CN109133007A - A kind of rectification and purification method of anhydrous hydrofluoric acid - Google Patents
A kind of rectification and purification method of anhydrous hydrofluoric acid Download PDFInfo
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- CN109133007A CN109133007A CN201810823152.XA CN201810823152A CN109133007A CN 109133007 A CN109133007 A CN 109133007A CN 201810823152 A CN201810823152 A CN 201810823152A CN 109133007 A CN109133007 A CN 109133007A
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- C01B7/00—Halogens; Halogen acids
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- C01B7/196—Separation; Purification by distillation
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Abstract
The invention discloses a kind of rectification and purification method of anhydrous hydrofluoric acid, include the following steps: that (a) is washed；(b) it condenses；(c) rectifying；(d) waste gas absorption；(e) double absorption.Present invention process is simple, saves energy consumption, improves resource utilization, and removal of impurity is high, improves final product quality, reduces tail gas absorption cost, reduce input cost, emission pollution is small, environmentally protective.
Description
Technical field
The invention belongs to anhydrous hydrofluoric acid preparation technical field more particularly to a kind of rectification and purification sides of anhydrous hydrofluoric acid
Method.
Background technique
Anhydrous hydrofluoric acid both anhydrous hydrogen fluoride, is a kind of widely used chemical products, and appearance is colourless fuming liquids
99% or more hydrofluoric acid easily gasifies under decompression or high temperature.It is mainly used as producing villiaumite, fluorohaloparaffin, fluorine refrigerant, corrosion
Glass, impregnated timber, electrolysis element fluorine etc., anhydrous hydrofluoric acid chemical property is extremely active, has very strong corrosivity, can with alkali,
The reaction such as metal, oxide and silicate.
The production technology of anhydrous hydrofluoric acid is to react to obtain thick hydrogen fluoride gas using sulfuric acid and fluorite, contains more powder
The impurity such as dirt, silicon fluoride, sulfur dioxide, sulfuric acid, moisture content, traditional method of purification complex process, the energy of consumption is more, and impurity
Separation it is difficult, not can guarantee the quality of finished product, absorb tail gas using multiple absorption towers, cause equipment cost investment high.
Summary of the invention
Above-mentioned technical problem present in present invention aims to solve the prior art provides a kind of essence of anhydrous hydrofluoric acid
Method of purification is evaporated, simple process saves energy consumption, improves resource utilization, and removal of impurity is high, improves into quality
Amount, reduces tail gas absorption cost, reduces input cost, emission pollution is small, environmentally protective.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme:
A kind of rectification and purification method of anhydrous hydrofluoric acid, it is characterised in that include the following steps:
(a) it washs: the sulfuric acid in sulfuric acid storage tank is squeezed into scrubbing tower, after spraying 5~10min, reaction is generated thick
Hydrogen fluoride gas is introduced from the lower part of scrubbing tower, and thick hydrogen fluoride gas rises, with spray and under acid solution counter current contacting, remove it
In dust and moisture；
(b) condense: the hydrogen fluoride gas being discharged at the top of from scrubbing tower, which is introduced into primary condenser, to be condensed, primary condenser
Air outlet temperature be 20~23 DEG C, uncooled hydrogen fluoride gas enters back into condensation in secondary condenser, and secondary condenser goes out
Temperature degree is 5~8 DEG C, and the liquid in primary condenser flows into spent acid storage tank, is taken out acid pump for the phegma in spent acid storage tank
It returns in scrubbing tower, the liquid in secondary condenser flows into storage acid tank, and the exhaust gas in secondary condenser is expelled to sulfuric acid absorption
Tower；
(c) rectifying: the liquid stored up in acid tank is driven into preheater through acid-proof pump and is preheated, rectifying is entered after preheating
Rectifying is carried out in tower, temperature is 25~30 DEG C in rectifying column, and the liquid at rectifying tower bottom flows into heating, partially liq in reboiler
It is returned in rectifying column together with remaining gas after vaporization, the remaining liq in reboiler is pumped into scrubbing tower through residual acid, warp
The hydrogen fluoride for crossing rectifying is discharged in gaseous form from the top of the distillation column, enters in degassing tower after the condensation of rectifying column condenser
Portion is de-gassed in degassing tower, and the air outlet temperature of rectifying column condenser is 18~20 DEG C, and the liquid in rectifying column condenser returns
It flows into rectifying column, the liquid assembled in degassing tower is discharged from bottom, collects in hydrofluoric acid storage tank；
(d) waste gas absorption: after the degassed tower condenser condensation of the gas being discharged at the top of from degassing tower, into sulfuric acid absorption tower
Interior carry out waste gas absorption, the temperature of degassing tower condenser are 5~10 DEG C, and the condensate liquid in degassing tower condenser passes back into degassing tower
Interior, the sulfuric acid absorption liquid in head tank enters from the top of sulfuric acid absorption tower, and the fixed gas and degassing tower in secondary condenser are cold
The fixed gas of condenser enters in sulfuric acid absorption tower from middle part, the two counter current contacting, and sulfuric acid absorption liquid is continuous in sulfuric acid absorption tower
Accumulation, then in overflow to scrubbing tower, the exhaust gas of sulfuric acid absorption column overhead discharge, which enters, carries out double absorption in waste gas absorption tower；
(e) double absorption: being absorbed in the aqueous solution that exhaust gas imports in waste gas absorption tower through diversion pipe, unabsorbed
Exhaust gas is arranged from the recirculation hole of cover board, the through hole in support plate, enters respiratory box through the venthole on respiratory box side wall
It is interior, it under the blocking of baffle plate, is contacted with sodium hydroxide solution, by abundant reactive absorption, purified exhaust gas is from respiratory box top
The gas vent in portion flows out, and empties through exhaust pipe.
