CN101249996A - Organic high polymer coagulant and preparation method thereof - Google Patents
Organic high polymer coagulant and preparation method thereof Download PDFInfo
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- CN101249996A CN101249996A CNA2007100507425A CN200710050742A CN101249996A CN 101249996 A CN101249996 A CN 101249996A CN A2007100507425 A CNA2007100507425 A CN A2007100507425A CN 200710050742 A CN200710050742 A CN 200710050742A CN 101249996 A CN101249996 A CN 101249996A
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Abstract
The invention relates to an organic polymer flocculating agent and a process for preparation thereof, in particular to a water-soluble polymer flocculating agent and a process for preparation thereof. The molecular weight of the water-soluble polymer flocculating agent is 1*10 4-1*10 6, and the flocculating agent is formed through mixing and copolymerization of three monomers of itaconate, quaternized alkyl acrylic dialkyl aminoethyl ester and tertiary amine alkyl acrylic dialkyl aminoethyl ester, a certain amount of polymerization promoter is added, previously redox initiator is employed, and latterly water-soluble azo type initiator is added, thereby guaranteeing sufficiently high molecular weight of the flocculating agent, increasing conversion rate and reducing monomer content. The monomers selected by the product are nontoxic, and the process for preparation is simple and is suitable for promotion and application, under the condition of unchanging the anion degree, the cationic degree can be freely regulated, and the application range is enabled to be wider. The flocculating agent combines the advantages of the three monomers; thereby the performance of the flocculating agent is more excellent with more varieties of processed wastewater, less input amount and more obvious social and economical benefits.
Description
Technical field
The present invention relates to a kind of organic polymer coargulator and preparation method thereof, especially a kind of water soluble organic polymer flocculation agent and preparation method thereof.
Background technology
Existing flocculation agent occupies an important position in the solid-liquid separation of water and wastewater treatment and production process.In the application practice of water treatment, hydrometallurgy both domestic and external, petrochemical industry, papermaking, iron and steel, weaving, printing and dyeing, food, the wastewater treatment of multiple industry such as brewageing use the water treatment ratio of flocculence to account for 55%～75%.And tap water industry almost 100% uses flocculence as the water purification means.Because flocculence has significantly technical economic benefit in water treatment and sludge dewatering, the production of external polymeric flocculant and the nearly annual growth rate that still kept about 6.5% in 5 years of consumption.China's inorganic flocculating agent and organic polymer coargulator maintain average annual 10% rate of growth.Wherein Amphiphatic high polymer coagulant and cationic flocculant are to develop two big classes faster.Cationic as quaternary amine polymerization or quaternary amine and acrylamide through the polyacrylamide that the Mannich reaction copolymerization forms, utilizing the synthetic cationic polyacrylamide of Mannich reaction modification and graft copolymerization is present most widely used positively charged ion synthetic polymeric flocculant.Chinese invention patent ZL03133998.0 discloses a kind of cationic high-molecular flocculant and preparation method thereof, is specially the cationic high-molecular flocculant that quaternized back of dimethylaminoethyl methacrylate and acrylamide copolymerization form.Because the organic content in modern industry and the sanitary wastewater increases greatly, the organic fine particles surface is electronegative, thereby cationic flocculant has flocculating effect preferably, but in sludge treatment, because mud is putrid to be proceeded, use separately cationic flocculant, can cause the rate of recovery of suspended substance low, dewatered cake water ratio height.The zwitterionic classes flocculation agent has the feature of zwitterion concurrently, than cationic flocculant stronger flocculation is arranged, settlement action, performance to sludge dewatering is more obvious, more effective, dosage is less, can also play the effect of metal chelator, owing to contain the subparticle and the colloid of positive and negative charge in many sewage, need to handle with the zwitter-ion flocculation agent, thereby the zwitterionic classes flocculation agent has more advantage in water treatment, amphoteric flocculating agent has the moon concurrently, the characteristics of cationic group, be applicable to various wastewater treatments of different nature, to sludge dewatering, electrical neutralization is arranged not only especially, the absorption bridge linking effect, and intermolecular " winding " package action is arranged, make the mud granule of processing