CN102874868B - Method for preparing potassium fluozirconate through fluosilicic acid - Google Patents
Method for preparing potassium fluozirconate through fluosilicic acid Download PDFInfo
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- CN102874868B CN102874868B CN201210432458.5A CN201210432458A CN102874868B CN 102874868 B CN102874868 B CN 102874868B CN 201210432458 A CN201210432458 A CN 201210432458A CN 102874868 B CN102874868 B CN 102874868B
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- leaching
- zrf
- silicofluoric acid
- filtrate
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Abstract
The invention provides a method for preparing potassium fluozirconate through fluosilicic acid. The method comprises the steps as follows: (1) adding a fluosilicic acid solution to a leaching groove, then heating to reach 40 to 100 DEG C, starting to agitate, and adding the zirconium oxychloride with the theoretical amount to the fluosilicic acid solution; reacting and leaching for 1 to 5 hours under constant temperature condition; (2) filtering the fluosilicic acid obtained by leaching; washing the filter residue, then parching the filter residue to obtain a white carbon black product; (3) adding sodium chloride with theoretical amount to the mixture of the filtrate and the first washing water to obtain the sodium fluosilicate size; (4) filtering the obtained size, washing, and drying to obtain sodium fluosilicate; (5) adding the filtrate in step (4) into the potassium chloride solution with the theoretical amount to react for 30 to 60 minutes, and filtering to obtain paste; and (6) washing the obtained paste through water, and then parching to obtain the finished product. According to the method provided by the invention, the raw materials are easy to obtain, and low in cost, thus the producing cost can be greatly reduced; and meanwhile, the valuable white carbon black and sodium fluosilicate can be produced.
Description
Technical field
The present invention relates to a kind of method of preparing potassium fluozirconate with silicofluoric acid, relate in particular to a kind of method of preparing potassium fluozirconate take silicofluoric acid, zirconium oxychloride and Repone K as main raw material.
Background technology
Potassium fluozirconate is of many uses, mainly for the production of metal zirconium and other zirconium compoundss, also for production of aluminum magnesium alloy, nuclear industry, pottery and glass etc.Use the related industries of potassium fluozirconate, scale is stable, and along with the development of nuclear industry, also can increase the demand of potassium fluozirconate, and therefore, having a great sale of potassium fluozirconate is wealthy.
At present, the traditional processing technology of potassium fluozirconate uses hydrofluoric acid Repone K method more, makes the production cost of potassium fluozirconate affected by raw material larger, lacks the market competitiveness.
Summary of the invention
Technical problem to be solved by this invention is that a kind of method of preparing potassium fluozirconate with silicofluoric acid is provided.The method is raw materials used be easy to get and cost low, can greatly reduce production costs, can also produce white carbon black and the Sodium Silicofluoride of utility value simultaneously.
The technical scheme that the present invention solves its technical problem employing is: a kind of method of preparing potassium fluozirconate with silicofluoric acid, take silicofluoric acid, zirconium oxychloride and Repone K as main raw material, specifically comprises the following steps:
(1) first in leaching groove, add silicate fluoride solution, then be heated to 40-100 ℃ (preferably 70-90 ℃), open and stir, the zirconium oxychloride of theoretical amount is added in silicate fluoride solution, reaction leaching 1-5 hour (preferably 3-4.5 hour) under heat-retaining condition, reaction equation is:
H
2SiF
6?+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2) fluorine zirconic acid solution filter leaching being obtained, filter residue, through 2-4 (preferably 3 times) post-drying of sand leaching water washing, obtains white carbon black product;
(3) the unreacted amount of silicofluoric acid completely in the filtrate that adopts acid base titration detecting step (2) and wash water mixture for the first time, then adds the sodium-chlor of theoretical amount, and reaction 10-30 minute, removes unreacted silicofluoric acid completely, and reaction equation is:
H
2siF
6+ 2NaCl → Na
2siF
6+ 2HCl; Obtain Sodium Silicofluoride slip;
(4) gained slip is filtered, washing, dry, obtain Sodium Silicofluoride;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2zrF
6amount, be then added in the Klorvess Liquid of theoretical amount, reaction 30-60 minute, reaction equation is:
H
2zrF
6+ 2KCl → K
2zrF
6+ 2HCl; After reacting completely, filter, obtain ointment;
(6) step (5) gained ointment is washed, then dried.
Further, in step (1), the mass concentration of described silicate fluoride solution is the preferred 10-35% of 5-50%().
