WO2023124104A1 - Low-cost resource utilization process for acid wastewater - Google Patents

Low-cost resource utilization process for acid wastewater Download PDF

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WO2023124104A1
WO2023124104A1 PCT/CN2022/112404 CN2022112404W WO2023124104A1 WO 2023124104 A1 WO2023124104 A1 WO 2023124104A1 CN 2022112404 W CN2022112404 W CN 2022112404W WO 2023124104 A1 WO2023124104 A1 WO 2023124104A1
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acid
wastewater
enters
water
acidic wastewater
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PCT/CN2022/112404
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French (fr)
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毛敏
张小艳
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中冶南方工程技术有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes

Definitions

  • the invention belongs to the technical field of water treatment, and in particular relates to a low-cost resource utilization process of acidic wastewater.
  • the acid wastewater mainly comes from cold rolling, silicon steel pickling unit discharge and stainless steel pickling unit.
  • the hydrochloric acid acid wastewater discharged from cold rolling and silicon steel pickling units mainly contains hydrochloric acid, metal ions (Me), etc.
  • the mixed acid acid wastewater of stainless steel pickling units mainly contains mixed acids (nitric acid, hydrofluoric acid), metal ions (Me), etc. .
  • Hydrochloric acid acid wastewater generally adopts the lime neutralization sedimentation tank method to neutralize the residual acid in the wastewater and produce metal hydroxide precipitation sludge.
  • the method has the advantages of simple process and low equipment investment.
  • the disadvantage is that a large amount of lime milk needs to be added to produce a large amount of sedimentation sludge, which cannot reduce the chloride ion content of the wastewater, and also increases the hardness of the wastewater, so that the wastewater cannot be reused.
  • the neutralized wastewater is a kind of wastewater containing high nitrate nitrogen, and the direct discharge of total nitrogen is very high, which is 20 to 100 times the national discharge standard. Therefore, a small number of stainless steel in China Enterprises such as Zhangjiagang Pohang and Guangzhou Lianzhong have added biological denitrification treatment of stainless steel pickling wastewater after neutralization, and the total nitrogen in the wastewater is removed before reuse or direct discharge into the water body. Due to the high operating cost of biological denitrification, most domestic stainless steel enterprises still neutralize the waste water of the stainless steel pickling unit and discharge it directly to the drainage pipe network of the whole plant, causing the total nitrogen of the production waste water discharged from the whole plant to exceed the standard.
  • acidic wastewater at home and abroad also adopts a process of mixing with cold-rolled alkaline wastewater.
  • the advantage of this process is that it saves the consumption of acid- base neutralizing agents.
  • the rate is as high as 4500-15000 ⁇ s/cm.
  • the high salt, high hardness, and high iron ions in the mixed wastewater will affect the biochemical treatment effect.
  • the high iron ions in the biochemical effluent cannot meet the influent requirements of the ultrafiltration + reverse osmosis membrane reuse process. Further deep reuse treatment of wastewater is limited.
  • the object of the present invention is to provide an acidic wastewater treatment process that can realize low operating cost and resource utilization.
  • the technical solution of the present invention is a low-cost resource utilization process for acidic wastewater, comprising the following steps:
  • the acidic wastewater discharged from the pickling unit enters the acid wastewater regulating tank to adjust the water volume and water quality; the waste acid solution discharged from the pickling unit enters the acid regeneration reactor for high-temperature thermal hydrolysis reaction, and the generated high-temperature flue gas containing acidic components enters the acid regenerative absorber;
  • the acidic wastewater in the middle pool 1 enters the first-level electro-adsorption device for treatment to obtain the first-level concentrated water and the first-level produced water;
  • the primary concentrated water enters the acid regeneration absorption device as the regeneration acid absorption liquid, and sprays and absorbs the high-temperature flue gas containing acidic components to form regeneration acid, which enters the pickling unit for recycling; the primary water enters the secondary
  • the electric adsorption device is used for treatment to obtain secondary concentrated water and secondary product water;
  • the secondary concentrated water enters the intermediate pool 1 using residual pressure, and the secondary produced water enters the intermediate pool 2 by gravity; the secondary produced water in the intermediate pool 2 enters the alkali wastewater treatment system for treatment and reuse, and/or the secondary produced water After being mixed with new acid, it enters the pickling unit as supplementary acid.
  • the pretreatment process in step 2) is as follows: the acidic wastewater in the acidic wastewater regulating tank enters into the sedimentation tank one, and the supernatant after removing suspended particles through sedimentation enters the acidic wastewater filter, and the filtered acidic wastewater filter The water enters the middle pool one.
  • the housing of the acid wastewater filter is made of acid-resistant material
  • the filter material is made of acid-resistant filter material
  • the metal ion concentration of the primary concentrated water in step 3 is 3-15 g/L, and the conductivity is 27000-100000 ⁇ s/cm. .
  • the acidic wastewater in step 1) is hydrochloric acidic wastewater
  • the regenerated acid in step 4) is hydrochloric acid
  • the concentration is 200g/L
  • the acidic wastewater in step 1) is mixed acid acidic wastewater
  • the regenerated acid in step 4) It is a mixed acid of HF and HNO3 , the concentration of HF is 5-60g/L, and the concentration of HNO3 is 80-160g/L.
  • the pH value of the secondary product water in step 4) is 2-4, the total iron content is 15-100 mg/L, and the conductivity is 100-500 ⁇ s/cm.
  • the secondary product water in step 5) is mixed with new acid and enters the pickling unit as supplementary acid, specifically: when the acidic wastewater in step 1) is hydrochloric acid acid wastewater, the secondary product water in step 5) is mixed with 18% The hydrochloric acid is blended until the concentration of hydrochloric acid is 200g/L and enters the pickling unit as supplementary acid; when the acidic wastewater in step 1) is mixed acidic acidic wastewater, the secondary product water in step 5) is mixed with 55% HF, 98% or 68% % HNO 3 is blended until the concentration of HF in the mixed acid is 5-60g/L, and the concentration of HNO 3 is 80-160g/L, and then enters the pickling unit as supplementary acid.
  • the treatment process of the secondary produced water entering the alkali wastewater treatment system in step 5) is as follows: the secondary produced water in the intermediate pool 2 enters the alkali wastewater regulating tank for neutralization reaction with the alkaline wastewater, and the reacted wastewater enters the middle Adjust the PH value, coagulation reaction, and flocculation reaction in the mixing, coagulation, and flocculation tanks, and the effluent from the neutralization, coagulation, and flocculation tanks enters the air flotation device, and the effluent from the air flotation device passes through the biochemical device, sedimentation tank 2, and filtration device in turn. Send reclaimed water to users for use or deep reuse.
