CN105600836A - Method for recycling useful ingredients in acid pickling waste liquid - Google Patents
Method for recycling useful ingredients in acid pickling waste liquid Download PDFInfo
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- CN105600836A CN105600836A CN201610047292.3A CN201610047292A CN105600836A CN 105600836 A CN105600836 A CN 105600836A CN 201610047292 A CN201610047292 A CN 201610047292A CN 105600836 A CN105600836 A CN 105600836A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
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- 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
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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Abstract
一种酸洗废液中有用成分的回收方法，包括以下步骤：（1）向盐酸酸洗废液中加入浓盐酸或向硫酸酸洗废液中加入浓硫酸，将废液的盐酸质量浓度或硫酸质量浓度调节为20%-25%；（2）将调节好酸浓度的废液降温至0-3℃，使其中的氯化亚铁或硫酸亚铁结晶析出；（3）将析出的氯化亚铁结晶或硫酸亚铁结晶从废液中分离出来。利用本发明，不仅能够回收酸洗废液中的有用成分，有效节约成本，而且可以实现酸洗废液的零排放，避免酸洗废液对环境造成污染。A method for recovering useful components in waste pickling liquid, comprising the following steps: (1) adding concentrated hydrochloric acid to waste hydrochloric acid pickling liquid or adding concentrated sulfuric acid to waste sulfuric acid pickling liquid, reducing the mass concentration of hydrochloric acid or The mass concentration of sulfuric acid is adjusted to 20%-25%; (2) The waste liquid with adjusted acid concentration is cooled to 0-3°C to crystallize the ferrous chloride or ferrous sulfate; (3) The precipitated chlorine Ferrous chloride crystals or ferrous sulfate crystals are separated from the waste liquid. The invention can not only recover the useful components in the pickling waste liquid, effectively save the cost, but also can realize the zero discharge of the pickling waste liquid, and avoid the pollution of the pickling waste liquid to the environment.
Description
技术领域 technical field
本发明涉及一种酸洗废液中有用成分的回收方法。 The invention relates to a method for recovering useful components in pickling waste liquid.
背景技术 Background technique
酸洗废液是为了清除钢材表面的氧化物，采用酸进行酸洗法处理钢材时产生的废液，废液多来源于钢铁厂、电镀厂和机械加工厂等。 Pickling waste liquid is to remove oxides on the surface of steel, and the waste liquid generated when acid is used to pickle the steel is used. Most of the waste liquid comes from steel plants, electroplating plants, and mechanical processing plants.
钢材表面的氧化物主要成分是铁的氧化物，当把这些氧化物浸泡在酸液中时，这些氧化物会与酸发生反应，生成溶于水或者酸溶液的盐，从而把这些氧化物从钢材表面去除。酸洗采用的酸主要是盐酸或硫酸。 The main component of oxides on the surface of steel is iron oxides. When these oxides are immersed in acid solution, these oxides will react with acid to form salts that are soluble in water or acid solution, thereby removing these oxides from Steel surface removal. The acid used in pickling is mainly hydrochloric acid or sulfuric acid.
酸洗是钢材处理必不可少的工艺步骤，此工艺一个很大的缺点就是会产生大量的酸洗废液。通常酸洗废液中盐酸或硫酸含量为3～10%，如未进行妥善处理，是重大的环境隐患。 Pickling is an essential process step for steel treatment. A big disadvantage of this process is that it will produce a large amount of pickling waste. Usually the content of hydrochloric acid or sulfuric acid in pickling waste liquid is 3-10%, if not properly treated, it will be a major environmental hazard.
目前，酸洗废液的最常见的处理方法为中和法，但该方法不但无法回收废液中有用的成分，还需要消耗大量的碱性物质作为中和剂，而且在处理废液的过程中，会产生大量的固体废弃物，造成二次污染。 At present, the most common treatment method for pickling waste liquid is the neutralization method, but this method not only cannot recover the useful components in the waste liquid, but also needs to consume a large amount of alkaline substances as neutralizers, and in the process of treating waste liquid In the process, a large amount of solid waste will be generated, causing secondary pollution.
