CN109052326A - A kind of application method preparing electron level hydrogen fluoride process unit - Google Patents
A kind of application method preparing electron level hydrogen fluoride process unit Download PDFInfo
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- CN109052326A CN109052326A CN201811207404.2A CN201811207404A CN109052326A CN 109052326 A CN109052326 A CN 109052326A CN 201811207404 A CN201811207404 A CN 201811207404A CN 109052326 A CN109052326 A CN 109052326A
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 63
- 230000008569 process Effects 0.000 title claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 190
- 239000007789 gas Substances 0.000 claims abstract description 112
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 38
- 239000011737 fluorine Substances 0.000 claims abstract description 38
- 238000009835 boiling Methods 0.000 claims abstract description 22
- 238000004821 distillation Methods 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910012213 MAsF6 Inorganic materials 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000003860 storage Methods 0.000 claims description 59
- 238000005406 washing Methods 0.000 claims description 59
- 238000010521 absorption reaction Methods 0.000 claims description 45
- 238000009833 condensation Methods 0.000 claims description 45
- 230000005494 condensation Effects 0.000 claims description 45
- 230000001590 oxidative effect Effects 0.000 claims description 35
- 239000004744 fabric Substances 0.000 claims description 26
- 230000003134 recirculating effect Effects 0.000 claims description 21
- 238000012546 transfer Methods 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 16
- 238000013461 design Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000006698 induction Effects 0.000 claims description 12
- 239000000498 cooling water Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 230000005484 gravity Effects 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 230000005068 transpiration Effects 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 238000002309 gasification Methods 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 230000000712 assembly Effects 0.000 claims description 5
- 238000000429 assembly Methods 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 abstract description 15
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 11
- 229910017049 AsF5 Inorganic materials 0.000 abstract description 4
- 229910019256 POF3 Inorganic materials 0.000 abstract description 4
- 229910004014 SiF4 Inorganic materials 0.000 abstract description 4
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 abstract description 4
- FFUQCRZBKUBHQT-UHFFFAOYSA-N phosphoryl fluoride Chemical compound FP(F)(F)=O FFUQCRZBKUBHQT-UHFFFAOYSA-N 0.000 abstract description 4
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 229960002050 hydrofluoric acid Drugs 0.000 description 34
- 239000000047 product Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001495 arsenic compounds Chemical class 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229960002163 hydrogen peroxide Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- 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
- B01D3/322—Reboiler specifications
Landscapes
- 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 application method for preparing electron level hydrogen fluoride process unit.It is characterized in that: generating high-boiling components HAsF using arsenic impurities in fluorine gas oxidation hydrogen fluoride6、MAsF6, recycle high-boiling components HAsF6、MAsF6With the volatilization gender gap of HF and other components, multiple equilibrium process is taken, multi-component mixture is isolated pure electron level hydrogen fluoride.The process flow of rectifying is all using phegma and to rise gas, forms gas-liquid counter current contact in a distillation column, from the higher volatile components product of the available purity in the top of tower, the higher difficult volatile component product of available purity in the bottom of tower.The aborning tail gas main component of hydrogen fluoride rectifying is HF steam, and there are also volatile components SO2、SiF4、PF3、POF3、AsF5、SF6、PF5Industrial stage hydrofluoric acid can be prepared with pure water condensing recovery completely Deng, this partial tail gas.
Description
Technical field
The present invention relates to technical field of fluorine chemical industry, and in particular to a kind of user for preparing electron level hydrogen fluoride process unit
Method.
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, making for electron level hydrogen fluoride process unit is prepared the object of the present invention is to provide a kind of
With method, it is characterized in that:
Step 1 injects anhydrous hydrogen fluoride to the circulating storage groove of rising recirculation reactor, is observed by visor, guarantee its liquid level position
It sets low in 3~5cm of gas-liquid separator plane in oxidizing reactor, is passed through fluorine gas to oxidizing reactor, keeps in oxidizing reactor
Air pressure and ambient pressure balance, and the II bottom U of multistage rotary filter press condenser of recirculating fluidized bed destilling tower is observed by liquidometer
The liquid level situation of type fluid-tight component guarantees that liquid level is higher than return pipe at least 300mm, it is ensured that U-shaped fluid-tight component, which is in, to be worked normally
State observes washing absorption by liquidometer and condenses the washing absorption tower of tower assembly, circulation storage tank, condensing tower liquid level situation, protects
It demonstrate,proves liquid level and is in and reach 1000mm away from air induction conduit and exhaust port, be higher than circulation 300 mm or more of sump outlet end, opening is followed
The emptying of ring storage tank exhaust valve mixes gas on a small quantity, it is ensured that fluid-tight is in normal operating conditions.