Further, the temperature of sulfuric acid storage tank is 92~95 DEG C in step (a), and the washing acid fluctuation of temperature will lead to matching for sulfuric acid
Specific discharge is difficult to control, be easy to cause waste, the excessively high moisture vaporization also resulted in washing acid of temperature, in air inlet pipeline and outlet
Air-resistance phenomenon is formed on pipeline.
Further, the temperature of degassing tower is 15~18 DEG C in step (c), ocratation, the dioxy being mixed in hydrogen fluoride
Change the light components such as sulphur to vaporize, from degassing column overhead discharge, separation is realized, to improve the purity of hydrogen fluoride.
Further, the concentration of sodium hydroxide solution in step (e) in respiratory box is 15~20g/mL, and reasonable concentration can protect
Good assimilation effect is demonstrate,proved, and production cost can be reduced, the silicon tetrafluoride gas, remaining in exhaust gas is absorbed by sodium hydroxide
Hydrogen fluoride gas and sulfur dioxide gas purify exhaust gas, reduce pollution.
Further, the hot water in sink is squeezed into reboiler by suction pump in step (c) to heat, the temperature of sink
It is 55~60 DEG C, reboiler is heated with hot water, heating is more uniform, and low energy consumption, reduces cost, and solution temperature is low, subtracts
Acid solution is delayed to the corrosion rate of reboiler tubulation, to extend the service life of reboiler.
Further, the inner top of the rectifying column in step (c) be equipped with mesh mist eliminator, mesh mist eliminator include outer ring plate,
Inner ring plate and spider are evenly distributed with reinforcing rib, are equipped with demisting silk screen between adjacent said rib between outer ring plate and inner ring plate,
It is equipped with fixing muscle between inner ring plate and spider, demisting silk screen is equipped between adjacent said rib, is equipped with center silk screen in spider,
Outer ring plate is set on the inner wall of rectifying column, and reinforcing rib improves the bonding strength between outer ring plate and inner ring plate, and fixing muscle improves
Bonding strength between inner ring plate and spider, so that overall structure is stronger, screen net structure is not readily susceptible to air-flow punching
The effect of hitting and deform, the service life is longer, and center silk screen cooperates demisting silk screen, and uniform segmentation, it is big to catch liquid range, and absorption is more complete
Face improves adsorption effect；The fine liquid droplet being entrained in gas is attached when by demisting silk screen and center silk screen
Or absorb, droplet gradually agglomeration, be coalesced as big drop, under gravity, drop drops down, and is absorbing
Cheng Zhong, due to being filled with the droplet absorbed on entire mesh mist eliminator, adsorption capacity enhances, and is mingled in prevention gas
Sulfuric acid, moisture pass through, and gas-liquid separation are realized, to improve the purity of hydrogen fluoride.
Further, diversion pipe, cover board, support plate and respiratory box, water conservancy diversion are respectively equipped in the waste gas absorption tower in step (e)
One end of pipe passes through cover board, and cover board is equipped with recirculation hole, and aqueous solution, support are equipped between cover board and the interior bottom of waste gas absorption tower
Plate is located at the top of cover board, and respiratory box is set in support plate, and support plate is equipped with through hole, and through hole is using respiratory box as center ring
Baffle is equipped between distribution, respiratory box and waste gas absorption tower, the side wall of respiratory box is equipped with venthole, and venthole is located at baffle
Lower section is respectively equipped with sodium hydroxide solution and baffle plate in respiratory box, and baffle plate is obliquely installed, and baffle plate is close to venthole, folding
One end of flowing plate is protruded into sodium hydroxide solution, and the top of respiratory box is equipped with gas vent, and in absorption process, diversion pipe is by exhaust gas
It imports in aqueous solution, hydrogen fluoride, ocratation, sulfur dioxide and the sulfuric acid droplets being mingled in exhaust gas is absorbed by water, substantially
Degree reduces the light component impurity content in exhaust gas, contacts exhaust gas by force with water, and raising assimilation effect, remaining exhaust gas is from circulation
Hole passes through, and gradually rises, and enters in the space that respiratory box, waste gas absorption inner wall of tower and baffle are formed through through hole, due to baffle
Blocking, exhaust gas can only enter in respiratory box through venthole, and by the blocking of baffle plate, exhaust gas can not directly rise, can only under
Stream is mixed into sodium hydroxide solution, and flow path lengthens, hydrogen fluoride, ocratation, sulfur dioxide in sodium hydroxide and exhaust gas
Reaction, these polluted gas are removed, to purify exhaust gas, air pollution is reduced after emptying, increase time of contact, are improved
Assimilation effect.It first passes through aqueous solution once to be absorbed, the light component impurity content in exhaust gas is greatly lowered, then pass through hydrogen
Sodium hydroxide solution carries out double absorption, and hydrogen fluoride and ocratation are absorbed completely, to purify exhaust gas, it is dirty to reduce emptying
Dye, and the consumption of sodium hydroxide solution is few, aqueous solution is at low cost, to reduce the cost of waste gas absorption.