发明内容 Contents of the invention
本发明所要解决的技术问题是，克服上述背景技术的不足，提供一种能够有效节约成本，实现酸洗废液的零排放，避免酸洗废液对环境造成污染的酸洗废液中有用成分的回收方法。 The technical problem to be solved by the present invention is to overcome the deficiencies of the above-mentioned background technology, provide a kind of useful components in pickling waste liquid that can effectively save costs, realize zero discharge of pickling waste liquid, and avoid environmental pollution caused by pickling waste liquid recycling method.
本发明解决其技术问题采用的技术方案是，一种酸洗废液中有用成分的回收方法，包括以下步骤： The technical solution adopted by the present invention to solve the technical problems is, a method for recovering useful components in the pickling waste liquid, comprising the following steps:
（1）向盐酸酸洗废液中加入浓盐酸或向硫酸酸洗废液中加入浓硫酸，将废液的盐酸质量浓度或硫酸质量浓度调节为20%-25%； (1) Add concentrated hydrochloric acid to the hydrochloric acid pickling waste liquid or add concentrated sulfuric acid to the sulfuric acid pickling waste liquid, and adjust the mass concentration of hydrochloric acid or sulfuric acid in the waste liquid to 20%-25%;
（2）将调节好酸浓度的废液降温至0-3℃，使其中的氯化亚铁或硫酸亚铁结晶析出； (2) Cool down the waste liquid with adjusted acid concentration to 0-3°C to crystallize ferrous chloride or ferrous sulfate;
（3）将析出的氯化亚铁结晶或硫酸亚铁结晶从废液中分离出来。 (3) Separate the precipitated ferrous chloride crystals or ferrous sulfate crystals from the waste liquid.
进一步，步骤（1）中，调节后的盐酸或硫酸的质量浓度为21%-24%。 Further, in step (1), the adjusted mass concentration of hydrochloric acid or sulfuric acid is 21%-24%.
进一步，步骤（1）中，调节后的盐酸或硫酸的质量浓度为22%-23%。 Further, in step (1), the adjusted mass concentration of hydrochloric acid or sulfuric acid is 22%-23%.
进一步，步骤（2）中，先将调节好酸浓度的废液静置冷却至室温；再将冷却至室温的废液降温至0-3℃。 Further, in step (2), the waste liquid whose acid concentration has been adjusted is first allowed to stand and cooled to room temperature; then the waste liquid cooled to room temperature is cooled to 0-3°C.
进一步，步骤（2）中，将调节好酸浓度的废液降温至1-2℃。 Further, in step (2), the temperature of the waste liquid whose acid concentration has been adjusted is lowered to 1-2°C.
利用本发明所得氯化亚铁结晶或硫酸亚铁结晶，为工业级氯化亚铁或硫酸亚铁；回收氯化亚铁结晶或硫酸亚铁结晶后的盐酸酸液或硫酸酸液，可重复用于钢材的酸洗。 Utilize ferrous chloride crystallization or ferrous sulfate crystallization gained in the present invention, be industrial grade ferrous chloride or ferrous sulfate; Hydrochloric acid acid solution or sulfuric acid acid solution after reclaiming ferrous chloride crystallization or ferrous sulfate crystallization, can repeat For pickling of steel.
与现有技术相比，本发明的优点如下：能够回收酸洗废液中的有用成分，有效节约成本；实现酸洗废液的零排放，避免酸洗废液对环境造成污染。 Compared with the prior art, the invention has the following advantages: the useful components in the pickling waste liquid can be recovered, effectively saving costs; the zero discharge of the pickling waste liquid can be realized, and the environmental pollution caused by the pickling waste liquid can be avoided.
具体实施方式 detailed description
下面结合具体实施例对本发明作进一步详细描述。 The present invention will be further described in detail below in conjunction with specific embodiments.
