CN1648066A - Method and device for treating multiple form heavy metal waste water by multiphase transfer method - Google Patents
Method and device for treating multiple form heavy metal waste water by multiphase transfer method Download PDFInfo
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- CN1648066A CN1648066A CN 200410073499 CN200410073499A CN1648066A CN 1648066 A CN1648066 A CN 1648066A CN 200410073499 CN200410073499 CN 200410073499 CN 200410073499 A CN200410073499 A CN 200410073499A CN 1648066 A CN1648066 A CN 1648066A
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Abstract
The present invention discloses multiphase transfer method for treating waste water with heavy metals in several forms. Multiphase transfer method including replacement, conversion, etc. is adopted to treat waste water with free mercury and compounds of Hg, Pb, Cr, Mn, Zn, Cd, As, Cu, etc. through flocculation, adsorption, etc. The treated water may be reused for closed loop circulation to eliminate water pollution and save water resource. The said water treating technological process may be used in the comprehensive treatment engineering of waste water with complicated heavy metal form. The present invention also discloses the apparatus for the said process.
Description
Technical Field
The invention relates to a wastewater treatment method, in particular to a method for treating heavy metal wastewater in various forms by a multiphase transfer method. The invention also relates to a device for implementing the method.
Background
Preliminary investigation shows that 3 hundred million people in China drink unsafe water, and 1.9 million people in China drink excessive harmful substance. With the concern of the country on the environmental protection work, water purification and wastewater recycling are more and more paid attention. In the process of comprehensive treatment of wastewater, organic wastewater and heavy metal wastewater with different forms exist. Enterprises such as non-ferrous smelting, chemical production and the like generate a large amount of composite wastewater in the production process. In these waste waters, a large amount of metal ions and non-metal ions are present. As raw materials containing mercury, zinc, manganese, starch and the like are used in the production process of the Guangzhou battery factory in the largest battery factory in China, the wastewater discharged in the production processes of electro-hydraulic proportioning, gelatinization, carbon rod head washing and the like contains 0.79mg/Lof mercury, 315mg/L of zinc and 73mg/L of manganese, and the environment is seriously polluted. As the wastewater contains various heavy metal pollutants, domestic equipment and facilities capable of treating all pollutants to reach the standard at the same time are not available. Therefore, the treatment of the production wastewater of domestic battery factories is still a difficult problem.
When the waste battery is treated, the first pollutants in the generated wastewater comprise mercury, cadmium, lead, arsenic, chromium and the like, and the second pollutants comprise copper, zinc, manganese and the like. Wherein the mercury is mainly Hg0，HgCl2，HgCl4As (III) As (V), Cr (III) Cr (VI), and Cu (II) and Cu (I); zinc has ZnCl2、ZnCl3 -、ZnCl4 2-、Zn(NH3)2、Zn(NH3)4 2-And Ni (II) and Li in the wastewater+、Na+，K+，NH4 +，Cl-And the like are typical polymorphous and polyvalent mixed polluted wastewater.
At present, the neutralization precipitation method and the sulfuration method are mostly used for treating heavy metal wastewater in the industry. The neutralization precipitation method is to add alkali into the waste water containing heavy metal to carry out neutralization reaction so as to lead the heavy metal to generate a water-insoluble hydroxide precipitate form for separation. This method requires attention to the following three problems in the actual wastewater treatment: (1) after the heavy metal wastewater is subjected to neutralization and precipitation treatment, the pH value of the wastewater is higher, and the wastewater can be discharged only after being treated; (2) in the actual wastewater, heavy metal ions can hardly exist alone, a plurality of heavy metal ions coexist frequently, when the wastewater contains amphoteric metals such as zinc, lead, chromium, tin, aluminum and the like, the wastewater has a redissolution tendency at a high pH value, and the pH value must be strictly controlled during treatment operation to implement a staged precipitation method; (3) halogen, cyanide, humic acid, humus and the like coexisting in the solution can form a complex with heavy metal ions, a neutralization method has great influence, sometimes even no precipitate is formed, and pretreatment is carried out before neutralization. The sulfide method is used for treating heavy metal wastewater, and sulfide precipitates are generally fine and are easy to form colloid; the precipitating agent is partially remained in water during the generation of sulfide precipitation, the residual precipitating agent is also a pollutant, and can generate odor and the like, and S2-Harmful gas H produced in acid environment2S, secondary pollution is formed. The excessive sulfide in the wastewater is easy to form soluble mercury-sulfur complex (HgS)2-) So that the sulfur mercury compound is precipitated and redissolved, and is easy to generate H for acid wastewater2S, secondary pollution; the residual sulfur in the treated effluent can also cause pollution.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a method for treating heavy metal wastewater in various forms by using a multiphase transfer method. The waste water treated by the method has coexistence of various forms and various heavy metals and has serious pollution to the environment, and can completely reach the recycling and discharge standards. The invention also provides a device for realizing the method.
