid disk is uniformly distributed, permanent Warm reboiler includes heat exchange tube assemblies and wing plate, and constant temperature reboiler heating temperature is 30 DEG C, and hydrogen fluoride drop flows to level-one under Upflowing vapor is formed by gasifying when grade wing plate, enters multistage rotary filter press condenser I, multistage rotary filter press condensation across cloth liquid disk It is 20~25 DEG C of cooling waters that the design of device I, which has collet and is passed through temperature, and the drop that upflowing vapor carries is revolved through cyclonic separation in multistage Continuous liquid film is formed on I stack shell wall of liquid separation condenser, enters recirculating fluidized bed after upflowing vapor and the abundant mass transfer of dirty liquid film Multistage rotary filter press condenser II outside distillation column body, multistage rotary filter press condenser II are similarly designed with collet and are passed through temperature For 19.5 ± 0.5 DEG C of cooling waters, the volatile components hydrogen fluoride content of upflowing vapor is continuously improved at this time, through multistage rotary filter press The hydrogen fluoride liquid purity that condenser II condenses out is continuously improved and draws from bottom, and multistage II bottom of rotary filter press condenser is set In respect of U-shaped fluid-tight component and return pipe, to adjust reflux ratio, partially fluorinated hydrogen liquid can be returned to cloth liquid disk becomes phegma, follows The phegma that multistage rotary filter press condenser I condenses out in ring fluidized bed distillation column body is also again through cloth liquid disk downstream to constant temperature Reboiler, then the difficult volatile component HAsF of tower bottom enrichment6、MAsF6Content is higher and higher, to realize heavy constituent HAsF6、 MAsF6Removing.
Inventors have found that the purpose that multistage rotary filter press condenser I is arranged in recirculating fluidized bed distillation column body is treated as increasing Interconderser uses the cooling water (temperature is 20~25 DEG C) of common room temperature range as cryogen, cheap, is not necessarily to The accurate high-quality cryogen of temperature control, and make operation lines closer to balanced line, reduce the invertibity of distillation process, improves heating power Learn efficiency.
Inventors have found that the structure relative to plate column column plate complexity, multistage cyclone condenser simple, price with structure Cheap advantage, while cyclone liquid gas separation, stack shell inner wall liquid film easy to form, upflowing vapor and the abundant mass transfer of dirty liquid film Feature makes it have the advantage that plate column liquid dispersion is small, film mass transfer coefficient is larger, at the same multi-cyclone have it is more A equilibrium stage or theoretical tray can be arranged according to actual needs, and the pressure drop of cyclone separator is lower, more than packed tower Have power savings advantages.
Inventors have found that HF steam and room temperature fixed gas SO in tail gas2、SiF4、PF3、POF3、AsF5、SF6、PF5It can use The method of pure water condensed absorbent recycles, and tends to occur condense in the implementation process of washing absorption tower and condensing tower The problem of liquid liquid level rises blocking air induction conduit and flows back, the reason is that washing absorption tower could not effectively be connected to condensing tower and be realized The reason of gas-liquid two-phase balance, the gas-liquid two-phase in washing absorption tower and condensing tower are in violent mass-and heat-transfer working condition, Its temperature, pressure are among extremely complicated variation, any one working face in working environment, which is all difficult to realize, balances its gas-liquid Two-phase requirement, such as the gas that circulation storage tank is mingled with are more, and washing absorption tower, which is transported in the pipeline of circulation storage tank, to be occurred Sealing gland phenomenon, cause the liquid storage of washing absorption tower bottom can not convey cause liquid level increase flood air induction conduit and flow back ask Topic, therefore as process conditions permit, realize that washing absorption tower is undoubtedly done well with being effectively connected to for condensing tower Method.Specific embodiment is exactly that the bottom of washing absorption tower, condensing tower is connected to storage tank is recycled, and forms U-shaped linker, the two Hydrofluoric acid condensate liquid collects in circulation storage tank, hydrofluoric acid condensate liquid liquid level away from air induction conduit and exhaust port 1000mm with On, so that fluid-tight is formed in the bottom of washing absorption tower and condensing tower, even if recycling the hydrofluoric acid condensate liquid in storage tank in work It endlessly prepares product or returns to washing absorption tower condensation washing tail gas, due to communicating with each other, liquid level can be maintained Effect balance, fluid-tight remain effective working condition.Tail gas is successively through air induction conduit, filler, cloth liquid screen, spray pipe fitting, row Airway, inlet exhaust gas, condensation tube sheet, liquid removing device, exhaust port complete condensation process, the hydrofluoric acid condensation condensed out Liquid is separated with gas to be pooled in circulation storage tank through collector tube and condensate outlet, and due to the effect of fluid-tight, tail gas can not channelling The problem of air-teturning mixed phenomenon occurs into circulation storage tank, the air induction conduit blocking for conveying tail gas would not occur or even flow back.
