CN1254444C - Method for comprehensive treating waste emulsion liquid and chromium containing waste water by metallurgy chemical industry technology - Google Patents

Method for comprehensive treating waste emulsion liquid and chromium containing waste water by metallurgy chemical industry technology Download PDF

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CN1254444C
CN1254444C CN 03128803 CN03128803A CN1254444C CN 1254444 C CN1254444 C CN 1254444C CN 03128803 CN03128803 CN 03128803 CN 03128803 A CN03128803 A CN 03128803A CN 1254444 C CN1254444 C CN 1254444C
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water
slag
waste water
waste
chromium
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CN 03128803
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CN1552639A (en
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李峻泰
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Abstract

The present invention belongs to the technical field of environmental pollution treatment. The existing high COD content waste water in waste deoiled emulsion is hard to discharge as standards, chromate containing waste water is processed and discharged with a certain amount of chromium all the time, and sludge thereof is hard to process. The present invention discloses chromate containing waste water which accords with environmental protection discharge standards, the high COD content waste water and hexavalent chromium in the deoiled waste emulsion are processed via chemical reduction, and the chromate containing waste water is used for processing high temperature metallurgy dregs. Therefore, generated different organic matter with high COD content is burnt or decomposed via high temperature heat sealing, and water is used as compensation water for dreg treatment close circuit circular water; the sludge and metallurgical dregs, such as powdery steel dregs, etc., are synthetically used as raw materials for producing cement or are used as sintering raw materials in metallurgic plants, so no water is discharged into natural environment, and the present invention completely solves the environmental pollution because of the two pollution factors.

Description

Method for comprehensively treating waste emulsion and chromium-containing wastewater by using metallurgical and chemical technology
The technical field is as follows: the invention belongs to the technical field of environmental pollution treatment. Mainly solves the secondary pollution caused by the discharge of high COD value waste water, chromium-containing waste water and chromium-containing sludge after deoiling waste emulsion to the environment.
Background art: the emulsion is prepared by mixing mineral oil, vegetable oil and animal oil in certain proportion, adding dispersant stabilizer, and emulsifying with water. The emulsion is used as lubricant and coolant in the processes of metallurgical steel rolling, automobile manufacture, equipment processing and maintenance and the like, and the components and the state of the emulsion are changed and discarded after being repeated for many times, namely the waste emulsion, which contains oil and has high COD value (chemical oxygen demand). Environmental protection requirements are carefully treated, and the wastewater can be discharged into a water environment after reaching the discharge standard. In order to meet the requirement of environmental protection, advanced enterprises use an ultrafiltration deoiling method and a biological method to remove COD, and the two processes are used in series. The COD value is still higher, some other waste water except COD is adsorbed by activated carbon, and because of huge equipment investment, complex operation and high operating cost, a plurality of enterprises adopt outsourcing treatment, while the waste emulsion is subjected to standing aeration and deoiling in rural private enterprises in suburbs, and the waste water with high COD value is simply treated by lime water and then discharged to the environment, thereby causing secondary environmental pollution.
A large amount of chromic acid, chromic anhydride, stainless steel smelting process and the like are used in the electroplating industry, the repairing industry, the metallurgical enterprise products, namely plate and pipe processing, and the like, and a large amount of chromium-containing wastewater is also generated. Chromium is a substance which is most strictly controlled in the environmental protection discharge standard, some enterprises reduce hexavalent chromium in the hexavalent chromium into trivalent chromium through chemical treatment, then adjust the pH value to precipitate the trivalent chromium, water is discharged to the environment, the treatment of the precipitate is a difficult problem, many enterprises treat the chromium-containing wastewater outsourcing suburb private enterprises, the civilian small plants reduce the hexavalent chromium into the trivalent chromium, then adjust the pH value to precipitate the trivalent chromium, water is discharged to the surrounding water body, and the precipitate is sent to brick factories to be baked or filled into deep pits.
Both COD (chemical oxygen demand) and chromium are pollution factors that are strictly controlled in environmental protection drainage standards. After deoiling, the COD value of the waste emulsion is up to 20000 mg/L-30000 mg/L (chromium method) or even higher, and far exceeds the national emission standard of 100mg/L (chromium method). After the chromium-containing wastewater is chemically reduced, a certain amount of chromium is always contained in the wastewater, and the precipitate of trivalent chromium is sent to a brick factory for brick baking or filled into a pit, which is not always a proper disposal method.
In the industrial production of metallurgy (blast furnaces, converters, electric furnaces, ferroalloy smelting furnaces and the like), a large amount of liquid slag (1400-1500 ℃) is generated while precious metals are obtained. At present, there are two kinds of slag treatment methods, one is to carry out water quenching granulation by using a large amount of high pressure water in front of or near the furnace, the other is to inject the slag into a slag tank for slight cooling (natural cooling or water spraying) to reach about 600 ℃, then send the slag blocks into the slag tank of the slag treatment hot disintegrating process, cover and spray water, and pulverize by using the characteristics of the slag (the process is mainly used for slag treatment). Because the slag temperature is very high, a large amount of water is needed for operation in the processes of water quenching and hot sealing in front of the furnace, a large amount of water is evaporated, and part of water is taken away. Although the slag treatment process employs a closed cycle of water, large quantities of industrial water are required to be replenished each day.
The invention content is as follows: the invention utilizes the waste water after being treated to adjust the PH value of the waste water containing chromium and the alkalization of the waste water with high COD value, and returns the generated slurry turbid matter to the water treatment system of the closed circulation water for treating the slag, thereby ensuring that the waste emulsion and the waste water containing chromium are not discharged to the natural environment, comprehensively utilizing the water, saving the water resource and the energy,and thoroughly solving the problems of the discharge pollution of the waste water with high COD value and the waste water containing chromium and the treatment problem of the sludge after the waste water containing chromium is treated.
The specific implementation mode is as follows: 1. and (3) treating the waste liquid after the waste emulsion is kept stand, carrying out microporous aeration for degreasing, and then treating the steel slag by using a hot sealing process, wherein the pH value of the water (pH value is 11-12) carrying fine slag is adjusted to be about 9. Then the water is returned to a slag treatment closed-loop circulating water treatment system to be used as make-up water of slag treatment closed-loop circulating water, and the organic matters in the high-COD value wastewater are burnt and boiled by boiling water for complete digestion through contact with high-temperature metallurgical slag, so that zero emission to the environment is achieved.
2. Using Fe in acidic medium for chromium-containing waste water and waste liquid2+,SO3 2-,S2O3 2-Or reducing hexavalent chromium to trivalent chromium by a reducing agent such as sodium metabisulfite. For example: reducing hexavalent chromium to trivalent chromium with sodium pyrosulfite at pH less than or equal to 4
Measurement of [ Cr]6+Is [ Cr]guaranteed6+0.5mg/L (national standard). Treating the steel slag by a hot smoldering process and adding water (pH is 11-12) with fine slag to adjust the pH to 8-9 so as to precipitate trivalent chromium
Cr3++OH→〔Cr(OH)3↓〕
Precipitate and powdered steel slag (phi less than 5)m/m) The water is returned to the slag treatment closed-loop circulating water treatment system and used as make-up water of the slag treatment closed-loop circulating water, so that zero emission to the environment is achieved.

