CN105948325A - Method for degrading lead zinc smelting contaminated acid COD (chemical oxygen demand) - Google Patents

Method for degrading lead zinc smelting contaminated acid COD (chemical oxygen demand) Download PDF

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Publication number
CN105948325A
CN105948325A CN201610468024.9A CN201610468024A CN105948325A CN 105948325 A CN105948325 A CN 105948325A CN 201610468024 A CN201610468024 A CN 201610468024A CN 105948325 A CN105948325 A CN 105948325A
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CN
China
Prior art keywords
cod
degrading
filtrate
zinc smelting
section
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610468024.9A
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Chinese (zh)
Inventor
马菲菲
段宏志
杨斌
张昱琛
李德磊
崔耀
王永红
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Baiyin Nonferrous Group Co Ltd
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Baiyin Nonferrous Group Co Ltd
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Priority to CN201610468024.9A priority Critical patent/CN105948325A/en
Publication of CN105948325A publication Critical patent/CN105948325A/en
Pending legal-status Critical Current

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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
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention aims to provides a method for degrading lead zinc smelting contaminated acid COD (chemical oxygen demand), which can ensure the discharged water COD to be less than or equal to 60 mg/L and achieve the goals of lowering the cost and reducing the oxidizer consumption. In the method, the primary lime milk neutralization and secondary mixed oxidizer oxidization are combined to degrade the COD; by using lime milk to separate out part of SO3<2-> reducible ions, the degradation rate is 20% or so, thereby lowering the oxidizer consumption and lowering the cost; and by using the NaClO-K2FeO4 combined mixed oxidizer to degrade the COD, the degradation rate is 80-88%. Therefore, the method has the advantages of high degradation rate and low cost.