Step 2, the anhydrous hydrogen fluoride for being stored in catch box rises through the heating and gasifying for the comb that boils is sent into oxidation reaction
30~31 DEG C of heating temperature, due to being in fluidized state after the hydrogen fluoride gasification in boiling comb, it is mixed as gas-liquid to be bubbled rising for kettle
Interflow enters oxidizing reactor, and after hydrogen fluoride gas-liquid mixed flows through liquid barrier, liquid phase part loses kinetic energy because of the obstruction of liquid barrier
And it is enriched to oxidizing reactor bottom in the effect of gravity, gas phase portion rises full of oxidizing reactor top and mixes with fluorine gas
Abundant mass transfer, 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, drop
Liquid comb condensation 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 fluorination
Hydrogen-cooled lime set separation returns to oxidizing reactor top, and condensate liquid is pooled in circulating storage groove through descending liquid comb, and circulating storage groove passes through
Reflux comb is connected to catch box, and partially fluorinated hydrogen-cooled lime set enters catch box, phegma flow and intermediate production through reflux comb
Product draw flow ratio, that is, reflux ratio and are designed as 0.2~0.25, and due to the effect of transpiration circulation, hydrogen fluoride constantly repeats gasification and steams
Rise rising, condensation liquefaction flows down two-phase circulation change process, mixes with fluorine gas that quickly complete oxidation anti-through fluorine gas in gas phase stage
Condensate liquid should be formed at once again to be enriched in circulating storage groove, after running a period of time, through the hydrogen fluoride of peroxidating in circulating storage groove
Condensate liquid concentration is higher and higher, draws after up to standard as intermediate products and is sent into the rectifying of recirculating fluidized bed destilling tower.
Step 3, hydrogen fluoride liquid after oxidation processes from feed liquid port of the design in the middle part of recirculating fluidized bed distillation column body into
Enter, inject cloth liquid disk, injects 9~10 DEG C of temperature, hydrogen fluoride liquid drips constant temperature reboiler after cloth liquid disk is uniformly distributed, and constant temperature is again
Boiling device includes heat exchange tube assemblies and wing plate, and constant temperature reboiler heating temperature is 30 DEG C, and hydrogen fluoride drop flows to the level-one grade wing under
Upflowing vapor is formed by gasifying when plate, enters multistage rotary filter press condenser I, multistage rotary filter press condenser I across cloth liquid disk
It is 20~21 DEG C of cooling waters that design, which has collet and is passed through temperature, and the drop that upflowing vapor carries is through cyclonic separation in multistage spinning liquid point
From continuous liquid film is formed on I stack shell wall of condenser, enters recirculating fluidized bed after upflowing vapor and the abundant mass transfer of dirty liquid film and distill
Multistage rotary filter press condenser II outside tower body, multistage rotary filter press condenser II, which is similarly designed with collet and is passed through temperature, is
19.5 ± 0.5 DEG C of cooling waters, the volatile components hydrogen fluoride content of upflowing vapor is continuously improved at this time, cold through multistage rotary filter press
The hydrogen fluoride liquid purity that condenser II condenses out is continuously improved and draws from bottom, multistage II bottom of rotary filter press condenser design
There are 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, 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.