thick, dehydration property is good, even to the mud of different degree of spoilage of different nature, also can bring into play the filtrating aid function that dewaters preferably.Entered since the nineties in 20th century, the research and development to amphiprotic polyacrylamide (PAM) abroad is tending towards active, and the Japan amphoteric ion type PAM of exploitation has recently had industrial applications value technically and economically.MORl etc. is with quaternary ammonium salt alkylamino alkyl methacrylate, quaternary ammonium salt alkylamino alkyl acrylate, vinylformic acid (ester) and acrylamide quaternary monomer copolymerizable among the Japanese Patent JP2001179300, prepared Amphiphatic high polymer coagulant, paper-making industrial waste water has been had flocculating effect preferably.Particularly in recent years, the soluble amphoteric polymer had obtained bigger development in the application of water treatment field, mainly as flocculation agent, sludge dehydrating agent and metal chelator etc.Chinese invention patent ZL97123344.6 discloses a kind of amphoteric polyacrylamide flocculating agent and preparation method thereof, specifically is the Amphiphatic high polymer coagulant that is formed by third rare acid amides, vinylformic acid (salt) and the rare acyl-oxygen trimethyl ammonium chloride of methyl-prop binary polymerization.Liu those skilled in the art offers the tinkling of pieces of jade, and (nineteen eighty-two is graduated from South China Science ﹠ Engineering University's chemical engineering specialty, the researchist that smelting is visited of the Chinese Academy of Sciences, the chief of research office of equipment institute of incumbent Luoyang Petrochemical engineering corporation) can make well behaved APAM flocculation agent by hydrolysis reaction and mannich reaction, the synthetic amphiprotic polyacrylamide all is superior to cationic-type polyacrylamide to the flocculating effect of health paper plant sewage and yellow plate paper factory sewage.(nineteen eighty-two is graduated from Taiyuan engineering college to those skilled in the art Li Wanjie, the incumbent chemical industry dean of Institutes Of Technology Of Taiyuan, professor, master supervisor; Mainly be engaged in polymer chemistry, the instruction that the polymkeric substance synthesis technique is learned and the research of functional polymer) be that raw material passes through the Manny phase (Mannich) and reacts and synthesized the amphoteric polyacrylamide flocculating agent with carboxyl and amine methyl with partially hydrolyzed polyacrylamide, inquired into the influence of reaction conditions, studied factor that influences product stability and the method that keeps stability the amination degree.And its product performance have been carried out application test.To steelworks comprehensive wastewater, woollen mill's waste water, and the solid-liquid separation of Tai-Ace S 150 ore pulp carried out the simultaneous test of different flocculation agents.The result shows that the amphoteric flocculating agent treatment effect obviously is better than positively charged ion and anionic flocculant.Those skilled in the art Ma Xichen (the Chinese matrix material director of association, Daliang City's coating president of association, Dalian Polytechnic College professor) is a raw material with starch-acrylamide grafted copolymer, by Mannich reaction and hydrolysis reaction, synthesized the Amphiphatic high polymer coagulant that has the yin, yang ionic group simultaneously, and Amphiphatic high polymer coagulant has been used for handling printing and dyeing and papermaking wastewater.Chinese invention patent application 200610020227.8 discloses a kind of water-soluble organic amphiprotic polymeric flocculant and preparation method, specifically is the Amphiphatic high polymer coagulant that amino second fat of quaternary ammoniated (alkyl) propenoic acid dialkyl and methylene-succinic acid (salt) copolymerization form.This flocculation agent handle well-drilling waste water, leather-making waste water, rubbish oozes rate liquid that effect is preferably all arranged.But, above-mentioned synthetic polymeric flocculant still has some different defectives: 1, synthetic polymeric flocculant has been selected acrylamide, vinylformic acid (salt), the toxilic acid big monomers of toxicity such as (acid anhydrides) for use, and the small molecules after polymerization residual monomer and the decomposition all can produce secondary pollution like this; 2, Mannich modified polyacrylamide class amphoteric ion high polymer flocculation agent is not suitable for and handles the high waste water of pH, and package stability is not high; 3, from the angle of Green Chemistry environmental protection, Mannich reaction does not meet the Green Chemistry environmental protection requirement.Therefore, be badly in need of providing a kind of organic polymer coargulator that does not cause secondary pollution, package stability height and meet the Green Chemistry environmental requirement.
