CN104495875A - Preparation method of sodium fluoride - Google Patents
Preparation method of sodium fluoride Download PDFInfo
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- CN104495875A CN104495875A CN201410700703.5A CN201410700703A CN104495875A CN 104495875 A CN104495875 A CN 104495875A CN 201410700703 A CN201410700703 A CN 201410700703A CN 104495875 A CN104495875 A CN 104495875A
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- fluoride
- sodium fluoride
- preparation
- sodium
- silicon
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Abstract
The invention provides a preparation method of sodium fluoride. The preparation method utilizes a silicon fluoride-containing gas product produced by albite decomposition and sodium hydroxide as raw materials to product sodium fluoride. The preparation method comprises the following steps that the silicon fluoride-containing gas product is fed into an absorbing tower and is hydrolyzed to produce a fluosilicic acid solution, the fluosilicic acid solution is put into a reactor and reacts with added sodium hydroxide to produce sodium fluoride, sodium hydroxide is added into the reactor until the solution pH value in the reactor is greater than or equal to 10, and sodium fluoride crystals are precipitated, then are filtered and then are dried to form sodium fluoride finished products. The preparation method has the advantages of simple processes, low energy consumption, small environmental pollution and good application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of Sodium Fluoride, particularly relate to a kind of method utilizing albite to prepare Sodium Fluoride.
Background technology
Sodium Fluoride is a kind of important fluoride salt, is the raw material manufacturing other fluorochemicals.Sodium Fluoride tool has been widely used: be mainly used in the edge steel of mechanical bit and planing tool to strengthen welding strength; Secondly wood preservative, Brewing industry sterilant is used as, the fluorine treatment agent of agricultural insecticide, medical sanitas, welding fusing assistant, drinking-water; Also for the production of other fluorochemicals and casein glue, Sodium Fluoride toothpaste, and cakingagent, papermaking and metallurgy industry; In element fluorine is produced, for removing micro-hydrogen fluoride.In addition, also for the industry such as enamel and pharmacy.
Tradition Sodium Fluoride production method is: the Sodium Silicofluoride of 99% and the soda ash of excessive 5 ~ 8% are 8 ~ 9 in pH value, and temperature is 84 DEG C ~ 95 DEG C, and pressure is react 160 ~ 180 minutes obtained Sodium Fluorides under the condition of 0.15MPa.This technique needs High Temperature High Pressure, and loss is large, dangerous large.Simultaneously with the higher Sodium Silicofluoride of purity for raw material, cost is higher.
Summary of the invention
By Given this, the necessary a kind of preparation method of Sodium Fluoride that provides of the present invention is to solve the problems of the technologies described above.
A preparation method for Sodium Fluoride, comprises the following steps:
Albite decomposes: by albite, fluorite, 98% sulfuric acid according to 1: (1.55 ~ 2.57): the mass ratio mixing of (3.28 ~ 4.62), and under 100 DEG C ~ 200 DEG C and autogenous pressure, be obtained by reacting the solid residue containing calcium sulfate, sodium sulfate and Tai-Ace S 150 and the gaseous products containing silicon fluoride;
Silicon fluoride is hydrolyzed: be hydrolyzed to the silicon fluoride in described gaseous products, obtain the hydrolysate containing silicate fluoride solution;
Preparation contains the slurry of Sodium Fluoride and silicon-dioxide: described hydrolysate is placed in reactor, in described reactor, add that temperature is 85 DEG C ~ 100 DEG C, mass percentage concentration is the sodium hydroxide solution of 25% ~ 55%, and the solution stirred in described reactor makes the pH value of described solution reduce to 8 ~ 9 in 10 minutes ~ 20 minutes, obtains the slurry containing Sodium Fluoride and silicon-dioxide;
Be separated Sodium Fluoride: continue to add in described reactor pH value >=10 that described sodium hydroxide solution makes in described reactor, and within 25 minutes ~ 35 minutes, separate out Sodium Fluoride crystal at 95 DEG C ~ 100 DEG C constant temperature, filter also dry described Sodium Fluoride crystal of separating out and obtain Sodium Fluoride finished product.
