CN104906920A - System for recycling fluorine and silicon resources from wet-process phosphoric acid tail gas and recovery method thereof - Google Patents
System for recycling fluorine and silicon resources from wet-process phosphoric acid tail gas and recovery method thereof Download PDFInfo
- Publication number
- CN104906920A CN104906920A CN201510299096.0A CN201510299096A CN104906920A CN 104906920 A CN104906920 A CN 104906920A CN 201510299096 A CN201510299096 A CN 201510299096A CN 104906920 A CN104906920 A CN 104906920A
- Authority
- CN
- China
- Prior art keywords
- pipeline
- scrubbing tower
- fluorine
- difluoro
- subsider
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to the field of the tail gas treatment technology and in particular relates to a system for recycling fluorine and silicon resources from wet-process phosphoric acid tail gas and a recovery method of the system. Fluorosilicic acid solution is circularly treated in the system, the scale blockage phenomenon of the system can be avoided, fluorosilicic acid can flow out in a solution mode in a cooling process of the tail gas, then fluorosilicic acid is further treated so that the fluorine and silicon resources can be recycled; a small amount of water is adopted for absorption treatment in a tail gas absorption process, then the acquired fluorosilicic acid solution is used for washing tail gas circularly; thus, fluorosilicic acid solution from a fluorine washing tower I has high concentration, the fluorine washing tower I and a fluorine washing tower II are combined to ensure that the fluorine-containing substances during the tail gas empting treatment is low, the recovery rate of the fluorine and silicon resources is improved and the environment pollution rate is reduced.
Description
Technical field
The present invention relates to tail gas disposal technique field, the system of especially a kind of phosphoric acid by wet process vent gas treatment recovery fluorine, silicon resource and recovery method thereof.
Background technology
Phosphoric acid by wet process tail gas is SiF4 gas mainly, mainly silicate fluoride solution and silica gel in its cleaning solution, and what adopt due to washings is slag field backwater, also doped with a small amount of calcirm-fluoride (CaF in solid silicone
2).In actual mechanical process, there is following technological deficiency: exist during washing fluosilicic acid acid dense low and cannot utilize, in washings containing metal ion (Na
+, K
+, Ca
2+deng) and make the easy fouling and clogging of system and need periodic cleaning; Outer last person's gas is made to contain a certain amount of ammonia because temperature often can not be fallen when adopting ammonia to wash; Adopt time other cleaning solutions (as ammonium fluoride etc.) and cannot implement on a large scale.
Further, in the prior art, in the vent gas treatment process after phosphoric acid by wet process extraction process, the technology of employing has: lime WATER-WASHING METHOD, calcium lime powder and active carbon dry process fluorinated tail gas method, ammonia wash method and WATER-WASHING METHOD; But these technology only can will contain SiF
4tail gas carry out process up to standard, the cleaning solution of a large amount of fluorine-containing silicic acid of generation all processes as waste water, and it is quite high that tail washes cost.
Although compare separately among above-mentioned several technology and all have existence a little, the concentration of the silicate fluoride solution that can bring than WATER-WASHING METHOD as lime WATER-WASHING METHOD is higher, and then make the silicate fluoride solution product of acquisition more excellent, but its recovery for the fluorine resource in the silicate fluoride solution obtained is comparatively difficult, and then causes the cost recovery of fluorine resource higher;
Calcium lime powder and active carbon dry process fluorinated tail gas method are by fluorinated tail gas humidification and enter sack cleaner dedusting after mixing with calcium lime powder and active carbon, fluorine-containing ash is in landfill yard security landfill, this method process fluorinated tail gas is respond well, but treatment process is comparatively complicated and cause the waste of fluorine, silicon resource.Ammonia method of washing utilize exactly ammoniacal liquor as absorbent to absorb fluoro-gas, generate (NH
4)
2siF
6solution, (NH
4)
2siF
6solution and excess of ammonia water effect meeting generate NH further decomposition
4f and SiO
2nH
2o, ammonia washes the affirmative that method has obtained part researcher, but this process gained NH
4f is without purification, and impurity content is higher, cannot be directly used in the production of hydrofluoric acid, also needs to set up supporting NH
4f and SiO
2nH
2the purifying processing device of O, invests higher.
For this reason, the new technical scheme that will propose is badly in need of in the process for phosphoric acid by wet process tail gas and the recovery to the fluorine in vent gas treatment process, silicon resource, and then reduces the cost of phosphoric acid by wet process vent gas treatment, improves the added value of product of vent gas treatment.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the invention provides a kind of phosphoric acid by wet process vent gas treatment and reclaiming fluorine, the system of silicon resource and recovery method thereof.