Summary of the invention
The purpose of this invention is to provide and a kind ofly do not cause secondary pollution, package stability high and meet organic polymer coargulator of Green Chemistry environmental requirement and preparation method thereof.
Cationic monomer in of the present invention is selected quaternized (alkyl) propenoic acid dialkyl amino ethyl ester, with reference to polymethyl acyl-oxygen hexyl trimethyl ammonium chloride P (DMC) is a kind of cation polymeric flocculant of excellent property, it is controlled with its electric charge degree, charge distribution is even, the molecular weight height, the scope of application is wide, cost is low and get most of the attention, be widely used in the processing of various industry and sanitary wastewater, it is few that P in wastewater treatment (DMC) has a dosage, the product sludge quantity is few, the processing efficiency advantages of higher.And anionic monomer selects methylene-succinic acid, the intramolecularly of methylene-succinic acid to contain two active carboxyls and a two key.Depend on active pair of key of methylene-succinic acid intramolecularly and two carboxyls, can react, reach the de-odorised purpose with acid repugnant substance such as alkaline malodorant such as ammonia, amine or hydrogen sulfide.The amino second fat structure of other neutral monomer tertiary amineization (alkyl) propenoic acid dialkyl is close with positively charged ion can polymerization to obtain polymer, by in conjunction with three kinds of monomeric advantages.Can reach following purpose:
1, selects for use monomer nontoxic, do not cause secondary pollution substantially, more meet the Green Chemistry requirement.
2, overcome because the shortcoming of polyacrylamide flocculation agent costs and poor dehydration results, unstable properties.
3, under the condition that does not change the negatively charged ion degree, regulate the cationic degree of macromolecular chain.
4, improve water treatment effect.But improve the biochemical treatment of CODcr clearance and waste water etc.
A kind of organic polymer coargulator of the present invention is characterized in that its molecular weight is 1 * 10
4～1 * 10
6, it be by
Monomer 1: itaconate
X:H, Na or K;
Monomer 2: quaternized alkyl acrylic dialkyl amido ethyl ester
R in the formula
1Be H, CH
3R
2=R
3=R
4Or R
2=R
3≠ R
4, R
2, R
3, R
4Be C
1～C
4Alkyl; Y is Cl, Br;
Monomer 3: tertiary amine alkyl acrylic dialkyl amido ethyl ester
R in the formula
5Be H, CH
3R
6=R
7Or R
6≠ R
7, R
6, R
7Be C
1～C
4Alkyl;
Three kinds of terpolymers that monomer polymerization forms, its structure is:
X is H, Na or K; R
1Be H, CH
3R
2=R
3=R
4Or R
2=R
3≠ R
4, R
2, R
3, R
4Be C
1～C
4Alkyl; R
5Be H, CH
3R
6=R
7Or R
6≠ R
7, R
6, R
7Be C
1～C
4Alkyl, Y are Cl, Br.
The preparation method of a kind of organic polymer coargulator among the present invention is characterized in that adopting following process: with itaconate, quaternized alkyl acrylic dialkyl amido ethyl ester and tertiary amine alkyl acrylic dialkyl amido ethyl ester is the copolymerization monomer raw material, add reagent and additive in polymerization earlier, use redox initiator then, again with water-soluble azo class initiator trigger monomer, after aqueous solution copolymerization close and make.