Step 4, tail gas are imported through air induction conduit, and exhaust temperature is 19~21 DEG C at this time, and main component is hydrogen fluoride, tail
Gas flows up through filler and cloth liquid screen in washing absorption tower body, the hydrofluoric acid condensate liquid mass transfer sowed herein with spray pipe fitting
Heat transfer, the inlet exhaust gas of condensing tower is entered through cooling tail gas through exhaust manifolds, and inlet exhaust gas and the condensation tower body of condensing tower are adopted
It is designed with Venturi tube principle, it is therefore an objective to tail gas be made to enter the condensing tower being relatively large in diameter after the lesser inlet exhaust gas compression of diameter
Body diffusion, makes drop be evenly distributed in tail gas, to improve the condensation efficiency in condensation tube sheet, tail gas is completed through condensation tube sheet
It is discharged after heat exchange through liquid removing device and exhaust port, at 9~10 DEG C, washing absorption tower condenses the control of exhaust port temperature
The hydrofluoric acid condensate liquid to get off through filler collect along washing absorption tower body wall flow through collector tube be recovered to circulation storage tank in, condensing tower
The hydrofluoric acid condensate liquid condensed out is recovered in circulation storage tank through condensate outlet, and circulation pump assembly will recycle the hydrogen in storage tank
Fluoric acid condensate liquid returns to spray pipe fitting washing condensation tail gas, since the bottom of washing absorption tower, condensing tower is connected to circulation storage tank,
The cleaning solution of washing absorption tower and the condensate liquid of condensing tower are pooled in circulation storage tank, and condensate liquid is returned through circulation pump assembly conveying
Washing absorption tower persistently cooling washing tail gas is returned, then the hydrofluoric acid concentration of the absorbing pure water in circulation storage tank is higher and higher, it can
The industrial hydrofluoric acid of various concentration is obtained 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 for the application method for preparing electron level hydrogen fluoride process unit of the present invention.
Fig. 2 is that a kind of A-A section arragement construction for the application method for preparing electron level hydrogen fluoride process unit of the present invention is shown
It is intended to.
Fig. 3 is a kind of B full-page proof structural schematic diagram for the application method for preparing electron level hydrogen fluoride process unit of the present invention.
Fig. 4 is a kind of C partial enlargement structural representation for the application method for preparing electron level hydrogen fluoride process unit of the present invention
Figure.
Fig. 5 is that a kind of D-D section arragement construction for the application method for preparing electron level hydrogen fluoride process unit of the present invention is shown
It is intended to.
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 application method preparing electron level hydrogen fluoride process unit, it is special
Sign is:
Step 1 injects anhydrous hydrogen fluoride to the circulating storage groove 3 of rising recirculation reactor I, is observed by visor, guarantee its liquid level
Position is passed through fluorine gas lower than 2 3~5cm of plane of gas-liquid separator in oxidizing reactor 1, to oxidizing reactor 1, keeps oxidation reaction
Air pressure and ambient pressure balance in kettle 1, and the multistage rotary filter press condenser II of recirculating fluidized bed destilling tower is observed by liquidometer
The liquid level situation of the U-shaped fluid-tight component in bottom guarantees that liquid level is higher than return pipe at least 300mm, it is ensured that U-shaped fluid-tight component is in normal
Working condition observes washing absorption by liquidometer and condenses the washing absorption tower of tower assembly, circulation storage tank, condensing tower liquid level shape
Condition guarantees that liquid level is in and reaches 1000mm away from air induction conduit and exhaust port, is higher than circulation 300 mm or more of sump outlet end, beats
The emptying of open cycle storage tank exhaust valve mixes gas on a small quantity, it is ensured that fluid-tight is in normal operating conditions.
Step 2, the anhydrous hydrogen fluoride for being stored in catch box 8 rises through the heating and gasifying for the comb 6 that boils is sent into oxidation reaction
Kettle 1,30~31 DEG C of heating temperature, due to being in fluidized state after the hydrogen fluoride gasification in boiling comb 6, being bubbled to rise becomes gas-liquid
Mixed flow enters oxidizing reactor 1, and after hydrogen fluoride gas-liquid mixed flows through liquid barrier 10, liquid phase part loses because of the obstruction of liquid barrier 10
Remove kinetic energy and be enriched to 1 bottom of oxidizing reactor in the effect of gravity, gas phase portion rise full of 1 top of oxidizing reactor and with
Fluorine gas mixes abundant mass transfer, and due to the driving of the vaporizing volume bulbs of pressure and the effect of gravity, gas-liquid mixed stream enters descending liquid row
Pipe 5 condenses, and 5 condensation temperature of descending liquid comb is 9~10 DEG C, and hydrogen fluoride is condensed into liquid again, fluorine gas because boiling point it is lower
Separating tank 9 is separated with hydrogen fluoride condensate liquid returns to 1 top of oxidizing reactor, and condensate liquid is pooled to circulating storage groove 3 through descending liquid comb 5
In, circulating storage groove 3 is connected to by the comb 7 that flows back with catch box 8, and partially fluorinated hydrogen-cooled lime set enters catch box through reflux comb 7
8, phegma flow and intermediate products draw flow ratio, that is, reflux ratio and are designed as 0.2~0.25, due to the effect of transpiration circulation,
Hydrogen fluoride constantly repeat to gasify it is rising rise, condensation liquefaction flows down two-phase circulation change process, in gas phase stage and fluorine gas through fluorine
Gas mixing quickly completes oxidation reaction, and formation condensate liquid is enriched in circulating storage groove 3 at once again, after running a period of time, circulation storage
Hydrogen fluoride condensate liquid concentration in slot 3 through peroxidating is higher and higher, draws after up to standard as intermediate products and is sent into recirculating fluidized bed
II rectifying of destilling tower.