Be achieved particular by following technical scheme:
Phosphoric acid by wet process vent gas treatment reclaims a system for fluorine, silicon resource, is connected by Venturi scrubber, the circulating pump d be connected by pipeline with Venturi scrubber upper end, the sedimenting system be connected by pipeline with Venturi scrubber bottom, the fluorine scrubbing tower be connected by pipeline with Venturi scrubber stage casing, pipeline stage casing that the bottom of a fluorine scrubbing tower is connected with sedimenting system by pipeline and Venturi scrubber bottom; The side, bottom of one fluorine scrubbing tower offers outlet, and this outlet is connected by the entrance of pipeline with circulating pump c, and the outlet of circulating pump c is connected with the shower nozzle in a fluorine scrubbing tower by pipeline; The top of one fluorine scrubbing tower is connected with the side, bottom of demister by pipeline; The bottom of demister is connected with liquid seal trough by pipeline; Demister top is connected by the entrance of pipeline with tail gas pump, and tail gas delivery side of pump is connected with the side, bottom of difluoro scrubbing tower by pipeline; The top of difluoro scrubbing tower is provided with drain, and the bottom of difluoro scrubbing tower is connected with punch plate tank by pipeline; The two sides, bottom of difluoro scrubbing tower are positioned at horizontal level lower end that tail gas delivery side of pump pipeline connects with difluoro scrubbing tower and are respectively provided with one and export, the outlet being positioned at left surface is connected with circulating pump a by pipeline, and is provided with wash water entrance between this connecting line; The outlet being positioned at right flank is connected with circulating pump b by pipeline; Circulating pump a is connected with the shower nozzle in difluoro scrubbing tower respectively with the outlet of circulating pump b; The top of described sedimenting system is connected with the top of neutralization chamber by pipeline; The side, top of described sedimenting system is connected with fluosilicic acid cooling bath by the mode of overflow, the bottom lateral opening of fluosilicic acid cooling bath is connected with villiaumite workshop by pipeline, and the top lateral opening of fluosilicic acid cooling bath is connected with circulating pump d by pipeline; The side, bottom of neutralization chamber is connected with the top of centrifuge a, and the bottom of centrifuge a is connected with Acid of Hydrofluoric Acid Production workshop by pipeline; Side, the stage casing upper shed of centrifuge a is connected by the top of pipeline with ammonia fluid bowl; The side, bottom of ammonia fluid bowl is connected by the top of pipeline with centrifuge b, the bottom of centrifuge b is connected with extraction tank by pipeline, the side, bottom of centrifuge b is connected with countercurrent washer side by pipeline, the relative side that countercurrent washer and centrifuge b connect side is connected by pipeline with the accumulator tank of industry water, the top of countercurrent washer is connected with centrifuge c by pipeline, the top of centrifuge c is connected with the side, top of ammonia fluid bowl by pipeline, and white carbon workshop is gone to by pipeline in the side, stage casing of centrifuge c; The described top of ammonia fluid bowl and/or the top of neutralization chamber to be connected with ammonia tank by pipeline and to form.
In above-mentioned system, between a fluorine scrubbing tower 10 and difluoro scrubbing tower 4, be also provided with the device slurries of the bottom of difluoro scrubbing tower 4 being sent into washing gas in a fluorine scrubbing tower 10, and this device can carry out according to the change in concentration of the fluosilicic acid in a fluorine scrubbing tower 10 amount adjusting the slurries sent into, and then make the concentration of the fluosilicic acid cleaning solution in a fluorine scrubbing tower maintain between 8-12%, can be provided with in the apparatus the system of automatic detectable concentration or fluosilicic acid cleaning solution Concentration Testing or induction sensor, and then realize automation change feeding amount, also can by artificially detecting realization.
Described sedimenting system is by the subsider a be connected by pipeline with the bottom of Venturi scrubber, the bottom of subsider a is connected with the top of neutralization chamber by pipeline, described subsider a overflows in subsider b, and the pipeline stage casing that the bottom of subsider b is connected with neutralization chamber top by pipeline and subsider a bottom is connected; Described subsider b overflows in subsider c, and on the pipeline that subsider c is connected with subsider b and neutralization chamber top by pipeline, subsider c overflows in fluosilicic acid cooling bath and forms.
The present invention also provides said system to be applied to the method for a kind of phosphoric acid by wet process vent gas treatment recovery fluorine, silicon resource, tail gas is entered system by Venturi scrubber, after passing through to adopt silicate fluoride solution washing again in Venturi scrubber, get rid of cleaning solution from the bottom of Venturi scrubber and enter sedimenting system, make the temperature of the tail gas entered in Venturi scrubber be reduced to 45-55 DEG C by 70-85 DEG C, the intake of tail gas is 30000 ~ 50000m
3/ h, the above-mentioned silicate fluoride solution flow entered in Venturi scrubber is 60 ~ 140m
3/ h, the cleaning solution entering sedimenting system is carried out Multistage settling process, and then make the temperature of cleaning solution be reduced to 45-60 DEG C by 55-75 DEG C, be silicate fluoride solution from the upper end clear liquid out of sedimenting system, starch from the bottom silica gel slag that is precipitated as out of sedimenting system; Silicate fluoride solution enters fluosilicic acid cooling bath, after temperature is reduced to 5-25 DEG C, then by circulating pump d with 60 ~ 140m
3the flow of/h is sent in Venturi scrubber and is carried out carrying out washing treatment, and unnecessary silicate fluoride solution sends into villiaumite workshop; Neutralization chamber is passed into by the silica gel slag slurry obtained after Multistage settling, and passing into ammonia in neutralization chamber, to be neutralized to pH value be 6-9, then passed into centrifuge a process, obtain containing assorted silica gel solid and fluosilicic acid ammonia solution, silicate fluoride solution is for the production of hydrofluoric acid; Ammonia fluid bowl is passed into containing assorted silica gel solid, and pass into ammonia wherein, adjusting its pH value is 11-13, then is passed into centrifuge b process, obtains centrifugal slurry and centrifugate, centrifugate is sent in extraction tank and is reclaimed ammonia treatment, centrifugal slurry passes into countercurrent washer, and the reverse industry water that passes into washs centrifugal slurry, and is passed into by mixed liquor in centrifuge c, again the silica gel processing acquisition in centrifuge c is sent into white carbon black production workshop, the liquid processing acquisition in centrifuge c returns in ammonia fluid bowl as solvent; The described tail gas being reduced to 45-55 DEG C enters in a fluorine scrubbing tower, by to the partially liq that obtains after the washing of difluoro scrubbing tower for the spray in a fluorine scrubbing tower, and the fraction slurries of a fluorine wash tower bottoms is adopted to the inside spray process of circulating pump c extracting to fluorine scrubbing tower, and the slurries of remainder in fluorine scrubbing tower feeding sedimenting system is carried out settlement treatment; From a fluorine scrubbing tower, gas out passes into the bottom of demister, after the effect of demister and liquid seal trough goes out foam process, again it is pumped into difluoro scrubbing tower by tail gas, and by the circulating pump a that is separately positioned on difluoro scrubbing tower both sides and circulating pump b the fraction slurries of difluoro wash tower bottoms returned in difluoro scrubbing tower and carry out circulation cleaning process, and the pipeline simultaneously between circulating pump a and difluoro scrubbing tower sends into wash water by opening, and wash water feeding amount is 10 ~ 30m
3/ h, the fraction slurries of difluoro wash tower bottoms returns the washing carrying out tail gas in a fluorine scrubbing tower again, the remaining slurries of difluoro wash tower bottoms are sent in punch plate tank for punch plate process, through in difluoro scrubbing tower washing after temperature be the gas of <45 DEG C through drain emptying process, the recovery of fluorine, silicon resource in phosphoric acid by wet process tail gas can be completed.
