CN106563419A - Reagent and method for removing heavy metals from water - Google Patents
Reagent and method for removing heavy metals from water Download PDFInfo
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- CN106563419A CN106563419A CN201510664360.6A CN201510664360A CN106563419A CN 106563419 A CN106563419 A CN 106563419A CN 201510664360 A CN201510664360 A CN 201510664360A CN 106563419 A CN106563419 A CN 106563419A
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- heavy metal
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Abstract
The present invention relates to a reagent and a method for removing trace complexing heavy metals from wastewater, wherein a polymerizing heavy metal capture agent is linked and immobilized on a porous natural auxiliary filtration agent material through a chemical bond to prepare the reagent, the porous natural auxiliary filtration agent material comprises natural diatomaceous earth, calcined diatomaceous earth and fluxing calcined diatomaceous earth, and the polymerizing heavy metal capture agent is a thiocarbamate type polymerizing agent. According to the present invention, with the heavy metal capture agent and the method, the heavy metal ions such as copper, cadmium, zinc, lead, nickel, mercury, silver the like existing in electroplating wastewater, semiconductor industry wastewater and metal processing wastewater in the complexing form can be effectively removed, the residual heavy metal concentration in the treated effluent is reduced by 1-2 magnitude orders compared to the traditional treatment method, and the liquid-solid separation difficulty commonly existing in the traditional methods is overcome.
Description
Technical field：
The present invention relates to the removal reagent and method of a kind of complexation micro suitable for waste water and non-complexing heavy metal ion, belong to chemical agent category.Heavy metal chelating agent involved in the present invention and method, plating can effectively be removed, there is heavy metal ion such as copper, cadmium, zinc with form complexed in semi-conductor industry and intermetallic composite coating waste water, lead, nickel, hydrargyrum, silver etc., water outlet residual heavy metal concentration 1～2 order of magnitude low compared with traditional treatment method after removal, while the solid-liquor separation for overcoming traditional method generally existing is difficult.
Application background technology：
The present invention relates to, there is various heavy metal ion such as copper, cadmium, zinc, lead, nickel, hydrargyrum, silver etc. with form complexed in semi-conductor industry and intermetallic composite coating waste water in the removal reagent and method of a kind of complexation micro suitable for waste water and non-complexing heavy metal ion, plating.
The waste water containing heavy metal that heavy metal wastewater thereby is discharged in referring to the industrial processes such as plating, chemical industry, electronics, quasiconductor, intermetallic composite coating, generally comprises nickel-containing waste water, cadmium wastewater, copper-containing wastewater, zinc-containing water, lead waste water, silver-containing waste water etc..If heavy metal wastewater thereby cannot get effective process and discharge, severe contamination can be caused to environment, and high risks are caused to human health.At present, heavy metal pollution of water body has become global problem of environmental pollution, and drastically influence the healthy of the mankind, or even jeopardizes human life.
For with the current state of the art, process heavy metal wastewater thereby is carried out frequently with chemical precipitation method, ion exchange, electrolysis, absorption method, hyperfiltration, evaporation and concentration etc..
Chemical precipitation method is current widest processing method：For non-complexing heavy metal ion, more using OH-, CO3 2-And S2-Precipitated.Metal as hydroxide precipitation be by adjust waste water pH, the pH minimum to reach metal hydroxidess dissolubility, pass through coagulation again, flocculation, precipitate metal hydroxides is got off, to reach the purpose of removing heavy metals, the method processing cost is low, but due to by metal hydroxidess solubility limit, to some heavy metal ion such as zinc etc., it is difficult to reach and be satisfied with treatment effect；Meanwhile, to the waste water for there are several different heavy metal ion to coexist, as the pH that every kind of heavy metal hydroxide reaches minimum dissolubility is different, so suitable pH cannot be selected, make the removal of every metal ion species all reach optimum efficiency.Sulfide precipitation method passes through heavy metal ion S2-Form sulfide precipitation and reach removal purpose, it is however generally that, compared to metal hydroxidess, the dissolubility of metal sulfide is lower, so as to removal effect is more thorough, but will typically add excessive S to reach this purpose2-, so that there is the S of surplus in water outlet2-, exist to form H2S risks, cause another form of pollution.
When strong chelating agent such as ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid is contained in waste water, as chelating agent can form stable complex with heavy metal, on the one hand greatly improve the dissolubility of heavy metal, on the other hand also make conventional chemical precipitation agent difficult and chelating agent occurs competition, thus can not be by the dissolved heavy metals removal.It is now many that reinforced deposition is carried out using heavy metal chelating agents such as dimethyl-thiocarbamic acid salt.The shortcoming of the method is：Solid-liquor separation is difficult, and heavy metal chelating agent itself has stronger toxicity, causes secondary pollution of water to aquatile.Foreign countries are had been reported that thiocarbamate producing high-molecular, though reagent toxicity can be reduced, also cause the problems such as chemical feeding quantity is big, and processing cost is expensive simultaneously.
The content of the invention：
It is an object of the invention to synthesize/configure the removal reagent and method of micro complexation and non-complexing heavy metal ion suitable for waste water, plating can effectively be removed, there is heavy metal ion such as copper, cadmium, zinc with form complexed in semi-conductor industry and intermetallic composite coating waste water, lead, nickel, hydrargyrum, silver etc., water outlet residual heavy metal concentration 1～2 order of magnitude low compared with traditional treatment method after removal, while the solid-liquor separation for overcoming traditional method generally existing is difficult.From the point of view of manufacturing process, the present invention relates to absorption of the water-soluble polymer on natural porosity filter aid material kieselguhr surface is fixed with chemistry, and the sense dough of subsequent water-soluble polymer side base is modified.
Technical scheme involved in the present invention includes：
1. main chain or side base are contained absorption of the water-soluble polymer of amino or imino group on porous filter aid material kieselguhr surface and are fixed with chemistry：The water-soluble polymer solution that main chain or side base contain amino or imino group is contacted with porous filter aid material kieselguhr, surface adsorption is carried out, water-soluble polymer is fixed on into kieselguhr surface with tridimensional network with a small amount of cross-linking agent then.
2. in system add Carbon bisulfide (CS2), appropriate time, kieselguhr/polymer complex reagent of the surface with thiocarbamate functional group are reacted under the constant temperature under proper temperature.
3. rinse and be dried, obtain final powdery product.
Specific embodiment：
The present invention is specifically described below in conjunction with example.
The preparation (illustration) of reagent
1) the flux calcination kieselguhr that median particle diameter (D50) is 45 microns is scattered in tap water with 1: 10～1: 20 solid-to-liquid ratio, stirring forms kieselguhr suspension；
2) in suspension, the main chain or side base of 0.1～0.5 times of addition flux calcination kieselguhr quality contains the water-soluble polymer of amino or imino group, is stirred at room temperature 1～3 hour, water-soluble polymer is fully contacted with kieselguhr, and absorption occurs.
3) in suspension, addition main chain or side base contain the water-soluble cross-linker of 0.01～0.05 times of the water-soluble polymeric amount of substance of amino or imino group, stir 1～3 hour under room temperature, reaction is crosslinked between the macromolecule for making absorption, formation is attached to the tridimensional network on kieselguhr surface.
4) to suspension sodium hydroxide solution, pH is adjusted to alkalescence, then be added dropwise to the Carbon bisulfide (CS of middle 0.5～1.0 times of water-soluble polymeric amount of substance for adding main chain or side base to contain amino or imino group2), 3～6h is reacted under 30～45 DEG C of constant temperature, kieselguhr/Polymer complexation agents of the surface with thiocarbamate functional group are generated.
5) successively add dilute sodium hydroxide and tap water to be washed, filter, be dried, powdery product is obtained.
