CN102070233B - Quaternary ammonium salt positive ion-type organic polymeric flocculant and preparation method thereof - Google Patents

Quaternary ammonium salt positive ion-type organic polymeric flocculant and preparation method thereof Download PDF

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CN102070233B
CN102070233B CN2010105613579A CN201010561357A CN102070233B CN 102070233 B CN102070233 B CN 102070233B CN 2010105613579 A CN2010105613579 A CN 2010105613579A CN 201010561357 A CN201010561357 A CN 201010561357A CN 102070233 B CN102070233 B CN 102070233B
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quaternary ammonium
water
waste water
ammonium salt
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CN102070233A (en
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刘明华
郑堰日
黄漂漂
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福州大学
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Abstract

The invention relate to a quaternary ammonium salt positive ion-type organic polymeric flocculant and a preparation method thereof. The polymeric flocculant contains a quaternary ammonium group, the positive ion degree is between 40% and 50%, and the raw material of the flocculant comprises the following components in parts by mass: 5-50 parts of dimethylamine, 1-45 parts of urea, 20-60 parts of epichlorohydrin, 1-40 parts of water, 1-5 parts of catalyst and 2-8 parts of cross-linking agent. In the invention, the product is less in dosage, is obvious in waste water-treating effect, and is especially suitable for treating slurry-preparing and paper-making paper waste water, printing and dyeing waste water and organic waste water containing active groups; and the preparation method is simple, the process conditions are mild, the preparation method is carried out by adopting a conventional device under the ordinary pressure, and no three wastes are discharged.

Description

A kind of quaternary ammonium salt cationic type organic polymer coargulator and preparation method thereof

Technical field

The invention belongs to fine chemistry industry and field of environment protection, more specifically relate to a kind of quaternary ammonium salt cationic type organic polymer coargulator and preparation method thereof.

Background technology

Along with increasing rapidly of China's economy, more and more enterprises is about to face the problem of shortage of water resources, and meanwhile, water environment pollution is also more and more serious.Paper industry and dyeing are the water rich anies influential family of two great traditions, also are the important source of pollution that cause water pollution.At present, China's paper-making industry is in the period of high speed development, it is reported that the production and consumption average year amplification of China's paper industry is 18% over nearly 10 years.But be limited by the deficiency of fund and technology; China's paper-making industry production technology generally lags behind developed country; Utilization rate of raw materials is not high, and intermediate products a large amount of in the paper process do not change into product, are discharged into the pollutent that becomes the serious harm environment in the factory effluent.Simultaneously, along with developing rapidly of printing and dyeing and dyestuffs industries, the pollution problem that waste water from dyestuff brought is serious day by day.Characteristics such as this type waste water has that the water yield is big, the organic pollutant content of complicated component, difficult degradation is high, colourity is dark.According to statistics, the quantity discharged of China's paper-making industrial waste water and dyeing waste water and COD CrQuantity discharged occupies the first place of domestic other kinds industrial discharge amount; Its pollution to water surrounding is the most serious; Therefore; Paper waste and dyeing waste water are effectively handled, and the matter of utmost importance of paper industry and dyeing prevention and cure of pollution still is not the matter of utmost importance that national trade effluent carries out processing up to standard yet.。

At present; In the middle of the lot of domestic and foreign water treatment method; Flocculent precipitation is because of in its technology is simple, easy to operate, the processing efficiency advantages of higher is widely used in industry and domestic water the improvement and recycle, and the quality of its regulation effect is decided by the selection of flocculation agent.Organic cation flocculating agent with its positive polarity, throwing amount less, the mud generation is few etc., and advantage receives much attention; It not only can make the suspensoid particle take off steady flocculation through charge neutralization; But also can react with electronegative solute; Generate insoluble salt, it removed through the flocculation sediment effect, thus development of new efficiently organic cation flocculating agent become the research focus of water treatment field.At present; Study and use more organic cation flocculation agent and mainly contain the dimethyl diallyl ammonium chloride base polymer; Publication number is a kind of polymkeric substance that is formed by dimethyl diallyl ammonia chloride, acrylic amide, vinylformic acid, diethylammonium diallyl ammonia chloride and the poly dimethyl allyl ammonia chloride is composite forms for the patent of " CN 1451612A " promptly discloses; This flocculation agent need not prepared inorganics, can use separately.But at present commercially available flocculation agent kind is more single, and paper waste and dyeing waste water complicated component, presses for the effective organic cation flocculating agent of the more kinds of exploitation.