Claims (1)

  1. A method for comprehensively treating waste emulsion and chromium-containing wastewater by using a metallurgical and chemical technology is characterized by comprising the following steps of:
    (1) a blast furnace, a converter, an electric furnace, an iron alloy smelting furnace and the like of a metallurgical enterprise generate liquid slag with the temperature of 1400-1500 ℃ in the smelting process, the slag is quenched and granulated by closed circulating water in front of the furnace and near the furnace or massive converter slag cooled to 600 ℃ is fed into a slag tank of a hot-seal process to be covered, the closed circulating water is sprayed for pulverization, a high COD value factor of waste emulsion subjected to ultrafiltration or standing microporous aeration deoiling is a mixture of a plurality of organic matters, the high COD value wastewater subjected to deoiling by the process is added into the closed circulating water, the organic matters in the high COD value wastewater are burnt and boiled and digested through contact with the metallurgical slag, and the water is used as partial make-up water of the closed circulating water;
    (2) adjustment ofMaking the chromium-containing wastewater acidic in pH value by using Fe2+,SO3 2-,S2O3 2-Or sodium metabisulfite or other reducing agents to reduce hexavalent chromium ions into trivalent chromium ions, then using the steel slag treated by the hot disintegration process and carrying water of fine steel slag with phi less than 5mm, wherein the pH of the acid waste water is 11-12, adjusting the acid waste water reduced into trivalent chromium ions to ensure that the pH of the acid waste water is 8-9, and precipitating trivalent chromium ions [ Cr (OH)]3]Precipitating together with fine steel slag with the diameter of less than 5mm to achieve the aim of treating waste by waste, wherein the precipitate is used as a raw material for producing cement or a sintering raw material for metallurgical enterprises;
    (3) the two kinds of waste water are used as supplementary water for metallurgical slag closed circulating water after being treated, and the purpose of saving water resource and energy is achieved.
CN 03128803 2003-05-26 2003-05-26 Method for comprehensive treating waste emulsion liquid and chromium containing waste water by metallurgy chemical industry technology Expired - Fee Related CN1254444C (en)

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CN 03128803 CN1254444C (en) 2003-05-26 2003-05-26 Method for comprehensive treating waste emulsion liquid and chromium containing waste water by metallurgy chemical industry technology

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CN 03128803 CN1254444C (en) 2003-05-26 2003-05-26 Method for comprehensive treating waste emulsion liquid and chromium containing waste water by metallurgy chemical industry technology

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CN1254444C true CN1254444C (en) 2006-05-03

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101481221B (en) * 2008-01-07 2011-12-21 宝山钢铁股份有限公司 Method for treating silicate slag from wastewater treatment
CN105985033A (en) * 2015-02-28 2016-10-05 宝山钢铁股份有限公司 Method for treating and utilizing electric furnace circulating water sludge
CN105060665B (en) * 2015-08-26 2018-09-18 新疆八一钢铁股份有限公司 A kind of technique using slag adsorption treatment steel rolling oil-containing greasy filth
CN105347643B (en) * 2015-12-13 2017-12-22 宝钢集团新疆八一钢铁有限公司 A kind of technique for handling steel rolling oily sludge using steel slag waste heat
CN106241994A (en) * 2016-09-19 2016-12-21 上海中冶环境工程科技有限公司 Vessel slag purposes in preparation is containing cadmium sewage-treating agent
CN106241996A (en) * 2016-09-19 2016-12-21 上海中冶环境工程科技有限公司 Vessel slag purposes in preparing sewage containing copper inorganic agent
CN108083529A (en) * 2016-11-23 2018-05-29 宝山钢铁股份有限公司 A kind of method that chromate waste water cooperates with processing with acid waste water
CN108640333A (en) * 2018-04-27 2018-10-12 江苏和顺环保有限公司 The mixed processing method of waste emulsified mixture and useless chromic acid
CN109293041B (en) * 2018-09-25 2021-05-18 成都兴蓉环保科技股份有限公司 Combined treatment method of waste sodium dichromate and emulsion

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