CN102676852A - 一种工业生产金属锆并同步产出低温铝电解质的制备方法 - Google Patents
一种工业生产金属锆并同步产出低温铝电解质的制备方法 Download PDFInfo
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 15
- 239000003792 electrolyte Substances 0.000 title abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 230000001360 synchronised effect Effects 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 229910001610 cryolite Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- -1 sodium aluminum fluoride Chemical compound 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NGCWWPZTKGWTMB-UHFFFAOYSA-I [F-].[F-].[F-].[F-].[F-].[Na+].[Al+3].[K+] Chemical compound [F-].[F-].[F-].[F-].[F-].[Na+].[Al+3].[K+] NGCWWPZTKGWTMB-UHFFFAOYSA-I 0.000 description 2
- SRECPBVISUHZSZ-UHFFFAOYSA-I [Na+].[F-].[Al+3].[Na+].[F-].[F-].[F-].[F-] Chemical compound [Na+].[F-].[Al+3].[Na+].[F-].[F-].[F-].[F-] SRECPBVISUHZSZ-UHFFFAOYSA-I 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/14—Obtaining zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明提供一种工业生产金属锆并同步产出低温铝电解质的制备方法，包括如下步骤：A）将铝和氟锆酸盐置于密闭的反应器中，抽真空后通入惰性气体，升温至780~1000℃，快速搅拌；B）反应4~6h后，将上层熔融的液体抽出得到低温铝电解质，下层产物经酸浸或蒸馏去除表面残留得到金属锆。本发明提供的制备方法简单，反应周期短，可实现金属锆的大规模工业生产，并可同步产出低温铝电解质，该副产物用于铝电解工业，可降低电解温度，降低电能消耗，具有很好的应用前景。
Description
技术领域
本发明涉及金属锆的制备方法，尤其涉及一种工业生产金属锆并同步产出低温铝电解质的制备方法。
背景技术
锆是一种稀有金属，具有熔点高、硬度高和抗腐蚀性强等特性，广泛应用于航空、军工和原子能等领域。现有的金属锆工业制备方法主要有以下两种方法：
（1）还原法：在惰性气体的保护下，以四氯化锆为原料，使用金属镁、钠或其混合物作为还原剂进行还原制备金属锆，该方法存在反应装备复杂、制造综合成本高等缺点。
（2）电解法：以K2ZrF6为原料，用K2ZrF6–KCl或K2ZrF6–NaCl电解质熔盐电解法制备金属锆，该方法存在电解能耗高，金属锆得率低，生产成本高等缺点；除K2ZrF6熔盐电解法外，也可在含有ZrCl4的纯氯化物电解质体系中电解制取锆，但该方法存在电解能耗高，产品质量差等缺点。
发明内容
为解决现有技术中存在的技术问题，发明人在原料的选择以及制备方法方面进行了大量的探索，预料不到地发现，以氟锆酸盐为原料与铝反应可得到金属锆，制备方法简单，反应条件温和，反应周期短，目标产物的纯度高，且副产物冰晶石作为低温铝电解质具有很好的应用前景。
本发明提供一种以氟锆酸钾为原料制备锆的方法，其特征在于：包括如下步骤：
A）将铝和氟锆酸盐置于密闭的反应器中，抽真空后通入惰性气体，升温至780~1000℃，快速搅拌；
B）反应4~6h后，将上层熔融的液体抽出得到低温铝电解质，下层产物经酸浸或蒸馏去除表面残留得到金属锆。
采用上述技术方案，以氟锆酸盐为原料和铝在温和条件下反应即可制备得到纯锆，制备方法简单，反应周期短，可实现锆的大规模工业生产；副产物冰晶石可作为低温铝电解质用于铝电解工业，可降低电解温度，降低电能消耗，具有很好的应用前景。
作为本发明的进一步改进，所述氟锆酸盐选自氟锆酸钾或氟锆酸钠。涉及的化学反应式为： 
。
作为本发明的进一步改进，所述反应时间为5h。反应时间与反应温度、反应物的量密切相关，在780~1000℃条件下的工业生产中，反应时间为5h即可反应完全。
作为本发明的进一步改进，所述反应温度780~850℃。
作为本发明的进一步改进，所述惰性气体为氩气。
与现有技术相比，本发明的有益效果是：本发明提供一种以氟锆酸盐为原料制备锆的方法，制备方法简单，反应周期短，反应条件温和，可实现锆的大规模工业生产；副产物冰晶石可作为低温铝电解质用于铝电解工业，可降低电解温度，降低电能消耗，具有很好的应用前景。
具体实施方式
下面通过具体实施例对本发明做进一步详细说明。
实施例一
称取1吨铝和10.5吨氟锆酸钾于反应器中，该反应器为密闭容器，抽真空后通入氩气保护，升温至780℃，快速搅拌5h后，反应完全，生成锆和钾冰晶石，打开反应器盖，用虹吸泵抽出上层熔融的液态钾冰晶石。待反应器冷却后，在氩气保护下，将下层产物粉碎，加入稀硫酸浸泡去除表面残留的钾冰晶石，经真空干燥后称重，得到纯锆3.0吨。
实施例二
称取1吨铝和10.5吨氟锆酸钾于反应器中，该反应器为密闭容器，抽真空后通入氩气保护，升温至850℃，快速搅拌4h后，反应完全，生成锆和钾冰晶石，打开反应器盖，用虹吸泵抽出上层熔融的液态钾冰晶石。待反应器冷却后，在氩气保护下，蒸馏去除表面残留的钾冰晶石，经真空干燥后称重，得到纯锆3.1吨。
实施例三
