CN114015877A - 一种冶炼污酸和电镀污泥协同处置的方法 - Google Patents
一种冶炼污酸和电镀污泥协同处置的方法 Download PDFInfo
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0093—Treating solutions by chemical methods by gases, e.g. hydrogen or hydrogen sulfide
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- C22B34/00—Obtaining refractory metals
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Abstract
本发明提供一种冶炼污酸和电镀污泥协同处置的方法,将冶炼污酸蒸发浓缩获得高温高浓度污酸,再加入电镀污泥中搅拌浸出,获得混合溶液,经固液分离,得到浸出液和硫酸钙沉淀;在浸出液中加入高温高浓度污酸,并通入硫化氢气体进行硫离子诱导矿化处理,经固液分离得到硫化物沉淀和滤液;将硫化物沉淀采用选择性泡沫化处理进行分离,梯度回收硫化铜、硫化铅、硫化锌、硫化镍和硫化砷;在所得滤液中加入亚铁盐进行充氧搅拌后得到含铬尖晶石。该方法采用高温高浓度污酸浸出污泥中的有价元素,然后通过硫离子诱导矿化演变‑选择性泡沫化‑磁化转变联合技术,实现了污酸和污泥中所有有价元素的综合回收,达到了冶炼污酸和电镀污泥高效协同处置的目的。
Description
技术领域
本发明涉及环境工程和矿物加工工程技术领域,具体涉及一种冶炼污酸和电镀污泥协同处置的方法。
背景技术
有色冶炼和化工等行业的生产过程中会产生大量的污酸,这种污酸不仅含有大量的硫酸,而且还含有多种有价元素,如氟、氯、砷、铜、铅、锌等。对于这类污酸的处理,通常采用中和沉淀、中和铁盐和硫化沉淀三种技术。中和沉淀法需加入大量的碱,以中和污酸,产生的渣量特别大;中和铁盐法同样会消耗大量的碱和铁盐;硫化法流程长、处理费用高。除此之外,以上三种常用技术仅注重污酸的无害化处理而忽略了酸和有价元素的综合利用。
电镀污泥是电镀废水经过酸碱中和沉淀或絮凝沉淀的产物,是电镀废水处理之后的终极产物,属于固体危险废物。但电镀污泥中同样含有大量有价元素,如铜、锌、镍、铬、铁等,具有一定的回收价值。目前,电镀污泥的回收方法主要包括湿法回收、火法回收、生物法,其中湿法为最常用的方法。湿法回收处理主要包括酸浸法、氨浸法、焙烧-浸出法。酸浸法为目前电镀污泥中有价元素综合利用的主要方法。
基于上述情况,申请人提出采用污酸协同处理电镀污泥的新方法,将污酸和污泥中的有价元素汇集于浸出液中,然后采用联合技术集中处理,实现了污酸中的酸、污酸及污泥中的有价元素的综合回收,是一种绿色、高效、环保的新方法。
发明内容
本发明提供一种冶炼污酸和电镀污泥协同处置的方法,以实现有价元素梯度综合回收。首先采用蒸发浓缩技术将冶炼污酸中的氟离子和氯离子去除,获得高温高浓度的含砷、铜、铅、锌离子的废酸。然后直接用废酸浸出电镀污泥,浸出后获得硫酸钙沉淀和同时含有砷、铜、铅、铁、锌、镍和铬离子的浸出液。通过硫离子诱导矿化演变技术将一些离子选择性转变为相应的硫化物,采用选择性泡沫化分离技术梯度回收硫化铜、硫化铅、硫化锌镍和硫化砷。然后将硫离子诱导矿化反应-固液分离后获得的溶液中的铬离子制备成含铬尖晶石。
为实现上述目的,本发明采用的技术方案如下:一种冶炼污酸和电镀污泥协同处置的方法,经过下列各步骤:
(1)将冶炼污酸进行蒸发浓缩处理,以去除污酸中的氟离子和氯离子,提高污酸中硫酸和有价元素的浓度,获得高温高浓度污酸;
(2)将步骤(1)得到的高温高浓度污酸按液固比2:1~4:1,直接加入电镀污泥中,并进行搅拌浸出20~60min,使得污酸和污泥中所有有价元素溶为一体,获得含有多种有价元素的混合溶液;
(3)对于步骤(2)的混合溶液采用浓密机和压滤机进行固液分离,得到浸出液和硫酸钙沉淀;
(4)在步骤(3)的浸出液中加入步骤(1)所得高温高浓度污酸,并通入硫化氢气体,使溶液pH≤4,进行硫离子诱导矿化处理,以使浸出液中的有价元素铜、铅、锌、镍和砷转变为相应的硫化物沉淀,然后进行固液分离,得到硫化物沉淀和滤液;
(5)将步骤(4)所得硫化物沉淀的浓度调节至25%-35%,再采用选择性泡沫化处理技术进行分离,梯度回收硫化铜、硫化铅、硫化锌、硫化镍和硫化砷;
(6)在步骤(4)所得滤液中加入亚铁盐,使pH≥9,以气体流速为50~300ml/min,温度为25~80℃,进行充氧搅拌后得到含铬尖晶石。
其中,冶炼污酸主要指铜、铅、锌冶炼过程产生的污酸,其中主要含有氟离子、氯离子、砷离子、铜离子、铅离子和锌离子。电镀污泥主要含有硫酸钙和铜、锌、镍、铬、铁的氧化物或氢氧化物。
所述步骤(1)蒸发浓缩的条件为:加热温度为120~130℃,浓缩比为5~8,真空度为0.00~0.08MPa。
所述步骤(5)的选择性泡沫化处理技术是在硫化物沉淀中加入石灰、硫酸锌、腐殖酸钠、酯或黑药、松醇油组合试剂,泡沫化得到硫化铜和硫化铅的混合产物,再将混合产物进行机械搅拌后,加入重铬酸钾和石灰组合试剂,得到硫化铜和硫化铅两种产物,向铜铅泡沫化后槽内溶液中加入石灰、铵盐、硫酸铜、黄药、松醇油的组合试剂,得到硫化锌镍产物,最后经固液分离得到硫化砷产物。
所述重铬酸钾添加后产生的含铬废水返回到步骤(6),加入到滤液中。
与现有技术相比,本发明采用蒸发浓缩-协同浸出-硫离子诱导矿化-选择性泡沫化-磁化转变联合方法,梯度回收冶炼污酸和电镀污泥中的有价元素,有益效果是:
(a)本发明通过蒸发浓缩-协同浸出-硫离子诱导矿化-选择性泡沫化-磁化转变技术联合,实现了冶炼污酸和电镀污泥的协同处置,梯度回收了污酸和污泥中的有价元素,是一种绿色、高效的清洁处理方法;
(b)本发明利用蒸发浓缩污酸产生的余热,强化了污酸和污泥协同浸出的动力学,避免了氧化砷的析出,达到了节能减排的目的;
(c)本发明采用多种组合试剂,实现了硫化铜铅锌镍矿的选择性泡沫化和硫化铜、硫化铅、硫化锌镍、硫化砷的高效分离;
(d)本发明采用重铬酸钾分离硫化铜和硫化铅,并将产生的含铬废水返回至磁化转变环节,有效的解决了重铬酸钾使用造成的环境污染问题,实现了铬资源的综合高效利用。
附图说明
图1是本发明工艺流程图。
具体实施方式
下面结合附图和实施例对本发明作进一步阐述。
实施例1
处理对象为某铜冶炼污酸和汽车零部件电镀厂污泥。
铜冶炼污酸中氟、氯、铜、砷、铅、锌含量分别为3500mg/L、4450mg/L、620mg/L、6400mg/L、160mg/L、220mg/L。电镀污泥中铜、镍、铬、铁、锌含量分别为2.11%、2.64%、3.16%、5.78%、2.68%。
(1)将冶炼污酸以加热温度为120℃、浓缩比为5、真空度为0.00MPa进行蒸发浓缩处理,以去除污酸中的氟离子和氯离子,提高污酸中硫酸和有价元素的浓度,获得高温高浓度污酸;
(2)将步骤(1)得到的高温高浓度污酸按液固比2:1,直接加入电镀污泥中,并进行搅拌浸出20min,使得污酸和污泥中所有有价元素溶为一体,获得含有多种有价元素的混合溶液;
(3)对于步骤(2)的混合溶液采用浓密机和压滤机进行固液分离,得到浸出液和纯度为65.32%的硫酸钙沉淀;
(4)在步骤(3)的浸出液中加入步骤(1)所得高温高浓度污酸,并通入硫化氢气体,使溶液pH至4,进行硫离子诱导矿化处理,以使浸出液中的有价元素铜、铅、锌、镍和砷转变为相应的硫化物沉淀,然后进行固液分离,得到硫化物沉淀和滤液;
(5)将步骤(4)所得硫化物沉淀的浓度调节至25%,再采用选择性泡沫化处理技术进行分离,梯度回收硫化铜、硫化铅、硫化锌、硫化镍和硫化砷;具体是:
加入石灰1500g/t、硫酸锌3000g/t、腐殖酸钠100g/t、Z-200 60g/t、松醇油30g/t组合试剂,得到硫化铜和硫化铅的混合产物,然后向混合产物中加入石灰800g/t、重铬酸钾200g/t的组合试剂,实现硫化铜和硫化铅的高效分离,得到铜品位为15%、回收率56%的铜精矿和铅品位为35%、回收率65%的铅精矿。向铜铅混合泡沫化后得到的尾浆中加入石灰2000g/t、硫酸铵200g/t、硫酸铜400g/t、黄药100g/t、松醇油30g/t组合试剂,得到锌品位为42%、镍品位为5.63%、锌回收率88%、镍回收率75%的锌镍混合产物。然后通过过滤得到含砷37%、回收率72%的硫化砷精矿;
(6)在步骤(4)所得滤液中加入16倍的硫酸亚铁和铜铅泡沫化过程中产生的含铬废水,使pH至11,以气体流速为300ml/min,温度为60℃,进行充氧搅拌后得到三氧化二铬品位为32%、回收率为76%的含铬尖晶石。
实施例2
处理对象为某锌冶炼污酸和衣架电镀厂污泥。
锌冶炼污酸中氟、氯、铬、铁、镍、铅、锌、砷含量分别为950mg/L、810mg/L、96mg/L、320mg/L、62mg/L、140mg/L、640mg/L和560mg/L;电镀污泥中铜镍铬锌铁含量分别为2.66%、3.04%、8.46%、2.35%和15.46%。
(1)将冶炼污酸以加热温度为130℃、浓缩比为8、真空度为0.04MPa进行蒸发浓缩处理,以去除污酸中的氟离子和氯离子,提高污酸中硫酸和有价元素的浓度,获得高温高浓度污酸;
(2)将步骤(1)得到的高温高浓度污酸按液固比4:1,直接加入电镀污泥中,并进行搅拌浸出40min,使得污酸和污泥中所有有价元素溶为一体,获得含有多种有价元素的混合溶液;
(3)对于步骤(2)的混合溶液采用浓密机和压滤机进行固液分离,得到浸出液和纯度为82.5%的硫酸钙沉淀;
(4)在步骤(3)的浸出液中加入步骤(1)所得高温高浓度污酸,并通入硫化氢气体,使溶液pH至2.0,进行硫离子诱导矿化处理,以使浸出液中的有价元素铜、铅、锌、镍和砷转变为相应的硫化物沉淀,然后进行固液分离,得到硫化物沉淀和滤液;
(5)将步骤(4)所得硫化物沉淀的浓度调节至35%,再采用选择性泡沫化处理技术进行分离,梯度回收硫化铜、硫化铅、硫化锌、硫化镍和硫化砷;具体是:
加入石灰2000g/t、硫酸锌1500g/t、腐殖酸钠300g/t、黑药60g/t、松醇油20g/t的组合试剂,获得硫化铜和硫化铅的混合产物,然后向混合产物中加入石灰1000g/t、重铬酸钾 150g/t的组合试剂,实现硫化铜和硫化铅的泡沫化分离,得到铜品位为14.5%、回收率66%的铜精矿和铅品位为42%、回收率73%的铅精矿。向铜铅混合泡沫化后的尾浆中加入石灰1200g/t、硫酸铵400g/t、硫酸铜300g/t、黄药150g/t、松醇油20g/t的组合试剂,泡沫化分离后得到锌品位为45%、镍品位为5.43%、锌回收率91%、镍回收率76%的锌镍混合产品。然后通过过滤得到砷品位为28%、回收率85%的硫化砷产品;
(6)在步骤(4)所得滤液中加入10倍的硫酸亚铁和铜铅泡沫后分离后产生的含铬废水,使pH至9,以气体流速为50ml/min,温度为80℃,进行充氧搅拌后得到三氧化二铬品位为26%、回收率为74%的含铬尖晶石。
实施例3
处理对象为某铜冶炼污酸和某小型电镀厂污泥。
冶炼污酸中氟、氯、铜、铅和砷含量分别为5860mg/L、6820mg/L、320mg/L、30mg/L和14280mg/L;电镀污泥中铜、镍、锌、铬和铁含量分别为2.61%、2.74%、3.49%、13.26%和9.92%。
(1)将冶炼污酸以加热温度为125℃、浓缩比为6、真空度为0.08MPa进行蒸发浓缩处理,以去除污酸中的氟离子和氯离子,提高污酸中硫酸和有价元素的浓度,获得高温高浓度污酸;
(2)将步骤(1)得到的高温高浓度污酸按液固比3:1,直接加入电镀污泥中,并进行搅拌浸出60min,使得污酸和污泥中所有有价元素溶为一体,获得含有多种有价元素的混合溶液;
(3)对于步骤(2)的混合溶液采用浓密机和压滤机进行固液分离,得到浸出液和纯度为75%的硫酸钙沉淀;
(4)在步骤(3)的浸出液中加入步骤(1)所得高温高浓度污酸,并通入硫化氢气体,使溶液pH至1.0,进行硫离子诱导矿化处理,以使浸出液中的有价元素铜、铅、锌、镍和砷转变为相应的硫化物沉淀,然后进行固液分离,得到硫化物沉淀和滤液;
(5)将步骤(4)所得硫化物沉淀的浓度调节至30%,再采用选择性泡沫化处理技术进行分离,梯度回收硫化铜、硫化铅、硫化锌、硫化镍和硫化砷;具体是:
加入石灰3000g/t、硫酸锌2500g/t、腐殖酸钠120g/t、Z-200 100g/t、松醇油40g/t组合试剂,获得硫化铜和硫化铅的混合产物,然后向混合产物中加入石灰1500g/t、重铬酸钾250g/t组合试剂,实现硫化铜和硫化铅的泡沫化分离,得到铜品位为18%、回收率75%的含铜产品和铅品位为39%、回收率78%的含铅产品。向硫化铜铅泡沫化尾浆中加入石灰1800g/t、硫酸铵500g/t、硫酸铜400g/t、黄药200g/t、松醇油30g/t组合试剂,得到锌品位为42%、镍品位为6.49%、锌回收率88%、镍回收率69%的锌镍混合产品。然后通过过滤,得到含砷42%、回收率78%的硫化砷产品;
(6)在步骤(4)所得滤液中加入加入12倍的硫酸亚铁和铜铅泡沫化过程产生的含铬废水,使pH至10.0,以气体流速为200ml/min,温度为25℃,进行充氧搅拌后得到三氧化二铬品位为35%、回收率为86%的含铬尖晶石。
Claims (4)
1.一种冶炼污酸和电镀污泥协同处置的方法,其特征在于经过下列各步骤:
(1)将冶炼污酸进行蒸发浓缩处理,获得高温高浓度污酸;
(2)将步骤(1)得到的高温高浓度污酸按液固比2:1~4:1,直接加入电镀污泥中,并进行搅拌浸出20~60min,获得含有多种有价元素的混合溶液;
(3)对于步骤(2)的混合溶液进行固液分离,得到浸出液和硫酸钙沉淀;
(4)在步骤(3)的浸出液中加入步骤(1)所得高温高浓度污酸,并通入硫化氢气体,使溶液pH≤4,进行硫离子诱导矿化处理,然后进行固液分离,得到硫化物沉淀和滤液;
(5)将步骤(4)所得硫化物沉淀的浓度调节至25%~35%,再采用选择性泡沫化处理技术进行分离,梯度回收硫化铜、硫化铅、硫化锌、硫化镍和硫化砷;
(6)在步骤(4)所得滤液中加入亚铁盐,使pH≥9,以气体流速为50~300ml/min,温度为25~80℃,进行充氧搅拌后得到含铬尖晶石。
2.根据权利要求1所述的冶炼污酸和电镀污泥协同处置的方法,其特征在于:所述步骤(1)蒸发浓缩的条件为:加热温度为120~130℃,浓缩比为5~8,真空度为0.00~0.08MPa。
3.根据权利要求1所述的冶炼污酸和电镀污泥协同处置的方法,其特征在于:所述步骤(5)的选择性泡沫化处理技术是在硫化物沉淀中加入石灰、硫酸锌、腐殖酸钠、酯或黑药、松醇油组合试剂,泡沫化得到硫化铜和硫化铅的混合产物,再将混合产物进行机械搅拌后,加入重铬酸钾和石灰组合试剂,得到硫化铜和硫化铅两种产物,向铜铅泡沫化后槽内溶液中加入石灰、铵盐、硫酸铜、黄药、松醇油的组合试剂,得到硫化锌镍产物,最后经固液分离得到硫化砷产物。
4.根据权利要求3所述的冶炼污酸和电镀污泥协同处置的方法,其特征在于:所述重铬酸钾添加后产生的含铬废水返回到步骤(6),加入到滤液中。
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