Described Multistage settling is treated to three grades of settlement treatment.
Described Multistage settling is treated to three grades of natural subsidence process, and namely in infall process, silicate fluoride solution overflows to subsider b by subsider a, is overflowing to subsider c, then overflow to fluosilicic acid cooling bath by subsider c by subsider b; The silica gel slag slurry obtained that settles down enters neutralization chamber by pipeline.
The fraction slurries of described difluoro wash tower bottoms returns in a fluorine scrubbing tower again, and its back amount makes the concentration of silicate fluoride solution in the cleaning solution of a fluorine scrubbing tower maintain 8-12%.
Described temperature after washing in difluoro scrubbing tower is that the gas of <45 DEG C is through drain emptying process, wherein content of fluoride <9mg/m
3.
Compared with prior art, technique effect of the present invention is embodied in:
The present invention makes Wet-process Phosphoric Acid Production tail gas arrange up to standard outward and exhaust gas conversion one-tenth in tail gas is prepared the raw material of villiaumite, hydrofluoric acid, iodine, white carbon, and then improves the added value of product for phosphoric acid by wet process vent gas treatment, reduces the cost of vent gas treatment.
The present invention, by directly circulating in whole system with a small amount of water, produces without any waste water.There is the significant value of environmental protection.
Method of the present invention can make tail gas at temperature-fall period, makes fluosilicic acid be revealed out as a solution, through fluosilicic acid is done further process, and then make fluorine, silicon resource is recycled utilization; Again after adopting a small amount of water to carry out absorption process in tail gas absorption process, the silicate fluoride solution obtained again carries out circulation cleaning tail gas and to carry out making from a fluorine scrubbing tower concentration of silicate fluoride solution out higher, and in conjunction with the carrying out washing treatment of a fluorine scrubbing tower, difluoro scrubbing tower, the composition of fluorine-containing material when making tail gas emptying process is lower, and then the rate of recovery that improve fluorine, silicon resource, reduce environmental pollution rate.
Energy consumption in whole processing procedure of the present invention is low, without intensification heating steps, only just carries out cooling process to solution and gas, and then makes the energy consumption of whole processing step low.
Solve phosphoric acid by wet process tail washed Cheng Yi fouling by the circulation of fluosilicic acid, difficulty puies forward the acid difficult problem such as dense.
The present invention supports the use by carrying out combining, and makes phosphoric acid by wet process tail washing lotion as the raw materials for production of prodan and fluosilicic acid ammonia, and cooling carries out comprehensive cyclic utilization as the cooling liquid of tail gas except the fluosilicic acid after solid.Concrete principle is:
3SiF
4+2H
2O＝2H
2SiF
6+SiO
2↓
Again fluosilicic acid is used for villiaumite to produce, the mainly production of prodan:
H
2SiF
6+2NaOH＝Na
2SiF
6↓+2H
2O
Solid phase after separation is silica gel, be namely exactly silica, but it contains a small amount of Na
2siF
6, K
2siF
6deng slightly solubility villiaumite impurity, just can obtain the higher villiaumite of purity after removing, dedoping step utilizes Na
2siF
6, K
2siF
6siO can be had precedence over
2generate water-soluble good NaF, KF with ammonia react and remove:
Na
2SiF
6+4NH
3＝4NH
4F+2NaF+SiO
2
K
2SiF
6+4NH
3＝4NH
4F+2KF+SiO
2
As can be seen here, the present invention passes through the process of step one by one, and then makes the purity of the silica gel product of follow-up acquisition higher, and also makes the impurity in production process be recycled utilization, and then improve the added value of product of whole technique, and then reduce the production cost of whole technique.
The present invention adopts fluosilicic acid to process as circulation fluid, and then prevents the phenomenon of fouling and clogging in system, and then reduces the security risk of exhaust treatment system, reduces the cost of exhaust treatment system, improves added value of product.
Accompanying drawing explanation
Fig. 1 is the system flow schematic diagram that phosphoric acid by wet process vent gas treatment of the present invention reclaims fluorine, silicon resource.