Based on the preparation method of above-mentioned Sodium Fluoride, the step that described albite decomposes comprises elder generation and preheat 15 minutes ~ 30 minutes to described albite and fluorite at 100 DEG C ~ 200 DEG C, and the moisture in removing raw material, obtains dry albite and fluorite raw material; Again the sulfuric acid of described 98% is joined in the albite of described drying and fluorite raw material and react the solid residue obtained for 2 hours ~ 5 hours containing calcium sulfate, sodium sulfate and Tai-Ace S 150 and the gaseous products containing silicon fluoride.In this step, described temperature of reaction can be 100 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, is preferably 120 DEG C ~ 200 DEG C; The described reaction times is preferably 2.5 hours ~ 4 hours.
Based on the preparation method of above-mentioned Sodium Fluoride, the step of described silicon fluoride hydrolysis comprises: adopt dust removal filter to filter the described gaseous products containing silicon fluoride; Led to successively by gaseous products after described filtration in I and II absorption tower, silicon fluoride hydrolysis obtains the hydrolysate comprising concentrated phase thing and silicate fluoride solution.
Particularly, described gaseous products enters in one-level concentrated phase receiving tank after the absorption liquid absorption in described first grade absorption tower, hydrolysis, the concentrated phase thing that described one-level concentrated phase receiving tank is collected is transported in Sodium Fluoride reactor and reacts, wherein, the absorption liquid in described first grade absorption tower is the aqueous ethanolic solution of 10 ~ 30%; The liquid flooding that described one-level concentrated phase receiving tank is collected, to first order absorption circulation groove, is returned in described first grade absorption tower through pump and is continued to absorb; Enter the absorption liquid of described two-level absorption tower in described two-level absorption tower by described first grade absorption tower tail gas out to absorb, continue hydrolysis, liquid after described two-level absorption tower hydrolysis enters secondary concentrated phase absorption cell, the concentrated phase thing that described secondary concentrated phase absorption cell is collected is transported in described Sodium Fluoride reactor and reacts, wherein, the absorption liquid in described two-level absorption tower is the aqueous ethanolic solution of 10 ~ 30%; The liquid flooding that described secondary concentrated phase receiving tank is collected, to secondary absorption cycle groove, is returned in described two-level absorption tower through pump and is continued to absorb; When the fluorinion concentration detected in the described silicate fluoride solution in described first order absorption circulation groove, described secondary absorption cycle groove reaches 10mol/L, hydrolyzed solution reaches capacity, and is transported in described Sodium Fluoride reactor by described hydrolyzed solution and reacts.
Based on the preparation method of above-mentioned Sodium Fluoride, described preparation contains in the slurry process of Sodium Fluoride and silicon-dioxide, and the mass percentage concentration of described sodium hydroxide solution is 30% ~ 45%.
Based on the preparation method of above-mentioned Sodium Fluoride, described preparation contains in the slurry process of Sodium Fluoride and silicon-dioxide, and the time that the solution stirred in described reactor makes the pH value of described solution reduce to 8 ~ 9 is 15 minutes.
Based on the preparation method of above-mentioned Sodium Fluoride, the process of described separation Sodium Fluoride comprises further: reclaim the filtrate after the described Sodium Fluoride crystal filtering described precipitation for the preparation of water glass.
Compared with prior art, the silicon fluoride gas generation silicofluoric acid that the present invention mainly utilizes the decomposition of albite to discharge, and utilize silicofluoric acid and sodium hydroxide to react at ambient pressure to prepare Sodium Fluoride crystal; Filtrate after the present invention can also reclaim the described Sodium Fluoride crystal filtering described precipitation is used as water glass, so, the preparation method of Sodium Fluoride provided by the invention achieves the comprehensive utilization of albite, reduce the quantity discharged of fluorine element, there is good application prospect, but also reclaim byproduct as water glass, meet continuable development principle; In addition, the temperature of reaction of the technique of decomposition albite provided by the invention is at 100 DEG C ~ 200 DEG C, and reaction conditions is gentle, lower to the requirement of equipment, can reduce the consumption of raw material, and reduce production cost, comprehensive utilization degree is high, technique is advanced, economically feasible.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
A preparation method for Sodium Fluoride, comprises the following steps:
Albite decomposes: first albite and fluorite are preheated about 30 minutes at 100 DEG C, the sulfuric acid adding 98% again makes three react 5 hours under 100 DEG C and autogenous pressure, obtain the solid residue containing calcium sulfate, sodium sulfate and Tai-Ace S 150 and the gaseous products containing silicon fluoride, wherein, albite, fluorite, 98% the mass ratio of sulfuric acid be 1:1.55:3.28, reaction principle is:
CaF
2+ H
2SO
4= 2HF + CaSO
4
2NaAlSi
3O
8+ 24HF + 4H
2SO
4= Na
2SO
4+ Al
2(SO
4)
3+ 6SiF
4↑ + 16H
2O
Prepare silicate fluoride solution: the above-mentioned gaseous products containing silicon fluoride is introduced dedusting in dust removal filter; Gas after dust removal and filtration passes in first grade absorption tower and enters in one-level concentrated phase receiving tank after the absorption liquid absorption in described first grade absorption tower, hydrolysis, the concentrated phase thing that described one-level concentrated phase receiving tank is collected is transported in reactor and reacts, wherein, silicon fluoride hydrolysis principle is: 3SiF
4+ 2H
2o=2H
2siF
6+ SiO
2↓; The liquid flooding that described one-level concentrated phase receiving tank is collected, to first order absorption circulation groove, is returned in described first grade absorption tower through pump and is continued to absorb; Enter the absorption liquid of two-level absorption tower in described two-level absorption tower by described first grade absorption tower tail gas out to absorb, continue hydrolysis, liquid after described two-level absorption tower hydrolysis enters secondary concentrated phase absorption cell, and the concentrated phase thing that described secondary concentrated phase absorption cell is collected is transported in described Sodium Fluoride reactor and reacts; The liquid flooding that described secondary concentrated phase receiving tank is collected, to secondary absorption cycle groove, is returned in described two-level absorption tower through pump and is continued to absorb; When the fluorinion concentration detected in the silicate fluoride solution in described first order absorption circulation groove, described secondary absorption cycle groove reaches 10mol/L, hydrolyzed solution reaches capacity, described hydrolyzed solution is transported in described Sodium Fluoride reactor and reacts, wherein, the concentration of the absorption liquid in described I and II absorption tower is the aqueous ethanolic solution of about 20%;
Preparation contains the slurry of Sodium Fluoride and silicon-dioxide: the hydrolyzed solution comprising concentrated phase thing and silicate fluoride solution is placed in described reactor, add in described reactor temperature be 85 DEG C, mass percentage concentration is the sodium hydroxide solution of 25%, the solution stirred in described reactor made the pH value of described solution reduce to 8.2 in 20 minutes, obtain the slurry containing Sodium Fluoride and silicon-dioxide, reaction principle is:
H
2SiF
6+ 2NaOH ＝ Na
2SiF
6↓ + 2H
2O，
Na
2SiF
6+ 4NaOH ＝ 6NaF + SiO
2↓ + 2H
2O；
Be separated Sodium Fluoride: continue in described reactor, add described sodium hydroxide solution and make the pH value in described reactor rise to 10.1, then within 35 minutes, separate out Sodium Fluoride crystal at 95 DEG C of constant temperature, filter also dry described Sodium Fluoride crystal of separating out and obtain Sodium Fluoride finished product; The filtrate of filtering after simultaneously reclaiming after the described Sodium Fluoride crystal of described precipitation is used as water glass.
Embodiment 2
A preparation method for Sodium Fluoride, comprises the following steps:
Albite decomposes: the embodiment of this step of the present embodiment is substantially identical with the embodiment that the albite in embodiment 1 decomposes, and difference is: pre-warmed temperature is 150 DEG C, and the pre-warmed time is 20 minutes; The temperature of reaction is 150 DEG C, and the time of reaction is 3.5 hours; Wherein, albite, fluorite, 98% the mass ratio of sulfuric acid be 1:2:4;
Prepare silicate fluoride solution: the embodiment of this step of the present embodiment is identical with the embodiment preparing silicate fluoride solution in embodiment 1;
The slurry of preparation containing Sodium Fluoride and silicon-dioxide: it is substantially identical with the embodiment of the slurry of silicon-dioxide that embodiment and the preparation in embodiment 1 of this step of the present embodiment contain Sodium Fluoride, and difference is: the temperature of described Strong oxdiative sodium solution is 90 DEG C, mass percentage concentration is 40%; In described reactor, the pH value of solution reduced to 8.5 in 15 minutes;
Be separated Sodium Fluoride: the embodiment of this step of the present embodiment is substantially identical with the embodiment being separated the step of Sodium Fluoride in embodiment 1, and difference is: the pH value in reactor rises to 12, then 100 DEG C of constant temperature 25 minutes.
Embodiment 3
A preparation method for Sodium Fluoride, comprises the following steps:
Albite decomposes: the embodiment of this step of the present embodiment is substantially identical with the embodiment that the albite in embodiment 1 decomposes, and difference is: pre-warmed temperature is 200 DEG C, and the pre-warmed time is 15 minutes; The temperature of reaction is 200 DEG C, and the time of reaction is 2 hours, and albite, fluorite, 98% the mass ratio of sulfuric acid be 1:2.5:4.6;
Prepare silicate fluoride solution: the embodiment of this step of the present embodiment is identical with the embodiment preparing silicate fluoride solution in embodiment 1;
The slurry of preparation containing Sodium Fluoride and silicon-dioxide: it is substantially identical with the embodiment of the slurry of silicon-dioxide that embodiment and the preparation in embodiment 1 of this step of the present embodiment contain Sodium Fluoride, and difference is: the temperature of described Strong oxdiative sodium solution is 100 DEG C, mass percentage concentration is 55%; In described reactor, the pH value of solution reduced to 9 in 10 minutes;
Be separated Sodium Fluoride: the embodiment of this step of the present embodiment is substantially identical with the embodiment being separated the step of Sodium Fluoride in embodiment 1, and difference is: the pH value in reactor rises to 13, then 100 DEG C of constant temperature 30 minutes.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the field are to be understood that: still can modify to the specific embodiment of the present invention or carry out equivalent replacement to portion of techniques feature; And not departing from the spirit of technical solution of the present invention, it all should be encompassed in the middle of the technical scheme scope of request of the present invention protection.
Claims (6)
1. a preparation method for Sodium Fluoride, comprises the following steps:
Albite decomposes: by albite, fluorite, 98% sulfuric acid according to 1: (1.55 ~ 2.57): the mass ratio mixing of (3.28 ~ 4.62), and under 100 DEG C ~ 200 DEG C and autogenous pressure, be obtained by reacting the solid residue containing calcium sulfate, sodium sulfate and Tai-Ace S 150 and the gaseous products containing silicon fluoride;
Silicon fluoride is hydrolyzed: be hydrolyzed to the silicon fluoride in described gaseous products, obtain the hydrolysate containing silicate fluoride solution;
Preparation contains the slurry of Sodium Fluoride and silicon-dioxide: described hydrolysate is placed in reactor, in described reactor, add that temperature is 85 DEG C ~ 100 DEG C, mass percentage concentration is the sodium hydroxide solution of 25% ~ 55%, and the solution stirred in described reactor makes the pH value of described solution reduce to 8 ~ 9 in 10 minutes ~ 20 minutes, obtains the slurry containing Sodium Fluoride and silicon-dioxide;
Be separated Sodium Fluoride: continue to add in described reactor pH value >=10 that described sodium hydroxide solution makes in described reactor, and within 25 minutes ~ 35 minutes, separate out Sodium Fluoride crystal at 95 DEG C ~ 100 DEG C constant temperature, filter also dry described Sodium Fluoride crystal of separating out and obtain Sodium Fluoride finished product.
2. the preparation method of Sodium Fluoride according to claim 1, it is characterized in that: the step that described albite decomposes comprises elder generation and preheat 15 minutes ~ 30 minutes to described albite and fluorite at 100 DEG C ~ 200 DEG C, moisture in removing raw material, obtains dry albite and fluorite raw material; Again the sulfuric acid of described 98% is joined reaction in the albite of described drying and fluorite raw material and within 2 hours ~ 5 hours, obtain described solid residue containing calcium sulfate, sodium sulfate and Tai-Ace S 150 and the described gaseous products containing silicon fluoride.
3. the preparation method of Sodium Fluoride according to claim 1, is characterized in that: the step of described silicon fluoride hydrolysis comprises: adopt dust removal filter to filter the described gaseous products containing silicon fluoride; Led to successively by gaseous products after described filtration in I and II absorption tower, silicon fluoride hydrolysis obtains the hydrolysate comprising concentrated phase thing and silicate fluoride solution.
4. the preparation method of the Sodium Fluoride according to any one of claims 1 to 3, is characterized in that: described preparation contains in the slurry process of Sodium Fluoride and silicon-dioxide, and the mass percentage concentration of described sodium hydroxide solution is 30% ~ 45%.
5. the preparation method of Sodium Fluoride according to claim 4, is characterized in that: described preparation contains in the slurry process of Sodium Fluoride and silicon-dioxide, and the time that the solution stirred in described reactor makes the pH value of described solution reduce to 8 ~ 9 is 15 minutes.
6. the preparation method of Sodium Fluoride according to claim 1, is characterized in that: the process of described separation Sodium Fluoride comprises: reclaim the filtrate after the described Sodium Fluoride crystal filtering described precipitation for the preparation of water glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410700703.5A CN104495875A (en) | 2014-11-28 | 2014-11-28 | Preparation method of sodium fluoride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410700703.5A CN104495875A (en) | 2014-11-28 | 2014-11-28 | Preparation method of sodium fluoride |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698479A (en) * | 2017-01-24 | 2017-05-24 | 陈可 | Non-aqueous complete-dissolution refining method of sodium fluoride containing organic impurities |
| CN107032371A (en) * | 2017-02-28 | 2017-08-11 | 河北科技大学 | A kind of method that potassium fluoride is prepared by raw material of fluorite |
| CN112725642A (en) * | 2020-12-18 | 2021-04-30 | 四川省乐山锐丰冶金有限公司 | Method for recycling sodium hydroxide and co-producing sodium fluoride from fluorine carbon cerium alkali conversion process |
| CN114956071A (en) * | 2022-07-12 | 2022-08-30 | 鞍山市五色石新材料科技有限公司 | Graphite ore purification method capable of recycling fluorine element |
-
2014
- 2014-11-28 CN CN201410700703.5A patent/CN104495875A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698479A (en) * | 2017-01-24 | 2017-05-24 | 陈可 | Non-aqueous complete-dissolution refining method of sodium fluoride containing organic impurities |
| CN106698479B (en) * | 2017-01-24 | 2017-12-12 | 陈一可 | The non-aqueous complete molten process for purification of sodium fluoride containing organic impurities |
| CN107032371A (en) * | 2017-02-28 | 2017-08-11 | 河北科技大学 | A kind of method that potassium fluoride is prepared by raw material of fluorite |
| CN112725642A (en) * | 2020-12-18 | 2021-04-30 | 四川省乐山锐丰冶金有限公司 | Method for recycling sodium hydroxide and co-producing sodium fluoride from fluorine carbon cerium alkali conversion process |
| CN114956071A (en) * | 2022-07-12 | 2022-08-30 | 鞍山市五色石新材料科技有限公司 | Graphite ore purification method capable of recycling fluorine element |
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Application publication date: 20150408 |
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