In order to solve the technical problem of the method, the invention is realized as follows: it comprises the following steps:
(1) allowing the wastewater containing heavy metals in various forms to flow through a flocculation tank, depositing a large amount of organic matters by using a flocculating agent, and transferring the organic matters to solid waste for treatment;
(2) and the residual waste water flows through a device provided with a metal displacement column to ensure that Hg is contained0、Hg2+Organic mercury combines with metal to form amalgam, which is fixed on the surface of metal displacement column to convert Cr (VI), As (V) into low-price Cr (III), As (III);
(3) making the treated waste water flow through a device provided with a conversion column, and converting heavy metals in the waste water into more insoluble sulfides by utilizing a solubility deposition conversion principle;
(4) the treated wastewater flows through a device provided with a filter column, and sediments in the wastewater are filtered, so that the wastewater can be recycled;
(5) and the treated wastewater flows through a device provided with an adsorption column, so that the concentration of various heavy metals in the wastewater is reduced again, and the wastewater can be directly discharged.
The flocculating agent is polymeric ferric sulfate.
The metal replacement column adopts metal aluminum as a processing column.
The conversion column adopts FeS or FeS2Used as a processing column.
The adsorption column adopts fine sand and activated carbon as a treatment column.
The pH value range of the treated wastewater is as follows: the pH value is 1-13.
In order to solve the technical problem of the device, the invention is realized as follows: it includes flocculation basin (16), water pump (6), water treatment exchange device, characterized by: the water treatment exchange device comprises a displacement column (1), a conversion column (2), a filter column (3) and an adsorption column (4); the displacement column (1), the conversion column (2), the filter column (3) and the adsorption column (4) are connected in sequence through a pipeline (11).
And a replacement column valve, a conversion column valve, a filter column valve and an adsorption column valve are arranged on a pipeline (11) among the replacement column (1), the conversion column (2), the filter column (3) and the adsorption column (4).
The displacement column (1), the conversion column (2), the filter column (3) and the adsorption column (4) are respectively provided with a feed inlet (9), and a lower isolation net (7), a middle isolation net (8) and an upper isolation net (10) are respectively arranged in the feed inlets.
The invention has the beneficial effects that:
1. the composite and multi-body heavy metal wastewater can be treated simultaneously by a plurality of phase transfer methods such as replacement, conversion and the like, and the effect of the multi-stage treatment column for mixed heavy metal ions is more obvious than that of single ions due to the coprecipitation effect of a plurality of metal sulfides.
2. The displacement column (reduction column) not only effectively removes the free mercury which is difficult to be treated, but also reduces the heavy metal with high valence state to lower valence state, so that the heavy metal with coexisting multiple bodies is effectively treated.
3. Due to S2-、Fe3+、Fe2+The buffering effect and the acidity of the waste water have no great influence on the removal effect, and the pH value of the effluent tends to be neutral, so that the process adjustment in the waste water treatment can be positively facilitated due to the fluctuation of the components of the waste batteries.
4. The waste water produced in the comprehensive treatment process of the waste batteries can completely reach the national discharge standard by the process technology, and even individual indexes can reach the indexes of drinking water.
