CN107614434B - The regeneration treating method of formed body containing alkali metal salt and the acidic aqueous solution using the formed body - Google Patents
The regeneration treating method of formed body containing alkali metal salt and the acidic aqueous solution using the formed body Download PDFInfo
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- CN107614434B CN107614434B CN201780001367.7A CN201780001367A CN107614434B CN 107614434 B CN107614434 B CN 107614434B CN 201780001367 A CN201780001367 A CN 201780001367A CN 107614434 B CN107614434 B CN 107614434B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/22—Preparation in the form of granules, pieces, or other shaped products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/38—Preparation in the form of granules, pieces or other shaped products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D9/00—Nitrates of sodium, potassium or alkali metals in general
- C01D9/18—Preparation in the form of shaped products, e.g. granules
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/60—Silicon compounds
Abstract
The present invention, which provides one kind, efficiently to carry out the material and method from the acidic aqueous solution separation fluosilicic acid containing hydrofluoric acid and fluosilicic acid, the operation for carrying out regeneration treatment to acidic aqueous solution in the case where not making to deteriorate operating environment.Formed body containing alkali metal salt of the invention contains alkali metal salt A and at least one of alkali metal salt B and alkali metal salt C with regulated proportion, above-mentioned alkali metal salt A is selected from least one of sodium fluoride, two sodium bifluorides, potassium fluoride and potassium hydride difluoride, above-mentioned alkali metal salt B be selected from the solubility in 20 DEG C of water in the sodium salt of 10g/100ml or more and solubility in 20 DEG C of water at least one of the sylvite of 10g/100ml or more, above-mentioned alkali metal salt C is selected from least one of sodium carbonate, sodium bicarbonate, potassium carbonate and saleratus.
Description
Technical field
The present invention relates to the regeneration treatment sides of the formed body containing alkali metal salt and the acidic aqueous solution using the formed body
Method.In particular to the formed body containing alkali metal salt formed by the alkali metal salt composition of specific composition, for from containing
There is the formed body containing alkali metal salt that the fluosilicic acid as impurity is removed in the acidic aqueous solution of hydrofluoric acid and fluosilicic acid, and
Use the regeneration treating method of the acidic aqueous solution of the formed body.
Background technique
Hydrofluoric acid (HF, hydrofluoric acid) has the silicic acid (SiO that can be dissolved as various glass principal components2) property.Institute
With using this property, hydrofluoric acid is used for the glass surface etching and processing in ornamental glass manufacture；Industrial glass panel
Etching and processing, grinding, cleaning；Or the surface treatment of the materials such as organic silicon substrate.Especially requiring clean surface special
In the manufacture of the glassware of property, the treatment process using hydrofluoric acid is needed.
On the surface using the acidic aqueous solution containing hydrofluoric acid to various materials such as glass substrate, organic silicon substrates
It is handled and is carried out in the processes of surface treatments such as purifying, etching, because of silicic acid (SiO2) ingredient reacts with hydrofluoric acid, it will
Generate fluosilicic acid (H2SiF6).So the hydrofluoric acid in acidic aqueous solution is dense if reusing or reusing the acidic aqueous solution
Degree reduces, and fluosilicic acid (H2SiF6) accumulation, leading to etch capabilities, cleaning ability, (these abilities are collectively referred to as " processing energy
Power ") it gradually decreases.
In the past, the lowered acidic aqueous solution of processing capacity can regularly replace, the impure acidic aqueous solution after use
It is taken as trade waste to be handled, but from the viewpoint of carrying capacity of environment, is preferably not intended as trade waste discarding,
But it is used for regeneration treatment as far as possible, reuse acidic aqueous solution.As this kind of countermeasure, it is known to by impure acid water
Solution carries out regeneration method using electrolysis, but regeneration efficiency is relatively low, it is practical on there are problems.
As from the acidic aqueous solution removing fluosilicic acid containing hydrofluoric acid and fluosilicic acid thus by the acid water of hydrofluoric acid containing
The another method of solution recycling, it is known to following various alkali metal compound M are added in the spent acid aqueous solution+X?, then
Fluosilicate (the M that will be formed according to the reaction of following formula (1A)2SiF6) sediment separation, fluorine silicon is removed from spent acid aqueous solution
The method of acid.
H2SiF6+2M+X-→M2SiF6↓ (precipitating)+2HX (lA)
M+: alkali metal cation (Na+、K+Deng)
X-: anion (F-、Cl-、HF2 -、NO3 -、HCO3 -Deng)
In above formula, as fluosilicic acid except alkali metal compound M used in dereaction+X-, up to now report energy
Enough use various alkali metal compounds.
For example, Patent Document 1 discloses the various potassium ion donors such as potassium chloride, potassium hydroxide, potassium carbonate be made it is water-soluble
Liquid is come the method added.It is disclosed in patent document 2 in the method for aqueous solution addition sodium nitrate and is added with powder morphology
The method of sodium bicarbonate.
It is disclosed in patent document 3, patent document 4 and sodium carbonate or carbonic acid is added with powder shaped, pulp-like or aqueous solution
Hydrogen sodium, and the method for forming fluosilicate.The various alkali metal hydrogens of addition sodium hydroxide etc are disclosed in patent document 5~7
The method of oxide.Disclosed in patent document 8 and patent document 9 with powder morphology addition potassium fluoride, sodium fluoride, potassium chloride,
The method of the various alkali metal salts of sodium chloride etc.
The method that various alkali metal fluorides are added with solution morphology is disclosed in patent document 10.It is public in patent document 11
The method that powder or aqueous solution is made in various two bifluorides of two sodium bifluorides, potassium hydride difluoride etc to add is opened.
As described above, being able to use in dereaction although reporting removing for fluosilicic acid shown in above-mentioned formula (lA) so far
Various alkali metal compounds, but each have their own problem.
For example, working as alkali metal compound M+X-X-By be free of in acidic aqueous solution anion when, in above-mentioned (lA) formula
Reaction in, will form impurity sour component (HX) in acidic aqueous solution.So should not using such alkali metal compound as
The main component of alkali metal compound used in spent acid aqueous solution regeneration treatment.
In addition, working as alkali metal compound M+X-In the case where for alkali compounds, i.e. X-For hydroxyl, carbonate or carbonic acid
In the case where hydrogen radical, if the alkali metal compound is added to spent acid aqueous solution, which will horse back and hydrogen fluorine
Acid is reacted, and hydrofluoric acid is caused to be consumed.So should not be using the alkaline metal cpds as spent acid aqueous solution regeneration treatment
Used in alkali metal compound main component.Moreover, being alkali metal compound master in alkali carbonate, bicarbonate
In the case where wanting ingredient, after adding it to spent acid aqueous solution, it can also be reacted because sharply generating carbon dioxide bubble
Uncontrollable problem.
Compared with above-mentioned alkali metal compound, alkali metal fluoride MF used in patent document 8~11 (NaF, KF etc.)
Or two bifluoride MHF of alkali metal2(NaHF2、KHF2Deng) due to following reasons preferably as institute in spent acid aqueous solution regeneration treatment
With alkali metal compound M+X-Main component.
That is, in alkali metal compound M+X-For two bifluoride MHF of alkali metal fluoride MF or alkali metal2In the case where, it will
As shown in following formula (IA-l), (IA-2), formed fluosilicate precipitating simultaneously, also will form hydrofluoric acid HF.
H2SiF6+2MF→M2SiF6↓ (precipitating)+2HF (1A-l)
H2SiF6+2MHF2→M2SiF6↓ (precipitating)+4HF (IA-2)
Since the hydrofluoric acid HF formed using the reaction will be replenished in the surface treatment procedure of material because of dioxy
SiClx ingredient SiO2The following fluosilicic acid reacted with hydrofluoric acid HF form the hydrofluoric acid HF for reacting (2A) and being consumed, so it is excellent
Choosing.
SiO2+6HF→H2SiF6+2H2O (2A)
Patent document 12 is disclosed by the method for sodium fluoride powder and potassium fluoride aqueous solution manufacture sodium fluoride pellet.But,
Although in patent document 12, the purposes about the sodium fluoride pellet discloses the use of the adsorbent as hydrogen fluoride, hex
On the way, but to the purposes of the regeneration treatment agent as spent acid aqueous solution then without any record.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2013-046888 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2011-162388 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2012-143734 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2011-201770 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2011-152541 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2011-131128 bulletin
Patent document 7: Japanese Unexamined Patent Publication 2012-055841 bulletin
Patent document 8: Japanese Unexamined Patent Publication 2014-113583 bulletin
Patent document 9: Japanese Unexamined Patent Publication 2004-283736 bulletin
Patent document 10: Japanese Unexamined Patent Publication 2000-072482 bulletin
Patent document 11: Japanese Unexamined Patent Publication 2014-218416 bulletin
Patent document 12: Japanese Unexamined Patent Application 63-270310 bulletin
Summary of the invention
Invent technical task to be solved
In patent document 8~11, disclose by the way that the acidic aqueous solution containing hydrofluoric acid and fluosilicic acid, (spent acid is water-soluble
Liquid) in powdered or aqueous solution the alkali metal fluoride of addition and/or two bifluoride (NaF, KF, NaHF2、KHF2Deng), it is raw
It is separated at the sediment of fluosilicate, then by the sediment, the method that regeneration treatment thus is carried out to acidic aqueous solution.
However, the alkali metal fluoride and two bifluoride (NaF, KF, NaHF2、KHF2) powder all have it is easy to form
The property that dust disperses.So when the alkali metal fluoride, two bifluoride (NaF, KF, NaHF2、KHF2) powder with industry rule
When mould is largely used to the regeneration of spent acid aqueous solution, dust from flying is easily caused in operation, it is difficult to protect operating environment.
On the other hand, add to spent acid aqueous solution when aqueous solution is made in the alkali metal fluoride, two bifluoride of alkali metal
Added-time, though the problem of dust in the addition process of no longer oriented waste acid water solution disperses, if because in spent acid aqueous solution
The aqueous solution of the alkali metal fluoride aqueous solution, two bifluoride of alkali metal is added, then the spent acid aqueous solution can be by as solvent
The water dilution used, thus the acidic aqueous solution is difficult to reuse.
Therefore, the strategy of dilutionization when as reply using aqueous solution fluoride can be enumerated and remove alkali metal
After the sediment of fluosilicate, adjustment is concentrated and formed to acidic aqueous solution, then the method reused, or abandoned
Dilute the method for waste liquid.However, cost of energy can be also redundantly expended in the former concentration method other than process is miscellaneous, therefore
And it is impracticable.And the method for the latter be then due to that can be discharged a large amount of trade wastes, so from economic benefit and the sight of environmental protection
Point considers, also not preferred.
The present invention is in view of background as described above, and it is an object of the present invention to provide a kind of do not make operating environment deteriorate and not increase
In the case where carrying capacity of environment, it can efficiently implement to isolate fluosilicic acid from the acidic aqueous solution containing hydrofluoric acid and fluosilicic acid
Salt, to acidic aqueous solution carry out regeneration treatment operation new technology.