  • the biochemical device adopts an aerobic reaction tank; when the acidic wastewater in step 1) is mixed acidic wastewater, the biochemical device must use an anoxic reaction tank and an aerobic reaction tank In a series connection, the anoxic reaction pool uses the COD in the alkaline wastewater for denitrification to remove 15-50 mg/L of nitrate in the secondary product water.
  • iron ions (15-100 mg/L) in the secondary product water are used as coagulant for coagulation reaction.
  • the present invention has the following beneficial effects:
  • the present invention first adopts precipitation + filtration as pretreatment to meet the water intake requirements of the electro-adsorption device; then adopts the first-stage electro-adsorption device and the second-stage electro-adsorption device in series as the core treatment unit to treat acidic wastewater and reduce the salinity of the acidic wastewater , metal ions, improve the water quality of the electro-adsorption device, avoid the problem that the conductivity of the acidic wastewater after only one-stage electro-adsorption treatment, and the high metal ions cannot be reused, and also avoid the traditional mixed treatment process of acid-base wastewater
  • the concentrated water of the first-stage electric adsorption device enters the acid regeneration as the regeneration acid absorption liquid Absorption device, which sprays and absorbs the high-temperature flue gas containing acidic components produced by the acid regeneration reactor, forms
  • the iron ions contained in the produced water of the secondary electrosorption device can be used as a coagulant in the coagulation tank, which greatly reduces the traditional The amount of coagulant that needs to be added to the coagulation tank in the alkali wastewater treatment process;
  • the low-cost resource utilization process of acidic wastewater provided by the present invention can greatly reduce the consumption of chemicals (milk of lime, acid-base neutralizing agents, coagulants, etc.) and the amount of sludge, Significantly improve the salt increase in wastewater caused by the addition of acid-base neutralizers, the final reuse water quality is better, and the operating cost is low. At the same time, it can realize nearly 100% recycling of wastewater and metal ions and acids in wastewater, completely avoiding wastewater The impact of discharge on the environment has truly realized the low cost and resource utilization of acid wastewater. It is a new process route that is economical, environmentally friendly, green, energy-saving, occupies less land, and has high-quality and stable effluent quality.
  • Fig. 1 is the flowchart of the low-cost resource utilization process of acidic wastewater provided by the embodiment of the present invention
  • this embodiment provides a low-cost resource utilization process for acidic wastewater, including the following steps:
  • the acidic wastewater discharged by the pickling unit 1 (the iron ion concentration is 1500-3000 mg/L, and the conductivity is 4500-15000 ⁇ s/cm) is discharged into the acidic wastewater regulating pool 4 through the pipe network, and the water volume is adjusted in the acidic wastewater regulating pool 4. Water quality; the waste acid liquid discharged from the pickling unit 1 enters the acid regeneration reactor 2 for high-temperature thermal hydrolysis reaction, and the generated high-temperature flue gas containing acidic components enters the acid regeneration absorption device 3, and recovers metal oxides;
  • the acidic wastewater in the acidic wastewater regulating tank 4 enters the sedimentation tank 1 through the lifting pump, and the supernatant after the suspended particles are removed by sedimentation is lifted into the acidic wastewater filter 6, and the filtered water filtered by the acidic wastewater filter 6 enters the Intermediate pool 17; among them, precipitation + filter is used for pretreatment to meet the water intake requirements of the electro-adsorption device;
  • the shell of the acid waste water filter 6 is made of acid-resistant material, and the shell can be used for the treatment of hydrochloric acid acid waste water Fiberglass or steel-lined rubber material, the shell can be made of glass fiber reinforced plastic or steel-lined rubber material for mixed acid acid wastewater treatment, the filter material is acid-resistant filter material, and the filter material for hydrochloric acid acid wastewater treatment can be pickled quartz sand, Activated carbon filter material, fiber filter material, activated carbon filter material can be used for mixed acid acid wastewater treatment;
  • the acidic wastewater in the middle pool 7 enters the first-stage electro-adsorption device 8 through the lift pump for treatment to obtain the first-class concentrated water and the first-class product water; the first-stage electro-adsorption device 8 adsorbs and removes Fe 3+ and Fe in the wastewater. 2+ , H + , SiO 3 2- , Cl - plasma, reduce the ion concentration of the primary product water, the metal ion concentration of the produced primary concentrated water is 3-15g/L, and the conductivity is 27000-100000 ⁇ s/cm;
  • the primary concentrated water enters the acid regeneration absorption device 3 as the regeneration acid absorption liquid, and sprays and absorbs the high-temperature flue gas containing acid components that enters the acid regeneration absorption device 3 from the acid regeneration reaction furnace 2 to form regeneration acid.
  • the pump enters the pickling unit 1 for recycling, realizing nearly 100% resource utilization of metal ions and acids in wastewater;
  • middle acid waste water is hydrochloric acid waste water
  • regeneration acid is hydrochloric acid, and concentration is 200g/L
  • middle acid waste water is mixed acid acid waste water
  • regeneration acid is HF and HNO Mixed acid, the concentration of HF 5 ⁇ 60g/L, the concentration of HNO 3 is 80 ⁇ 160g/L;
  • the primary product water enters the secondary electro-adsorption device 9 through the lift pump for treatment to obtain secondary concentrated water and secondary product water; the secondary electro-adsorption device 9 further adsorbs and removes Fe 3+ , Fe 2+ , and H + in the wastewater , SiO 3 2- , Cl - plasma to further reduce the ion concentration of the product water; the pH value of the secondary product water is 2 ⁇ 4, the total iron content is 15 ⁇ 100mg/L, and the conductivity is 100 ⁇ 500 ⁇ s/cm;
  • the secondary produced water flows into the intermediate pool 2 10 by itself, and the secondary produced water in the intermediate pool 2 10 enters the alkali wastewater treatment system for treatment and reuse, and/or the secondary produced water is mixed with new acid and enters the pickling unit as supplementary acid 1;
  • the reuse of the secondary produced water after entering the alkali wastewater treatment system is specifically: the secondary produced water (acidic, pH value 2-4) in the middle pool 2 10 enters the alkali wastewater regulating tank 11 of the waste water station through the lift pump,
  • the acid-base neutralization reaction between the secondary produced water and the alkaline wastewater in the wastewater regulating tank 11 reduces the dosage of the acid neutralizer for the alkaline wastewater and the dosage of the alkaline neutralizer for the acidic wastewater in the secondary electrosorption device 9, greatly reducing While reducing the consumption of chemicals, the salt introduced by the addition of acid-base neutralizers in the wastewater is reduced;
  • the wastewater after the neutralization reaction enters the neutralization, coagulation, and flocculation tank 12 through the lift pump, and the pH value is further adjusted in the neutralization unit , carry out the coagulation reaction in the coagulation tank, add PAM in the coagulation tank to carry out the flocculation reaction, neutralize, coagulate, and the water from the flocculation tank 12 flows into the air flo
  • the secondary product water After the secondary product water is mixed with the new acid, it enters the pickling unit 1 as supplementary acid, specifically: when the acidic wastewater in step 1) is hydrochloric acid acid wastewater, the secondary product water and 18% hydrochloric acid in step 5) are in the acid mixing pool After blending in 17 until the concentration of hydrochloric acid is 200g/L, enter the pickling unit 1 as normal supplementary acid; when the acidic wastewater in step 1) is mixed acidic acidic wastewater, the secondary product water in step 5) is mixed with 55% HF, 98 % or 68% HNO3 is blended in the acid mixing tank 17 until the concentration of HF in the mixed acid is 5-60g/L, and the concentration of HNO3 is 80-160g/L, and then enters the pickling unit 1 as normal supplementary acid.