Further, in step (5), the filtrate of step (4) joins in Klorvess Liquid, and the mass concentration of Klorvess Liquid is 18-22%(preferably 20%).
Compared with prior art, the present invention replaces hydrofluoric acid to prepare potassium fluozirconate take silicofluoric acid as raw material, have the following advantages:
(1) silicofluoric acid is the by-product harmful waste of phophatic fertilizer production process, purposes is few, have a strong impact on environment protection, and utilize the present invention, not only make silicofluoric acid be developed, greatly alleviate the environmental protection pressure of production of phosphate fertilizer and the impact on surrounding environment thereof, and due to the silicofluoric acid by product that is Phosphate Fertilizer Industry, be easy to get and cost low, thereby can significantly reduce the production cost of potassium fluozirconate;
(2) in reaction process, can produce white carbon black and the Sodium Silicofluoride of utility value, also can reduce production costs to a certain extent, productivity effect is provided;
(3) every quality index of product can reach relevant criterion, and the potassium fluozirconate product proportion making reaches more than 1.8, can meet better client's service requirements.
In sum, the present invention has good economic worth and social value, is easy to apply.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The present embodiment, take silicofluoric acid, zirconium oxychloride and Repone K as main raw material, specifically comprises the following steps:
(1) first in leaching groove, add silicate fluoride solution 1000mL, be then heated to 70 ℃, open and stir, the zirconium oxychloride of 180g is added in silicate fluoride solution, reaction leaching 5 hours under heat-retaining condition, reaction equation is:
H
2SiF
6?+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2) fluorine zirconic acid solution filter leaching being obtained, filter residue, through 3 post-dryings of sand leaching water washing, obtains white carbon black product;
(3) the unreacted amount of silicofluoric acid completely in the filtrate that adopts acid base titration detecting step (2) and wash water mixture for the first time, then adds 30g sodium-chlor, removes unreacted silicofluoric acid completely, reacts 10 minutes, and reaction equation is:
H
2siF
6+ 2NaCl → Na
2siF
6+ 2HCl; Obtain Sodium Silicofluoride slip;
(4) gained slip is filtered, washing, dry, obtain Sodium Silicofluoride;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2zrF
6amount, then join 540ml mass concentration and be in 20% Klorvess Liquid, react 30 minutes, reaction equation is:
H
2zrF
6+ 2KCl → K
2zrF
6+ 2HCl; After reacting completely, filter, obtain ointment;
(6) step (5) gained ointment is washed, then dried.
In the present embodiment, the mass concentration of silicate fluoride solution is 10%, and zirconium oxychloride is general industry product.Zirconium content in gained potassium fluozirconate product is 32.76wt%, and product proportion is 1.83.
Embodiment 2
The present embodiment, take silicofluoric acid, zirconium oxychloride and Repone K as main raw material, specifically comprises the following steps:
(1) first in leaching groove, add silicate fluoride solution 1000ml, be then heated to 80 ℃, open and stir, the zirconium oxychloride of 560g is added in silicate fluoride solution, reaction leaching 4 hours under heat-retaining condition, reaction equation is:
H
2SiF
6?+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2), by the fluorine zirconic acid solution filter of leaching gained, filter residue, through 3 post-dryings of sand leaching water washing, obtains white carbon black product;
(3) the unreacted amount of silicofluoric acid completely in the filtrate that adopts acid base titration detecting step (2) and wash water mixture for the first time, then adds 80g sodium-chlor, removes unreacted silicofluoric acid completely, reacts 20 minutes, and reaction equation is:
H
2siF
6+ 2NaCl → Na
2siF
6+ 2HCl; Obtain Sodium Silicofluoride slip;
(4) gained slip is filtered, washing, dry, obtain Sodium Silicofluoride;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2zrF
6amount, then join 1600ml mass concentration and be in 20% Klorvess Liquid, react 40 minutes, reaction equation is:
H
2zrF
6+ 2KCl → K
2zrF
6+ 2HCl; After reacting completely, filter, obtain ointment;
(6) step (5) gained ointment is washed, then dried.
In the present embodiment, the mass concentration of silicate fluoride solution is 30%, and zirconium oxychloride is general industry product.Zirconium content in gained potassium fluozirconate product is 31.84wt%, and product proportion is 2.03.
Embodiment 3
The present embodiment, take silicofluoric acid, zirconium oxychloride and Repone K as main raw material, specifically comprises the following steps:
(1) first in leaching groove, add silicate fluoride solution 1000ml, be then heated to 90 ℃, open and stir, the zirconium oxychloride of 1300g is added in silicate fluoride solution, reaction leaching 3 hours under heat-retaining condition, reaction equation is:
H
2SiF
6?+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2), by the fluorine zirconic acid solution filter of leaching gained, filter residue, through 3 post-dryings of sand leaching water washing, obtains white carbon black product;
(3) the unreacted amount of silicofluoric acid completely in the filtrate that adopts acid base titration detecting step (2) and wash water mixture for the first time, then adds 150g sodium-chlor, removes unreacted silicofluoric acid completely, reacts 30 minutes, and reaction equation is:
H
2siF
6+ 2NaCl → Na
2siF
6+ 2HCl; Obtain Sodium Silicofluoride slip;
(4) gained slip is filtered, washing, dry, obtain Sodium Silicofluoride;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2zrF
6amount, then join 2700ml mass concentration and be in 20% Klorvess Liquid, react 50 minutes, reaction equation is:
H
2zrF
6+ 2KCl → K
2zrF
6+ 2HCl; After reacting completely, filter, obtain ointment;
(6) step (5) gained ointment is washed, then dried.
In the present embodiment, the mass concentration of silicate fluoride solution is 50%, and zirconium oxychloride is general industry product.Zirconium content in gained potassium fluozirconate product is 32.51%, and product proportion is 1.92.
Claims (3)
1. a method of preparing potassium fluozirconate with silicofluoric acid, is characterized in that, take silicofluoric acid, zirconium oxychloride and Repone K as main raw material, specifically comprises the following steps:
(1) first in leaching groove, add silicate fluoride solution, be then heated to 40-100 ℃, open and stir, the zirconium oxychloride of theoretical amount is added in silicate fluoride solution, reaction leaching 1-5 hour under heat-retaining condition, reaction equation is:
H
2SiF
6+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2) fluorine zirconic acid solution filter leaching being obtained, filter residue, through 2-4 post-drying of sand leaching water washing, obtains white carbon black product;
(3) the unreacted amount of silicofluoric acid completely in the filtrate that adopts acid base titration detecting step (2) and wash water mixture for the first time, then adds the sodium-chlor of theoretical amount, removes unreacted silicofluoric acid completely, reaction 10-30 minute, and reaction equation is:
H
2siF
6+ 2NaCl → Na
2siF
6+ 2HCl; Obtain Sodium Silicofluoride slip;
(4) gained slip is filtered, washing, is dried to obtain Sodium Silicofluoride;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2zrF
6amount, then join in the Klorvess Liquid of theoretical amount, reaction 30-60 minute, reaction equation is:
H
2zrF
6+ 2KCl → K
2zrF
6+ 2HCl; After reacting completely, filter, obtain ointment;
(6) step (5) gained ointment is washed, then dried.
2. the method for preparing potassium fluozirconate with silicofluoric acid according to claim 1, is characterized in that, in step (1), the mass concentration of described silicate fluoride solution is 5-50%.
3. the method for preparing potassium fluozirconate with silicofluoric acid according to claim 1 and 2, is characterized in that, in step (5), the filtrate of step (4) joins in Klorvess Liquid, and the mass concentration of Klorvess Liquid is 18-22%.
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|---|---|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092417A (en) * | 2019-04-17 | 2019-08-06 | 南通金星氟化学有限公司 | A kind of preparation method of potassium fluorozirconate |
| CN111689517B (en) * | 2020-05-29 | 2022-09-20 | 福建省漳平市九鼎氟化工有限公司 | Method for preparing potassium fluozirconate and co-producing polyaluminium chloride |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2537354C3 (en) * | 1975-08-21 | 1978-03-09 | Fa. Hermann C. Starck Berlin, 1000 Berlin | Process for the production of crystalline potassium tantalum fluoride |
| US4442082A (en) * | 1982-12-27 | 1984-04-10 | Sri International | Process for obtaining silicon from fluosilicic acid |
| CN101289195B (en) * | 2007-04-19 | 2010-08-04 | 多氟多化工股份有限公司 | Process for preparing potassium borofluoride and co-production of white carbon black and sodium fluosilicate |
| CN101423224A (en) * | 2008-11-28 | 2009-05-06 | 湖南有色氟化学有限责任公司 | Potassium borofluoride preparation method based on fluosilicic acid and boron rock |
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Granted publication date: 20140528 Termination date: 20191102 |