Epoxy chloropropane-amine polymer is the new and effective water-soluble cationic polymkeric substance of functional groups such as a kind of hydroxyl, amido, quaternary ammonium group; Has the positive charge density height; Molecular weight is big; Advantages such as efficient low-consume are widely used in the oil exploration industry as clay stabilizer, expansion-resisting agent the flocculation agent of oil extraction waste water, emulsion splitter and flotation agent.Meanwhile, because of its outstanding flocculation decoloration performance, also can be applicable to COD such as height such as paper waste and dyeing waste water grade CrIn the Industrial Wastewater Treatment hard to manage of value and high chroma.

Research report about epoxy chloropropane-dimethylamine polymer mainly contains high precious jade, Zhang Hua in recent years; Yue Qinyan etc. the preparation of polyepichlorohydrin amine and decoloration performance thereof [J]. fine chemistry industry, 2005,22 (8): 611-615. opens prosperous army; Zhang Bo, Ai Shiyun etc. the preparation of quaternary ammoniated functional polymer flocculation agent and performance study thereof [J]. journal of Shandong university (version of science), 2006; 41 (5): 134-137. Sun Xun, high precious jade, Zhang Donghua etc. epoxy chloropropane-dimethylamine polymer and Poly aluminum Chloride (PAC) are used for the processing [J] of dyeing waste water. environmental chemistry; 2007,26 (1): 51-54. Wang Su virtue, Lin Bei; Ma Ying etc. the synthetic and performance evaluation [J] of polyquaternium reverse-phase emulsifier. Treatment of Industrial Water, 2008,28 (6): 56-58. Pu carbuncle. the synthetic and application [J] of cation-modified Hydrin. the Guangzhou chemical industry; 2008,36 (6): the yellow new photograph of 31-33., Zhang Zhongyi; Zhang Xiaodong. the preparation of cationic polymers and application performance [J]. chemical industry and engineering, 2009,26 (2): 114-118. but in the building-up process of epoxy chloropropane-dimethylamine polymer; With urea moiety substituted dimethyl amine,, do not see bibliographical information at present both at home and abroad as yet to reduce cost and to improve water treatment effect.

Summary of the invention

In order to overcome the deficiency of prior art; The object of the present invention is to provide a kind of quaternary ammonium salt cationic type organic polymer coargulator; This flocculation agent is applicable to high chroma, high turbidity, contains the processing of the waste water of hardly degraded organic substance, is specially adapted to paper-making effluent, dyeing waste water, contains the processing of the organic waste water of reactive group.

Another object of the present invention is to provide a kind of preparation method of quaternary ammonium salt cationic type organic polymer coargulator, its preparation method is simple, processing condition are gentle, adopts conventional equipment, under normal pressure, carries out, and does not have " three wastes " and discharges.

The present invention implements through following technical scheme.

A kind of quaternary ammonium salt cationic type organic polymer coargulator contains quaternary ammonium group, and cationic degree is between 40%~50%.

The raw material of this flocculation agent and mass fraction thereof are: n n dimetylaniline: 5 parts~50 parts; Urea: 1 part~45 parts; Epoxy chloropropane: 20 parts~60 parts; Water: 1 part~40 parts; Catalyzer: 1 part~5 parts; Linking agent: 2 parts~8 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 50~60 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 75~95 ℃;

(3) add linking agent, reaction 4~7h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature

(4) products therefrom is purified with acetone-absolute ethyl alcohol,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry.

The volume ratio of acetone-absolute ethyl alcohol is 1:1-1:5 in the step (4).

Described catalyzer is sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood one or more a mixture wherein.

Described linking agent is a 1,1,3-tn, 1,4-tetramethylenediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine one or more mixture wherein.

This flocculation agent can be applied in and handle paper-making effluent, dyeing waste water, contain in the organic waste water of reactive group.