称取1吨铝和9.3吨氟锆酸钠于反应器中，该反应器为密闭容器，抽真空后通入氩气保护，升温至800℃，快速搅拌5h后，反应完全，生成锆和钠冰晶石，打开反应器盖，用虹吸泵抽出上层熔融的液态钠冰晶石。待反应器冷却后，在氩气保护下，将下层产物粉碎，加入稀硫酸浸泡去除表面残留的钠冰晶石，经真空干燥后称重，得到纯锆3.0吨。
实施例四
称取1吨铝和9.3吨氟锆酸钠于反应器中，该反应器为密闭容器，抽真空后通入氩气保护，升温至850℃，快速搅拌4h后，反应完全，生成锆和钠冰晶石，打开反应器盖，用虹吸泵抽出上层熔融的液态钠冰晶石。待反应器冷却后，在氩气保护下，蒸馏去除表面残留的钠冰晶石，经真空干燥后称重，得到纯锆3.1吨。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明的保护范围。
Claims (5)
1.一种工业生产金属锆并同步产出低温铝电解质的制备方法，其特征在于：包括如下步骤：
A）将铝和氟锆酸盐置于密闭的反应器中，抽真空后通入惰性气体，升温至780~1000℃，快速搅拌；
B）反应4~6h后，将上层熔融的液体抽出得到低温铝电解质，下层产物经酸浸或蒸馏去除表面残留得到金属锆。
2.根据权利要求1所述的工业生产金属锆并同步产出低温铝电解质的制备方法，其特征在于：所述氟锆酸盐选自氟锆酸钾或氟锆酸钠。
3.根据权利要求1或2所述的工业生产金属锆并同步产出低温铝电解质的制备方法，其特征在于：所述反应时间为5h。
4.根据权利要求3所述的工业生产金属锆并同步产出低温铝电解质的制备方法，其特征在于：所述反应温度为780~850℃。
5.根据权利要求4所述的工业生产金属锆并同步产出低温铝电解质的制备方法，其特征在于：所述惰性气体为氩气。
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101728534A CN102676852A (zh) | 2012-05-30 | 2012-05-30 | 一种工业生产金属锆并同步产出低温铝电解质的制备方法 |
| PCT/CN2012/078374 WO2013177847A1 (zh) | 2012-05-30 | 2012-07-09 | 一种工业生产金属锆并同步产出低温铝电解质的制备方法 |
| EP20120195415 EP2669393B1 (en) | 2012-05-30 | 2012-12-04 | Method for producing metal zirconium industrially and producing low-temperature aluminum electrolyte as byproduct |
| ES12195415.0T ES2524429T3 (es) | 2012-05-30 | 2012-12-04 | Procedimiento para la producción de circonio metálico industrialmente y la producción de un electrolito de aluminio de baja temperatura como producto secundario |
| US13/709,026 US8709130B2 (en) | 2012-05-30 | 2012-12-09 | Method for producing metal zirconium industrially and producing low-temperature aluminum electrolyte as byproduct |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101728534A CN102676852A (zh) | 2012-05-30 | 2012-05-30 | 一种工业生产金属锆并同步产出低温铝电解质的制备方法 |
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| Publication Number | Publication Date |
|---|---|
| CN102676852A true CN102676852A (zh) | 2012-09-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2012101728534A Pending CN102676852A (zh) | 2012-05-30 | 2012-05-30 | 一种工业生产金属锆并同步产出低温铝电解质的制备方法 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US8709130B2 (zh) |
| EP (1) | EP2669393B1 (zh) |
| CN (1) | CN102676852A (zh) |
| ES (1) | ES2524429T3 (zh) |
| WO (1) | WO2013177847A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014015590A1 (zh) * | 2012-07-25 | 2014-01-30 | 深圳市新星轻合金材料股份有限公司 | 铝电解过程中的电解质及其补充体系的制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390365A (en) * | 1980-12-15 | 1983-06-28 | Occidental Research Corporation | Process for making titanium metal from titanium ore |
