CN101638249A - Zirconium tetrachloride purification method - Google Patents
Zirconium tetrachloride purification method Download PDFInfo
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- CN101638249A CN101638249A CN200910187265A CN200910187265A CN101638249A CN 101638249 A CN101638249 A CN 101638249A CN 200910187265 A CN200910187265 A CN 200910187265A CN 200910187265 A CN200910187265 A CN 200910187265A CN 101638249 A CN101638249 A CN 101638249A
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- CN
- China
- Prior art keywords
- molten salt
- furnace
- fused salt
- zrcl
- purification method
- Prior art date
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- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000000746 purification Methods 0.000 title claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 230000005496 eutectics Effects 0.000 claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- 229910007926 ZrCl Inorganic materials 0.000 claims description 23
- 238000007599 discharging Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 14
- 238000009835 boiling Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000001704 evaporation Methods 0.000 abstract description 6
- 230000008020 evaporation Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 229910007932 ZrCl4 Inorganic materials 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract 2
- 238000005086 pumping Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 6
- 238000013022 venting Methods 0.000 description 5
- 238000011027 product recovery Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a zirconium tetrachloride purification method solving the problems that the prior purification method has a certain risk, hardly ensures the yield and the quality due to manual discharge adjustment when separating impurities with low boiling points and has continuous production incapability, very low productivity and low recovery rate. The method comprises the following steps: firstly, mixing crude ZrCl4 as well as NaCl and KCl to a molten salt furnace; heating to 290-350 DEG C to form eutectic molten salt with a low boiling point; continuously and additionally addingZrCl4 to the molten salt furnace, wherein the weight ratio of the ZrCl4 to the molten salt every hour is from 1:44 to 1:88; pumping 20-30 percent of molten salt by total weight into an evaporation furnace by a pump; controlling the furnace temperature at 500-650 DEG C to evaporate and condense the ZrCl4; intermittently exchanging the molten salt by returning 10-20 percent of added molten salt by total weight from the evaporation furnace to the molten salt furnace; adding new molten salt by the pump according to the amount of the returned molten salt; and repeating the steps to continuously discharge. The purification method is riskless, ensures the safe production and has simple process for removing the product impurities, stable quality, continuous production, high productivity and high recovery rate without high-temperature and low-temperature discharge links.
Description
Technical field
The present invention relates to a kind of Zirconium tetrachloride purification method.
Background technology
Thick zirconium tetrachloride contains Si≤0.1, Al≤0.1, Fe≤0.1, Ti≤0.1, and the smart ZrCl4 in back that purifies contains Fe≤0.02, Si≤0.003, Al≤0.005, Ti≤0.003, and these four kinds of impurity all are to be present in the zirconium tetrachloride with muriate.It mainly is that impurity Si, Al in the zirconium tetrachloride, Fe, Ti impurity are separated with zirconium tetrachloride that zirconium tetrachloride is purified, and makes the zirconium tetrachloride quality product improve.Zirconium tetrachloride is purified mainly by means such as low temperature venting, high-temperature outgassing, hydrogenating reductions at present, realizes by zirconium tetrachloride evaporative condenser process.Be specially: the hydrogenation thick ZrCl that purifies
4, with 1 to 1.2 ton of thick zirconium tetrachloride pack into heated sealed, venting, hydrogenation, evaporative condenser in the purification furnace, dismantle, get material, 80-90 hour every stove cycle.This method is utilized ZrCl
4Separate with vapour pressure difference and with impurity with the boiling point of impurity chlorides and to remove, as ZrCl
4: 331 ℃ of distillations, SiCl
4: 57 ℃ of boiling points, AlCl
3: 183 ℃ of boiling points, TiCl
4: 138 ℃ of boiling points, FeCl
3: 319 ℃ of boiling points.Low boilers can be exitted by high low temperature and be realized removal of impurity purpose, because FeCl
3With ZrCl
4Close being difficult to of boiling point removed, and therefore will add the hydrogen reduction, and reaction formula is: FeCl
3+ H
2→ FeCl
2+ HCl, FeCl
2Boiling point becomes high-boiling-point impurity and stays in the residue more than 1200 ℃, and the zirconium tetrachloride of evaporative condenser is collected in the condenser.The problem that aforesaid method exists is: 1, hydrogen storage is used and is had certain risk, 2, separate lower-boiling impurity and be difficult to guarantee output and quality by artificial venting adjustment, 3, can not continuous production, production capacity is very low, 4, because the often venting removal of impurity, the rate of recovery is low, has only 90%.