Comonomer described in the present invention is the copolymerization monomer of itaconate, quaternized alkyl acrylic dialkyl amido ethyl ester and tertiary amine alkyl acrylic dialkyl amido ethyl ester, the polymerization single polymerization monomer total concn is 10%～40% in the aqueous solution, the mol ratio that quaternized alkyl acrylic dialkyl amido ethyl ester accounts for total monomer is 40%～80%, the mol ratio that itaconate accounts for total monomer is 3%～30%, and the mol ratio that tertiary amine alkyl acrylic dialkyl amido ethyl ester accounts for total monomer is 15%～40%.
Redox initiator is made of Oxidizing and Reducing Agents described in the present invention, described oxygenant be hydrogen peroxide, ammonium persulphate, Sodium Persulfate and Potassium Persulphate one of them, reductive agent is an one or more combination in sodium bisulfite, S-WAT, Sulfothiorine, sodium hyposulfate, Sodium Pyrosulfite, Potassium hydrogen sulfite, potassium sulfite, ammonium sulphite and the sulfurous acid iron, the mole dosage ratio of Oxidizing and Reducing Agents is 1.0: 1～2.5: 1, and consumption is 0.05%～5% of a monomer mass.
Among the present invention water-soluble azo class initiator be the two 2-methyl propanamide hydrochlorides of azo diisobutyl amidine hydrochloride, azo-bis-iso-dimethyl, azo and the two 4-cyanovaleric acids of azo one of them, consumption is 0.05%～1.0% of a monomer mass.
What can be used as reagent and additive in polymerization among the present invention is one or more mixture in diethanolamine, trolamine, the edta and its sodium salt, and consumption is 0.025%～1.0% of a monomer mass.
The method for preparing organic polymer coargulator among the present invention is at room temperature itaconate, tertiary amine alkyl acrylic dialkyl amido ethyl ester and distilled water to be packed in the reactor; Begin to stir, regulate pH to 2.0～8.0; Vacuumize three times, each time is 10min, middle logical nitrogen twice, and each time is 5min; Under continuously logical nitrogen situation, slowly drip quaternized alkyl acrylic dialkyl amido ethyl ester and add reagent and additive in polymerization, redox initiator, be warming up to 30 ℃～50 ℃, the copolyreaction time is controlled at 2～8h; Add water-soluble azo class initiator, be warming up to 70 ℃～100 ℃, continue reaction 2～6h; Be cooled to room temperature and promptly obtain water-soluble organic cation high molecular polymer.Employed reaction unit such as thermometer, logical nitrogen device and agitator four neck reactors etc. are existing test and produce commercially available equipment commonly used among the present invention.
The pH of the aqueous solution of telo merization is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash and the sodium bicarbonate aqueous solution among the present invention.Guaranteed that so used initiator can reach optimal efficiency of initiation.
The preparation method of organic polymer coargulator is to above-mentioned polymerization single polymerization monomer, redox initiator, water-soluble azo class initiator, reagent and additive in polymerization etc. and have no special requirements among the present invention.For example, to copolymerization monomer, can be expressed as general formula at general formula is CH2=C (COOH)
2, X is H, Na or K; General formula is that R can be for containing the alkyl of 1～4 carbon atom in the compound of quaternized alkyl diallyl of (CH2=CH-CH2) 2NR2Y, and Y can be Cl, Br; General formula is CH
2=C (R
1) COOCH
2CH
2N (R
2R
3R
4) in the compound of quaternized alkyl acrylic dialkyl amido ethyl ester of Y, R
1Can be H, CH
3, R
2, R
3, R
4Can be for containing the alkyl of 1～4 carbon atom, Y can be Cl, Br, general formula is CH
2=C (R
5) COOCH
2CH
2N (R
6R
7) the compound of tertiary amine alkyl acrylic dialkyl amido ethyl ester in, R
5Can be H, CH
3, R
6, R
7Can be for containing the alkyl of 1～4 carbon atom.Experimental result shows, for use properties and the economy that makes the prepared water soluble organic amphoteric high molecule copolymer of the present invention reaches best effect, the monomer whose total concn is controlled at 10%～40%, the mol ratio that quaternized alkyl acrylic dialkyl amido ethyl ester accounts for monomer 1, monomer 2 and monomer 3 total amounts is 40%-80%, the mol ratio that itaconate accounts for total monomer is 3%-30%, and the mol ratio that tertiary amine alkyl acrylic dialkyl amido ethyl ester accounts for total monomer is 15%-40%.
