CN102674254A - Separation method and separation device - Google Patents
Separation method and separation device Download PDFInfo
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- CN102674254A CN102674254A CN2012100542307A CN201210054230A CN102674254A CN 102674254 A CN102674254 A CN 102674254A CN 2012100542307 A CN2012100542307 A CN 2012100542307A CN 201210054230 A CN201210054230 A CN 201210054230A CN 102674254 A CN102674254 A CN 102674254A
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Abstract
The invention provides a separation method and a separation device, which can simply separate high-purity hydrofluoric acid from a mixed acid at least containing hydrofluoric acid, ammonium bifluoride, silicon and water. The separation method of separating the hydrofluoric acid from the mixed acid (100) at least containing hydrofluoric acid, ammonium bifluoride, silicon and water, comprises the following steps: a first distillation step of distilling the mixed acid (100) to recover a distillate (200) containing the hydrofluoric acid and water and recover a residual fluid (500) containing the ammonium bifluoride and the silicon; a second distillation step of distilling the distillate (200) to mainly separate water from the distillate (200) and furthermore recover a residual fluid (600) containing the hydrofluoric acid with relatively higher concentration than that of the hydrofluoric acid in the distillate (200).
Description
Technical field
The present invention relates to separation method and tripping device.
Background technology
All the time, as etching solution, the goods of known packets hydrofluoric acid containing and Neutral ammonium fluoride.In addition, from this etching solution and the technology that reclaims hydrofluoric acid (fluorine) of the etching waste liquor after being used for etching also be widely known by the people (for example, with reference to patent documentation 1).
Put down in writing following method in the patent documentation 1; Promptly; Through making lime carbonate and the etching solution reaction that comprises hydrofluoric acid and Neutral ammonium fluoride, thereby fluoridize the form of calcium and reclaim fluorine, make the hydrofluoric acid that etching solution is used once more by the Calcium Fluoride (Fluorspan) of recovery again with the less high purity of silicon-dioxide containing ratio.
But, in this method, can't be from etching solution direct separation, reclaim hydrofluoric acid.That is, after the form recovery with Calcium Fluoride (Fluorspan), need this Calcium Fluoride (Fluorspan) is processed the operation of hydrofluoric acid, thereby can't reclaim efficiently.In addition, it is more to play the operation of making till the etching solution (hydrofluoric acid) make new advances from etching waste liquor, and the way can produce the secondary waste liquid in large quantities therein.Therefore, also there is the relatively poor problem of environment property.In addition, because operation is more, have also therefore that apparatus structure maximizes, complicated problem.
Patent documentation 1: japanese kokai publication hei 5-170435 communique
Summary of the invention
The objective of the invention is to, a kind of separation method and the tripping device that can from the nitration mixture that contains hydrofluoric acid, ammonium acid fluoride, silicon and water at least, isolate highly purified hydrofluoric acid simply is provided.
The present invention is the invention of accomplishing at least a portion that solves above-mentioned problem, and it can be realized through following mode or application examples.
Application examples 1
Separation method of the present invention does, from the nitration mixture that contains hydrofluoric acid, ammonium acid fluoride, silicon and water at least, isolates the method for said hydrofluoric acid, it is characterized in that, comprising:
First distillation process through said nitration mixture is distilled, thereby reclaims first liquid that contains said hydrofluoric acid and water with as distillate, and reclaims second liquid that contains said ammonium acid fluoride and said silicon with as debris;
The after-fractionating operation through said first liquid is distilled, thereby is mainly isolated said water from said first liquid, so recovery and said first liquid phase than higher the 3rd liquid of the concentration of said hydrofluoric acid with as debris.
Thus, can be from nitration mixture simple and to separate, to reclaim highly purified hydrofluoric acid than higher concentration.
Application examples 2
In separation method of the present invention, be preferably, the Heating temperature of said first liquid in the said after-fractionating operation is made as, and is lower than the design temperature of the Heating temperature of the said nitration mixture in said first distillation process.
Thus, when from first liquid, removing moisture, can reduce since in the distillate of being removed by sneaking into and with the moisture amount of removed hydrofluoric acid together.Therefore, can improve the yield of hydrofluoric acid.
Application examples 3
In separation method of the present invention, be preferably, crystallization contains the solid of said ammonium acid fluoride and said silicon from said second liquid,
And will from said second liquid, separate said solid and the 4th liquid, handle through said first operation once more with said nitration mixture.
Thus, can from nitration mixture, separate, reclaim more hydrofluoric acid.
Application examples 4
In separation method of the present invention, be preferably, said first distillation process carries out when said nitration mixture is stirred.
Thus, the crystallization in the retort is inhibited.
Application examples 5
In separation method of the present invention, be preferably, comprise the separation circuit that from said solid, separates said ammonium acid fluoride.
Thus, can from nitration mixture, further separate, reclaim ammonium acid fluoride.
Application examples 6
In separation method of the present invention, be preferably, in said separation engineering, from said solid, separate said ammonium acid fluoride through crystallization process.
Thus, can carry out the separation of ammonium acid fluoride simply.
Application examples 7
In separation method of the present invention, be preferably, in said separation engineering, comprising: first Crystallization Procedure, first Crystallization Procedure be through preparing to make said solid dissolved solution, and make said solution be cooled to preset temperature to carry out; Second Crystallization Procedure, said second Crystallization Procedure is carried out under the temperature of the temperature that is lower than said first Crystallization Procedure.
Thus, can separate, reclaim more highly purified Neutral ammonium fluoride.
Application examples 8
In separation method of the present invention, be preferably, said nitration mixture is for through carrying out the etching waste liquor that etch processes produces to the material that contains silicon.
Thus, can utilize again, and can realize the cost degradation of etch processes etching waste liquor.In addition, owing to can reduce the amount of the waste liquid that goes out of use, therefore comparatively excellent aspect environment.
Application examples 9
Tripping device of the present invention is characterised in that, has used separation method of the present invention.
Thus, the device that separates, reclaims highly purified hydrofluoric acid or ammonium acid fluoride can be provided from nitration mixture.
Description of drawings
Fig. 1 is the synoptic diagram of the related tripping device of preferred implementation of the present invention.
Fig. 2 is used for synoptic diagram that the related separation method of preferred implementation of the present invention is described.
Fig. 3 is used for table that embodiment is described.
Fig. 4 is used for table that embodiment is described.
Fig. 5 is used for table that embodiment is described.
Embodiment
Below, based on preferred implementation shown in the drawings, separation method of the present invention and tripping device are elaborated.
Fig. 1 is the synoptic diagram of the related tripping device of preferred implementation of the present invention; Fig. 2 is used for synoptic diagram that the related separation method of preferred implementation of the present invention is described; Fig. 3～Fig. 5 is used for table that embodiment is described.
1. tripping device
At first, the structure to tripping device 1 describes.
1 pair of water distilling apparatus of tripping device shown in Figure 1 has carried out illustration; And carry out following explanation as an example with batch-wise separation method; Wherein, said batch-wise separation method is to take out the distillate that obtains from the water distilling apparatus of each operation to returnable 300; Perhaps take out debris, above-mentioned distillate and debris are transferred to the supply unit of the water distilling apparatus of subsequent processing from retort.But, also can constitute, arrange a plurality of above-mentioned water distilling apparatus, and between installing, connect, thereby carry out isolating separation method with straight-through (inline) mode through valve operation through tubing.
This tripping device 1 is to be used for from containing hydrofluoric acid [HF], ammonium acid fluoride [(NH
4) HF
2], silicon [Si] and water [H
2O] nitration mixture 100 in, separate, reclaim the device (water distilling apparatus) of hydrofluoric acid and ammonium acid fluoride respectively with high purity and than higher concentration.In addition, said silicon is in nitration mixture 100, with silicon compound, particularly with ammonium silicofluoride [(NH
4)
2SiF
6)] form exist.
In this nitration mixture 100, unreacted hydrofluoric acid and ammonium acid fluoride are with separately composition and residual in a large number in etch processes.Therefore, can pass through, thereby assign to use as the one-tenth of etching solution once more respectively with they independent recovery.
So, through from etching waste liquor, separating unreacted etching composition, thereby can realize the utilization again of etching waste liquor, and can realize the cost degradation of etch processes.In addition, because the amount of the etching waste liquor of the processing that goes out of use reduces, therefore can bring into play excellent environment property.
Though the concentration of the hydrofluoric acid before the separation in the nitration mixture 100 is not specially limited, and for example is about 10～20wt%.In addition, though the concentration of the ammonium acid fluoride before the separation in the nitration mixture 100 is not specially limited, for example be about 25～35wt%.In addition, though the concentration of the silicon before the separation in the nitration mixture 100 is not specially limited, for example be about 0.1～1.0wt%.
At this, the concentration of the hydrofluoric acid in the nitration mixture 100, ammonium acid fluoride, silicon can be obtained as follows.
The concentration determination of silicon
Use the qualitative and quantitative analysis of the metallic element that IPC emmission spectrum device (for example, (strain) island Feng makes made, ProductName " ICPS-7510 ") carries out being contained in the nitration mixture 100.Thus, because the atoms metal in the nitration mixture 100 is merely silicon, therefore, can obtain the concentration A (mol/l) of the silicon in the nitration mixture 100.
The concentration determination of ammonium acid fluoride
Use ultraviolet-visible spectrophotometer (for example, (strain) island Feng makes made, ProductName " IUV-1240 ") to implement the indophenol blue absorption spectrophotometry, thus, can obtain (the NH that ammonium acid fluoride and ammonium silicofluoride had in the nitration mixture 100
4 +) total concentration B (mol/l).As indicated above, owing to the form of the silicon in the nitration mixture 100 with ammonium silicofluoride exists, through deducting (the NH that ammonium silicofluoride has from amounting to concentration B
4 +) concentration 2A, thereby can obtain the concentration C (mol/l) of the ammonium acid fluoride in the nitration mixture 100.That is C=B-2A.
The concentration determination of hydrofluoric acid
Use current potential automatic titration device (for example, capital of a country electronic industry (strain) system, ProductName " AT-510 ") that the acid concentration of nitration mixture 100 is measured.Particularly, through utilizing 0.1mol/dm
3Aqueous sodium hydroxide solution carries out neutralization titration, thereby the acid concentration of nitration mixture 100 is measured.Thus, can obtain the total acid concentration D that hydrofluoric acid, ammonium acid fluoride and ammonium silicofluoride had in the nitration mixture 100.In mentioned above; Because ammonium silicofluoride concentration A and ammonium acid fluoride concentration B in the known nitration mixture 100; Therefore through deducting the acid concentration B that acid concentration 4A, ammonium acid fluoride had that ammonium silicofluoride has, thereby can obtain the hydrofluoric acid concentration E (mol/l) in the nitration mixture 100 from amounting to acid concentration D.That is E=D-4A-B.
More than, an example of the measuring method of the concentration of the hydrofluoric acid in the nitration mixture 100, ammonium acid fluoride, silicon is illustrated.
As shown in Figure 1, the tripping device 1 of this embodiment has: retort (distil container) 11; Supply unit 12, it supplies with nitration mixture 100 to retort 11; Heating part 13, it heats retort 11; Agitating unit 14, it stirs the nitration mixture 100 in the retort 11; Cooling end 15, it cools off the steam that is generated by retort 11 and obtains distillate 200; Recoverer 16, it reclaims distillate 200; Off gas treatment unit 17.
In the various piece that constitutes tripping device 1, the part that can contact with nitration mixture 100 all has acid resistance.In this embodiment, can constitute by polytetrafluoroethylene (PTFE) with the position that nitration mixture 100 contacts through making, thereby given acid resistance.
In addition; Be not limited to aforesaid method as giving acid proof method; For example also can adopt, make method that the position that can contact with nitration mixture 100 is made up of the acid resistance plastics of vinyl chloride resin, vinyl resin etc., or on the surface of the main body that constitutes by metallic substance, apply fluorine-type resin and the method that constitutes.Because the thermal conductivity of the mixing material of these metals and acid resistance resin is good, therefore can carry out at short notice through the liquid temperature adjustment of carrying out from external heated, cooling, thereby more convenient.
Stored nitration mixture 100 in the supply unit 12.This supply unit 12 is set at the top of retort 11.The runner that is communicated with supply unit 12 and retort 11 be provided with cock 181 midway, through this cock 181 is operated, stored the nitration mixture 100 in supply unit 12 thereby can supply with, otherwise perhaps stopped this supply to retort 11.
In addition, as heating part 13,, then be not limited to above-mentioned structure as long as can heat to nitration mixture 100.
Agitating unit 14
Tripping device 1 preferably has agitating unit 14.
Agitating unit 14 has the function that the nitration mixture 100 in the retort 11 is stirred.Through when utilizing 14 pairs of nitration mixture 100 of agitating unit to stir, distilling, obtain promoting thereby in nitration mixture 100, material is moved, and then can suppress the crystallization etc. of solid (solids component).Particularly, can suppress crystallization that near the concentration of local of the concentration the inwall owing to liquid level or container causes etc.
This agitating unit 14 has; Be configured in the stirring rod (stirring rod) 141 in the retort 11 and be mounted with retort 11 and the heated and stirred machine of heating part 13 (whipping appts) 142; And be constituted as; Through utilizing heated and stirred machine 142 to make stirring rod 141 rotation, thereby nitration mixture 100 is stirred.
In addition, also can use whisking appliance to replace possessing the heated and stirred machine 142 of heating unit with heating unit.In addition, even do not possess whisking appliance, also can make the liquid-flow in the retort 11, thereby stir through the physical method that the wall of a container face is applied vibration etc.
Cooling end 15
Cooling end 15 has, and to cooling off through the steam that generates of heating nitration mixture 100, thereby obtains the function of distillate 200.As this cooling end 15, can use well-known cooling tube usually.That is, cooling end 15 is constituted as, pipe 151 and outer tube 152 in having, and steam flow cross in the pipe 151, and water coolant flows through between interior pipe 151 and outer tube 152.Thus, the steam in flowing through in the pipe 151 is cooled water cooling and liquefies, thereby can access distillate 200.
In addition, as long as can access distillate 200, then the length of interior pipe 151 or the temperature of water coolant etc. are not specially limited.
Off gas treatment unit 17
Off gas treatment unit (purge of gas portion) 17 has, and the waste gas of portion's 15 liquefaction that are not cooled is carried out the function of neutralizing treatment.This off gas treatment unit 17 has the container of taking in water or alkaline cleaning fluid 400, through waste gas is guided in the scavenging solution 400, thereby carries out the neutralizing treatment of waste gas.
More than, the structure of tripping device 1 is illustrated.
2. the separation method of hydrofluoric acid
Next, the method (separation method of the present invention) of from nitration mixture 100, separating, reclaim hydrofluoric acid is described.
The separation method of the present invention of synoptic diagram has been shown in Fig. 2, has had first distillation process and after-fractionating operation.Below illustrated separation method do, in first distillation process, from nitration mixture 100, take out distillate 200 after, in the after-fractionating operation, from this distillate 200, take out the separation method of debris 600.Can adopt any mode in the following mode, that is, after first distillation process finishes, the method for handling through the batch mode of implementing the after-fractionating operation; Employed separately water distilling apparatus in first distillation process and the after-fractionating operation is arranged side by side, and through tubing to connecting between them, thereby the direct-passing mode of handling through valve operation and pump operated etc.
First distillation process
For example, supply with nitration mixture 100 to retort 11 from supply unit 12, and through utilizing heating part 13 that nitration mixture 100 is heated to preset temperature, thereby under atmospheric pressure nitration mixture 100 is distilled.At this moment, also can stir through the nitration mixture 100 in 14 pairs of retorts of agitating unit 11.As the Heating temperature (said preset temperature) of nitration mixture 100,, it for example is about 120～140 ℃ though it is not specially limited.
Thus, main vaporize water and hydrofluoric acid from nitration mixture 100, and these steams arrive cooling end 15 respectively via guiding channel 111.The steam that arrives cooling end 15 is cooled portion's 15 coolings and becomes distillate (first liquid) 200, and then is recovered to recoverer 16.The distillate 200 that is recovered to recoverer 16 does, is the lower hydrofluoric acid (hydrofluoric acid aqueous solution) of concentration ratio of staple with water and hydrofluoric acid.
At this, as the hydrofluoric acid concentration of distillate 200,, be preferably though it is not specially limited, when the hydrofluoric acid concentration with nitration mixture 100 is made as A (wt%), be about 0.75A～1.1A (wt%).
The yield (%) of the hydrofluoric acid that reclaims as distillate 200 in addition,, promptly { (amount of the hydrofluoric acid that is contained in the amount/nitration mixture 100 of the hydrofluoric acid that is contained in the distillate 200) * 100} is preferably, approximately more than or equal to 55%.Thus, can make the amount of the hydrofluoric acid that reclaims as distillate 200 sufficient.
In addition, the distillation amount (%) of distillate 200, promptly (weight of the weight/nitration mixture 100 of distillate 200) though * 100} is not specially limited, and is preferably about 55～70%.Thus, can in the security of guaranteeing device, obtain the distillate 200 of competent amount.
Through carrying out this first distillation process fully, can from nitration mixture 100, divide dried up and hydrofluoric acid.
The after-fractionating operation
After first distillation process mentioned above was accomplished, discharge was present in the debris (second liquid) 500 in the retort 11 from retort 11, and is transferred in the not shown returnable.In addition, this debris 500 is used like other processing of the civilian said confession in back.
Next, in the water distilling apparatus 1 of sky, supply with above-mentioned distillate 200 to retort 11, through utilizing heating part 13 distillate 200 is heated to preset temperature, thereby under atmospheric pressure distillate 200 is distilled from supply unit 12.At this moment, also can stir through the distillate 200 in 14 pairs of retorts of agitating unit 11.As the Heating temperature (said preset temperature) of distillate 200,, it for example is about 100～120 ℃ though it is not specially limited.
Thus, water and a spot of hydrofluoric acid evaporate from distillate 200, and its steam arrives cooling end 15 via guiding channel 111.The steam that arrives cooling end 15 portion's 15 coolings that are cooled, thus the lower hydrofluoric acid of concentration ratio is recovered to recoverer 16.
Through carrying out this after-fractionating operation fully, thereby can from distillate 200, isolate many water of comparing with hydrofluoric acid.That is, can distillate 200 be concentrated, thereby the after-fractionating operation finishes and remains in the debris (the 3rd liquid) 600 in the retort 11, will become the hydrofluoric acid (hydrofluoric acid aqueous solution) that hydrofluoric acid concentration is higher than distillate 200.
Particularly; Through with first distillation process in the Heating temperature of nitration mixture 100 compare; The Heating temperature of the distillate 200 in the after-fractionating operation is set lowlyer; Thereby when from distillate 200, removing moisture, can reduce since in the distillate of being removed by sneaking into and with the moisture amount of removed hydrofluoric acid together.Therefore, can improve the yield of hydrofluoric acid.
At this, as the hydrofluoric acid concentration of debris 600,, be preferably though it is not specially limited, when the hydrofluoric acid concentration with nitration mixture 100 is made as A (wt%), be about 2.0A～3.0A (wt%).
The yield (%) of the hydrofluoric acid that reclaims as debris 600 in addition,, promptly { (amount of the hydrofluoric acid that is contained in the amount/nitration mixture 100 of the hydrofluoric acid that is contained in the debris 600) * 100} is preferably, and is about more than 30%.Thus, can make the amount of the hydrofluoric acid that reclaims as debris 600 sufficient.
Can use as etching solution once more through as above operating the debris 600 (hydrofluoric acid) that obtains.When utilizing, for example can mix with new etching solution and use as etching solution.In addition, can also debris 600 be used for the purposes that the hydrofluoric acid concentration of new etching solution is regulated.
More than, the method for from nitration mixture 100, isolating hydrofluoric acid is illustrated.
According to this method, can simply and have efficiently and from nitration mixture, separate, reclaim the higher highly purified hydrofluoric acid of concentration ratio.In addition, owing to mix through the medicine that will from etching waste liquor, separate, reclaim, thereby can generate new etching solution, therefore the utilization again of etching waste liquor can be realized, and then the cost degradation of etch processes can be realized.In addition, reduced by the amount of the etching waste liquor of off gas treatment, therefore can also bring into play excellent environment property owing to do not utilize again.
3. the separation method of ammonium acid fluoride
From the debris that obtains 500 of the separation method of hydrofluoric acid mentioned above, can separate, reclaim ammonium acid fluoride midway.Below, based on Fig. 2 this separation method is described.
Through cooling etc., and the debris 500 that in first distillation process mentioned above, obtains is carried out crystallization, thereby separate out the solid that comprises ammonium acid fluoride and ammonium silicofluoride.In addition, according to evaporation of water amount,, also separate out the situation of the solid 900 that comprises ammonium acid fluoride and ammonium silicofluoride even also can occur sometimes not carrying out said cooling from nitration mixture 100.
Therefore, at first, separate solid 900 from debris 500.As separation method,, for example can use the general precipitator method though it is not specially limited.That is, precipitate in debris 500 through making solid 900, thereby can from debris 500, isolate solid 900.
At this, from debris 500, separated solid 900 and liquid (the 4th liquid) 700 in, residual have incomplete isolating hydrofluoric acid in first distillation process.Therefore, can make this liquid 700 return supply unit 12, and handle through first distillation process once more with nitration mixture 100.Thus, can from nitration mixture 100, further separate, reclaim more hydrofluoric acid.In addition, this is treated to preferred processing, and also nonessential, so the arrow among Fig. 2 is with single-point line expression.
Next, after making solid 900 dryings, this solid 900 is dissolved in the solvent (about 50～70 ℃) of water etc. for example fully, and obtains solution (the 5th liquid) 801.Below, in two stages this solution 801 is cooled off, and utilize the difference of solubleness, thereby separate out the different solid of weight ratio of ammonium acid fluoride and ammonium silicofluoride in each stage.
At first, solution 801 is cooled to about 35～60 ℃ (first Crystallization Procedure).Thus, in solution 801, separate out solid 810.Next, after from solution 801, removing solid 810 (will from solution 801, remove solid 810 and solution be called " solution 802 "), solution 802 is cooled to about 5～20 ℃ (second Crystallization Procedure).Thus, in solution 802, separate out solid 820.
In drying solid 810 in, for example, contain the ammonium acid fluoride of the 70～80wt% that has an appointment, and contain the ammonium silicofluoride of the 20～30wt% that has an appointment.In addition, in drying solid 820 in, contain the ammonium acid fluoride of the 95～99wt% that has an appointment, and contain the ammonium silicofluoride of the 1～5wt% that has an appointment.
In this way, through separating out solid 820, thereby can from nitration mixture 100, separate, reclaim ammonium acid fluoride with high density (high purity).
In addition,, in first Crystallization Procedure,, also can not carry out second Crystallization Procedure with regard under enough situation according to the concentration of the ammonium acid fluoride of obtaining, and with the solid 810 of the gained raw material as new etching solution.
At this, from solution 802, having removed solid 820 solution 803 in, residual have in this operation, do not have complete isolating ammonium acid fluoride.Therefore, can make this solution 803 return supply unit 12, and handle through first distillation process once more with nitration mixture 100.Thus, can further separate, reclaim more ammonium acid fluoride.
More than, though based on illustrated embodiment separation method of the present invention and tripping device are illustrated, separation method of the present invention and tripping device are not limited thereto, and works arbitrarily or the operation that can add other.In addition, though the combination of a plurality of distillation engineerings and crystallization engineering is illustrated, with the isolating separation method of hydrofluoric acid, also can provide environment property good regeneration techniques even only implement to use a plurality of distillation engineerings.
Embodiment
Below, concrete embodiment of the present invention is described.
Embodiment 1
Prepared nitration mixture as etching waste liquor.In addition, the hydrofluoric acid concentration before the separation of this nitration mixture is 12.6wt%, and the concentration before the separation of ammonium acid fluoride is 27.6wt%, and the concentration before the separation of silicon is 0.4wt%, and residue nearly all is a water.(concentration about the following stated is also identical) that the mensuration of these concentration is to use above-mentioned device and method to carry out.
First distillation process
Nitration mixture 500g is dropped in the retort, under atmospheric pressure, thereby distill through nitration mixture being heated to 120 ℃.Thus, obtained hydrofluoric acid (hydrofluoric acid aqueous solution) with as distillate A.Carry out this operation and reach 60%, thereby obtained the distillate A of 297g up to the distillation amount.
The concentration of each composition among the distillate A has been carried out the result who measures, and the concentration of hydrofluoric acid is 10.5wt%, and the concentration of ammonium acid fluoride is 0.01wt%, and the concentration of silicon is 0.02wt%.Yield with respect to the hydrofluoric acid of nitration mixture is 49.6%.
The after-fractionating operation
Next, will drop in the retort, under atmospheric pressure, thereby distill through distillate A is heated to 120 ℃ through the distillate A that first distillation process obtains.Thus, obtained the lower hydrofluoric acid of concentration ratio with as distillate B.Carry out this operation and reach 80%, thereby obtained the distillate B of 223g up to the distillation amount.In addition, the concentration of each composition among the distillate B has been carried out the result who measures, the concentration of hydrofluoric acid is 4.8wt%, and the concentration of ammonium acid fluoride is 0wt%, and the concentration of silicon is 0.008wt%.
On the other hand, from retort, obtained the debris C of 53g.The concentration of each composition among the debris C has been carried out the result who measures, and the concentration of hydrofluoric acid is 32.1wt%, and the concentration of ammonium acid fluoride is 0.08wt%, and the concentration of silicon is 0.08wt%.In addition, the yield with respect to the hydrofluoric acid of nitration mixture is 27.0%.
In this way, as debris C, recovery high density and highly purified hydrofluoric acid have been realized.
Separation engineering
In first distillation process, from retort, obtained the debris D of 193g.In debris D, solid (solids component) is separated out, and from debris D, separates this solid through the precipitator method, and has carried out drying.Thus, obtained the solid E of 97g.Composition to solid E has carried out the result who measures, and in solid E, contains: the ammonium acid fluoride of 85.1wt%, the ammonium silicofluoride of 11.0wt%.
Next, the solid of the 80g that will in debris, separate out (dry before solid E) mixes with the zero(ppm) water of 50g, and it is dissolved fully and has obtained the solution F of 130g.Then, F is cooled to 35 ℃ with this solution, thereby solid G is separated out in solution F.Then, through the precipitator method, from solution F, isolated solid G, and solid G has been carried out drying.Thus, obtained the solid G of 13g.Composition to solid G has carried out the result who measures, and contains among the solid G: the ammonium acid fluoride of 77.7wt%, the ammonium silicofluoride of 21.3wt%.
Next, with the separation of 108g the solution F behind the solid G be cooled to 20 ℃, solid H is separated out in solution F.Then, through the precipitator method, from solution F, isolated solid H, and solid H has been carried out drying.Thus, obtained the solid H of 14g.Composition to solid H has carried out the result who measures, and contains among the solid H: the ammonium acid fluoride of 96.6wt%, the ammonium silicofluoride of 3.4wt%.Yield with respect to the ammonium acid fluoride of nitration mixture is 29.1%.
As stated, as solid H, realized reclaiming highly purified ammonium acid fluoride.
In addition, above result is shown in Fig. 3 and Fig. 4.
Embodiment 2
Prepared nitration mixture as etching waste liquor.In addition, the hydrofluoric acid concentration of this nitration mixture is 16.8wt%, and the concentration of ammonium acid fluoride is 31.2wt%, and the concentration of silicon is 0.11wt%, and residue nearly all is a water.
First distillation process
Next, nitration mixture 500g is dropped in the retort, under atmospheric pressure, thereby distill through nitration mixture being heated to 120 ℃.Thus, obtained hydrofluoric acid (hydrofluoric acid aqueous solution) with as distillate A '.Carry out this operation and reach 65%, thereby obtained the distillate A ' of 322g up to the distillation amount.
The concentration of each composition among the distillate A ' has been carried out the result who measures, and the concentration of hydrofluoric acid is 18.2wt%, and the concentration of ammonium acid fluoride is 0.01wt%, and the concentration of silicon is 0.01wt%.Yield with respect to the hydrofluoric acid of nitration mixture is 69.8%.
The after-fractionating operation
Next, the distillate A ' that will obtain through first distillation process drops in the retort, under atmospheric pressure, through with distillate A ' thus being heated to 120 ℃ distills.Thus, obtained the lower hydrofluoric acid of concentration ratio and as distillate B '.Carry out this operation and reach 69%, thereby obtained the distillate B ' of 222g up to the distillation amount.In addition, the concentration of each composition among the distillate B ' has been carried out the result who measures, the concentration of hydrofluoric acid is 12.4wt%, and the concentration of ammonium acid fluoride is 0wt%, and the concentration of silicon is 0.004wt%.
On the other hand, from retort, obtained the debris C ' of 80g.The concentration of each composition among the debris C ' has been carried out the result who measures, and the concentration of hydrofluoric acid is 34.5wt%, and the concentration of ammonium acid fluoride is 0.23wt%, and the concentration of silicon is 0.01wt%.In addition, the yield with respect to the hydrofluoric acid of nitration mixture is 32.8%.
As stated, as debris C ', recovery high density and highly purified hydrofluoric acid have been realized.
Separation engineering
In first distillation process, from retort, obtained the debris D ' of 171g.In debris D ', solid (solids component) is separated out, and from debris D ', isolates this solid, and has carried out drying.Thus, obtained the solid E ' of 76g.Composition to solid E ' has carried out the result who measures, and in solid E ', contains: the ammonium acid fluoride of 96.6wt%, the ammonium silicofluoride of 3.0wt%.
Carry out 1 identical operations, thereby reclaimed highly purified ammonium acid fluoride with embodiment.
In addition, above result is shown in Fig. 5.
Nomenclature
1 · · · · separating means 11 · · retorts 111 · · · · guide channel 12 · · · · supply unit 13 · · · heating unit 14 · · · mixing unit 141 · · stirring bar 142 · · heating mixer 15 · · cooling unit 151 · · inner tube 152 · · outer tube 16 · · · recovery unit 17 · · · gas treatment unit 181 · · cock 182 · · cock 191 ... · thermometer 192 100 · · · · · · · · thermometer mixed acid 200 · · distillate 300 · · recycling containers 400 · · cleaning fluid 500 · · residual liquid 600 · · residual liquid 700 · · · · Liquid 801 · · · · solution 802 · · · · solution 803 · · · · solution 810 · · · · Solid 820 · · · · Solid 900 · · · · Solid
Claims (9)
1. a separation method is characterized in that, from the nitration mixture that contains hydrofluoric acid, ammonium acid fluoride, silicon and water at least, isolates said hydrofluoric acid, and it comprises:
First distillation process through said nitration mixture is distilled, thereby reclaims first liquid that contains said hydrofluoric acid and water with as distillate, and reclaims second liquid that contains said ammonium acid fluoride and said silicon with as debris;
The after-fractionating operation through said first liquid is distilled, thereby is mainly isolated said water from said first liquid, so recovery and said first liquid phase than higher the 3rd liquid of the concentration of said hydrofluoric acid with as debris.
2. separation method as claimed in claim 1, wherein,
The Heating temperature of said first liquid in the said after-fractionating operation is made as, is lower than the design temperature of the Heating temperature of the said nitration mixture in said first distillation process.
3. like claim 1 or the described separation method of claim 2, wherein,
Crystallization contains the solid of said ammonium acid fluoride and said silicon from said second liquid,
And will from said second liquid, separate said solid and the 4th liquid, handle through said first operation once more with said nitration mixture.
4. like claim 1 or the described separation method of claim 2, wherein,
Said first distillation process carries out when said nitration mixture is stirred.
5. separation method as claimed in claim 1, wherein,
Comprise separation circuit, from contain said ammonium acid fluoride and said silicon and crystallization goes out from said second liquid solid, separate said ammonium acid fluoride.
6. separation method as claimed in claim 5, wherein,
In said separation engineering, from said solid, separate said ammonium acid fluoride through crystallization process.
7. separation method as claimed in claim 5, wherein,
In said separation circuit, comprising: first Crystallization Procedure, said first Crystallization Procedure be through preparing to make said solid dissolved solution, and make said solution be cooled to preset temperature to carry out; Second Crystallization Procedure, said second Crystallization Procedure is carried out under the temperature of the temperature that is lower than said first Crystallization Procedure.
8. like claim 1 or the described separation method of claim 2, wherein,
Said nitration mixture does, through the material that contains silicon is carried out the etching waste liquor that etch processes produces.
9. a tripping device is characterized in that,
Used any described separation method in the claim 1,2,5.
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| JP2011046718A JP2012183457A (en) | 2011-03-03 | 2011-03-03 | Separation method and separation device |
| JP2011-046718 | 2011-03-03 |
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| CN102674254A true CN102674254A (en) | 2012-09-19 |
| CN102674254B CN102674254B (en) | 2014-12-03 |
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| JP (1) | JP2012183457A (en) |
| CN (1) | CN102674254B (en) |
| TW (1) | TWI465280B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566606A (en) * | 2013-11-04 | 2014-02-12 | 中国地质大学（武汉） | Multifunctional purification device and method for purifying ammonium bifluoride by using same |
| CN103818992A (en) * | 2012-11-15 | 2014-05-28 | Og株式会社 | Method for removing Si from waste liquid of Si-containing hydrofluoric acid, method for recovering hydrofluoric acid from mixed acid waste liquid of Si-containing hydrofluoric acid, and recovery device |
| CN110104864A (en) * | 2019-06-06 | 2019-08-09 | 盛隆资源再生（无锡）有限公司 | A kind of processing method of the fluorine-containing ammonia-containing water of acid phosphorus acid type |
| CN110272159A (en) * | 2019-06-17 | 2019-09-24 | 苏州乔发环保科技股份有限公司 | The recycling processing method and device of inorganic salts in a kind of industrial wastewater |
| CN113045089A (en) * | 2021-03-15 | 2021-06-29 | 盛隆资源再生（无锡）有限公司 | Method for refining and purifying etching waste liquid |
| CN113880048A (en) * | 2021-09-30 | 2022-01-04 | 中化蓝天霍尼韦尔新材料有限公司 | Efficient hydrofluoric acid recovery system and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5941028B2 (en) * | 2012-11-15 | 2016-06-29 | オー・ジー株式会社 | Method for removing Si from Si-containing hydrofluoric acid waste liquid and method for recovering hydrofluoric acid from Si-containing hydrofluoric acid mixed acid waste liquid |
| JP2014151269A (en) * | 2013-02-08 | 2014-08-25 | Seiko Epson Corp | Method for regenerating an etchant and etchant regenerating apparatus |
| CN113358436B (en) * | 2021-06-11 | 2022-12-30 | 中国科学技术大学 | Device and method for purifying ammonium bifluoride |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI465280B (en) | 2014-12-21 |
| CN102674254B (en) | 2014-12-03 |
| JP2012183457A (en) | 2012-09-27 |
| TW201236738A (en) | 2012-09-16 |
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