CN110372080A - The inorganic agent of combined removal heavy metals in industrial wastewater ion - Google Patents
The inorganic agent of combined removal heavy metals in industrial wastewater ion Download PDFInfo
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- CN110372080A CN110372080A CN201910758516.5A CN201910758516A CN110372080A CN 110372080 A CN110372080 A CN 110372080A CN 201910758516 A CN201910758516 A CN 201910758516A CN 110372080 A CN110372080 A CN 110372080A
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
Abstract
The invention discloses a kind of inorganic agents of combined removal heavy metals in industrial wastewater ion, raw material includes polystyrene divinyl benzene resin microsphere, ethylenediamine tetra-acetic acid, dithiocar-bamate, polyethyleneimine, glutaraldehyde, acacia mearnsii tannin, poly- (2- acrylamide-2-methyl propane sulfonic), maleic anhydride, dialkyl dithiophosphate, poly-aspartate, 2- amino -3- mercaptopropionyl chitosan, polyethyleneimine amido sodium xanthogenate, thioacetic acid, dibutyl phthalate, poly-epoxy succinic acid, sodium dioctyl sulphosuccinate, crosslinking agent, coupling agent；Can not be influenced by ion interference in combined removal heavy metals in industrial wastewater ion under coexisting ion, can with the heavy metal ion of most of monovalencies and divalent in aqueous solution, such as: Fe2+, Ni2+, Pb2+, Ag+, Zn2+, Cd2+, Hg2+, Ti+And Cr3+Plasma forms stable compound and is precipitated out, to achieve the purpose that heavy-metal ion removal, no matter heavy metal ions in wastewater concentration level, is attained by removal effect.When various metals ion coexists, can also remove simultaneously；In the presence of heavy metal ion is to be complexed salt form (EDTA, tetramine etc.), good removal effect can be also played.
Description
Technical field
The present invention relates to water treatment field, in particular to a kind of processing of combined removal heavy metals in industrial wastewater ion
Agent.
Background technique
Heavy metal wastewater thereby, i.e., all kinds of waste water being derived by heavy metal.And heavy metal is in environmental ecology, from toxicity
And from the point of view of migration of element transformation rule, the waste water containing As, Se and Al etc. is generally also included within heavy metal wastewater thereby scope
Interior, heavy metal described in traditional environment field is primarily referred to as Hg, Pb, Cd, Cr and the eka-gold with heavy metal characteristic at this stage
Belong to the significant elements of bio-toxicities such as As, sometimes referred to as with the Zn, Cu, Co of certain toxicity, the general heavy metal such as Ni, Sn.
Industrial wastewater containing heavy metal ion is mainly derived from smelting and the portion of machining, mining industry, steel and non-ferrous metal
Divide chemical company.The waste water that mine generates mainly is dug up mine and beneficiation wastewater, wherein containing various mineral suspensions objects and
Related metal ion.In the waste water that nonferrous metallurgy, processing industry are discharged, mostly containing elements such as mercury, arsenic, chromium.In addition, some light industry
Also contain the heavy metals such as mercury, cadmium, arsenic with the waste water of chemical industry discharge.Some heavy metal conducts in the development of modern chemical industry production
Raw material or catalyst are widely used in production, and the heavy metal-containing waste water of generation is all greatly increased from value volume and range of product, cause serious
Environmental pollution and the wasting of resources.At present, commercialized ion exchange resin is many kinds of, but the warp of practical heavy metal water process
It tests and shows, the poor selectivity of traditional cation or anion exchange resin to heavy metal.Contain a large amount of Ca in processing2+,Mg2+,
Na+,SO4 2-And Cl-When the practical heavy metal wastewater thereby of plasma, the removal of heavy metal is easily coexisted in ion exchange resin by these
The interference of ion, causes it to be restricted in practical applications.Aiming at the problem that ion interference, the measure industrially taken mostly
It is before handling heavy metal by the Ca in water2+,Mg2+,Na+,SO4 2-And Cl-Plasma removal.Though processing weight can be reached in this way
The final purpose of metal, but treatment process is more complex.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of processing of combined removal heavy metals in industrial wastewater ion
Agent can not be influenced in combined removal heavy metals in industrial wastewater ion under coexisting ion by ion interference, energy and aqueous solution
In most of monovalencies and divalent heavy metal ion, such as: Fe2+, Ni2+, Pb2+, Ag+, Zn2+, Cd2+, Hg2+, Ti+And Cr3+
Plasma forms stable compound and is precipitated out, to achieve the purpose that heavy-metal ion removal, is formed after processing
Sediment will not be dissolved by substances such as rainwater, be not present secondary pollution environmental problem.
The inorganic agent of combined removal heavy metals in industrial wastewater ion of the invention, raw material include with the following group by weight
Point: 40-50 parts of polystyrene divinyl benzene resin microsphere, 5-15 parts of ethylenediamine tetra-acetic acid, 5-12 parts of dithiocar-bamate,
5-15 parts of polyethyleneimine, 10-20 parts of glutaraldehyde, 5-12 parts of acacia mearnsii tannin, poly- (2- acrylamide-2-methyl propane sulfonic)
10-15 parts, 8-12 parts of maleic anhydride, 4-12 parts of dialkyl dithiophosphate, 10-20 parts of poly-aspartate, 2- amino -3- mercapto
5-15 parts of base propionyl chitosan, 2-6 parts of polyethyleneimine amido sodium xanthogenate, 2-6 parts of thioacetic acid, dibutyl phthalate 1-
6 parts, 6-12 parts of poly-epoxy succinic acid, 1-5 parts of sodium dioctyl sulphosuccinate, 1-3 parts of crosslinking agent, 1-3 parts of coupling agent；
Further, raw material includes following components by weight: 45 parts of polystyrene divinyl benzene resin microsphere, ethylenediamine tetraacetic
10 parts of acetic acid, 8 parts of dithiocar-bamate, 8 parts of polyethyleneimine, 15 parts of glutaraldehyde, 7 parts of acacia mearnsii tannin, poly- (2- propylene
Amide -2- methyl propane sulfonic acid) 12 parts, 10 parts of maleic anhydride, 8 parts of dialkyl dithiophosphate, 15 parts of poly-aspartate, 2- ammonia
10 parts of base -3- mercaptopropionyl chitosan, 4 parts of polyethyleneimine amido sodium xanthogenate, 4 parts of thioacetic acid, dibutyl phthalate 3
Part, 8 parts of poly-epoxy succinic acid, 3 parts of sodium dioctyl sulphosuccinate, 2 parts of crosslinking agent, 2 parts of coupling agent；
Further, the polystyrene-divinylbenzene microspheres aperture is 110-130nm, specific surface area 200-600m2﹒ g-1；
Further, the crosslinking agent is the mixed of divinylbenzene, glycolmethacrylate and ethylene glycol acrylate
Close object；
Further, by weight divinylbenzene: glycolmethacrylate and: ethylene glycol acrylate=1:1:1；
Further, the coupling agent is KH570.
Beneficial effects of the present invention: the inorganic agent of combined removal heavy metals in industrial wastewater ion of the invention, Neng Gou
Combined removal heavy metals in industrial wastewater ion, is not influenced by ion interference under coexisting ion, can with it is most in aqueous solution
The heavy metal ion of number monovalence and divalent, such as: Fe2+, Ni2+, Pb2+, Ag+, Zn2+, Cd2+, Hg2+, Ti+And Cr3+Plasma shape
It is precipitated out at stable compound, to achieve the purpose that heavy-metal ion removal, no matter heavy metal ions in wastewater is dense
Degree height, is attained by removal effect.When various metals ion coexists, can also remove simultaneously；When heavy metal ion is to be complexed
In the presence of salt form (EDTA, tetramine etc.), good removal effect can be also played.The inorganic agent is in precipitation of heavy metals not by useless
The influence of salt coexists in liquid, and metal precipitates are very stable, even if heavy metal will not be released 200-250 DEG C of high temperature,
Metal precipitates are not oozed out in dilute acid soln, and being formed by sediment after processing will not be dissolved by substances such as rainwater, are not deposited
In secondary pollution environmental problem.Inorganic agent of the invention passes through chemical actions and the waddings such as trapping, physical absorption, ligand complex
Modes effective combined removal heavy metals in industrial wastewater ions under coexisting ion such as solidifying, precipitating.
Specific embodiment
The inorganic agent of the combined removal heavy metals in industrial wastewater ion of the present embodiment, raw material include with the following group by weight
Point: 40-50 parts of polystyrene divinyl benzene resin microsphere, 5-15 parts of ethylenediamine tetra-acetic acid, 5-12 parts of dithiocar-bamate,
5-15 parts of polyethyleneimine, 10-20 parts of glutaraldehyde, 5-12 parts of acacia mearnsii tannin, poly- (2- acrylamide-2-methyl propane sulfonic)
10-15 parts, 8-12 parts of maleic anhydride, 4-12 parts of dialkyl dithiophosphate, 10-20 parts of poly-aspartate, 2- amino -3- mercapto
5-15 parts of base propionyl chitosan, 2-6 parts of polyethyleneimine amido sodium xanthogenate, 2-6 parts of thioacetic acid, dibutyl phthalate 1-
6 parts, 6-12 parts of poly-epoxy succinic acid, 1-5 parts of sodium dioctyl sulphosuccinate, 1-3 parts of crosslinking agent, 1-3 parts of coupling agent；Two is thio
Carbamate groups contain S, N coordination atom, and alkali metal, alkaline-earth metal ions cannot react therewith, easily and heavy metal from
Son is combined into stable complex compound；Poly- (2- acrylamide-2-methyl propane sulfonic) and maleic anhydride synergistic effect are improved to Pb2+、
Cu2+And Zn2+Absorption property, improve the rate of adsorption；Sodium dioctyl sulphosuccinate enhancing polystyrene divinyl benzene resin is gone
Except Ni2+,Pb2+And Cd2+Effect；Pass through dialkyl dithiophosphate, sodium dioctyl sulphosuccinate and polyethyleneimine amido
Sodium xanthogenate expansion space reticular structure, it is easier to introduce object ion, improve the ability of ligand complex, while can reduce again useless
The turbidity of liquid, and also helping for sulfydryl present in inorganic agent removes organic heavy metal ion, such as methyl mercury；Poly- epoxy succinic
The binding ability of acid and other components synergistic effect raising and heavy metal ion, enhancing and representative heavy metal ion Zn~(2+),
Coordinative Chemistry effect between pb~(2+), Cd~(2+), Ni~(2+), Cr~(3+), Cu~(2+).
In the present embodiment, raw material includes following components by weight: 45 parts of polystyrene divinyl benzene resin microsphere, second two
10 parts of amine tetraacethyl, 8 parts of dithiocar-bamate, 8 parts of polyethyleneimine, 15 parts of glutaraldehyde, 7 parts of acacia mearnsii tannin, poly- (2-
Acrylamide-2-methyl propane sulfonic) 12 parts, 10 parts of maleic anhydride, 8 parts of dialkyl dithiophosphate, 15 parts of poly-aspartate,
10 parts of 2- amino -3- mercaptopropionyl chitosan, 4 parts of polyethyleneimine amido sodium xanthogenate, 4 parts of thioacetic acid, phthalic acid two
3 parts of butyl ester, 8 parts of poly-epoxy succinic acid, 3 parts of sodium dioctyl sulphosuccinate, 2 parts of crosslinking agent, 2 parts of coupling agent；To be preferably implemented
Example.
In the present embodiment, the polystyrene-divinylbenzene microspheres aperture is 110-130nm, specific surface area 200-
600m2﹒ g-1。
In the present embodiment, the crosslinking agent is divinylbenzene, glycolmethacrylate and ethylene glycol acrylate
Mixture；By weight divinylbenzene: glycolmethacrylate and: ethylene glycol acrylate=1:1:1；
In the present embodiment, the coupling agent is KH570.
Embodiment one
The inorganic agent of the combined removal heavy metals in industrial wastewater ion of the present embodiment, raw material include with the following group by weight
Point: 40 parts of polystyrene divinyl benzene resin microsphere, 5 parts of ethylenediamine tetra-acetic acid, 5 parts of dithiocar-bamate, polyethyleneimine
5 parts of amine, 10 parts of glutaraldehyde, 5 parts of acacia mearnsii tannin, 10 parts of poly- (2- acrylamide-2-methyl propane sulfonic), 8 parts of maleic anhydride, two
4 parts of aerofloat, 10 parts of poly-aspartate, 5 parts of 2- amino -3- mercaptopropionyl chitosan, polyethyleneimine amido are yellow
2 parts of ortho acid sodium, 2 parts of thioacetic acid, 1 part of dibutyl phthalate, 6 parts of poly-epoxy succinic acid, sodium dioctyl sulphosuccinate 1
Part, 1 part of crosslinking agent, 1 part of coupling agent.
Embodiment two
The inorganic agent of the combined removal heavy metals in industrial wastewater ion of the present embodiment, raw material include with the following group by weight
Point: 50 parts of polystyrene divinyl benzene resin microsphere, 15 parts of ethylenediamine tetra-acetic acid, 12 parts of dithiocar-bamate, polyethylene
15 parts of imines, 20 parts of glutaraldehyde, 12 parts of acacia mearnsii tannin, 15 parts of poly- (2- acrylamide-2-methyl propane sulfonic), maleic anhydride 12
Part, 12 parts of dialkyl dithiophosphate, 20 parts of poly-aspartate, 15 parts of 2- amino -3- mercaptopropionyl chitosan, polyethyleneimine
6 parts of amido sodium xanthogenate, 6 parts of thioacetic acid, 6 parts of dibutyl phthalate, 12 parts of poly-epoxy succinic acid, sulphur are for succinic acid two
5 parts of pungent sodium ester, 3 parts of crosslinking agent, 3 parts of coupling agent.
Embodiment three
The inorganic agent of the combined removal heavy metals in industrial wastewater ion of the present embodiment, raw material include with the following group by weight
Point: 40 parts of polystyrene divinyl benzene resin microsphere, 15 parts of ethylenediamine tetra-acetic acid, 5 parts of dithiocar-bamate, polyethyleneimine
15 parts of amine, 10 parts of glutaraldehyde, 12 parts of acacia mearnsii tannin, 10 parts of poly- (2- acrylamide-2-methyl propane sulfonic), maleic anhydride 12
Part, 4 parts of dialkyl dithiophosphate, 20 parts of poly-aspartate, 5 parts of 2- amino -3- mercaptopropionyl chitosan, polyethyleneimine
6 parts of base sodium xanthogenate, 2 parts of thioacetic acid, 6 parts of dibutyl phthalate, 6 parts of poly-epoxy succinic acid, sulphur are pungent for succinic acid two
5 parts of sodium ester, 1 part of crosslinking agent, 3 parts of coupling agent.
Example IV
The inorganic agent of the combined removal heavy metals in industrial wastewater ion of the present embodiment, raw material include with the following group by weight
Point: 50 parts of polystyrene divinyl benzene resin microsphere, 5 parts of ethylenediamine tetra-acetic acid, 12 parts of dithiocar-bamate, polyethyleneimine
5 parts of amine, 20 parts of glutaraldehyde, 5 parts of acacia mearnsii tannin, 15 parts of poly- (2- acrylamide-2-methyl propane sulfonic), 8 parts of maleic anhydride, two
12 parts of aerofloat, 10 parts of poly-aspartate, 15 parts of 2- amino -3- mercaptopropionyl chitosan, polyethyleneimine amido
2 parts of sodium xanthogenate, 6 parts of thioacetic acid, 1 part of dibutyl phthalate, 12 parts of poly-epoxy succinic acid, sulphur are for the pungent sodium of succinic acid two
1 part of ester, 3 parts of crosslinking agent, 1 part of coupling agent.
Embodiment five
The inorganic agent of the combined removal heavy metals in industrial wastewater ion of the present embodiment, raw material include with the following group by weight
Point: 45 parts of polystyrene divinyl benzene resin microsphere, 15 parts of ethylenediamine tetra-acetic acid, 5 parts of dithiocar-bamate, polyethyleneimine
10 parts of amine, 20 parts of glutaraldehyde, 52 parts of acacia mearnsii tannin, 12 parts of poly- (2- acrylamide-2-methyl propane sulfonic), 8 parts of maleic anhydride,
12 parts of dialkyl dithiophosphate, 15 parts of poly-aspartate, 7 parts of 2- amino -3- mercaptopropionyl chitosan, polyethyleneimine amido
4 parts of sodium xanthogenate, 2 parts of thioacetic acid, 6 parts of dibutyl phthalate, 8 parts of poly-epoxy succinic acid, sulphur are for the pungent sodium of succinic acid two
2 parts of ester, 2 parts of crosslinking agent, 3 parts of coupling agent.
Embodiment six
The inorganic agent of the combined removal heavy metals in industrial wastewater ion of the present embodiment, raw material include with the following group by weight
Point: 45 parts of polystyrene divinyl benzene resin microsphere, 10 parts of ethylenediamine tetra-acetic acid, 8 parts of dithiocar-bamate, polyethyleneimine
8 parts of amine, 15 parts of glutaraldehyde, 7 parts of acacia mearnsii tannin, 12 parts of poly- (2- acrylamide-2-methyl propane sulfonic), 10 parts of maleic anhydride,
8 parts of dialkyl dithiophosphate, 15 parts of poly-aspartate, 10 parts of 2- amino -3- mercaptopropionyl chitosan, polyethyleneimine amido
4 parts of sodium xanthogenate, 4 parts of thioacetic acid, 3 parts of dibutyl phthalate, 8 parts of poly-epoxy succinic acid, sulphur are for the pungent sodium of succinic acid two
3 parts of ester, 2 parts of crosslinking agent, 2 parts of coupling agent.
In above-described embodiment, the polystyrene-divinylbenzene microspheres aperture is 110-130nm, specific surface area 200-
600m2﹒ g-1；The crosslinking agent is the mixture of divinylbenzene, glycolmethacrylate and ethylene glycol acrylate；It presses
Weight ratio divinylbenzene: glycolmethacrylate and: ethylene glycol acrylate=1:1:1；The coupling agent is
KH570。
Inorganic agent of the invention is used to handle electroplating wastewater, input amount 8mg/L is direct plungeed into waste water and stirred, knot
Fruit is as follows:
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (6)
1. a kind of inorganic agent of combined removal heavy metals in industrial wastewater ion, it is characterised in that: raw material include by weight with
Lower component: 40-50 parts of polystyrene divinyl benzene resin microsphere, 5-15 parts of ethylenediamine tetra-acetic acid, dithiocar-bamate 5-
12 parts, 5-15 parts of polyethyleneimine, 10-20 parts of glutaraldehyde, 5-12 parts of acacia mearnsii tannin, poly- (2- acrylamide -2- methyl-prop sulphur
Acid) 10-15 parts, 8-12 parts of maleic anhydride, 4-12 parts of dialkyl dithiophosphate, 10-20 parts of poly-aspartate, 2- amino-
5-15 parts of 3- mercaptopropionyl chitosan, 2-6 parts of polyethyleneimine amido sodium xanthogenate, 2-6 parts of thioacetic acid, two fourth of phthalic acid
1-6 parts of ester, 6-12 parts of poly-epoxy succinic acid, 1-5 parts of sodium dioctyl sulphosuccinate, 1-3 parts of crosslinking agent, 1-3 parts of coupling agent.