Solve the technological means of project
The present inventor has been repeated and has deeply been studied intensively to reach such purpose, as a result, it has been found that: when will be by containing
Have and is contained by what the alkali metal salt composition of specific alkali metal fluoride, two bifluorides specific composition as main component was formed
When the formed body of alkali metal salt is used as alkali metal salt, dust will not be caused and dispersed problem (will not operating environment be made to deteriorate), energy
It is enough quickly and efficiently to form fluosilicate precipitating, so as to complete the present invention.
That is, the present invention relates to the regeneration treating methods of following formed bodys containing alkali metal salt, acidic aqueous solution to be used
Alkali metal salt formed body and using the formed body acidic aqueous solution regeneration treating method.
1. a kind of formed body containing alkali metal salt, which is characterized in that
Containing alkali metal salt A and at least one of alkali metal salt B and alkali metal salt C,
(1) above-mentioned alkali metal salt A is at least one in sodium fluoride, two sodium bifluorides, potassium fluoride and potassium hydride difluoride
Kind,
(2) above-mentioned alkali metal salt B is the solubility in 20 DEG C of water in the sodium salt of 10g/100m1 or more and 20 DEG C of water
Solubility 10g/100ml or more at least one of sylvite,
(3) above-mentioned alkali metal salt C be selected from least one of sodium carbonate, sodium bicarbonate, potassium carbonate and saleratus,
(4) every 100 matter of the content of above-mentioned alkali metal salt A in the solid state component of the above-mentioned formed body containing alkali metal salt
Measure is 10 mass % or more and 99 mass % or less in %；The content of above-mentioned alkali metal salt B it is above-mentioned containing alkali metal salt at
It is 0 mass % or more and 85 mass % or less in every 100 mass % of the solid state component of type body；The content of above-mentioned alkali metal salt C
In every 100 mass % of the solid state component of the above-mentioned formed body containing alkali metal salt for 0 mass % or more and 60 mass % with
Under,
Above-mentioned alkali metal salt B is the alkali metal salt except alkali metal salt included by alkali metal salt A and alkali metal salt C,
Also, the content summation of above-mentioned alkali metal salt B and above-mentioned alkali metal salt C is in the above-mentioned formed body containing alkali metal salt
Solid state component every 100 mass % in be 1 mass % or more.
2. the formed body containing alkali metal salt as described in above-mentioned item 1, which is characterized in that above-mentioned alkali metal salt B be selected from
In sodium chloride, sodium sulphate, sodium bisulfate, sodium nitrate, sodium acetate, potassium chloride, potassium sulfate, potassium acid sulfate, potassium nitrate and potassium acetate
At least one.
3. the formed body containing alkali metal salt as described in above-mentioned item 1 or 2, which is characterized in that above-mentioned alkali metal salt A is choosing
From at least one of sodium fluoride and two sodium bifluorides.
4. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~3, which is characterized in that
(1) above-mentioned alkali metal salt A be selected from least one of sodium fluoride and two sodium bifluorides,
(2) above-mentioned alkali metal salt B is at least one in sodium chloride, sodium sulphate, sodium bisulfate, sodium nitrate and sodium acetate
Kind,
(3) above-mentioned alkali metal salt C is selected from least one of sodium carbonate and sodium bicarbonate.
5. the formed body containing alkali metal salt as described in above-mentioned item 1 or 2, which is characterized in that above-mentioned alkali metal salt A is choosing
From at least one of potassium fluoride and potassium hydride difluoride.
6. the formed body containing alkali metal salt as described in any one of above-mentioned item 1,2 or 5, which is characterized in that
(1) above-mentioned alkali metal salt A be at least one of potassium fluoride and potassium hydride difluoride,
(2) above-mentioned alkali metal salt B is at least one selected from potassium chloride, potassium sulfate, potassium acid sulfate, potassium nitrate and potassium acetate
Kind,
(3) above-mentioned alkali metal salt C is at least one of potassium carbonate and saleratus.
7. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~6, which is characterized in that above-mentioned alkali gold
The content for belonging to salt A is 25 mass % or more in every 100 mass % of the solid state component of the above-mentioned formed body containing alkali metal salt
And 98 below mass %；The content of above-mentioned alkali metal salt B the above-mentioned formed body containing alkali metal salt solid state component every 100
It is 0 mass % or more and 60 mass % or less in quality %；The content of above-mentioned alkali metal salt C it is above-mentioned containing alkali metal salt at
In every 100 mass % of the solid state component of type body for 0 mass % or more and 50 mass % hereinafter,
Also, the content summation of above-mentioned alkali metal salt B and above-mentioned alkali metal salt C is in the above-mentioned formed body containing alkali metal salt
Solid state component every 100 mass % in be 2 mass % or more.
8. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~6, which is characterized in that above-mentioned alkali gold
Belong to salt A content in every 100 mass % of the solid state component of the above-mentioned formed body containing alkali metal salt 40 mass % or more and
98 mass % or less；Every 100 matter of the content of above-mentioned alkali metal salt B in the solid state component of the above-mentioned formed body containing alkali metal salt
Measure is 2 mass % or more and 60 mass % or less in %；The content of above-mentioned alkali metal salt C is in the above-mentioned molding containing alkali metal salt
It is 0 mass % in every 100 mass % of the solid state component of body more than or lower than 1 mass %.
9. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~6, which is characterized in that above-mentioned alkali gold
The content for belonging to salt A is 50 mass % or more in every 100 mass % of the solid state component of the above-mentioned formed body containing alkali metal salt
And 98 below mass %；The content of above-mentioned alkali metal salt B the above-mentioned formed body containing alkali metal salt solid state component every 100
For 0 mass % and lower than 1 mass % in quality %；The content of above-mentioned alkali metal salt C is in the above-mentioned formed body containing alkali metal salt
Solid state component every 100 mass % in be 2 mass % or more and 50 mass % or less.
10. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~9, to contain above-mentioned alkali metal
The compression forming object of the mixture of at least one of salt A and above-mentioned alkali metal salt B and above-mentioned alkali metal salt C.
11. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~9, selected from Aquo-composition
Formed body and its hirudo leech, above-mentioned Aquo-composition is by containing above-mentioned alkali metal salt A and above-mentioned alkali metal salt B and above-mentioned alkali
The mixture of at least one of metal salt C is formed with water.
12. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~9, for by Aquo-composition at
Type and be dried and the formed body that manufactures, above-mentioned Aquo-composition is by containing above-mentioned alkali metal salt A and above-mentioned alkali metal salt
The mixture of at least one of B and above-mentioned alkali metal salt C is formed with water.
13. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~12 is granular, pellet, ingot
Shape, plate or clastic.
14. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~13, by containing hydrogen fluorine
Acid generates the sediment of alkali metal fluorosilicates, by from above-mentioned acid with alkali metal salt is added in the acidic aqueous solution of fluosilicic acid
Property aqueous solution separate above-mentioned sediment and above-mentioned acidic aqueous solution carried out in the method for regeneration treatment, as above-mentioned alkali metal salt
It uses.
15. the formed body containing alkali metal salt as described in any one of above-mentioned item 1~4 or above-mentioned item 7~14, logical
Cross into the acidic aqueous solution containing hydrofluoric acid and fluosilicic acid add alkali metal salt and generate alkali metal fluorosilicates sediment,
In the method for carrying out regeneration treatment to above-mentioned acidic aqueous solution and separating above-mentioned sediment from above-mentioned acidic aqueous solution again, make
For the use of above-mentioned alkali metal salt, wherein
This contain alkali metal salt A used in the formed body of alkali metal salt be in sodium fluoride and two sodium bifluorides extremely
Few one kind, and
Alkali metal salt B is selected from least one of potassium fluoride and potassium hydride difluoride.
16. a kind of acidic aqueous solution regeneration method made containing hydrofluoric acid and fluosilicic acid comprising following processes 1 and 2,
(process 1) is added described in any one of above-mentioned item 1~15 in above-mentioned acidic aqueous solution containing alkali metal salt
Formed body, the process for obtaining the reaction solution of the sediment containing alkali metal fluorosilicates,
The process that (process 2) separates above-mentioned sediment from the obtained reaction solution of process 1.
17. the method as described in above-mentioned item 16, wherein above-mentioned acidic aqueous solution contains the hydrochloric acid of 3 mass % or more.
18. the method as described in above-mentioned item 17, wherein in process 1, above-mentioned item 3 is added in above-mentioned acidic aqueous solution
Or contain the formed body of alkali metal salt described in 4.
19. the method as described in above-mentioned item 16, wherein above-mentioned acidic aqueous solution is not hydrochloric or content of hydrochloric acid is lower than 3 matter
Measure %.
20. the method as described in above-mentioned item 19, wherein in process 1, above-mentioned item 5 is added in above-mentioned acidic aqueous solution
Or contain the formed body of alkali metal salt described in 6.
The effect of invention
When the acid that the formed body of the invention containing alkali metal salt is used for the fluosilicic acid containing hydrofluoric acid and as impurity
Property aqueous solution regeneration treatment when, can not make operating environment deteriorate and efficiently to acidic aqueous solution carry out regeneration treatment.
That is, of the invention can not only prevent alkali metal fluosilicate containing alkali metal salt formed body when making an addition in acidic aqueous solution
The micro mists such as compound disperse, moreover, with only by its main component, that is, alkali metal salt A (NaF, KF, NaHF2、KHF2) constitute formed body
It compares, more quickly formed body can be made to be disintegrated in acidic aqueous solution, it is heavy can faster and more efficiently to form fluosilicate
It forms sediment.
More surprising place is that it is possible to confirm: the formed body of the invention containing alkali metal salt and the alkali gold equally formed
The powder mixture for belonging to salt is compared, and has the precipitating that fluosilicate can more rapidly and be more efficiently formed in acidic aqueous solution
Epoch-making effect.
Specific embodiment
Hereinafter, the regeneration of the acidic aqueous solution to the formed body of the invention containing alkali metal salt and using the formed body
Processing method is described in detail.
<formed body containing alkali metal salt>
Formed body containing alkali metal salt of the invention is characterized in that, containing alkali metal salt A and alkali metal salt B and
At least one of alkali metal salt C, wherein
(1) alkali metal salt A be selected from least one of sodium fluoride, two sodium bifluorides, potassium fluoride and potassium hydride difluoride,
(2) alkali metal salt B is that the solubility in 20 DEG C of water is molten in the sodium salt of 10g/100m1 or more and 20 DEG C of water
Xie Du 10g/100ml or more at least one of sylvite,
(3) alkali metal salt C be selected from least one of sodium carbonate, sodium bicarbonate, potassium carbonate and saleratus,
(4) content of alkali metal salt A is in every 100 mass % of the solid state component of the above-mentioned formed body containing alkali metal salt
For 10 mass % or more and 95 mass % or less；The content of above-mentioned alkali metal salt B is in the above-mentioned formed body containing alkali metal salt
It is 0 mass % or more and 85 mass % or less in every 100 mass % of solid state component；The content of above-mentioned alkali metal salt C is above-mentioned
It is 0 mass % or more and 60 mass % or less in every 100 mass % of the solid state component of formed body containing alkali metal salt.