1-drain 2-circulating pump a3-circulating pump b4-difluoro scrubbing tower 5-wash water 6-punch plate tank 7-tail gas pump 8-demister 9-liquid seal trough 10-mono-fluorine scrubbing tower 11-circulating pump c12-Venturi scrubber 13-tail gas 14-sedimenting system 15-fluosilicic acid cooling bath 16-circulating pump d17-villiaumite workshop 18-neutralization chamber 19-centrifuge a20-ammonia fluid bowl 21-Acid of Hydrofluoric Acid Production workshop 22-centrifuge b23-extraction tank 24-countercurrent washer 25-centrifuge c26-ammonia tank 27-industry water 28-goes to white carbon workshop.
14-1 subsider b;
14-2 subsider a;
14-3 subsider c.
Detailed description of the invention
Below in conjunction with accompanying drawing and concrete embodiment, further restriction is done to technical scheme of the present invention, but claimed scope is not only confined to done description.
Embodiment
As shown in Figure 1, phosphoric acid by wet process vent gas treatment reclaims a system for fluorine, silicon resource, and the pipeline stage casing be connected with sedimenting system 14 by pipeline and Venturi scrubber 12 bottom by Venturi scrubber 12, the circulating pump d16 be connected by pipeline with Venturi scrubber 12 upper end, the sedimenting system 14 be connected by pipeline with Venturi scrubber 12 bottom, the bottom of fluorine scrubbing tower 10, fluorine scrubbing tower 10 that is connected by pipeline with Venturi scrubber 12 stage casing is connected, the side, bottom of one fluorine scrubbing tower 10 offers outlet, and this outlet is connected by the entrance of pipeline with circulating pump c11, and the outlet of circulating pump c11 is connected with the shower nozzle in a fluorine scrubbing tower 10 by pipeline, the top of one fluorine scrubbing tower 10 is connected with the side, bottom of demister 8 by pipeline, the bottom of demister 8 is connected with liquid seal trough 9 by pipeline, demister 8 top is connected by the entrance of pipeline with tail gas pump 7, and the outlet of tail gas pump 7 is connected with the side, bottom of difluoro scrubbing tower 4 by pipeline, the top of difluoro scrubbing tower 4 is provided with drain 1, and the bottom of difluoro scrubbing tower 4 is connected with punch plate tank 6 by pipeline, the horizontal level lower end that the export pipeline that the two sides, bottom of difluoro scrubbing tower 4 are positioned at tail gas pump 7 connects with difluoro scrubbing tower 4 is respectively provided with one and exports, the outlet being positioned at left surface is connected with circulating pump a2 by pipeline, and is provided with wash water entrance between this connecting line, the outlet being positioned at right flank is connected with circulating pump b3 by pipeline, circulating pump a2 is connected with the shower nozzle in difluoro scrubbing tower 4 respectively with the outlet of circulating pump b3, the top of described sedimenting system 14 is connected by the top of pipeline with neutralization chamber 18, the side, top of described sedimenting system 14 is connected with fluosilicic acid cooling bath 15 by the mode of overflow, the bottom lateral opening of fluosilicic acid cooling bath 15 is connected with villiaumite workshop by pipeline, and the top lateral opening of fluosilicic acid cooling bath 15 is connected with circulating pump d16 by pipeline, the side, bottom of neutralization chamber 18 is connected with the top of centrifuge a19, and the bottom of centrifuge a19 is connected with Acid of Hydrofluoric Acid Production workshop 21 by pipeline, side, the stage casing upper shed of centrifuge a19 is connected by the top of pipeline with ammonia fluid bowl 20, the side, bottom of ammonia fluid bowl 20 is connected by the top of pipeline with centrifuge b22, the bottom of centrifuge b22 is connected with extraction tank 23 by pipeline, the side, bottom of centrifuge b22 is connected with countercurrent washer 24 side by pipeline, the relative side that countercurrent washer 24 and centrifuge b22 connect side is connected by pipeline with the accumulator tank of industry water 27, the top of countercurrent washer 24 is connected with centrifuge c25 by pipeline, the top of centrifuge c25 is connected with the side, top of ammonia fluid bowl 20 by pipeline, white carbon workshop 28 is gone to by pipeline in the side, stage casing of centrifuge c25, the top of described ammonia fluid bowl 20 and/or the top of neutralization chamber 18 to be connected with ammonia tank 26 by pipeline and to form.
In above-mentioned system, between a fluorine scrubbing tower 10 and difluoro scrubbing tower 4, be also provided with the device slurries of the bottom of difluoro scrubbing tower 4 being sent into washing gas in a fluorine scrubbing tower 10, and this device can carry out according to the change in concentration of the fluosilicic acid in a fluorine scrubbing tower 10 amount adjusting the slurries sent into, and then make the concentration of the fluosilicic acid cleaning solution in a fluorine scrubbing tower maintain between 8-12%, can be provided with in the apparatus the system of automatic detectable concentration or fluosilicic acid cleaning solution Concentration Testing or induction sensor, and then realize automation change feeding amount, also can by artificially detecting realization.
Described sedimenting system 14 is by the subsider a14-2 be connected by pipeline with the bottom of Venturi scrubber 12, the bottom of subsider a14-2 is connected by the top of pipeline with neutralization chamber 18, described subsider a14-2 overflows in subsider b14-1, and the pipeline stage casing that the bottom of subsider b14-1 is connected with neutralization chamber 18 top by pipeline and subsider a14-2 bottom is connected; Described subsider b14-1 overflows in subsider c14-3, and on the pipeline that subsider c14-3 is connected with subsider b14-1 and neutralization chamber 18 top by pipeline, subsider c14-3 overflows in fluosilicic acid cooling bath 15 and forms.