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Abstract

The present invention provides a low-cost resource utilization process for acid wastewater. The acidic wastewater discharged by a pickling unit is subjected to pretreatment after adjusting the amount and quality of water, the pretreated acidic wastewater enters a first-stage electric adsorption device, the obtained first-stage concentrated water enters an acid regeneration absorption device, discharged acid pickle enters an acid regeneration reaction furnace for spray absorption, and regenerated acid is formed and enters the pickling unit for cyclic utilization; the obtained first-stage produced water enters a second-stage electric adsorption device for treatment, the obtained second-stage produced water enters an alkali wastewater treatment system for treatment and then is recycled, and/or the second-stage produced water and a new acid are mixed to enter the pickling unit as a replenish acid. According to the present invention, the reagent consumption and the sludge amount can be greatly reduced, the salt increase is avoided, the final water quality is better, the cost is low, the problem that the effluent of the conventional acidic wastewater treatment process cannot meet the water inlet requirements of the ultrafiltration + reverse osmosis membrane deep reuse process is solved, meanwhile, nearly 100% recycling of wastewater and metal ions and acids in the wastewater is realized, and the influence of wastewater discharge on the environment is avoided.

Description

一种酸性废水低成本资源化利用工艺A low-cost resource utilization process for acidic wastewater 技术领域technical field
本发明属于水处理技术领域，具体涉及一种酸性废水低成本资源化利用工艺。The invention belongs to the technical field of water treatment, and in particular relates to a low-cost resource utilization process of acidic wastewater.
背景技术Background technique
钢铁企业在生产过程中会产生大量酸性废水，酸性废水主要来源于冷轧、硅钢酸洗机组排放和不锈钢酸洗机组。冷轧、硅钢酸洗机组排放的盐酸酸性废水，主要含有盐酸、金属离子(Me)等，不锈钢酸洗机组的混酸酸性废水，主要含有混酸(硝酸、氢氟酸)、金属离子(Me)等。Iron and steel enterprises will produce a large amount of acid wastewater in the production process, and the acid wastewater mainly comes from cold rolling, silicon steel pickling unit discharge and stainless steel pickling unit. The hydrochloric acid acid wastewater discharged from cold rolling and silicon steel pickling units mainly contains hydrochloric acid, metal ions (Me), etc. The mixed acid acid wastewater of stainless steel pickling units mainly contains mixed acids (nitric acid, hydrofluoric acid), metal ions (Me), etc. .
盐酸酸性废水一般采用石灰中和沉淀池法，将废水中残余酸中和，产生金属氢氧化物沉淀污泥。该方法的优点是工艺简单、设备投资少。缺点是需要投加大量石灰乳，生产大量的沉淀污泥，无法降低废水的氯离子含量，还增加了废水的硬度，废水无法实现回用。Hydrochloric acid acid wastewater generally adopts the lime neutralization sedimentation tank method to neutralize the residual acid in the wastewater and produce metal hydroxide precipitation sludge. The method has the advantages of simple process and low equipment investment. The disadvantage is that a large amount of lime milk needs to be added to produce a large amount of sedimentation sludge, which cannot reduce the chloride ion content of the wastewater, and also increases the hardness of the wastewater, so that the wastewater cannot be reused.
混酸酸性废水一般也是采用石灰中和处理，此中和后的废水是一种高含硝态氮的废水，直接排放总氮很高，是国家排放标准的20～100倍，所以国内的少数不锈钢企业例如张家港浦项、广州联众等在中和之后增加了不锈钢酸洗废水生物脱氮处理，将废水中的总氮脱除后再回用或直接排放水体。由于生物脱氮的运行成本很高，所以国内大部分不锈钢企业还是将不锈钢酸洗机组废水中和后直接排放到全厂排水管网，造成了全厂外排生产废水总氮超标。Mixed acid acid wastewater is generally treated by lime neutralization. The neutralized wastewater is a kind of wastewater containing high nitrate nitrogen, and the direct discharge of total nitrogen is very high, which is 20 to 100 times the national discharge standard. Therefore, a small number of stainless steel in China Enterprises such as Zhangjiagang Pohang and Guangzhou Lianzhong have added biological denitrification treatment of stainless steel pickling wastewater after neutralization, and the total nitrogen in the wastewater is removed before reuse or direct discharge into the water body. Due to the high operating cost of biological denitrification, most domestic stainless steel enterprises still neutralize the waste water of the stainless steel pickling unit and discharge it directly to the drainage pipe network of the whole plant, causing the total nitrogen of the production waste water discharged from the whole plant to exceed the standard.
此外，国内外酸性废水也有采用与冷轧碱性废水混合处理的工艺，该工艺的优点是节省了酸碱中和药剂的消耗，缺点是因酸性废水Fe 2+高达1500-3000mg/L、电导率高达4500-15000μs/cm，酸碱废水混合后，混合废水高 盐、高硬度、高铁离子影响生化处理效果，生化出水的高铁离子无法满足超滤+反渗透膜回用工艺的进水要求，限制了废水的进一步深度回用处理。 In addition, acidic wastewater at home and abroad also adopts a process of mixing with cold-rolled alkaline wastewater. The advantage of this process is that it saves the consumption of acid- base neutralizing agents. The rate is as high as 4500-15000μs/cm. After the acid-base wastewater is mixed, the high salt, high hardness, and high iron ions in the mixed wastewater will affect the biochemical treatment effect. The high iron ions in the biochemical effluent cannot meet the influent requirements of the ultrafiltration + reverse osmosis membrane reuse process. Further deep reuse treatment of wastewater is limited.
发明内容Contents of the invention
为了克服上述现有技术存在的不足，本发明的目的是提供一种可实现运行成本低、并能实现资源化利用的酸性废水处理工艺。In order to overcome the deficiencies in the above-mentioned prior art, the object of the present invention is to provide an acidic wastewater treatment process that can realize low operating cost and resource utilization.
