CN101391793A - Method for preparing kryocide - Google Patents
Method for preparing kryocide Download PDFInfo
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- CN101391793A CN101391793A CNA2008101434996A CN200810143499A CN101391793A CN 101391793 A CN101391793 A CN 101391793A CN A2008101434996 A CNA2008101434996 A CN A2008101434996A CN 200810143499 A CN200810143499 A CN 200810143499A CN 101391793 A CN101391793 A CN 101391793A
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- fluoride
- sodium
- aluminum
- aluminum fluoride
- cryolite
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Abstract
The invention relates to a method for preparing cryolite, comprising the following steps: fluosilicic acid reacts with aluminum salt so as to prepare aluminum fluoride solution and then phosphorus removal treatment is conducted; and finally cryolite is obtained when the prepared aluminum fluoride solution reacts with solid sodium fluoride. The invention mainly uses a technical proposal in which the fluosilicic acid reacts with the aluminum salt so as to prepare the aluminum fluoride solution and then phosphorus removal treatment is carried out, and later the prepared aluminum fluoride solution reacts with solid sodium fluoride for generating cryolite; the technical proposal overcomes the disadvantages that the cryolite preparation process with a traditional fluoride aluminum acid method has diluted concentration of sodium fluoride, tremendous logistics amount, high energy consumption, low equipment capacity and the like. The prepared cryolite can be used as the flux for electrolytic aluminum smelting, the wear-resistant filler of rubber and grinding wheel, the brightener of enamel, the flux of metal and the like.
Description
Technical field
The present invention relates to a kind of method of sodium aluminum fluoride preparation, this method can utilize phosphate fertilizer byproduct silicofluoric acid to prepare sodium aluminum fluoride.
Technical background
The chemical name of sodium aluminum fluoride is a sodium fluoroaluminate, and molecular formula is Na
3AlF
6Sodium aluminum fluoride has natural and artificial branch.At industrial main flux, the wear-resistant filler of rubber, emery wheel, enamelled whitening agent, the flux of metal etc. as electrolytic aluminum smelting.The traditional technology of sodium aluminum fluoride production is a hydrofluoaluminic acid soda ash method, and clay bittern method, Sodium Silicofluoride method etc. are arranged in addition.
The reaction formula of traditional technology hydrofluoaluminic acid soda ash method is:
This technology is traditional classical technology, and technology is very ripe, and main raw material is to use hydrofluoric acid, because hydrofluoric acid costs an arm and a leg product cost height, Market competition.
Having reported a kind of among the US:3656894 is the method that raw material is produced sodium aluminum fluoride with phosphate fertilizer industry byproduct Sodium Silicofluoride.Its reaction formula is as follows:
This technology can be utilized the byproduct Sodium Silicofluoride of phosphate fertilizer industry, helps comprehensive utilization of resources and environment protection.But because this technology can only make the mixing solutions of fluorinated sodium, and Sodium Fluoride solubleness is little, in the reaction process logistics huge, the energy consumption height, equipment capacity is low.Other has report, and the reaction of available silicofluoric acid and soda ash makes Fluorinse, makes sodium aluminum fluoride with the aluminun fluoride solution reaction, and this technology can only be used the lower silicofluoric acid of phosphorus content, uses that phosphorus can not be up to standard in the high phosphorated silicofluoric acid product.This technology also exists because Fluorinse concentration is rare, and logistics capacity is huge, energy consumption height, the shortcoming that equipment capacity is low.
In addition, the patent No. is 200410027054.3 disclosures, make hydrofluoaluminic acid solution with silicofluoric acid and clay pit reaction, make sodium aluminum fluoride with the bittern reaction again, this technology can only be used the lower silicofluoric acid of phosphorus content equally, uses that phosphorus can not be up to standard in the high phosphorated silicofluoric acid product, and this worker's raw materials technology utilization ratio is low, produce a large amount of abraum salt acid in the reaction process, environmental pollution is serious.
Summary of the invention
At above-mentioned situation, the method that the purpose of this invention is to provide a kind of sodium aluminum fluoride preparation, it is the feedstock production sodium aluminum fluoride with silicofluoric acid, aluminium salt, Sodium Fluoride, and its raw material silicofluoric acid is from the byproduct of phosphate fertilizer, and clay pit and bauxite resource be abundant and cheap, be easy to get.
For achieving the above object, technical scheme of the present invention:
A kind of method of sodium aluminum fluoride preparation, it is a raw material with silicofluoric acid, aluminium salt, Sodium Fluoride, makes aluminun fluoride solution and carries out the dephosphorization processing with silicofluoric acid and aluminium reactant salt, with aluminun fluoride solution and the Sodium Fluoride reaction that makes, Sodium Fluoride adds with solid form, the chemical equation of its synthetic cryolite as:
For achieving the above object, further measure of the present invention is:
Described aluminium salt is clay pit, bauxite or aluminium hydroxide.The mol ratio of described silicofluoric acid and aluminium salt (representing with aluminum oxide) is: H
2SiF
6: Al
2O
31:0.6～1.6.The mol ratio of described aluminum fluoride and Sodium Fluoride is: AlF
3: NaF 1:0.85～3.35.The temperature of reaction of described silicofluoric acid and aluminium salt is 50～115 ℃.The temperature of reaction of described aluminum fluoride and Sodium Fluoride is 60～110 ℃.The concentration of described silicofluoric acid is at 50-400g/L, SiO in the Sodium Fluoride
2＜1.5%.
The present invention mainly adopts silicofluoric acid and aluminium reactant salt to make aluminun fluoride solution and carries out dephosphorization and handle, the synthetic technical scheme of producing sodium aluminum fluoride of Sodium Fluoride reaction that the aluminun fluoride solution that makes and solid form are added again, overcome the product preparation cost height that traditional hydrofluoaluminic acid method sodium aluminum fluoride preparation technology exists, market competitiveness difference and Sodium Silicofluoride are that the Fluorinse concentration that exists of the method for feedstock production sodium aluminum fluoride is rare, logistics capacity is huge, the energy consumption height, defective such as equipment capacity is low.
The beneficial effect that the present invention is produced compared to existing technology:
The sodium aluminum fluoride of I, the present invention's preparation, it adopts silicofluoric acid to substitute more expensive hydrofluoric acid, and clay pit and bauxite source are abundant and cheap, production cost is low, regional available hydrogen aluminum oxide at no clay pit and bauxite substitutes, and enlarges subject range of the present invention, and economic benefit is obvious.II, the present invention substitute Fluorinse with the Sodium Fluoride that solid form adds, and have significantly reduced the mother liquor amount, cut down the consumption of energy, and raise labour productivity.Increase the dephosphorization step among III, the preparation technology of the present invention, can handle some high phosphorated silicofluoric acid, enlarged the purposes of silicofluoric acid.IV, technical process of the present invention weak point are convenient to production control.V, technology of the present invention can also be produced the sodium aluminum fluoride of high, medium and low molecular ratio, can satisfy different clients' demand.The slag that produces in VI, the present invention's preparation can be used as the raw material of producing cement, adopt the silica gel of production of aluminum hydroxide to can be used as the raw material of producing water glass, the waste water of production can be used as absorption silicofluoric acid, recycle after treatment, carry out zero release, the present invention does not have influence to environment.
The present invention is fit to the flux of the sodium aluminum fluoride of preparation as electrolytic aluminum smelting, the wear-resistant filler of rubber, emery wheel, enamelled whitening agent, the flux of metal etc.
Embodiment
A kind of method of sodium aluminum fluoride preparation, its concrete processing step is as follows:
1, mix by a certain percentage with phosphate fertilizer byproduct silicofluoric acid and aluminium salt (clay pit, bauxite, aluminium hydroxide) earlier, its ratio is (Al in silicofluoric acid and the aluminium salt
2O
3Mol ratio be 1:0.6～1.6), silicofluoric acid concentration is 50-400g/L, temperature is controlled at 60-110 ℃, reaction 1h in the reactive tank (Φ 2000*2500, anticorrosion PVC material) that band stirs.
2, add dephosphorization agent in reactive tank, dephosphorization agent is a molysite, by with silicofluoric acid in P
2O
5Proportioning is carried out in mol ratio 1:0.9～1.3, reacted again 10-60 minute, and through the dephosphorization step, the requirement that is up to state standards of the finished product phosphorus content.Reaction end is a terminal point with the requirement that foreign matter content in the analytical solution reaches regulation.
2, Fan Ying slip obtains aluminun fluoride solution by filtration.
3, (aluminum fluoride and Sodium Fluoride mol ratio are: AlF for aluminun fluoride solution and Sodium Fluoride solid
3: NaF1:0.85～3.35) synthetic at reactor, owing to adopt the Sodium Fluoride solid, the resulting solution volume is less than US:3656894 greatly, reduces logistics capacity and energy expenditure.Temperature is controlled at 60-110 ℃.Building-up reactions is carried out with intermittent type, also can carry out continuously.Slip adopts vacuum filtration, also can adopt the method for press filtration or centrifuging.The dry air stream drying that adopts also can adopt rotary kiln drying.
Each embodiment is as follows:
Embodiment 1
The concrete processing step of method of producing sodium aluminum fluoride with hydrogen silicic acid, aluminium hydroxide, Sodium Fluoride is as follows:
A, silicofluoric acid concentration 50g/L, volume 12m
3, 650 kilograms in aluminium hydroxide, silicofluoric acid and aluminium hydroxide is H in molar ratio
2SiF
6: Al (OH)
31:1 prepares burden, and in reactive tank silicofluoric acid is warming up to 50 ℃, adds aluminium hydroxide and starts stirring, reaction 1h.
B, in above-mentioned mixed solution, add dephosphorization agent, stirred 10 minutes.
C, obtain aluminun fluoride solution by filtration.
D, Sodium Fluoride and aluminum fluoride be the 2:1 proportioning in molar ratio, and 670 kilograms of stirrings of solid Sodium Fluoride add down in the aluminun fluoride solution, and synthesis temperature keeps 90 ℃, and stirring reaction 1h obtains cryolite slurry.
E, cryolite slurry obtain ointment and filtrate through vacuum filtration; Ointment adopts air-flow expansion drying method drying; Obtain the sodium aluminum fluoride product, meet standard GB/T4291-1999.Calculate by analysis, the sodium aluminum fluoride product yield reaches 95.9%.
Embodiment 2
Embodiment 2 is identical with embodiment 1 operation steps, its difference:
Silicofluoric acid concentration is 400g/L among the step a, and aluminium hydroxide is 380 kilograms; Silicofluoric acid is warming up to 110 ℃.
Sodium Fluoride is 390 kilograms among the step c.
The steps d synthesis temperature is 110 ℃.
As calculated, product yield reaches 94.8%.
Embodiment 3
Embodiment 3 is identical with embodiment 1 operation steps, difference:
Silicofluoric acid concentration is 320g/L among the step a, and aluminium hydroxide is 1730 kilograms.
Sodium Fluoride is 1780 kilograms among the step c.
As calculated, product yield reaches 95.8%.
Embodiment 4
Embodiment 4 is identical with embodiment 1 operation steps, difference:
Synthesis temperature is 60 ℃ among the step c.
Calculate by analysis, the sodium aluminum fluoride product yield reaches 95.9%.
Embodiment 5
Embodiment 5 is identical with embodiment 1 operation steps, difference:
Aluminum fluoride and Sodium Fluoride 1:3.35 proportioning in molar ratio among the step c, 940 kilograms of Sodium Fluorides.
As calculated, product yield reaches 95.0%.
Embodiment 6
Embodiment 6 is identical with embodiment 1 operation steps, difference:
Aluminum fluoride and Sodium Fluoride 1:0.85 proportioning in molar ratio among the step c, 503 kilograms of Sodium Fluorides.
Calculate by analysis, the sodium aluminum fluoride product yield reaches 95.5%.
Embodiment 7
Embodiment 7 is identical with embodiment 1 operation steps, difference:
With bauxite instead of hydrogen aluminum oxide, bauxite is 945 kilograms among the step a.
Calculate by analysis, the sodium aluminum fluoride product yield reaches 94.5%.
Embodiment 8
Embodiment 8 is identical with embodiment 1 operation steps, difference:
With clay pit instead of hydrogen aluminum oxide, clay pit is 2500 kilograms among the step a.
Calculate by analysis, the sodium aluminum fluoride product yield reaches 94.4%.
Below only be preferred embodiment of the present invention, according to above-mentioned design of the present invention, those skilled in the art also can make various modifications and conversion to this.For example, the modification of the removal of impurities of the solid of Sodium Fluoride adding mode, aluminun fluoride solution and conversion etc.Yet similar this conversion and modification all belong to essence of the present invention.
Claims (7)
1, a kind of method of sodium aluminum fluoride preparation, it is a raw material with silicofluoric acid, aluminium salt, Sodium Fluoride, make aluminun fluoride solution and carry out the dephosphorization processing with silicofluoric acid and aluminium reactant salt, with aluminun fluoride solution and the Sodium Fluoride reaction that makes, Sodium Fluoride adds with solid form, the chemical equation of its synthetic cryolite as:
2, the method for a kind of sodium aluminum fluoride preparation according to claim 1 is characterized in that described aluminium salt is clay pit, bauxite or aluminium hydroxide.
3, the method for a kind of sodium aluminum fluoride preparation according to claim 1 is characterized in that the mol ratio of described silicofluoric acid and aluminium salt is: H
2SiF
6: Al
2O
31:0.6～1.6.
4, the method for a kind of sodium aluminum fluoride preparation according to claim 1 is characterized in that the mol ratio of described aluminum fluoride and Sodium Fluoride is: AlF
3: NaF 1:0.85～3.35.
5, the method for a kind of sodium aluminum fluoride preparation according to claim 1, the temperature of reaction that it is characterized in that described silicofluoric acid and aluminium salt is 50～115
0C.
6, the method for a kind of sodium aluminum fluoride preparation according to claim 1, the temperature of reaction that it is characterized in that described aluminum fluoride and Sodium Fluoride is 60～110
0C.
7, the method for a kind of sodium aluminum fluoride preparation according to claim 1, the concentration that it is characterized in that described silicofluoric acid be at 50-400g/L, SiO in the Sodium Fluoride
2＜1.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101434996A CN101391793A (en) | 2008-11-05 | 2008-11-05 | Method for preparing kryocide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101434996A CN101391793A (en) | 2008-11-05 | 2008-11-05 | Method for preparing kryocide |
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| Publication Number | Publication Date |
|---|---|
| CN101391793A true CN101391793A (en) | 2009-03-25 |
Family
ID=40492335
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|---|---|---|---|
| CNA2008101434996A Pending CN101391793A (en) | 2008-11-05 | 2008-11-05 | Method for preparing kryocide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502451A (en) * | 2015-12-29 | 2016-04-20 | 湖北祥福化工科技有限公司 | Method for producing aluminum fluoride and co-produced high-molecular ratio cryolite |
| CN105645447A (en) * | 2015-12-29 | 2016-06-08 | 湖北祥福化工科技有限公司 | Method for producing high-molecular ratio cryolite by utilizing low-concentration fluosilicic acid |
| CN106062541A (en) * | 2015-02-04 | 2016-10-26 | 俄罗斯工程技术中心 | Method for determining the composition and cryolite ratio of solid samples of potassium-containing electrolyte in aluminium production by XRD |
| CN106629800A (en) * | 2016-09-30 | 2017-05-10 | 王显权 | Method for producing cryolite from fluosilicic acid waste liquid |
-
2008
- 2008-11-05 CN CNA2008101434996A patent/CN101391793A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106062541A (en) * | 2015-02-04 | 2016-10-26 | 俄罗斯工程技术中心 | Method for determining the composition and cryolite ratio of solid samples of potassium-containing electrolyte in aluminium production by XRD |
| CN106062541B (en) * | 2015-02-04 | 2019-04-30 | 俄铝工程技术中心有限责任公司 | The method for measuring the composition and cryolite ratio of the solid sample of electrolyte containing potassium |
| CN105502451A (en) * | 2015-12-29 | 2016-04-20 | 湖北祥福化工科技有限公司 | Method for producing aluminum fluoride and co-produced high-molecular ratio cryolite |
| CN105645447A (en) * | 2015-12-29 | 2016-06-08 | 湖北祥福化工科技有限公司 | Method for producing high-molecular ratio cryolite by utilizing low-concentration fluosilicic acid |
| CN105502451B (en) * | 2015-12-29 | 2018-01-09 | 湖北祥福化工科技有限公司 | A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio |
| CN106629800A (en) * | 2016-09-30 | 2017-05-10 | 王显权 | Method for producing cryolite from fluosilicic acid waste liquid |
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Application publication date: 20090325 |