实施例1 Example 1
本实施例包括以下步骤： This embodiment includes the following steps:
（1）向盐酸酸洗废液中加入浓盐酸，将废酸液的盐酸质量浓度调节为25%； (1) Add concentrated hydrochloric acid to the hydrochloric acid pickling waste liquid, and adjust the hydrochloric acid mass concentration of the waste acid liquid to 25%;
（2）将调节好酸浓度的废液静置冷却至室温； (2) Cool the waste liquid with adjusted acid concentration to room temperature;
（3）将冷却至室温的废液通过冷冻机进行冷冻降温，将废液的温度降低至0℃，使其中的氯化亚铁形成水合物结晶析出； (3) The waste liquid cooled to room temperature is refrigerated and cooled by a freezer, and the temperature of the waste liquid is lowered to 0°C, so that the ferrous chloride in it forms hydrate crystallization;
（4）将析出的氯化亚铁水合物结晶从废酸液中离心分离出来，所得氯化亚铁水合物结晶为工业级的氯化亚铁。 (4) The precipitated ferrous chloride hydrate crystals are centrifuged and separated from the waste acid solution, and the obtained ferrous chloride hydrate crystals are industrial-grade ferrous chloride.
回收氯化亚铁后的盐酸酸液，重复用于钢材的酸洗。 The hydrochloric acid solution after recovering the ferrous chloride is reused for pickling of steel.
某钢管厂，年产生酸洗废液约5000吨，废液中含盐酸约10wt%。利用本发明方法回收其中的有用成分。回收装置投资约60万元，回收装置运行后，当年回收氯化亚铁约600吨，质量浓度25%左右的稀盐酸约2000吨，当年即收回了投资成本，不仅仅为企业创造了一定的经济价值；还能实现酸洗废液的零排放，为企业节约酸洗废液的外排处理费用。 A steel pipe factory produces about 5,000 tons of pickling waste liquid annually, and the waste liquid contains about 10wt% hydrochloric acid. Utilize the method of the present invention to recover the useful components therein. The recovery device invested about 600,000 yuan. After the recovery device was in operation, about 600 tons of ferrous chloride and about 2,000 tons of dilute hydrochloric acid with a mass concentration of about 25% were recovered that year. Economic value; it can also realize zero discharge of pickling waste liquid, which saves the cost of external discharge treatment of pickling waste liquid for enterprises.
实施例2 Example 2
本实施例包括以下步骤： This embodiment includes the following steps:
（1）向硫酸酸洗废液中加入浓硫酸，将废酸液的硫酸质量浓度调节为20%； (1) Add concentrated sulfuric acid to the sulfuric acid pickling waste liquid, and adjust the sulfuric acid mass concentration of the waste acid liquid to 20%;
（2）将调节好酸浓度的废液静置冷却至室温； (2) Cool the waste liquid with adjusted acid concentration to room temperature;
（3）将冷却至室温的废液通过冷冻机进行冷冻降温，将废液的温度降低至3℃，使其中的硫酸亚铁形成水合物结晶析出； (3) The waste liquid cooled to room temperature is frozen and cooled by a refrigerator, and the temperature of the waste liquid is lowered to 3°C, so that the ferrous sulfate in it forms hydrate crystallization;
（4）将析出的硫酸亚铁水合物结晶从废液中离心分离出来，得到的硫酸亚铁水合物结晶为工业级的硫酸亚铁。 (4) The precipitated ferrous sulfate hydrate crystals are centrifuged and separated from the waste liquid, and the obtained ferrous sulfate hydrate crystals are industrial-grade ferrous sulfate.
分离出硫酸亚铁水合物结晶后的硫酸酸液，重复用于钢材的酸洗。 The sulfuric acid liquid after ferrous sulfate hydrate crystallization is separated and reused for pickling of steel.