Embodiment 1：
Waste water from plating plant：Raw wastewater takes FeCl containing 150ppm or so EDTA complex copper ions, the first step3Precipitation process is closed in contact break, copper ion concentration is down to into about 5～10ppm, but subsequently the such as heavy metal chelating agent such as dimethyl-thiocarbamic acid salt carries out the modes such as reinforced deposition in several ways, due to solid-liquor separation effect it is poor, water outlet is muddy, copper ion concentration remains above 0.5ppm simultaneously, and the discharge for not reaching 0.2ppm is limited.
By kieselguhr/polymer complex reagent powder of the surface with thiocarbamate functional group by precoating, it is coated on vacuum-type drum filter, forms functional group's SiClx diatomaceous earth coating that thickness is 12cm.The waste water that copper ion concentration is down to about 5～10ppm will be introduced into empty rotary drum filter tank, filter is started through first step bulk processing, filtered with rotary drum rotating speed 1 rotating speed speed per minute, detection effluent quality is obtained：
Copper ion concentration (atomic absorption spectrum AA)： 0.01ppm
Delivery turbidity： 1NTU
Embodiment 2：
Electronics Factory's waste water：Lead containing complexation, each about 3～6ppm of zinc, without suitable treatments method, draining always cannot be up to standard for client.
The waste water is taken, kieselguhr/polymer complex reagent powder of the 300ppm surfaces with thiocarbamate functional group is added, is stirred 5 minutes after mixing, suspension system is filtered by filter press, detect effluent quality, obtain：
Plumbum ion concentration (atomic absorption spectrum AA)： 0.01ppm
Zinc ion concentration (atomic absorption spectrum AA)： 0.05ppm
Delivery turbidity： 1.6NTU
List of references：
1. United States Patent (USP) US6403726 B1
2. United States Patent (USP) US5500133 A
3. United States Patent (USP) US5164095
4. Chinese patent CN100558460 C
5. European patent EP 0581164A1.
Claims (3)
1. it is a kind of remove waste water in micro complexing heavy metal reagent and method, it is characterised in that comprising following percentage by weight
Component：
The natural filter aid material of porous type：50～90%
Producing high-molecular heavy metal chelating agent：10～50%
The natural filter aid material of the porous type includes natural type kieselguhr, calcined diatomite and flux calcination kieselguhr, described
Producing high-molecular heavy metal chelating agent is thiocarbamate type producing high-molecular type reagent.
2. the main body of producing high-molecular heavy metal chelating agent according to claim 1 contains the high score of amino or imino group for main chain
Son.
3. the side base of producing high-molecular heavy metal chelating agent according to claim 1 is thiocarbamate type chelate functional
Group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510664360.6A CN106563419A (en) | 2015-10-13 | 2015-10-13 | Reagent and method for removing heavy metals from water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510664360.6A CN106563419A (en) | 2015-10-13 | 2015-10-13 | Reagent and method for removing heavy metals from water |
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| CN106563419A true CN106563419A (en) | 2017-04-19 |
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| CN201510664360.6A Pending CN106563419A (en) | 2015-10-13 | 2015-10-13 | Reagent and method for removing heavy metals from water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107050733A (en) * | 2017-04-26 | 2017-08-18 | 南京鑫豪高分子材料有限公司 | A kind of stabilization agent of incineration of refuse flyash, its preparation method and its application |
| CN110770583A (en) * | 2017-06-19 | 2020-02-07 | 保障生物系统控股有限公司 | Three-dimensional polymer networks and uses thereof |
-
2015
- 2015-10-13 CN CN201510664360.6A patent/CN106563419A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107050733A (en) * | 2017-04-26 | 2017-08-18 | 南京鑫豪高分子材料有限公司 | A kind of stabilization agent of incineration of refuse flyash, its preparation method and its application |
| CN110770583A (en) * | 2017-06-19 | 2020-02-07 | 保障生物系统控股有限公司 | Three-dimensional polymer networks and uses thereof |
| CN110770583B (en) * | 2017-06-19 | 2023-12-08 | 保障生物系统控股有限公司 | Three-dimensional polymer networks and uses thereof |
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Application publication date: 20170419 |