Further, it is equipped with partition in the rectifying column in step (c), is equipped with stainless steel cloth filler between partition, on partition
It is evenly distributed with through-hole, partition blows unrest for separating, protecting stainless steel cloth filler, to prevent being raised air-flow, guarantees arrangement rule
Whole, uniform, gas can only be flowed through from through-hole, and circulation becomes smaller, and extend residence time of the gas in stainless steel cloth filler,
To improve mass transfer effect.
The present invention is by adopting the above-described technical solution, have the advantages that
Present invention process is simple, saves energy consumption, improves resource utilization, and removal of impurity is high, improves into
Quality reduces tail gas absorption cost, reduces input cost, and emission pollution is small, environmentally protective；The thick fluorine that reaction is generated
Change hydrogen to wash by acid solution, remove dust and moisture therein, then passes through condensation twice, fluorination is greatly reduced
The impurity such as sulfuric acid, moisture in hydrogen, condensed hydrogen fluoride liquid enter rectifying column rectifying, remove the sulphur in hydrogen fluoride liquid
The impurity such as acid, moisture realize the separation of hydrogen fluoride and heavy constituent, improve the purity of hydrogen fluoride, hydrogen-cooled by the fluorination of rectifying
Enter in degassing tower after solidifying and be de-gassed, be stripped of the light-component gas such as ocratation, sulfur dioxide, realizes hydrogen fluoride and light group
The separation divided, purity greatly improve, and the liquid assembled in degassing tower is finished product anhydrous hydrogen fluoride, is discharged from bottom, and collection is in hydrogen
In fluoric acid storage tank；The not condensed hydrogen fluoride to get off in tail gas is absorbed by sulfuric acid absorption liquid, residual exhaust enters waste gas absorption
Double absorption is carried out in tower to first pass through aqueous solution in waste gas absorption tower and once absorbed, and the fluorine in exhaust gas is greatly lowered
Change hydrogen and silicon tetrafluoride content, then double absorption carried out by sodium hydroxide solution, hydrogen fluoride and ocratation are absorbed completely,
To purify exhaust gas, emission pollution is reduced, and the consumption of sodium hydroxide solution is few, aqueous solution is at low cost, to reduce
The cost of waste gas absorption.
In distillation process, the liquid into reboiler is sulfuric acid solution, wherein light-component gas is mixed with, after heating vaporization
Continuation rectifying in rectifying column is returned to improve the purity of sulfuric acid solution to reduce the impurity content in sulfuric acid solution, be pumped into
It is re-used in scrubbing tower, improves the utilization rate of resource, reduce production cost；In absorption process, pass through sulfuric acid absorption
Tower absorbs the fixed gas of fixed gas and degassing tower condenser in secondary condenser, reduces emission pollution, sulfuric acid absorption liquid is in sulphur
It constantly accumulates in acid absorption column, then in overflow to scrubbing tower, recycles, improve the utilization rate of sulfuric acid, reduce costs.
Detailed description of the invention
The present invention will be further explained below with reference to the attached drawings:
Fig. 1 is a kind of structural schematic diagram of the rectification and purification method of anhydrous hydrofluoric acid of the present invention；
Fig. 2 is the structural schematic diagram that sulfuric acid absorption tower is connected with waste gas absorption tower in the present invention；
Fig. 3 is the structural schematic diagram of mesh mist eliminator in the present invention；
Fig. 4 is the structural schematic diagram of waste gas absorption tower in the present invention.
