CN104925929A - Composite flocculant for treating printing and dyeing wastewater - Google Patents
Composite flocculant for treating printing and dyeing wastewater Download PDFInfo
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- CN104925929A CN104925929A CN201510255114.5A CN201510255114A CN104925929A CN 104925929 A CN104925929 A CN 104925929A CN 201510255114 A CN201510255114 A CN 201510255114A CN 104925929 A CN104925929 A CN 104925929A
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- flocculation agent
- flocculant
- composite flocculation
- dyeing wastewater
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Abstract
The invention discloses a composite flocculant for treating printing and dyeing wastewater. The composite flocculant is prepared from three ingredients, i.e., an ingredient A, an ingredient B and an ingredient C, wherein the A is an organic natural anionic flocculant with low molecular weight, i.e., sodium lignosulfonate, the B is a dendritic organic high-polymer flocculant, i.e., a propenol polyoxyethylene ether sulfonate/maleimide trimethyl sulfonate/propylene sulfonate copolymer, and the C is a zeolite metal organic frame material. The flocculability of the flocculant disclosed by the invention mainly comes from the organic high-polymer flocculant B, and a dendritic structure of the B is subjected to swelling strutting in water, so that the space volume is large, and the effect of sweeping and capturing particles in a suspension system is very strong. The A can be used for accelerating the electric charge adsorption of the flocculant on the surfaces of suspended particles, so as to realize the rapid flocculation of small flocs; and the C is large in specific surface area and high in porosity, so that the performance of adsorption to hydrophilic dyes is very good. According to the composite flocculant, the three ingredients are in synergism, so that the rapid flocculation settling of large flocs is realized, and hydrophilic organic dyes in the printing and dyeing wastewater are effectively removed.
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 country that water resources is poorer, and shortage of water resources and contaminated wastewater have become the principal element of restriction China Economic development.Dyeing is water consumption rich and influential family, and wastewater discharge and the total amount of pollutant occupy the second of national industrial sector 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 quantity discharged is large, pollutent is many, and usually containing dyestuff, slurry, auxiliary agent, finish, soda acid, fiber impurity, sand class material, inorganic salt etc. in waste water, therefore, the process of dyeing waste water is more difficult.At present, method of wastewater treatment mainly contains biochemical treatment process and materialization treatment process two class.The research of biochemical process is ripe, be widely used, but there is the phenomenon of effluent quality instability.Physico-chemical process, usually used as the preprocessing process of biochemical process, guarantees 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, the process making most of non-water-soluble dye granule and colloidal organic matter in dyeing waste water be condensed into mutually large particle then to remove.Compared to other treatment processs, Coagulation Method has the advantages such as technical process is simple, convenient operating maintenance, facility investment is low, floor space is little, and the decreasing ratio of suspension organic pollutant reaches more than 80%, and the clearance of colourity also can reach more than 50%.But traditional chemical coagulation process is not very desirable to the treatment effect of dyeing waste water, flocculation agent hydrophilic dye poor processing effect, flocculation sediment body refuse amount are large and dehydration is difficult.Efficient flocculation agent is the prerequisite of coagulating treatment technique widespread use in treatment of dyeing wastewater.
Single flocculation agent is difficult to the needs meeting treatment of dyeing wastewater, and the composite flocculation agent mutually supplemented by various ingredients combination, each component function is the emphasis that present treatment of dyeing wastewater flocculation agent is studied.Have scholar's research to point out, dendrimer, dendritic polymer polymkeric substance makees flocculation agent, and volume is swept, trapping ability is stronger, and the mutual winding between flocculation agent, adsorptive power are also stronger.
For the problem of flocculation treatment process to hydrophilic dye poor processing effect, it is crucial for preparing the material of hydrophilic fuel advantages of good adsorption effect.Metal-organic framework materials (MOFs) is the novel porous material of a class, and specific surface area is large, porosity is high, and plane of crystal has undersaturated metal active position.Not only different from the porous material such as molecular sieve, gac, MOFs is the compound of organic ligand and metal ion, has good consistency but also has good wetting ability, have good adsorptivity to hydrophilic organics hydrophilicity with organism.