| CN101386920A (zh) * | 2007-09-13 | 2009-03-18 | 贵阳铝镁设计研究院 | 海绵钛的还原蒸馏方法及u型联合装置 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX143963A (es) * | 1975-10-17 | 1981-08-11 | Teledyne Ind | Mejoras en un metodo para reducir zirconico con un metal reductor tal como el aluminio |
| US4072506A (en) * | 1975-10-17 | 1978-02-07 | Teledyne Industries, Inc. | Method of separating hafnium from zirconium |
| US4468248A (en) * | 1980-12-22 | 1984-08-28 | Occidental Research Corporation | Process for making titanium metal from titanium ore |
| FR2505364A1 (fr) * | 1981-05-06 | 1982-11-12 | Rhone Poulenc Spec Chim | Procede de fabrication d'alliages de titane et d'aluminium |
| EP0134643A3 (en) * | 1983-07-08 | 1986-12-30 | Solex Research Corporation of Japan | Preparing metallic zirconium, hafnium or titanium |
| JPS6017027A (ja) * | 1983-07-08 | 1985-01-28 | Nishimura Watanabe Chiyuushiyutsu Kenkyusho:Kk | 金属ジルコニウム及び金属ハフニウムの製造方法 |
| RU2190031C2 (ru) * | 2000-11-17 | 2002-09-27 | Государственное унитарное предприятие "Всероссийский научно-исследовательский институт химической технологии" | Способ получения гафния или циркония и их сплавов |
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- 2012-05-30 CN CN2012101728534A patent/CN102676852A/zh active Pending
- 2012-07-09 WO PCT/CN2012/078374 patent/WO2013177847A1/zh not_active Ceased
- 2012-12-04 EP EP20120195415 patent/EP2669393B1/en not_active Not-in-force
- 2012-12-04 ES ES12195415.0T patent/ES2524429T3/es active Active
- 2012-12-09 US US13/709,026 patent/US8709130B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390365A (en) * | 1980-12-15 | 1983-06-28 | Occidental Research Corporation | Process for making titanium metal from titanium ore |
| CN101386920A (zh) * | 2007-09-13 | 2009-03-18 | 贵阳铝镁设计研究院 | 海绵钛的还原蒸馏方法及u型联合装置 |
Non-Patent Citations (3)
| Title |
|---|
| RAJAGOPALAN P. K. ET AL.: "Aluminothermic Reduction of K2ZrF6 for Preparation of Al-Zr Master Alloy", 《RARE METALS》, vol. 18, no. 2, 30 June 1999 (1999-06-30), pages 119 - 122, XP008175234 * |
| 徐如人主编: "《无机合成化学》", 31 October 1991, article "4.3.3 金属还原法", pages: 118-123 * |
| 汪小燕等: "Al-K2ZrF6体系熔体反应法合成复合材料的微观组织和力学性能", 《稀有金属材料与工程》, vol. 36, no. 2, 28 February 2007 (2007-02-28), pages 259 - 263 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014015590A1 (zh) * | 2012-07-25 | 2014-01-30 | 深圳市新星轻合金材料股份有限公司 | 铝电解过程中的电解质及其补充体系的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2524429T3 (es) | 2014-12-09 |
| EP2669393B1 (en) | 2014-10-08 |
| US20130091988A1 (en) | 2013-04-18 |
| EP2669393A1 (en) | 2013-12-04 |
| US8709130B2 (en) | 2014-04-29 |
| WO2013177847A1 (zh) | 2013-12-05 |
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Application publication date: 20120919 |