In figure: 1- sulfuric acid storage tank；2- scrubbing tower；3- primary condenser；4- secondary condenser；5- spent acid storage tank；6- takes out acid
Pump；7- sulfuric acid absorption tower；8- stores up acid tank；9- rectifying column；10- mesh mist eliminator；11- outer ring plate；12- inner ring plate；The center 13-
Disk；14- reinforcing rib；15- demisting silk screen；The center 16- silk screen；17- fixing muscle；18- partition；19- stainless steel cloth filler；20-
Through-hole；21- acid-proof pump；22- preheater；23- suction pump；24- sink；25- reboiler；The residual acid pump of 26-；The condensation of 27- rectifying column
Device；28- degassing tower；29- hydrofluoric acid storage tank；30- degassing tower condenser；31- head tank；32- waste gas absorption tower；33- diversion pipe；
34- cover board；35- support plate；36- respiratory box；37- aqueous solution；38- baffle；39- venthole；40- sodium hydroxide solution；41- folding
Flowing plate；42- gas vent；43- exhaust pipe；44- recirculation hole；45- through hole.
Specific embodiment
As shown in Figures 1 to 4, it is a kind of rectification and purification method of anhydrous hydrofluoric acid of the present invention, includes the following steps:
(a) it washs: the sulfuric acid in sulfuric acid storage tank 1 is squeezed into scrubbing tower 2, after spraying 5~10min, guarantee in scrubbing tower 2
Full of acid solution, acidic environment is built, to increase the contact area of sulfuric acid Yu thick hydrogen fluoride gas, improves washing effect.It will be anti-
The thick hydrogen fluoride gas that should be generated is introduced from the lower part of scrubbing tower 2, and thick hydrogen fluoride gas rises, and lower acid solution is countercurrently with spray
Contact, contact more directly, sufficiently, improve the removal effect to dust and moisture in thick hydrogen fluoride gas.The temperature of sulfuric acid storage tank 1
Degree is 92~95 DEG C, and the washing acid fluctuation of temperature will lead to the difficult to control with specific discharge of sulfuric acid, be easy to cause waste, and temperature is excessively high also
It will lead to the moisture vaporization in washing acid, form air-resistance phenomenon on air inlet pipeline and outlet pipe.
(b) condense: the hydrogen fluoride gas being discharged at the top of scrubbing tower 2 is introduced into primary condenser 3 and condenses, primary condensation
The air outlet temperature of device 3 is 20~23 DEG C, and uncooled hydrogen fluoride gas enters back into condensation, secondary condenser 4 in secondary condenser 4
Air outlet temperature be 5~8 DEG C, the liquid in primary condenser 3 flows into spent acid storage tank 5, and being taken out acid pump 6 will be in spent acid storage tank 5
Phegma return in scrubbing tower 2, containing impurity such as more sulfuric acid, moisture in first condensed hydrogen fluoride, be unfavorable for essence
Purification is evaporated, returns to vaporization removal of impurities again in scrubbing tower 2, the liquid in secondary condenser 4 flows into storage acid tank 8, after time condensation
Hydrogen fluoride in impurity be greatly reduced, be conducive to rectification and purification, the exhaust gas in secondary condenser 4 is expelled to sulfuric acid absorption tower 7, gives up
There is also the not condensed hydrogen fluoride to get off in gas reduces emission pollution by sulfuric acid absorption.
(c) rectifying: the inner top of rectifying column 9 is equipped with mesh mist eliminator 10, and mesh mist eliminator 10 includes outer ring plate 11, inner ring
Plate 12 and spider 13 are evenly distributed with reinforcing rib 14, are equipped between adjacent said rib 14 between outer ring plate 11 and inner ring plate 12
Demisting silk screen 15 is equipped with fixing muscle 17, is equipped with demisting silk screen 15 between adjacent said rib 14 between inner ring plate 12 and spider 13,
Center silk screen 16 is equipped in spider 13, outer ring plate 11 is set on the inner wall of rectifying column 9, reinforcing rib 14 improve outer ring plate 11 with
Bonding strength between inner ring plate 12, fixing muscle 17 improve the bonding strength between inner ring plate 12 and spider 13, so that whole
Body structure is stronger, and screen net structure is not readily susceptible to gas shock effect and deforms, and the service life is longer, and center silk screen 16 is matched
Demisting silk screen 15 is closed, uniform segmentation, it is big to catch liquid range, adsorbs more comprehensive, improves adsorption effect.It is entrained in thin in gas
Small liquid mist is attached or absorbs when by demisting silk screen 15 and center silk screen 16, droplet gradually agglomeration, be agglomerated into
For big drop, under gravity, drop drops down, upper due to entire mesh mist eliminator 10 in absorption process
It is filled with the droplet absorbed, adsorption capacity enhancing prevents the sulfuric acid, the moisture that are mingled in gas from passing through, realizes gas-liquid separation,
To improve the purity of hydrogen fluoride.It is equipped with partition 18 in rectifying column 9, is equipped with stainless steel cloth filler 19, partition between partition 18
Through-hole 20 is evenly distributed on 18, partition 18 is used to separate, protect stainless steel cloth filler 19, unrest is blown to prevent being raised air-flow,
Guarantee that arrangement is regular, uniform, gas can only be flowed through from through-hole 20, and circulation becomes smaller, and extend gas in stainless steel cloth filler
Residence time in 19, to improve mass transfer effect.