In addition, being characterized in that, above-mentioned alkali metal salt B is except alkali metal salt included by alkali metal salt A and alkali metal salt C
Alkali metal salt, also, the content summation of above-mentioned alkali metal salt B and above-mentioned alkali metal salt C it is above-mentioned containing alkali metal salt at
It is 1 mass % or more in every 100 mass % of the solid state component of type body.
Formed body containing alkali metal salt of the invention contains in alkali metal salt A and alkali metal salt B and alkali metal salt C
At least one.That is, the formed body of the invention containing alkali metal salt includes: 1) alkali metal salt A, alkali metal salt B and alkali metal
The mixture of salt C；2) mixture of alkali metal salt A and alkali metal salt B；And 3) the mixture of alkali metal salt A and alkali metal salt C
The invention of this 3 kinds of modes.
Hereinafter, to alkali metal salt A, alkali metal salt B contained in the formed body of the invention containing alkali metal salt and alkali
Metal salt C is described in detail.
Alkali metal salt A
Alkali metal salt A is not particularly limited.Specifically, two bifluoride of alkali metal fluoride or alkali metal can be enumerated
Deng the alkali metal salt etc. containing fluorine atom.Wherein, the viewpoint practical from accessibility and price, preferably sodium fluoride, difluoro hydrogen
Change sodium, potassium fluoride and potassium hydride difluoride etc..
These alkali metal fluorides and two bifluoride of alkali metal are in the alkali metal that slightly solubility is reacted and generated with fluosilicic acid
When the sediment of fluosilicate, hydrofluoric acid is generated.That is, alkali metal salt A is additionally aided while forming alkali metal fluorosilicates
The regeneration and supplement of hydrofluoric acid are special in the various alkali metal salts of the invention that formed contained by body containing alkali metal salt
Not important alkali metal salt.
But above-mentioned various alkali metal salt A all have and are easy to disperse and dust is easy the characteristic flown upward, when with industry
Property scale it is a large amount of in use, there are problems that operating environment obviously deteriorates.In contrast, containing alkali gold by using of the invention
The formed body containing alkali metal salt for belonging to salt A, can be avoided dust and disperses, and can carry out as described later rapidly acid water-soluble
The processing of liquid.
In the fluoride of alkali metal and two bifluorides, the sodium salt of sodium fluoride, two sodium bifluorides etc compared with sylvite, because
It is attractive as industrial materials to be easy and cheap.However, the sodium salt of sodium fluoride, two sodium bifluorides etc
Compared with sylvite, the solubility in acidic aqueous solution is far below the latter.So even if by alkali metal salt A only by sodium fluoride, two
The formed body that the sodium salt of sodium bifluoride etc is constituted makes an addition in acidic aqueous solution, and the disintegration of formed body also can expend the time, because
This, the formation speed of alkali metal silicon fluorinated metal acid salt sediment is extremely slow, does not have practicability.
On the other hand, even the sodium salt of sodium fluoride, two sodium bifluorides etc, if production and aftermentioned alkali metal salt B and alkali
The formed body of specific composition obtained from least one of metal salt C is combined, then made an addition in acidic aqueous solution, then
The formed body is disintegrated in a short time, as a result, dissolution or micro disperse various alkali metal salts in water and fluosilicic acid react
It carries out rapidly, and quickly forms the sediment of alkali metal silicon fluorinated metal acid salt.
In addition, even if in the case where the preferable potassium fluoride of dissolubility, potassium hydride difluoride, if production and aftermentioned alkali metal salt
The formed body of specific composition obtained from least one of B and alkali metal salt C are combined, then made an addition to acidic aqueous solution
In, compared with the separately formed body of potassium fluoride or potassium hydride difluoride, alkali metal silicon metal fluoride acid can be formed with shorter time
The sediment of salt.
Above-mentioned various alkali metal salt A can be used alone, two or more can be also applied in combination.
Alkali metal salt B
Alkali metal salt B is alkali metal salt soluble easily in water or acidic aqueous solution, when of the invention containing alkali metal salt
Containing sometimes in formed body, acidic aqueous solution is dissolved in rapidly by the ingredient, promotes formed body disintegration, to promote alkali metal salt A
Micro disperse.As a result, playing makes the alkali metal silicon fluorinated metal acid salt sediment of slightly solubility generate the effect promoted.
Alkali metal salt B is selected from least one of sodium salt soluble easily in water and sylvite soluble easily in water.These sodium salts
Or solubility of the sylvite in 20 DEG C of water is respectively 10g/l00ml or more, preferably 20g/l00ml or more, more preferably 30g/
L00ml or more.
Alkali metal salt B can be anhydride, or hydrate is equivalent to the hydrate in the case where hydrate
In the quality of anhydride must satisfy the condition of above-mentioned solubility.
As long as meeting the condition of above-mentioned solubility in water i.e. as the alkali metal salt B alkali metal salt used in the present invention
It can.Wherein, alkali metal (salt) B used in the formed body of the invention containing alkali metal salt is set as institute in above-mentioned alkali metal salt A
The institute of alkali metal compound contained in the alkali metal compound and aftermentioned alkali metal salt C contained alkali metal salt not to be covered.
As the alkali metal salt B concrete example for the condition of solubility in above-mentioned water that meets, for example, sodium chloride, sulphur can be enumerated
Sour sodium, sodium bisulfate, sodium nitrate, sodium dihydrogen phosphate, sodium acetate, potassium chloride, potassium sulfate, potassium acid sulfate, potassium nitrate, tricresyl phosphate
Potassium, dipotassium hydrogen phosphate, potassium oxalate and potassium acetate etc., but it is not limited only to these.
In above-mentioned various alkali metal salt B, because being easy to get and excellent in stability, particularly preferably selected from sodium chloride, sodium sulphate,
At least one of sodium bisulfate, nitrate nonahydrate, sodium acetate, potassium chloride, potassium sulfate, potassium acid sulfate, potassium nitrate and potassium acetate.
Above-mentioned various alkali metal salt B can be used alone, two or more can be also applied in combination.
Alkali metal salt C
Alkali metal salt C is the alkali metal selected from least one of sodium carbonate, sodium bicarbonate, potassium carbonate and saleratus
Salt.It when such alkali metal salt C dissolves in acidic aqueous solution, is reacted on one side with acid, generates carbon dioxide (carbonic acid gas on one side
Body).So the double action of the dissolution of alkali metal C in this way and generation carbon dioxide (carbonic acid gas), promotes to contain
There is the disintegration of the formed body of alkali metal salt, thus plays and promote alkali metal salt A dissolution or microdispersed effect.As a result, playing
The effect for accelerating the generation of the alkali metal silicon fluorinated metal acid salt sediment of slightly solubility.
Above-mentioned various alkali metal salt C can be used alone, two or more can be also applied in combination.
It should be noted that alkali metal salt A, alkali metal salt B and alkali metal salt C can be anhydride, it is also possible to be hydrated
Object or wet absorbent.It should also be noted that, in the present invention, in the case where these alkali metal salts are hydrate or wet absorbent,
According to the quality of anhydride contained therein, it can be determined that the composition (quality %) and alkali metal salt of the formed body containing alkali metal salt
Solubility etc. in water.
Hereinafter, the composition of the formed body to the present invention containing alkali metal salt is illustrated.
Formed body containing alkali metal salt of the invention contains in alkali metal salt A and alkali metal salt B and alkali metal salt C
At least one.
The present invention contains in the formed body of alkali metal salt, and the content of alkali metal salt A is in the formed body containing alkali metal salt
It is 10 mass % or more and 99 mass % or less in every 100 mass % of solid state component；The content of alkali metal salt B is containing alkali gold
Belong to is 0 mass % or more and 85 mass % or less in every 100 mass % of the solid state component of the formed body of salt；Alkali metal salt C's
Content in every 100 mass % of the solid state component of the formed body containing alkali metal salt for 0 mass % or more and 60 mass % with
Under.
It should be noted that content summation the consolidating in the formed body containing alkali metal salt of alkali metal salt B and alkali metal salt C
It is 1 mass % or more in every 100 mass % of state ingredient, if be lower than 1 mass %, the disintegration of the formed body containing alkali metal salt
Speed is slow, as a result, the alkali metal silicon fluorinated metal acid salt sediment of the dissolution of alkali metal salt A and micro disperse and slightly solubility
Formation speed is slack-off, does not have practicability.
In addition, when making the content of alkali metal salt C in every 100 mass % of the solid state component of the formed body containing alkali metal salt
In be higher than 60 mass % when, will should formed body containing alkali metal salt make an addition in acidic aqueous solution when, bubble generate excessively
Acutely, reaction system is caused to be difficult to control,
So not preferably.
Hereinafter, representative 3 kinds of modes that the formed body to the present invention containing alkali metal salt is included are described in detail.
1) the case where containing alkali metal salt A, alkali metal salt B and alkali metal salt C
When the constituent of the formed body of the invention containing alkali metal salt is alkali metal salt A, alkali metal salt B and alkali metal
When the mixture of salt C, in order to synergistically play the obtained formed body disintegration facilitation of alkali metal salt B and alkali metal salt C institute
Obtained formed body disintegration facilitation, and an adequate amount of hydrofluoric acid is supplied in oxytropism aqueous solution, composition is preferably by alkali
The content of metal salt A be set as in every 100 mass % of the solid state component of the formed body containing alkali metal salt for 25 mass % with
Upper and 98 mass % or less；By the content of alkali metal salt B be set as the formed body containing alkali metal salt solid state component every 100
It is 0 mass % or more and 60 mass % or less in quality %；The content of alkali metal salt C is set as in the molding containing alkali metal salt
It is 0 mass % or more and 50 mass % or less in every 100 mass % of the solid state component of body.
Wherein, preferably the content summation of above-mentioned alkali metal salt B and above-mentioned alkali metal salt C are set as above-mentioned containing alkali metal
It is 2 mass % or more in every 100 mass % of the solid state component of the formed body of salt.
2) the case where containing alkali metal salt A and alkali metal salt B
When the constituent of the formed body of the invention containing alkali metal salt is based on alkali metal salt A and alkali metal salt B
When the mixture of ingredient, in order to play the obtained formed body disintegration facilitation of alkali metal salt B, and supplied in oxytropism aqueous solution
An adequate amount of hydrofluoric acid is answered, the content of alkali metal salt A is preferably set as the solid-state in the formed body containing alkali metal salt by composition
It is 40 mass % or more and 98 mass % or less in every 100 mass % of ingredient；The content of alkali metal salt B is set as to contain alkali
It is 2 mass % or more and 60 mass % or less in every 100 mass % of the solid state component of the formed body of metal salt.
The content of alkali metal salt A in every 100 mass % of the solid state component of the formed body containing alkali metal salt be usually
40 mass % or more and 98 mass % hereinafter, more preferably 45 mass % or more and 97 mass % hereinafter, particularly preferably 50 matter
Measure % or more and 96 mass % or less.The content of alkali metal salt B is in the every of the solid state component of the formed body containing alkali metal salt
It is usually 2 mass % or more and 60 mass % in 100 mass % hereinafter, more preferably 4 mass % or more and 50 mass % or less.