A kind of phosphoric acid by wet process vent gas treatment reclaims the method for fluorine, silicon resource, tail gas 13 is entered system by Venturi scrubber 12, after passing through to adopt silicate fluoride solution washing again in Venturi scrubber 12, get rid of cleaning solution from the bottom of Venturi scrubber 12 and enter sedimenting system 14, make the temperature of the tail gas 13 entered in Venturi scrubber 12 be reduced to 45-55 DEG C by 70-85 DEG C, the intake of tail gas 13 is 30000 ~ 50000m
3/ h, the above-mentioned silicate fluoride solution flow entered in Venturi scrubber 12 is 60 ~ 140m
3/ h, the cleaning solution entering sedimenting system 14 is carried out Multistage settling process, and then make the temperature of cleaning solution be reduced to 45-60 DEG C by 55-75 DEG C, be silicate fluoride solution from the upper end clear liquid out of sedimenting system 14, starch from the bottom silica gel slag that is precipitated as out of sedimenting system 14; Silicate fluoride solution enters fluosilicic acid cooling bath, after temperature is reduced to 5-25 DEG C, then by circulating pump d16 with 60 ~ 140m
3the flow of/h is sent in Venturi scrubber 12 and is carried out carrying out washing treatment, and unnecessary silicate fluoride solution sends into villiaumite workshop; Neutralization chamber 18 is passed into by the silica gel slag slurry obtained after Multistage settling, and passing into ammonia in neutralization chamber 18, to be neutralized to pH value be 6-9, then passed into centrifuge a19 process, obtain containing assorted silica gel solid and fluosilicic acid ammonia solution, silicate fluoride solution is for the production of hydrofluoric acid; Ammonia fluid bowl 20 is passed into containing assorted silica gel solid, and pass into ammonia wherein, adjusting its pH value is 11-13, passed into centrifuge b22 process again, obtain centrifugal slurry and centrifugate, centrifugate is sent in extraction tank 23 and is reclaimed ammonia treatment, centrifugal slurry passes into countercurrent washer 24, and the reverse industry water that passes into washs centrifugal slurry, and mixed liquor is passed in centrifuge c25, again the silica gel processing acquisition in centrifuge c25 is sent into white carbon black production workshop, the liquid processing acquisition in centrifuge c25 returns in ammonia fluid bowl 20 as solvent; The described tail gas being reduced to 45-55 DEG C enters in a fluorine scrubbing tower 10, by the partially liq that obtains after washing difluoro scrubbing tower 4 for the spray in a fluorine scrubbing tower 10, and the fraction slurries bottom a fluorine scrubbing tower 10 is adopted to the inside spray process of circulating pump c11 extracting to fluorine scrubbing tower 10, and the slurries of remainder in a fluorine scrubbing tower 10 feeding sedimenting system 14 is carried out settlement treatment; From a fluorine scrubbing tower 10, gas out passes into the bottom of demister 8, after demister 8 and the effect of liquid seal trough 9 go out foam process, again it is sent into difluoro scrubbing tower 4 by tail gas pump 7, and by the circulating pump a2 that is separately positioned on difluoro scrubbing tower 4 both sides and circulating pump b3 the fraction slurries bottom difluoro scrubbing tower 4 returned in difluoro scrubbing tower 4 and carry out circulation cleaning process, and the pipeline simultaneously between circulating pump a2 and difluoro scrubbing tower 4 sends into wash water by opening, and wash water feeding amount is 10 ~ 30m
3/ h, fraction slurries bottom difluoro scrubbing tower 4 returns the washing carrying out tail gas in a fluorine scrubbing tower 10 again, bottom difluoro scrubbing tower 4, remaining slurries are sent in punch plate tank 6 for punch plate process, through in difluoro scrubbing tower 4 washing after temperature be the gas of <45 DEG C through drain 1 emptying process, the recovery of fluorine, silicon resource in phosphoric acid by wet process tail gas can be completed.
Described Multistage settling is treated to three grades of settlement treatment.
Described Multistage settling is treated to three grades of natural subsidence process, and namely in infall process, silicate fluoride solution overflows to subsider b by subsider a, is overflowing to subsider c, then overflow to fluosilicic acid cooling bath by subsider c by subsider b; The silica gel slag slurry obtained that settles down enters neutralization chamber by pipeline.
Fraction slurries bottom described difluoro scrubbing tower 4 returns in a fluorine scrubbing tower 10 again, and its back amount makes the concentration of silicate fluoride solution in the cleaning solution of a fluorine scrubbing tower 10 maintain 8-12%.
Described after washing in difluoro scrubbing tower 4 temperature be the gas of <45 DEG C through drain 1 emptying process, wherein content of fluoride <9mg/m
3.