As described above, the present invention adds redox initiator when polymerization low temperature in early stage, its objective is to obtaining the multipolymer of macromolecule.The oxygenant of selecting for use can be in hydrogen peroxide, ammonium persulphate, Sodium Persulfate and the Potassium Persulphate any one, reductive agent can be in sodium bisulfite, S-WAT, Sulfothiorine, sodium hyposulfate, sodium pyrosulfate, Potassium hydrogen sulfite, potassium sulfite, ammonium sulphite and the sulfurous acid iron any one.Experimental result shows the mole dosage ratio of redox initiator at 1.0: 1 ~ 2.5: 1, and consumption can reach the ideal effect in 0.05% ~ 5% scope of monomer 1, monomer 2 and monomer 3 total masses.
As described above, the present invention adds water-soluble azo class initiator during comparatively high temps in the polymerization later stage, can select in azo diisobutyl amidine hydrochloride, azo-bis-iso-dimethyl, the two 2-methyl propanamide hydrochlorides of azo and the two 4-cyanovaleric acids of azo any one for use.Experimental result shows that its consumption monomer whose transformation efficiency in 0.05% ~ 1.0% scope of monomer 1, monomer 2 and monomer 3 total masses can reach more than 90%.
As described above, the present invention adds reagent and additive in polymerization in polyreaction, the mixture of one or more in diethanolamine, trolamine, the edta and its sodium salt.Experimental result shows that its consumption is in 0.025% ~ 1.0% scope of monomer 1, monomer 2 and monomer 3 total masses, the copolymerization that redox initiator is caused obtains the water-soluble organic cation high-molecular copolymer of macromolecule, and its rate of polymerization is controlled.
The present invention is with three kinds of monomer mixing copolymerization, adds a certain amount of reagent and additive in polymerization, adopts redox initiator in early stage, add water-soluble azo class initiator in the later stage, guaranteed that flocculation agent has sufficiently high molecular weight, improved transformation efficiency again, reduced monomer content.
The present invention compares with the existing water soluble organic polymer flocculation agent that is used for water treatment, has the following advantages:
1, selected monomer is nontoxic;
2, the preparation method is simple, is suitable for and applies;
3, under the condition that does not change the negatively charged ion degree, can regulate cationic degree arbitrarily, it is more extensive to make it the scope of application;
4, combine three monomeric advantages, performance is excellent more, and it is more to handle kind of waste water, and input amount is little (to be 1 ~ 100mg/L) only, to have tangible economic and social benefit.
Content of the present invention further illustrates with the following Examples, but content of the present invention is not limited only to content related among the embodiment.
Description of drawings
Fig. 1 is the infrared spectrum of a kind of organic polymer coargulator among the present invention.
Embodiment
Embodiment 1:
Embodiment 2:
Embodiment 3:
NO1,2, the 3 water-soluble organic cation high-molecular copolymers of above embodiment 1,2 preparations are used for the data that well-drilling waste water obtains and see Table 1,2.
Table 1. waste water quality index
| Water-quality guideline | Well-drilling waste water |
| pH COD Cr(mg/L) turbidity (NTU) | 7.8 38278 167 |
Table 2. flocculation agent is handled the well-drilling waste water result
| Flocculation agent | COD CrClearance (%) | Turbidity removal rate (%) |
| NO.1 NO.2 NO.3 | 56.77 88.18 89.24 | 78.13 90.61 91.91 |
Annotate: the flocculation agent consumption is 10mg/L, can be earlier before handling the pH of waste water be transferred to 3 ~ 5.
