CN104925929B - A kind of composite flocculation agent for treatment of dyeing wastewater - Google Patents
A kind of composite flocculation agent for treatment of dyeing wastewater Download PDFInfo
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- CN104925929B CN104925929B CN201510255114.5A CN201510255114A CN104925929B CN 104925929 B CN104925929 B CN 104925929B CN 201510255114 A CN201510255114 A CN 201510255114A CN 104925929 B CN104925929 B CN 104925929B
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Abstract
The invention discloses a kind of composite flocculation agent for treatment of dyeing wastewater, it is to be grouped into by tri-kinds of one-tenth of A, B, C, wherein A is the organic natural Flokal B sodium lignin sulfonate of a kind of low-molecular-weight, B is dendroid organic polymer coargulator allyl alcohol polyethenoxy ether sulfonate/maleimide trimethyl sulfonate/propene sulfonic acid salt copolymer, and C is zeolites metal-organic framework material.The flocculability of flocculant of the present invention mostlys come from organic polymer coargulator B, and the dendritic structure of B is swelling in water to be strutted, and spatial volume is big, has the strongest volume to sweep trapping effect the granule in suspension system.A can accelerate the flocculant charge adsorption on particle surface, it is achieved the quick cohesion of little flco；The specific surface area of C is big, porosity is high, has good absorption property to hydrophilic dye.Three kinds of component synergism in the present invention, it is achieved that the rapid flocculation sedimentation of big flocculating body, effectively eliminate the hydrophilic organic dyestuff in dyeing waste water.
Description
Technical field
The present invention relates to treatment of dyeing wastewater field, especially relate to a kind of composite flocculation agent for treatment of dyeing wastewater.
Background technology
China is the principal element that the country that water resource is poorer, shortage of water resources and contaminated wastewater have become as the economic development of restriction China.Dyeing is that water consumption rich and influential family, wastewater discharge and the total amount of pollutant occupy the whole nation second of industrial department and the 4th respectively, is that China's emphasis pollutes one of industry.How effective for dyeing waste water Treatment and recovery reuse is become a vital task of dyeing research.
Dyeing waste water has the features such as discharge capacity is big, pollutant are many, usually contains dyestuff, slurry, auxiliary agent, oil preparation, soda acid, fiber impurity, sand class material, inorganic salt etc. in waste water, and therefore, the process of dyeing waste water is more difficult.At present, method of wastewater treatment mainly has biochemical treatment process and materialization treatment process two class.The research of biochemical process is ripe, be widely used, but there is the phenomenon that effluent quality is unstable.Physico-chemical process is usually used as the preprocessing process of biochemical process, it is ensured that biochemical process stable effluent quality.Coagulation Method is as the one of materialization treatment process, and it is by adding chemical floc in waste water, makes most of non-water-soluble dye granule and colloidal organic matter in dyeing waste water be condensed into mutually the process that then big granule is removed.Compared to other processing methods, Coagulation Method has the advantages such as technological process is simple, convenient operating maintenance, equipment investment is low, floor space is little, and the removal efficiency of suspension organic pollution reaches more than 80%, and the clearance of colourity also can reach more than 50%.But, traditional chemical coagulation process is less desirable to the treatment effect of dyeing waste water, and flocculant hydrophilic dye poor processing effect, flocculation sediment body refuse amount are big and dehydration is difficult.Efficient flocculant is coagulating treatment technique wide variety of premise in treatment of dyeing wastewater.
Single flocculant is difficult to meet the needs for the treatment of of dyeing wastewater, various ingredients combination, each component function the composite flocculation agent being complementary to one another is the emphasis of present treatment of dyeing wastewater flocculant research.Having scholar's research to point out, dendrimer, dendritic polymer polymer makees flocculant, and volume is swept, trapping ability is higher, and being mutually wound around between flocculant, absorbability are the most higher.
For the flocculation treatment process problem to hydrophilic dye poor processing effect, it is crucial for preparing the material to hydrophilic fuel advantages of good adsorption effect.Metal-organic framework materials (MOFs) is the porous material that a class is novel, and specific surface area is big, porosity is high, and plane of crystal has undersaturated metal active position.Different from the porous material such as molecular sieve, activated carbon, what MOFs was organic ligand with metal ion is compound, i.e. has with Organic substance the preferable compatibility to have again good hydrophilic, has good adsorptivity to hydrophilic organics hydrophilicity.
Summary of the invention
Present invention aims to some problems that current dyeing waste water coagulating treatment technique exists, a kind of efficient when treatment of dyeing wastewater, composite flocculation agent of rapid flocculation sedimentation is provided, this composite flocculation agent not only float abjection ability is strong, hydrophilic dye is also had the highest removal ability, at dyeing, there is good application prospect.
For achieving the above object, the present invention can take following technical proposals:
Composite flocculation agent for treatment of dyeing wastewater of the present invention, it is to be grouped into by tri-kinds of one-tenth of A, B, C, wherein A is the organic natural Flokal B-sodium lignin sulfonate of a kind of low-molecular-weight, B is dendroid organic polymer coargulator-allyl alcohol polyethenoxy ether sulfonate/maleimide trimethyl sulfonate/propene sulfonic acid salt copolymer, and C is zeolites metal-organic framework material (ZIF series).
The proportioning of each component of described composite flocculation agent is as follows: A:B:C=10 ~ 50%:30 ~ 70%:5 ~ 25%.
The molar content of the allyl alcohol polyethenoxy ether sulfonate in the B component of described composite flocculation agent/maleimide trimethyl sulfonate/three kinds of monomer components of propene sulfonic acid salt copolymer is as follows: molar percentage 20 ~ 60% shared by allyl alcohol polyethenoxy ether sulfonate；Molar percentage 20 ~ 60% shared by maleimide trimethyl sulfonate；Molar percentage 20 ~ 60% shared by Sodium allyl sulphonate.
The molecular weight of the monomer allyl alcohol polyethenoxy ether sulfonate used by described synthetic copolymer B is 500 ~ 10000.
The synthon of the composition C-zeolites metal-organic framework material in described composite flocculation agent can be one or more in imidazoles or pyridine derivatives；Metal ion bunch is one or more in transition metal ions.
The flocculability of the composite flocculation agent of the present invention mostlys come from organic polymer coargulator B, and the dendritic structure of B is swelling in water to be strutted, and spatial volume is big, has the strongest volume to sweep trapping effect the granule in suspension system, promotes the quick formation of big coagulated particles.B individually makees flocculant and has had preferably to flocculating effect, and the flocculant charge adsorption on particle surface is mainly accelerated in adding of A, it is achieved the quick cohesion of little flco；On the other hand lignin is a kind of complicated phenol polymer formed by four kinds of alcohol monomers, has the good compatibility with organic polymer coargulator B, can promote that the volume of B flocculant is swept trapping, accelerated the flocculation process of little floccule body.The specific surface area of C is big, porosity is high, and surface is the most electronegative, but also have preferable hydrophilic, has good absorption property to hydrophilic dye.And the organic component in C frame structure makes it be wound around with A and B absorption, forms super large flco, further speeds up settling of floccus.Three kinds of components A in composite flocculation agent of the present invention, B, C synergism, not only achieve the rapid flocculation sedimentation of big flocculating body, and effectively eliminate the hydrophilic organic dyestuff in dyeing waste water, and flocculation process is effective, speed is fast.
Advantages of the present invention be mainly reflected in following some:
(1) the tree-shaped copolymerized macromolecule flocculant itself from synthesis has had higher flocculating property, can be used alone as flocculant；
(2) introducing has hydrophilic and organophilic MOFs material simultaneously, improves the traditional flocculant problem to hydrophilic dye poor removal effect；
(3) mutually adsorbing winding between three kinds of components in composite flocculation agent, the flco of formation is big and closely knit, and flocculation settling velocity is fast.This composite flocculation agent is used for dye wastewater treatment, and float, colourity and COD clearance are high.Further, the preparation of this composite flocculation agent is simple, and consumption is few, thus the mud produced is few, secondary pollution is low, has huge application potential.
Detailed description of the invention
Below by specific embodiment, the present invention will be further described in detail.The present embodiment is given premised on inventive technique scheme, but protection scope of the present invention is not limited to following embodiment.
Embodiment
1
The dyeing waste water in certain paper mill is processed:
The composite flocculation agent used is formulated by following mass percent by tri-kinds of compositions of A, B, C: A:B:C=30%:60%:10%；Wherein the mol ratio of three kinds of components in B is allyl alcohol polyethenoxy ether sulfonate: maleimide trimethyl sulfonate: propene sulfonic acid salt copolymer=1:1:1.
First being regulated between 6 ~ 9 by the pH value of dyeing waste water, water temperature is maintained at 30 ~ 45oC.Then according to add 300mg component A, 600mg component B and the ratio of 100mg component C in the pending waste water of 1L, A, B, C being sequentially added in waste water, dosing process is with stirring, each dosing interval 30s.Treat that flocculant concentration is complete, then be slowly stirred standing after 1min, flocculating sedimentation time 3.5min.COD removal efficiency is up to 92%, and percent of decolourization is up to 98.5%.The flco formed is big, sedimentation velocity is fast.
Embodiment
2
:
The dyeing waste water of printing and dyeing mill same as in Example 1 is processed:
The composite flocculation agent used is formulated by following mass percent by tri-kinds of compositions of A, B, C: A:B:C=40%:45%:15%；Wherein the mol ratio of three kinds of components in B is still 1:1:1.
First being regulated between 6 ~ 9 by the pH value of dyeing waste water, water temperature is maintained at 30 ~ 45oC.Then according to add 400mg component A, 450mg component B and the ratio of 150mg component C in the pending waste water of 1L, A, B, C being sequentially added in waste water, dosing process is with stirring, each dosing interval 30s.Treat that flocculant concentration is complete, then be slowly stirred standing after 1min, flocculating sedimentation time 5min.COD removal efficiency is up to 86%, and percent of decolourization is up to 99%.The flco formed is big, sedimentation velocity is fast.
