CN1048889A - 消除钇精矿酸溶液萃取乳化的方法 - Google Patents
消除钇精矿酸溶液萃取乳化的方法 Download PDFInfo
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000012141 concentrate Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 238000000605 extraction Methods 0.000 title abstract description 9
- 238000004945 emulsification Methods 0.000 title abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 12
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- 229940045511 barium chloride Drugs 0.000 claims description 20
- 229910001626 barium chloride Inorganic materials 0.000 claims description 20
- 235000010265 sodium sulphite Nutrition 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
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Classifications
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- 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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- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明涉及分离提纯钇时,消除钇精矿酸溶溶液
萃取乳化的方法。用硫化钠为沉淀剂。除去铝、铁和
重金属杂质,再加入氯化钡进行沉淀,本工艺方法除
去铝、铁和重金属杂质彻底,适用于各种钇精矿的前
处理,经净化的料液均可达到萃取料液的要求,萃取
分离钇时不发生乳化现象。节省了原材料消耗,提高
了稀土回收率。
Description
本发明涉及湿法冶金中消除乳化的方法,更具体的说在分离提纯稀土元素时,特别是分离提纯钇时,稀土矿的酸溶溶液的前处理消除萃取乳化的方法。
我国南方低钇稀土矿组份复杂,非稀土元素种类多,而且含量高,其矿石经盐酸分解后,必须进行除铁、铝、硅等杂质的前处理工序,否则在下一步分离萃取提纯钇时,产生严重的乳化现象,使萃取过程难以进行下去。
在已有的技术文献中,有的研究者(王风鸣,南昌硬质合金厂,稀土,2,1985,P32-36),提出将混合稀土矿物用水调成浆状,在搪玻璃反应罐中放入适量盐酸,搅拌,徐徐把矿浆加入到盐酸中去,加完料后加热煮沸0.5-1小时,调PH=3-4,冷却至46℃,再徐徐加入净化剂硫化铵,继续搅拌0.5小时,静置6-12小时,过滤,得到分离萃取钇的料液。在该工艺中,由于所用的净化剂是硫化铵,铁、铝等杂质除去的不完全。由于混合稀土矿物中,根据其产地不同,其成分亦有所不同,有的矿含的钙、镁、硫酸根较高。有许多种矿石经上述的工艺前处理后,在以后的分离萃取钇时,仍出现乳化现象,使萃取分离钇的工艺难以进行下去。
本发明的目的就在于研究出一种新的消除钇精矿酸溶溶液的萃取乳化的方法,用本发明的工艺方法进行前处理后能将铁、铝、重金属等杂质除去完全,适用于各种钇精矿的前处理,而使下一步的萃取分离时不发生乳化现象。
本发明的一种消除钇精矿酸溶溶液萃取乳化的方法,用盐酸酸溶的钇精矿溶液,经除硅后作为料液,用碱金属的硫化物作为沉淀剂,料液的酸度为PH0.5-6.3,使料液温度保持在10℃-沸点之间,搅拌下加入沉淀剂碱金属硫化物,进行固液分离,调节滤液的PH值在0.5-4.5之间,使料液的温度保持在50℃-沸点之间,加入氯化钡,进行固液分离。
所说的碱金属的硫化物沉淀剂是硫化锂、硫化钠、硫化钾其中的一种,但以硫化钠为佳,硫化钠价格便宜,碱性强,不但能除去铅等重金属杂质亦能使铁铝等杂质完全除去。
在本发明中所说的钇精矿是南方低钇稀土矿(离子型矿)经硫酸铵或氯化钠浸出后得到的浸出液经草酸沉淀,煅烧得到的氧化物称为钇精矿,南方低钇稀土矿因产地不同,其化学成分亦不同,例如有安远,赣州地区的低钇稀土矿和某些龙南稀土矿。这些低钇稀土矿经上述处理得到的钇精矿杂质含量仍高,必须前处理,而且这些钇精矿通常含钇比较低。这些钇精矿中除了含有镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、等稀土元素外还含有三氧化二钇30%以上,三氧化二铁0.050-0.15%,二氧化硅0.017-1.2%,氧化钙、氧化镁合量0.080-3.5%,含硫酸根0.040-1.40%。
将上述钇精矿矿石加少量水将料润湿调浆,按每公斤稀土氧化物加入1.8-2.2升工业盐酸,搅拌加热至沸,控制PH0.5-1,煮沸搅拌30分钟,趁热过滤,进行固液分离,除去硅的滤液作为本发明的工艺的料液,料液的酸度控制在PH0.3-6.3,以控制料液酸度PH3-4为佳,(可用氢氧化铵,碳酸稀土或盐酸调节PH),料液中氯化稀土的浓度控制在0.7-3摩尔/升,料液中氯化稀土的较佳浓度为1.5-2.3摩尔/升。料液中氯化稀土浓度小于0.7摩尔/升,净化不易合格,设备利用率亦低,经济效益低,但料液中氯化稀土浓度亦不应达到饱和。
将上述除去硅的氯化稀土溶液作为料液,控制料液的酸度PH为0.5-6.3,较佳的料液酸度为PH3-4,控制料液的温度为10℃-沸点,如果料液的温度大于90℃,沉淀剂硫化钠有部分分解而损失,如果料液的温度小于10℃,沉淀难以过滤,易透滤,料液达不到净化的要求,所以控制料液较佳的温度为40°-70℃,按稀土氧化物∶硫化钠=1000∶25-60(重量比),在搅拌下缓慢加入硫化钠溶液,加入硫化钠的量以稀土氧化物∶硫化钠=1000∶30-40(重量比)为佳,加入硫化钠后再继续搅拌15分钟以上,静置澄清,进行固液分离,固液分离的方法有过滤、真空过滤、吸滤、离心分离,压滤等。除杂后的溶液的酸度控制在PH4-6.5,但控制在PH4.5-5.5较佳。所加入的硫化钠溶液为工业级含硫化钠大于60%(重量百分数)的硫化钠溶液亦可以加固体硫化钠,但加入硫化钠溶液为佳,易混合均匀。
经加入硫化钠除去铝、铁和重金属离子例如铅等杂质后的滤液,滤液中氯化稀土的浓度为0.7-3摩尔/升,滤液中氯化稀土的浓度为1.5-2.3摩尔/升较佳,滤液的酸度控制在0.5-4.5,滤液的酸度最好控制在PH0.5-1,滤液的温度控制在50℃-沸点,最好控制在90℃-沸点,在搅拌下加入氯化钡的量按稀土氧化物∶氯化钡=1000∶30-80(重量比),加入氯化钡的量以稀土氧化物∶氯化钡=1000∶35-50(重量比)为佳,加完氯化钡后再搅拌5分钟以上,进行固液分离。所加入的氯化钡可以以固体状加入亦可以以氯化钡水溶液的形式加入。
加入氯化钡溶液后经过滤所得的滤液,由环烷酸萃取检验后不发生乳化为合格的萃取分离钇的料液。其检验的方法是将经过氯化钡沉淀后的滤液,使其氯化稀土的含量为1.0摩尔/升,其PH为2-3,一般控制在PH2.5,有机相组成为22%环烷酸-18%工业级混合醇-60%磺化煤油,氨化度90%,有机相∶水相=5∶1,萃取5分钟以上,分层时间在10分钟以内,界面净两相清亮为合格。
在本发明的工艺中所用的分析方法是,总稀土氧化物用EDTA容量滴定法,酸度用酸度计测定,或用酸碱滴定法、PH试纸法测定。
本发明的工艺方法的优点在于消除乳化的方法工艺简单,将铝、铁和重金属,例如铅等杂质除去彻底,适用于各种钇精矿的前处理,经净化后的料液均可达到萃取料液的要求,萃取分离钇时,不发生乳化现象。节省了原材料消耗,提高了稀土回收率。
用以下非限定实施例更具体地描述本发明,本发明的保护范围不受这些实施例的限定。
实施例1
所用的钇精矿的化学成分如下(重量百分数)
三氧化二镧 5.2 二氧化铈 <0.30
十一氧化六镨 2.3 三氧化二钕 8.0
三氧化二钐 4.0 三氧化二铕 <0.3
三氧化二钆 6.0 七氧化四铽 1.6
三氧化二镝 8.0 三氧化二钬 2.6
三氧化二铒 5.6 三氧化二铥 1.1
三氧化二镱 5.2 三氧化二镥 1.1
三氧化二钇 42.39 三氧化二铁 0.091
总稀土氧化物 93.39 二氧化硅 0.027
二氧化钍 0.024 硫酸根 0.67
氧化钙和氧化镁合量0.82
称取上述1000克钇精矿放入5000毫升的烧杯中,加少量水将料润湿调浆,在搅拌下按每公斤稀土氧化物加入2.0升工业盐酸,搅拌下加热至沸,煮沸搅拌30分钟,至料溶解完全清亮后,控制PH为0.7,趁热过滤,其滤液作为本实施例的料液。
调整料液中氯化稀土的浓度为2.25摩尔/升,用稀氨水(或碳酸稀土)调节料液的PH为3.5,控制料液温度为60℃,在搅拌下按稀土氧化物∶硫化钠=1000克∶40克(重量比)加入工业级含硫化钠60%(重量百分数)的硫化钠溶液,加入硫化钠后继续搅拌15分钟,静置澄清,用布氏漏斗吸滤瓶过滤,得到滤液。
将上述所得到的滤液调节其PH0.6,加热至沸,按稀土氧化物∶氯化钡=1000克∶45克,在搅拌下加入20%的氯化钡溶液,加完氯化钡后再搅拌10分钟,静止几分钟后,用滤纸过滤,所得滤液为净化料液,用上述环烷酸萃取检验法检查合格。
实施例2-11
所用的操作程序与实施例1相同,唯不同的是所用的钇精矿的产地不同,其钇精矿的化学成分亦有不同,或略有不同,其各实施例的操作条件列表于表1、表2中,若加入的氯化钡量大,则加入固体氯化钡。
表1 实施例2-11中的操作条件
硫化钠第一步除杂质
表2 实施例2-11的操作条件
氯化钡第二步除杂质
Claims (6)
1、一种消除钆精矿酸溶溶液萃取乳化的方法,用盐酸酸溶的钆精矿溶液,经除硅后作为料液,本发明的特征是,
1)用碱金属的硫化物作为沉淀剂,料液的酸度为PH0.5-6.3,料液的温度保持在10℃-沸点之间,搅拌下加入沉淀剂碱金属硫化物,进行固液分离,
2)调节滤液的PH值在0.5-4.5之间,使料液的温度保持在50℃-沸点之间,加入氯化钡,进行固液分离。
2、根据权利要求1的一种消除钇精矿酸溶溶液萃取乳化的方法,其特征是所说的碱金属硫化物沉淀剂为硫化钠。
3、根据权利要求2的一种消除钇精矿酸溶溶液萃取乳化的方法,其特征是加入硫化钠的量为稀土氧化物∶硫化钠=1000∶25-60(重量比)
4、根据权利要3的一种消除钇精矿酸溶溶液萃取乳化的方法,其特征是,加入硫化钠的量为稀土氧化物∶硫化钠=1000∶30-40(重量比)
5、根据权利要求1的一种消除钇精矿酸溶溶液萃取乳化的方法,其特征是,加入氯化钡的量按稀土氧化物∶氯化钡=1000∶30-80(重量比)
6、根据权利要求5的一种消除钇精矿酸溶溶液萃取乳化的方法,其特征是,加入氯化钡的量按稀土氧化物∶氯化钡=1000∶35-50(重量比)。
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CN102776375A (zh) * | 2012-05-24 | 2012-11-14 | 北京工业大学 | 一种从废旧钕铁硼材料中回收稀土的方法 |
CN113667842A (zh) * | 2021-07-14 | 2021-11-19 | 四川省冕宁县方兴稀土有限公司 | 一种稀土湿法冶炼中除去非稀土杂质的方法 |
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CN102776375A (zh) * | 2012-05-24 | 2012-11-14 | 北京工业大学 | 一种从废旧钕铁硼材料中回收稀土的方法 |
CN113667842A (zh) * | 2021-07-14 | 2021-11-19 | 四川省冕宁县方兴稀土有限公司 | 一种稀土湿法冶炼中除去非稀土杂质的方法 |
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