Inventors have found that the inlet exhaust gas of condensing tower and condensation tower body are designed using Venturi tube principle, it is therefore an objective to make tail Gas enters the condensation tower body being relatively large in diameter diffusion after the lesser inlet exhaust gas compression of diameter, is distributed drop in tail gas It is even, to improve the condensation efficiency in condensation tube sheet.
Inventors have found that since the bottom of washing absorption tower, condensing tower is connected to circulation storage tank, the washing of washing absorption tower The condensate liquid of liquid and condensing tower is pooled in circulation storage tank, and condensate liquid, which returns to washing absorption tower through circulation pump assembly conveying, to be continued Cooling washing tail gas can obtain various as needed then the hydrofluoric acid concentration of the absorbing pure water in circulation storage tank is higher and higher The industrial hydrofluoric acid of concentration.
Compared with the existing technology, the present invention, which at least contains, has the advantage that first, the knot relative to plate column column plate complexity Structure, multistage cyclone condenser have the advantages that structure is simple, cheap, while cyclone liquid gas separation, stack shell inner wall are easy shape Make it have that plate column liquid dispersion is small, film mass transfer coefficient at the characteristics of liquid film, upflowing vapor and dirty liquid film abundant mass transfer Larger advantage, while multi-cyclone has multiple equilibrium stages or theoretical tray, can be arranged according to actual needs, And the pressure drop of cyclone separator is lower, has more power savings advantages than packed tower；Second, the interior setting of recirculating fluidized bed distillation column body is more The purpose of grade rotary filter press condenser I is treated as increasing interconderser, use common room temperature range cooling water (temperature for 20~25 DEG C), it is cheap, without the cryogen of GOOD TASTE, and make operation lines closer to balanced line, reduces distillation process Invertibity improves thermodynamic efficiency；Third, due to the effect of transpiration circulation, hydrogen fluoride constantly repeats gasification transpiration and rises, cold Lime setization flows down two-phase circulation change process, mixes through fluorine gas in gas phase stage with fluorine gas and quickly completes oxidation reaction shape at once again It is enriched in circulating storage groove at condensate liquid, after running a period of time, the hydrogen fluoride condensate liquid concentration in circulating storage groove through peroxidating It is higher and higher, it is drawn after up to standard as intermediate products.
Detailed description of the invention
Fig. 1 is a kind of schematic view of the front view of electron level hydrogen fluoride preparation section of the present invention.
Fig. 2 is a kind of A-A section arragement construction schematic diagram of electron level hydrogen fluoride preparation section of the present invention.
Fig. 3 is a kind of B full-page proof structural schematic diagram of electron level hydrogen fluoride preparation section of the present invention.
Fig. 4 is a kind of C partial enlargement structural representation of electron level hydrogen fluoride preparation section of the present invention.
Fig. 5 is a kind of D-D section arragement construction schematic diagram of electron level hydrogen fluoride preparation section of the present invention.
I-rising recirculation reactor II-recirculating fluidized bed destilling tower
III-washing absorption condenses tower assembly
1- oxidizing reactor 2- gas-liquid separator 3- circulating storage groove 4- sedimentation basin
5- descending liquid comb 6- boiling comb 7- reflux comb 8- catch box 9- separating tank 10- liquid barrier I 12- recirculating fluidized bed distillation column body 13- feed liquid port 14- constant temperature reboiler of 11- multistage rotary filter press condenser 15- heat exchange tube assemblies 16- wing plate
II 18-U type fluid-tight component 19- return pipe of 17- multistage rotary filter press condenser
20- cloth liquid disk 21- washing absorption tower 22- recycles storage tank 23- and recycles pump assembly
24- condensing tower 25- collector tube 26- washing absorption tower body 27- air induction conduit
28- filler 29- cloth liquid screen 30- sprays pipe fitting 31- exhaust manifolds
32- inlet exhaust gas 33- condenses tower body 34- and condenses tube sheet 35- liquid removing device
36- exhaust port 37- condensate outlet.
