CN102602993A - Method for recovering zirconium element from zirconium oxychloride crystallized mother liquor raffinate - Google Patents
Method for recovering zirconium element from zirconium oxychloride crystallized mother liquor raffinate Download PDFInfo
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- CN102602993A CN102602993A CN2012100967788A CN201210096778A CN102602993A CN 102602993 A CN102602993 A CN 102602993A CN 2012100967788 A CN2012100967788 A CN 2012100967788A CN 201210096778 A CN201210096778 A CN 201210096778A CN 102602993 A CN102602993 A CN 102602993A
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Abstract
The invention discloses a method for recovering a zirconium element from zirconium oxychloride crystallized mother liquor raffinate, which comprises the following steps of: a) pressurizing and filtering after the zirconium oxychloride crystallized mother liquor raffinate is neutralized by sodium hydroxide; b) dissolving a filter cake obtained by filtering via sulfuric acid in step a), flocculating, pressurizing and filtering; c) crystalizing after the zirconium sulfate solution obtained by filtering in step b) is condensed and cooled, drying the mother liquor raffinate to obtain crystal, and leaching by prepared acid liquor; and d) dissolving the zirconium sulfate crystal obtained in step c) with water, pressurizing, filtering, precipitating and filtering the solution of the zirconium sulfate crystal with ammonia water, and washing, drying and roasting the filter cake to obtain a zirconium dioxide finished product with high purity. The method for recovering the zirconium element from zirconium oxychloride crystallized mother liquor raffinate has the characteristics that silicon and other substances which are insoluble in acid can be very easily separated from the solution, the efficiency of the filtering technology is substantially improved, and the zirconium element in the acidic mother liquor raffinate is fully recovered and separated.
Description
Technical field:
The present invention relates to a kind of method that reclaims zr element, especially relate to a kind of method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element.
Background technology:
Zirconium oxychloride (ZrOCl28H2O) is a midbody of producing ZIRCONIUM DIOXIDE 99.5, zirconium sulfate, zirconium nitrate, zirconium carbonate.Surplus solution appellation mother liquor raffinate after crystallization is separated out in the concentration technology process during domestic common employing alkali fusion explained hereafter zirconium oxychloride is acid, except that containing residual zr element, also has iron, aluminium, sodium, silicon etc. to reach other impurity.Because above-mentioned impurity because the mother liquor raffinate recycle can the amount of causing accumulation, directly influence the quality product of zirconium oxychloride.For guaranteeing the quality of zirconium oxychloride, big multiple enterprises does not recycle the mother liquor raffinate usually or circulation primary is used the back dilution discharge.According to statistics, 1 ton of zirconium oxychloride of every production generates 0.5 ton of acid mother liquid raffinate approximately.Mother liquor raffinate such as direct dilution discharge, waste resource and contaminate environment.In sodium hydroxide solution with back pressure filtration, but the qualified discharge of filtrating, filter residue promptly contains the zirconium filter residue, recyclable zirconium resource wherein.Containing the zirconium filter residue is the higher gum polymers of a kind of water cut, and outward appearance is pistac, and staple has soluble zirconium, water, silicon-dioxide, zircon sand, a spot of iron, aluminium, sodium etc. and other impurity, and wherein solids content is about 20%.To contain the zirconium filter residue and mix the stirring heating dissolving with the finite concentration hydrochloric acid soln with proper ratio, soluble zirconium gets into liquid phase, utilizes plate-and-frame filter press with liquid-solid separation again, obtains soluble zirconium (zirconium oxychloride) solution and white residue filter cake.
Contain zirconium filter residue and finite concentration hydrochloric acid soln and can produce gum polymers after with suitable mixed heating for dissolving, be difficult to filter the process implementing difficulty.
Summary of the invention:
Technical problem to be solved by this invention is to provide a kind of technology simply from zirconium oxychloride crystalline mother solution raffinate, to reclaim the method for zr element.
In order to solve the problems of the technologies described above; The present invention realizes through following technical scheme: a kind of method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element, this method comprises: a. with zirconium oxychloride crystalline mother solution raffinate with in the sodium hydroxide with pressure filtration afterwards; B. with the filter cake that obtains after filtering among the sulfuric acid dissolution step a, flocculation pressure filtration; C. with obtaining zirconium sulfate solution after filtering among the step b through concentrating the cooling post crystallization, take off fundatrix liquid raffinate, the crystal that obtains is again with the acid solution drip washing that configures; D. with the zirconium sulfate crystal that obtains among the step c with water dissolution, pressure filtration, its solution is with ammonia precipitation process, filtration, filter cake washing, oven dry, roasting obtain the higher ZIRCONIUM DIOXIDE 99.5 finished product of purity.
Preferably, the mother liquor raffinate acidity among the said step a is the 2-4 mol, and described sodium hydroxide quality is 5%-15% than concentration, and the neutralization reaction condition is normal temperature (20 ℃), and normal pressure (0.1MPa) is about time 5-15 minute.
Preferably, the pressure filtration pressure among described step a, b and the d is the 2-4 kg/cm.
Preferably, the sulfuric acid quality among the described step b wants 93% at least than concentration, and solvent temperature is 90 ℃, normal pressure (0.1MPa), time 25-35 minute.
Preferably, negative pressure is the 0.7-0.9 kg/cm when concentrating among the said step c, and temperature 80-100 ℃, time 3-5 hour, described drip washing used acid solution to be the dilute sulphuric acid of quality than concentration 5%.
Preferably, the ammoniacal liquor quality in the said steps d is 16%-20% than concentration, and described maturing temperature is 600 ℃, time 3-4 hour.
Compared with prior art; Usefulness of the present invention is: this method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element is to adopt sulfuric acid dissolution zirconium slag; Silicon sol becomes very easily filtering silicon gel, through flocculation filtration, silicon and other be insoluble to acid material easily with solution separating; The efficient of filtration process increases substantially, and fully reclaims and isolates the zr element in the acid mother liquid raffinate.
Description of drawings:
Below in conjunction with accompanying drawing the present invention is further specified.
Fig. 1 is a kind of method process flow sheet that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element of the present invention.
Embodiment:
Describe the present invention below in conjunction with accompanying drawing and embodiment:
A kind of method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element as shown in Figure 1 adopts following steps:
A. with the mother liquor raffinate with in the sodium hydroxide with the back pressure filtration; Transfer to neutral back and produce zirconium slag throw out; The zirconium slag staple of output has zirconium nitrate, ironic hydroxide, water, silicon-dioxide, a spot of sodium and other impurity after filtering; The neutral water reusable edible has been avoided the acid solution pollution simultaneously and has been settled out zirconium wherein, and impurity such as the iron in the mother liquor raffinate, silicon also are precipitated out thereupon simultaneously.Reaction formula is following;
Main reaction: ZrOCl
2+ 2NaOH==ZrO (OH)
2↓+2NaCl
B. with the filter cake that obtains after filtering among the sulfuric acid dissolution step a, zirconium, iron, calcium etc. get in the solution with ionic species, and silicon sol becomes the silicon gel, obtain zirconium sulfate solution through flocculation pressure filtration desiliconization.
Main reaction: ZrO (OH)
2+ H2SO4==ZrOSO4+2H2O
C. with obtaining zirconium sulfate solution after filtering among the step b through concentrating the cooling post crystallization, take off fundatrix liquid raffinate, crystal is again with the acid solution drip washing that configures, and can remove iron in the crystal, sodium preferably and other are dissolved in the impurity of acid.
D. with the zirconium sulfate crystal that obtains among the step c with water dissolution, filtration, further remove water-fast impurity, solution is with ammonia precipitation process, filtration, filter cake washing, oven dry, roasting obtain the higher ZIRCONIUM DIOXIDE 99.5 finished product of purity.
Main reaction: ZrOSO4+2NH4OH==ZrO (OH)
2↓+(NH4)
2SO4
ZrO(OH)
2＝＝ZrO2+2H2O
Described mother liquor raffinate acidity is the 2-4 mol, preferred 2.5-3 mol, and described sodium hydroxide quality is 5%-15% than concentration; Preferred 8%-11%, the neutralization reaction condition is normal temperature (20 ℃), normal pressure (0.1MPa); Time 5-15 minute, preferred 9-12 minute.
Sulfuric acid quality among the described step b wants 93% at least than concentration, and solvent temperature is 90 ℃, normal pressure (0.1MPa), time 25-35 minute.
Negative pressure is the 0.7-0.9 kg/cm when concentrating among the said step c, and temperature 80-100 ℃, time 3-5 hour, described drip washing used acid solution to be the dilute sulphuric acid of quality than concentration 5%.
Ammoniacal liquor quality in the said steps d is 16%-20% than concentration, and described maturing temperature is 600 ℃, time 3-4 hour.
Pressure filtration pressure among described step a, b and the d is the 2-4 kg/cm.
It is emphasized that: above only is preferred embodiment of the present invention; Be not that the present invention is done any pro forma restriction; Every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (6)
1. method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element, this method comprises:
A. with zirconium oxychloride crystalline mother solution raffinate with in the sodium hydroxide with the back pressure filtration;
B. with the filter cake that obtains after filtering among the sulfuric acid dissolution step a, flocculation pressure filtration;
C. with obtaining zirconium sulfate solution after filtering among the step b through concentrating the cooling post crystallization, take off fundatrix liquid raffinate, the crystal that obtains is again with the acid solution drip washing that configures;
D. with the zirconium sulfate crystal that obtains among the step c with water dissolution, pressure filtration, its solution is with ammonia precipitation process, filtration, filter cake washing, oven dry, roasting, the ZIRCONIUM DIOXIDE 99.5 finished product that obtains.
2. a kind of method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element according to claim 1; It is characterized in that: described mother liquor raffinate acidity is the 2-4 mol; Described sodium hydroxide quality is 5%-15% than concentration; The neutralization reaction condition is 20 ℃ of normal temperature, normal pressure 0.1MPa, time 5-15 minute.
3. a kind of method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element according to claim 1, it is characterized in that: the sulfuric acid quality among the described step b wants 93% at least than concentration, and solvent temperature is 90 ℃, normal pressure 0.1MPa, time 25-35 minute.
4. a kind of method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element according to claim 1; It is characterized in that: negative pressure is the 0.7-0.9 kg/cm when concentrating among the said step c; Temperature 80-100 ℃; Time 3-5 hour, described acid solution quality was 5% dilute sulphuric acid than concentration.
5. a kind of method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element according to claim 1, it is characterized in that: the ammoniacal liquor quality in the said steps d is 16%-20% than concentration, described maturing temperature is 600 ℃, time 3-4 hour.
6. a kind of method that from zirconium oxychloride crystalline mother solution raffinate, reclaims zr element according to claim 1, it is characterized in that: the pressure filtration pressure among described step a, b and the d is the 2-4 kg/cm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003438A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for desiliconization of zirconium oxychloride acidolysis solution |
| CN105819504A (en) * | 2016-03-21 | 2016-08-03 | 河南佰利联化学股份有限公司 | Method utilizing hydrogen chloride gas method to prepare zirconium oxychloride |
| CN107021517A (en) * | 2017-05-23 | 2017-08-08 | 天津市光复科技发展有限公司 | The production method of high pure electronic grade strontium nitrate |
| CN109536718A (en) * | 2018-12-07 | 2019-03-29 | 江苏科技大学 | A method of zr element in recycling abraum salt containing zirconium monochloride |
| CN110878389A (en) * | 2019-11-04 | 2020-03-13 | 江西晶安高科技股份有限公司 | Method for treating crystallization mother liquor in zirconium oxychloride production process |
| CN111302394A (en) * | 2020-02-28 | 2020-06-19 | 神华准能资源综合开发有限公司 | Regeneration method of deep purification agent used in production of alumina by one-step acid dissolution method |
| CN111362289A (en) * | 2020-03-19 | 2020-07-03 | 神华准能资源综合开发有限公司 | Preparation method of high-purity aluminum oxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132181A (en) * | 1995-03-31 | 1996-10-02 | 广东工学院 | Method for prepn. of electronic grade ZrO2 by Zircon |
| CN101565202A (en) * | 2009-06-08 | 2009-10-28 | 浙江升华拜克生物股份有限公司 | Silicon slag treating process in zirconyl chloride production |
-
2012
- 2012-04-05 CN CN2012100967788A patent/CN102602993A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132181A (en) * | 1995-03-31 | 1996-10-02 | 广东工学院 | Method for prepn. of electronic grade ZrO2 by Zircon |
| CN101565202A (en) * | 2009-06-08 | 2009-10-28 | 浙江升华拜克生物股份有限公司 | Silicon slag treating process in zirconyl chloride production |
Non-Patent Citations (1)
| Title |
|---|
| 张建东等: "氯氧化锆生产中废碱水和锆硅渣回收利用研究进展", 《稀有金属》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003438A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for desiliconization of zirconium oxychloride acidolysis solution |
| CN104003438B (en) * | 2013-02-26 | 2016-04-06 | 中国科学院过程工程研究所 | The method of a kind of zirconium oxychloride acid hydrolysis solution desiliconization |
| CN105819504A (en) * | 2016-03-21 | 2016-08-03 | 河南佰利联化学股份有限公司 | Method utilizing hydrogen chloride gas method to prepare zirconium oxychloride |
| CN107021517A (en) * | 2017-05-23 | 2017-08-08 | 天津市光复科技发展有限公司 | The production method of high pure electronic grade strontium nitrate |
| CN109536718A (en) * | 2018-12-07 | 2019-03-29 | 江苏科技大学 | A method of zr element in recycling abraum salt containing zirconium monochloride |
| CN110878389A (en) * | 2019-11-04 | 2020-03-13 | 江西晶安高科技股份有限公司 | Method for treating crystallization mother liquor in zirconium oxychloride production process |
| CN111302394A (en) * | 2020-02-28 | 2020-06-19 | 神华准能资源综合开发有限公司 | Regeneration method of deep purification agent used in production of alumina by one-step acid dissolution method |
| CN111302394B (en) * | 2020-02-28 | 2022-09-02 | 神华准能资源综合开发有限公司 | Regeneration method of deep purification agent used in production of alumina by one-step acid dissolution method |
| CN111362289A (en) * | 2020-03-19 | 2020-07-03 | 神华准能资源综合开发有限公司 | Preparation method of high-purity aluminum oxide |
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Application publication date: 20120725 |