Summary of the invention
The objective of the invention is to solve the problems referred to above that prior art exists, provide a kind of and ensure safety in production, product removal of impurities process is simple, steady quality, can continuous production and production capacity height, there is not high low temperature venting link, the Zirconium tetrachloride purification method that the rate of recovery is high.
Technical solution of the present invention is:
1) earlier with thick ZrCl
4Add in the molten salt furnace according to 5: 1: 1～12: 1: 1 mixed of ratio of weight and number with NaCl, KCl, be heated to 290～350 ℃ and make it form low melting point eutectic fused salt;
2) get thick ZrCl in addition
4Add in the molten salt furnace, per hour the thick ZrCl of Jia Ruing
4With the weight ratio of fused salt 1: 44～1: 80, continuous charging;
3) add after, with pump 20～30% of fused salt gross weight is squeezed in the vapourizing furnace, 500～650 ℃ of furnace temperature of control make ZrCl
4Evaporative condenser is collected in condenser;
4) interruption is changed fused salt, per hour puts back to the fused salt weight of squeezing into 10～20% to molten salt furnace in vapourizing furnace, stamps new fused salt with pump according to the fused salt amount of putting back to again, so repeatedly, and discharging continuously.
Above-mentioned Zirconium tetrachloride purification method, the waste gas that produces in reinforced process is discharged by blower fan after eluting column drip washing.
The thick ZrCl of this method utilization
4Mix by a certain percentage, heat with NaCl, KCl, form the low melting point eutectic, fusing point utilizes this melt to do carrier, with thick ZrCl at 290 ℃
4Add continuously in this melt, with pump melt is got to and made ZrCl in the vapourizing furnace
4Constantly be evaporated thick ZrCl
4In impurity SiCl
4TiCl
4When adding bath surface since melt temperature about 300 ℃, can directly all volatilize away; And AlCl
3, FeCl
3A part vapors away, a part is fusible in melt directly and K, Na ion in the fused salt form high boiling mixture; FeKNa
+, AlKNa
+Stay in the fused salt, make ZrCl by the second-heating fused salt
4Evaporate again, be condensate in the condenser and collect.This process can heat continuously, the consecutive evaporation discharging, and waste gas is discharged by blower fan after eluting column drip washing (can carry out the NaOH neutralizing treatment again); The production continuously feeding, discharging has continuously realized producing and has carried out continuously, and production capacity improves more than 6 times, and product recovery rate improves 6% (reaching 96%); Do not use hydrogen, do not have danger, ensure safety in production.
Embodiment
Embodiment 1
Earlier with the thick ZrCl of 6000kg
4Mix with 1000kgNaCl, 1000kgKCl in the adding molten salt furnace, be heated to 290 ℃ and make it form 8 tons of low melting point eutectic fused salts;
Per hour in melt, add thick zirconium tetrachloride 100kg, continuous charging;
After adding, with pump the 2200kg fused salt is squeezed in the vapourizing furnace, 500～550 ℃ of vapourizing furnace control furnace temperature make ZrCl
4Evaporative condenser is collected in condenser;
Be interrupted and change fused salt, per hour in vapourizing furnace, put back to 220kg, in vapourizing furnace, replenish the 220kg fused salt with pump again to molten salt furnace, so repeatedly, consecutive evaporation in the vapourizing furnace, discharging continuously, per tour 8 hourly outputs reach 770kg.
Embodiment 2
Earlier with the thick ZrCl of 6400kg
4Mix with 800kgNaCl, 800kgKCl in the adding molten salt furnace, be heated to 330 ℃ and make it form 8 tons of low melting point eutectic fused salts;
Per hour in melt, add thick zirconium tetrachloride 180kg, continuous charging;
After adding, with pump the 2000kg melt is squeezed into vapourizing furnace continuously, 600～650 ℃ of vapourizing furnace control furnace temperature make ZrCl
4Evaporative condenser is collected in condenser;
Be interrupted and change fused salt, per hour in vapourizing furnace, put back to 360kg again with pump additional 360kg fused salt in vapourizing furnace to molten salt furnace, so repeatedly, consecutive evaporation in the vapourizing furnace, discharging continuously, per tour 8 hourly outputs reach 1380kg.