Specific embodiment
The present invention is described further with specific embodiment with reference to the accompanying drawing.
As shown in figure 1, figure 2, figure 3, figure 4 and figure 5, a kind of electron level hydrogen fluoride preparation section, it is characterized in that: including transpiration Cyclic oxidation reaction process, recirculating fluidized bed rectification working process, washing absorption condensation procedure.
Process one, rising cyclic oxidation reaction process, rising recirculation reactor I keep normal pressure state, are stored in catch box 8 Anhydrous hydrogen fluoride through boil comb 6 heating and gasifying rise be sent into oxidizing reactor 1,30~31 DEG C of heating temperature, due to boiling It rises after the hydrogen fluoride in comb 6 gasifies in fluidized state, is bubbled rising as gas-liquid mixed stream and enters oxidizing reactor 1, fluorination After the mixing of hydrogen liquid flows through liquid barrier 10, liquid phase part loses kinetic energy because of the obstruction of liquid barrier 10 and is enriched in the effect of gravity 1 bottom of oxidizing reactor, gas phase portion rises full of 1 top of oxidizing reactor and mixes abundant mass transfer with fluorine gas, due to gasification The driving of volume expansion pressure and the effect of gravity, gas-liquid mixed stream enter the condensation of descending liquid comb 5,5 condensation temperature of descending liquid comb It is 9~10 DEG C, hydrogen fluoride is condensed into liquid again, and fluorine gas is separated in separating tank 9 with hydrogen fluoride condensate liquid because boiling point is lower 1 top of oxidizing reactor is returned to, condensate liquid is pooled in circulating storage groove 3 through descending liquid comb 5, and circulating storage groove 3 passes through reflux comb 7 It is connected to catch box 8, partially fluorinated hydrogen-cooled lime set enters catch box 8 through reflux comb 7, and phegma flow and intermediate products are drawn Flow ratio, that is, reflux ratio is designed as 0.2~0.25, and due to the effect of transpiration circulation, hydrogen fluoride constantly repeats to gasify in transpiration It rises, condensation liquefaction flows down two-phase circulation change process, mixes with fluorine gas through fluorine gas in gas phase stage and quickly completes oxidation reaction again At once it forms condensate liquid to be enriched in circulating storage groove 3, after running a period of time, the fluorination in circulating storage groove 3 through peroxidating is hydrogen-cooled Lime set concentration is higher and higher, draws after up to standard as intermediate products and is sent into II rectifying of recirculating fluidized bed destilling tower.
Process two, feed liquid port of the hydrogen fluoride liquid from design at 12 middle part of recirculating fluidized bed distillation column body after oxidation processes 13 enter, and inject cloth liquid disk 20, inject 9~10 DEG C of temperature, hydrogen fluoride liquid drips constant temperature after cloth liquid disk 20 is uniformly distributed and boils again Device 14, constant temperature reboiler 14 include heat exchange tube assemblies 15 and wing plate 16, and 14 heating temperature of constant temperature reboiler is 30 DEG C, hydrogen fluoride liquid Upflowing vapor is formed by gasifying when drop flows to level-one grade wing plate 16 under, cloth liquid disk 20 is passed through and enters multistage rotary filter press condenser I 11, it is 20~21 DEG C of cooling waters that the multistage design of rotary filter press condenser I 11, which has collet and is passed through temperature, what upflowing vapor carried Drop forms continuous liquid film, upflowing vapor and dirty liquid film through cyclonic separation on multistage I 11 stack shell wall of rotary filter press condenser Enter the multistage rotary filter press condenser II 17 outside recirculating fluidized bed distillation column body 12, multistage rotary filter press condensation after abundant mass transfer It is 19.5 ± 0.5 DEG C of cooling waters that device II 17, which is similarly designed with collet and is passed through temperature, at this time the volatile components fluorine of upflowing vapor Change hydrogen content to be continuously improved, the hydrogen fluoride liquid purity that condenses out through multistage rotary filter press condenser II 17 is continuously improved and the bottom of from Portion is drawn, and multistage II 17 bottom of rotary filter press condenser design has U-shaped fluid-tight component 18 and return pipe 19, by partially fluorinated hydrogen liquid Returning to cloth liquid disk 20 becomes phegma, and reflux ratio is designed as 0.2~0.25, multistage spinning liquid point in recirculating fluidized bed distillation column body 12 The phegma condensed out from condenser I 11 is also again through cloth liquid disk 20 downstream to constant temperature reboiler 14, then tower bottom enrichment Difficult volatile component HAsF6、MAsF6Content is higher and higher, to realize heavy constituent HAsF6、MAsF6Removing, from multistage spinning liquid The fixed gas that separation condenser II 17 discharges is sent into washing absorption condensation tower assembly III as tail gas and is handled.
