CN102060366B - Composite for treating waste water containing cadmium compound and preparation method thereof - Google Patents
Composite for treating waste water containing cadmium compound and preparation method thereof Download PDFInfo
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- CN102060366B CN102060366B CN2010105600278A CN201010560027A CN102060366B CN 102060366 B CN102060366 B CN 102060366B CN 2010105600278 A CN2010105600278 A CN 2010105600278A CN 201010560027 A CN201010560027 A CN 201010560027A CN 102060366 B CN102060366 B CN 102060366B
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Abstract
The invention relates to a composite for treating waste water containing cadmium compounds and a preparation method thereof. The composite for treating waste water containing cadmium compounds is characterized by being prepared by mixing and stirring a persimmon tannin solution-crylic acid super absorbent polymer aqueous solution and a cement dust solution, the composite comprises following components in percent by weight: 20-60% of persimmon tannin solution-crylic acid super absorbent polymer aqueous solution and 40-80% of cement dust solution. In the persimmon tannin solution-crylic acid super absorbent polymer aqueous solution, the mass percentage concentration of the persimmon tannin solution-crylic acid super absorbent polymer is 0.04-0.1%; the mass percentage concentration of the cement dust in the cement dust solution is 0.96-1.92%, and the cement dust is the common industrial cement powder. The composite for treating waste water containing cadmium compounds, which is provided by the invention, has advantages of simpleness in preparation process and favorable cadmium ion absorption performance. The price and the production cost of the adopted cement dust are low.
Description
Technical field
The present invention relates to a kind of cadmic compound use in waste water treatment matrix material and preparation method thereof that contains, be applicable to the efficient absorption that contains cadmium ion in the cadmic compound waste water.
Background technology
In many commercial runs, like plating, process hides, mining, steel-making, dyeing etc., all can produce the waste water that contains the cadmium heavy metal ion in a large number, be discharged in the environment harm humans health and ecotope.Therefore, be emphasis and the difficult point that people pay close attention to and study to the improvement that contains the cadmium effluent containing heavy metal ions always.In recent years, the development that the cadmium heavy metal ion content in the aqueous solution is reduced to the innovative technology of safety range has caused extensive concern and attention.The improvement method roughly has active carbon adsorption both at home and abroad at present, biological degradation method, and modified alta-mud absorption method and photocatalyst for degrading method etc., it is big that above method ubiquity the supplies consumption amount, and the treatment time is long, shortcomings such as cost height.
The patent No. is the index method that 200710052582.8 Chinese patent discloses a kind of persimmon tannin solution-acroleic acid macromolecular absorbent resin; Persimmon tannin solution-acroleic acid macromolecular absorbent resin that this method prepares is particularly suitable for doing water-retaining agent; Heavy metal is caught and is grabbed agent, uses such as pigment is wetting with high molecule multifunction, dispersing auxiliary material.
Summary of the invention
Technical problem to be solved by this invention provide a kind of cost low, can efficient absorption contain use in waste water treatment matrix material of cadmium ion in the cadmic compound waste water and preparation method thereof.
In order to solve the problems of the technologies described above, technical scheme of the present invention is:
Contain cadmic compound use in waste water treatment matrix material; It is characterized in that: it is mixed by the persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution and the concrete grey aqueous solution and forms, and the shared weight percent of each component is: the persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution 20～60%, the concrete grey aqueous solution 40～80%; The mass percent concentration of persimmon tannin solution-acroleic acid macromolecular absorbent resin is 0.04～0.1% in described persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution; The mass percent concentration of concrete grey is 0.96～1.92% in the described concrete grey aqueous solution; Described persimmon tannin solution-acroleic acid macromolecular absorbent resin is number to be that the method for 200710052582.8 disclosed a kind of synthetic persimmon tannin solution-acrylic acid series hydroscopic high-molecular resins prepares according to one Chinese patent application, and described concrete grey is industrial Portland cement powder.
Press such scheme, described water is zero(ppm) water, is preferably deionized water.The ionic impurity that contains in the general water can influence and contain cadmic compound use in waste water treatment matrix material to containing the absorption property of cadmic compound.