Description

A kind of method of lead-zinc smelting waste acid COD of degrading
Technical field
The present invention relates to lead-zinc smelting technical field, a kind of method being specifically related to lead-zinc smelting waste acid COD of degrading.
Background technology
Acid water derives from sulphuric acid dynamic wave scrubbing in Lead-Zinc Sintering Process, has high Hg, high F, high COD(chemistry need Oxygen amount) feature, COD mainly with mineral form exist, including SO3 2-、S2-Etc. reproducibility ion, concentration is typically at 200- 600mg/l。
At present, in lead-zinc smelting waste acid, the degraded of COD mainly uses single oxidizing process, such as Fenton process, inorganic oxidizer oxygen Change methods etc., exist that reagent consumption is big, cost is high, and the quantity of slag is big, and to shortcomings such as COD degradation effect are the most notable.
Summary of the invention
It is an object of the invention to provide one and guarantee outer draining COD≤60mg/l, reduce cost simultaneously, reduce oxidation The method of degraded lead-zinc smelting waste acid COD of the usage amount of agent.
The present invention adopts the following technical scheme that a kind of method of lead-zinc smelting waste acid COD of degrading, and uses in one section of lime cream With, two-stage mixing oxidizing two-section joint degraded COD.
Further, it is to be added by lime cream in the waste acid filtrate having removed hydrargyrum and arsenic that described one section of lime cream neutralizes, and controls PH is 8-9, reacts 30-40min, sediment fraction SO3 2-Reproducibility ion, after solid-liquor separation, filtering residue is gypsum tailings, stores up danger Waste residue storehouse, filtrate carries out two-stage nitration degraded COD.
Further, described two-stage mixing is oxidizing is by electronic belt scale, is that 2-4:1 connects according to mass ratio Addition NaClO and K in one section of degraded COD filtrate continuous, uniform2FeO4, react 40-50min, solid-liquor separation, obtain COD≤ 60mg/l filtrate, filtering residue stores up danger waste residue storehouse.
The invention have the benefit that
(1) lime cream sediment fraction SO is used3 2-Reproducibility ion, degradation rate about 20%, reduce the consumption of oxidant, fall Low cost.
(2) NaClO degradation rate only has 70-75%, but cost is relatively low；K2FeO4Degradation rate can reach 90-92%, and degradation rate is relatively Height, generates Fe (OH)3Colloid has good flocculating effect, but relatively costly, uses NaClO and K2FeO4According to mass ratio it is The hybrid oxidant combined degradation COD of 2-4:1, degradation rate is 80-88%, has degradation rate high, the advantage of low cost.
(3) NaClO and K2FeO4Cl Yu Fe mono-step is reverted to-1 valency and+trivalent by two kinds of oxidants, without middle valence state, and will not Introduce new COD composition.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further details.
Embodiment 1
Step one: will be 30m except the volume of complete hydrargyrum and arsenic3, COD content be that 200mg/l waste acid filtrate pumps into reactive tank, pass through stone Ash breast regulation PH is 8, reacts 30min, sediment fraction SO3 2-Etc. reproducibility ion.After solid-liquor separation, filtering residue is gypsum tailings, heap Depositing danger waste residue storehouse, liquor C OD is 160mg/l, carries out two-stage nitration degraded COD.
Step 2: by electronic belt scale, be 2:1 according to mass ratio, adds continuously, uniformly in one section of degraded COD filtrate Enter NaClO and K2FeO4, NaClO adds 17.44kg, K2FeO4Add 8.72kg, react 40min.Solid-liquor separation, obtaining COD is 42mg/l filtrate, filtering residue stores up danger waste residue storehouse.
Embodiment 2
Step one: will be 30m except the volume of complete hydrargyrum and arsenic3, COD concentration be that 400mg/l waste acid filtrate pumps into reactive tank, pass through stone Ash breast regulation PH is 8.5, reacts 35min, sediment fraction SO3 2-Reproducibility ion.After solid-liquor separation, filtering residue is gypsum tailings, heap Depositing danger waste residue storehouse, liquor C OD is 320mg/l, carries out two-stage nitration degraded COD.
Step 2: by electronic belt scale, be 3:1 according to mass ratio, adds continuously, uniformly in one section of degraded COD filtrate Enter NaClO and K2FeO4, NaClO adds 37.62kg, K2FeO4Add 12.54kg, react 45min.Solid-liquor separation, obtains COD For 51mg/l filtrate, filtering residue stores up danger waste residue storehouse.
Embodiment 3
Step one: will be 30m except the volume of complete hydrargyrum and arsenic3, COD concentration be that 600mg/l waste acid filtrate pumps into reactive tank, pass through stone Ash breast regulation PH is 9, reacts 40min, sediment fraction SO3 2-Reproducibility ion.After solid-liquor separation, filtering residue is gypsum tailings, stores up Danger waste residue storehouse, liquor C OD is 480mg/l, carries out two-stage nitration degraded COD.
Step 2: by electronic belt scale, be 4:1 according to mass ratio, adds continuously, uniformly in one section of degraded COD filtrate Enter NaClO and K2FeO4, NaClO adds 58.76kg, K2FeO4Add 14.69kg, react 50min.Solid-liquor separation, obtains COD For 56mg/l filtrate, filtering residue stores up danger waste residue storehouse.
Using effect
Since on April 1st, 2015 uses this new technique, acid water COD realizes stably reaching standard, and testing result see table.
1, one section uses lime cream degraded COD, creation data such as table 1.
The degraded COD data statistics of 1 one sections of table
2, two-stage nitration uses NaClO and K2FeO4According to the hybrid oxidant degraded COD that mass ratio is 2-4:1, creation data such as table 2.
The degraded COD data statistics of table 2 two-stage nitration
3, cost compares
Waste acid is according to 200m3/ d, COD concentration 450mg/l, the K of 95%2FeO4Price 40,000 yuan/t, 95%NaClO price 0.9 ten thousand yuan/ T calculates
(1) if all using K2FeO4Degraded COD, consumes K2FeO4750kg/d, then totle drilling cost is 30,000 yuan/d；
(2) neutralize and hybrid oxidant oxidation two-section joint degraded COD, NaClO and K according to lime cream2FeO4Mass ratio is pressed Count according to 3:1, consume K2FeO4: 95kg/d, NaClO:280 kg/d, then totle drilling cost is 0.64 ten thousand yuan.
To sum up, cost reduces by 2.36 ten thousand yuan/d, annual reduction cost 7,800,000 yuan.

Claims (3)

1. the method for lead-zinc smelting waste acid COD of degrading, it is characterised in that: use one section of lime cream neutralization, two-stage mixing oxygen Agent oxidation two-section joint degraded COD.
The method of a kind of lead-zinc smelting waste acid COD of degrading the most according to claim 1, it is characterised in that: described one section of stone Ash Ruzhong and be to add lime cream remove in the waste acid filtrate of hydrargyrum and arsenic, control PH is 8-9, reaction 30-40min, precipitation portion Divide SO3 2-Reproducibility ion, after solid-liquor separation, filtering residue is gypsum tailings, stores up danger waste residue storehouse, and filtrate carries out two-stage nitration degraded COD.
The method of a kind of lead-zinc smelting waste acid COD of degrading the most according to claim 1, it is characterised in that: described two-stage nitration mixes Closing oxidizing is by electronic belt scale, is that 2-4:1 adds continuously, uniformly in one section of degraded COD filtrate according to mass ratio Enter NaClO and K2FeO4, reacting 40-50min, solid-liquor separation, obtain COD≤60mg/l filtrate, filtering residue stores up danger waste residue storehouse.
CN201610468024.9A 2016-06-24 2016-06-24 Method for degrading lead zinc smelting contaminated acid COD (chemical oxygen demand) Pending CN105948325A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610468024.9A CN105948325A (en) 2016-06-24 2016-06-24 Method for degrading lead zinc smelting contaminated acid COD (chemical oxygen demand)

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CN201610468024.9A CN105948325A (en) 2016-06-24 2016-06-24 Method for degrading lead zinc smelting contaminated acid COD (chemical oxygen demand)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58196888A (en) * 1982-05-12 1983-11-16 Mitsubishi Heavy Ind Ltd Treatment of waste water
CN101628764A (en) * 2009-07-30 2010-01-20 浙江华友钴业股份有限公司 Processing method of industrial waste water generated in hydrometallurgical process of nickel, cobalt and copper
CN101830583A (en) * 2010-03-25 2010-09-15 云南铜业股份有限公司 Method for treating waste acid by gypsum sedimentation, arsenic oxidizing sedimentation and iron salt neutralization and co-precipitation
CN102603097A (en) * 2012-03-23 2012-07-25 郑州鸿跃环保科技有限公司 Advanced treatment and recycling process for wastewater containing heavy metal ions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58196888A (en) * 1982-05-12 1983-11-16 Mitsubishi Heavy Ind Ltd Treatment of waste water
CN101628764A (en) * 2009-07-30 2010-01-20 浙江华友钴业股份有限公司 Processing method of industrial waste water generated in hydrometallurgical process of nickel, cobalt and copper
CN101830583A (en) * 2010-03-25 2010-09-15 云南铜业股份有限公司 Method for treating waste acid by gypsum sedimentation, arsenic oxidizing sedimentation and iron salt neutralization and co-precipitation
CN102603097A (en) * 2012-03-23 2012-07-25 郑州鸿跃环保科技有限公司 Advanced treatment and recycling process for wastewater containing heavy metal ions

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
乌锡康等: "《有机水污水治理技术》", 30 April 1989, 华东化工学院出版社 *
蒋剑虹等: "锌冶炼厂重金属废水处理试验研究", 《工业水处理》 *
陆晓华等: "《环境污染控制原理》", 28 February 2010, 武汉：华中科技大学出版社 *

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Application publication date: 20160921