When the content of alkali metal salt B is low in every 100 mass % of the solid state component of the formed body containing alkali metal salt
When 2 mass %, the disintegration rate of formed body is slow, as a result, the alkali metal fluosilicic of the micro disperse of alkali metal salt A and slightly solubility
The formation speed of metal acid-salt sediment is slack-off, does not have practicability.
It should be noted that although being defined as alkali metal salt containing alkali metal salt A and alkali metal in mode 2)
The formation body containing alkali metal salt of the mode of salt B, but be also included in such formation body containing alkali metal salt unintentionally
If ground contains the case where above-mentioned alkali metal salt C of dry measure.The content of specific alkali metal salt C at this time can be set as containing alkali
It is usually 0 mass % in every 100 mass % of the solid state component of the formation body of metal salt and is lower than 1 mass %.
3) the case where containing alkali metal salt A and alkali metal salt C
When the constituent of the formed body of the invention containing alkali metal salt is based on alkali metal salt A and alkali metal salt C
When the mixture of ingredient, in order to play the obtained formed body disintegration facilitation of alkali metal salt C, and supplied in oxytropism aqueous solution
An adequate amount of hydrofluoric acid is answered, the content of alkali metal salt A is preferably set as consolidating in the formed body containing alkali metal salt by composition
It is 50 mass % or more and 98 mass % or less in every 100 mass % of state ingredient；The content of alkali metal salt C is set as containing
Have in every 100 mass % of the solid state component of the formed body of alkali metal salt for 2 mass % or more and 50 mass % or less.
The content of alkali metal salt A is usually 50 in every 100 mass % of the solid state component of the formed body containing alkali metal
Quality % or more and 98 mass % hereinafter, more preferably 55 mass % or more and 97 mass % hereinafter, particularly preferably 60 matter
Measure % or more and 96 mass % or less.
The content of alkali metal salt C is usually 2 matter in every 100 mass % of the solid state component of the formed body containing alkali metal
Measure % or more and 50 mass % hereinafter, more preferably 3 mass % or more and 45 mass % hereinafter, particularly preferably 4 mass % with
Upper and 40 mass % or less.
When the content of alkali metal salt C is lower than 2 matter in every 100 mass of the solid state component of the formed body containing alkali metal salt
When measuring %, the disintegration rate of the formed body containing alkali metal salt is slow, as a result the dissolution of alkali metal salt A and micro disperse and slightly solubility
Alkali metal silicon fluorinated metal acid salt sediment formation speed it is slack-off, do not have practicability.
It should be noted that although in mode 3), as alkali metal salt define containing substantially by alkali metal salt A and
The formation body containing alkali metal salt for the mode that alkali metal salt C is constituted, but it is also included within such formation containing alkali metal salt
If the case where inadvertently containing the above-mentioned alkali metal salt B of dry measure in body.The content of specific alkali metal salt B at this time can be set
To be usually 0 mass % in every 100 mass % of the solid state component of the formation body containing alkali metal salt and being lower than 1 mass %.
It is water-soluble to be added to above-mentioned acidity either artificially or non-artificial for formed body containing alkali metal salt of the invention
Liquid, as long as can not be restricted the formed body for the shape that it is safely added by above-mentioned condition.
The concrete example of shape as the formed body used in the present invention containing alkali metal salt, for example, grain can be enumerated
Shape, pellet, ingot shape, plate small pieces, clastic or broken sheet formed body, but be not limited only to this.
Formed body of various shapes containing alkali metal salt as described above can utilize as described below various
Forming machine device, prilling granulator are manufactured.As its concrete example, for example, various compacting shape machines, powder molding can be enumerated
Machine, stamping of powder molding machine make ingot molding machine, ball milling forming machine, extrusion shaping machine, pelletizer, roll-in granulator, mixing granulator
Machine, stirring granulating machine, fluidized bed pelletizer, rolls pelletizer, compression pelletizer, broken pelletizer, crushes and make extruding granulator
Grain machine, spray drying granulation machine, flake type molding machine etc., it is not limited to this.
As the formed body of the invention containing alkali metal salt, it is able to use the various shapes as made from various feedstock compositions
The formed body of shape, as its example, for example, can enumerate it is following i) or ii) shown in formed body.
I) mixture containing at least one of alkali metal salt A and alkali metal salt B and alkali metal salt C is compressed into Type object。
The compression forming object be so-called punch forming body, as specific shape, for example, can enumerate granular, ingot shape,
The formed body of various shapes such as pellet, plate.
For manufacturing the device of compression forming object, various compression-molding apparatus are able to use, there is no particular limitation.Specifically
For, it is compressed into for example, single-lift compacting shape machine, double-lift compacting shape machine or rotary compression molding press etc. can be enumerated
Type device etc..
In addition, the compression such as punching press condition formation condition can be set as producing when making an addition to acidic aqueous solution not
It will appear the degree of the compression forming object of the hardness of the degree of shape disintegration.
Specifically, face pressure (molding load ÷ formed body contact area) is typically set to the punching press of 0.1 ton~10 tons degree
Pressure, preferably 0.2 ton to 8 tons.
Ii) by the mixture containing at least one of alkali metal salt A and alkali metal salt B and alkali metal salt C and water structure At Aquo-composition formed body and/or its hirudo leech。
It, will be by containing alkali metal salt A and alkali metal salt B and alkali gold for example, can enumerate as the example of the formed body
The Aquo-composition that the mixture and water for belonging at least one of salt C are constituted forms, according still further to needing to be dried
The formed body of manufacture.Specific manufacturing method can for example be enumerated above-mentioned will be mixed using above-mentioned various molding machines, prilling granulator
Close the molding method of Aquo-composition of the various moisture content of the aqueous paste of object or the moisturizing compositions of said mixture etc.
If the formed body becomes fragile in addition, the formed body moisture content of such Aquo-composition is excessive, operability drop
It is low, and additional water also will lead to the moisture content increase of acidic aqueous solution, so not preferably.So aqueous when the formed body
It when rate is higher than 20 mass %, is preferably implemented and is dried, form moisture content and 20 mass % hirudo leech below is reduced to use.
As the formed body of such Aquo-composition or the shape of its hirudo leech, for example, can enumerate granular, ingot shape,
The various shapes such as pellet, plate.
The water content in Aquo-composition used as raw material is not particularly limited, can be using the aqueous of wide scope
Amount.As the example of Aquo-composition used in this method, for example, the aqueous slurry of said mixture, above-mentioned can be enumerated
The Aquo-composition of the various water content such as the moisturizing compositions of the aqueous paste of mixture or said mixture.
It should be noted that either above-mentioned Aquo-composition or its hirudo leech, fragment are also included within of the invention
In formed body.
There is no particular limitation for broken degree, for example, when such fragment is made an addition to acidic aqueous solution, preferably
Be crushed to the fragment for the size that micro mist will not disperse, or be adjusted to the fragment will not remain on acidic aqueous solution surface and
It is the degree of precipitating.
As manufacturing above-mentioned ii) when the drying means of Aquo-composition of intermediate there is no particular limitation, can adopt
The seasoning implemented with commonly used various drying devices.Drying condition is also limited without special.Specifically, can
Using under normal pressure, decompression under, air-supply under the conditions of, stirring or rotating condition under, under static conditions, shake under the conditions of etc. various items
Seasoning under part.Drying temperature is suitably selected according to drying mode, time restriction etc., and there is no particular limitation.For example, usually
Can be set as 50 DEG C or more and 300 DEG C hereinafter, preferably 70 DEG C or more and 250 DEG C hereinafter, more preferably 90 DEG C or more and 200
DEG C or less.
In addition, dry degree is contemplated that use condition, operability, the system of the formed body of the invention containing alkali metal salt
This grade is caused suitably to select.
According to it is above-mentioned i) or ii) manufacture the formed body of the invention containing alkali metal salt either hirudo leech, can also
Be how much the water content containing water.But if moisture content is excessive, which can become fragile, and operability reduces, and additional water
Branch causes the moisture content of acidic aqueous solution to increase, so not preferably.So the formed body of the invention containing alkali metal salt
Moisture content be ordinarily selected to 20 mass % hereinafter, preferably 10 mass % hereinafter, more preferably 5 mass % hereinafter, particularly preferably
For 2 mass % or less.In addition, the moisture content indicates to further include the containing relative to the formed body gross mass water including hydrate water
Rate (quality %).
As it is above-mentioned i) or ii) shown in the formed body containing alkali metal salt manufactured by Aquo-composition, because making an addition to acid
Property aqueous solution in when, can not only prevent dispersing for the micro mists such as alkali metal fluoride, and formed body in acidic aqueous solution rapidly
Disintegration rapidly forms fluosilicate precipitating, so it is particularly useful.
That is, by containing sodium fluoride, two sodium bifluorides etc the lower alkali metal salt of solubility and in water in water
In the case where the formed body of the Aquo-composition manufacture of solubility higher alkali metal salt B or alkali metal salt C, the formed body and alkali
The same powder mixture of metal salt component is compared, and it is heavy that fluosilicate can be more quickly formed in acidic aqueous solution
It forms sediment, so it is useful.
The formed body of the shape made from such Aquo-composition and the formed body being only made of rapid alkali metal salt A
It compares, more quickly formed body can be made to be disintegrated in acidic aqueous solution, it can more rapidly and that fluosilicate is efficiently formed is heavy
It forms sediment.More surprising place is, confirms the formed body and contains only the powder of the powder of alkali metal salt A or the alkali metal salt of same composition
Body mixture is compared, and the epoch-making effect of fluosilicate precipitating is more quickly and efficiently formed in acidic aqueous solution.The molding
Such high response of body, the such ordinary skill also lower than powder reactivity from formed body reactivity is can not be pre-
Phase, be the industrial epochmaking property confirmed for the first time by the present invention.
Although the mechanism of action for making the speed to form fluosilicate precipitating become faster in the case where having used the formed body is still
Not yet explicitly, for example, in ii) documented by formed body containing alkali metal salt in the case where, as one of hypothesis, infer
For following mechanism.
That is, in above-mentioned ii) documented by used Aquo-composition the formed body containing alkali metal salt manufacturing method
In, so that the alkali metal salt for being equivalent to alkali metal salt B and/or alkali metal salt C soluble easily in water is infiltrated into sodium fluoride, two sodium bifluorides
In grade water inside the offspring of the low alkali metal salt powder for being equivalent to alkali metal salt A of solubility, and then forms to contain and be somebody's turn to do
The structure that the surface of offspring is covered by the alkali metal salt for being equivalent to alkali metal salt B and/or alkali metal salt C soluble easily in water
The formed body containing alkali metal salt of aggregate.
When making an addition to the formed body containing alkali metal salt made from as described above operate in acidic aqueous solution, it is soluble in
Water be equivalent to alkali metal salt B and/or the alkali metal salt of alkali metal salt C dissolves rapidly, (when there are alkali metal salt C, utilize
The synergistic effect of bubble is generated with carbonate), thus formed body is disintegrated at once.At the same time, low suitable of solubility in water
It is primary particle in offsprings micro disperses such as sodium fluoride, two sodium bifluorides of alkali metal salt A, which facilitates fluorine silicon
The acceleration of the formation speed of the precipitating of hydrochlorate.