The above-mentioned preparation method who contains cadmic compound use in waste water treatment matrix material is characterized in that it comprises the steps:
1) persimmon tannin solution-acroleic acid macromolecular absorbent resin is added to the water; Soak 5～8h in advance; Stirring then and obtaining mass percent concentration is persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution of 0.04～0.1%, subsequent use, under stirring action; Persimmon tannin solution-acroleic acid macromolecular absorbent resin can be in the aqueous solution homodisperse, disperse the length of back hydroscopic high-molecular resin molecular chain to be the number nanometers;
2) concrete grey be added to the water soak 5～8h in advance, and constantly stir, mass percent concentration is 0.96～1.92% the concrete grey aqueous solution, subsequent use, under stirring action, concrete grey can be in the aqueous solution homodisperse;
3) by the shared weight percent of each component be: the persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution 20～60%, the concrete grey aqueous solution 40～80%; Choose the persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution and the concrete grey aqueous solution; Stir more than the 1h, obtain the cadmium wastewater processing and use matrix material.
Press such scheme, described concrete grey is industrial Portland cement powder, and its staple is tricalcium silicate, Dicalcium Phosphate (Feed Grade), tricalcium aluminate, and tricalcium silicate belongs to triclinic(crystalline)system, has characteristics such as good cation exchange property and high-specific surface area; Dicalcium Phosphate (Feed Grade) is generated through high temperature solid state reaction by quicklime and silicon-dioxide, is one of essential mineral of cement clinker, and the content in grog is generally 20%.Dicalcium Phosphate (Feed Grade) is having six kinds of variant: α, α ' below 1450 ℃
H, α '
L(coarse-grain), α '
L(crystallite), β
H, β
L, γ, subscript H is a high temperature modification, L is a low temperature modification.The α type is the high temperature variant, belongs to trigonal system, α '
HAnd α '
LAll belong to rhombic system, and the γ type belongs to rhombic system stable below 500 ℃.Wherein α, α '
H, α '
L, β type Dicalcium Phosphate (Feed Grade) has the hydraulicity, has characteristics such as good cation exchange property and high-specific surface area.
Contain the application of cadmic compound use in waste water treatment matrix material: the cadmium wastewater processing is joined with matrix material fill a certain amount of containing in the cadmic compound solution; Stir 3-5h; Separate with supercentrifuge then; Separate the liquid of discharging the back and be processing back cadmium-containing solution, using atomic absorption instrument can measure its cadmium ion residual quantity is below the 5 μ g/mL.Solid matter after the processing is the solid mixture that contains cadmic compound and matrix material, can be used as plastics after the oven dry and material of construction is used pigment.
Concrete grey has unique crystalline structure, and specific surface area is high, and cation exchange property is good, and therefore the sorbent material as wastewater treatment at home and abroad is widely used, but concrete grey when directly being used to handle cadmium wastewater effect relatively poor.The cadmium ion that the present invention adopts persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution and the compound back of the concrete grey aqueous solution to form is handled and is used matrix material; Utilize concrete grey to have charging property, bigger specific surface area and the strong character of adsorptivity; Can be with containing the cadmic compound molecular adsorption in its small cyberspace in the cadmium-containing solution; Thereby reach the effect that efficient absorption contains the cadmic compound molecule, the solid waste after the absorption can be used as plastics and material of construction is used pigment.This contains cadmic compound and handles and also can be used to absorb other objectionable impuritiess in the waste water with matrix material simultaneously, like other types waste dyestuff, heavy metal, organic and inorganic toxic substance etc.
The invention has the beneficial effects as follows: 1, provided by the invention to contain cadmic compound use in waste water treatment matrix material cadmium ion absorption property good; Can be that the mass concentration of cadmium ion in 3% the cadmium ion waste water drops to below the 0.1 μ g/mL with weight percent concentration; Reach the emission standard (BG8978-1996) of trade effluent; Simultaneously, the concrete grey low price of employing, production cost is low.2, this technological process that contains the production of cadmic compound use in waste water treatment matrix material is simple, is beneficial to large-scale production.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
It is 200710052582.8 Chinese patent disclosed method that the preparation method of persimmon tannin solution-acroleic acid macromolecular absorbent resin described in the embodiment 1-5 adopts number of patent application, and concrete steps are following: (1) weighing: by weight, the proportioning of each reactant is: 20～200 parts of normal hexanes; 1～12 part of persimmon tannin solution; 0.5～100 part of AS, N, 0.01～0.5 part of N '-methylene-bisacrylamide; 0.01～1 part of ammonium persulphate; 10～50 parts in vinylformic acid, 3～10 parts in sodium hydroxide, 8～20 parts in water; (2) synthetic: the reactant that takes by weighing is added in the reaction kettle, under feeding nitrogen and stirring, react, under normal pressure, make then progressively to be warmed up to 60～70 ℃ in the reaction kettle and to react: the entire reaction time is 1～4 hour; (3) after reaction finishes, make reaction kettle reduce to room temperature, emit reaction soln again; (4) with drier separating reaction solution: with promptly obtaining persimmon tannin solution-acroleic acid macromolecular absorbent resin after the reaction mass drying that dries, it is the brown colloidal solid.Described persimmon tannin solution is to form (seeing the farming and sericulture basic necessities of life summary that trecento publishes) by fermentation by persimmon fruit juice, and special odor is arranged, and contains persimmon tannin (3%-5%), after the air contact, becomes dark brownly, forms epithelium easily.