The liquid stored up in acid tank 8 is driven into preheater 22 through acid-proof pump 21 and is preheated, rectifying column 9 is entered after preheating
Interior carry out rectifying, temperature is 25~30 DEG C in rectifying column 9, removes the impurity such as sulfuric acid, moisture in hydrogen fluoride liquid, realizes fluorination
Hot water in sink 24 is squeezed into reboiler 25 by suction pump 23 and heated by the separation of hydrogen and heavy constituent, the temperature of sink 24
Degree is 55~60 DEG C, is heated with hot water to reboiler 25, and heating is more uniform, and low energy consumption, reduces cost, solution temperature
It is low, acid solution is slowed down to the corrosion rate of 25 tubulation of reboiler, to extend the service life of reboiler 25.9 tower of rectifying column
The liquid at bottom flows into heating in reboiler 25, returns in rectifying column 9 together with remaining gas after partially liq vaporization, reboiler
Remaining liq in 25 is pumped into scrubbing tower 2 through residual acid pump 26, and the liquid into reboiler 25 is sulfuric acid solution, wherein being mixed with light
Component gas returns to after heating vaporization and continues rectifying in rectifying column 9, to reduce the impurity content in sulfuric acid solution, improves
The purity of sulfuric acid solution is pumped into scrubbing tower 2 and re-uses, improves the utilization rate of resource, reduce production cost.
Hydrogen fluoride by rectifying is discharged in gaseous form from 9 tower top of rectifying column, condenses through rectifying column condenser 27 laggard
The middle part for entering degassing tower 28 is de-gassed in degassing tower 28, and the temperature of degassing tower 28 is 15~18 DEG C, is mixed in hydrogen fluoride
The light components such as ocratation, sulfur dioxide vaporize, be discharged from 28 tower top of degassing tower, separation realized, to improve fluorine
Change the purity of hydrogen.The air outlet temperature of rectifying column condenser 27 is 18~20 DEG C, and the liquid reflux in rectifying column condenser 27 enters essence
It evaporates in tower 9, the heavy constituents impurity such as sulfuric acid, moisture is mixed into hydrogen fluoride gas in droplets, and rectifying column 9 is passed back into after condensation
It is interior, to reduce impurity content, the purity of hydrogen fluoride is improved, the liquid assembled in degassing tower 28 is discharged from bottom, collects
In hydrofluoric acid storage tank 29, gleanings are finished product anhydrous hydrogen fluoride.
(d) it waste gas absorption: after the degassed tower condenser 30 of the gas being discharged at the top of degassing tower 28 condenses, is inhaled into sulfuric acid
It receives and carries out waste gas absorption in tower 7, the temperature of degassing tower condenser 30 is 5~10 DEG C, and the condensate liquid in degassing tower condenser 30 returns
It flows into degassing tower 28, reduces hydrogen fluoride as fixed gas is discharged, the collection of degassing tower 28 is returned after condensation, improve returning for hydrogen fluoride
Yield.Sulfuric acid absorption liquid in head tank 31 from the fixed gas in the top of sulfuric acid absorption tower 7 entrance, secondary condenser 4 and takes off
The fixed gas of gas tower condenser 30 enters in sulfuric acid absorption tower 7 from middle part, absorbs not condensed to get off by sulfuric acid absorption liquid
Hydrogen fluoride, the two counter current contacting contacts more direct, and sulfuric acid absorption liquid is constantly accumulated in sulfuric acid absorption tower 7, and then overflow is to washing
It washs in tower 2, recycles, improve the utilization rate of sulfuric acid, reduce costs, the exhaust gas of 7 tower top of sulfuric acid absorption tower discharge enters
Double absorption is carried out in waste gas absorption tower 32.
(e) double absorption: being respectively equipped with diversion pipe 33, cover board 34, support plate 35 and respiratory box 36 in waste gas absorption tower 32,
One end of diversion pipe 33 passes through cover board 34, and cover board 34 is equipped with recirculation hole 44, the interior bottom of cover board 34 and waste gas absorption tower 32 it
Between be equipped with aqueous solution 37, support plate 35 is located at the top of cover board 34, and in support plate 35, support plate 35 is equipped with respiratory box 36
Through hole 45, through hole 45, around distribution, are equipped with baffle centered on respiratory box 36 between respiratory box 36 and waste gas absorption tower 32
38, the side wall of respiratory box 36 is equipped with venthole 39, and venthole 39 is located at 38 lower section of baffle, is respectively equipped with hydrogen-oxygen in respiratory box 36
Change sodium solution 40 and baffle plate 41, baffle plate 41 are obliquely installed, baffle plate 41 is protruded into close to venthole 39, one end of baffle plate 41
In sodium hydroxide solution 40, the top of respiratory box 36 is equipped with gas vent 42, and in absorption process, exhaust gas is imported water by diversion pipe 33
In solution 37, hydrogen fluoride, ocratation, sulfur dioxide and the sulfuric acid droplets being mingled in exhaust gas are absorbed by water, are significantly dropped
Light component impurity content in low exhaust gas, contacts exhaust gas by force with water, improves assimilation effect, and remaining exhaust gas is from recirculation hole 44
Pass through, gradually rise, enters in the space that respiratory box 36,32 inner wall of waste gas absorption tower and baffle 38 are formed through through hole 45, by
In the blocking of baffle 38, exhaust gas can only enter in respiratory box 36 through venthole 39, and by the blocking of baffle plate 41, exhaust gas can not be straight
Liter is connected, can only flow down and be mixed into sodium hydroxide solution 40, flow path lengthens, hydrogen fluoride in sodium hydroxide and exhaust gas, four
Silicon fluoride, sulfur dioxide reaction, these polluted gas are removed, to purify exhaust gas, air pollution is reduced after emptying, are increased
Time of contact, improve assimilation effect.40 concentration of sodium hydroxide solution is 15~20g/mL, and reasonable concentration both can guarantee well
Assimilation effect, and production cost can be reduced, pass through sodium hydroxide and absorb silicon tetrafluoride gas in exhaust gas, remaining hydrogen fluoride
Gas and sulfur dioxide gas purify exhaust gas, reduce pollution.