Claims (7)
1. a phosphoric acid by wet process vent gas treatment reclaims fluorine, the system of silicon resource, it is characterized in that, by Venturi scrubber (12), the circulating pump d (16) be connected by pipeline with Venturi scrubber (12) upper end, the sedimenting system (14) be connected by pipeline with Venturi scrubber (12) bottom, the fluorine scrubbing tower (10) be connected by pipeline with Venturi scrubber (12) stage casing, the pipeline stage casing that the bottom of one fluorine scrubbing tower (10) is connected with sedimenting system (14) by pipeline and Venturi scrubber (12) bottom is connected, the side, bottom of one fluorine scrubbing tower (10) offers outlet, this outlet is connected by the entrance of pipeline with circulating pump c (11), and the outlet of circulating pump c (11) is connected with the shower nozzle in a fluorine scrubbing tower (10) by pipeline, the top of one fluorine scrubbing tower (10) is connected by the side, bottom of pipeline with demister (8), the bottom of demister (8) is connected with liquid seal trough (9) by pipeline, demister (8) top is connected by the entrance of pipeline with tail gas pump (7), and the outlet of tail gas pump (7) is connected by the side, bottom of pipeline with difluoro scrubbing tower (4), the top of difluoro scrubbing tower (4) is provided with drain (1), and the bottom of difluoro scrubbing tower (4) is connected with punch plate tank (6) by pipeline, the horizontal level lower end that the export pipeline that the two sides, bottom of difluoro scrubbing tower (4) are positioned at tail gas pump (7) connects with difluoro scrubbing tower (4) is respectively provided with one and exports, the outlet being positioned at left surface is connected with circulating pump a (2) by pipeline, and is provided with wash water entrance between this connecting line, the outlet being positioned at right flank is connected with circulating pump b (3) by pipeline, circulating pump a (2) is connected with the shower nozzle in difluoro scrubbing tower (4) respectively with the outlet of circulating pump b (3), the top of described sedimenting system (14) is connected by the top of pipeline with neutralization chamber (18), the side, top of described sedimenting system (14) is connected with fluosilicic acid cooling bath (15) by the mode of overflow, the bottom lateral opening of fluosilicic acid cooling bath (15) is connected with villiaumite workshop by pipeline, and the top lateral opening of fluosilicic acid cooling bath (15) is connected with circulating pump d (16) by pipeline, the side, bottom of neutralization chamber (18) is connected with the top of centrifuge a (19), and the bottom of centrifuge a (19) is connected with Acid of Hydrofluoric Acid Production workshop (21) by pipeline, side, the stage casing upper shed of centrifuge a (19) is connected by the top of pipeline with ammonia fluid bowl (20), the side, bottom of ammonia fluid bowl (20) is connected by the top of pipeline with centrifuge b (22), the bottom of centrifuge b (22) is connected with extraction tank (23) by pipeline, the side, bottom of centrifuge b (22) is connected with countercurrent washer (24) side by pipeline, the relative side that countercurrent washer (24) and centrifuge b (22) connect side is connected by pipeline with the accumulator tank of industry water (27), the top of countercurrent washer (24) is connected with centrifuge c (25) by pipeline, the top of centrifuge c (25) is connected by the side, top of pipeline with ammonia fluid bowl (20), white carbon workshop (28) is gone to by pipeline in the side, stage casing of centrifuge c (25), the top of described ammonia fluid bowl (20) and/or the top of neutralization chamber (18) to be connected with ammonia tank (26) by pipeline and to form.
2. phosphoric acid by wet process vent gas treatment as claimed in claim 1 reclaims fluorine, the system of silicon resource, it is characterized in that, described sedimenting system (14) is by the subsider a (14-2) be connected by pipeline with the bottom of Venturi scrubber (12), the bottom of subsider a (14-2) is connected by the top of pipeline with neutralization chamber (18), described subsider a (14-2) overflows in subsider b (14-1), the pipeline stage casing that the bottom of subsider b (14-1) is connected with neutralization chamber (18) top by pipeline and subsider a (14-2) bottom is connected, described subsider b (14-1) overflows in subsider c (14-3), on the pipeline that subsider c (14-3) is connected with subsider b (14-1) and neutralization chamber (18) top by pipeline, subsider c (14-3) overflows to composition in fluosilicic acid cooling bath (15).
3. a phosphoric acid by wet process vent gas treatment reclaims the method for fluorine, silicon resource, it is characterized in that, tail gas (13) is entered system by Venturi scrubber (12), again by after employing silicate fluoride solution washing in Venturi scrubber (12), get rid of cleaning solution from the bottom of Venturi scrubber (12) and enter sedimenting system (14), make the temperature of the tail gas (13) entered in Venturi scrubber (12) be reduced to 45-55 DEG C by 70-85 DEG C, the intake of tail gas (13) is 30000 ~ 50000m
3/ h, the above-mentioned silicate fluoride solution flow entered in Venturi scrubber (12) is 60 ~ 140m
3/ h, the cleaning solution entering sedimenting system (14) is carried out Multistage settling process, and then make the temperature of cleaning solution be reduced to 45-60 DEG C by 55-75 DEG C, be silicate fluoride solution from the upper end clear liquid out of sedimenting system (14), from the bottom of sedimenting system (14) out be precipitated as silica gel slag slurry, silicate fluoride solution enters fluosilicic acid cooling bath, after temperature is reduced to 5-25 DEG C, then by circulating pump d (16) with 60 ~ 140m
3the flow of/h is sent in Venturi scrubber (12) and is carried out carrying out washing treatment, and unnecessary silicate fluoride solution sends into villiaumite workshop, neutralization chamber (18) is passed into by the silica gel slag slurry obtained after Multistage settling, and passing into ammonia in neutralization chamber (18), to be neutralized to pH value be 6-9, then centrifuge a (19) process is passed into, obtain containing assorted silica gel solid and fluosilicic acid ammonia solution, silicate fluoride solution is for the production of hydrofluoric acid, ammonia fluid bowl (20) is passed into containing assorted silica gel solid, and pass into ammonia wherein, adjusting its pH value is 11-13, passed into centrifuge b (22) process again, obtain centrifugal slurry and centrifugate, centrifugate is sent in extraction tank (23) and is reclaimed ammonia treatment, centrifugal slurry passes into countercurrent washer (24), and the reverse industry water that passes into washs centrifugal slurry, and mixed liquor is passed in centrifuge c (25), again the silica gel that process in centrifuge c (25) obtains is sent into white carbon black production workshop, the liquid that in centrifuge c (25), process obtains returns in ammonia fluid bowl (20) as solvent, the described tail gas being reduced to 45-55 DEG C enters in a fluorine scrubbing tower (10), by to the partially liq that obtains after difluoro scrubbing tower (4) washing for the spray in a fluorine scrubbing tower (10), and the fraction slurries bottom a fluorine scrubbing tower (10) is adopted to the inside spray process of circulating pump c (11) extracting to fluorine scrubbing tower (10), and the slurries of remainder in a fluorine scrubbing tower (10) feeding sedimenting system (14) are carried out settlement treatment, from a fluorine scrubbing tower (10), gas out passes into the bottom of demister (8), after demister (8) and the effect of liquid seal trough (9) go out foam process, passed through tail gas pump (7) again and sent into difluoro scrubbing tower (4), and by the circulating pump a (2) that is separately positioned on difluoro scrubbing tower (4) both sides and circulating pump b (3) fraction slurries of difluoro scrubbing tower (4) bottom returned in difluoro scrubbing tower (4) and carry out circulation cleaning process, and the pipeline simultaneously between circulating pump a (2) and difluoro scrubbing tower (4) sends into wash water by opening, wash water feeding amount is 10 ~ 30m
3/ h, the fraction slurries of difluoro scrubbing tower (4) bottom returns the washing carrying out tail gas in a fluorine scrubbing tower (10) again, the remaining slurries in difluoro scrubbing tower (4) bottom are sent in punch plate tank (6) for punch plate process, after washing in the difluoro scrubbing tower (4) temperature be the gas of <45 DEG C through drain (1) emptying process, the recovery of fluorine, silicon resource in phosphoric acid by wet process tail gas can be completed.
4., as right wants the phosphoric acid by wet process vent gas treatment as described in 3 to reclaim the method for fluorine, silicon resource, it is characterized in that, described Multistage settling is treated to three grades of settlement treatment.
5. as right wants the phosphoric acid by wet process vent gas treatment as described in 3 to reclaim the method for fluorine, silicon resource, it is characterized in that, described Multistage settling is treated to three grades of natural subsidence process, namely in infall process, silicate fluoride solution overflows to subsider b by subsider a, overflow to subsider c by subsider b, then overflow to fluosilicic acid cooling bath by subsider c; The silica gel slag slurry obtained that settles down enters neutralization chamber by pipeline.
6. as right wants the phosphoric acid by wet process vent gas treatment as described in 3 to reclaim the method for fluorine, silicon resource, it is characterized in that, the fraction slurries of described difluoro scrubbing tower (4) bottom returns in a fluorine scrubbing tower (10) again, and its back amount makes the concentration of silicate fluoride solution in the cleaning solution of a fluorine scrubbing tower (10) maintain 8-12%.
7. as right wants the phosphoric acid by wet process vent gas treatment as described in 3 to reclaim the method for fluorine, silicon resource, it is characterized in that, described temperature after washing in difluoro scrubbing tower (4) is that the gas of <45 DEG C is through drain (1) emptying process, wherein content of fluoride <9mg/m
3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510299096.0A CN104906920B (en) | 2015-06-03 | 2015-06-03 | System for recycling fluorine and silicon resources from wet-process phosphoric acid tail gas and recovery method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510299096.0A CN104906920B (en) | 2015-06-03 | 2015-06-03 | System for recycling fluorine and silicon resources from wet-process phosphoric acid tail gas and recovery method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104906920A true CN104906920A (en) | 2015-09-16 |
| CN104906920B CN104906920B (en) | 2017-01-18 |
Family
ID=54076610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510299096.0A Expired - Fee Related CN104906920B (en) | 2015-06-03 | 2015-06-03 | System for recycling fluorine and silicon resources from wet-process phosphoric acid tail gas and recovery method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104906920B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879610A (en) * | 2016-06-27 | 2016-08-24 | 温州泓呈祥科技有限公司 | Method for removing fluorides in waste gas using gas-liquid-solid three-phase adsorption purifying reactor |
| CN106166432A (en) * | 2016-08-31 | 2016-11-30 | 贵阳开磷化肥有限公司 | Iodine retracting device and recovery method thereof in a kind of Wet-process Phosphoric Acid Production tail gas |
| CN108479356A (en) * | 2018-05-25 | 2018-09-04 | 广州吉必盛科技实业有限公司 | Tail gas acid elution system in the preparation of fumed nano powder and tail gas acid elution technique |