As described above, the formed body of the invention containing alkali metal salt can from for example granular, pellet, ingot shape, plate or
Selected shape in clastic etc..Among these shapes, the manufacture of the formed body of pellet, ingot shape or plate is easy, and operability is also good
It is good, so more preferably.
Formed body containing alkali metal salt of the invention is particularly suitable for by being added to containing hydrofluoric acid and fluosilicic acid
Acidic aqueous solution in, the sediment of alkali metal fluorosilicates can be generated, by separating the sediment from acidic aqueous solution
The method that regeneration treatment is carried out to acidic aqueous solution.
In addition, being disclosed in patent document 12 by the side of sodium fluoride powder and potassium fluoride aqueous solution manufacture sodium fluoride pellet
Method.Wherein, although patent document 12 is disclosed because the sodium fluoride pellet has high compressive strength, thus as hydrogen fluoride, six
The adsorbent of the fluoride gas such as uranium fluoride is useful, still, easily collapses for being utilized in acidic aqueous solution as the present invention
The regeneration treatment agent purposes as spent acid aqueous solution of solution property has no any record.
In general, when use hydrofluoric acid containing acidic aqueous solution carry out various glass materials, organosilicon material etching,
When the surface treatment such as cleaning, the fluosilicic acid (H generated is reacted with hydrofluoric acid by silicon ingredient2SiF6, fluosilicic acid) dissolution is to acid water-soluble
In liquid.When reusing or reusing such acidic aqueous solution containing hydrofluoric acid, the fluosilicic acid in acidic aqueous solution is dense
Degree is gradually increasing, as a result, surface treatment capabilities is caused to gradually decrease.
Since the formed body of the invention containing alkali metal salt can make fluorine formed in the surface treatment procedures such as glass
Silicic acid is precipitated as insoluble salt into acidic aqueous solution, therefore can remove from acidic aqueous solution as impurity, makees
It is useful to carry out regenerated inorganic agent to acidic aqueous solution.
It is not particularly limited in addition, being somebody's turn to do sour component contained in the acidic aqueous solution containing hydrofluoric acid.For example, can enumerate
The inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, boric acid；Organic acids such as formic acid, acetic acid, oxalic acid, citric acid, lactic acid etc..These acid
Ingredient can combine two or more contained in acidic aqueous solution.
<regeneration treating method for having used the acidic aqueous solution of the formed body containing alkali metal salt>
Of the invention makes the acidic aqueous solution regeneration method containing hydrofluoric acid and fluosilicic acid include process 1 and work below
Sequence 2:
Formation body of the invention containing alkali metal salt is added to the acid water containing hydrofluoric acid and fluosilicic acid by (process 1)
In solution, the process that obtains the reaction solution containing alkali metal fluorosilicates sediment；
The process that (process 2) separates above-mentioned sediment from reaction solution obtained by process 1.
1) about process 1
Make in the acidic aqueous solution regeneration method containing hydrofluoric acid and fluosilicic acid in of the invention, process 1 is to send out this
The bright formation body containing alkali metal salt makes an addition in the acidic aqueous solution containing hydrofluoric acid and fluosilicic acid, obtains containing alkali metal
The process of the reaction solution of the sediment of fluosilicate.
When in the acidic aqueous solution containing hydrofluoric acid and fluosilicic acid addition containing alkali metal salt A and alkali metal salt B and
When the formed body containing alkali metal salt of at least one of alkali metal salt C, these alkali metal salts will as following various (1B),
Shown in (2B) and (3B), reacted with fluosilicic acid, to form insoluble fluosilicate.
[the reaction example of alkali metal salt A]
2MF+H2SiF6→M2SiF6↓+2HF (1B)
[the reaction example (example of chloride) of alkali metal salt B]
2MCl+H2SiF6→M2SiF6↓+2HCl (2B)
[the reaction example of alkali metal salt C]
M2CO3+H2SiF6→M2SiF6↓+H2O+CO2 (3B)
In addition, the M in above formula (1B)~(3B) indicates Na atom or K atom.
Therefore, process 1 needed for forming insoluble fluosilicate for the fluosilicic acid as contained in acidic aqueous solution
In the added formed body of the invention containing alkali metal salt amount, can be water-soluble according to above formula (1), (2) and (3) and acidity
Fluosilicic acid amount in liquid is estimated.
Specifically, containing alkali metal salt A and alkali metal salt B and alkali metal added by being scaled in acid solution
Alkali metal ion total amount in the formed body containing alkali metal salt of at least one of salt C can be set as making acid water-soluble
40% or more and 100% degree below of the theoretical amount that fluosilicic acid contained in liquid all precipitates.
In the case where being added to the alkali metal ion more than theoretical amount, due to water-soluble in the acidity for eliminating fluosilicate
Therefore the superfluous alkali metal ion of remaining in liquid is added to such formed body containing alkali metal salt treated and is acid
Aqueous solution is unsuitable for reusing (recycling), so not preferably.
On the other hand, though in the acidic aqueous solution reused several fluosilicic acid of remaining, will not substantially undermine glass
The surface treatment capabilities of material, silicon materials.Such as even if contain 9 mass % fluorine silicon below in the acidic aqueous solution reused
In the case where acid, the surface treatment for glass material, silicon materials is remained to.
Given this situation, the molding of the invention containing alkali metal salt being added in process l in acidic aqueous solution
When being scaled the total amount of the alkali metal ion contained by it, 40 moles of %'s body or more and 100 that can be set as theoretical amount rub
Your % hereinafter, preferably 45 moles of % or more and 98 mole of % hereinafter, particularly preferably 50 moles of % or more and 95 mole of % with
Under.
When the formed body of the invention containing alkali metal salt added in process l is reacted with hydrofluoric acid or fluosilicic acid,
If using the alkali metal salt that can be generated with the ion species in the presence of acidic aqueous solution for same ion kind, regeneration treatment is contained
The ion species in acidic aqueous solution afterwards will not change, so particularly preferably.Therefore, because alkali metal salt A and fluosilicic acid generate
Hydrofluoric acid is reacted and generates, so particularly preferably.
Even if not being same ion kind, it is also preferred that not making the changed alkali of the ion species in acidic aqueous solution using containing
The formed body containing alkali metal salt of metal salt.Specifically, the alkali of carbon dioxide is reacted and generated with hydrofluoric acid and fluosilicic acid
Metal salt C is discharged into carbon dioxide except acidic aqueous solution, does not remain the ion species other than alkali metal, it is therefore preferable that being contained in
In formed body containing alkali metal salt of the invention.
In addition, as alkali metal salt contained in the formed body of the invention containing alkali metal salt used in process 1
B is able to use the high alkali metal salt of various dissolubilities in water, when containing the acid other than hydrofluoric acid and fluosilicic acid as sour component
In the case where, as alkali metal salt B, it is preferable to use containing the alkali metal salt of ion species corresponding with various acid.
For example, for saliferous acid solution, it is preferable to use chloride, for sulfur-bearing acid solution, it is preferable to use sulfate or sulphur
Sour hydrogen salt, for containing nitric acid solution, it is preferable to use nitrate.
There is report to point out, also contains other than containing hydrofluoric acid and fluosilicic acid in the acidic aqueous solution of regeneration treatment object
In the case where hydrochloric acid, even if fluosilicic acid sylvite has been temporarily forming precipitating, which is easy to be re-dissolved in acidic aqueous solution.Another party
Face, fluosilicic acid sodium salt have the characteristic for being not easy to be re-dissolved in hydrochloric acidic aqueous solution instead.In view of such property, contain
There is the constituent of the acidic aqueous solution of hydrochloric acid used formed body containing alkali metal salt when regenerating, preferably based on sodium salt
Ingredient.
Specifically, when the acidic aqueous solution containing hydrofluoric acid and fluosilicic acid contains the hydrochloric acid of 3 mass % or more, process
The formed body of the invention containing alkali metal salt made an addition in acidic aqueous solution in 1 preferably comprises choosing as alkali metal salt A
From at least one of sodium fluoride and two sodium bifluorides.
Additionally, it is preferred that the following formed body containing alkali metal salt: as alkali metal salt A, containing selected from sodium fluoride, difluoro
At least one of sodium hydride, as alkali metal salt B, containing selected from sodium chloride, sodium sulphate, sodium bisulfate, sodium nitrate and acetic acid
At least one of sodium, as alkali metal salt C, containing selected from least one of sodium carbonate and sodium bicarbonate.When above-mentioned alkali gold
Belong to salt B using sodium chloride or using sodium chloride as the salt-mixture of principal component in the case where, ion species in regenerated acidic aqueous solution
It is less there is no changing or changing, so it is particularly useful.In addition, from easily accessible and cheap viewpoint, preferably also chlorination
Sodium.
On the other hand, the acidic aqueous solution containing hydrofluoric acid and fluosilicic acid is not hydrochloric or content of hydrochloric acid is lower than 3 matter
In the case where measuring %, made an addition in process l in the formed body of the invention containing alkali metal salt in acidic aqueous solution, as alkali
Metal salt A is preferably comprised selected from least one of the excellent potassium fluoride of dissolubility and potassium hydride difluoride.
Additionally, it is preferred that for the following formed body containing alkali metal salt: as alkali metal salt A, containing selected from potassium fluoride and
At least one of potassium hydride difluoride, as alkali metal salt B, containing selected from potassium chloride, potassium sulfate, potassium acid sulfate, potassium nitrate and
At least one of potassium acetate, as alkali metal salt C, containing selected from least one of potassium carbonate and saleratus.
In process 1, the formed body containing alkali metal is usually put into while stirring acidic aqueous solution.It is stirred such
Under the conditions of mixing, compared with the case where not stirring, the disintegration of the added formed body containing alkali metal salt is accelerated.It is tied
Fruit carries out reacting for alkali metal salt and fluosilicic acid in a short time, then more quickly carries out the formation of fluosilicate precipitating, therefore
And it is preferred that.
Such agitating procedure can use well known method, and there is no particular limitation.For example, can be various using utilizing
Stirring that the stirring blade of shape carries out is blown into air and is stirred.
In addition, being made an addition to acid water-soluble when the formed body containing alkali metal salt is containing the case where alkali metal salt C
Carbon dioxide gas is generated after in liquid and generates bubble, therefore can utilize the mixing effect obtained by the bubble sometimes.Example
Such as, according to the content of the alkali metal salt C in the formed body containing alkali metal salt, using the stirring action obtained by above-mentioned bubble,
It is still it can be expected that same with above-mentioned agitating procedure even if not providing using the agitating procedure of external impetus or only slight agitating procedure
Reacting for alkali metal salt and fluosilicic acid is carried out to sample in a short time, and the precipitating for carrying out fluosilicate rapidly is formed.
2) about process 2
Make in the acidic aqueous solution regeneration method containing hydrofluoric acid and fluosilicic acid in of the invention, process 2 is from process 1
The process of the sediment of the obtained alkali metal fluorosilicates of separation process 1 in obtained reaction solution.