Embodiment 1:
Cadmium wastewater is handled the preparation method with matrix material, and it comprises the steps:
1) the persimmon tannin solution-acroleic acid macromolecular absorbent resin with 1.0g adds water; Soak 5h in advance; Stir; Make persimmon tannin solution-acroleic acid macromolecular absorbent resin homodisperse in the aqueous solution, mass percent concentration is persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution of 0.04%, subsequent use;
2) the 12g concrete grey is added water, soak 5h in advance, and constantly stir to such an extent that mass percent concentration is 1.68% the concrete grey aqueous solution, subsequent use;
3) weight percent concentration by the persimmon tannin-acroleic acid macromolecular absorbent fat aqueous solution and the concrete grey aqueous solution is respectively 23% and 77%, and both are mixed with matrix material, stirs 1h, gets the cadmium wastewater processing and uses matrix material.
Cadmium wastewater is handled the application with matrix material: handle by cadmium wastewater that to use matrix material and mass percent concentration that need processing be that the weight proportion of 3% cadmium nitrate solution is 1:4; The cadmium wastewater processing is joined in the cadmium nitrate waste water with matrix material; Stir 3h; Separate with supercentrifuge then, separate the liquid of discharging the back and after handling, contain cadmium nitrate waste water, using GBA AVANTA M Atomic Absorption Spectroscopy AAS can measure its cadmium ion residual quantity is below the 0.5 μ g/mL; The solid matter that obtains after the spinning is the solid mixture of cadmium nitrate and matrix material, can be used as plastics and material of construction is used pigment after its oven dry.
Embodiment 2:
Cadmium wastewater is handled the preparation method with matrix material, and it comprises the steps:
1) the persimmon tannin solution-acroleic acid macromolecular absorbent resin with 1.0g adds water; Soak 6h in advance; Stir; Make persimmon tannin solution-acroleic acid macromolecular absorbent resin homodisperse in the aqueous solution, mass percent concentration is persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution of 0.05%, subsequent use;
2) the 12g concrete grey is added water, soak 6h in advance, and constantly stir to such an extent that mass percent concentration is 1.20% the concrete grey aqueous solution, subsequent use;
3) weight percent concentration by the persimmon tannin-acroleic acid macromolecular absorbent fat aqueous solution and the concrete grey aqueous solution is respectively 50% and 50%, and both are mixed with matrix material, stirs 1h, gets the cadmium wastewater processing and uses matrix material.
Cadmium wastewater is handled the application with matrix material: handle by cadmium wastewater that to use matrix material and mass percent concentration that need processing be that the weight proportion of 3% cadmium nitrate solution is 1:4; The cadmium wastewater processing is joined in the cadmium nitrate waste water with matrix material; Stir 3h; Separate with supercentrifuge then, separate the liquid of discharging the back and after handling, contain cadmium nitrate waste water, using GBA AVANTA M Atomic Absorption Spectroscopy AAS can measure its cadmium ion residual quantity is below the 2 μ g/mL; The solid matter that obtains after the spinning is the solid mixture of cadmium nitrate and matrix material, can be used as plastics and material of construction is used pigment after its oven dry.
Embodiment 3:
Cadmium wastewater is handled the preparation method with matrix material, and it comprises the steps:
1) the persimmon tannin solution-acroleic acid macromolecular absorbent resin with 1.0g adds water; Soak 8h in advance; Stir; Make persimmon tannin solution-acroleic acid macromolecular absorbent resin homodisperse in the aqueous solution, mass percent concentration is persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution of 0.10%, subsequent use;
2) the 12g concrete grey is added water, soak 8h in advance, and constantly stir to such an extent that mass percent concentration is 0.96% the concrete grey aqueous solution, subsequent use;
3) weight percent concentration by the persimmon tannin-acroleic acid macromolecular absorbent fat aqueous solution and the concrete grey aqueous solution is respectively 60% and 40%, and both are mixed with matrix material, stirs 1h, gets the cadmium wastewater processing and uses matrix material.
Cadmium wastewater is handled the application with matrix material: handle by cadmium wastewater that to use matrix material and mass percent concentration that need processing be that the weight proportion of 3% cadmium nitrate solution is 1:4; The cadmium wastewater processing is joined in the cadmium nitrate waste water with matrix material; Stir 3h; Separate with supercentrifuge then, separate the liquid of discharging the back and after handling, contain cadmium nitrate waste water, using GBA AVANTA M Atomic Absorption Spectroscopy AAS can measure its cadmium ion residual quantity is below the 1 μ g/mL; The solid matter that obtains after the spinning is the solid mixture of cadmium nitrate and matrix material, can be used as plastics and material of construction is used pigment after its oven dry.
Embodiment 4:
Cadmium wastewater is handled the preparation method with matrix material, and it comprises the steps:
1) the persimmon tannin solution-acroleic acid macromolecular absorbent resin with 1.0g adds water; Soak 5h in advance; Stir; Make persimmon tannin solution-acroleic acid macromolecular absorbent resin homodisperse in the aqueous solution, mass percent concentration is persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution of 0.04%, subsequent use;
2) the 12g concrete grey is added water, soak 5h in advance, and constantly stir to such an extent that mass percent concentration is 1.92% the concrete grey aqueous solution, subsequent use;
3) weight percent concentration by the persimmon tannin-acroleic acid macromolecular absorbent fat aqueous solution and the concrete grey aqueous solution is respectively 20% and 80%, and both are mixed with matrix material, stirs 1h, gets the cadmium wastewater processing and uses matrix material.
Cadmium wastewater is handled the application with matrix material: handle by cadmium wastewater that to use matrix material and mass percent concentration that need processing be that the weight proportion of 3% cadmium nitrate solution is 1:4; The cadmium wastewater processing is joined in the cadmium nitrate waste water with matrix material; Stir 3h; Separate with supercentrifuge then, separate the liquid of discharging the back and after handling, contain cadmium nitrate waste water, using GBA AVANTA M Atomic Absorption Spectroscopy AAS can measure its cadmium ion residual quantity is below the 5 μ g/mL; The solid matter that obtains after the spinning is the solid mixture of cadmium nitrate and matrix material, can be used as plastics and material of construction is used pigment after its oven dry.
Embodiment 5:
Cadmium wastewater is handled the preparation method with matrix material, and it comprises the steps:
1) the persimmon tannin solution-acroleic acid macromolecular absorbent resin with 1.0g adds water; Soak 5h in advance; Stir; Make persimmon tannin solution-acroleic acid macromolecular absorbent resin homodisperse in the aqueous solution, mass percent concentration is persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution of 0.06%, subsequent use;
2) the 12g concrete grey is added water, soak 5h in advance, and constantly stir to such an extent that mass percent concentration is 1.2% the concrete grey aqueous solution, subsequent use;
3) weight percent concentration by the persimmon tannin-acroleic acid macromolecular absorbent fat aqueous solution and the concrete grey aqueous solution is respectively 30% and 70%, and both are mixed with matrix material, stirs 1h, gets the cadmium wastewater processing and uses matrix material.
Cadmium wastewater is handled the application with matrix material: handle by cadmium wastewater that to use matrix material and mass percent concentration that need processing be that the weight proportion of 3% cadmium nitrate solution is 1:4; The cadmium wastewater processing is joined in the cadmium nitrate waste water with matrix material; Stir 3h; Separate with supercentrifuge then, separate the liquid of discharging the back and after handling, contain cadmium nitrate waste water, using GBA AVANTA M Atomic Absorption Spectroscopy AAS can measure its cadmium ion residual quantity is below the 0.1 μ g/mL; The solid matter that obtains after the spinning is the solid mixture of cadmium nitrate and matrix material, can be used as plastics and material of construction is used pigment after its oven dry.
Cadmium wastewater provided by the invention is handled and used matrix material can be that cadmium ion drops to below the 0.1 μ g/mL in 3% the cadmium ion waste water with weight percent concentration; Reach the emission standard (BG8978-1996) of trade effluent; And can be used for the processing of all cadmium wastewater, not enumerate one by one at this.
