CN101134591B - Method for preparing aluminun fluoride and waterless magnesium sulfate - Google Patents
Method for preparing aluminun fluoride and waterless magnesium sulfate Download PDFInfo
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- CN101134591B CN101134591B CN2006101069781A CN200610106978A CN101134591B CN 101134591 B CN101134591 B CN 101134591B CN 2006101069781 A CN2006101069781 A CN 2006101069781A CN 200610106978 A CN200610106978 A CN 200610106978A CN 101134591 B CN101134591 B CN 101134591B
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Abstract
The process of producing aluminum fluoride and anhydrous magnesium sulfate with fluorosilicic acid, magnesia and aluminum hydroxide as material includes the following steps: 1.reacting fluorosilicic acid solution and magnesia, filtering to obtain magnesium fluorosilicate solution, concentrating to obtain crystal magnesium fluorosilicate hexahydrate; 2. decomposing magnesium fluorosilicate hexahydrate at 100-500 deg.c to produce magnesium fluoride solid, silicon tetrafluoride gas and water vapor; 3. absorbing silicon tetrafluoride gas and water vapor with water and hydrolyzing, filtering to obtain fluorosilicic acid solution for reuse, and washing and drying silica to obtain carbon white; 4. reacting magnesium fluoride and sulfuric acid to produce anhydrous magnesium sulfate, condensing and rectifying to obtain anhydrous hydrofluoric acid; and 5. reacting anhydrous hydrofluoric acid and aluminum hydroxide to produce aluminum fluoride.
Description
Technical field
The present invention relates to a kind of method for preparing aluminum fluoride, anhydrous magnesium sulfate, relating in particular to a kind of is the method for feedstock production aluminum fluoride, anhydrous magnesium sulfate with silicofluoric acid, magnesium oxide and aluminium hydroxide.
Background technology
Aluminum fluoride is used as auxiliary agent in Aluminum Electrolysis Production, be used to reduce electrolytical fusing point, improve electrolytical electric conductivity.Its traditional processing technology is a hydrofluoric acid---dry process and hydrofluoric acid---wet processing.The raw material of hydrofluoric acid---dry process is hydrogen fluoride and aluminium hydroxide, its production technique is for comprising that aluminium hydroxide is carried out pre-treatment removes crystal water, the thorough mixing reaction under 500-600 ℃ temperature with powdery aluminium hydroxide and hydrogen fluoride gas then, generate aluminum trifluoride at reactor bottom, with aluminum trifluoride send into rotary drum cool off finished product; The raw material of hydrofluoric acid---wet processing is hydrofluoric acid and aluminium hydroxide, and production technique is that hydrofluoric acid and aluminum hydroxide slime react, crystallization, gets aluminum fluoride trihydrate, and drying dehydration again makes aluminium fluoride product.Above-mentioned production technique cost of material height, production cost height, and strategic resource---the fluorite mineral products of use national precious.
Anhydrous a, water, magnesium sulfate heptahydrate and sulphate of potash magnesia all can be used as the kieserite material and use.Since kieserite (comprising the sulphur Mg, K fertilizer) in resource, fertilizer efficiency, economy, grade characteristics aspect a lot of of sulphur magnesium two breedings can be provided again simultaneously, since nineteen ninety, on agricultural, obtain widespread use.Traditional method is that sulfuric acid and magnesia (magnesia) reaction make magnesium sulfate monohydrate, again through two-section calcining, makes anhydrous magnesium sulfate.
Summary of the invention
The object of the invention is to provide a kind of method for preparing aluminum fluoride, anhydrous magnesium sulfate, to reduce production costs.
To achieve these goals, having technical program of the present invention lies in adopting a kind of method for preparing aluminum fluoride, anhydrous magnesium sulfate, is raw material with silicofluoric acid, magnesium oxide, aluminium hydroxide, specifically may further comprise the steps:
(1) silicate fluoride solution and magnesium oxide were reacted 10～60 minutes, filter and obtain magnesium silicofluoride solution, condensing crystal obtains six water magnesium silicofluorides;
(2) six water magnesium silicofluorides were decomposed under 100～500 ℃ temperature 1～5 hour, generate magnesium fluoride solid and silicon tetrafluoride gas and steam;
(3) silicon tetrafluoride gas and steam water are absorbed and hydrolysis, the silicate fluoride solution that filtration obtains returns makes magnesium silicofluoride, and silica solid washing, drying obtain white carbon black;
(4) magnesium fluoride solid and concentration are that sulfuric acid more than 98% reacted 2-5 hours under 150-300 ℃ temperature, and condensation of gas rectifying obtains anhydrous hydrofluoric acid, and solid is the anhydrous slufuric acid magnesium products;
(5) anhydrous hydrofluoric acid is sent to thorough mixing and rapid reaction in the fluidized-bed reactor with solid aluminum hydroxide by reaction ratio after heating up and gasifying, and reaction generates the solid phase prod aluminum fluoride.
The concentration of described silicate fluoride solution is 10～40%.
Described magnesium oxide is the slip of solid or 10～30%.
The temperature of reaction of described step (5) is 500-600 ℃.
Reaction formula of the present invention is:
H
2SiF
6+MgO+5H
2O→MgSiF
6·6H
2O
MgSiF
6·6H
2O→MgF
2+SiF
4↑+6H
2O
3SiF
4+2H
2O→2H
2SiF
6+SiO
2↓
MgF
2+H
2SO
4→2HF↑+MgSO
4
3HF+Al(OH)
3＝AlF
3+3H
2O
Method of the present invention is to be main raw material with the silicofluoric acid, and silicofluoric acid is the by-product harmful waste of phophatic fertilizer production process, and purposes seldom and has caused surrounding environment and to have a strong impact on, and the development process of silicofluoric acid is badly in need of solving.The present invention is a main raw material with the silicofluoric acid, turns waste into wealth, and has alleviated the pollution that surrounding environment is caused of overstocking of silicofluoric acid greatly.In addition, the prepared silicate fluoride solution of method of the present invention returns makes magnesium silicofluoride, recycles, and has saved cost to a certain extent.Technology of the present invention is simple, and the production cost that greatly reduces has good economic worth and social value, is easy to apply.
The aluminium fluoride product mass analysis result that method of the present invention is produced
Anhydrous magnesium sulfate product quality analysis result
| GB | Present method 1# | Present method 2# | |
| Outward appearance | White powder | White powder | White powder |
| MgSO 4 | 98％min | 98.2％ | 98.5％ |
| MgO | 32.66％min | 32.88％ | 32.96％ |
| Mg | 19.6％min | 19.8％ | 19.9％ |
| pH(5W/V％Sol) | 6-8 | 6.8 | 7.8 |
| Iron level (Fe) | 0.0015％max | 0.0012％ | 0.0011％ |
| Heavy metal (Pb) | 0.0008％max | 0.0006％ | 0.0005％ |
| Arsenic content (As) | 0.0002％max | 0.0001％ | 0.0001％ |
| Water is insoluble | 0.01％max | 0.01％ | 0.01％ |
| Granular size (mm) | 0.1 | 0.1 | 0.1 |
Embodiment
Embodiment 1
The present invention prepares the method for aluminum fluoride, anhydrous magnesium sulfate, may further comprise the steps:
(1) with concentration is 15% silicate fluoride solution and magnesium oxide solid reaction 30 minutes, filters and obtain magnesium silicofluoride solution that condensing crystal obtains six water magnesium silicofluorides;
(2) six water magnesium silicofluorides were decomposed 4 hours at 200 ℃, generate magnesium fluoride solid and silicon tetrafluoride gas and steam;
(3) silicon tetrafluoride gas and steam water are absorbed and hydrolysis, filtering and obtaining concentration is that 15% silicate fluoride solution returns and makes magnesium silicofluoride, and silica solid washing, drying obtain white carbon black;
(4) the magnesium fluoride solid that generates of step (2) and concentration are that 98% sulfuric acid reacted 5 hours under 150 ℃ temperature, and the condensation of gas rectifying of generation obtains anhydrous hydrofluoric acid, and solid is the anhydrous slufuric acid magnesium products;
(5) anhydrous hydrofluoric acid is fed in thorough mixing and rapid reaction in the fluidized-bed reactor with solid aluminum hydroxide by reaction ratio after heating up and gasifying, and temperature of reaction is controlled at 500 ℃, and reaction has generated the solid phase prod aluminum fluoride.
Embodiment 2
The present invention prepares the method for aluminum fluoride, anhydrous magnesium sulfate, may further comprise the steps:
(1) with concentration is the slurry reaction 30 minutes of 25% silicate fluoride solution and magnesium oxide 30%, filters and obtain magnesium silicofluoride solution that condensing crystal obtains six water magnesium silicofluorides;
(2) six water magnesium silicofluorides were decomposed 3 hours at 300 ℃, generate magnesium fluoride solid and silicon tetrafluoride gas and steam;
(3) silicon tetrafluoride gas and steam water are absorbed and hydrolysis, filter and obtain 25% silicate fluoride solution and return and make magnesium silicofluoride, silica solid washing, drying obtain white carbon black;
(4) magnesium fluoride solid that step (2) is generated and concentration are that 99% sulfuric acid reacted 3 hours under 250 ℃ temperature, and the condensation of gas rectifying of generation obtains anhydrous hydrofluoric acid, and solid is the anhydrous slufuric acid magnesium products;
(5) anhydrous hydrofluoric acid is fed in thorough mixing and rapid reaction in the fluidized-bed reactor with solid aluminum hydroxide by reaction ratio after heating up and gasifying, and temperature of reaction is controlled at 550 ℃, and reaction has generated the solid phase prod aluminum fluoride.