2. the inorganic agent of combined removal heavy metals in industrial wastewater ion according to claim 1, it is characterised in that: raw material
It by weight include following components: 45 parts of polystyrene divinyl benzene resin microsphere, 10 parts of ethylenediamine tetra-acetic acid, dithiocarbamates
8 parts of formates, 8 parts of polyethyleneimine, 15 parts of glutaraldehyde, 7 parts of acacia mearnsii tannin, poly- (2- acrylamide-2-methyl propane sulfonic)
12 parts, 10 parts of maleic anhydride, 8 parts of dialkyl dithiophosphate, 15 parts of poly-aspartate, 2- amino -3- mercaptopropionyl shell it is poly-
Sugared 10 parts, 4 parts of polyethyleneimine amido sodium xanthogenate, 4 parts of thioacetic acid, 3 parts of dibutyl phthalate, poly-epoxy succinic acid 8
Part, 3 parts of sodium dioctyl sulphosuccinate, 2 parts of crosslinking agent, 2 parts of coupling agent.
3. the inorganic agent of combined removal heavy metals in industrial wastewater ion according to claim 1, it is characterised in that: described
Polystyrene-divinylbenzene microspheres aperture is 110-130nm, specific surface area 200-600m2﹒ g-1。
4. the inorganic agent of combined removal heavy metals in industrial wastewater ion according to claim 2, it is characterised in that: described
Crosslinking agent is the mixture of divinylbenzene, glycolmethacrylate and ethylene glycol acrylate.
5. the inorganic agent of combined removal heavy metals in industrial wastewater ion according to claim 3, it is characterised in that: by weight
Amount than divinylbenzene: glycolmethacrylate and: ethylene glycol acrylate=1:1:1.
6. the inorganic agent of combined removal heavy metals in industrial wastewater ion according to claim 2, it is characterised in that: described
Coupling agent is KH570.
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| CN111591977A (en) * | 2020-06-04 | 2020-08-28 | 山东丰益泰和科技有限公司 | Application of polyepoxysuccinic acid as carbon source in preparation of carbon quantum dots |
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| CN111018177A (en) * | 2019-12-12 | 2020-04-17 | 清华大学 | Heavy metal sewage treatment process |
| CN111018016A (en) * | 2019-12-12 | 2020-04-17 | 清华大学 | Heavy metal sewage treatment agent |
| CN111018016B (en) * | 2019-12-12 | 2021-04-09 | 清华大学 | Heavy metal sewage treatment agent |
| CN111229176A (en) * | 2020-01-17 | 2020-06-05 | 广西壮族自治区农业科学院 | Tannin-polyethyleneimine composite material and application thereof |
| CN111229176B (en) * | 2020-01-17 | 2023-03-03 | 广西壮族自治区农业科学院 | Tannin-polyethyleneimine composite material and application thereof |
| CN111663043A (en) * | 2020-04-28 | 2020-09-15 | 西北矿冶研究院 | Method for enriching and recovering valuable metals from acidic sewage in nonferrous smelting process |
| CN111663043B (en) * | 2020-04-28 | 2022-01-18 | 西北矿冶研究院 | Method for enriching and recovering valuable metals from acidic sewage in nonferrous smelting process |
| CN111825191A (en) * | 2020-05-22 | 2020-10-27 | 西北矿冶研究院 | Acid sewage heavy metal capture agent |
| CN111591977A (en) * | 2020-06-04 | 2020-08-28 | 山东丰益泰和科技有限公司 | Application of polyepoxysuccinic acid as carbon source in preparation of carbon quantum dots |
| CN115779875A (en) * | 2022-11-25 | 2023-03-14 | 广州康盛生物科技股份有限公司 | Polysaccharide microsphere, preparation method thereof and adsorption column |
| CN115779875B (en) * | 2022-11-25 | 2024-01-30 | 广州康盛生物科技股份有限公司 | Polysaccharide microsphere, preparation method thereof and adsorption column |
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