5. Because the waste water generated in the waste battery full-wet treatment process is large in quantity, the recycling of the waste water is considered in the whole process, so that an adsorption column (tower) can be omitted, and the treatment cost is reduced.
6. The above process should be properly adjusted according to the amount and concentration of the wastewater. Wherein the flow rate of the wastewater is 120-200L/cm2.min。
7. The obvious effect of the above wastewater treatment process is the comprehensive effect of flocculation, neutralization, conversion, reduction, adsorption and coprecipitation.
Drawings
FIG. 1 is a block diagram of an apparatus for carrying out the present invention.
Detailed Description
The method for treating heavy metal wastewater with various forms by using the multiphase transfer method is further described below.
The method for treating the heavy metal wastewater in various forms by using the multiphase transfer method comprises the following steps:
(1) in the process of comprehensive treatment of waste water, aiming at a large amount of waste water generated by a battery plant and a waste battery treatment plant, because the waste batteries contain a large amount of organic matters besides a large amount of metal and nonmetal ions, a large flocculation tank is selected in the first step of the process, and polyferric sulfate is used as a flocculating agent. A large amount of organic matter is deposited and transferred to solid waste treatment.
(2) Hg is treated by conversion method because Hg, Cr and As in waste water have various forms0The conversion treatment cannot be carried out, and generally, the oxidation is carried out to divalent state before the conversion. The wastewater with complex components and various valence states can cause some disadvantages if the wastewater is oxidized first. Because Hg is easy to combine with metal to form amalgam, and the mercury (0) in waste water is fixed on the surface of metal by using this characteristic, a displacement column is added, and aluminium powder is used as treatment column, no matter the form of mercury in waste water is Hg0，Hg2+Or organic mercury (such as methyl mercury) can be removed by the displacement column.
In this displacement column there is a portion of Hg2+Is reduced and converted into Hg by aluminum powder0And then further amalgam is formed for separation. When the aluminum powder is contacted with mercury ions, mercury is separated to form aluminum amalgam with aluminum and attached to the surface of the aluminum powder, and when the metal aluminum loses activity, the whole metal filler can be heated under high-degree vacuum, and can be regenerated, and the mercury is also recovered. The filler filtering method has better effect than adding aluminum powder, and the treatment method can ensure that various mercury-containing wastewater can reach the discharge standard.
(3) According to the principle of solubility product, becauseHg. The solubility product constant of heavy metals such As Cd, Pb, Cu, As, Cr and the like is far smaller than that of FeS (FeS)2) The solubility product constant allows the equilibrium trend of the conversion reaction to proceed in a positive direction.
The chemical principle of the conversion method can be expressed by the following equation:
in addition, other heavy metal high valence ions are also mostly converted to lower valence state (such As Cr, As, etc.), so the treatment column can be called As a reduction column. Because the replacement column is added, the retention time can be shortened and the conversion rate can be improved when the wastewater flows through the conversion column.
(4) The treated wastewater flows through a device provided with a filter column, and sediments in the wastewater are filtered, so that the wastewater can be recycled;
(5) and the treated waste water flows through a device provided with an adsorption column, so that the concentration of various heavy metals in the waste water is reduced to below ppb level again, (Hg is less than 0.2ppb, Pb is less than 1ppb), and the heavy metals can be directly discharged.
The device for treating heavy metal wastewater with various forms by using the multiphase transfer method is further described in detail by combining the attached drawings as follows:
as shown in figure 1, the structure of the displacement column, the structure of the conversion column, the structure of the filter column and the structure of the adsorption column are the same, the displacement column, the conversion column, the structure of the filter column and the structure of the adsorption column are respectively provided with a feed inlet, and the displacement column, the conversion column, the structure of the filter column and the structure of the adsorption column are respectively provided with a lower isolation.
The heavy metal wastewater with various forms is injected into a flocculation tank, and polyferric sulfate is used as a flocculating agent to remove heavy metalDepositing organic matters, transferring the organic matters to solid waste for treatment, injecting flocculated wastewater into a displacement column (1) through a water pump (6), and discharging Hg in the displacement column (1)0、Hg2+Mercury and organic mercury can be removed through conversion, the feeding port (9) is arranged for replacing and adding replacement materials, the lower isolation net (7) plays a role in isolating materials, the middle isolation net (8) enables the materials to be loose and not hardened, the replacement reaction is facilitated, and the upper isolation net (10) mainly relievesWater pressure and isolating material. The wastewater treated by the displacement column (1) is injected into a conversion column (2) through a valve (12), the wastewater converts high-valence heavy metal ions into lower valence state in the conversion column, and then heavy metal ions such as cadmium, mercury, lead, copper, zinc, arsenic, chromium and the like are converted into correspondingmetal sulfides. After the conversion treatment, the wastewater flows through the mixed filter column (3) to intercept the nascent state fine sulfide for recycling. The wastewater from the mixed column effluent after being treated by the adsorption column (4) can be directly discharged.
Example (b):
and (3) comprehensive treatment result of wastewater:
| waste water | Mn | Zn | Cu | Hg | Cd | Pb | Cr | Ni |
| Waste water before treatment (g/L) | 3.8 | 5.1 | 0.5 | 0.8 | 2.0 | 2.5 | 0.5 | 1.6 |
| Treated water is discharged (mg/L) | 0.02 | 0.02 | 0.01 | ＜0.001 | ＜0.05 | ＜0.05 | ＜0.03 | ＜0.02 |
| GB8987-88 (mg/L) | ＜0.5 | ＜2.0 | 1.0 | 0.001 | 0.01 | 0.1 | 0.1 |
Claims (9)
1. A method for treating heavy metal wastewater with various forms by a multiphase transfer method comprises the following steps:
(1) allowing the wastewater containing heavy metals in various forms to flow through a flocculation tank, depositing a large amount of organic matters by using a flocculating agent, and transferring the organic matters to solid waste for treatment;
(2) and the residual waste water flows through a device provided with a metal displacement column to ensure that Hg is contained0、Hg2+Organic mercury combines with metal to form amalgam, which is fixed on the surface of metal displacement column to convert Cr (VI), As (V) into low-price Cr (III), As (III);
(3) making the treated waste water flow through a device provided with a conversion column, and converting heavy metals in the waste water into more insoluble sulfides by utilizing a solubility deposition conversion principle;
(4) the treated wastewater flows through a device provided with a filter column, and sediments in the wastewater are filtered, so that the wastewater can be recycled;
(5) and the treated wastewater flows through a device provided with an adsorption column, so that the concentration of various heavy metals in the wastewater is reduced again, and the wastewater can be directly discharged.
2. The method for treating heavy metal wastewater with various forms by using the multiphase transfer method as claimed in claim 1, which is characterized in that: the flocculating agent is polymeric ferric sulfate.
3. The method for treating heavy metal wastewater with various forms by using the multiphase transfer method as claimed in claim 1, which is characterized in that: the metal replacement column adopts metal aluminum as a processing column.
4. The method for treating heavy metal wastewater with various forms by using the multiphase transfer method as claimed in claim 1, which is characterized in that: the conversion column adopts FeS or FeS2Used as a processing column.
5. The method for treating heavy metal wastewater with various forms by using the multiphase transfer method as claimed in claim 1, which is characterized in that: the adsorption column adopts fine sand and activated carbon as a treatment column.
6. The method for treating heavy metal wastewater with various forms by using the multiphase transfer method as claimed in claim 1, which is characterized in that: the pH value range of the treated wastewater is as follows: the pH value is 1-13.
7. The utility model provides a handle multiple form heavy metal waste water device with multiphase transfer method, it includes flocculation basin (16), water pump (6), water treatment exchange device, characterized by: the water treatment exchange device comprises a displacement column (1), a conversion column (2), a filter column (3) and an adsorption column (4); the displacement column (1), the conversion column (2), the filter column (3) and the adsorption column (4) are connected in sequence through a pipeline (11).
8. The apparatus for treating heavy metal wastewater by multiphase transfer method as claimed in claim 1, wherein: and a replacement column valve, a conversion column valve, a filter column valve and an adsorption column valve are arranged on a pipeline (11) among the replacement column (1), the conversion column (2), the filter column (3) and the adsorption column (4).
9. The apparatus for treating heavy metal wastewater by multiphase transfer method as claimed in claim 1, wherein: the displacement column (1), the conversion column (2), the filter column (3) and the adsorption column (4) are respectively provided with a feed inlet (9), and a lower isolation net (7), a middle isolation net (8) and an upper isolation net (10) are respectively arranged in the feed inlets.
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| CN 200410073499 CN1286740C (en) | 2004-12-27 | 2004-12-27 | Method and device for treating multiple form heavy metal waste water by multiphase transfer method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400668C (en) * | 2005-09-19 | 2008-07-09 | 南京农业大学 | Biosynthesis of obligate adsorbent and its usage in adsorbing to eliminate As and Cr from water |
| CN103819025A (en) * | 2014-03-10 | 2014-05-28 | 西安建筑科技大学 | Method and device for synchronous phosphorus removal and turbidity removal of thickened sludge water |
| CN105713615A (en) * | 2016-01-15 | 2016-06-29 | 北京大学 | Hexavalent chromium pollution in-situ repairing agent FeSx, preparation and application |
| CN105906105A (en) * | 2016-06-13 | 2016-08-31 | 深圳市绿恩环保技术有限公司 | Processing method of COD measurement wastewater |
| CN107459056A (en) * | 2017-08-18 | 2017-12-12 | 西北矿冶研究院 | Process for extracting mercury from acid-making wastewater by smelting flue gas |
| CN108687114A (en) * | 2018-05-16 | 2018-10-23 | 扬州杰嘉工业固废处置有限公司 | A kind of Organomercurial waste is stable and cures disposing technique |
| CN111499038A (en) * | 2020-04-22 | 2020-08-07 | 沈阳鑫迪环境技术有限公司 | Method for combined demercuration in complex chemical high-mercury-content waste acid liquid |
-
2004
- 2004-12-27 CN CN 200410073499 patent/CN1286740C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400668C (en) * | 2005-09-19 | 2008-07-09 | 南京农业大学 | Biosynthesis of obligate adsorbent and its usage in adsorbing to eliminate As and Cr from water |
| CN103819025A (en) * | 2014-03-10 | 2014-05-28 | 西安建筑科技大学 | Method and device for synchronous phosphorus removal and turbidity removal of thickened sludge water |
| CN103819025B (en) * | 2014-03-10 | 2015-02-25 | 西安建筑科技大学 | Method and device for synchronous phosphorus removal and turbidity removal of thickened sludge water |
| CN105713615A (en) * | 2016-01-15 | 2016-06-29 | 北京大学 | Hexavalent chromium pollution in-situ repairing agent FeSx, preparation and application |
| CN105713615B (en) * | 2016-01-15 | 2019-05-31 | 北京大学 | A kind of hexavalent chromium polluted in-situ immobilization agent FeSx, preparation, application |
| CN105906105A (en) * | 2016-06-13 | 2016-08-31 | 深圳市绿恩环保技术有限公司 | Processing method of COD measurement wastewater |
| CN107459056A (en) * | 2017-08-18 | 2017-12-12 | 西北矿冶研究院 | Process for extracting mercury from acid-making wastewater by smelting flue gas |
| CN108687114A (en) * | 2018-05-16 | 2018-10-23 | 扬州杰嘉工业固废处置有限公司 | A kind of Organomercurial waste is stable and cures disposing technique |
| CN108687114B (en) * | 2018-05-16 | 2021-05-11 | 扬州杰嘉工业固废处置有限公司 | Mercury-containing reagent waste stabilization and solidification treatment process |
| CN111499038A (en) * | 2020-04-22 | 2020-08-07 | 沈阳鑫迪环境技术有限公司 | Method for combined demercuration in complex chemical high-mercury-content waste acid liquid |
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| CN1286740C (en) | 2006-11-29 |
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