为实现上述目的，本发明的技术方案为一种酸性废水低成本资源化利用工艺，包括如下步骤：In order to achieve the above purpose, the technical solution of the present invention is a low-cost resource utilization process for acidic wastewater, comprising the following steps:
1)酸洗机组排放的酸性废水进入酸性废水调节池内调节水量、水质；酸洗机组排放的废酸液进入酸再生反应炉进行高温热水解反应，产生的含酸性成分的高温烟气进入酸再生吸收装置；1) The acidic wastewater discharged from the pickling unit enters the acid wastewater regulating tank to adjust the water volume and water quality; the waste acid solution discharged from the pickling unit enters the acid regeneration reactor for high-temperature thermal hydrolysis reaction, and the generated high-temperature flue gas containing acidic components enters the acid regenerative absorber;
2)酸性废水调节池内的酸性废水经预处理后进入中间水池一；2) The acidic wastewater in the acidic wastewater regulating tank enters the intermediate pool 1 after being pretreated;
3)中间水池一内的酸性废水进入一级电吸附装置进行处理，得到一级浓水和一级产水；3) The acidic wastewater in the middle pool 1 enters the first-level electro-adsorption device for treatment to obtain the first-level concentrated water and the first-level produced water;
4)一级浓水作为再生酸吸收液进入酸再生吸收装置，对含酸性成分的高温烟气进行喷淋吸收，形成再生酸，再生酸进入酸洗机组循环利用；一级产水进入二级电吸附装置进行处理，得到二级浓水和二级产水；4) The primary concentrated water enters the acid regeneration absorption device as the regeneration acid absorption liquid, and sprays and absorbs the high-temperature flue gas containing acidic components to form regeneration acid, which enters the pickling unit for recycling; the primary water enters the secondary The electric adsorption device is used for treatment to obtain secondary concentrated water and secondary product water;
5)二级浓水利用余压进入中间水池一，二级产水自流进入中间水池二；中间水池二中的二级产水进入碱废水处理***处理后回用，和/或二级产水与新酸混合后作为补充酸进入酸洗机组。5) The secondary concentrated water enters the intermediate pool 1 using residual pressure, and the secondary produced water enters the intermediate pool 2 by gravity; the secondary produced water in the intermediate pool 2 enters the alkali wastewater treatment system for treatment and reuse, and/or the secondary produced water After being mixed with new acid, it enters the pickling unit as supplementary acid.
进一步地，步骤2)中的预处理过程如下：酸性废水调节池内的酸性废水进入沉淀池一中，经沉淀去除悬浮颗粒物后的上清液进入酸性废水过滤器，酸性废水过滤器过滤后的滤水进入中间水池一。Further, the pretreatment process in step 2) is as follows: the acidic wastewater in the acidic wastewater regulating tank enters into the sedimentation tank one, and the supernatant after removing suspended particles through sedimentation enters the acidic wastewater filter, and the filtered acidic wastewater filter The water enters the middle pool one.
更进一步地，所述酸性废水过滤器的壳体采用耐酸材质，滤料采用耐酸滤 料。Further, the housing of the acid wastewater filter is made of acid-resistant material, and the filter material is made of acid-resistant filter material.
进一步地，步骤3)中一级浓水的金属离子浓度为3～15g/L，电导率27000～100000μs/cm。。Further, the metal ion concentration of the primary concentrated water in step 3) is 3-15 g/L, and the conductivity is 27000-100000 μs/cm. .
进一步地，当步骤1)中酸性废水为盐酸酸性废水时，步骤4)中再生酸为盐酸，浓度为200g/L；当步骤1)中酸性废水为混酸酸性废水时，步骤4)中再生酸为HF和HNO 3的混酸，HF的浓度为5～60g/L，HNO 3的浓度为80～160g/L。 Further, when the acidic wastewater in step 1) is hydrochloric acidic wastewater, the regenerated acid in step 4) is hydrochloric acid, and the concentration is 200g/L; when the acidic wastewater in step 1) is mixed acid acidic wastewater, the regenerated acid in step 4) It is a mixed acid of HF and HNO3 , the concentration of HF is 5-60g/L, and the concentration of HNO3 is 80-160g/L.
进一步地，步骤4)中二级产水的PH值为2～4，总铁含量为15～100mg/L，电导率为100～500μs/cm。Further, the pH value of the secondary product water in step 4) is 2-4, the total iron content is 15-100 mg/L, and the conductivity is 100-500 μs/cm.
进一步地，步骤5)中二级产水与新酸混合后作为补充酸进入酸洗机组具体为：当步骤1)中酸性废水为盐酸酸性废水时，步骤5)中二级产水与18％的盐酸勾兑至盐酸浓度为200g/L后作为补充酸进入酸洗机组；当步骤1)中酸性废水为混酸酸性废水时，步骤5)中二级产水与55％的HF、98％或68％的HNO 3勾兑至混酸中HF浓度为5～60g/L、HNO 3浓度为80～160g/L后作为补充酸进入酸洗机组。 Further, the secondary product water in step 5) is mixed with new acid and enters the pickling unit as supplementary acid, specifically: when the acidic wastewater in step 1) is hydrochloric acid acid wastewater, the secondary product water in step 5) is mixed with 18% The hydrochloric acid is blended until the concentration of hydrochloric acid is 200g/L and enters the pickling unit as supplementary acid; when the acidic wastewater in step 1) is mixed acidic acidic wastewater, the secondary product water in step 5) is mixed with 55% HF, 98% or 68% % HNO 3 is blended until the concentration of HF in the mixed acid is 5-60g/L, and the concentration of HNO 3 is 80-160g/L, and then enters the pickling unit as supplementary acid.
进一步地，步骤5)中二级产水进入碱废水处理***处理的处理过程如下：中间水池二中的二级产水进入碱废水调节池内与碱废水进行中和反应，反应后的废水进入中和、混凝、絮凝槽中进行调整PH值、混凝反应、絮凝反应，中和、混凝、絮凝槽出水进入气浮装置，气浮装置出水依次经过生化装置、沉淀池二、过滤装置后送中水用户使用或深度回用。Further, the treatment process of the secondary produced water entering the alkali wastewater treatment system in step 5) is as follows: the secondary produced water in the intermediate pool 2 enters the alkali wastewater regulating tank for neutralization reaction with the alkaline wastewater, and the reacted wastewater enters the middle Adjust the PH value, coagulation reaction, and flocculation reaction in the mixing, coagulation, and flocculation tanks, and the effluent from the neutralization, coagulation, and flocculation tanks enters the air flotation device, and the effluent from the air flotation device passes through the biochemical device, sedimentation tank 2, and filtration device in turn. Send reclaimed water to users for use or deep reuse.
进一步地，当步骤1)中酸性废水为盐酸酸性废水时，生化装置采用好氧反应池；当步骤1)中酸性废水为混酸酸性废水时，生化装置必须采用缺氧反应池与好氧反应池串联的方式，缺氧反应池利用碱废水中的COD进行反硝化，以去除二级产水中含有15～50mg/L的硝酸根。Further, when the acidic wastewater in step 1) is hydrochloric acidic wastewater, the biochemical device adopts an aerobic reaction tank; when the acidic wastewater in step 1) is mixed acidic wastewater, the biochemical device must use an anoxic reaction tank and an aerobic reaction tank In a series connection, the anoxic reaction pool uses the COD in the alkaline wastewater for denitrification to remove 15-50 mg/L of nitrate in the secondary product water.
更进一步地，二级产水中的铁离子(15～100mg/L)作为混凝反应的混凝剂。Furthermore, iron ions (15-100 mg/L) in the secondary product water are used as coagulant for coagulation reaction.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明先采用沉淀+过滤作为预处理，满足电吸附装置的进水要求；然后采用一级电吸附装置和二级电吸附装置串联作为核心处理单元处理酸性废水，降低酸性废水的盐分、金属离子，提升电吸附装置的产水水质，避免了酸性废水仅采用一级电吸附处理后出水电导率、金属离子过高导致无法回用的问题，也避免了传统酸碱废水混合处理工艺中混合废水高盐、高硬度、高铁离子对生化处理效果的影响以及生化出水的高铁离子无法进一步深度回用处理的问题；其中，一级电吸附装置的浓水作为再生酸吸收液进入酸再生吸收装置，对由酸再生反应炉产生的含酸性成分的高温烟气进行喷淋吸收，形成再生酸后送至酸洗机组循环利用；二级电吸附装置的产水与新酸混合后作为补充酸进入酸洗机组，实现了废水以及废水中酸近100％的回收利用，真正实现了酸性废水零排放，或者二级电吸附装置的产水送碱废水处理***进行酸碱中和反应，能够大幅降低药剂消耗量的同时减少废水中因投加酸碱中和剂引入的盐分；此外，二级电吸附装置的产水含有的铁离子可作为混凝槽的混凝剂使用，大幅降低传统碱废水处理工艺中混凝槽需要投加的混凝剂使用量；(1) The present invention first adopts precipitation + filtration as pretreatment to meet the water intake requirements of the electro-adsorption device; then adopts the first-stage electro-adsorption device and the second-stage electro-adsorption device in series as the core treatment unit to treat acidic wastewater and reduce the salinity of the acidic wastewater , metal ions, improve the water quality of the electro-adsorption device, avoid the problem that the conductivity of the acidic wastewater after only one-stage electro-adsorption treatment, and the high metal ions cannot be reused, and also avoid the traditional mixed treatment process of acid-base wastewater The impact of high salt, high hardness, and high iron ions on the biochemical treatment effect of mixed wastewater and the problem that the high iron ions in the biochemical effluent cannot be further reused for further treatment; among them, the concentrated water of the first-stage electric adsorption device enters the acid regeneration as the regeneration acid absorption liquid Absorption device, which sprays and absorbs the high-temperature flue gas containing acidic components produced by the acid regeneration reactor, forms regenerated acid and sends it to the pickling unit for recycling; the water produced by the secondary electric adsorption device is mixed with fresh acid as a supplement The acid enters the pickling unit, which realizes nearly 100% recycling of waste water and acid in waste water, and truly realizes zero discharge of acid waste water. While greatly reducing the consumption of chemicals, it also reduces the salt introduced by the addition of acid-base neutralizers in wastewater; in addition, the iron ions contained in the produced water of the secondary electrosorption device can be used as a coagulant in the coagulation tank, which greatly reduces the traditional The amount of coagulant that needs to be added to the coagulation tank in the alkali wastewater treatment process;
(2)本发明提供的酸性废水低成本资源化利用工艺与传统酸性废水处理工艺相比，能够大幅降低药剂消耗量(石灰乳、酸碱中和药剂、混凝剂等)和污泥量，显著改善废水中因投加酸碱中和剂引起的盐分增加，最终回用水水质更好，运行成本低，同时可以实现废水以及废水中金属离子、酸近100％的回收利用，完全避免了废水排放对环境的影响，真正实现了酸性废水低成本、资源化利用，是一种经济、环保、绿色、节能、占地面积省、出水水质优且稳定的新工艺路线。(2) Compared with the traditional acid wastewater treatment process, the low-cost resource utilization process of acidic wastewater provided by the present invention can greatly reduce the consumption of chemicals (milk of lime, acid-base neutralizing agents, coagulants, etc.) and the amount of sludge, Significantly improve the salt increase in wastewater caused by the addition of acid-base neutralizers, the final reuse water quality is better, and the operating cost is low. At the same time, it can realize nearly 100% recycling of wastewater and metal ions and acids in wastewater, completely avoiding wastewater The impact of discharge on the environment has truly realized the low cost and resource utilization of acid wastewater. It is a new process route that is economical, environmentally friendly, green, energy-saving, occupies less land, and has high-quality and stable effluent quality.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. Those skilled in the art can also obtain other drawings based on these drawings without creative work.