某机械企业下属车桥厂，年产生酸洗废液约3000吨，废液中含硫酸约8wt%。利用本发明方法回收其中的有用成分。回收装置投资约40万元，回收装置运行后，年回收硫酸亚铁约360吨；质量浓度20%左右的稀硫酸约1200吨，重复用于钢材的酸洗。每年回收物料的经济价值约30万元，不仅为企业创造经济效益，还能实现酸洗废液的零排放，为企业节约酸洗废液的外排处理费用。 The axle factory of a machinery company produces about 3,000 tons of pickling waste liquid annually, and the waste liquid contains about 8wt% sulfuric acid. Utilize the method of the present invention to recover the useful components therein. The investment in the recovery device is about 400,000 yuan. After the recovery device is in operation, the annual recovery of ferrous sulfate is about 360 tons; the dilute sulfuric acid with a mass concentration of about 20% is about 1,200 tons, which can be reused for pickling of steel. The economic value of recycled materials is about 300,000 yuan per year, which not only creates economic benefits for the enterprise, but also realizes zero discharge of pickling waste, and saves the cost of disposal of pickling waste for the enterprise.
本领域的技术人员可以对本发明实施例进行各种修改和变型，倘若这些修改和变型在本发明权利要求及其等同技术的范围之内，则这些修改和变型也在本发明的保护范围之内。 Those skilled in the art can make various modifications and variations to the embodiments of the present invention, if these modifications and variations are within the scope of the claims of the present invention and their equivalent technologies, then these modifications and variations are also within the protection scope of the present invention .
说明书中未详细描述的内容为本领域技术人员公知的现有技术。 The content not described in detail in the specification is the prior art known to those skilled in the art.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046213A (en) * | 2017-12-11 | 2018-05-18 | 珠海绿水环保科技有限公司 | A kind of recovery method of the waste hydrochloric acid of metal ion |
| CN110028041A (en) * | 2019-05-30 | 2019-07-19 | 李永飞 | For handling the waste acidity recovery method and acid-restoring plant of acid washing rolled steel waste liquid |
| CN112897589A (en) * | 2021-02-09 | 2021-06-04 | 鞍钢股份有限公司 | Method for separating iron ions in low-alloy steel corrosion product chemical cleaning solution |
| CN113716787A (en) * | 2021-10-13 | 2021-11-30 | 江苏效玄机电科技有限公司 | Regeneration treatment method and system for metal pickling waste liquid |
| CN116119699A (en) * | 2023-01-31 | 2023-05-16 | 浙江金洁环境股份有限公司 | A method for recovering aluminum sulfate from aluminum profile processing waste liquid |
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| CN1043535A (en) * | 1988-12-24 | 1990-07-04 | 由正明 | Sulfuric acid pickling waste liquid regenerated processing method |
| CN1164579A (en) * | 1996-05-05 | 1997-11-12 | 大连市金州区环境监测站 | Process for treatment of sulfuric acid pickling waste liquor for pickling steel |
| CN102040196A (en) * | 2009-10-15 | 2011-05-04 | 盐城师范学院 | Method for reclaiming hydrochloric acid and ferrous sulfate from steel hydrochloric acid washing waste liquid |
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2016
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| CN1043535A (en) * | 1988-12-24 | 1990-07-04 | 由正明 | Sulfuric acid pickling waste liquid regenerated processing method |
| CN1164579A (en) * | 1996-05-05 | 1997-11-12 | 大连市金州区环境监测站 | Process for treatment of sulfuric acid pickling waste liquor for pickling steel |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046213A (en) * | 2017-12-11 | 2018-05-18 | 珠海绿水环保科技有限公司 | A kind of recovery method of the waste hydrochloric acid of metal ion |
| CN110028041A (en) * | 2019-05-30 | 2019-07-19 | 李永飞 | For handling the waste acidity recovery method and acid-restoring plant of acid washing rolled steel waste liquid |
| CN112897589A (en) * | 2021-02-09 | 2021-06-04 | 鞍钢股份有限公司 | Method for separating iron ions in low-alloy steel corrosion product chemical cleaning solution |
| CN113716787A (en) * | 2021-10-13 | 2021-11-30 | 江苏效玄机电科技有限公司 | Regeneration treatment method and system for metal pickling waste liquid |
| CN116119699A (en) * | 2023-01-31 | 2023-05-16 | 浙江金洁环境股份有限公司 | A method for recovering aluminum sulfate from aluminum profile processing waste liquid |
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Application publication date: 20160525 |