There is no particular limitation for separation means, can use well known method.For example, can enumerate centrifugally operated, filtering,
The method of the separation of solid and liquid such as UF membrane.
The regenerated acidic aqueous solution that such method by including above-mentioned operation (1) and process (2) obtains, can be direct
It is recycled in the processing of glass or silicon materials etc..
Embodiment
Hereinafter, illustrating for the embodiment of the present invention to be described in more detail.But the present invention is not limited to these implementations
Example.
1 compression forming body of embodiment and mixed powder (HF-HCl waste liquid)
By NaF powder, NaC1 powder and Na2CO3Powder is according to NaF ︰ NaCl ︰ Na2CO3The quality of 37.5 ︰ 25 of=37.5 ︰
It is mixed than (hereinafter also referred to " ratio of components "), powder mixture is made, uses hand punch (NPSystem (strain) desktop layer
Press) load that applies face pressure 3.4t to it forms, compressed shape adult is made.Formed body at this time is the circle of every agreement that contracts a film or TV play to an actor or actress 1g
Shape ingot (14 × 14 × 1mm).
According to 1 weight of the compression forming body, waste liquid amount is adjusted, it is made to be calculated as H according to theoretical value2SiF650%
Equivalent is removed, when above-mentioned 1 compression forming body (1.0g) to be added in spent acid model aqueous solution (27.6g), because of carbonate
Reaction start generate bubble.After the reaction solution stands 3 hours in the case where not stirring, (2000rpm, 10 points are centrifuged
Clock), supernatant is supplied to the nonaquepous tration carried out using potential difference titration outfit and acid-base titration is analyzed, is found out various dense
Degree.Based on this as a result, calculating the reactivity and removal rate of fluosilicic acid.
In addition, as comparative example, mixed powder with same composition than making same quality, by its according to above-mentioned compression
The same condition of formed body situation, carry out with spent acid model aqueous solution react and processing, and evaluated.Its result arranges
As shown in table 1.
In addition, using 55% hydrofluoric acid (industrial, gloomy field in the preparation of spent acid model aqueous solution (waste liquid processed)
Learn industrial (strain)), 35% hydrochloric acid (industrial, xun, one of the Eight Diagrams synthesizes chemical (strain)), hexafluorosilicic acid (CICA level-one, the Northeast are chemical (strain)),
The concentration being prepared as in table.
[table 1]
It is so-called " removal rate " in 1~table of table 9, indicate the removal rate that fluosilicic acid is removed from waste liquid processed；It is so-called
" removal efficiency " indicates ratio of the practical removal rate relative to theoretical removal rate (50%).
As shown in Table 1, in the case where having used compression forming body, compared with the case where having used mixed powder, substantially
Improve the removal rate and removal efficiency of fluosilicic acid.It also knows, in the case where adding compression forming body into waste liquid, with addition
The case where mixed powder, is compared, and alkali metal salt micro mist disperses also few.
Embodiment 2 is crushed body shape formed body (by the method for forming of moisturizing compositions: 3 ingredients) (HF-HCl waste liquid)
Relative to by NaF powder, NaCl powder and Na2CO3Powder is according to NaF ︰ NaCl ︰ Na2CO337.5 ︰ 25 of=37.5 ︰
The 100 mass % of powder mixture that is mixed to get of ratio of components, add 20 mass % of water, be allowed to wet, by obtained combination
Object moves in bucket, is made it dry 2 hours using drier at 200 DEG C, is crushed after placing cooling, and broken body shape molding is made
Body.The size (length) of each flinders of operation broken body shape formed body obtained in this way is most of in 1mm or more.
In waste liquid 25.0g processed, addition according to made of above-mentioned manufacturing method be crushed body shape formed body 1.0g, by
When the bubble that the reaction of carbonate obtains generates slack-off, stirred strongly 1 minute using turbine-type mixer.Then, centrifugation point is carried out
From (2000rpm, 10 minutes), supernatant is supplied to the nonaquepous tration carried out using potential difference titration outfit and acid-base titration point
Analysis, finds out various composition.
In addition, as comparative example, it will be with the mixed powder with above-mentioned broken body shape formed body same composition and phase homogenous quantities
It makes an addition in waste liquid, and is reacted and handled with the same terms, have rated the removal rate and reactivity of fluosilicic acid.As a result such as table
Shown in 2.
In addition, using 55% hydrofluoric acid (industrial, gloomy field in the preparation of spent acid model aqueous solution (waste liquid processed)
Chemical industry (strain)), 35% hydrochloric acid (industrial, xun, one of the Eight Diagrams synthesizes chemical (strain)), hexafluorosilicic acid (CICA level-one, Northeast chemistry
(strain)), the concentration being prepared as in table.
[table 2]
As shown in Table 2, in the case where having used the broken body shape formed body, with phase the case where having used mixed powder
Than the removal rate and reactivity of fluosilicic acid are improved.Moreover, it is found that when the feelings for adding the broken body shape formed body to waste liquid
Under condition, compared with the case where adding mixed powder, alkali metal salt micro mist disperses also few.
Embodiment 3 is crushed body shape formed body (by the method for forming of moisturizing compositions: 2 ingredients) (HF-HCl waste liquid)
It is mixed relative to by NaF powder and NaCl powder according to the powder that the ratio of components of NaF ︰ NaCl=50 ︰ 50 is mixed to get
100 mass % of object is closed, 33 mass % of water is added, is allowed to wet, obtained composition is moved in bucket, is existed using drier
200 DEG C make it dry 2 hours, are crushed after placing cooling, and broken body shape formed body is made.Operation broken body obtained in this way
The size (length) of each flinders of shape formed body is most of in 1mm or more.
In waste liquid 25.0g processed, addition according to made of above-mentioned manufacturing method be crushed body shape formed body 1.0g, by
When the bubble that the reaction of carbonate obtains generates slack-off, stirred strongly 1 minute using turbine-type mixer.Then, centrifugation point is carried out
From (2000rpm, 10 minutes), supernatant is subjected to nonaquepous tration using potential difference titration outfit and acid-base titration is analyzed, is found out
Various composition.
In addition, as comparative example, it will be with the mixed powder with above-mentioned broken body shape formed body same composition and phase homogenous quantities
It makes an addition in waste liquid, and is reacted and handled with the same terms, have rated the removal rate and reactivity of fluosilicic acid.As a result such as table
Shown in 3.
In addition, using 55% hydrofluoric acid (industrial, gloomy field in the preparation of spent acid model aqueous solution (waste liquid processed)
Chemical industry (strain)), 35% hydrochloric acid (industrial, xun, one of the Eight Diagrams synthesizes chemical (strain)), hexafluorosilicic acid (CICA level-one, Northeast chemistry
(strain)), the concentration being prepared as in table.
[table 3]
As shown in Table 3, in the case where having used the broken body shape formed body, with phase the case where having used mixed powder
Than the removal rate and reactivity of fluosilicic acid are improved.Moreover, it is found that when the feelings for adding the broken body shape formed body to waste liquid
Under condition, compared with the case where adding mixed powder, alkali metal salt micro mist disperses also few.
4 compression forming body (compression forming methods) of embodiment, 3 ingredient (HF-HCl waste liquid)
By NaF powder (A), NaCl powder (B) and Na2CO3Powder (C) is mixed according to ratio of components shown in following table 4, system
At powder mixture, using hand punch (NPSystem (strain) desktop laminating machine) it is applied the load of face pressure 3.4t into
Row molding, is made compressed shape adult.Formed body at this time is the round ingot (14 × 14 × 1mm) of every agreement that contracts a film or TV play to an actor or actress 1g.
According to 1 weight of the compression forming body, waste liquid amount is adjusted, it is made to be calculated as H according to theoretical value2SiF650%
Remove equivalent, by above-mentioned formed body devote using in blender (MAGNESTER MGM-66) stirring (speed scale 3) it is useless
In liquid.Stirring after five minutes, is separated by solid-liquid separation it, which is supplied to the non-water droplet using potential difference titration outfit
The analysis of fixed and acid-base titration, finds out various composition.
In addition, the compression forming body that production contains only NaF is (identical as above-mentioned 3 ingredient system's formed body at profile bar as comparative example
Part, same shape), it is made an addition in spent acid model liquid, it is anti-to be carried out with above-mentioned 3 ingredient compression forming body situation the same terms
It should and handle, have rated the removal rate and reactivity of fluosilicic acid.As a result it arranges as shown in table 4.
In addition, using 55% hydrofluoric acid (industrial, gloomy field in the preparation of spent acid model aqueous solution (waste liquid processed)
Chemical industry (strain)), 35% hydrochloric acid (industrial, xun, one of the Eight Diagrams synthesizes chemical (strain)), hexafluorosilicic acid (CICA level-one, Northeast chemistry
(strain)), the concentration being prepared as in table.
[table 4]
As shown in Table 4,3 ingredient compression forming bodies are compared with the compression forming body for containing only NaF, fluosilicic acid removal rate and reaction
Rate improves.
5 compression forming body of embodiment (compression forming methods of wetting body) 3 ingredients (HF-HCl waste liquid)
To by NaF powder (A), NaCl powder (B) and Na2CO3Powder (C) is mixed according to ratio of components shown in following table 5 and is made
At 100 mass % of powder mixture in add the water of 5 mass %, be allowed to wet, wet mixture be made, uses manual stamping
The load that machine (NPSystem (strain) desktop laminating machine) applies face pressure 3.4t to it forms, and compressed shape adult is made.At
After type object places 24 hours or more under atmospheric pressure, for verifying.Formed body at this time is the round ingot (14 of every 1 agreement that contracts a film or TV play to an actor or actress 1g
×14×1mm)
According to 1 weight of the compression forming body, waste liquid amount is adjusted, it is made to be calculated as H according to theoretical value2SiF650%
Remove equivalent, by above-mentioned formed body devote using in blender (MAGNESTER MGM-66) stirring (speed scale 3) it is useless
In liquid.Stirring after five minutes, is separated by solid-liquid separation it, which is supplied to the non-water droplet using potential difference titration outfit
The analysis of fixed and acid-base titration, finds out various composition.
In addition, the compression forming body that production contains only NaF is (identical as above-mentioned 3 ingredient system's formed body at profile bar as comparative example
Part, same shape), it is made an addition in spent acid model liquid, it is anti-to be carried out with above-mentioned 3 component compression forming body situation the same terms
It should and handle, have rated the removal rate and reactivity of fluosilicic acid.As a result it arranges as shown in table 5.
In addition, using 55% hydrofluoric acid (industrial, gloomy field in the preparation of spent acid model aqueous solution (waste liquid processed)
Chemical industry (strain)), 35% hydrochloric acid (industrial, xun, one of the Eight Diagrams synthesizes chemical (strain)), hexafluorosilicic acid (CICA level-one, Northeast chemistry
(strain)), the concentration being prepared as in table.
[table 5]
As shown in Table 5, compared with the compression forming body for containing only NaF, the fluosilicic acid removal rate of 3 ingredient compression forming bodies and anti-
Should rate greatly improve.