Summary of the invention
The object of the invention is to some problems existed for current dyeing waste water coagulating treatment technique, there is provided a kind of for composite flocculation agent that is efficient during treatment of dyeing wastewater, rapid flocculation sedimentation, this composite flocculation agent not only suspended substance to deviate from ability strong, to hydrophilic dye, also there is very high 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, be grouped into by A, B, C tri-kinds of one-tenth, wherein A is a kind of low-molecular-weight organic natural anionic flocculant-sodium lignosulfonate, B is dendroid organic polymer coargulator-allyl alcohol polyethenoxy ether sulfonate/maleimide trimethylammonium 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 trimethylammonium sulfonate/propene sulfonic acid salt copolymer three kinds of monomer components is as follows: molar percentage 20 ~ 60% shared by allyl alcohol polyethenoxy ether sulfonate; Molar percentage 20 ~ 60% shared by maleimide trimethylammonium sulfonate; Molar percentage 20 ~ 60% shared by Sodium allyl sulphonate.
The molecular weight of the monomer allyl alcohol polyethenoxy ether sulfonate that described synthetic copolymer B is used 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 ion.
The flocculence of composite flocculation agent of the present invention mainly comes from organic polymer coargulator B, and the dendritic structure of B is swelling in water to be strutted, and spatial volume is large, has very strong volume to sweep trapping effect, promote the quick formation of large coagulated particles to the particle in suspension system.B makees separately flocculation agent and has had better to flocculating effect, and adding of A mainly accelerates the charge adsorption of flocculation agent on suspended particle surface, realizes the quick cohesion of little flco; Xylogen is the complicated phenol polymer of one formed by four kinds of alcohol monomers on the other hand, has good consistency, the volume of B flocculation agent can be promoted to sweep trapping, accelerates the flocculation process of little flocs unit with organic polymer coargulator B.The specific surface area of C is large, porosity is high, surface not only electronegative, but also have good wetting ability, to hydrophilic dye, there is good absorption property.And the organic constituent in C skeleton construction makes itself and A and B adsorb to be wound around, to form super large flco, accelerate settling of floccus further.Three kinds of component A in composite flocculation agent of the present invention, B, C synergy, not only achieve the rapid flocculation sedimentation of big flocculating body, and effectively eliminate the wetting ability organic dye in dyeing waste water, flocculation process is effective, speed is fast.
Advantage of the present invention be mainly reflected in following some:
(1) from the tree-shaped copolymerized macromolecule flocculation agent of synthesis itself, there is higher flocculating property, can flocculation agent be used alone as;
(2) introducing has wetting ability and organophilic MOFs material simultaneously, improves the problem of traditional flocculant to hydrophilic dye poor removal effect;
(3) mutually adsorb winding between three kinds of components in composite flocculation agent, the flco of formation is large and closely knit, and flocculation settling velocity is fast.This composite flocculation agent is used for dye wastewater treatment, and suspended substance, colourity and COD clearance are high.Further, the preparation of this composite flocculation agent is simple, and consumption is few, and the mud thus produced is few, secondary pollution is low, has huge application potential.
Embodiment
Below by specific embodiment, the present invention will be further described in detail.The present embodiment provides premised on invention technical 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 adopted is formulated by following mass percent by A, B, C tri-kinds of compositions: A:B:C=30%:60%:10%; The mol ratio of three kinds of components wherein in B is allyl alcohol polyethenoxy ether sulfonate: maleimide trimethylammonium sulfonate: propene sulfonic acid salt copolymer=1:1:1.
First be adjusted between 6 ~ 9 by the pH value of dyeing waste water, water temperature remains on 30 ~ 45
oc.Then according to the ratio adding 300mg component A, 600mg B component and 100mg component C in the pending waste water of 1L, A, B, C are added in waste water successively, dosing process with stirring, each dosing interval 30s.Treat that flocculant concentration is complete, then leave standstill after slowly stirring 1min, flocculating settling time 3.5min.COD decreasing ratio can reach 92%, and percent of decolourization is up to 98.5%.The flco formed is large, settling velocity is fast.
embodiment 2:
The dyeing waste water of printing and dyeing mill identical with embodiment 1 is processed:
The composite flocculation agent adopted is formulated by following mass percent by A, B, C tri-kinds of compositions: A:B:C=40%:45%:15%; The mol ratio of three kinds of components wherein in B is still 1:1:1.