Step 3, 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, to adjust reflux ratio,
Partially fluorinated hydrogen liquid can be returned to cloth liquid disk 20 becomes phegma, multistage rotary filter press condensation in recirculating fluidized bed distillation column body 12
The phegma that device I 11 condenses out is also again through cloth liquid disk 20 downstream to constant temperature reboiler 14, then the difficult volatilization of tower bottom enrichment
Component HAsF6、MAsF6Content is higher and higher, to realize heavy constituent HAsF6、MAsF6Removing, it is cold from multistage rotary filter press
The fixed gas that condenser II 17 discharges is sent into washing absorption condensation tower assembly III as tail gas and is handled.
Step 4, 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 (6)
1. a kind of application method for preparing electron level hydrogen fluoride process unit, it is characterized in that: step 1, to rising recirculation reactor
Circulating storage groove inject anhydrous hydrogen fluoride, observed by visor, guarantee its liquid level position lower than gas-liquid separation in oxidizing reactor
Device 3~5cm of plane is passed through fluorine gas to oxidizing reactor, keeps air pressure and ambient pressure in oxidizing reactor to balance, passes through liquid level
The liquid level situation of the multistage U-shaped fluid-tight component in II bottom of rotary filter press condenser of meter observation recirculating fluidized bed destilling tower, guarantees liquid
Face is higher than return pipe at least 300mm, it is ensured that U-shaped fluid-tight component is in normal operating conditions, observes washing absorption by liquidometer
Washing absorption tower, the circulation storage tank, condensing tower liquid level situation for condensing tower assembly, guarantee that liquid level is in and arrange away from air induction conduit and tail gas
Mouth is put up to 1000mm, is higher than circulation 300 mm or more of sump outlet end, circulation storage tank exhaust valve emptying is opened and mixes gas on a small quantity,
Ensure that fluid-tight is in normal operating conditions；Step 2 is stored in the anhydrous hydrogen fluoride of catch box through the heating and gasifying for the comb that boils
Rise and is sent into oxidizing reactor, 30~31 DEG C of heating temperature, due to being in fluidized state, drum after the hydrogen fluoride gasification in boiling comb
Bubble, which rises, enters oxidizing reactor as gas-liquid mixed stream, and after hydrogen fluoride gas-liquid mixed flows through liquid barrier, liquid phase part is because keeping off liquid
The obstruction of plate loses kinetic energy and is enriched to oxidizing reactor bottom in the effect of gravity, and gas phase portion, which rises, is full of oxidizing reactor
Top simultaneously mixes abundant mass transfer with fluorine gas, and due to the driving of the vaporizing volume bulbs of pressure and the effect of gravity, gas-liquid mixed is flowed into
Enter the condensation of descending liquid comb, descending liquid comb condensation temperature is 9~10 DEG C, and hydrogen fluoride is condensed into liquid again, and fluorine gas is because of boiling point
Lower separate in separating tank with hydrogen fluoride condensate liquid returns to oxidizing reactor top, and condensate liquid is pooled to circulation storage through descending liquid comb
In slot；Step 3, 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,
Cloth liquid disk is injected, injects 9~10 DEG C of temperature, hydrogen fluoride liquid drips constant temperature reboiler after cloth liquid disk is uniformly distributed, and constant temperature boils again
Device 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 grade wing plate under
When by gasifying to form upflowing vapor, enter multistage rotary filter press condenser I across cloth liquid disk, multistage rotary filter press condenser I is set
In respect of collet and temperature is passed through as 20~21 DEG C of cooling waters, and the drop that upflowing vapor carries is through cyclonic separation in multistage rotary filter press
Continuous liquid film is formed on I stack shell wall of condenser, enters recirculating fluidized bed destilling tower after upflowing vapor and the abundant mass transfer of dirty liquid film
External multistage rotary filter press condenser II, it is 19.5 that multistage rotary filter press condenser II, which is similarly designed with collet and is passed through temperature,
± 0.5 DEG C of cooling water, the volatile components hydrogen fluoride content of upflowing vapor is continuously improved at this time, through multistage rotary filter press condenser
The II hydrogen fluoride liquid purity condensed out is continuously improved and draws from bottom, multistage rotary filter press in recirculating fluidized bed distillation column body