Process three, tail gas are imported through air induction conduit 27, and exhaust temperature is 19~21 DEG C at this time, and main component is hydrogen fluoride, Tail gas flows up through filler 28 and cloth liquid screen 29 in washing absorption tower body 26, the hydrofluoric acid sowed herein with spray pipe fitting 30 Condensate liquid mass-and heat-transfer enters the inlet exhaust gas 32 of condensing tower 24, the tail of condensing tower 24 through cooling tail gas through exhaust manifolds 31 Gas import 32 and condensation tower body 33 are designed using Venturi tube principle, it is therefore an objective to press tail gas through the lesser inlet exhaust gas 32 of diameter Enter the condensation tower body 33 being relatively large in diameter after contracting to spread, drop is made to be evenly distributed in tail gas, to improve in condensation tube sheet 34 Condensation efficiency, tail gas is discharged after condensation tube sheet 34 completes heat exchange through liquid removing device 35 and exhaust port 36, tail gas row The control of 36 temperature of mouth is put at 9~10 DEG C, the hydrofluoric acid condensate liquid that washing absorption tower 21 condenses out collects through filler 28 along washing 26 wall of absorption tower body flows through collector tube 25 and is recovered in circulation storage tank 22, and the hydrofluoric acid condensate liquid that condensing tower 24 condenses out is through cold Condensate outlet 37 is recovered in circulation storage tank 22, and circulation pump assembly 23 returns to spray for the hydrofluoric acid condensate liquid in storage tank 22 is recycled The washing condensation tail gas of pipe fitting 30, since the bottom of washing absorption tower 21, condensing tower 24 is connected to circulation storage tank 22, washing absorption tower 21 cleaning solution and the condensate liquid of condensing tower 24 are pooled in circulation storage tank 22, and condensate liquid is returned through the circulation conveying of pump assembly 23 Washing absorption tower 21 is persistently cooling to wash tail gas, then the hydrofluoric acid concentration of the absorbing pure water in circulation storage tank 22 is higher and higher, The industrial hydrofluoric acid of various concentration can be obtained as needed.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to of the invention Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.

Claims (1)

1. a kind of electron level hydrogen fluoride preparation section, it is characterized in that: including rising cyclic oxidation reaction process, recirculating fluidized bed essence Evaporate process, washing absorption condensation procedure；Process one, rising cyclic oxidation reaction process, rising recirculation reactor keep normal pressure shape State, the anhydrous hydrogen fluoride for being stored in catch box rises through the heating and gasifying for the comb that boils is sent into oxidizing reactor, heating temperature 30 ~31 DEG C, since, in fluidized state, bubbling rising becomes gas-liquid mixed stream and enters oxidation after the hydrogen fluoride gasification in boiling comb Reaction kettle, after hydrogen fluoride gas-liquid mixed flows through liquid barrier, liquid phase part loses kinetic energy and in the work of gravity because of the obstruction of liquid barrier With oxidizing reactor bottom is enriched to, gas phase portion rises full of oxidizing reactor top and mixes abundant mass transfer with fluorine gas, by In the driving of the vaporizing volume bulbs of pressure and the effect of gravity, gas-liquid mixed stream enters the condensation of descending liquid comb, the condensation of descending liquid comb Temperature is 9~10 DEG C, and hydrogen fluoride is condensed into liquid again, and fluorine gas is because boiling point is lower in separating tank and hydrogen fluoride condensate liquid point From oxidizing reactor top is returned to, condensate liquid is pooled in circulating storage groove through descending liquid comb, circulating storage groove by reflux comb with Catch box connection, partially fluorinated hydrogen-cooled lime set enter catch box through reflux comb, and phegma flow and intermediate products draw flow Ratio, that is, reflux ratio is designed as 0.2~0.25, and due to the effect of transpiration circulation, hydrogen fluoride constantly repeats gasification transpiration and rises, cold Lime setization flows down two-phase circulation change process, mixes through fluorine gas in gas phase stage with fluorine gas and quickly completes oxidation reaction shape at once again It is enriched in circulating storage groove at condensate liquid, after running a period of time, the hydrogen fluoride condensate liquid concentration in circulating storage groove through peroxidating It is higher and higher, it is drawn after up to standard as intermediate products and is sent into the rectifying of recirculating