Embodiment 3
Earlier with the thick ZrCl of 6800kg
4Mix with 600kgNaCl, 600kgKCl in the adding molten salt furnace, be heated to 350 ℃ and make it form 8 tons of low melting point eutectic fused salts;
Per hour in melt, add thick zirconium tetrachloride 150kg, continuous charging;
After adding, with pump the 1800kg melt is squeezed into vapourizing furnace continuously, 550～600 ℃ of vapourizing furnace control furnace temperature make ZrCl
4Evaporative condenser is collected in condenser;
Be interrupted and change fused salt, per hour in vapourizing furnace, put back to 280kg, in vapourizing furnace, replenish the 280kg fused salt with pump again to molten salt furnace, so repeatedly, consecutive evaporation in the vapourizing furnace, discharging continuously, per tour 8 hourly outputs reach 1160kg.
The result that the zirconium tetrachloride that embodiment 1～embodiment 3 purifies records is as follows:
Embodiment 1
Fe 0.05 Al 0.04 Si 0.08 Ti 0.076 before purifying
Back Fe 0.016 Al 0.002 Si 0.0025 Ti 0.0022 purifies
Product recovery rate 96.25%
Embodiment 2
Fe 0.06 Al 0.11 Si 0.13 Ti 0.066 before purifying
Back Fe 0.011 Al 0.0026 Si 0.0011 Ti 0.0015 purifies
Product recovery rate 95.83%
Embodiment 3
Fe 0.068 Al 0.088 Si 0.076 Ti 0.055 before purifying
Back Fe 0.013 Al 0.0022 Si 0.0008 Ti 0.0010 purifies
Product recovery rate 96.66%
By the physico-chemical analysis of above three batch materials, this method is finished the impurity composition requirement that can reach anticipation, and quality is highly stable, and production can be carried out continuously,
Can be high, atmospheric operation safety and environmental protection, rate of recovery height.
Claims (2)
1, a kind of Zirconium tetrachloride purification method is characterized in that:
1.1 earlier with thick ZrCl
4Add in the molten salt furnace according to 5: 1: 1～12: 1: 1 mixed of ratio of weight and number with NaCl, KCl, be heated to 290～350 ℃ and make it form low melting point eutectic fused salt;
1.2 get thick ZrCl in addition
4Add in the molten salt furnace, per hour the thick ZrCl of Jia Ruing
4With the weight ratio of fused salt 1: 44～1: 80, continuous charging;
1.3 after adding, with pump 20～30% of fused salt gross weight is squeezed in the vapourizing furnace, 500～650 ℃ of control furnace temperature make ZrCl
4Evaporative condenser is collected in condenser;
Change fused salt 1.4 be interrupted, per hour in vapourizing furnace, put back to the fused salt weight of squeezing into 10～20%, stamp new fused salt with pump according to the fused salt amount of putting back to again to molten salt furnace, so repeatedly, discharging continuously.
2, Zirconium tetrachloride purification method according to claim 1 is characterized in that: the waste gas that produces in reinforced process is discharged by blower fan after eluting column drip washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101872656A CN101638249B (en) | 2009-09-04 | 2009-09-04 | Zirconium tetrachloride purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101872656A CN101638249B (en) | 2009-09-04 | 2009-09-04 | Zirconium tetrachloride purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101638249A true CN101638249A (en) | 2010-02-03 |
| CN101638249B CN101638249B (en) | 2010-10-27 |
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|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107235509A (en) * | 2017-06-29 | 2017-10-10 | 赤峰盛森硅业科技发展有限公司 | A kind of fluidizing chlorination method zirconium oxychloride process units and method |
| CN109019682A (en) * | 2018-08-20 | 2018-12-18 | 新特能源股份有限公司 | A kind of zirconium oxychloride and preparation method thereof |
| CN110453084A (en) * | 2019-08-06 | 2019-11-15 | 辽宁华祥新材料有限公司 | A kind of preparation method of atomic energy level sponge zirconium |