Claims (4)
1. contain cadmic compound use in waste water treatment matrix material; It is characterized in that: it is mixed by the persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution and the concrete grey aqueous solution and forms, and the shared weight percent of each component is: the persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution 20～60%, the concrete grey aqueous solution 40～80%; The mass percent concentration of persimmon tannin solution-acroleic acid macromolecular absorbent resin is 0.04～0.1% in described persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution; The mass percent concentration of concrete grey is 0.96～1.92% in the described concrete grey aqueous solution, and described concrete grey is industrial Portland cement powder.
2. the cadmic compound use in waste water treatment matrix material that contains according to claim 1, it is characterized in that: described water is zero(ppm) water.
3. the cadmic compound use in waste water treatment matrix material that contains according to claim 1, it is characterized in that: described water is deionized water.
4. the preparation method who contains cadmic compound use in waste water treatment matrix material according to claim 1, it is characterized in that: it comprises the steps:
1) persimmon tannin solution-acroleic acid macromolecular absorbent resin is added to the water, soaks 5～8h in advance, stirring then and obtaining mass percent concentration is persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution of 0.04～0.1%, subsequent use;
2) concrete grey be added to the water soak 5～8h in advance, and constantly stir, mass percent concentration is 0.96～1.92% the concrete grey aqueous solution, subsequent use;
3) by the shared weight percent of each component be: the persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution 20～60%, the concrete grey aqueous solution 40～80%; Choose the persimmon tannin solution-acroleic acid macromolecular absorbent resin aqueous solution and the concrete grey aqueous solution; Stir more than the 1h, obtain containing cadmic compound use in waste water treatment matrix material.
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| CN2010105600278A CN102060366B (en) | 2010-11-26 | 2010-11-26 | Composite for treating waste water containing cadmium compound and preparation method thereof |
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| CN2010105600278A CN102060366B (en) | 2010-11-26 | 2010-11-26 | Composite for treating waste water containing cadmium compound and preparation method thereof |
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| CN102060366B true CN102060366B (en) | 2012-06-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103649349B (en) * | 2011-05-10 | 2016-09-07 | 凯米罗总公司 | For the method removing pollutant from water-based system |
| CN102872831A (en) * | 2012-09-04 | 2013-01-16 | 常州大学 | Compound adsorption material capable of removing cadmium ions in native water and preparation method thereof |
| CN104016436A (en) * | 2014-06-12 | 2014-09-03 | 南昌大学 | Zinc-containing wastewater treatment method |
| CN104445499A (en) * | 2014-11-18 | 2015-03-25 | 华中农业大学 | Method for adsorbing and recycling heavy metal cadmium by using metal adsorbent employing persimmon leaves as raw material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180023B1 (en) * | 1998-12-12 | 2001-01-30 | Sultan I. Amer | Composition and process for remediation of waste streams |
| DE10314416A1 (en) * | 2003-03-28 | 2004-11-04 | Otto-Von-Guericke-Universität Magdeburg | Separation of toxic heavy metal ions from waste waters, adsorbs them onto porous concrete adsorbents produced by calcining under given conditions |
| CN101096395A (en) * | 2007-06-28 | 2008-01-02 | 武汉理工大学 | Method for synthesizing persimmon tannin-crylic acid series macromolecule bibulous resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5419876B2 (en) * | 1974-09-12 | 1979-07-18 | ||
| JP3897727B2 (en) * | 2003-04-11 | 2007-03-28 | 電気化学工業株式会社 | Hazardous material collector |
| GB0816378D0 (en) * | 2008-09-08 | 2008-10-15 | Johnson Matthey Plc | Adsorbents |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180023B1 (en) * | 1998-12-12 | 2001-01-30 | Sultan I. Amer | Composition and process for remediation of waste streams |
| DE10314416A1 (en) * | 2003-03-28 | 2004-11-04 | Otto-Von-Guericke-Universität Magdeburg | Separation of toxic heavy metal ions from waste waters, adsorbs them onto porous concrete adsorbents produced by calcining under given conditions |
| CN101096395A (en) * | 2007-06-28 | 2008-01-02 | 武汉理工大学 | Method for synthesizing persimmon tannin-crylic acid series macromolecule bibulous resin |
Non-Patent Citations (2)
| Title |
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| JP特开2004-313826A 2004.11.11 |
| JP特开昭51-31724 1976.03.18 |
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