CN1041811C - 再生含金属硫酸盐的废硫酸的方法 - Google Patents
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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- C—CHEMISTRY; METALLURGY
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- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
- C01B17/903—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids by liquid-liquid extraction
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
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- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
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Abstract
为了有效而容易地以高浓度硫酸形式回收无用的废硫酸,例如,在酸性洗液中或用硫酸盐法生产二氧化钛后产生的废硫酸中,首先将含有金属硫酸盐的废硫酸中的二价铁离子氧化成三价铁离子,向该液体中加入盐酸,然后进行溶剂萃取。
Description
本发明涉及采用再生法循环使用废硫酸的方法,例如,生产二氧化钛阶段所产生的废硫酸。
二氧化钛作为白色颜料已大量应用于涂料工业,并在许多领域中作为染料应用。在生产二氧化钛的方法中,所谓“硫酸盐法”是最常用的。在该方法中,钛铁矿或钛矿渣被研磨成粒度不大于200筛目单位的颗粒,然后用浓硫酸处理生成硫酸钛溶液;加入水或稀硫酸调节该溶液浓度;加入碎屑铁以防止其中含的杂质铁离子沉淀,使三价铁离子还原为二价铁离子,接着冷却该溶液,分离出硫酸亚铁。除去硫酸亚铁后,热水解硫酸钛溶液生成氢氧化钛,过滤,洗涤,最后锻烧,生成二氧化钛。
在生产二氧化钛的这些阶段中,在氢氧化钛固体和液体间的分离阶段中,主要的废物是大量的废硫酸。常规处理废硫酸的方法是使其转化成石膏埋地或中和后扔入海洋。但是当前对环境问题予以高度重视,再者提出了安全地堆放石膏和需要承担大量费用的问题。如何解决这些问题是非常重要的。
为了解决这些问题,已经提出了许多从废硫酸中分离杂质,然后回收硫酸的方法。例如,有一种方法是浓缩废硫酸(见日本专利公开昭46-5568号等)。另一种方法是将真空结晶阶段和上述的浓缩阶段结合起来处理废硫酸。由于大量金属硫酸盐沉积,使用这些方法存在的问题在于得不到所希望的高浓度硫酸。
当前,日本专利公开平3-80103号和3-88718号公开了溶剂萃取法除去杂质的方法。然而,在这些方法中,因为强酸性的硫酸溶液是通过溶剂萃取法来处理的,铁离子萃取的实际效率并没有这些专利申请中所描述的那么好。而且由此法回收的铁含量是低纯度的,再者,这些专利申请中提出用甲基异丁基酮回收铁离子,但是,用甲基异丁基酮这种中性萃取剂直接萃取三价铁离子是不可能的,在这种情况下,铁是作为络合物,如氯络合物而被萃取的。也有另一种情况,利用一种酸性萃取剂,直接以硫酸溶液中萃取三价铁离子,由于它的萃取率低,必然会涉及到多级萃取。
本发明的一个目的是要解决上述存在的问题,并提供一种从大量排放的含有金属硫酸盐的废硫酸中,例如从酸洗废液中或通过硫酸盐法生产二氧化钛(Ⅳ)过程中的废硫酸中,再生高浓度硫酸的方法。
本发明的另一个目的是在一封闭系统中通过从含有金属硫酸盐的废硫酸中有效地回收高浓度硫酸而达到防止环境污染的目的。
本发明还有一个目的是把铁,钛等作为附产物回收,提出一种有效利用资源的方法。
为了达到这些目的,本发明提出了将含金属硫酸盐的废硫酸中的二价铁离子氧化为三价铁离子,接着向该溶液中加入盐酸并进行溶剂萃取。
更具体地讲,本发明提出了度硫酸的再生方法,它包括以下步骤:将含有金属硫酸盐的废硫酸中的二价铁离子氧化为三价铁离子;向该液体中加入盐酸以调节溶液中氯离子的摩尔数至少为铁离子的4倍;溶剂萃取该液体以除去杂质金属离子如铁离子;溶剂萃取后,使溶液浓缩至硫酸浓度为60-75%(重量),以回收盐酸;此时,分离沉淀的金属硫酸盐;分离后的溶液再浓缩至硫酸浓度不低于80%(重量)。
再生含金属硫酸盐的废硫酸的本发明方法的基本想法是有效地清除含在废硫酸中的主要杂质金属离子,例如铁、钛和锰,然后浓缩该溶液,使其再生成高浓度硫酸。
在杂质金属离子中,大量的铁离子是以二价离子形成存在,清除二价铁离子是有效再生废硫酸必不可少的。然而,由于直接用溶剂萃取的方法来清除二价铁离子是有很大困难的。所以,二价铁离子首先被氧化成三价铁离子,然后用溶剂萃取的方法来清除三价铁离子。此时,盐酸被加入到废硫酸中,用氯离子来置换金属硫酸盐,从而在溶剂萃取完成后给出离子氯化络合物。已经发现,上述方法可提取99%以上的铁离子,这一提取方法比溶剂萃取更有效。
还发现:当在溶剂萃取法中大量使用萃取剂时,能分别分离铁离子和钛离子。
在本发明中,作为氧化废硫酸中二价铁离子的方法,不是用常用的氯氧化,就是用电解法来氧化,此外,也可用空气氧化。在这一氧化过程中,例如,在用氯氧化的情况下,相对于废硫酸中含的二价铁离子,通入化学计量的或过量的氯气到废硫酸中进行氧化,能容易地氧化99%或更多的二价铁离子。
在用氯氧化的情况下,溶解于溶液中的氯离子经浓缩回收,然后重复利用。
向氧化后的废硫酸中加入盐酸,然后溶剂萃取处理。在此种情况下,废硫酸中氯离子的摩尔数被调整到至少是液体中铁离子的4倍。如图1所示,已知在这种溶液中如果盐酸的浓度少于3N(N=mol/L),三价铁离子的萃取率会急剧地降低,因此,盐酸的浓度最好调整到不少于3N。
加入的盐酸在浓缩的步骤中回收,并可再利用。
用于从溶液中萃取杂质金属离子(例如三价铁离子)的有机溶剂包括酸性有机磷化合物,羧酸、磺酸羟基肟、8-羟基喹啉、β-二酮、中性磷酸酯、氧化磷、酮类、醇类、胺类等等。这些有机溶剂可单独应用,也可应用他们的混合物。为了分离除铁离子外的其它微量金属离子,最好联合使用几种溶剂,这些溶剂既可以逐一使用,也可用他们的混合物。
在这一方面,苯、三氯甲烷、甲苯、煤油、正己烷等都可用作稀释剂,来调节萃取剂的粘度。合适稀释剂的选择能改善有机溶剂的萃取能力。
在实施溶剂萃取时,为了分别地分离三价铁离子和钛离子,首先用煤油,乙醇,中性磷酸酯等萃取三价铁离子,然后用酸性有机磷化合物、羧酸、磺酸、羟基肟等萃取钛离子。
为了从溶液中优选萃取三价铁离子,例如使用煤油来萃取,在此情况下,可具体地采用甲基异丁基酮优先萃取三价铁离子,而几乎不萃取钛离子。然后用酸性有机磷化合物从已萃取了三价铁离子的溶液中萃取钛离子。在酸性有机磷化合物中,二(2-乙基己基)磷酸是特别理想的。
用甲基异丁基酮萃取的三价铁离子用水洗提,并作为其氢氧化物回收。在回收后,通过煅烧可得氧化铁,他们可以作为助凝剂或铁的原材料。在三价铁离子反萃取时,与三价铁离子一起萃取的部分氯离子也被反萃取进入反萃取溶液中,加硫酸到该溶液中进行置换,然后浓缩,氯离子作为盐酸而回收。
用二(2-乙基己基)磷酸萃取的钛离子是用氢氟酸溶液或者碱性溶液(例如氢氧化钠)反萃取的,并作为其氢氧化物回收的。回收后,可通过煅烧获得二氧化钛,二氧化钛可作为钛的原料。
本发明中,已分离除去杂质金属离子(如铁离子)的废硫酸,然后通过两个步骤回收成浓度不少于80%的硫酸。
铁离子,钛离子以及钪都能用上述溶剂萃取处理而除去。但是除去锰离子、铝离子等是很困难的,他们以相当大的量存在于溶液中,通过浓缩该溶液至硫酸浓度为60-70%(重量)回收盐酸后,让溶液冷却,它们以相应的硫酸盐沉淀。在这种情况下,锰以硫酸锰-水合物的形式被除去,在溶液中微量存在的其它金属离子,同时以相似的金属硫酸盐形式被除去。然后,没有金属硫酸盐的溶液经浓缩,得浓度不低于80%(重量)的高浓度硫酸。
在浓缩的第一步中,差不多回收所有的盐酸,回收的盐酸在溶剂萃取步骤中可重复使用。
图1表示使用甲基异丁基酮,盐酸的浓度与铁离子和钛离子萃取率之间的关系。
图2是流程图,表示本发明的处理方法。
下面描述本发明的操作实例,当然,本发明并不局限于这些实施例。实施例1
向生产二氧化钛过程中产生的5升废硫酸中,将1.5当量(相对于二价铁离)的氯气和空气一起通入,以氧化二价铁离子至三价铁离子。所述废硫酸含有下列组成:360g/L的硫酸;1g/L的三价铁离子;38g/L的二价铁离子;2.9g/L的钛;以及5.3g/L的锰。得到5升氧化过的溶液,其中含有下列成分:360g/L的硫酸,39g/L的三价铁离子,0.06g/L的二价铁离子,2.9g/L的钛和5.3g/L的锰,25g/L的氯。
往这种溶液中加2.5升的浓盐酸使溶液中盐酸的浓度为约4N,这样得到7.5升的溶液,其组成包括:240g/L的硫酸,26g/L的三价铁离子,1.9g/L的钛,3.58/L的锰和158g/L的氯。接着将该溶液与10升甲基异丁基酮接触,三价铁离子选择性地被萃取而除去。得到的溶液然后与10升二(2-乙基己基)磷酸的煤油溶液(1mol/L)接触。这样钛离子就被萃取出来。上述的溶剂萃取后,得7.5升溶液,它的组成是:240g/L的硫酸,0.10g/L的三价铁离子,0.03g/L的钛,3.5g/L的锰和92g/L的氯。
用甲基异丁基酮萃取的三价铁离子,用10升水洗提。获得的水溶液,它含的成份是:19g/L的铁和49g/L的氯,然后作为氢氧化铁被回收。回收后,大约270g的铁通过煅烧,以Fe2O3形式回收。回收率约97%。
用二(2-乙基己基)磷酸的煤油溶液(1mol/L)萃取的钛离子,用10升氢氧化钠水溶液(2mol/L)洗提,回收形成的氢氧化物,煅烧后大约回收23g的二氧化钛(Ⅳ),回收率约95%。
经过溶剂萃取后的溶液在温度约120℃,压力为74mmHg的状态下浓缩至硫酸浓度为70%(重量),回收约5.9升的盐酸(116g/L的氯)、冷却浓缩的溶液,分离出大约70g的金属硫酸盐沉淀,主要是一水合硫酸锰。然后在温度约180℃,压力为10mmHg的状态下浓缩该溶液,回收到1.1升浓度约为82%(重量)的硫酸溶液。它包括的成分为:1510g/L的硫酸,0.00g/L的三价铁离子,0.04g/L的钛,3.5g/L的锰和0.02g/L或更少的氯。硫酸的回收率约为92%。实施例2
7升废硫酸溶液,其中所含成份为:450g/L的硫酸,1g/L的三价铁离子,42g/L的二价铁离子,5.3g/L的钛以及5.2g/L的锰。经过电解氧化,使溶液中的二价铁离子氧化成三价铁离子。然后加入3升浓盐酸,调节该溶液为约3N的溶液,这样,得到10升溶液,其中组成包括:315g/L的硫酸,30g/L的三价铁离子,0.00g/L的二价铁离子,3.7g/L的钛、3.6g/L的锰和128g/L的氯。
然后将该溶液与20升的甲基异丁基酮接触,三价铁离子选择性地被萃取并除去。得到的溶液然后与20升二(2-乙基己基)磷酸的煤油溶液(1mol/L)接触,萃取钛离子。上述溶剂萃取处理后得10升溶液,其组成包括:315g/L的硫酸,0.00g/L的三价铁离子,0.03g/L的钛,3.68/L的锰和50g/L的氯。
用甲基异丁基酮萃取的三价铁离子,用30升水洗提,获得水溶液。它的组成包括:10g/L的铁和26g/L的氯。然后以氢氧化物的形式回收。回收后,约420g铁通过煅烧以Fe2O3形式回收,回收率为98%。
用1mol/L的二(2-乙基己基)磷酸煤油溶液萃取的钛离子,再用20升浓度为2mol/L的氢氧化钠水溶液洗提,回收形成的氢氧化物,煅烧后得约60g二氧化钛(Ⅳ),回收率约97%。
用溶剂萃取处理后的溶液在温度约110℃,压力为74mmHg的条件下浓缩成浓度为65%的硫酸,同时回收到约6.9升的盐酸(72g/L氯)。让浓缩的溶液冷却,分离出约94g沉淀的金属硫酸盐(主要是硫酸锰一水合物)。然后溶液在温度180℃和压力10mmHg的条件下浓缩,回收到2.0升浓度为约81%(重量)的硫酸溶液。它的组成包括:149g/L的硫酸,0.1g/L的钛,3.2g/L的锰,和0.02g/L或更少的氯。硫酸的回收率约为95%。
除上述的实施例外,表1显示通过加盐酸而改变的三价铁离子的萃取率。表中,有机相与水相的体积比为1∶1。除了甲基异丁基酮外,所有的稀释剂都用煤油稀释。所有条件同实施例2。
表1
三价铁离子的萃取率萃取剂的浓度 水相 只氧化 氧化+HCl
萃取剂 (不加HCl) (氧化液体∶浓HCl=1∶1)浓溶液 甲基异 <1% 99%
丁基酮20Vol% 磷酸三 <1% 93%
丁酯20Vol% 2-乙基己基 17% 53%
膦酸2-乙基
己基酯
商品名:PC88A20Vol% 二(2-乙基
己基)磷酸 14% 38%
商品名:DP8R20Vol% 双(2,2,4- 11% 73%
三甲基戊基)次
膦酸
商品名:CYANEX27220Vol% 叔胺 <1% 94%
商品名:ALamine 33620Vol% 羟基肟
商品名:LIX63-70 <1% 58%20Vol% β-二酮
商品名:LIX54 <1% 7%
Claims (3)
1.一种再生含有金属硫酸盐的废硫酸的方法,其特征在于:在第一步骤中,把废硫酸中的二价铁离子氧化成三价铁离子;在第二步骤中,把至少4M量的盐酸加入该液体中;然后,在第三步骤中进行溶剂萃取,从除去至少三价铁离子和钛离子。
2.权利要求1的再生含有金属硫酸盐的废硫酸的方法,其中:
在加入盐酸的所述第二步中,使所述液体中氯离子的摩尔数至少是铁离子的4倍;
在溶剂萃取的所述第三步骤中,除去该液体中的杂质金属离子,如铁离子;
所述方法还进一步包括:
第四步骤,将溶剂萃取后的溶液浓缩至硫酸浓度为60-75%(重量),以回收盐酸;
第五步,此时,分离沉淀的金属硫酸盐;和
第六步,再次浓缩分离后的溶液至硫酸浓度不少于80%(重量)。
3.按权利要求1或2的方法,其特征在于:进行所述的溶剂萃取,单独地分离三价铁离子和钛离子。
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JP3293126A JP2968877B2 (ja) | 1991-11-08 | 1991-11-08 | 金属硫酸塩含有の廃硫酸から硫酸を回収する方法 |
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CN101172647B (zh) * | 2007-10-19 | 2010-06-09 | 杨绍泉 | 硫酸法制备钛白粉的方法 |
CN101759158B (zh) * | 2009-12-23 | 2011-06-29 | 河南豫光金铅股份有限公司 | 从废污酸中再生回收硫酸的方法 |
CN102191387B (zh) * | 2010-03-08 | 2013-06-19 | 沙立林 | 钛液的提纯方法 |
US9278860B2 (en) * | 2014-07-22 | 2016-03-08 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method and apparatus for recycling waste sulfuric acid |
CN104555949A (zh) * | 2014-12-28 | 2015-04-29 | 贵州兰鑫石墨机电设备制造有限公司 | 一种钛白废酸浓缩工艺 |
CN104760938B (zh) * | 2015-03-18 | 2017-10-13 | 安庆师范学院 | 一种去除浓硫酸中铁离子的方法 |
RU2651019C2 (ru) * | 2016-09-19 | 2018-04-18 | Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Способ переработки жидких отходов производства диоксида титана |
CN109818099B (zh) * | 2019-01-31 | 2019-12-17 | 襄阳金湛技术开发有限公司 | 一种废旧硫酸回收再生系统及方法 |
CN109987588A (zh) * | 2019-04-24 | 2019-07-09 | 成都先进金属材料产业技术研究院有限公司 | 利用焦磷酸钠处理废硫酸溶液的方法 |
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JPH05132304A (ja) | 1993-05-28 |
MY109068A (en) | 1996-11-30 |
AU2813392A (en) | 1993-05-13 |
EP0541002A1 (en) | 1993-05-12 |
EP0541002B1 (en) | 1997-04-23 |
CN1072154A (zh) | 1993-05-19 |
DE69219274D1 (de) | 1997-05-28 |
TW227989B (zh) | 1994-08-11 |
RU2098349C1 (ru) | 1997-12-10 |
JP2968877B2 (ja) | 1999-11-02 |
DE69219274T2 (de) | 1997-08-07 |
SG46572A1 (en) | 1998-02-20 |
AU649573B2 (en) | 1994-05-26 |
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