图1为本发明实施例提供的酸性废水低成本资源化利用工艺的流程图；Fig. 1 is the flowchart of the low-cost resource utilization process of acidic wastewater provided by the embodiment of the present invention;
图中：1、酸洗机组；2、酸再生反应炉；3、酸再生吸收装置；4、酸性废水调节池；5、沉淀池一；6、酸性废水过滤器；7、中间水池一；8、一级电吸附装置；9、二级电吸附装置；10、中间水池二；11、碱废水调节池；12、中和、混凝、絮凝槽；13、气浮装置；14、生化装置；15、沉淀池二；16、过滤装置；17、配酸池。In the figure: 1. Pickling unit; 2. Acid regeneration reaction furnace; 3. Acid regeneration absorption device; 4. Acidic wastewater regulating tank; 5. Settling tank 1; 6. Acidic wastewater filter; 7. Intermediate pool 1; 8 1. Primary electric adsorption device; 9. Secondary electric adsorption device; 10. Two intermediate pools; 11. Alkali wastewater regulating tank; 12. Neutralization, coagulation and flocculation tank; 13. Air flotation device; 14. Biochemical device; 15. Sedimentation tank two; 16. Filtration device; 17. Acid distribution tank.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
如图1所示，本实施例提供一种酸性废水低成本资源化利用工艺，包括如下步骤：As shown in Figure 1, this embodiment provides a low-cost resource utilization process for acidic wastewater, including the following steps:
1)酸洗机组1排放的酸性废水(铁离子浓度为1500-3000mg/L，电导率为4500-15000μs/cm)经管网排入酸性废水调节池4，在酸性废水调节池4内调节水量、水质；酸洗机组1排放的废酸液进入酸再生反应炉2进行高温热水解反应，产生的含酸性成分的高温烟气进入酸再生吸收装置3，并回收金属氧化物；1) The acidic wastewater discharged by the pickling unit 1 (the iron ion concentration is 1500-3000 mg/L, and the conductivity is 4500-15000 μs/cm) is discharged into the acidic wastewater regulating pool 4 through the pipe network, and the water volume is adjusted in the acidic wastewater regulating pool 4. Water quality; the waste acid liquid discharged from the pickling unit 1 enters the acid regeneration reactor 2 for high-temperature thermal hydrolysis reaction, and the generated high-temperature flue gas containing acidic components enters the acid regeneration absorption device 3, and recovers metal oxides;
2)酸性废水调节池4内的酸性废水通过提升泵进入沉淀池一5中，经沉淀 去除悬浮颗粒物后的上清液提升进入酸性废水过滤器6，酸性废水过滤器6过滤后的滤水进入中间水池一7；其中，采用沉淀+过滤器的方式进行预处理，满足电吸附装置的进水要求；酸性废水过滤器6的壳体采用耐酸材质，用于盐酸酸性废水处理时壳体可采用玻璃钢材质或钢衬胶材质，用于混酸酸性废水处理时壳体可采用玻璃钢材质或钢衬胶材质，滤料采用耐酸滤料，用于盐酸酸性废水处理时滤料可采用酸洗石英砂、活性炭滤料、纤维滤料，用于混酸酸性废水处理时滤料可采用活性炭滤料；2) The acidic wastewater in the acidic wastewater regulating tank 4 enters the sedimentation tank 1 through the lifting pump, and the supernatant after the suspended particles are removed by sedimentation is lifted into the acidic wastewater filter 6, and the filtered water filtered by the acidic wastewater filter 6 enters the Intermediate pool 17; among them, precipitation + filter is used for pretreatment to meet the water intake requirements of the electro-adsorption device; the shell of the acid waste water filter 6 is made of acid-resistant material, and the shell can be used for the treatment of hydrochloric acid acid waste water Fiberglass or steel-lined rubber material, the shell can be made of glass fiber reinforced plastic or steel-lined rubber material for mixed acid acid wastewater treatment, the filter material is acid-resistant filter material, and the filter material for hydrochloric acid acid wastewater treatment can be pickled quartz sand, Activated carbon filter material, fiber filter material, activated carbon filter material can be used for mixed acid acid wastewater treatment;
3)中间水池一7内的酸性废水通过提升泵进入一级电吸附装置8进行处理，得到一级浓水和一级产水；一级电吸附装置8吸附去除废水中的Fe 3+、Fe 2+、H +、SiO 3 2-、Cl -等离子，降低一级产水的离子浓度，产生的一级浓水的金属离子浓度为3～15g/L，电导率为27000～100000μs/cm； 3) The acidic wastewater in the middle pool 7 enters the first-stage electro-adsorption device 8 through the lift pump for treatment to obtain the first-class concentrated water and the first-class product water; the first-stage electro-adsorption device 8 adsorbs and removes Fe 3+ and Fe in the wastewater. 2+ , H + , SiO 3 2- , Cl - plasma, reduce the ion concentration of the primary product water, the metal ion concentration of the produced primary concentrated water is 3-15g/L, and the conductivity is 27000-100000μs/cm;
4)一级浓水作为再生酸吸收液进入酸再生吸收装置3，对由酸再生反应炉2进入酸再生吸收装置3的含酸性成分的高温烟气进行喷淋吸收，形成再生酸，再生酸通过泵进入酸洗机组1循环利用，实现了对废水中金属离子、酸近100％资源化利用；4) The primary concentrated water enters the acid regeneration absorption device 3 as the regeneration acid absorption liquid, and sprays and absorbs the high-temperature flue gas containing acid components that enters the acid regeneration absorption device 3 from the acid regeneration reaction furnace 2 to form regeneration acid. The pump enters the pickling unit 1 for recycling, realizing nearly 100% resource utilization of metal ions and acids in wastewater;
当步骤1)中酸性废水为盐酸酸性废水时，再生酸为盐酸，浓度为200g/L；当步骤1)中酸性废水为混酸酸性废水时，再生酸为HF和HNO 3的混酸，HF的浓度为5～60g/L，HNO 3的浓度为80～160g/L； When step 1) middle acid waste water is hydrochloric acid waste water, regeneration acid is hydrochloric acid, and concentration is 200g/L; When step 1) middle acid waste water is mixed acid acid waste water, regeneration acid is HF and HNO Mixed acid, the concentration of HF 5~60g/L, the concentration of HNO 3 is 80~160g/L;
一级产水通过提升泵进入二级电吸附装置9进行处理，得到二级浓水和二级产水；二级电吸附装置9进一步吸附去除废水中的Fe 3+、Fe 2+、H +、SiO 3 2-、Cl -等离子，进一步降低产水的离子浓度；二级产水的水PH值为2～4，总铁含量为15～100mg/L，电导率为100～500μs/cm； The primary product water enters the secondary electro-adsorption device 9 through the lift pump for treatment to obtain secondary concentrated water and secondary product water; the secondary electro-adsorption device 9 further adsorbs and removes Fe 3+ , Fe 2+ , and H + in the wastewater , SiO 3 2- , Cl - plasma to further reduce the ion concentration of the product water; the pH value of the secondary product water is 2~4, the total iron content is 15~100mg/L, and the conductivity is 100~500μs/cm;
5)二级浓水利用余压进入中间水池一7，之后再次进入一级电吸附装置8 循环处理，提高电吸附装置整体回收率；5) The secondary concentrated water enters the intermediate pool 17 using the residual pressure, and then enters the primary electrosorption device 8 for recycling treatment to improve the overall recovery rate of the electrosorption device;
二级产水自流进入中间水池二10，中间水池二10中的二级产水进入碱废水处理***处理后回用，和/或二级产水与新酸混合后作为补充酸进入酸洗机组1；The secondary produced water flows into the intermediate pool 2 10 by itself, and the secondary produced water in the intermediate pool 2 10 enters the alkali wastewater treatment system for treatment and reuse, and/or the secondary produced water is mixed with new acid and enters the pickling unit as supplementary acid 1;