First be adjusted between 6 ~ 9 by the pH value of dyeing waste water, water temperature remains on 30 ~ 45
oc.Then according to the ratio adding 400mg component A, 450mg B component and 150mg component C in the pending waste water of 1L, A, B, C are added in waste water successively, dosing process with stirring, each dosing interval 30s.Treat that flocculant concentration is complete, then leave standstill after slowly stirring 1min, flocculating settling time 5min.COD decreasing ratio can reach 86%, and percent of decolourization is up to 99%.The flco formed is large, settling velocity is fast.
embodiment 3:
Process the dyeing waste water from the printing and dyeing mill being different from embodiment 1, the COD content in this factory's dyeing waste water and colourity are all higher than the dyeing waste water in embodiment 1.
The composite flocculation agent adopted is formulated by following mass percent by A, B, C tri-kinds of compositions: A:B:C=25%:60%:15%; The mol ratio of three kinds of components wherein in B is still 1:1:1.
First be adjusted between 6 ~ 9 by the pH value of dyeing waste water, water temperature remains on 30 ~ 45
oc.Then according to the ratio adding 250mg component A, 600mg B component and 150mg component C in the pending waste water of 1L, A, B, C are added in waste water successively, dosing process with stirring, each dosing interval 30s.Treat that flocculant concentration is complete, then leave standstill after slowly stirring 1.5min, flocculating settling time 4min.COD decreasing ratio can reach 87%, and percent of decolourization is up to 98%.The flco formed is large, settling 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 A, B, C tri-kinds of one-tenth, wherein A is a kind of low-molecular-weight organic natural anionic flocculant-sodium lignosulfonate, B is dendroid organic polymer coargulator-allyl alcohol polyethenoxy ether sulfonate/maleimide trimethylammonium sulfonate/propene sulfonic acid salt copolymer, and C is zeolites metal-organic framework material.
2. the composite flocculation agent for treatment of dyeing wastewater according to claim 1, is characterized in that: the proportioning of each component of described composite flocculation agent is as follows: A:B:C=10 ~ 50%:30 ~ 70%:5 ~ 25%.
3. the composite flocculation agent for treatment of dyeing wastewater according to claim 1, is characterized in that: the molar content of the allyl alcohol polyethenoxy ether sulfonate in the B component of described composite flocculation agent/maleimide trimethylammonium sulfonate/propene sulfonic acid salt copolymer three kinds of monomer components is as follows:
Allyl alcohol polyethenoxy ether sulfonate proportion 20 ~ 60%; Maleimide trimethylammonium sulfonate proportion 20 ~ 60%; Sodium allyl sulphonate proportion 20 ~ 60%.
4. the composite flocculation agent for treatment of dyeing wastewater according to claim 1, is characterized in that: the molecular weight of the monomer allyl alcohol polyethenoxy ether sulfonate of described synthetic copolymer is 500 ~ 10000.
5. the composite flocculation agent for treatment of dyeing wastewater according to claim 1, is characterized 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 ion.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108178266A (en) * | 2018-03-09 | 2018-06-19 | 王欣欣 | A kind of 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 |
| CN111635530A (en) * | 2020-06-05 | 2020-09-08 | 广西大学 | Hyperbranched alkali lignin-based amphoteric adsorption material and preparation method and application thereof |
| CN112320878A (en) * | 2020-09-30 | 2021-02-05 | 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 |
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| JPS55104691A (en) * | 1978-10-23 | 1980-08-11 | Kurita Water Ind Ltd | Detoxication of cathionic coagulant |
| 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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2015
- 2015-05-19 CN CN201510255114.5A patent/CN104925929B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS55104691A (en) * | 1978-10-23 | 1980-08-11 | Kurita Water Ind Ltd | Detoxication of cathionic coagulant |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108178266A (en) * | 2018-03-09 | 2018-06-19 | 王欣欣 | A kind of efficient sewage treatment flocculant and preparation method thereof |
| 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 |
| CN111635530A (en) * | 2020-06-05 | 2020-09-08 | 广西大学 | Hyperbranched alkali lignin-based amphoteric adsorption material and preparation method and application thereof |
| 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 |
| CN112320878A (en) * | 2020-09-30 | 2021-02-05 | 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 |
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