| CN112028023A (en) * | 2020-09-15 | 2020-12-04 | 湖南澎越新材料有限公司 | Method and device for purifying and pulverizing metal chloride |
| CN112047378A (en) * | 2020-09-21 | 2020-12-08 | 宝钛华神钛业有限公司 | Zirconium tetrachloride purification method based on hydrogen reduction method |
| CN112209436A (en) * | 2020-10-29 | 2021-01-12 | 锦州中特电炉有限公司 | Method for enriching hafnium tetrachloride by taking crude zirconium tetrachloride as raw material |
| CN112357885A (en) * | 2020-12-02 | 2021-02-12 | 中国科学院上海应用物理研究所 | Purification method of single component in chloride molten salt |
| CN112551567A (en) * | 2020-12-02 | 2021-03-26 | 中国科学院上海应用物理研究所 | Purification method of chloride |
| CN112624193A (en) * | 2020-12-31 | 2021-04-09 | 三祥新材股份有限公司 | Method for purifying hafnium tetrachloride |
| CN113772724A (en) * | 2021-10-20 | 2021-12-10 | 辽宁华锆新材料有限公司 | Method and equipment for preparing refined zirconium tetrachloride by molten salt purification method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2120021B1 (en) * | 1970-12-28 | 1974-06-07 | Ishizuka Hiroshi | |
| US5009866A (en) * | 1989-11-16 | 1991-04-23 | Westinghouse Electric Corp. | Fused salt process for purifying zirconium and/or hafnium tetrachlorides |
| CN1052148A (en) * | 1989-11-29 | 1991-06-12 | 泰利达因工业有限公司 | High-purity zirconium and Hf metals and method for making thereof |
| FR2823740B1 (en) * | 2001-04-18 | 2004-02-06 | Cezus Co Europ Zirconium | PROCESS FOR SEPARATING ZIRCONIUM AND HAFNIUM TETRACHLORIDES |
-
2009
- 2009-09-04 CN CN2009101872656A patent/CN101638249B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107235509A (en) * | 2017-06-29 | 2017-10-10 | 赤峰盛森硅业科技发展有限公司 | A kind of fluidizing chlorination method zirconium oxychloride process units and method |
| CN109019682A (en) * | 2018-08-20 | 2018-12-18 | 新特能源股份有限公司 | A kind of zirconium oxychloride and preparation method thereof |
| CN109019682B (en) * | 2018-08-20 | 2020-01-17 | 新特能源股份有限公司 | Zirconium oxychloride and preparation method thereof |
| CN110453084A (en) * | 2019-08-06 | 2019-11-15 | 辽宁华祥新材料有限公司 | A kind of preparation method of atomic energy level sponge zirconium |
| CN112028023A (en) * | 2020-09-15 | 2020-12-04 | 湖南澎越新材料有限公司 | Method and device for purifying and pulverizing metal chloride |
| CN112047378A (en) * | 2020-09-21 | 2020-12-08 | 宝钛华神钛业有限公司 | Zirconium tetrachloride purification method based on hydrogen reduction method |
| CN112209436A (en) * | 2020-10-29 | 2021-01-12 | 锦州中特电炉有限公司 | Method for enriching hafnium tetrachloride by taking crude zirconium tetrachloride as raw material |
| CN112357885A (en) * | 2020-12-02 | 2021-02-12 | 中国科学院上海应用物理研究所 | Purification method of single component in chloride molten salt |
| CN112551567A (en) * | 2020-12-02 | 2021-03-26 | 中国科学院上海应用物理研究所 | Purification method of chloride |
| CN112551567B (en) * | 2020-12-02 | 2022-11-08 | 中国科学院上海应用物理研究所 | Purification method of chloride |
| CN112624193A (en) * | 2020-12-31 | 2021-04-09 | 三祥新材股份有限公司 | Method for purifying hafnium tetrachloride |
| CN112624193B (en) * | 2020-12-31 | 2023-11-10 | 三祥新材股份有限公司 | Purification method of hafnium tetrachloride |
| CN113772724A (en) * | 2021-10-20 | 2021-12-10 | 辽宁华锆新材料有限公司 | Method and equipment for preparing refined zirconium tetrachloride by molten salt purification method |
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| Publication number | Publication date |
|---|---|
| CN101638249B (en) | 2010-10-27 |
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Effective date of registration: 20181018 Address after: 122000 Chaoyang Liucheng Economic Development Zone, Chaoyang City, Liaoning Patentee after: Liaoning Hua Zan New Material Co., Ltd. Address before: 121000 Lingnan 31-12 East Baodi City, Linghe District, Jinzhou, Liaoning Patentee before: Shi Zhengjun |
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