Exhaust gas through diversion pipe 33 import waste gas absorption tower 32 in aqueous solution 37 in absorbed, unabsorbed exhaust gas from
It arranges on the recirculation hole 44 of cover board 34, the through hole 45 in support plate 35, enters through the venthole 39 on 36 side wall of respiratory box
In respiratory box 36, under the blocking of baffle plate 41, contacted with sodium hydroxide solution 40, it is purified useless by abundant reactive absorption
Gas is flowed out from the gas vent 42 at 36 top of respiratory box, is emptied through exhaust pipe 43.It first passes through aqueous solution 37 once to be absorbed, substantially
Degree reduces the hydrogen fluoride and silicon tetrafluoride content in exhaust gas, then carries out double absorption by sodium hydroxide solution 40, by hydrogen fluoride
It is absorbed completely with ocratation, to purify exhaust gas, reduces emission pollution, and the consumption of sodium hydroxide solution 40 is few, water
Solution 37 is at low cost, to reduce the cost of waste gas absorption.
Present invention process is simple, saves energy consumption, improves resource utilization, and removal of impurity is high, improves into
Quality reduces tail gas absorption cost, reduces input cost, and emission pollution is small, environmentally protective；The thick fluorine that reaction is generated
Change hydrogen to wash by acid solution, remove dust and moisture therein, then passes through condensation twice, fluorination is greatly reduced
The impurity such as sulfuric acid, moisture in hydrogen, condensed hydrogen fluoride liquid enter 9 rectifying of rectifying column, remove the sulphur in hydrogen fluoride liquid
The impurity such as acid, moisture realize the separation of hydrogen fluoride and heavy constituent, improve the purity of hydrogen fluoride, hydrogen-cooled by the fluorination of rectifying
Enter in degassing tower 28 after solidifying and be de-gassed, be stripped of the light-component gas such as ocratation, sulfur dioxide, realizes hydrogen fluoride and light
The separation of component, purity greatly improve, and the liquid assembled in degassing tower 28 is finished product anhydrous hydrogen fluoride, is discharged from bottom, collect
In hydrofluoric acid storage tank 29；The not condensed hydrogen fluoride to get off in tail gas is absorbed by sulfuric acid absorption liquid, residual exhaust enters useless
Double absorption is carried out in aspiration tower 32 to first pass through aqueous solution 37 in waste gas absorption tower 32 and once absorbed, significantly dropped
Hydrogen fluoride and silicon tetrafluoride content in low exhaust gas, then double absorption is carried out by sodium hydroxide solution 40, by hydrogen fluoride and four
Silicon fluoride absorbs completely, to purify exhaust gas, reduces emission pollution, and the consumption of sodium hydroxide solution 40 is few, aqueous solution
37 is at low cost, to reduce the cost of waste gas absorption.
In distillation process, the liquid into reboiler 25 is sulfuric acid solution, wherein it is mixed with light-component gas, heating vaporization
After return in rectifying column 9 and continue rectifying and improve the purity of sulfuric acid solution to reduce the impurity content in sulfuric acid solution,
It is pumped into scrubbing tower 2 and re-uses, improve the utilization rate of resource, reduce production cost；In absorption process, pass through sulfuric acid
Absorption tower 7 absorbs the fixed gas of fixed gas and degassing tower condenser 30 in secondary condenser 4, reduces emission pollution, and sulfuric acid is inhaled
It receives liquid constantly to accumulate in sulfuric acid absorption tower 7, then in overflow to scrubbing tower 2, recycles, improve the utilization rate of sulfuric acid,
It reduces costs.
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technical effect is realized, made simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (8)
1. a kind of rectification and purification method of anhydrous hydrofluoric acid, it is characterised in that include the following steps:
(a) it washs: the sulfuric acid in sulfuric acid storage tank is squeezed into scrubbing tower, after spraying 5~10min, by the thick fluorination of reaction generation
Hydrogen is introduced from the lower part of scrubbing tower, and thick hydrogen fluoride gas rises, the lower acid solution counter current contacting with spray, and removing is therein
Dust and moisture；
(b) condense: the hydrogen fluoride gas being discharged at the top of from scrubbing tower, which is introduced into primary condenser, to be condensed, and primary condenser goes out
Temperature degree is 20~23 DEG C, and uncooled hydrogen fluoride gas enters back into condensation in secondary condenser, and secondary condenser goes out temperature
Degree is 5~8 DEG C, and the liquid in primary condenser flows into spent acid storage tank, is taken out acid pump and returns the phegma in spent acid storage tank
In scrubbing tower, the liquid in secondary condenser is flowed into storage acid tank, and the exhaust gas in secondary condenser is expelled to sulfuric acid absorption tower；
(c) rectifying: the liquid stored up in acid tank is driven into preheater through acid-proof pump and is preheated, is entered in rectifying column after preheating
Rectifying is carried out, temperature is 25~30 DEG C in rectifying column, and the liquid at rectifying tower bottom flows into heating in reboiler, partially liq vaporization
It is returned in rectifying column together with remaining gas afterwards, the remaining liq in reboiler is pumped into scrubbing tower through residual acid, by essence
The hydrogen fluoride evaporated is discharged in gaseous form from the top of the distillation column, and the middle part of degassing tower is entered after the condensation of rectifying column condenser,
It is de-gassed in degassing tower, the air outlet temperature of rectifying column condenser is 18~20 DEG C, and the liquid reflux in rectifying column condenser enters
In rectifying column, the liquid assembled in degassing tower is discharged from bottom, collects in hydrofluoric acid storage tank；
(d) waste gas absorption: after the degassed tower condenser condensation of the gas being discharged at the top of the degassing tower, into sulfuric acid absorption tower in into
Row waste gas absorption, the temperature of degassing tower condenser are 5~10 DEG C, and the condensate liquid in degassing tower condenser passes back into degassing tower,
Sulfuric acid absorption liquid in head tank enters from the top of sulfuric acid absorption tower, the fixed gas and degassing tower condenser in secondary condenser
Fixed gas enter in sulfuric acid absorption tower from middle part, the two counter current contacting, sulfuric acid absorption liquid is constantly accumulated in sulfuric acid absorption tower,
Then in overflow to scrubbing tower, the exhaust gas of sulfuric acid absorption column overhead discharge, which enters, carries out double absorption in waste gas absorption tower；
(e) it double absorption: is absorbed in the aqueous solution that exhaust gas imports in waste gas absorption tower through diversion pipe, unabsorbed exhaust gas
It is arranged from the recirculation hole of cover board, the through hole in support plate enters in respiratory box through the venthole on respiratory box side wall,
It under the blocking of baffle plate, is contacted with sodium hydroxide solution, by abundant reactive absorption, purified exhaust gas is from the row at the top of respiratory box
Stomata outflow, empties through exhaust pipe.
2. a kind of rectification and purification method of anhydrous hydrofluoric acid according to claim 1, it is characterised in that: sulphur in step (a)
The temperature of acid storage tank is 92~95 DEG C.
3. a kind of rectification and purification method of anhydrous hydrofluoric acid according to claim 1, it is characterised in that: taken off in step (c)
The temperature of gas tower is 15~18 DEG C.
4. a kind of rectification and purification method of anhydrous hydrofluoric acid according to claim 1, it is characterised in that: inhaled in step (e)
Receiving the concentration of sodium hydroxide solution in case is 15~20g/mL.
5. a kind of rectification and purification method of anhydrous hydrofluoric acid according to claim 1, it is characterised in that: lead in step (c)
It crosses suction pump the hot water in sink is squeezed into reboiler and heat, the temperature of sink is 55~60 DEG C.
6. a kind of rectification and purification method of anhydrous hydrofluoric acid according to claim 1, it is characterised in that: in step (c)
The inner top of the rectifying column is equipped with mesh mist eliminator, and the mesh mist eliminator includes outer ring plate, inner ring plate and spider, described
It is evenly distributed with reinforcing rib between outer ring plate and the inner ring plate, demisting silk screen is equipped between the adjacent reinforcing rib, it is described interior
It is equipped with fixing muscle between ring flat-plate and the spider, is equipped with the demisting silk screen, the spider between the adjacent reinforcing rib
Interior to be equipped with center silk screen, the outer ring plate is set on the inner wall of the rectifying column.
