CN102674397A - Separation method and separation device - Google Patents
Separation method and separation device Download PDFInfo
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- CN102674397A CN102674397A CN2012100659575A CN201210065957A CN102674397A CN 102674397 A CN102674397 A CN 102674397A CN 2012100659575 A CN2012100659575 A CN 2012100659575A CN 201210065957 A CN201210065957 A CN 201210065957A CN 102674397 A CN102674397 A CN 102674397A
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Abstract
The present invention provides a separation method and a separation device. The separation method can simply separate highly purified ammonium bifluoride from solid mixture at least containing ammonium bifluoride and silicon compounds. The method used for separating the ammonium bifluoride from the solid mixture (100) containing the ammonium bifluoride and the silicon compounds comprises the steps of: a preparation process for obtaining a first solution (201) by dissolving the mixture (100) in a solvent (300); a first crystallizing process for precipitating solid (400) which contains more silicon compounds than the mixture (100) by cooling the first solution (201); and a second crystallizing process for precipitating solid (500) which contains more ammonium bifluoride than the mixture (100) by cooling a second solution (202) obtained by removing the solid (400) to a temperature lower than the temperature in the first crystallizing process.
Description
Technical area
The present invention relates to separation method and tripping device.
Background technology
All the time, as employed etching solution in the processing of glass material, crystal etc., the known goods that contain hydrofluoric acid and Neutral ammonium fluoride.In addition, from also be widely known by the people as technology this etching solution, that supply recovery fluorine the etching usefulness etching waste liquor afterwards (for example, with reference to patent documentation 1).
In patent documentation 1, put down in writing following method; Promptly; Through lime carbonate and the etching solution that comprises hydrofluoric acid and Neutral ammonium fluoride are reacted, 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) that is reclaimed again with the less high purity of silicon-dioxide containing ratio.
But, in this method, can't be from etching solution direct separation, reclaim Neutral ammonium fluoride.That is, after reclaiming with the form of Calcium Fluoride (Fluorspan), need this Calcium Fluoride (Fluorspan) is processed the operation of Neutral ammonium fluoride, thereby can't reclaim efficiently.In addition, it is more to play the operation of making till the etching solution (Neutral ammonium fluoride) 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
Summary of the invention
The objective of the invention is to, a kind of tripping device that can from the mixture of the solid-like that contains ammonium acid fluoride and silicon compound at least, isolate the separation method of highly purified ammonium acid fluoride simply and be used to implement related separation method is provided.
The present invention is the invention of accomplishing at least a portion that solves above-mentioned problem, and it can be realized as following mode or application examples.
Application examples 1
Separation method of the present invention does, from the mixture of the solid-like that contains ammonium acid fluoride and silicon compound, isolates the separation method of said ammonium acid fluoride, it is characterized in that, comprising:
Preparatory process obtains said mixture is dissolved in the solvent and first solution that forms;
First Crystallization Procedure is carried out crystallization through cooling off said first solution, thereby is separated out first solid of comparing the solid-like that contains more how said silicon compound with said mixture, is said first solid and second solution with said first solution separating thus;
Second Crystallization Procedure; Through said second solution being cooled to carry out crystallization with the lower temperature of said first Crystallization Procedure; Thereby separate out the second higher solid of containing ratio of comparing said ammonium acid fluoride with said mixture, from said second solution, isolate said second solid thus.
Thus, can separate, reclaim highly purified ammonium acid fluoride simply.
Application examples 2
In separation method of the present invention, be preferably, in said first Crystallization Procedure, said first solution is cooled to 30～60 ℃.
Thus, can separate, reclaim more highly purified ammonium acid fluoride with as second solid.
Application examples 3
In separation method of the present invention, be preferably, in said second Crystallization Procedure, said second solution is cooled to 5～20 ℃.
Thus, can separate, reclaim more highly purified ammonium acid fluoride.
Application examples 4
In separation method of the present invention, be preferably, in said preparatory process,, said solvent and said mixture make its dissolving when being heated.
Thus, can in first Crystallization Procedure and second Crystallization Procedure, carry out crystallization efficiently.
Application examples 5
In separation method of the present invention, be preferably, the containing ratio of the said ammonium acid fluoride in dry said second solid is more than the 95wt%.
Thus, can make the concentration (purity) of the ammonium acid fluoride that is separated as second solid comparatively abundant for utilizing again.
Application examples 6
Tripping device of the present invention is characterised in that, has used separation method of the present invention.
Thus, the device that can separate simply, reclaim highly purified ammonium acid fluoride can be provided.
Description of drawings
Fig. 1 is related synoptic diagram separation method, tripping device of preferred implementation that is used for embodiment 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.
Embodiment
Below, based on preferred implementation shown in the drawings, separation method of the present invention and tripping device are elaborated.
Fig. 1 is to be used for related synoptic diagram separation method, tripping device of preferred implementation of embodiment of the present invention; Fig. 2 is to be used for the synoptic diagram that the related separation method of preferred implementation of the present invention is described; Fig. 3 is to be used for the table that embodiment is described.
1. crystallization apparatus (tripping device of the present invention)
As shown in Figure 1, crystallization apparatus 1 have the container 11 of taking in solution 200 and to the solution 200 in the container 11 heat, refrigerative register 12.In addition, as the structure of register 12, as long as can then not be specially limited with the temperature regulation of solution 200 to preset temperature.
In addition, in this crystallization apparatus 1, preferably possess the agitating unit 13 that solution 200 is stirred, this agitating unit 13 has the stirring rod 131 that is positioned at solution 200 and makes the whisking appliance 132 of stirring rod 131 rotations.In addition, even do not possess whisking appliance, the method for physics that also can be through the wall of a container face being applied vibration etc. flows the contents in the container 11, thereby stirs.
Crystallization apparatus 1 does, is used for through in container 11, supplying with solution 200, and utilizes register 12 and cooling solution 200 so that the temperature of solution 200 drops to preset temperature, thereby is separated out the solid device from solution 200.Through this device, thus first Crystallization Procedure and second Crystallization Procedure to stating after solution 200 enforcements.
In addition, solution 200 does, mixture 100 is dissolved in solvent 300 and first solution 201 that forms or second solution 202 that is obtained in first Crystallization Procedure, and wherein, said mixture 100 does, with ammonium acid fluoride [(NH
4) HF
2] be the solid 101 of staple and as the ammonium silicofluoride [(NH of silicon compound
4)
2SiF
6] be the mixture of the solid 102 of staple.
2. the separation method of ammonium acid fluoride
Below, based on Fig. 2, the method (separation method of the present invention) of separating, reclaim the ammonium acid fluoride of high density from mixture 100 is described.
The method of separating ammonium acid fluoride from mixture 100 comprises preparatory process, first Crystallization Procedure and second Crystallization Procedure.Below, these operations are described successively.
(preparatory process)
This operation is to obtain mixture 100 is dissolved in the solvent 300 and the operation of first solution 201 that forms.
At first, prepare mixture 100, said mixture 100 is to be the solid 101 of staple with the ammonium acid fluoride and to be the mixture of the solid 102 of staple with the ammonium silicofluoride.As the containing ratio (concentration of ammonium acid fluoride) of the solid in the mixture 100 101,, for example be about 80～90wt% though it is not specially limited.
Next, this mixture 100 of dissolving in solvent 300, thus obtain first solution 201.As solvent 300, as long as can dissolving mixt 100, then be specially limited, for example can use the water of zero(ppm) water etc.
In addition, in this operation, be preferably, when solvent 300 and mixture 100 are heated, implement the dissolving of mixture 100 in solvent 300.Thus, owing to can improve the solubleness of mixture 100, therefore can carry out the dissolving of mixture 100 efficiently with respect to solvent 300.In addition, when said and when solution 200 cooled off, can precipitate separated out like back literary composition.
As the Heating temperature of the solvent in this operation 300, it is not specially limited, and for example, when using zero(ppm) water as solvent 300, is preferably about 50～70 ℃.
(first Crystallization Procedure)
This operation is following operation; Promptly; Carry out crystallization through first solution 201 is cooled off, contain the more solid of polyfluoro ammonium silicate (first solid) 400, thus first solution 201 is separated into the solid 400 and second solution 202 thereby separate out to compare with mixture 100.
For example, with first solution 201 container 11 of packing into, and when first solution 201 is stirred, first solution 201 is cooled to preset temperature through register 12.Thus, will separate out to compare from first solution 201 and contain the more solid of polyfluoro ammonium silicate (first solid) 400 with mixture 100.Then, use the precipitator method, from first solution 201, isolate solid 400.In addition, below, will from first solution 201 removed solid 400 and solution as second solution 202.
As the cooling temperature of first solution 201, it is not specially limited, but is preferably about 30～60 ℃, more preferably about 35～40 ℃.Therefore, finally can separate, reclaim more highly purified ammonium acid fluoride.