Embodiment
3
:
Processing the dyeing waste water from the printing and dyeing mill being different from embodiment 1, COD content and colourity in this factory's dyeing waste water are above the dyeing waste water in embodiment 1.
The composite flocculation agent used is formulated by following mass percent by tri-kinds of compositions of A, B, C: A:B:C=25%:60%:15%；Wherein the mol ratio of three kinds of components in B is still 1:1:1.
First being regulated between 6 ~ 9 by the pH value of dyeing waste water, water temperature is maintained at 30 ~ 45oC.Then according to add 250mg component A, 600mg component B and the ratio of 150mg component C in the pending waste water of 1L, A, B, C being sequentially added in waste water, dosing process is with stirring, each dosing interval 30s.Treat that flocculant concentration is complete, then be slowly stirred standing after 1.5min, flocculating sedimentation time 4min.COD removal efficiency is up to 87%, and percent of decolourization is up to 98%.The flco formed is big, sedimentation velocity is fast.
Claims (5)
1. the composite flocculation agent for treatment of dyeing wastewater, it is characterized in that: described composite flocculation agent is grouped into by tri-kinds of one-tenth of A, B, C, wherein A is the organic natural Flokal B-sodium lignin sulfonate of a kind of low-molecular-weight, B is dendroid organic polymer coargulator-allyl alcohol polyethenoxy ether sulfonate/maleimide trimethyl sulfonate/propene sulfonic acid salt copolymer, and C is zeolites metal-organic framework material.
Composite flocculation agent for treatment of dyeing wastewater the most according to claim 1, it is characterised in that: the proportioning of each component of described composite flocculation agent is as follows: A:B:C=10 ~ 50%:30 ~ 70%:5 ~ 25%.
Composite flocculation agent for treatment of dyeing wastewater the most according to claim 1, it is characterised in that: the molar content of the allyl alcohol polyethenoxy ether sulfonate in the B component of described composite flocculation agent/maleimide trimethyl sulfonate/three kinds of monomer components of propene sulfonic acid salt copolymer is as follows:
Allyl alcohol polyethenoxy ether sulfonate proportion 20 ~ 60%；Maleimide trimethyl sulfonate proportion 20 ~ 60%；Sodium allyl sulphonate proportion 20 ~ 60%.
Composite flocculation agent for treatment of dyeing wastewater the most according to claim 3, it is characterised in that: the molecular weight of the monomer allyl alcohol polyethenoxy ether sulfonate of described synthetic copolymer is 500 ~ 10000.
Composite flocculation agent for treatment of dyeing wastewater the most according to claim 1, it is characterised in that: the synthon of the composition C-zeolites metal-organic framework material in described composite flocculation agent is one or more in imidazoles or pyridine derivatives；Metal ion bunch is one or more in transition metal ions.
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| CN108178266B (en) * | 2018-03-09 | 2020-08-11 | 湖南中测玉成环境科技有限公司 | Efficient sewage treatment flocculant and preparation method thereof |
| CN110743508A (en) * | 2019-11-19 | 2020-02-04 | 北京林业大学 | Preparation method of biomass-based composite material |
| CN111635530B (en) * | 2020-06-05 | 2021-10-19 | 广西大学 | Hyperbranched alkali lignin-based amphoteric adsorption material and preparation method and application thereof |
| CN112320878B (en) * | 2020-09-30 | 2023-01-17 | 神美科技有限公司 | Composite phosphorus removal agent for wastewater treatment and preparation method thereof |
| CN114426325A (en) * | 2020-10-29 | 2022-05-03 | 中国石油天然气股份有限公司 | Composite flocculant and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229957A (en) * | 2013-06-24 | 2014-12-24 | 张家领 | Compound flocculant taking natural minerals as main components |
| CN104276641A (en) * | 2014-10-29 | 2015-01-14 | 山东华亚环保科技有限公司 | Flocculating agent for textile printing and dyeing wastewater |
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| CA1116324A (en) * | 1978-10-23 | 1982-01-12 | Grace Dearborn Inc. | Detoxification of cationic flocculants |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104229957A (en) * | 2013-06-24 | 2014-12-24 | 张家领 | Compound flocculant taking natural minerals as main components |
| CN104276641A (en) * | 2014-10-29 | 2015-01-14 | 山东华亚环保科技有限公司 | Flocculating agent for textile printing and dyeing wastewater |
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Address after: 451191, Henan Province, Xinzheng City, Longhu Town, 107 National Road on the west side of Zhengzhou Applicant after: HENAN ZHENGJIA ENERGY ENVIRONMENTAL PROTECTION CO., LTD. Address before: 451191, Henan Province, Xinzheng City, Longhu Town, 107 National Road on the west side of Zhengzhou Applicant before: ZHENGZHOU ZHENGJIA ENERGY ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. |
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