7. a kind of rectification and purification method of anhydrous hydrofluoric acid according to claim 1, it is characterised in that: in step (e)
Diversion pipe, cover board, support plate and respiratory box are respectively equipped in the waste gas absorption tower, one end of the diversion pipe passes through the lid
Plate, the cover board are equipped with recirculation hole, and aqueous solution, the branch are equipped between the cover board and the interior bottom of the waste gas absorption tower
Fagging is located at the top of the cover board, and the respiratory box is set in the support plate, and the support plate is equipped with through hole, described
Through hole, around distribution, is equipped with baffle centered on the respiratory box between the respiratory box and the waste gas absorption tower, described
The side wall of respiratory box is equipped with venthole, and the venthole is located at below the baffle, is respectively equipped with hydrogen-oxygen in the respiratory box
Change sodium solution and baffle plate, the baffle plate are obliquely installed, the baffle plate is close to the venthole, one end of the baffle plate
It protrudes into the sodium hydroxide solution, the top of the respiratory box is equipped with gas vent.
8. a kind of rectification and purification method of anhydrous hydrofluoric acid according to claim 1, it is characterised in that: in step (c)
It is equipped with partition in the rectifying column, stainless steel cloth filler is equipped between the partition, is evenly distributed with through-hole on the partition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810823152.XA CN109133007A (en) | 2018-07-25 | 2018-07-25 | A kind of rectification and purification method of anhydrous hydrofluoric acid |
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| CN201810823152.XA CN109133007A (en) | 2018-07-25 | 2018-07-25 | A kind of rectification and purification method of anhydrous hydrofluoric acid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683514A (en) * | 2019-10-29 | 2020-01-14 | 贵州新东浩化工材料科技有限公司 | Method for purifying and preparing hydrogen fluoride |
| CN111732117A (en) * | 2020-06-19 | 2020-10-02 | 锦洋高新材料股份有限公司 | Method for preparing anhydrous aluminum fluoride by purification and evaporation integration |
| CN112028022A (en) * | 2020-09-18 | 2020-12-04 | 宣城亨泰电子化学材料有限公司 | Pretreatment method for preparing electronic-grade high-purity hydrofluoric acid |
| CN112374463A (en) * | 2020-11-19 | 2021-02-19 | 苏州金宏气体股份有限公司 | Purification method and purification system of hydrogen fluoride |
| CN112595758A (en) * | 2020-11-09 | 2021-04-02 | 中核四0四有限公司 | Measuring device suitable for moisture content in anhydrous hydrogen fluoride |
| CN113426154A (en) * | 2021-07-12 | 2021-09-24 | 宣城亨泰电子化学材料有限公司 | Electron-grade anhydrous hydrogen fluoride anion removing device |
| CN113620252A (en) * | 2020-07-10 | 2021-11-09 | 陈义平 | Electronic grade hydrofluoric acid manufacturing system and method for manufacturing electronic grade hydrofluoric acid |
| CN115120998A (en) * | 2022-07-11 | 2022-09-30 | 多氟多新材料股份有限公司 | Method for improving hydrogen fluoride yield, and method and device for treating hydrogen fluoride tail gas |
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2018
- 2018-07-25 CN CN201810823152.XA patent/CN109133007A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683514A (en) * | 2019-10-29 | 2020-01-14 | 贵州新东浩化工材料科技有限公司 | Method for purifying and preparing hydrogen fluoride |
| CN110683514B (en) * | 2019-10-29 | 2021-07-06 | 贵州新东浩化工材料科技有限公司 | Method for purifying and preparing hydrogen fluoride |
| CN111732117A (en) * | 2020-06-19 | 2020-10-02 | 锦洋高新材料股份有限公司 | Method for preparing anhydrous aluminum fluoride by purification and evaporation integration |
| CN113620252A (en) * | 2020-07-10 | 2021-11-09 | 陈义平 | Electronic grade hydrofluoric acid manufacturing system and method for manufacturing electronic grade hydrofluoric acid |
| CN112028022A (en) * | 2020-09-18 | 2020-12-04 | 宣城亨泰电子化学材料有限公司 | Pretreatment method for preparing electronic-grade high-purity hydrofluoric acid |
| CN112595758A (en) * | 2020-11-09 | 2021-04-02 | 中核四0四有限公司 | Measuring device suitable for moisture content in anhydrous hydrogen fluoride |
| CN112374463A (en) * | 2020-11-19 | 2021-02-19 | 苏州金宏气体股份有限公司 | Purification method and purification system of hydrogen fluoride |
| CN113426154A (en) * | 2021-07-12 | 2021-09-24 | 宣城亨泰电子化学材料有限公司 | Electron-grade anhydrous hydrogen fluoride anion removing device |
| CN115120998A (en) * | 2022-07-11 | 2022-09-30 | 多氟多新材料股份有限公司 | Method for improving hydrogen fluoride yield, and method and device for treating hydrogen fluoride tail gas |
| CN115120998B (en) * | 2022-07-11 | 2024-02-02 | 多氟多新材料股份有限公司 | Method for improving hydrogen fluoride yield, and treatment method and treatment device for hydrogen fluoride tail gas |
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