fluidized bed destilling tower；Process two, recirculating fluidized bed rectifying Process, the hydrogen fluoride liquid after oxidation processes enter from feed liquid port of the design in the middle part of recirculating fluidized bed distillation column body, inject cloth Liquid disk injects 9~10 DEG C of temperature, and hydrogen fluoride liquid drips constant temperature reboiler after cloth liquid disk is uniformly distributed, and constant temperature reboiler includes Heat exchange tube assemblies and wing plate, constant temperature reboiler heating temperature is 30 DEG C, by gas when hydrogen fluoride drop flows to level-one grade wing plate under Change forms upflowing vapor, enters multistage rotary filter press condenser I across cloth liquid disk, the multistage design of rotary filter press condenser I has folder Covering and being passed through temperature is 20~21 DEG C of cooling waters, and the drop that upflowing vapor carries is through cyclonic separation in multistage rotary filter press condenser Continuous liquid film is formed on I stack shell wall, is entered outside recirculating fluidized bed distillation column body after upflowing vapor and the abundant mass transfer of dirty liquid film Multistage rotary filter press condenser II, it is 19.5 ± 0.5 that multistage rotary filter press condenser II, which is similarly designed with collet and is passed through temperature, DEG C cooling water, the volatile components hydrogen fluoride content of upflowing vapor is continuously improved at this time, cold through multistage rotary filter press condenser II It coagulates the hydrogen fluoride liquid purity got off to be continuously improved and draw from bottom, multistage II bottom of rotary filter press condenser design has U-shaped liquid Sealing assembly and return pipe, partially fluorinated hydrogen liquid, which is returned to cloth liquid disk, becomes phegma, and reflux ratio is designed as 0.2~0.25, circulation The phegma that multistage rotary filter press condenser I condenses out in fluidized distillation tower body also again through cloth liquid disk downstream to constant temperature again Device is boiled, then the difficult volatile component HAsF of tower bottom enrichment6、MAsF6Content is higher and higher, to realize heavy constituent HAsF6、 MAsF6Removing, from multistage rotary filter press condenser II discharge fixed gas as tail gas be sent into washing absorption condensation tower assembly Processing；Process three, washing absorption condensation procedure, tail gas are imported through air induction conduit, and exhaust temperature is 19~21 DEG C, main group at this time It is divided into hydrogen fluoride, tail gas flows up through filler and cloth liquid screen in washing absorption tower body, the hydrogen sowed herein with spray pipe fitting Fluoric acid condensate liquid mass-and heat-transfer, enters the inlet exhaust gas of condensing tower through cooling tail gas through exhaust manifolds, the tail gas of condensing tower into Mouth is designed with condensation tower body using Venturi tube principle, it is therefore an objective to make tail gas after the lesser inlet exhaust gas compression of diameter into straight The biggish condensation tower body diffusion of diameter, makes drop be evenly distributed in tail gas, to improve the condensation efficiency in condensation tube sheet, tail gas It being discharged after condensation tube sheet completes heat exchange through liquid removing device and exhaust port, exhaust port temperature is controlled at 9~10 DEG C, The hydrofluoric acid condensate liquid that washing absorption tower condenses out, which collects to flow through collector tube along washing absorption tower body wall and be recovered to through filler, to follow In ring storage tank, the hydrofluoric acid condensate liquid that condensing tower condenses out is recovered in circulation storage tank through condensate outlet, recycles pump assembly The hydrofluoric acid condensate liquid in storage tank will be recycled and return to spray pipe fitting washing condensation tail gas, due to the bottom of washing absorption tower, condensing tower Portion is connected to circulation storage tank, and the cleaning solution of washing absorption tower and the condensate liquid of condensing tower are pooled in circulation storage tank, condensate liquid Washing absorption tower persistently cooling washing tail gas is returned to through circulation pump assembly conveying, then the hydrogen fluorine of the absorbing pure water in circulation storage tank Acid concentration is higher and higher, can obtain the industrial hydrofluoric acid of various concentration as needed.
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CN112897467A (en) * 2021-03-18 2021-06-04 福建省建阳金石氟业有限公司 Production method of electronic-grade hydrofluoric acid

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