The present invention compares with currently available products, has the following advantages and positively effect:

1) dosage is little in wastewater treatment, and the add-on of this flocculation agent is merely 1.0~100mg/L.

2) contained quaternary ammonium group can be used as the COD that flocculation agent is used to reduce waste water CrValue also can be used as discoloring agent and is used for high-colour intensity wastewater to reduce water body chroma.

3) water treatment effect is desirable, waste water COD after treatment CrCan reduce by 66%~86%, colourity can reduce by 95%~100%.

4) compare with currently available products, the water ratio of waste residue can reduce by 50%~60%, and the volume of mud can reduce 50%~70%.

5) waste residue after the processing can be used as the raw material of products such as synthol, super strength water absorbent, paint filler, realizes turning waste into wealth.

6) product stability is good, and is nontoxic, uses and do not receive season and region limits, is convenient to transportation and storage.

7) production technique is simple, and reaction conditions is gentle, and raw materials for production are easy to get, and are with short production cycle, and required equipment is a conventional equipment, is easy to existing chemical plant and practices midwifery.

8) whole process flow does not have the generation of " three wastes " basically, is a kind of free of contamination process for cleanly preparing.

Description of drawings

8 kinds of embodiment flocculant products of Fig. 1 are handled the effect of waste water, annotate: before handling waste water ph is transferred to 7~8; The dosage of flocculation agent is 50mg/L.

The water treatment effect of the flocculant product of Fig. 2 embodiment 5 and PAMC, PAC, PFS is relatively annotated: before handling waste water ph is transferred to 7~8; The dosage of flocculation agent is 50mg/L.

Embodiment

A kind of raw material and mass fraction thereof of quaternary ammonium salt cationic type organic polymer coargulator are: n n dimetylaniline: 5 parts~50 parts; Urea: 1 part~45 parts; Epoxy chloropropane: 20 parts~60 parts; Water: 1 part~40 parts; Catalyzer: 1 part~5 parts; Linking agent: 2 parts~8 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 50~60 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 75~95 ℃;

(3) add linking agent, reaction 4~7h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;

(4) products therefrom is purified with acetone-absolute ethyl alcohol,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry.

The volume ratio of acetone-absolute ethyl alcohol is 1:1-1:5 in the step (4).

Described catalyzer is sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood one or more a mixture wherein.

Described linking agent is a 1,1,3-tn, 1,4-tetramethylenediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine one or more mixture wherein.

The quaternary ammonium salt cationic type organic polymer coargulator that more than prepares is light yellow liquid or pulverulent solids; Contain quaternary ammonium group; Cationic degree is used for paper-making effluent, dyeing waste water, contains the processing of the organic waste water of reactive group between 40%~50%, and its treatment effect is good.

Embodiment 1

A kind of raw material and mass fraction thereof of quaternary ammonium salt cationic type organic polymer coargulator are: n n dimetylaniline: 50 parts; Urea: 2 parts; Epoxy chloropropane: 20 parts; Water: 1 part; Catalyzer: 1 part; Linking agent: 8 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 50 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 95 ℃;

(3) add linking agent, reaction 4h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;

(4) use acetone-absolute ethyl alcohol to purify as 1:1 products therefrom,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry in volume ratio.

Described catalyzer is a sodium hydroxide.

Described linking agent is 1, the 3-tn.

Embodiment 2

A kind of raw material and mass fraction thereof of quaternary ammonium salt cationic type organic polymer coargulator are: n n dimetylaniline: 5 parts; Urea: 45 parts; Epoxy chloropropane: 30 parts; Water: 10 parts; Catalyzer: 2 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 60 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 75 ℃;

(3) add linking agent, reaction 7h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;

(4) use acetone-absolute ethyl alcohol to purify as 1:2 products therefrom,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry in volume ratio.

Described catalyzer is Pottasium Hydroxide and yellow soda ash.

Described linking agent is a 1,1, the mixture of 3-tn.

Embodiment 3

A kind of raw material and mass fraction thereof of quaternary ammonium salt cationic type organic polymer coargulator are: n n dimetylaniline: 45 parts; Urea: 30 parts; Epoxy chloropropane: 35 parts; Water: 20 parts; Catalyzer: 5 parts; Linking agent: 3 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 55 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 80 ℃;

(3) add linking agent, reaction 6h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;

(4) use acetone-absolute ethyl alcohol to purify as 1:3 products therefrom,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry in volume ratio.

Described catalyzer is the mixture of sodium hydroxide, Pottasium Hydroxide and yellow soda ash.

Described linking agent is 1, the 4-tetramethylenediamine.

Embodiment 4

A kind of raw material and mass fraction thereof of quaternary ammonium salt cationic type organic polymer coargulator are: n n dimetylaniline: 40 parts; Urea: 10 parts; Epoxy chloropropane: 60 parts; Water: 40 parts; Catalyzer: 5 parts; Linking agent: 8 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 60 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 95 ℃;

(3) add linking agent, reaction 5h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;

(4) use acetone-absolute ethyl alcohol to purify as 1:4 products therefrom,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry in volume ratio.

Described catalyzer is a salt of wormwood.

Described linking agent is 1,5-pentamethylene diamine, 1, the mixture of 6-hexanediamine.

Embodiment 5

A kind of raw material and mass fraction thereof of quaternary ammonium salt cationic type organic polymer coargulator are: n n dimetylaniline: 30 parts; Urea: 5 parts; Epoxy chloropropane: 40 parts; Water: 30 parts; Catalyzer: 4 parts; Linking agent: 2 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 55 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 90 ℃;

(3) add linking agent, reaction 4h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;

(4) use acetone-absolute ethyl alcohol to purify as 1:5 products therefrom,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry in volume ratio.

Described catalyzer is the mixture of yellow soda ash, salt of wormwood.

Described linking agent is a 1,1,3-tn, 1, the mixture of 4-tetramethylenediamine.

Embodiment 6

A kind of raw material and mass fraction thereof of quaternary ammonium salt cationic type organic polymer coargulator are: n n dimetylaniline: 10 parts; Urea: 1 part; Epoxy chloropropane: 60 parts; Water: 5 parts; Catalyzer: 3 parts; Linking agent: 2 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 60 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 95 ℃;

(3) add linking agent, reaction 7h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;

(4) use acetone-absolute ethyl alcohol to purify as 1:1 products therefrom,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry in volume ratio.

Described catalyzer is the mixture of sodium hydroxide, salt of wormwood.

Described linking agent is 1,3-tn, 1,5-pentamethylene diamine and 1, the mixture of 6-hexanediamine.

Embodiment 7

A kind of raw material and mass fraction thereof of quaternary ammonium salt cationic type organic polymer coargulator are: n n dimetylaniline: 25 parts; Urea: 20 parts; Epoxy chloropropane: 25 parts; Water: 7 parts; Catalyzer: 1 part; Linking agent: 5 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 50 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 75 ℃;

(3) add linking agent, reaction 6h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;

(4) use acetone-absolute ethyl alcohol to purify as 1:3 products therefrom,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry in volume ratio.

Described catalyzer is the mixture of sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood.

Described linking agent is a 1,1,3-tn, 1,4-tetramethylenediamine, 1,5-pentamethylene diamine, 1, the mixture of 6-hexanediamine.

Embodiment 8

A kind of raw material and mass fraction thereof of quaternary ammonium salt cationic type organic polymer coargulator are: n n dimetylaniline: 15 parts; Urea: 40 parts; Epoxy chloropropane: 35 parts; Water: 15 parts; Catalyzer: 5 parts; Linking agent: 2 parts.

The concrete steps that prepare this flocculation agent are:

(1) under 60 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said massfraction;

(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 80 ℃;

(3) add linking agent, reaction 44h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;

(4) use acetone-absolute ethyl alcohol to purify as 1:4 products therefrom,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry in volume ratio.

Described catalyzer is a yellow soda ash.

Described linking agent is 1,4-tetramethylenediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine mixture wherein.

The quaternary ammonium salt cationic type organic polymer coargulator product that will make by method and the step of above 8 kinds of embodiment is used for flocculation, the decolouring of paper-making effluent and dyeing waste water to be handled, and makes comparisons with the treatment effect of cationic polyacrylamide (PAMC), Poly aluminum Chloride (PAC) (PAC), bodied ferric sulfate (PFS) simultaneously.

Adopt beaker stirring means research quaternary ammonium salt cationic type organic high molecular polymer and cationic polyacrylamide (PAMC), Poly aluminum Chloride (PAC) (PAC), bodied ferric sulfate (PFS) as flocculation agent, the discoloring agent flocculating settling effect in water treatment; Get 1000mL paper waste or dyeing waste water in beaker; Regulate the pH value and add a certain amount of flocculation agent; Stir 20s with 300r/min; After stirring 5min with 150r/min again, leave standstill 30min, get supernatant and survey its flocculating settling effect.The water-quality guideline of paper-making effluent and dyeing waste water is seen table 1; The effect of 8 kinds of embodiment flocculant product processing waste water is as shown in Figure 1, and any one embodiment flocculant product (selecting embodiment 5) is more as shown in Figure 2 with the water treatment effect of PAMC, PAC, PFS.

The water-quality guideline of table 1 waste water

Water-quality guideline Paper-making effluent Dyeing waste water The pH value 3.8 12.3 Colourity (doubly) 75 2000 COD Cr(mg/L) 1350 1860

Can know that by Fig. 1 the flocculating property of the quaternary ammonium salt cationic type organic polymer coargulator product of 8 kinds of embodiment is all fine, can effectively handle paper-making effluent and dyeing waste water, reduce the COD in the waste water CrValue and colourity.

Can know by Fig. 2; Under equal dosage condition, the effect that quaternary ammonium salt cationic type organic polymer coargulator is handled paper-making effluent and dyeing waste water obviously is superior to cationic polyacrylamide (PAMC), Poly aluminum Chloride (PAC) (PAC) and three kinds of flocculation agents of bodied ferric sulfate (PFS).

The above is merely preferred embodiment of the present invention, and all equalizations of doing according to claim of the present invention change and modify, and all should belong to covering scope of the present invention.

Claims (3)

1. a quaternary ammonium salt cationic type organic polymer coargulator contains quaternary ammonium group, and cationic degree is characterized in that between 40%~50%: the raw material of this flocculation agent and mass fraction thereof are: n n dimetylaniline: 5 parts~50 parts; Urea: 1 part~45 parts; Epoxy chloropropane: 20 parts~60 parts; Water: 1 part~40 parts; Catalyzer: 1 part~5 parts; Linking agent: 2 parts~8 parts; Described catalyzer is one or more the mixture in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, the salt of wormwood; Described linking agent is a 1,1,3-tn, 1,4-tetramethylenediamine, 1,5-pentamethylene diamine, 1, the mixture of one or more in the 6-hexanediamine;
The concrete steps that prepare this flocculation agent are:
(1) under 50~60 ℃ of conditions, in reactor drum, adds urea, n n dimetylaniline, catalyzer, water successively, be stirred to urea and dissolve fully and mix by said mass fraction;
(2) in reaction system, drip epoxy chloropropane, after dropwising, the temperature of reaction system is slowly risen to 75~95 ℃;
(3) add linking agent, reaction 4~7h postcooling obtains the flaxen organic high molecular polymer liquid product that contains quaternary amines to room temperature;
(4) products obtained therefrom is purified with acetone-absolute ethyl alcohol,, promptly obtain flaxen organic high molecular polymer powdery product 85 ℃ of oven dry.
2. quaternary ammonium salt cationic type organic polymer coargulator according to claim 1 is characterized in that: the volume ratio of acetone-absolute ethyl alcohol is 1:1-1:5 in the step (4).
3. the application of a quaternary ammonium salt cationic type organic polymer coargulator as claimed in claim 1 is characterized in that: this flocculation agent is applied in and handles paper-making effluent, dyeing waste water, contains in the organic waste water of reactive group.
CN2010105613579A 2010-11-27 2010-11-27 Quaternary ammonium salt positive ion-type organic polymeric flocculant and preparation method thereof CN102070233B (en)

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刘明华等.一种新型高效有机无机复合絮凝剂处理制药废水的研究.《福州大学学报(自然科学版)》.2005,第33卷(第1期), *

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