二级产水进入碱废水处理***处理后回用具体为：中间水池二10中的二级产水(酸性，PH值2～4)通过提升泵进入废水站的碱废水调节池11，在碱废水调节池11内二级产水与碱废水进行酸碱中和反应，减少碱性废水酸中和剂投加量和二级电吸附装置9酸性产水碱中和剂投加量，大幅降低药剂消耗量的同时减少废水中因投加酸碱中和剂引入的盐分；中和反应后的废水通过提升泵进入中和、混凝、絮凝槽12中，在中和单元内进一步调整PH值，在混凝槽内进行混凝反应，在絮凝槽内投加PAM进行絮凝反应，中和、混凝、絮凝槽12出水自流进入气浮装置13，气浮装置13出水依次经过生化装置14、沉淀池二15、过滤装置16后送中水用户使用或采用双膜法等工艺深度回用，实现了废水的资源化利用；其中，二级产水中总铁含量约15～100mg/L，该铁离子可作为混凝槽的混凝剂使用，大幅降低传统碱废水处理工艺中混凝槽需要投加的混凝剂使用量；此外，需要特别说明的是，当步骤1)中酸性废水为盐酸酸性废水时，生化装置14采用好氧反应池；当步骤1)中酸性废水为混酸酸性废水时，生化装置14必须采用缺氧反应池与好氧反应池串联的方式，缺氧反应池利用碱废水中的COD进行反硝化，以去除二级产水中含有15～50mg/L的硝酸根，实现低成本去除硝酸根污染物的目的。The reuse of the secondary produced water after entering the alkali wastewater treatment system is specifically: the secondary produced water (acidic, pH value 2-4) in the middle pool 2 10 enters the alkali wastewater regulating tank 11 of the waste water station through the lift pump, The acid-base neutralization reaction between the secondary produced water and the alkaline wastewater in the wastewater regulating tank 11 reduces the dosage of the acid neutralizer for the alkaline wastewater and the dosage of the alkaline neutralizer for the acidic wastewater in the secondary electrosorption device 9, greatly reducing While reducing the consumption of chemicals, the salt introduced by the addition of acid-base neutralizers in the wastewater is reduced; the wastewater after the neutralization reaction enters the neutralization, coagulation, and flocculation tank 12 through the lift pump, and the pH value is further adjusted in the neutralization unit , carry out the coagulation reaction in the coagulation tank, add PAM in the coagulation tank to carry out the flocculation reaction, neutralize, coagulate, and the water from the flocculation tank 12 flows into the air flotation device 13 by itself, and the water from the air flotation device 13 passes through the biochemical device 14, Sedimentation tank 2 15 and filter device 16 are sent to reclaimed water users for use or deep reuse by double-membrane method and other processes, realizing the resource utilization of waste water; among them, the total iron content in the secondary product water is about 15-100 mg/L, which is Iron ions can be used as a coagulant in the coagulation tank, which greatly reduces the amount of coagulant that needs to be added to the coagulation tank in the traditional alkaline wastewater treatment process; in addition, it needs to be specially noted that when the acidic wastewater in step 1) is During hydrochloric acid acid wastewater, the biochemical device 14 adopts an aerobic reaction pool; when the acidic waste water in step 1) is mixed acidic acid waste water, the biochemical device 14 must adopt an anoxic reaction pool and an aerobic reaction pool in series, and the anoxic reaction pool utilizes The COD in the alkaline wastewater is denitrified to remove 15-50mg/L nitrate in the secondary product water, so as to achieve the purpose of low-cost removal of nitrate pollutants.
二级产水与新酸混合后作为补充酸进入酸洗机组1具体为：当步骤1)中酸性废水为盐酸酸性废水时，步骤5)中二级产水与18％的盐酸在配酸池17中勾兑至盐酸浓度为200g/L后作为正常的补充酸进入酸洗机组1；当步骤1)中酸性废水为混酸酸性废水时，步骤5)中二级产水与55％的HF、98％或68％的HNO 3 在配酸池17中勾兑至混酸中HF浓度为5～60g/L、HNO 3浓度为80～160g/L后作为正常的补充酸进入酸洗机组1。 After the secondary product water is mixed with the new acid, it enters the pickling unit 1 as supplementary acid, specifically: when the acidic wastewater in step 1) is hydrochloric acid acid wastewater, the secondary product water and 18% hydrochloric acid in step 5) are in the acid mixing pool After blending in 17 until the concentration of hydrochloric acid is 200g/L, enter the pickling unit 1 as normal supplementary acid; when the acidic wastewater in step 1) is mixed acidic acidic wastewater, the secondary product water in step 5) is mixed with 55% HF, 98 % or 68% HNO3 is blended in the acid mixing tank 17 until the concentration of HF in the mixed acid is 5-60g/L, and the concentration of HNO3 is 80-160g/L, and then enters the pickling unit 1 as normal supplementary acid.
尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特诊进行等同替换，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。Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical special diagnoses. Within the spirit and principles of the present invention, any modifications, equivalent replacements, improvements, etc., shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种酸性废水低成本资源化利用工艺，其特征在于，包括如下步骤：A low-cost resource utilization process for acidic wastewater, characterized in that it comprises the following steps:
    1)酸洗机组排放的酸性废水进入酸性废水调节池内调节水量、水质；酸洗机组排放的废酸液进入酸再生反应炉进行高温热水解反应，产生的含酸性成分的高温烟气进入酸再生吸收装置；1) The acidic wastewater discharged from the pickling unit enters the acid wastewater regulating tank to adjust the water volume and water quality; the waste acid solution discharged from the pickling unit enters the acid regeneration reactor for high-temperature thermal hydrolysis reaction, and the generated high-temperature flue gas containing acidic components enters the acid regenerative absorber;
    2)酸性废水调节池内的酸性废水经预处理后进入中间水池一；2) The acidic wastewater in the acidic wastewater regulating tank enters the intermediate pool 1 after being pretreated;
    3)中间水池一内的酸性废水进入一级电吸附装置进行处理，得到一级浓水和一级产水；3) The acidic wastewater in the middle pool 1 enters the first-level electro-adsorption device for treatment to obtain the first-level concentrated water and the first-level produced water;
    4)一级浓水作为再生酸吸收液进入酸再生吸收装置，对含酸性成分的高温烟气进行喷淋吸收，形成再生酸，再生酸进入酸洗机组循环利用；一级产水进入二级电吸附装置进行处理，得到二级浓水和二级产水；4) The primary concentrated water enters the acid regeneration absorption device as the regeneration acid absorption liquid, and sprays and absorbs the high-temperature flue gas containing acidic components to form regeneration acid, which enters the pickling unit for recycling; the primary water enters the secondary The electric adsorption device is used for treatment to obtain secondary concentrated water and secondary product water;
    5)二级浓水利用余压进入中间水池一，二级产水自流进入中间水池二；中间水池二中的二级产水进入碱废水处理***处理后回用，和/或二级产水与新酸混合后作为补充酸进入酸洗机组。5) The secondary concentrated water enters the intermediate pool 1 using residual pressure, and the secondary produced water enters the intermediate pool 2 by gravity; the secondary produced water in the intermediate pool 2 enters the alkali wastewater treatment system for treatment and reuse, and/or the secondary produced water After being mixed with new acid, it enters the pickling unit as supplementary acid.
  2. 如权利要求1所述的一种酸性废水低成本资源化利用工艺，其特征在于：步骤2)中的预处理过程如下：酸性废水调节池内的酸性废水进入沉淀池一中，经沉淀去除悬浮颗粒物后的上清液进入酸性废水过滤器，酸性废水过滤器过滤后的滤水进入中间水池一。A low-cost resource utilization process for acidic wastewater as claimed in claim 1, characterized in that: the pretreatment process in step 2) is as follows: the acidic wastewater in the acidic wastewater regulating tank enters the first sedimentation tank, and the suspended particles are removed by sedimentation The final supernatant enters the acid waste water filter, and the filtered water after the acid waste water filter enters the intermediate pool one.
  3. 如权利要求2所述的一种酸性废水低成本资源化利用工艺，其特征在于：所述酸性废水过滤器的壳体采用耐酸材质，滤料采用耐酸材质滤料。A low-cost resource utilization process for acidic wastewater as claimed in claim 2, characterized in that: the housing of the acidic wastewater filter is made of acid-resistant material, and the filter material is made of acid-resistant material.
  4. 如权利要求1所述的一种酸性废水低成本资源化利用工艺，其特征在于：步骤3)中，一级浓水的金属离子浓度为3～15g/L，电导率为27000～100000μs/cm。A low-cost resource utilization process for acidic wastewater as claimed in claim 1, characterized in that: in step 3), the metal ion concentration of the primary concentrated water is 3-15g/L, and the conductivity is 27000-100000μs/cm .
  5. 如权利要求1所述的一种酸性废水低成本资源化利用工艺，其特征在于：当步骤1)中酸性废水为盐酸酸性废水时，步骤4)中再生酸为盐酸，浓度为200g/L； 当步骤1)中酸性废水为混酸酸性废水时，步骤4)中再生酸为HF和HNO 3的混酸，HF的浓度为5～60g/L，HNO 3的浓度为80～160g/L。 A low-cost resource utilization process for acidic wastewater as claimed in claim 1, characterized in that: when the acidic wastewater in step 1) is hydrochloric acid acidic wastewater, the regenerated acid in step 4) is hydrochloric acid, and the concentration is 200g/L; When the acidic wastewater in step 1) is mixed acidic wastewater, the regenerated acid in step 4) is a mixed acid of HF and HNO3 , the concentration of HF is 5-60g/L, and the concentration of HNO3 is 80-160g/L.
  6. 如权利要求1所述的一种酸性废水低成本资源化利用工艺，其特征在于：步骤4)中二级产水的PH值为2～4，总铁含量为15～100mg/L，电导率为100～500μs/cm。A low-cost resource utilization process for acidic wastewater as claimed in claim 1, characterized in that: the pH value of the secondary product water in step 4) is 2 to 4, the total iron content is 15 to 100 mg/L, and the electrical conductivity 100-500 μs/cm.
  7. 如权利要求1所述的一种酸性废水低成本资源化利用工艺，其特征在于：步骤5)中二级产水与新酸混合后作为补充酸进入酸洗机组具体为：当步骤1)中酸性废水为盐酸酸性废水时，步骤5)中二级产水与18％的盐酸勾兑至盐酸浓度为200g/L后作为补充酸进入酸洗机组；当步骤1)中酸性废水为混酸酸性废水时，步骤5)中二级产水与55％的HF、98％或68％的HNO 3勾兑至混酸中HF浓度为5～60g/L、HNO 3浓度为80～160g/L后作为补充酸进入酸洗机组。 A low-cost resource utilization process for acidic wastewater as claimed in claim 1, characterized in that: in step 5), the secondary produced water is mixed with new acid and then enters the pickling unit as supplementary acid, specifically: when in step 1), When the acidic wastewater is hydrochloric acidic wastewater, the secondary product water in step 5) is blended with 18% hydrochloric acid until the concentration of hydrochloric acid is 200g/L and enters the pickling unit as supplementary acid; when the acidic wastewater in step 1) is mixed acidic wastewater , Step 5) The secondary product water is blended with 55% HF, 98% or 68% HNO3 until the concentration of HF in the mixed acid is 5-60g/L, and the concentration of HNO3 is 80-160g/L, and then enters as supplementary acid Pickling unit.
  8. 如权利要求1所述的一种酸性废水低成本资源化利用工艺，其特征在于：步骤5)中二级产水进入碱废水处理***处理的处理过程如下：中间水池二中的二级产水进入碱废水调节池内与碱废水进行中和反应，反应后的废水进入中和、混凝、絮凝槽中进行调整PH值、混凝反应、絮凝反应，中和、混凝、絮凝槽出水进入气浮装置，气浮装置出水依次经过生化装置、沉淀池二、过滤装置后送中水用户使用或深度回用。A low-cost resource utilization process for acidic wastewater as claimed in claim 1, characterized in that: in step 5), the secondary produced water enters the alkali wastewater treatment system for treatment as follows: the secondary produced water in the middle pool two Enter the alkali wastewater adjustment tank for neutralization reaction with alkali wastewater, and the reacted wastewater enters the neutralization, coagulation, and flocculation tank to adjust the pH value, coagulation reaction, and flocculation reaction. The flotation device, the water from the air flotation device passes through the biochemical device, the second sedimentation tank, and the filter device in turn, and then is sent to the reclaimed water user for use or deep reuse.
  9. 如权利要求8所述的一种酸性废水低成本资源化利用工艺，其特征在于：当步骤1)中酸性废水为盐酸酸性废水时，生化装置采用好氧反应池；当步骤1)中酸性废水为混酸酸性废水时，生化装置必须采用缺氧反应池与好氧反应池串联的方式，缺氧反应池利用碱废水中的COD进行反硝化，以去除二级产水中含有15～50mg/L的硝酸根。A low-cost resource utilization process for acidic wastewater as claimed in claim 8, characterized in that: when the acidic wastewater in step 1) is hydrochloric acid acidic wastewater, the biochemical device adopts an aerobic reaction pool; when the acidic wastewater in step 1) When it is mixed acidic wastewater, the biochemical device must adopt the method of connecting the anoxic reaction pool and the aerobic reaction pool in series. The anoxic reaction pool uses the COD in the alkaline wastewater for denitrification to remove 15-50 mg/L in the secondary product water. Nitrate.
  10. 如权利要求8所述的一种酸性废水低成本资源化利用工艺，其特征在于：二 级产水中的铁离子作为碱性废水处理***混凝反应的混凝剂。A kind of low-cost resource utilization process of acidic waste water as claimed in claim 8, is characterized in that: the iron ion in the secondary product water is used as the coagulant for the coagulation reaction of the alkaline waste water treatment system.
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