6 compression forming body of embodiment (compression forming methods of wetting body: 2 ingredients) (HF-HCl waste liquid)
To the mixed powder for being mixed and made into NaF powder (A) and NaCl powder (B) according to ratio of components shown in following table 6
The water that 5 mass % are added in 100 mass %, is allowed to wet, and wet mixture is made, and uses hand punch (NPSystem
(strain) desktop laminating machine) load that applies face pressure 3.4t to it forms, compressed shape adult is made.Molding is in atmospheric pressure
After lower placement 24 hours or more, for verifying.Formed body at this time is the round ingot (14 × 14 × 1mm) of every 1 agreement that contracts a film or TV play to an actor or actress 1g
According to 1 weight of the compression forming body, waste liquid amount is adjusted, it is made to be calculated as H according to theoretical value2SiF650%
Remove equivalent, by above-mentioned formed body devote using in blender (MAGNESTER MGM-66) stirring (speed scale 3) it is useless
In liquid.Stirring after five minutes, is separated by solid-liquid separation it, which is supplied to the non-water droplet using potential difference titration outfit
The analysis of fixed and acid-base titration, finds out various composition.
In addition, the compression forming body that production contains only NaF is (identical as above-mentioned 2 component system's formed body at profile bar as comparative example
Part, same shape), it is made an addition in spent acid model liquid, it is anti-to be carried out with above-mentioned 2 ingredient compression forming body situation the same terms
It should and handle, have rated the removal rate and reactivity of fluosilicic acid.As a result it arranges as shown in table 6.
In addition, using 55% hydrofluoric acid (industrial, gloomy field in the preparation of spent acid model aqueous solution (waste liquid processed)
Chemical industry (strain)), 35% hydrochloric acid (industrial, xun, one of the Eight Diagrams synthesizes chemical (strain)), hexafluorosilicic acid (CICA level-one, Northeast chemistry
(strain)), the concentration being prepared as in table.
[table 6]
As shown in Table 6, compared with the compression forming body for containing only NaF, the fluosilicic acid removal rate of 2 ingredient compression forming bodies and anti-
Should rate greatly improve.
7 compression forming body of embodiment (compression forming methods of wetting body: 2 ingredients) (HF-HCl waste liquid)
To by NaF powder (A) and Na2CO3Powder (C) is according to the mixed powder that each ratio of components is mixed shown in following table 7
The water that 5 mass % are added in 100 mass % of body, is allowed to wet, wet mixture is made, use hand punch (NPSystem
(strain) desktop laminating machine) load that applies face pressure 3.4t to it forms, compressed shape adult is made.Molding is in atmospheric pressure
After lower placement 24 hours or more, for verifying.Formed body at this time is the round ingot (14 × 14 × 1mm) of every 1 agreement that contracts a film or TV play to an actor or actress 1g
According to 1 weight of the compression forming body, waste liquid amount is adjusted, it is made to be calculated as H according to theoretical value2SiF650%
Remove equivalent, by above-mentioned formed body devote using in blender (MAGNESTER MGM-66) stirring (speed scale 3) it is useless
In liquid.Stirring after five minutes, is separated by solid-liquid separation it, which is supplied to the non-water droplet using potential difference titration outfit
The analysis of fixed and acid-base titration, finds out various composition.
In addition, the compression forming body that production contains only NaF is (identical as above-mentioned 2 ingredient system's formed body at profile bar as comparative example
Part, same shape), it is made an addition in spent acid model liquid, it is anti-to be carried out with above-mentioned 2 component compression forming body situation the same terms
It should and handle, have rated the removal rate and reactivity of fluosilicic acid.As a result it arranges as shown in table 7.
In addition, using 55% hydrofluoric acid (industrial, gloomy field in the preparation of spent acid model aqueous solution (waste liquid processed)
Chemical industry (strain)), 35% hydrochloric acid (industrial, xun, one of the Eight Diagrams synthesizes chemical (strain)), hexafluorosilicic acid (CICA level-one, Northeast chemistry
(strain)), the concentration being prepared as in table.
[table 7]
As shown in Table 7, compared with the compression forming body for containing only NaF, the fluosilicic acid removal rate of 2 ingredient compression forming bodies and anti-
Should rate especially improve.
8 compression forming body of embodiment (compression forming methods: 3 ingredients) (HF-HNO3Waste liquid)
To by NaF powder, NaCl powder and Na2CO3Powder is according to NaF ︰ Na2NO3︰ Na2CO3The group of 37.5 ︰ 25 of=37.5 ︰
At the powder mixture than being mixed to get, face pressure is applied to it using hand punch (NPSystem (strain) desktop laminating machine)
The load of 3.4t is formed, and compression forming body is made.Formed body at this time be every 1 agreement that contracts a film or TV play to an actor or actress 1g round ingot (14 × 14 ×
1mm)。
According to 1 weight of the compression forming body, waste liquid amount is adjusted, it is made to be calculated as H according to theoretical value2SiF650%
Remove equivalent, by above-mentioned formed body devote using in blender (MAGNESTER MGM-66) stirring (speed scale 3) it is useless
In liquid.Stirring after five minutes, is separated by solid-liquid separation it, which is found out various composition using ion chromatography.
In addition, as comparative example, production contain only NaF compression forming body (with above-mentioned 3 ingredient system formed body same shape,
Phase homogenous quantities) and compression forming before mixing Na salt powder, NaF compression forming body is added into spent acid model liquid I, is compressed into
Mixing Na salt powder before type is added into spent acid model liquid II, is carried out with condition identical with above-mentioned compression forming body situation anti-
It should and handle, have rated the removal rate and reactivity of fluosilicic acid.As a result it is shown in table 8.
In addition, using the (industry of 55% hydrofluoric acid in the preparation of spent acid model aqueous solution I, II (waste liquid I, II processed)
With, gloomy field chemical industry (strain)), 42 ° of Baume nitric acid (the industrial emerging production in space portion), hexafluorosilicic acid (CICA level-one, Northeast chemistry
(strain)), the concentration being prepared as in table.
[table 8]
As shown in Table 8, when being added to liquid to be treated I, 3 ingredient compression forming bodies of embodiment 8 and the NaF of comparative example 5 are mono-
The compression forming body of ingredient is compared, and fluosilicic acid removal rate is especially improved with reactivity.
In addition, it is thus identified that compared with the result when mixed powder for being added to comparative example 6 when being added to liquid to be treated II,
Removal rate and removal efficiency are higher, it is known that even if effect same or even above when processing and forming is still available and powder adds.
In addition, knowing that dispersing for droplet of the compression forming body in reaction is few.
9 compression forming body of embodiment (compression forming methods: 3 ingredients) (HF-H2SO4Waste liquid)
To by KF powder, K2SO4Powder and K2CO3Powder is according to KF ︰ K2SO4︰ K2CO3The ratio of components of 46 ︰ 25 of=29 ︰ mixes
Obtained powder mixture applies face pressure 3.4t to it using hand punch (NPSystem (strain) desktop laminating machine) and bears
Lotus is formed, and compression forming body is made.Formed body at this time is the round ingot (14 × 14 × 1mm) of every 1 agreement that contracts a film or TV play to an actor or actress 1g.
According to 1 weight of the compression forming body, waste liquid amount is adjusted, it is made to be calculated as H according to theoretical value2SiF650%
Remove equivalent, by above-mentioned formed body devote using in blender (MAGNESTER MGM-66) stirring (speed scale 3) it is useless
In liquid.After stirring 2.5 minutes, it is separated by solid-liquid separation, which is supplied to titrimetry, finds out various composition.
In addition, as comparative example, production and above-mentioned compression forming body it is same form, the mixed powder of same quality and only
The compression forming body of same quality containing KF, is added in waste liquid, when with above-mentioned compression forming body identical condition into
Row reaction and processing, have rated the removal rate and reactivity of fluosilicic acid.As a result it is shown in table 9.
In addition, using 55% hydrofluoric acid (industrial, gloomy field in spent acid model aqueous solution (waste liquid processed) preparation
Learn industrial (strain)), 50 ° of Baume sulfuric acid (industrial Northeast electrochemical industry (strain)), hexafluorosilicic acid (CICA level-one, Northeast chemistry
(strain)), the concentration being prepared as in table.
[table 9]
As shown in Table 9,3 ingredient compression forming bodies are compared with the compression forming body for containing only KF one pack system of comparative example 7, fluorine silicon
Sour removal rate and reactivity improve.In addition, also confirming removal rate compared with result when adding the mixed powder of comparative example 8
Higher, even if carrying out processing and forming, superior fluosilicic acid removes effect when can still obtain than addition powder.In addition, know with
Mixed powder is compared, and droplet of the compression forming body in reaction disperses few.
Claims (24)
1. a kind of formed body containing alkali metal salt, it is characterised in that:
Containing alkali metal salt A and at least one of alkali metal salt B and alkali metal salt C,
(1) the alkali metal salt A be selected from least one of sodium fluoride and two sodium bifluorides,
(2) the alkali metal salt B is sodium salt of the solubility in 20 DEG C of water in 10g/100ml or more,
(3) the alkali metal salt C be selected from least one of sodium carbonate and sodium bicarbonate,
(4) content of the alkali metal salt A is in every 100 mass % of the solid state component of the formed body containing alkali metal salt
For 10 mass % or more and 99 mass % or less；The content of the alkali metal salt B is in the formed body containing alkali metal salt
It is 0 mass % or more and 85 mass % or less in every 100 mass % of solid state component；The content of the alkali metal salt C is described
It is 0 mass % or more and 60 mass % or less in every 100 mass % of the solid state component of formed body containing alkali metal salt；
The alkali metal salt B is the alkali metal salt except alkali metal salt included by alkali metal salt A and alkali metal salt C,
Also, content summation the consolidating in the formed body containing alkali metal salt of the alkali metal salt B and alkali metal salt C
It is 1 mass % or more in every 100 mass % of state ingredient,
The formed body containing alkali metal salt is by adding alkali gold into the acidic aqueous solution containing hydrofluoric acid and fluosilicic acid
Belong to salt and generates the sediment of alkali metal fluorosilicates, again and separating the sediment from the acidic aqueous solution to described
Acidic aqueous solution use in the method for regeneration treatment as the alkali metal salt.
2. the formed body as claimed in claim l containing alkali metal salt, it is characterised in that:
Metal salt B is selected from least one of sodium chloride, sodium sulphate, sodium bisulfate, sodium nitrate and sodium acetate.
3. as claimed in claim 1 or 2 containing the formed body of alkali metal salt, it is characterised in that:
(1) the alkali metal salt A be selected from least one of sodium fluoride and two sodium bifluorides,
(2) the alkali metal salt B be selected from least one of sodium chloride, sodium sulphate, sodium bisulfate, sodium nitrate and sodium acetate,
(3) the alkali metal salt C is selected from least one of sodium carbonate and sodium bicarbonate.
4. as claimed in claim 1 or 2 containing the formed body of alkali metal salt, it is characterised in that:
The content of the alkali metal salt A is in every 100 mass % of the solid state component of the formed body containing alkali metal salt
25 mass % or more and 98 mass % or less；Content the consolidating in the formed body containing alkali metal salt of the alkali metal salt B
It is 0 mass % or more and 60 mass % or less in every 100 mass % of state ingredient；The content of the alkali metal salt C contains described
Have in every 100 mass % of the solid state component of the formed body of alkali metal salt for 0 mass % or more and 50 mass % hereinafter,
Also, content summation the consolidating in the formed body containing alkali metal salt of the alkali metal salt B and alkali metal salt C
It is 2 mass % or more in every 100 mass % of state ingredient.
5. as claimed in claim 1 or 2 containing the formed body of alkali metal salt, it is characterised in that:
The content of the alkali metal salt A is in every 100 mass % of the solid state component of the formed body containing alkali metal salt
40 mass % or more and 98 mass % or less；Content the consolidating in the formed body containing alkali metal salt of the alkali metal salt B
It is 2 mass % or more and 60 mass % or less in every 100 mass % of state ingredient；The content of the alkali metal salt C contains described
Have in every 100 mass % of the solid state component of the formed body of alkali metal salt is 0 mass % more than or lower than 1 mass %.
6. as claimed in claim 1 or 2 containing the formed body of alkali metal salt, it is characterised in that:
The content of the alkali metal salt A is in every 100 mass % of the solid state component of the formed body containing alkali metal salt
50 mass % or more and 98 mass % or less；Content the consolidating in the formed body containing alkali metal salt of the alkali metal salt B
It is 0 mass % in every 100 mass % of state ingredient more than or lower than 1 mass %；The content of the alkali metal salt C contains described
It is 2 mass % or more and 50 mass % or less in every 100 mass % of the solid state component of the formed body of alkali metal salt.
7. as claimed in claim 1 or 2 containing the formed body of alkali metal salt, it is characterised in that:
It is the mixing containing at least one of the alkali metal salt A and alkali metal salt B and alkali metal salt C
The compression forming object of object.
8. as claimed in claim 1 or 2 containing the formed body of alkali metal salt, it is characterised in that:
Its formed body and its hirudo leech for being selected from Aquo-composition, the Aquo-composition by containing the alkali metal salt A and
The mixture of at least one of the alkali metal salt B and alkali metal salt C is formed with water.
9. as claimed in claim 1 or 2 containing the formed body of alkali metal salt, it is characterised in that:
The formed body is granular, pellet, ingot shape, plate or clastic.
10. a kind of acidic aqueous solution regeneration method made containing hydrofluoric acid and fluosilicic acid, which is characterized in that including following processes
1 and 2:
Process 1: the formed body containing alkali metal salt is added in the acidic aqueous solution, is obtained containing alkali metal fluorosilicates
The process of the reaction solution of sediment, wherein the formed body containing alkali metal salt contains alkali metal salt A and alkali metal salt B
At least one of with alkali metal salt C,
(1) the alkali metal salt A be selected from least one of sodium fluoride, two sodium bifluorides, potassium fluoride and potassium hydride difluoride,
(2) the alkali metal salt B is that the solubility in 20 DEG C of water is molten in the sodium salt of 10g/100ml or more and 20 DEG C of water
Xie Du 10g/100ml or more at least one of sylvite,
(3) the alkali metal salt C be selected from least one of sodium carbonate, sodium bicarbonate, potassium carbonate and saleratus,
(4) content of the alkali metal salt A is in every 100 mass % of the solid state component of the formed body containing alkali metal salt
For 10 mass % or more and 99 mass % or less；The content of the alkali metal salt B is in the formed body containing alkali metal salt
It is 0 mass % or more and 85 mass % or less in every 100 mass % of solid state component；The content of the alkali metal salt C is described
It is 0 mass % or more and 60 mass % or less in every 100 mass % of the solid state component of formed body containing alkali metal salt；
The alkali metal salt B is the alkali metal salt except alkali metal salt included by alkali metal salt A and alkali metal salt C,
Also, content summation the consolidating in the formed body containing alkali metal salt of the alkali metal salt B and alkali metal salt C
It is 1 mass % or more in every 100 mass % of state ingredient；
Process 2: the process for separating the sediment from the obtained reaction solution of process l.
11. method as claimed in claim 10, it is characterised in that:
Alkali metal salt B is selected from sodium chloride, sodium sulphate, sodium bisulfate, sodium nitrate, sodium acetate, potassium chloride, potassium sulfate, hydrogen sulfate
At least one of potassium, potassium nitrate and potassium acetate.
12. method as claimed in claim 10, it is characterised in that:
The acidic aqueous solution contains the hydrochloric acid of 3 mass % or more.
13. method as claimed in claim 12, it is characterised in that:
In process 1, in the acidic aqueous solution add the formed body containing alkali metal salt, it is described containing alkali metal salt at
In type body, the alkali metal salt A is selected from least one of sodium fluoride and two sodium bifluorides.
14. method as claimed in claim 12, it is characterised in that:
In process 1, in the acidic aqueous solution add the formed body containing alkali metal salt, it is described containing alkali metal salt at
In type body,
(1) the alkali metal salt A be selected from least one of sodium fluoride and two sodium bifluorides,
(2) the alkali metal salt B be selected from least one of sodium chloride, sodium sulphate, sodium bisulfate, sodium nitrate and sodium acetate,
(3) the alkali metal salt C is selected from least one of sodium carbonate and sodium bicarbonate.
15. method as claimed in claim 10, it is characterised in that:
The acidic aqueous solution is not hydrochloric or content of hydrochloric acid is lower than 3 mass %.
16. method as claimed in claim 15, it is characterised in that:
In process 1, in the acidic aqueous solution add the formed body containing alkali metal salt, it is described containing alkali metal salt at
In type body, the alkali metal salt A is selected from least one of potassium fluoride and potassium hydride difluoride.
17. method as claimed in claim 15, it is characterised in that:
In process 1, in the acidic aqueous solution add the formed body containing alkali metal salt, it is described containing alkali metal salt at
In type body,
(1) the alkali metal salt A is at least one of potassium fluoride and potassium hydride difluoride；
(2) the alkali metal salt B is selected from least one of potassium chloride, potassium sulfate, potassium acid sulfate, potassium nitrate and potassium acetate；
(3) the alkali metal salt C is at least one of potassium carbonate and saleratus.
18. method as described in claim 10 or 11, it is characterised in that:
The content of the alkali metal salt A is in every 100 mass % of the solid state component of the formed body containing alkali metal salt
25 mass % or more and 98 mass % or less；Content the consolidating in the formed body containing alkali metal salt of the alkali metal salt B
It is 0 mass % or more and 60 mass % or less in every 100 mass % of state ingredient；The content of the alkali metal salt C contains described
Have in every 100 mass % of the solid state component of the formed body of alkali metal salt for 0 mass % or more and 50 mass % hereinafter,
Also, content summation the consolidating in the formed body containing alkali metal salt of the alkali metal salt B and alkali metal salt C
It is 2 mass % or more in every 100 mass % of state ingredient.
19. method as described in claim 10 or 11, it is characterised in that:
The content of the alkali metal salt A is in every 100 mass % of the solid state component of the formed body containing alkali metal salt
40 mass % or more and 98 mass % or less；Content the consolidating in the formed body containing alkali metal salt of the alkali metal salt B
It is 2 mass % or more and 60 mass % or less in every 100 mass % of state ingredient；The content of the alkali metal salt C contains described
Have in every 100 mass % of the solid state component of the formed body of alkali metal salt is 0 mass % more than or lower than 1 mass %.
20. method as described in claim 10 or 11, it is characterised in that:
The content of the alkali metal salt A is in every 100 mass % of the solid state component of the formed body containing alkali metal salt
50 mass % or more and 98 mass % or less；Content the consolidating in the formed body containing alkali metal salt of the alkali metal salt B
It is 0 mass % in every 100 mass % of state ingredient more than or lower than 1 mass %；The content of the alkali metal salt C contains described
It is 2 mass % or more and 50 mass % or less in every 100 mass % of the solid state component of the formed body of alkali metal salt.
21. method as described in claim 10 or 11, it is characterised in that:
The formed body containing alkali metal salt is to contain the alkali metal salt A and alkali metal salt B and the alkali metal
The compression forming object of the mixture of at least one of salt C.
22. method as described in claim 10 or 11, it is characterised in that:
The formed body containing alkali metal salt is formed body and its hirudo leech selected from Aquo-composition, the Aquo-composition
By mixture and water containing at least one of the alkali metal salt A and alkali metal salt B and alkali metal salt C
It is formed.
23. method as described in claim 10 or 11, it is characterised in that:
The formed body containing alkali metal salt is granular, pellet, ingot shape, plate or clastic.
24. method as described in claim 10 or 11, it is characterised in that:
Alkali metal salt A used in the formed body containing alkali metal salt be in sodium fluoride and two sodium bifluorides at least
One kind,
And alkali metal salt B is selected from least one of potassium fluoride and potassium hydride difluoride.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016074506 | 2016-04-01 | ||
| JP2016-074506 | 2016-04-01 | ||
| JP2016175974A JP6095837B1 (en) | 2016-04-01 | 2016-09-08 | Alkaline metal salt-containing molded body and method for regenerating acidic aqueous solution using the same |
| JP2016-175974 | 2016-09-08 | ||
| PCT/JP2017/007424 WO2017169428A1 (en) | 2016-04-01 | 2017-02-27 | Alkali metal salt-containing molded article and method for reprocessing aqueous acid solution using same |
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| Publication Number | Publication Date |
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| CN107614434A CN107614434A (en) | 2018-01-19 |
| CN107614434B true CN107614434B (en) | 2019-09-13 |
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| CN201780001367.7A Active CN107614434B (en) | 2016-04-01 | 2017-02-27 | The regeneration treating method of formed body containing alkali metal salt and the acidic aqueous solution using the formed body |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6095837B1 (en) |
| KR (1) | KR102031475B1 (en) |
| CN (1) | CN107614434B (en) |
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| WO (1) | WO2017169428A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4527329Y1 (en) * | 1966-03-01 | 1970-10-22 | ||
| US3969485A (en) * | 1971-10-28 | 1976-07-13 | Flemmert Goesta Lennart | Process for converting silicon-and-fluorine-containing waste gases into silicon dioxide and hydrogen fluoride |
| JPS63270310A (en) | 1987-04-27 | 1988-11-08 | Central Glass Co Ltd | Production of sodium fluoride pellet |
| US4981664A (en) * | 1988-04-14 | 1991-01-01 | International Minerals & Chemical Corporation | Method of production of high purity silica and ammonium fluoride |
| JPH07222927A (en) * | 1993-11-19 | 1995-08-22 | Ube Ind Ltd | Dimerization catalyst of lower alpha-olefin |
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| WO2017169428A1 (en) | 2017-10-05 |
| CN107614434A (en) | 2018-01-19 |
| KR20170131688A (en) | 2017-11-29 |
| JP6095837B1 (en) | 2017-03-15 |
| JP2017186221A (en) | 2017-10-12 |
| TW201736281A (en) | 2017-10-16 |
| KR102031475B1 (en) | 2019-10-11 |
| TWI742002B (en) | 2021-10-11 |
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