| CN111099647A (en) * | 2019-12-30 | 2020-05-05 | 龙蟒大地农业有限公司 | Process method for preparing calcium fluoride product by using wet-process phosphoric acid extraction tail gas |
| CN116281904A (en) * | 2023-01-17 | 2023-06-23 | 昆明川金诺化工股份有限公司 | Method for reducing content of byproduct phosphorus fluosilicate in semi-water wet method phosphoric acid production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0053409A1 (en) * | 1980-12-03 | 1982-06-09 | Stamicarbon B.V. | Process for the recovery of a uranium-containing concentrate and phosphoric acid |
| CN103172027A (en) * | 2013-04-18 | 2013-06-26 | 瓮福（集团）有限责任公司 | Method and device for recovering fluorine from tail gas of wet process phosphoric acid reaction |
| CN103657329A (en) * | 2013-12-25 | 2014-03-26 | 贵州开磷（集团）有限责任公司 | Yellow phosphorus exhaust gas centralized control, recycling and purifying device |
-
2015
- 2015-06-03 CN CN201510299096.0A patent/CN104906920B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0053409A1 (en) * | 1980-12-03 | 1982-06-09 | Stamicarbon B.V. | Process for the recovery of a uranium-containing concentrate and phosphoric acid |
| CN103172027A (en) * | 2013-04-18 | 2013-06-26 | 瓮福（集团）有限责任公司 | Method and device for recovering fluorine from tail gas of wet process phosphoric acid reaction |
| CN103657329A (en) * | 2013-12-25 | 2014-03-26 | 贵州开磷（集团）有限责任公司 | Yellow phosphorus exhaust gas centralized control, recycling and purifying device |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879610A (en) * | 2016-06-27 | 2016-08-24 | 温州泓呈祥科技有限公司 | Method for removing fluorides in waste gas using gas-liquid-solid three-phase adsorption purifying reactor |
| CN106166432A (en) * | 2016-08-31 | 2016-11-30 | 贵阳开磷化肥有限公司 | Iodine retracting device and recovery method thereof in a kind of Wet-process Phosphoric Acid Production tail gas |
| CN108479356A (en) * | 2018-05-25 | 2018-09-04 | 广州吉必盛科技实业有限公司 | Tail gas acid elution system in the preparation of fumed nano powder and tail gas acid elution technique |
| CN108479356B (en) * | 2018-05-25 | 2023-10-20 | 湖北兴发化工集团股份有限公司 | Tail gas acid washing system and tail gas acid washing process in gas phase method nanometer powder preparation |
| CN111099647A (en) * | 2019-12-30 | 2020-05-05 | 龙蟒大地农业有限公司 | Process method for preparing calcium fluoride product by using wet-process phosphoric acid extraction tail gas |
| CN116281904A (en) * | 2023-01-17 | 2023-06-23 | 昆明川金诺化工股份有限公司 | Method for reducing content of byproduct phosphorus fluosilicate in semi-water wet method phosphoric acid production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104906920B (en) | 2017-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104906920A (en) | System for recycling fluorine and silicon resources from wet-process phosphoric acid tail gas and recovery method thereof | |
| CN103172074B (en) | Process for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization | |
| CN106268180B (en) | Device and method for washing and absorbing tail gas generated in wet-process phosphoric acid production | |
| CN107601434A (en) | A kind of method and apparatus that hydrogen fluoride is prepared by fluosilicic acid | |
| CN103539157B (en) | The technique of fluorine resource is reclaimed from potassium feldspar decomposition residue | |
| CN104071820A (en) | Method for producing calcium fluoride by waste LCD panel glass etching liquid | |
| CN103539132B (en) | The method of Neutral ammonium fluoride is reclaimed from potassium felspar sand gas phase adsorption liquid | |
| CN112028040A (en) | Method for recycling fluorine-containing waste liquid | |
| CN103011084A (en) | Method for extracting iodine from dehydrate wet method diluted phosphoric acid reaction iodic waste gas | |
| CN103043684A (en) | Method for producing ammonium hydrogen fluoride by recovering fluorine in wet process phosphoric acid tail gas | |
| CN104058539B (en) | A kind of half fine treatment process based on wastewater from viscose fiber producing | |
| CN104028083B (en) | A kind of fluorinated tail gas treating apparatus and method | |
| CN205730752U (en) | A kind of acid mist recycling purifier of cold-rolling pickling line | |
| CN107265463B (en) | The method that calcium fluoride containing waste material prepares fluosilicic acid | |
| CN110054190A (en) | A kind of method that prodan production waste absorbs moisturizing for phosphoric acid by wet process fluorine | |
| CN102211782A (en) | Treatment method for producing sodium silicofluoride as byproduct in inorganic fluoride production process | |
| CN104445219A (en) | Preparation method of white carbon black | |
| CN114984728B (en) | Wet phosphoric acid extraction tank tail gas treatment system and method thereof | |
| CN115010091B (en) | Impurity removal method for hydrogen fluoride, purification method for hydrogen fluoride and purification device for hydrogen fluoride | |
| CN107188129B (en) | Method for preparing hydrogen fluoride and silicon tetrafluoride from calcium fluoride-containing waste | |
| CN203816429U (en) | Device for treating tail gas in sintering of polished rod | |
| CN207287062U (en) | A kind of exhaust gas processing device prepared using fluosilicic acid during anhydrous hydrogen fluoride | |
| CN202181214U (en) | Device for using tail gas washing objects for ammonium phosphate production | |
| CN106006557B (en) | A kind of method of chlorosilane raffinate production hydrogen chloride gas | |
| CN101745293B (en) | Novel method for washing tail gas of monoammonium phosphate device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20161026 Address after: Xifeng County in Guizhou Province, Guiyang city town 551109 Applicant after: Guiyang Kailin Chemical Co. Ltd. Address before: No. 237 Jinyang City Kailin Lake District Road 550009 Guizhou city of Guiyang Province Applicant before: Phosphorylcholine group limited-liability company is opened in Guizhou |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170118 Termination date: 20210603 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |