CN102874868A - Method for preparing potassium fluozirconate through fluosilicic acid - Google Patents
Method for preparing potassium fluozirconate through fluosilicic acid Download PDFInfo
- Publication number
- CN102874868A CN102874868A CN2012104324585A CN201210432458A CN102874868A CN 102874868 A CN102874868 A CN 102874868A CN 2012104324585 A CN2012104324585 A CN 2012104324585A CN 201210432458 A CN201210432458 A CN 201210432458A CN 102874868 A CN102874868 A CN 102874868A
- Authority
- CN
- China
- Prior art keywords
- leaching
- zrf
- silicofluoric acid
- filtrate
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Silicon Compounds (AREA)
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 for preparing potassium fluozirconate with silicofluoric acid, relate in particular to a kind of method for 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 is used for the 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, so that the production cost of potassium fluozirconate is affected by raw material is larger, lacks the market competitiveness.
Summary of the invention
Technical problem to be solved by this invention is that a kind of method for 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 simultaneously and utilize white carbon black and the Sodium Silicofluoride that is worth.
The technical scheme that the present invention solves its technical problem employing is: a kind of method for preparing potassium fluozirconate with silicofluoric acid take silicofluoric acid, zirconium oxychloride and Repone K as main raw material, specifically may further comprise the steps:
(1) in the leaching groove, adds silicate fluoride solution first, then be heated to 40-100 ℃ (preferred 70-90 ℃), open and stir, in the zirconium oxychloride adding silicate fluoride solution with theoretical amount, reaction leaching 1-5 hour (preferred 3-4.5 hour) under the heat-retaining condition, reaction equation is:
H
2SiF
6?+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2) will leach the fluorine zirconic acid solution filter that obtains, filter residue gets white carbon black product through 2-4 (preferred 3 times) post-drying of sand leaching water washing;
(3) adopt in the filtrate of acid base titration detecting step (2) and the wash water mixture for the first time the completely amount of silicofluoric acid of unreacted, then add the sodium-chlor of theoretical amount, reacted 10-30 minute, remove completely silicofluoric acid of unreacted, reaction equation is:
H
2SiF
6+ 2NaCl → Na
2SiF
6+ 2HCl; Get the Sodium Silicofluoride slip;
(4) the gained slip is filtered, washing, drying gets Sodium Silicofluoride;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2ZrF
6Amount, then be added in the Klorvess Liquid of theoretical amount, reacted 30-60 minute, reaction equation is:
H
2ZrF
6+ 2KCl → K
2ZrF
6+ 2HCl; After reacting completely, filter, get ointment;
(6) step (5) gained ointment is washed, again oven dry.
Further, in the step (1), the mass concentration of described silicate fluoride solution is the preferred 10-35% of 5-50%().
Further, in the step (5), the filtrate of step (4) joins in the Klorvess Liquid, and the mass concentration of Klorvess Liquid is 18-22%(preferred 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 so that silicofluoric acid is developed, greatly alleviate the environmental protection pressure of production of phosphate fertilizer and on the impact of surrounding environment, and because silicofluoric acid is the by product of Phosphate Fertilizer Industry, be easy to get and cost low, thereby but the production cost of decrease potassium fluozirconate;
(2) can produce white carbon black and the Sodium Silicofluoride that utilizes value in the reaction process, also can reduce production costs to a certain extent, productivity effect is provided;
(3) every quality index of product can both reach relevant criterion, and the potassium fluozirconate product proportion that makes reaches more than 1.8, can satisfy better client's service requirements.
In sum, the present invention has good economic worth and social value, is easy to apply.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
The present embodiment specifically may further comprise the steps take silicofluoric acid, zirconium oxychloride and Repone K as main raw material:
(1) elder generation adds silicate fluoride solution 1000mL in the leaching groove, then is heated to 70 ℃, opens and stirs, and in the zirconium oxychloride adding silicate fluoride solution with 180g, the reaction leaching is 5 hours under the heat-retaining condition, and reaction equation is:
H
2SiF
6?+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2) will leach the fluorine zirconic acid solution filter that obtains, filter residue gets white carbon black product through 3 post-dryings of sand leaching water washing;
(3) adopt in the filtrate of acid base titration detecting step (2) and the wash water mixture for the first time the completely amount of silicofluoric acid of unreacted, then add 30g sodium-chlor, remove completely silicofluoric acid of unreacted, reacted 10 minutes, reaction equation is:
H
2SiF
6+ 2NaCl → Na
2SiF
6+ 2HCl; Get the Sodium Silicofluoride slip;
(4) the gained slip is filtered, washing, drying gets Sodium Silicofluoride;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2ZrF
6Amount, then join the 540ml mass concentration and be in 20% the Klorvess Liquid, reacted 30 minutes, reaction equation is:
H
2ZrF
6+ 2KCl → K
2ZrF
6+ 2HCl; After reacting completely, filter, get ointment;
(6) step (5) gained ointment is washed, again oven dry.
The mass concentration of silicate fluoride solution is 10% in the present embodiment, and zirconium oxychloride is the general industry product.Zirconium content in the gained potassium fluozirconate product is 32.76wt%, and product proportion is 1.83.
Embodiment 2
The present embodiment specifically may further comprise the steps take silicofluoric acid, zirconium oxychloride and Repone K as main raw material:
(1) elder generation adds silicate fluoride solution 1000ml in the leaching groove, then is heated to 80 ℃, opens and stirs, and in the zirconium oxychloride adding silicate fluoride solution with 560g, the reaction leaching is 4 hours under the heat-retaining condition, and reaction equation is:
H
2SiF
6?+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2) will leach the fluorine zirconic acid solution filter of gained, filter residue gets white carbon black product through 3 post-dryings of sand leaching water washing;
(3) adopt in the filtrate of acid base titration detecting step (2) and the wash water mixture for the first time the completely amount of silicofluoric acid of unreacted, then add 80g sodium-chlor, remove completely silicofluoric acid of unreacted, reacted 20 minutes, reaction equation is:
H
2SiF
6+ 2NaCl → Na
2SiF
6+ 2HCl; Get the Sodium Silicofluoride slip;
(4) the gained slip is filtered, washing, drying gets Sodium Silicofluoride;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2ZrF
6Amount, then join the 1600ml mass concentration and be in 20% the Klorvess Liquid, reacted 40 minutes, reaction equation is:
H
2ZrF
6+ 2KCl → K
2ZrF
6+ 2HCl; After reacting completely, filter, get ointment;
(6) step (5) gained ointment is washed, again oven dry.
The mass concentration of silicate fluoride solution is 30% in the present embodiment, and zirconium oxychloride is the general industry product.Zirconium content in the gained potassium fluozirconate product is 31.84wt%, and product proportion is 2.03.
Embodiment 3
The present embodiment specifically may further comprise the steps take silicofluoric acid, zirconium oxychloride and Repone K as main raw material:
(1) elder generation adds silicate fluoride solution 1000ml in the leaching groove, then is heated to 90 ℃, opens and stirs, and in the zirconium oxychloride adding silicate fluoride solution with 1300g, the reaction leaching is 3 hours under the heat-retaining condition, and reaction equation is:
H
2SiF
6?+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2) will leach the fluorine zirconic acid solution filter of gained, filter residue gets white carbon black product through 3 post-dryings of sand leaching water washing;
(3) adopt in the filtrate of acid base titration detecting step (2) and the wash water mixture for the first time the completely amount of silicofluoric acid of unreacted, then add 150g sodium-chlor, remove completely silicofluoric acid of unreacted, reacted 30 minutes, reaction equation is:
H
2SiF
6+ 2NaCl → Na
2SiF
6+ 2HCl; Get the Sodium Silicofluoride slip;
(4) the gained slip is filtered, washing, drying gets Sodium Silicofluoride;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2ZrF
6Amount, then join the 2700ml mass concentration and be in 20% the Klorvess Liquid, reacted 50 minutes, reaction equation is:
H
2ZrF
6+ 2KCl → K
2ZrF
6+ 2HCl; After reacting completely, filter, get ointment;
(6) step (5) gained ointment is washed, again oven dry.
The mass concentration of silicate fluoride solution is 50% in the present embodiment, and zirconium oxychloride is the general industry product.Zirconium content in the gained potassium fluozirconate product is 32.51%, and product proportion is 1.92.
Claims (3)
1. a method for preparing potassium fluozirconate with silicofluoric acid is characterized in that, take silicofluoric acid, zirconium oxychloride and Repone K as main raw material, specifically may further comprise the steps:
(1) add silicate fluoride solution first in the leaching groove, then be heated to 40-100 ℃, open and stir, in the zirconium oxychloride adding silicate fluoride solution with theoretical amount, the reaction leaching is 1-5 hour under the heat-retaining condition, and reaction equation is:
H
2SiF
6+ZrOCl
2·8H
2O→H
2ZrF
6+SiO
2+2HCl+7H
2O；
(2) will leach the fluorine zirconic acid solution filter that obtains, filter residue gets white carbon black product through 2-4 post-drying of sand leaching water washing;
(3) adopt in the filtrate of acid base titration detecting step (2) and the wash water mixture for the first time the completely amount of silicofluoric acid of unreacted, then add the sodium-chlor of theoretical amount, remove completely silicofluoric acid of unreacted, reacted 10-30 minute, reaction equation is:
H
2SiF
6+ 2NaCl → Na
2SiF
6+ 2HCl; Get the Sodium Silicofluoride slip;
(4) the gained slip is filtered washing, the dry Sodium Silicofluoride that gets;
(5) H in the filtrate of employing EDTA complexometry detecting step (4)
2ZrF
6Amount, then join in the Klorvess Liquid of theoretical amount, reacted 30-60 minute, reaction equation is:
H
2ZrF
6+ 2KCl → K
2ZrF
6+ 2HCl; After reacting completely, filter, get ointment;
(6) step (5) gained ointment is washed, again oven dry.
2. the method for preparing potassium fluozirconate with silicofluoric acid according to claim 1 is characterized in that, in the 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 the step (5), the filtrate of step (4) joins in the Klorvess Liquid, and the mass concentration of Klorvess Liquid is 18-22%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210432458.5A CN102874868B (en) | 2012-11-02 | 2012-11-02 | Method for preparing potassium fluozirconate through fluosilicic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210432458.5A CN102874868B (en) | 2012-11-02 | 2012-11-02 | Method for preparing potassium fluozirconate through fluosilicic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102874868A true CN102874868A (en) | 2013-01-16 |
| CN102874868B CN102874868B (en) | 2014-05-28 |
Family
ID=47476433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210432458.5A Expired - Fee Related CN102874868B (en) | 2012-11-02 | 2012-11-02 | Method for preparing potassium fluozirconate through fluosilicic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102874868B (en) |
Cited By (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 |
| CN111689517A (en) * | 2020-05-29 | 2020-09-22 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4041138A (en) * | 1975-08-21 | 1977-08-09 | Hermann C. Starck | Process for the preparation of crystalline potassium tantalum fluoride |
| US4442082A (en) * | 1982-12-27 | 1984-04-10 | Sri International | Process for obtaining silicon from fluosilicic acid |
| CN101289195A (en) * | 2007-04-19 | 2008-10-22 | 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 |
-
2012
- 2012-11-02 CN CN201210432458.5A patent/CN102874868B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4041138A (en) * | 1975-08-21 | 1977-08-09 | Hermann C. Starck | Process for the preparation of crystalline potassium tantalum fluoride |
| US4442082A (en) * | 1982-12-27 | 1984-04-10 | Sri International | Process for obtaining silicon from fluosilicic acid |
| CN101289195A (en) * | 2007-04-19 | 2008-10-22 | 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 |
Non-Patent Citations (3)
| Title |
|---|
| 《化工百科全书 第5卷 氟化合物--工业溶剂》 19931130 陈嘉甫等 《化工百科全书 第5卷 氟化合物--工业溶剂》 北京市：化学工业出版社 第781页 1-3 , 第1版 * |
| JACK SCHUBERT ET AL.: "《The use of ion exchangers for the determination of physicochemical properties of substances, particularly radiotracers, in solution. III. The radiocolloids of zirconium and niobium》", 《JOURNAL OF COLLOID SCIENCE》, vol. 5, no. 4, 31 August 1950 (1950-08-31), pages 376 - 385 * |
| 陈嘉甫等: "《化工百科全书 第5卷 氟化合物——工业溶剂》", 30 November 1993, article "《化工百科全书 第5卷 氟化合物——工业溶剂》", pages: 781 * |
Cited By (3)
| 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 |
| CN111689517A (en) * | 2020-05-29 | 2020-09-22 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102874868B (en) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103991882B (en) | The fluorine in phosphoric acid by wet process liquid phase is utilized to prepare the method for Potassium monofluoride | |
| CN101289195B (en) | Process for preparing potassium borofluoride and co-production of white carbon black and sodium fluosilicate | |
| CN101376507A (en) | Method for producing sodium fluoride | |
| CN101397141A (en) | Method for preparing potassium fluoborate | |
| CN102161505A (en) | Recycling preparation process of potassium fluotitanate | |
| CN101734701B (en) | Method for producing cryolite by using fluorine-containing slag of electrolytic aluminum | |
| CN102874868B (en) | Method for preparing potassium fluozirconate through fluosilicic acid | |
| US20130098207A1 (en) | Method for cyclically preparing titanium sponge and coproducing potassium cryolite using potassium fluotitanate as intermediate material | |
| CN102786081A (en) | Method for preparing potassium fluotitanate from titanium alloy chemical milling waste liquid | |
| CN104692436A (en) | Method for preparing cryolite from coal ash | |
| CN105174269B (en) | A kind of technique that potassium fluosilicate is reclaimed in potassium fluotitanate production process | |
| CN106629800A (en) | Method for producing cryolite from fluosilicic acid waste liquid | |
| GB2513931A (en) | Method for cyclically preparing titanium sponge and simultaneously producing sodium cryolite using sodium fluorotitanate as an intermediate material | |
| CN101967003A (en) | Method for preparing barium fluoride from organic fluoridation waste | |
| CN101423224A (en) | Potassium borofluoride preparation method based on fluosilicic acid and boron rock | |
| US8562931B2 (en) | Method for cyclically preparing monomer boron and coproducing potassium cryolite using potassium fluoborate as intermediate material | |
| CN107857286A (en) | A kind of method that ice crystal is produced using fluosilicic acid waste liquid | |
| CN108083295A (en) | A kind of method that potassium fluoride is directly prepared using wet process phosphoric acid by-product fluosilicic acid | |
| CN102815680A (en) | Method for producing lithium phosphate by using lithium-containing waste liquid | |
| CN113800525A (en) | Method for co-producing fluosilicate and hydrochloric acid by using boron salt tail gas | |
| CN101391793A (en) | Method for preparing kryocide | |
| CN102874855A (en) | Lithium-containing sodium cryolite and preparation method thereof | |
| CN104671290B (en) | A kind of method utilizing pickling mud to prepare iron oxide red | |
| CN104209128A (en) | Composite catalyst for direct chlorination reaction to prepare dichloroethane | |
| CN104192852A (en) | Method for performing gas phase desilication on silicon-containing minerals and recycling halogen-containing substances |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140528 Termination date: 20191102 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |