CN106746111A - 一种不锈钢酸洗废水资源化回收方法 - Google Patents

一种不锈钢酸洗废水资源化回收方法 Download PDF

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CN106746111A
CN106746111A CN201611103524.9A CN201611103524A CN106746111A CN 106746111 A CN106746111 A CN 106746111A CN 201611103524 A CN201611103524 A CN 201611103524A CN 106746111 A CN106746111 A CN 106746111A
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张圆圆
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/38—Nitric acid
    • C01B21/46—Purification; Separation ; Stabilisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/195—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/046—Treatment of water, waste water, or sewage by heating by distillation or evaporation under vacuum produced by a barometric column
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5254—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using magnesium compounds and phosphoric acid for removing ammonia
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

本发明涉及一种不锈钢酸洗废水资源化回收方法，包括以下步骤:向不锈钢酸洗废水中加入浓硝酸,调节pH 值至1.5‑2.5之间；再将该废水过滤，得铁和铬沉淀物；对不锈钢酸洗废水进行浓缩,得浓缩酸水,将浓缩酸水进行减压蒸发，收集蒸发液体得氢氟酸和硝酸；将分离氢氟酸和硝酸后的溶液进行冷却过滤，完成溶液中铁的回收；将回收酸之后得到的溶液加入预中和剂控制 pH 值，沉淀过滤；往中和除酸之后的过滤液中加入硫化剂，控制硫化 pH 值，采用硫化法完成镍铬分离，实现镍的回收。相对现有技术，本发明可以从废液中提取镍离子，在不引入新的杂质的情况下，能回收废水。

Description

一种不锈钢酸洗废水资源化回收方法
技术领域
本发明涉及一种不锈钢酸洗废水资源化回收方法。
背景技术
不锈钢被誉为钢铁产品中的精品，以其优越的耐蚀性、独特的表面和优异的加工性能，发展十分迅速，应用领域越来越广阔。不锈钢带钢的酸洗是冷轧不锈钢生产中关键的一道工序，对保证产品表面质量具有决定性的作用。酸洗工艺也由六、七十年代的纯化学酸洗发展到目前的化学酸洗与电解酸洗相结合的工艺。在不锈钢酸洗中产生会产生包含重金属镍、铬的的废水。传统上，这些废水直接排放，严重污染了环境。
不锈钢钢渣中含有大量的镍、铬、铁等有价金属，如果不加处理，这部分含铁资源就会白白流失；而与之相对应的是我国不锈钢生产所需的红土镍矿等原料严重不足，每年需花巨资从菲律宾、印度尼西亚等地进口。另外， 不锈钢钢渣中含有Cr6+有毒化合物，若不加以处理，排放的尾渣也会给周围的环境造成严重危害，破坏土壤植被结构，污染空气与水体。
发明内容
本发明所要解决的技术问题是提供一种不锈钢酸洗废水资源化回收方法。
本发明解决上述技术问题的技术方案如下：一种不锈钢酸洗废水资源化回收方法，包括以下步骤:
铁和铬的回收：向不锈钢酸洗废水中加入浓硝酸, 调节pH 值至1.5-2.5之间；再将该废水过滤，得铁和铬沉淀物；
氢氟酸和硝酸的回收：对不锈钢酸洗废水进行浓缩,得浓缩酸水,将浓缩酸水进行减压蒸发，收集蒸发液体得氢氟酸和硝酸；
铁的分离回收：将分离氢氟酸和硝酸后的溶液进行冷却过滤，完成溶液中铁的回收；
中和除酸：将回收酸之后得到的溶液加入预中和剂控制 pH 值，沉淀过滤；
镍的回收：往中和除酸之后的过滤液中加入硫化剂，控制硫化 pH 值，采用硫化法完成镍铬分离，实现镍的回收。
进一步，中和剂为NaOH、Na2CO3、NaHCO3、CaO、CaCO3、MgO、MgCO3、电石渣中的一种或几种，pH 范围为5.50～8.50。
进一步，硫化剂为硫化氢、硫氢化钠、硫化钠、硫化钡、硫化钙中的一种或几种，硫化时 pH 范围为3.50～5.50。
本发明的有益效果是：循环蒸酸和膜处理的有益结合，实现了有价资源的全回收，废水中硝酸和氢氟酸的回收率高，有利于蒸酸系统的顺利运行，可减少渣量，通过渣的分离易于实现渣的资源化，水处理过程无二次污染，可基本实现硝态氮和氟的闭路循环，极大减轻后续水处理的负担，保障水处理稳定达标，有利于处理后水的回用，同时能产生可观的经济效益。
具体实施方式
以下结合对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
一种不锈钢酸洗废水资源化回收方法，包括以下步骤:
铁和铬的回收：向不锈钢酸洗废水中加入浓硝酸, 调节pH 值至1.5-2.5之间；再将该废水过滤，得铁和铬沉淀物；
氢氟酸和硝酸的回收：对不锈钢酸洗废水进行浓缩,得浓缩酸水,将浓缩酸水进行减压蒸发，收集蒸发液体得氢氟酸和硝酸；
铁的分离回收：将分离氢氟酸和硝酸后的溶液进行冷却过滤，完成溶液中铁的回收；
中和除酸：将回收酸之后得到的溶液加入预中和剂控制 pH 值，沉淀过滤；
镍的回收：往中和除酸之后的过滤液中加入硫化剂，控制硫化 pH 值，采用硫化法完成镍铬分离，实现镍的回收。
上述实施例中，中和剂为NaOH、Na2CO3、NaHCO3、CaO、CaCO3、MgO、MgCO3、电石渣中的一种或几种，pH 范围为5.50～8.50。
上述实施例中，硫化剂为硫化氢、硫氢化钠、硫化钠、硫化钡、硫化钙中的一种或几种，硫化时 pH 范围为3.50～5.50。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (3)

1.一种不锈钢酸洗废水资源化回收方法，其特征在于：包括以下步骤:
铁和铬的回收：向不锈钢酸洗废水中加入浓硝酸, 调节pH 值至1.5-2.5之间；再将该废水过滤，得铁和铬沉淀物；
氢氟酸和硝酸的回收：对不锈钢酸洗废水进行浓缩,得浓缩酸水,将浓缩酸水进行减压蒸发，收集蒸发液体得氢氟酸和硝酸；
铁的分离回收：将分离氢氟酸和硝酸后的溶液进行冷却过滤，完成溶液中铁的回收；
中和除酸：将回收酸之后得到的溶液加入预中和剂控制 pH 值，沉淀过滤；
镍的回收：往中和除酸之后的过滤液中加入硫化剂，控制硫化 pH 值，采用硫化法完成镍铬分离，实现镍的回收。
2.根据权利要求 1 所述一种不锈钢酸洗废水资源化回收方法，其特征在于，中和剂为NaOH、Na2CO3、NaHCO3、CaO、CaCO3、MgO、MgCO3、电石渣中的一种或几种，pH 范围为5.50～8.50。
3.根据权利要求 1 所述一种不锈钢酸洗废水资源化回收方法，其特征在于，硫化剂为硫化氢、硫氢化钠、硫化钠、硫化钡、硫化钙中的一种或几种，硫化时 pH 范围为3.50～5.50。
CN201611103524.9A 2016-12-05 2016-12-05 一种不锈钢酸洗废水资源化回收方法 Pending CN106746111A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107162305A (zh) * 2017-07-07 2017-09-15 金川集团股份有限公司 一种酸性废水处理装置及其使用方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659274A (zh) * 2012-05-09 2012-09-12 南京大学 一种不锈钢酸洗废水资源化无害化处理方法
CN104805291A (zh) * 2015-04-16 2015-07-29 南阳师范学院 一种不锈钢酸洗废液的处理及铁、铬、镍的回收方法
CN105060599A (zh) * 2015-08-28 2015-11-18 中南大学 一种不锈钢酸洗废水资源化回收方法
CN105481202A (zh) * 2016-01-26 2016-04-13 湖州森诺膜技术工程有限公司 一种不锈钢酸洗废水处理系统及处理方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659274A (zh) * 2012-05-09 2012-09-12 南京大学 一种不锈钢酸洗废水资源化无害化处理方法
CN104805291A (zh) * 2015-04-16 2015-07-29 南阳师范学院 一种不锈钢酸洗废液的处理及铁、铬、镍的回收方法
CN105060599A (zh) * 2015-08-28 2015-11-18 中南大学 一种不锈钢酸洗废水资源化回收方法
CN105481202A (zh) * 2016-01-26 2016-04-13 湖州森诺膜技术工程有限公司 一种不锈钢酸洗废水处理系统及处理方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107162305A (zh) * 2017-07-07 2017-09-15 金川集团股份有限公司 一种酸性废水处理装置及其使用方法

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Application publication date: 20170531