Embodiment 3
The present invention prepares the method for aluminum fluoride, anhydrous magnesium sulfate, may further comprise the steps:
(1) with concentration is the slurry reaction 30 minutes of 35% silicate fluoride solution and magnesium oxide 20%, filters and obtain magnesium silicofluoride solution that condensing crystal obtains six water magnesium silicofluorides;
(2) six water magnesium silicofluorides were decomposed 2 hours at 400 ℃, generate magnesium fluoride solid and silicon tetrafluoride gas and steam;
(3) silicon tetrafluoride gas and steam water are absorbed and hydrolysis, filter and obtain 35% silicate fluoride solution and return and prepare magnesium silicofluoride, silica solid washing, drying obtain white carbon black;
(4) the magnesium fluoride solid that generates of step (2) and concentration are that 100% sulfuric acid reacted 2 hours under 300 ℃ temperature, and the condensation of gas rectifying of generation obtains anhydrous hydrofluoric acid, and solid is the anhydrous slufuric acid magnesium products;
(5) anhydrous hydrofluoric acid is fed in thorough mixing and rapid reaction in the fluidized-bed reactor with solid aluminum hydroxide by reaction ratio after heating up and gasifying, and temperature of reaction is controlled at 600 ℃, and reaction has generated the solid phase prod aluminum fluoride.
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that: still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (4)
1. method for preparing aluminum fluoride, anhydrous magnesium sulfate, it is characterized in that: with silicofluoric acid, magnesium oxide, aluminium hydroxide is raw material, wherein silicofluoric acid is the by-product harmful waste in the phophatic fertilizer production process, specifically may further comprise the steps:
(1) silicate fluoride solution and magnesium oxide were reacted 10～60 minutes, filter and obtain magnesium silicofluoride solution, condensing crystal obtains six water magnesium silicofluorides;
(2) six water magnesium silicofluorides were decomposed under 100～500 ℃ temperature 1～5 hour, generate magnesium fluoride solid and silicon tetrafluoride gas and steam;
(3) silicon tetrafluoride gas and steam water are absorbed and hydrolysis, the silicate fluoride solution that filtration obtains returns makes magnesium silicofluoride, and silica solid washing, drying obtain white carbon black;
(4) magnesium fluoride solid and concentration are the sulfuric acid reaction more than 98%, and condensation of gas rectifying obtains anhydrous hydrofluoric acid, and solid is the anhydrous slufuric acid magnesium products;
(5) anhydrous hydrofluoric acid is sent to thorough mixing and rapid reaction in the fluidized-bed reactor with solid aluminum hydroxide by reaction ratio after heating up and gasifying, and reaction generates the solid phase prod aluminum fluoride.
2. the method for preparing aluminum fluoride, anhydrous magnesium sulfate according to claim 1 is characterized in that: the concentration of described silicate fluoride solution is 10～40%.
3. the method for preparing aluminum fluoride, anhydrous magnesium sulfate according to claim 1 is characterized in that: described magnesium oxide is the slip of solid or 10-30%.
4. the method for preparing aluminum fluoride, anhydrous magnesium sulfate according to claim 1 is characterized in that: the temperature of reaction of described step (5) is 500-600 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101069781A CN101134591B (en) | 2006-09-01 | 2006-09-01 | Method for preparing aluminun fluoride and waterless magnesium sulfate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101069781A CN101134591B (en) | 2006-09-01 | 2006-09-01 | Method for preparing aluminun fluoride and waterless magnesium sulfate |
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| Publication Number | Publication Date |
|---|---|
| CN101134591A CN101134591A (en) | 2008-03-05 |
| CN101134591B true CN101134591B (en) | 2010-09-15 |
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|---|---|---|---|
| CN2006101069781A Expired - Fee Related CN101134591B (en) | 2006-09-01 | 2006-09-01 | Method for preparing aluminun fluoride and waterless magnesium sulfate |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2462418C1 (en) * | 2011-06-07 | 2012-09-27 | Эдвард Петрович Ржечицкий | Method of producing aluminium fluoride |
| CN106277097B (en) * | 2016-08-30 | 2019-11-05 | 云南凯威特新材料股份有限公司 | Phosphatic fertilizer company fluosilicic acid waste water totally-enclosed method for innocent treatment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116609A (en) * | 1994-08-06 | 1996-02-14 | 温宝礼 | Method for producing aluminium fluoride and cryolite with kaoline |
| CN1626445A (en) * | 2003-12-12 | 2005-06-15 | 焦作市多氟多化工有限公司 | Method of preparing aluminum fluoride |
-
2006
- 2006-09-01 CN CN2006101069781A patent/CN101134591B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116609A (en) * | 1994-08-06 | 1996-02-14 | 温宝礼 | Method for producing aluminium fluoride and cryolite with kaoline |
| CN1626445A (en) * | 2003-12-12 | 2005-06-15 | 焦作市多氟多化工有限公司 | Method of preparing aluminum fluoride |
Non-Patent Citations (5)
| Title |
|---|
| 《化学化工大辞典》编委会.化学化工大辞典（上册） 1.化学工业出版社,2003,701. |
| 《化学化工大辞典》编委会.化学化工大辞典(上册) 1.化学工业出版社,2003,701. * |
| JP 特开2004-846 A,说明书第2页第3行至第5页第3行. |
| 司徒杰生等.化工产品手册-无机化工产品 4.化学工业出版社,2004,261. |
| 司徒杰生等.化工产品手册-无机化工产品 4.化学工业出版社,2004,261. * |
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| CN101134591A (en) | 2008-03-05 |
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