CN103373708A - Treatment method for recycling hydrofluoric acid waste liquor - Google Patents
Treatment method for recycling hydrofluoric acid waste liquor Download PDFInfo
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- CN103373708A CN103373708A CN2012101225728A CN201210122572A CN103373708A CN 103373708 A CN103373708 A CN 103373708A CN 2012101225728 A CN2012101225728 A CN 2012101225728A CN 201210122572 A CN201210122572 A CN 201210122572A CN 103373708 A CN103373708 A CN 103373708A
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Abstract
The invention discloses a treatment method for recycling hydrofluoric acid waste liquor. The treatment method comprises the following steps of: analyzing the content of silicon in hydrofluoric acid waste liquor; adding a compound of sodium, potassium or barium, which is more than the content of silicon by once, into the hydrofluoric acid waste liquor in a treatment slot, so that the fluorine and silicon is combined with sodium, potassium or barium in the hydrofluoric acid waste liquor for a reaction to generate fluosilicate solids of sodium fluosilicate, potassium fluosilicate or barium fluosilicate; extracting the upper layer of liquor after settling the fluosilicate solids, and conveying back to the original process for use after adding high-concentration hydrofluoric acid to achieve a hydrofluoric acid concentration value satisfying the use of the original use. The hydrofluoric acid waste liquor is only added with a little sodium, potassium or barium ions to prepare the hydrofluoric acid which can be recycled, so that less chemical drug is consumed, the wastewater emission is greatly lowered, the hydrofluoric acid usage amount of the original process is saved and the extra purchase cost is saved, and therefore, the treatment steps are simplified, the treatment cost is lowered and environment-friendly benefits are achieved.
Description
Technical field
The present invention relates to a kind of hydrofluoric acid waste liquid and reclaim the treatment process that re-uses, be specifically related to a kind of method that the hydrofluoric acid in the hydrofluoric acid waste liquid can be reclaimed and can be re-used in etch process, it has the purchase cost of saving former etch process hydrofluoric acid usage quantity, and treatment capacity not only greatly but also fast simple, and avoid high thermal conductance to cause fire producing the multi-efficiencies such as hydrofluoric acid dense smoke injury human body.
Background technology
Flourish along with industries such as semi-conductor, liquid crystal panel and solar cells uses hydrofluoric acid (Hydrofluoric Acid in its Production Flow Chart; HF (aq)) being used as the usage quantity of etching silicon and silicon compound also can be more and more many, and the amount of the siliceous hydrofluoric acid waste liquid that produces is also followed increase behind hydrofluoric acid etch silicon or silicon compound; Because the silicone content in the hydrofluoric acid waste liquid is higher, not only allow the etch capabilities of hydrofluoric acid reduce, and can allow the etchant surface produce ridge and affect etched precision, and cause the growth that expends time in of quality of products, etch processes, so siliceous hydrofluoric acid waste liquid is Reusability again just, and when the silicone content in the hydrofluoric acid arrive preset value when (generally being about more than the 10000ppm) just because can not re-using, and formation hydrofluoric acid waste liquid.
Moreover, some industry is then used hydrofluoric acid in the nitration mixture mode, for example hydrofluoric acid adds nitric acid in order to the silicon of etching solar panels, or hydrofluoric acid adds nitric acid and hydrochloric acid comes the etching glass plate, or hydrofluoric acid adds hydrochloric acid formation etching solution, so just can cause not only containing in the general hydrofluoric acid waste liquid silicon that 2～10% hydrogen fluoride and concentration is slightly less than 1% (10000ppm) of having an appointment, and contain simultaneously 1～3% nitric acid or contain the result of 5% the hydrochloric acid of having an appointment, yet, no matter be hydrofluoric acid or the pure hydrofluoric acid of nitration mixture mode, when after being used, becoming the hydrofluoric acid waste liquid, its contained hydrofluoric acid but has highly corrosive and fat-solubility, not only can cause serious burn to the skin of human body, also very easily pass human body and with body in calcium, magnesium ion is in conjunction with corroding bone and muscle, if the steam that suction hydrofluoric acid distributes then can cause pulmonary edema, and suck excessive especially can be fatal, in addition, the hydrofluoric acid discharging of waste liquid also can destroy holocoenotic balance to occurring in nature, so the hydrofluoric acid waste liquid all must just can discharge after treatment, to avoid harmful to human and contaminate environment.
Prior art all is the fluorine in the hydrofluoric acid waste liquid to be taken out make all kinds of fluorine chemicals for the processing mode of hydrofluoric acid waste liquid, main methods have three kinds as follows:
One, first method such as TaiWan, China invent I233158 number exposure, it is to add calcium chloride in the hydrofluoric acid waste liquid, make calcium ion that fluorion is changed into Calcium Fluoride (Fluorspan), and allow fluorion and calcium ion effect generate calcium fluoride sludge, reach the fluorine composition of removing in the hydrofluoric acid waste liquid, its reaction formula is:
2HF(aq)+CaCl
2(aq)→CaF
2(s)+2HCl(aq)
Then, add liquid caustic soda (aqueous sodium hydroxide solution) again the waste liquid pH-value is transferred to neutrality (pH value is between 6～9), its reaction formula is:
NaOH+HCl→NaCl+H
2O
Then be that use calcium hydroxide or calcium carbonate are added into the mode in the hydrofluoric acid waste liquid in addition, the acid in reaching and in the hydrofluoric acid waste liquid and removal fluorion.
Yet, add calcium chloride in the hydrofluoric acid waste liquid no matter be, with liquid caustic soda the waste liquid pH-value is transferred to neutral mode again, or the interior mode that adds calcium hydroxide or calcium carbonate of hydrofluoric acid waste liquid, the capital produces a large amount of mud, take the hydrofluoric acid waste liquid of l kilogram concentration 49% as example, if use calcium chloride to process, will produce about 5 kilograms calcium fluoride sludge; If using calcium hydroxide processes, about 10 kilograms calcium fluoride sludge will be produced, and the wastewater flow rate of supervening greatly and all must treatedly could discharge, the calcium fluoride sludge amount of deposition is also extremely many simultaneously, so that the bulk treatment cost is high, and the buying expenseses such as calcium chloride, calcium hydroxide or calcium carbonate expenditure is also many, is not good treatment process therefore, is unfavorable for very that also industrial community adopts.
Two, second method is for adding sodium aluminate in the hydrofluoric acid waste liquid, fluorion is changed into sodium fluoroaluminate, see through interpolation aluminum contained compound and compounds containing sodium (generally being to add sodium aluminate) in the hydrofluoric acid waste liquid, to generate the sodium fluoroaluminate xln (Na of non-dissolving
3AlF
6), its reaction formula is:
3Na
++Al
3++6F
-→Na
3AlF
6
But the wastewater flow rate of supervening is quite a lot of, and treated could the discharging of palpus, the sodium fluoroaluminate commodity are called sodium aluminum fluoride, main high temperature fusing assistant as electrolytic process extracting metals aluminium, aluminium has good ductility, but ductility then can significantly reduce during the silicon compound that it is excessive that aluminium mixes, so though this method can be from hydrofluoric acid waste liquid output sodium aluminum fluoride, so its purposes limited and be worth on the low side, in addition, extract the waste liquid that produces behind the sodium aluminum fluoride because having acidity, still need add liquid caustic soda and carry out acid-base neutralisation, because acid-base neutralisation is thermopositive reaction, operator be had certain danger, also need use heat exchanger just to be promoted processing speed in addition, moreover sodium fluoroaluminate (sodium aluminum fluoride) belongs to xln, and its crystallization rate is slow, also can cause can't the fast processing waste liquid, so also non-good treatment process.
Three, the third method such as Republic of China's disclosure of the Invention number No. 200930663 exposure, it is to add hydrofluoric acid first in the hydrofluoric acid waste liquid, after making the hydrofluoric acid waste liquid be adjusted to a concentration, add again silicon and sodium in the described hydrofluoric acid waste liquid that has after adjusting concentration, and fluorion is changed into Sodium Silicofluoride, seeing through the excessive silicon-containing compound of interpolation and compounds containing sodium (generally is to add water glass; Commodity are called water glass) in the hydrofluoric acid waste liquid, to generate the Sodium Silicofluoride xln (Na of non-solubility
2SiF
6), more described Sodium Silicofluoride xln drying is reached the recovery fluorine at last; Therefore, the cost of its chemical agent is large, and the wastewater flow rate that produces also extremely wastewater treatment expenses that cause high more, can produce simultaneously the shortcoming of jelly in the treating processes, cause the formation speed that delays Sodium Silicofluoride, and the impact that is subjected to jelly also causes very difficulty of follow-up processed, because water glass is alkaline matter but hydrofluoric acid is acidic substance, so can be formed with the acid-base neutralisation reaction of heat release, need on the contrary to use heat exchanger just to be promoted processing speed, but because hydrofluoric acid tool metal protection only can use the poor plastic material heat exchanger of heat-conductive characteristic, also so that its processing speed is slow, rather than a good treatment process.
Above-mentioned three kinds of existing hydrofluoric acid method for treating waste liquid, there is again a common shortcoming, it all is confined to the fluorine in the waste liquid is taken out the fluorine chemical of making cheapness, waste on the contrary the recycling of hydrofluoric acid, the contriver is for above-mentioned weak point, by a large amount of theoretical analysises and experiment, final design goes out method of the present invention.
Summary of the invention
Main purpose of the present invention is to provide a kind of hydrofluoric acid waste liquid to reclaim the treatment process that re-uses, the method is at first analyzed the content of silicon (Si) in hydrofluoric acid (HF) waste liquid, again will be greater than the compound of sodium, potassium or the barium of silicone content numerical value more than one times, be added in the hydrofluoric acid waste liquid in the treatment trough, make the reaction that combines with sodium, potassium or barium of fluorine in the hydrofluoric acid waste liquid and silicon generate Sodium Silicofluoride (Na
2SiF
6(s)), potassium silicofluoride (K
2SiF
6Or barium silicofluoride (BaSiF (s))
6(s)) silicofluoride solids, after the sedimentation of silicofluoride solids, whether the fluohydric acid content that extracts upper strata liquid again and detect described upper strata liquid is higher than the hydrofluoric acid concentration value that former processing procedure uses, if be higher than the hydrofluoric acid concentration value that former processing procedure uses, namely directly be transmitted back to former processing procedure and use; Otherwise, then add again high concentration of hydrofluoric acid, make it reach hydrofluoric acid concentration value that former processing procedure uses after, be transmitted back to again former processing procedure and use.
Simultaneously, the described silicofluoride slurry with after the described treatment trough bottom sedimentation obtains the silicofluoride solids through dewatering, cleaning.
The sodium compound that adds among the above-mentioned steps c is Sodium Fluoride or sodium-chlor.
The numerical value of the sodium ion in the sodium compound that adds among the above-mentioned steps c be the silicone content value 1.64 quality doubly.
The potassium compound that adds among the above-mentioned steps c is Potassium monofluoride or Repone K.
The numerical value of the potassium ion in the potassium compound that adds among the above-mentioned steps c be the silicone content value 2.787 quality doubly.
The barium compound that adds among the above-mentioned steps c is barium fluoride or bariumchloride.
The numerical value of the barium ion in the barium compound that adds among the above-mentioned steps c be the silicone content value 4.889 quality doubly.
Owing to only need add a small amount of sodium, potassium or barium ion in the hydrofluoric acid waste liquid, can make reusable hydrofluoric acid, need not consume a large amount of chemical agents, also significantly reduce wastewater discharge, and can save the hydrofluoric acid usage quantity of former processing procedure and the expenditure of extra purchase cost thereof, and then reach and simplify treatment step, reduce processing cost and have environmental benefit concurrently.
A kind of hydrofluoric acid waste liquid provided by the present invention reclaims the treatment process that re-uses, it is processed in the hydrofluoric acid waste liquid process, because not emitting without not having heat with thermopositive reaction in the soda acid, so the treatment trough that only need use plastic material to make gets final product, while can be avoided again high thermal conductance to cause fire and produce the hydrofluoric acid dense smoke of injury human body, not only can reach the purpose that reduces equipment cost, more can reach the function that promotes the Working environment security.
A kind of hydrofluoric acid waste liquid provided by the present invention reclaims the treatment process that re-uses, because the silicofluoride that reaction produces in the hydrofluoric acid liquid waste disposal process, it waits for that can not be subject to jelly in the settling process disturbs, and is conducive to reach the effect of a large amount of processing hydrofluoric acid waste liquids so settling velocity is fast.
The present invention is behind a large amount of operational testings of reality, and it is as follows really to have plurality of advantages:
1. the present invention only need add a small amount of sodium, potassium or barium ion, can make reusable hydrofluoric acid, need not consume a large amount of chemical agents, the also problem of non-wastewater discharge, and except reducing the chemical agent cost payout, the hydrofluoric acid usage quantity that more can save former processing procedure.
2. the present invention is in treating processes, because can not emit heat, the processing bucket groove that only need use plastic material to make can be processed, and can avoid again high thermal conductance to cause fire generation hydrofluoric acid dense smoke and injure human body.
3. the present invention is in treating processes, Sodium Silicofluoride (Na
2SiF
6(s)), potassium silicofluoride (K
2SiF
6Or barium silicofluoride (BaSiF (s))
6(s)) silicofluoride solids only need be waited for the sedimentation of silicofluoride solids after producing, because silicofluoride particles settling speed is about 150～180 centimeters/hour, and can not be subject to again jelly during the silicofluoride sedimentation disturbs, the processing bucket groove of general about 4 meters high liquid levels, just sedimentation is complete but need approximately 3 hours consuming time, and its processing speed is fast.
Description of drawings
The accompanying drawing of relevant described embodiment is:
Fig. 1 is the process block diagram that hydrofluoric acid waste liquid of the present invention reclaims the treatment process that re-uses.
Fig. 2 is the operation chart that hydrofluoric acid waste liquid of the present invention reclaims the treatment process that re-uses.
The accompanying drawing sign:
1-hydrofluoric acid waste liquid; 2-sodium, potassium or barium compound; 3-silicofluoride solids; 4-upper strata liquid; The 10-treatment trough; The 20-accumulator tank.
Embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail, can further understands technology contents of the present invention and purpose effect thereof;
Embodiment 1
See also Figure 1 and Figure 2, hydrofluoric acid waste liquid of the present invention reclaims the treatment process that re-uses, and its step comprises:
A, hydrofluoric acid (HF) waste liquid l water conservancy diversion is entered treatment trough 10;
The content of silicon (Si) among b, the analyzing and processing groove 10 interior hydrofluoric acid waste liquid l, and draw described silicone content numerical value;
C, will be added in the hydrofluoric acid waste liquid l in the treatment trough 10 greater than the sodium compound 2 of silicone content numerical value more than one times, make the reaction that combines with sodium of fluorine among the hydrofluoric acid waste liquid l and silicon generate Sodium Silicofluoride solids (Na
2SiF
6(s)) 3;
D, wait Sodium Silicofluoride solids 3 fall to the bottom for the treatment of trough 10;
Upper strata liquid 4 in e, the extraction treatment trough 10 is to accumulator tank 20;
Whether the fluohydric acid content of f, detection accumulator tank 20 interior upper strata liquid 4 is higher than the hydrofluoric acid concentration value that former processing procedure uses, if be higher than the hydrofluoric acid concentration value that former processing procedure uses, namely directly described upper strata liquid 4 be transmitted back to former processing procedure and use; If be lower than the hydrofluoric acid concentration value that former processing procedure uses, then add again high concentration of hydrofluoric acid, make described upper strata liquid 4 reach the hydrofluoric acid concentration value that former processing procedure uses after, again it is transmitted back to former processing procedure and uses;
G, with the Sodium Silicofluoride slurry after the treatment trough 10 bottom sedimentations, through dehydration, clean and obtain Sodium Silicofluoride solids 3.
Wherein, owing to silicone content and the on-fixed of hydrofluoric acid waste liquid l, so need analyze first the silicone content of hydrofluoric acid waste liquid l, the silicone content in the hydrofluoric acid waste liquid l after the industrial community etch process uses at present is between 1～2% among the step b.
And the sodium compound 2 that adds among the step c is to be Sodium Fluoride or sodium-chlor, and the optimal values of its sodium ion be the silicone content value 1.64 quality doubly; If add Sodium Fluoride (NaF), can react generation Sodium Silicofluoride throw out and hydrofluoric acid, its reaction formula is:
2NaF+H
2SiF
6→Na
2SiF
6+2HF
Hydrofluoric acid through above-mentioned reaction output is identical with the hydrofluoric acid that hydrofluoric acid waste liquid l Central Plains exists, and can be sent back to former processing procedure so can not change its composition and use.
If add sodium-chlor (NaCl), then reaction produces Sodium Silicofluoride throw out and hydrochloric acid, and its reaction formula is:
2NaCl(aq)+H
2SiF
6(aq)→Na
2SiF
6(s)+2HCl(aq)
Hydrochloric acid through above-mentioned reaction output, can mutually mix and form mixing acid with the hydrofluoric acid that hydrofluoric acid waste liquid l Central Plains exists, because the hydrofluoric acid kind that the Different Industries etch process uses comprises pure hydrofluoric acid or hydrofluoric acid nitration mixture, so the described mixing acid that contains hydrochloric acid still can be applied to the Different Industries etch process fully, uses and can be transmitted back to former processing procedure.
Hydrofluoric acid or the hydrofluoric acid mixing acid of working concentration 49% in the industrial community etch process at present, the sodium compound 2 that the present invention adds in step c; Can with hydrofluoric acid waste liquid l in fluorine and silicon (existing with the silicofluoric acid form) combine to generate and separate out the Sodium Silicofluoride solid 3 that is slightly soluble in acid, described Sodium Silicofluoride solubleness in water is about 0.652% (in the time of 17 ℃), at this moment, silicon saturation solubility in the solution is 0.0097%, according to Le Satelie principle (LeChatelier ' s Principle), when a system that is in balance, when being subject to External force interference, system can be towards the direction adjustment that reduces External force interference, and reach new balance, so in the Sodium Silicofluoride system, improve the solubleness that fluorine concentration can reduce silicon, in the general hydrofluoric acid waste liquid, fluorine concentration is approximately between 20000～200000ppm, silicon concentration is about 10000ppm, fluorine concentration is higher than silicon concentration, after adding sodium ion, the solubleness of silicon in spent acid can be lower than solubleness in water, its solubleness (is estimated in the solubility product mode below can being down to 0.42ppm, when fluorine concentration was 5%, the solubleness of silicon was 6.7ppm), therefore, mode of the present invention can be removed the silicon more than 99% in the hydrofluoric acid waste liquid 1, through inventor's actually operating learn the suitableeest addition of sodium ion be silicone content 1.64 quality doubly.
And the Sodium Silicofluoride particles settling speed in the steps d is about 150 centimeters/hour (cm/hour), about 4 meters (m) high liquid levels in the general treatment trough 10, need approximately 3 hours ability consuming time sedimentation complete, so as long as a treatment trough 10 that holds 20 tonnes is set, just can reach the effect of processing 20 tons of hydrofluoric acid waste liquid l in per 3 hours, its processing speed all existing treatment processs is faster.
The upper strata liquid 4 in the treatment trough 10 among step e and the f again, namely be not siliceous clean hydrofluoric acid, if its fluohydric acid content is on the low side, after the interpolation high concentration of hydrofluoric acid is supplied concentration, just can again carry and get back to former processing procedure use, and then reduce the expense of buying in addition hydrofluoric acid, relatively also significantly reduce synchronously the generation of hydrofluoric acid waste liquid l, and have environmental benefit concurrently.
Moreover, the slurry for the treatment of trough 10 bottoms is after dehydration is cleaned in the step g, just can get Sodium Silicofluoride, and there are not a large amount of water glass that need add in the existing treatment process, so also do not have a large amount of Sodium Silicofluoride outputs and the generation of jelly, therefore, the settling velocity of described Sodium Silicofluoride also can be faster than existing method, the processing that simultaneously its dehydration, cleaning etc. continue is simple and fast more also, so that the thereupon significantly reduction of bulk treatment cost.
In addition, in each step of the present invention because of without any neutralization of acid with base, so can not emit heat in the treating processes, its treatment trough 10 only need use plastic material to make and get final product, high-valency metal bucket groove need not be used and the equipment cost expenditure can be reduced, also can avoid because of the process careless mistake, equipment is old or Gao Re that structure deteriorate causes produces fire, even generation hydrofluoric acid allows the staff suck along with dense smoke flies away, cause human injury or fatal danger, and then can promote the security of overall work environment.
Embodiment 2
See also Figure 1 and Figure 2, hydrofluoric acid waste liquid of the present invention reclaims the treatment process that re-uses, and its step comprises:
A, hydrofluoric acid (HF) waste liquid l water conservancy diversion is entered treatment trough 10;
The content of silicon (Si) among b, the analyzing and processing groove 10 interior hydrofluoric acid waste liquid l, and draw described silicone content numerical value;
C, will be added in the hydrofluoric acid waste liquid l in the treatment trough 10 greater than the potassium compound 2 of silicone content numerical value more than one times, make the reaction that combines with potassium of fluorine among the hydrofluoric acid waste liquid l and silicon generate potassium silicofluoride solids (K
2SiF
6(s)) 3;
D, wait potassium silicofluoride solids 3 fall to the bottom for the treatment of trough 10;
Upper strata liquid 4 in e, the extraction treatment trough 10 is to accumulator tank 20;
Whether the fluohydric acid content of f, detection accumulator tank 20 interior upper strata liquid 4 is higher than the hydrofluoric acid concentration value that former processing procedure uses, if be higher than the hydrofluoric acid concentration value that former processing procedure uses, namely directly described upper strata liquid 4 be transmitted back to former processing procedure and use; If be lower than the hydrofluoric acid concentration value that former processing procedure uses, then add again high concentration of hydrofluoric acid, make described upper strata liquid 4 reach the hydrofluoric acid concentration value that former processing procedure uses after, again it is transmitted back to former processing procedure and uses;
G, with the potassium silicofluoride slurry after the treatment trough 10 bottom sedimentations, through dehydration, clean and obtain potassium silicofluoride solids 3.
Wherein, owing to silicone content and the on-fixed of hydrofluoric acid waste liquid l, so need analyze first the silicone content of hydrofluoric acid waste liquid l, the silicone content in the hydrofluoric acid waste liquid l after the industrial community etch process uses at present is between 1～2% among the step b.
And the potassium compound 2 that adds among the step c is to be Potassium monofluoride or Repone K, and the optimal values of its potassium ion be the silicone content value 2.787 quality doubly; If add Potassium monofluoride (KF), can react generation potassium silicofluoride throw out and hydrofluoric acid, its reaction formula is:
2KF+H
2SiF
6→K
2SiF
6+2HF
Hydrofluoric acid through above-mentioned reaction output is identical with the hydrofluoric acid that hydrofluoric acid waste liquid l Central Plains exists, and can be sent back to former processing procedure so can not change its composition and use.
If add Repone K (KCl), then reaction produces potassium silicofluoride throw out and hydrochloric acid, and its reaction formula is:
2KCl(aq)+H
2SiF
6(aq)→K
2SiF
6(s)+2HCl(aq)
Hydrochloric acid through above-mentioned reaction output, can mutually mix and form mixing acid with the hydrofluoric acid that hydrofluoric acid waste liquid l Central Plains exists, because the hydrofluoric acid kind that the Different Industries etch process uses comprises pure hydrofluoric acid or hydrofluoric acid nitration mixture, so the described mixing acid that contains hydrochloric acid still can be applied to the Different Industries etch process fully, uses and can be transmitted back to former processing procedure.
Hydrofluoric acid or the hydrofluoric acid mixing acid of working concentration 49% in the industrial community etch process at present, the potassium compound 2 that the present invention adds in step c, can with hydrofluoric acid waste liquid l in fluorine and silicon (existing with the silicofluoric acid form) combine to generate and separate out the potassium silicofluoride solids 3 that is slightly soluble in acid, described potassium silicofluoride solubleness in water is about 0.177gm/100ml (in the time of 25 ℃), at this moment, silicon saturation solubility in the solution is 0.022%, according to Le Satelie principle (LeChatelier ' s Principle), when a system that is in balance, when being subject to External force interference, system can be towards the direction adjustment that reduces External force interference, and reach new balance, so in the potassium silicofluoride system, improve the solubleness that fluorine concentration can reduce silicon, in the general hydrofluoric acid waste liquid, fluorine concentration is approximately between 20000～200000ppm, silicon concentration is about 10000ppm, fluorine concentration is higher than silicon concentration, after adding potassium ion, the solubleness of silicon in spent acid can be lower than solubleness in water, its solubleness (is estimated in the solubility product mode below can being down to 0.0016ppm, when fluorine concentration is 5%, the solubleness of silicon is 0.026ppm), therefore, mode of the present invention can be removed the silicon more than 99% in the hydrofluoric acid waste liquid 1, through inventor's actually operating learn the suitableeest addition of potassium ion be silicone content 2.787 quality doubly.
And the potassium silicofluoride particles settling speed in the steps d is about 155 centimeters/hour (cm/hour), about 4 meters (m) high liquid levels in the general treatment trough 10, need approximately 3 hours ability consuming time sedimentation complete, so as long as a treatment trough 10 that holds 20 tonnes is set, just can reach the effect of processing 20 tons of hydrofluoric acid waste liquid l in per 3 hours, its processing speed all existing treatment processs is faster.
The upper strata liquid 4 in the treatment trough 10 among step e and the f again, namely be not siliceous clean hydrofluoric acid, if its fluohydric acid content is on the low side, after the interpolation high concentration of hydrofluoric acid is supplied concentration, just can again carry and get back to former processing procedure use, and then reduce the expense of buying in addition hydrofluoric acid, relatively also significantly reduce synchronously the generation of hydrofluoric acid waste liquid l, and have environmental benefit concurrently.
Moreover, the slurry for the treatment of trough 10 bottoms is after dehydration is cleaned in the step g, just can get potassium silicofluoride, and there are not a large amount of water glass that need add in the existing treatment process, so also do not have a large amount of potassium silicofluoride outputs and the generation of jelly, therefore, the settling velocity of described potassium silicofluoride also can be faster than existing method, the processing that simultaneously its dehydration, cleaning etc. continue is simple and fast more also so that the bulk treatment cost with significantly reduction.
In addition, in each step of the present invention because of without any neutralization of acid with base, so can not emit heat in the treating processes, its treatment trough 10 only need use plastic material to make and get final product, high-valency metal bucket groove need not be used and the equipment cost expenditure can be reduced, also can avoid because of the process careless mistake, equipment is old or Gao Re that structure deteriorate causes produces fire, even generation hydrofluoric acid allows the staff suck along with dense smoke flies away, cause human injury or fatal danger, and then can promote the security of overall work environment.
See also Figure 1 and Figure 2, hydrofluoric acid waste liquid of the present invention reclaims the treatment process that re-uses, and its step comprises:
A, hydrofluoric acid (HF) waste liquid l water conservancy diversion is entered treatment trough 10;
The content of silicon (Si) among b, the analyzing and processing groove 10 interior hydrofluoric acid waste liquid l, and draw described silicone content numerical value;
C, will be added in the hydrofluoric acid waste liquid l in the treatment trough 10 greater than the barium compound 2 of silicone content numerical value more than one times, make the reaction that combines with barium of fluorine among the hydrofluoric acid waste liquid l and silicon generate barium silicofluoride solids (BaSiF
6(s)) 3;
D, wait barium silicofluoride solids 3 fall to the bottom for the treatment of trough 10;
Upper strata liquid 4 in e, the extraction treatment trough 10 is to accumulator tank 20;
Whether the fluohydric acid content of f, detection accumulator tank 20 interior upper strata liquid 4 is higher than the hydrofluoric acid concentration value that former processing procedure uses, if be higher than the hydrofluoric acid concentration value that former processing procedure uses, namely directly described upper strata liquid 4 be transmitted back to former processing procedure and use; If be lower than the hydrofluoric acid concentration value that former processing procedure uses, then add again high concentration of hydrofluoric acid, make described upper strata liquid 4 reach the hydrofluoric acid concentration value that former processing procedure uses after, again it is transmitted back to former processing procedure and uses;
G, with the barium silicofluoride slurry after the treatment trough 10 bottom sedimentations, through dehydration, clean and obtain barium silicofluoride solids 3.
Wherein, owing to silicone content and the on-fixed of hydrofluoric acid waste liquid l, so need analyze first the silicone content of hydrofluoric acid waste liquid l, the silicone content in the hydrofluoric acid waste liquid l after the industrial community etch process uses at present is between 1～2% among the step b.
And the barium compound 2 that adds among the step c is to be barium fluoride or bariumchloride, and the optimal values of its barium ion be the silicone content value 4.889 quality doubly; If add barium fluoride (BaF
2), can react generation barium silicofluoride throw out and hydrofluoric acid, its reaction formula is:
BaF
2+H
2SiF
6→BaSiF
6+2HF
Hydrofluoric acid through above-mentioned reaction output is identical with the hydrofluoric acid that hydrofluoric acid waste liquid l Central Plains exists, and can be sent back to former processing procedure so can not change its composition and use.
If add bariumchloride (BaCl
2), then reaction produces barium silicofluoride throw out and hydrochloric acid, and its reaction formula is:
2BaCl
2(aq)+H
2SiF
6(aq)→BaSiF
6(s)+2HCl(aq)
Hydrochloric acid through above-mentioned reaction output, can mutually mix and form mixing acid with the hydrofluoric acid that hydrofluoric acid waste liquid l Central Plains exists, because the hydrofluoric acid kind that the Different Industries etch process uses comprises pure hydrofluoric acid or hydrofluoric acid nitration mixture, so the described mixing acid that contains hydrochloric acid still can be applied to the Different Industries etch process fully, uses and can be transmitted back to former processing procedure.
Hydrofluoric acid or the hydrofluoric acid mixing acid of working concentration 49% in the industrial community etch process at present, the barium compound 2 that the present invention adds in step c; Can with hydrofluoric acid waste liquid l in fluorine and silicon (existing with the silicofluoric acid form) combine to generate and separate out the barium silicofluoride solids 3 that is slightly soluble in acid, described barium silicofluoride solubleness in water is about 0.177gm/100ml (in the time of 25 ℃), at this moment, silicon saturation solubility in the solution is 0.022%, according to Le Satelie principle (LeChatelier ' s Principle), when a system that is in balance, when being subject to External force interference, system can be towards the direction adjustment that reduces External force interference, and reach new balance, so in the potassium silicofluoride system, improve the solubleness that fluorine concentration can reduce silicon, in the general hydrofluoric acid waste liquid, between 20000～200000ppm, silicon concentration is about 10000ppm to fluorine concentration approximately, fluorine concentration is higher than silicon concentration, after adding barium ion, the solubleness of silicon in spent acid can be lower than solubleness in water, and its solubleness can be down to 3.62 * 10
-8Ppm is following (to estimate that in the solubility product mode when fluorine concentration was 5%, the solubleness of silicon was 2.9 * 10
-7Ppm), therefore, mode of the present invention can be removed the silicon more than 99% in the hydrofluoric acid waste liquid 1, through inventor's actually operating learn the suitableeest addition of barium ion be silicone content 4.889 quality doubly.
And the barium silicofluoride particles settling speed in the steps d is about 180 centimeters/hour (cm/hour), about 4 meters (m) high liquid levels in the general treatment trough 10, need approximately 3 hours ability consuming time sedimentation complete, so as long as a treatment trough 10 that holds 20 tonnes is set, just can reach the effect of processing 20 tons of hydrofluoric acid waste liquid l in per 3 hours, its processing speed all existing treatment processs is faster.
The upper strata liquid 4 in the treatment trough 10 among step e and the f again, namely be not siliceous clean hydrofluoric acid, if its fluohydric acid content is on the low side, after the interpolation high concentration of hydrofluoric acid is supplied concentration, just can again carry and get back to former processing procedure use, and then reduce the expense of buying in addition hydrofluoric acid, relatively also significantly reduce synchronously the generation of hydrofluoric acid waste liquid l, and have environmental benefit concurrently.
Moreover, the slurry for the treatment of trough 10 bottoms is after dehydration is cleaned in the step g, just can get barium silicofluoride, and there are not a large amount of water glass that need add in the existing treatment process, so also do not have a large amount of barium silicofluoride outputs and the generation of jelly, therefore, the settling velocity of described barium silicofluoride also can be faster than existing method, the processing that simultaneously its dehydration, cleaning etc. continue is simple and fast more also, so that the thereupon significantly reduction of bulk treatment cost.
In addition, in each step of the present invention because of without any neutralization of acid with base, so can not emit heat in the treating processes, its treatment trough 10 only need use plastic material to make and get final product, high-valency metal bucket groove need not be used and the equipment cost expenditure can be reduced, also can avoid because of the process careless mistake, equipment is old or Gao Re that structure deteriorate causes produces fire, even generation hydrofluoric acid allows the staff suck along with dense smoke flies away, cause human injury or fatal danger, and then can promote the security of overall work environment.
In sum, the present invention reuses hydrofluoric acid because of recyclable hydrofluoric acid waste liquid, its consumption of chemical agent and wastewater discharge etc. all reduce 90 percent than existing methods, and processing speed also can not emitted during the course heat soon and be caused causing danger, really having the high industrial usability and meet patent requirement, files an application in the whence in accordance with the law.
Above-listed detailed description is specifying for a possible embodiments of the present invention, only described embodiment limits claim of the present invention, allly do not break away from the equivalence that skill spirit of the present invention does and implement or change, all should be contained in the claim of this case.
In sum, be preferred embodiment of the present invention, its non-limitation scope of patent protection of the present invention so the reasonable change that specification sheets of the present invention and graphic content are done all is contained in the scope of the present invention, is closed and is given Chen Ming.
Claims (7)
1. a hydrofluoric acid waste liquid reclaims the treatment process that re-uses, and it is characterized in that: the method comprises the steps:
A, described hydrofluoric acid waste liquid water conservancy diversion is entered treatment trough;
B, analyze in the described treatment trough in the described hydrofluoric acid waste liquid content of silicon and draw described silicone content numerical value;
C, will be greater than the compound that contain sodium, potassium or barium of described silicone content numerical value more than one times, be added in the described hydrofluoric acid waste liquid in the described treatment trough, make fluorine in the described hydrofluoric acid waste liquid and described silicon and described sodium, described potassium or described barium generate the silicofluoride solids of Sodium Silicofluoride, potassium silicofluoride or barium silicofluoride;
D, the described silicofluoride solids of wait fall to the bottom of described treatment trough;
Upper strata liquid in e, the described treatment trough of extraction is to accumulator tank;
Whether the described fluohydric acid content of upper strata liquid is higher than the described hydrofluoric acid concentration value that former processing procedure uses in f, the described accumulator tank of detection, if be higher than the described hydrofluoric acid concentration value that former processing procedure uses, namely directly described upper strata liquid being transmitted back to former processing procedure uses, if be lower than the described hydrofluoric acid concentration value that former processing procedure uses, then add again high concentration of hydrofluoric acid, after making described upper strata liquid reach the described hydrofluoric acid concentration value of former processing procedure use, again it is transmitted back to former processing procedure and uses;
G, with the described silicofluoride slurry after the bottom sedimentation of described treatment trough, through dehydration, clean and obtain the silicofluoride solids.
2. reclaim the treatment process that re-uses according to hydrofluoric acid waste liquid claimed in claim 1, it is characterized in that: the sodium compound that adds among the step c is Sodium Fluoride or sodium-chlor.
3. reclaim the treatment process that re-uses according to hydrofluoric acid waste liquid claimed in claim 1, it is characterized in that: the numerical value of the sodium ion in the sodium compound that adds among the step c be the silicone content value 1.64 quality doubly.
4. reclaim the treatment process that re-uses according to hydrofluoric acid waste liquid claimed in claim 1, it is characterized in that: the potassium compound that adds among the step c is Potassium monofluoride or Repone K.
5. reclaim the treatment process that re-uses according to hydrofluoric acid waste liquid claimed in claim 1, it is characterized in that: the numerical value of the potassium ion in the potassium compound that adds among the step c be the silicone content value 2.787 quality doubly.
6. reclaim the treatment process that re-uses according to hydrofluoric acid waste liquid claimed in claim 1, it is characterized in that: the barium compound that adds among the step c is barium fluoride or bariumchloride.
7. reclaim the treatment process that re-uses according to hydrofluoric acid waste liquid claimed in claim 1, it is characterized in that: the numerical value of the barium ion in the barium compound that adds among the step c be the silicone content value 4.889 quality doubly.
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| CN105439108A (en) * | 2016-01-06 | 2016-03-30 | 昆明理工大学 | Method and device for resource recycling of silicon core corrosion waste liquor |
| CN105583058A (en) * | 2016-01-07 | 2016-05-18 | 阮正华 | Magnetic separation method for electrolytic aluminum solid waste |
| CN105951102A (en) * | 2016-05-13 | 2016-09-21 | 巫协森 | Method for reclamation of waste acid in hydrofluoric acid etching process |
| TWI574923B (en) * | 2016-04-06 | 2017-03-21 | 百德光電有限公司 | Method for producing calcium fluoride by wastewater comprising hydrofluoric acid, hexafluoro silicate and hexafluoro aluminate |
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| CN104591189A (en) * | 2015-02-10 | 2015-05-06 | 湖南有色氟化学科技发展有限公司 | Recycling method for purifying cryolite waste acid |
| CN105439108A (en) * | 2016-01-06 | 2016-03-30 | 昆明理工大学 | Method and device for resource recycling of silicon core corrosion waste liquor |
| CN105583058A (en) * | 2016-01-07 | 2016-05-18 | 阮正华 | Magnetic separation method for electrolytic aluminum solid waste |
| CN107614434A (en) * | 2016-04-01 | 2018-01-19 | 佐佐木化学药品株式会社 | The regeneration treating method of formed body containing alkali metal salt and the acidic aqueous solution using the formed body |
| TWI574923B (en) * | 2016-04-06 | 2017-03-21 | 百德光電有限公司 | Method for producing calcium fluoride by wastewater comprising hydrofluoric acid, hexafluoro silicate and hexafluoro aluminate |
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| CN112794333A (en) * | 2021-01-13 | 2021-05-14 | 赣州帝晶光电科技有限公司 | Preparation method of fluosilicic acid byproduct of fluorine-containing waste liquid |
| CN114985365A (en) * | 2022-04-18 | 2022-09-02 | 江苏鑫华半导体科技股份有限公司 | Polycrystalline silicon sample core cleaning analysis method and system |
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