And, though the containing ratio of the ammonium acid fluoride in the dry solid 400 is not specially limited, be 70～80wt%.
(second Crystallization Procedure)
This operation is following operation; Promptly; Through being cooled to compare lower temperature with first Crystallization Procedure, second solution 202 carries out crystallization; Thereby separate out the higher solid (second solid) 500 of containing ratio of comparing ammonium acid fluoride with mixture 100, from second solution 202, isolate solid 500 thus.
With second solution 202 container 11 of packing into, and through register 12 with solution 200 ' be cooled to preset temperature.At this moment, can, implement solution cooling when being stirred.Thus, will from second solution 202, separate out the solid 500 that contains more ammonium acid fluoride.Then, use the precipitator method, from second solution 202, separate, reclaim solid 500.
In drying solid 500 in comprise, compare the higher ammonium acid fluoride of containing ratio with mixture 100.That is, can separate, reclaim highly purified ammonium acid fluoride with as solid 500.As the containing ratio of the ammonium acid fluoride in the solid 500, though it is not specially limited, be preferably more than the 95wt%, more preferably more than the 96wt%.
In addition, as the cooling temperature of second solution 202,, be preferably about 5～20 ℃, more preferably about 5～10 ℃ though it is not specially limited.Thus, can separate, reclaim more highly purified ammonium acid fluoride with as solid 500.
More than, the separation method of the ammonium acid fluoride in the mixture 100 is illustrated.
According to this method, can simply and efficiently separate, reclaim highly purified ammonium acid fluoride.The ammonium acid fluoride that is reclaimed for example can use as the raw material of etching solution.Thus, can realize the cost degradation of etch processes.
3. mixture 100
Mixture 100 is the material that for example obtains through following mode.
For example, as can be when glass material, crystal etc. be carried out etch processes employed etching solution, known hydrofluoric acid (HF), the ammonium acid fluoride [(NH of containing
4) HF
2] and water [H
20] goods.In addition, also contain silicon in the etching solution after use (etching waste liquor), this silicon in etching waste liquor with silicon compound, particularly with ammonium silicofluoride [(NH
4)
2SiF
6] form and exist.
In this etching waste liquor, the residual unreacted ammonium acid fluoride in etch processes that quite a lot of quantity is arranged.Therefore, through separation, recovery ammonium acid fluoride, thereby can the ammonium acid fluoride that reclaim be used as etching solution (perhaps, the material of etching solution) once more.Separation method of the present invention can suitably be used for reclaiming from etching waste liquor the purposes of ammonium acid fluoride.
Through generating new etching solution from etching waste liquor, thereby the utilization again of etching waste liquor can be realized, and then the cost degradation of etch processes can be realized.In addition, because the amount of the etching waste liquor of the processing that goes out of use reduces, therefore can also bring into play excellent environment property.
Though the concentration of the hydrofluoric acid in the etching waste liquor is not specially limited, for example be about 10～20wt%.In addition, though the concentration of the ammonium acid fluoride in the etching waste liquor is not specially limited, for example be about 25～35wt%.In addition, though the silicon in the etching waste liquor (ammonium silicofluoride) compound concentrations is not specially limited, for example be about 0.1～1.Owt%.
At this, the concentration of the hydrofluoric acid of etching waste liquor, ammonium acid fluoride, silicon can be obtained through following mode.
(concentration determination of silicon)
Use the qualitative and quantitative analysis of the metallic element that IPC emmission spectrometric analysis device (for example, (strain) Shimadzu Seisakusho Ltd. system, name of product " ICPS-7510 ") carries out being contained in the etching waste liquor.Thus, can obtain the concentration A (mol/l) of the silicon (ammonium silicofluoride) in the etching waste liquor.
(concentration determination of ammonium acid fluoride)
Use ultraviolet ray-visual spectrophotometer (for example, (strain) Shimadzu Seisakusho Ltd. system, name of product " IUV-1240 "), implement the indophenol blue absorption spectrophotometry, thus, can obtain (the NH that ammonium acid fluoride and ammonium silicofluoride had in the etching waste liquor
4 +) total concentration B (mol/l).As indicated above, because the silicon in the etching waste liquor exists with the form of ammonium silicofluoride,, thereby can obtain the concentration C (mol/l) of the ammonium acid fluoride in the etching waste liquor therefore through from amount to concentration B, deducting concentration A.That is C=B-2A.
(concentration determination of hydrofluoric acid)
Use potential difference automatic titrator (for example, capital of a country electronic industry (strain) system, name of product " AT-510 ") to measure the acid concentration of etching waste liquor.Particularly, through utilizing 0.1mol/dm
3Aqueous sodium hydroxide solution carry out neutralization titration, thereby measure the acid concentration of etching waste liquor.Thus, can obtain the concentration of the hydrofluoric acid in the etching waste liquor.In mentioned above; Because ammonium silicofluoride concentration A and ammonium acid fluoride concentration B in the known etching waste liquor; Therefore through from amount to acid concentration D, deducting the acid concentration B that acid concentration 4A and ammonium acid fluoride had that ammonium silicofluoride has, thereby can obtain the hydrofluoric acid concentration E (mol/l) in the etching waste liquor.That is E=D-4A-B.
More than, an example of the measuring method of the concentration of the hydrofluoric acid in the etching waste liquor, ammonium acid fluoride, silicon is illustrated.
When this etching waste liquor is distilled, when recovery contains the distillate of hydrofluoric acid and water, reclaim the debris that contains ammonium acid fluoride and ammonium silicofluoride.And, for example, carry out crystallization through the cooling debris, thereby separate out the mixture that contains ammonium acid fluoride and ammonium silicofluoride.At last, through from debris, removing said mixture, and the mixture of being removed is carried out drying, thereby can obtain to contain the mixture 100 of the solid-like of ammonium acid fluoride and ammonium silicofluoride.
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 can also add other works arbitrarily or operation.
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 of this nitration mixture is 12.6wt%, and the concentration of ammonium acid fluoride is 27.6wt%, and the concentration of silicon (ammonium silicofluoride) is 0.4wt%, and residue nearly all is a water.Use above-mentioned device and method and carried out the mensuration (concentration about the following stated is also identical) of these concentration.
[distillation process]
Then, drop into nitration mixture 500g in the retort, and under atmospheric pressure, distill thereby nitration mixture is heated to 120 ℃.Carry out this operation and reach 60%, thereby obtained the debris A of 193g up to the distillation amount.
Then, debris A is cooled to 20 ℃, so that separate out solid in the debris A.Through from debris A, isolating said solid and carry out drying, thereby obtained the solid B of 97g.Composition to solid B has carried out the result who measures, and in solid B, contains the ammonium acid fluoride of 85.1wt%, contains the ammonium silicofluoride of 11.Owt%.
[preparatory process]
Next, the solid B of 80g is blended in the zero(ppm) water of 50g, and dissolving fully under 50 ℃, thereby has obtained first solution C (below, abbreviate " solution C " as) of 130g.
[first Crystallization Procedure]
Then, solution C is cooled to 35 ℃, thereby separates out the first solid D (below, abbreviate " solid D " as) in solution C.Next, from solution C, isolate solid D, and solid D has been carried out drying through the precipitator method.Thus, obtained the solid D of 13g.Composition to solid D has carried out the result who measures, and in solid D, contains the ammonium acid fluoride of 77.7wt%, contains the ammonium silicofluoride of 21.3wt%.
[second Crystallization Procedure]
Next, the second solution 108g behind the solid D that will isolate (removal) from solution C is cooled to 1O ℃, separates out the second solid E (below, abbreviate " solid E " as) in second solution thereby make.Next, from second solution, isolate solid E, and solid E has been carried out drying through the precipitator method.Thus, or obtained the solid E of 14g.To the result that the composition of solid E has carried out, in solid E, contain the ammonium acid fluoride of 96.6wt%, contain the ammonium silicofluoride of 3.4wt%.From the recovery of the ammonium acid fluoride of solution A is 29.1%.
Thus, can reclaim highly purified ammonium acid fluoride with as solid E.
In addition, above result is shown in Fig. 3.
Nomenclature
1: crystallization apparatus 11: container 12: register
13: agitating unit 131: stirring rod 132: whisking appliance
100: mixture 101: solid 102: solid
200: 202: the second solution of 201: the first solution of solution
300: 500: the second solids of 400: the first solids of solvent
Claims (6)
1. a separation method is characterized in that, from the mixture of the solid-like that contains ammonium acid fluoride and silicon compound, isolates said ammonium acid fluoride, and said separation method comprises:
Preparatory process obtains said mixture is dissolved in the solvent and first solution that forms;
First Crystallization Procedure; Through being cooled off, said first solution carries out crystallization; Thereby separating out first solid of comparing the solid-like that contains more how said silicon compound with said mixture, is said first solid and second solution with said first solution separating thus;
Second Crystallization Procedure; Through being cooled to compare lower temperature with said first Crystallization Procedure, said second solution carries out crystallization; Thereby separate out the second higher solid of containing ratio of comparing said ammonium acid fluoride with said mixture, from said second solution, isolate said second solid thus.
2. separation method as claimed in claim 1, wherein,
In said first Crystallization Procedure, said first solution is cooled to 30～60 ℃.
3. according to claim 1 or claim 2 separation method, wherein,
In said second Crystallization Procedure, said second solution is cooled to 5～20 ℃.
4. according to claim 1 or claim 2 separation method, wherein,
In said preparatory process,, said solvent and said mixture make its dissolving when being heated.
5. according to claim 1 or claim 2 separation method, wherein,
The containing ratio of the said ammonium acid fluoride in dry said second solid is more than the 95wt%.
6. a tripping device is characterized in that,
Claim 1 or 2 described separation methods have been used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011058559A JP2012193074A (en) | 2011-03-16 | 2011-03-16 | Separation method and separation apparatus |
| JP2011-058559 | 2011-03-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102674397A true CN102674397A (en) | 2012-09-19 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100659575A Pending CN102674397A (en) | 2011-03-16 | 2012-03-13 | Separation method and separation device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2012193074A (en) |
| CN (1) | CN102674397A (en) |
| TW (1) | TW201238899A (en) |
Cited By (1)
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045089B (en) * | 2021-03-15 | 2023-04-18 | 盛隆资源再生（无锡）有限公司 | Method for refining and purifying etching waste liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03265514A (en) * | 1990-01-26 | 1991-11-26 | Kawasaki Steel Corp | Method for treatment of etching waste liquid containing fluorine compd. |
| CN101066767A (en) * | 2007-05-25 | 2007-11-07 | 浙江三美化工股份有限公司 | Improved wet process and apparatus for producing ammonium bifluoride |
| CN101898769A (en) * | 2010-02-11 | 2010-12-01 | 多氟多化工股份有限公司 | Method for producing high-purity ammonium bifluoride |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1021831B (en) * | 1956-10-25 | 1958-01-02 | Wasagchemie Ag | Process for the production of pure crystallized ammonium bifluoride from fluosilicic acid and ammonia |
| US3106449A (en) * | 1961-07-17 | 1963-10-08 | Grace W R & Co | Production of ammonium hydrogen fluoride |
| US3705007A (en) * | 1970-08-25 | 1972-12-05 | Allied Chem | Process for the preparation of ammonium bifluoride from ammonium fluoride |
| JPS539585B2 (en) * | 1974-03-23 | 1978-04-06 | ||
| JPS5337599A (en) * | 1976-09-20 | 1978-04-06 | Hitachi Zosen Corp | Recovering method for fluorine in wet-process phosphoric acid production |
| US4981664A (en) * | 1988-04-14 | 1991-01-01 | International Minerals & Chemical Corporation | Method of production of high purity silica and ammonium fluoride |
| JP2852355B2 (en) * | 1989-06-26 | 1999-02-03 | ステラケミファ株式会社 | Fine processing surface treatment agent |
| JPH03218914A (en) * | 1989-11-16 | 1991-09-26 | Nissan Chem Ind Ltd | Production of high purity silica and ammonium fluorosilicate |
| US5028407A (en) * | 1990-01-25 | 1991-07-02 | International Minerals & Chemical Corp. | Method of production of high purity fusible silica |
-
2011
- 2011-03-16 JP JP2011058559A patent/JP2012193074A/en not_active Withdrawn
-
2012
- 2012-03-13 TW TW101108531A patent/TW201238899A/en unknown
- 2012-03-13 CN CN2012100659575A patent/CN102674397A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03265514A (en) * | 1990-01-26 | 1991-11-26 | Kawasaki Steel Corp | Method for treatment of etching waste liquid containing fluorine compd. |
| CN101066767A (en) * | 2007-05-25 | 2007-11-07 | 浙江三美化工股份有限公司 | Improved wet process and apparatus for producing ammonium bifluoride |
| CN101898769A (en) * | 2010-02-11 | 2010-12-01 | 多氟多化工股份有限公司 | Method for producing high-purity ammonium bifluoride |
Cited By (1)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201238899A (en) | 2012-10-01 |
| JP2012193074A (en) | 2012-10-11 |
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Application publication date: 20120919 |