The phegma that condenser I condenses out is also again through cloth liquid disk downstream to constant temperature reboiler, then the difficult volatilization group of tower bottom enrichment
Divide HAsF6、MAsF6Content is higher and higher, to realize heavy constituent HAsF6、MAsF6Removing, from multistage rotary filter press condense
The fixed gas that device II discharges is sent into washing absorption condensation tower assembly processing as tail gas；Step 4, tail gas are imported through air induction conduit,
Exhaust temperature is 19~21 DEG C at this time, and main component is hydrogen fluoride, and tail gas flows up through filler and cloth in washing absorption tower body
Liquid screen enters through cooling tail gas through exhaust manifolds cold herein with the hydrofluoric acid condensate liquid mass-and heat-transfer sowed of spray pipe fitting
The inlet exhaust gas of solidifying tower, tail gas are discharged after condensation tube sheet completes heat exchange through liquid removing device and exhaust port, exhaust emissions
At 9~10 DEG C, the hydrofluoric acid condensate liquid that washing absorption tower condenses out collects through filler along washing absorption tower body for mouth temperature control
Wall flows through collector tube and is recovered in circulation storage tank, and the hydrofluoric acid condensate liquid that condensing tower condenses out is recovered to through condensate outlet to follow
In ring storage tank.
2. a kind of application method for preparing electron level hydrogen fluoride process unit according to claim 1, it is characterized in that: circulation
Storage tank is connected to by the comb that flows back with catch box, and partially fluorinated hydrogen-cooled lime set enters catch box, phegma flow through reflux comb
Flow ratio, that is, reflux ratio, which is drawn, with intermediate products is designed as 0.2~0.25.
3. a kind of application method for preparing electron level hydrogen fluoride process unit according to claim 1, it is characterized in that: due to
The effect of transpiration circulation, hydrogen fluoride constantly repeat to gasify it is rising rise, condensation liquefaction flows down two-phase circulation change process, in gas phase
Stage mixes to quickly complete oxidation reaction and form condensate liquid at once through fluorine gas with fluorine gas and be enriched in circulating storage groove, runs one section
After time, the hydrogen fluoride condensate liquid concentration in circulating storage groove through peroxidating is higher and higher, send after up to standard as intermediate products extraction
Enter recirculating fluidized bed destilling tower rectifying.
4. a kind of application method for preparing electron level hydrogen fluoride process unit according to claim 1, it is characterized in that: multistage
The design of II bottom of rotary filter press condenser has U-shaped fluid-tight component and return pipe, to adjust reflux ratio, can return partially fluorinated hydrogen liquid
Returning cloth liquid disk becomes phegma.
5. a kind of application method for preparing electron level hydrogen fluoride process unit according to claim 1, it is characterized in that: condensation
The inlet exhaust gas and condensation tower body of tower are designed using Venturi tube principle, it is therefore an objective to make tail gas through the lesser inlet exhaust gas pressure of diameter
Enter the condensation tower body diffusion being relatively large in diameter after contracting, drop is made to be evenly distributed in tail gas, to improve in the cold of condensation tube sheet
Solidifying efficiency.
6. a kind of application method for preparing electron level hydrogen fluoride process unit according to claim 1, it is characterized in that: circulation
Pump assembly 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, condensation
The bottom of tower 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 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 it is higher and higher, the industrial hydrofluoric acid of various concentration can be obtained as needed.
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| CN111661860A (en) * | 2020-06-19 | 2020-09-15 | 锦洋高新材料股份有限公司 | Production method of anhydrous aluminum fluoride |
| TWI717295B (en) * | 2020-06-24 | 2021-01-21 | 陳義平 | Electronic grade hydrofluoric acid manufacturing system and method for manufacturing electronic grade hydrofluoric acid using the system |
| 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 |
| CN113651294A (en) * | 2021-07-02 | 2021-11-16 | 北京化工大学 | Continuous preparation system and method of electronic-grade hydrofluoric acid |
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| CN109052326B (en) | 2020-01-10 |
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