Claims (8)
1, a kind of organic polymer coargulator is characterized in that its molecular weight is 1 * 10
4～1 * 10
6, it is by monomer 1: itaconate
X:H, Na or K;
Monomer 2: quaternized alkyl acrylic dialkyl amido ethyl ester
R in the formula
1Be H, CH
3R
2=R
3=R
4Or R
2=R
3≠ R
4, R
2, R
3, R
4Be C
1～C
4Alkyl; Y is Cl, Br;
Monomer 3: tertiary amine alkyl acrylic dialkyl amido ethyl ester
R in the formula
5Be H, CH
3R
6=R
7Or R
6≠ R
7, R
6, R
7Be C
1～C
4Alkyl; Three kinds of terpolymers that monomer polymerization forms, its structure is:
X is H, Na or K; R
1Be H, CH
3R
2=R
3=R
4Or R
2=R
3≠ R
4, R
2, R
3, R
4Be C
1～C
4Alkyl; R
5Be H, CH
3R
6=R
7Or R
6≠ R
7, R
6, R
7Be C
1～C
4Alkyl, Y are Cl, Br.
2, a kind of preparation method of claim 1 organic polymer coargulator, it is characterized in that adopting following process: with itaconate, quaternized alkyl acrylic dialkyl amido ethyl ester and tertiary amine alkyl acrylic dialkyl amido ethyl ester is the copolymerization monomer raw material, add reagent and additive in polymerization earlier, use redox initiator then, again with water-soluble azo class initiator trigger monomer, after aqueous solution copolymerization close and make.
3, method as claimed in claim 2, it is characterized in that comonomer is the copolymerization monomer of itaconate, quaternized alkyl acrylic dialkyl amido ethyl ester and tertiary amine alkyl acrylic dialkyl amido ethyl ester, the polymerization single polymerization monomer total concn is 10%～40% in the aqueous solution, the mol ratio that quaternized alkyl acrylic dialkyl amido ethyl ester accounts for total monomer is 40%～80%, the mol ratio that itaconate accounts for total monomer is 3%～30%, and the mol ratio that tertiary amine alkyl acrylic dialkyl amido ethyl ester accounts for total monomer is 15%～40%.
4, method as claimed in claim 2, it is characterized in that described redox initiator is made of Oxidizing and Reducing Agents, described oxygenant be hydrogen peroxide, ammonium persulphate, Sodium Persulfate and Potassium Persulphate one of them, reductive agent is an one or more combination in sodium bisulfite, S-WAT, Sulfothiorine, sodium hyposulfate, Sodium Pyrosulfite, Potassium hydrogen sulfite, potassium sulfite, ammonium sulphite and the sulfurous acid iron, the mole dosage ratio of Oxidizing and Reducing Agents is 1.0: 1～2.5: 1, and consumption is 0.05%～5% of a monomer mass.
5, method as claimed in claim 2, it is characterized in that water-soluble azo class initiator be the two 2-methyl propanamide hydrochlorides of azo diisobutyl amidine hydrochloride, azo-bis-iso-dimethyl, azo and the two 4-cyanovaleric acids of azo one of them, consumption is 0.05%～1.0% of a monomer mass.
6, method as claimed in claim 2, what it is characterized in that can be used as reagent and additive in polymerization is one or more mixture in diethanolamine, trolamine, the edta and its sodium salt, consumption is 0.025%～1.0% of a monomer mass.
7, method as claimed in claim 2 is in the reactor that it is characterized in that at room temperature itaconate, tertiary amine alkyl acrylic dialkyl amido ethyl ester and distilled water being packed into; Begin to stir, regulate pH to 2.0～8.0; Vacuumize three times, each time is 10min, middle logical nitrogen twice, and each time is 5min; Under continuously logical nitrogen situation, slowly drip quaternized alkyl acrylic dialkyl amido ethyl ester, add reagent and additive in polymerization, redox initiator simultaneously, be warming up to 30 ℃～50 ℃, the copolyreaction time is controlled at 2～8h; Add water-soluble azo class initiator again, be warming up to 70 ℃～100 ℃, continue reaction 2～6h; Be cooled to room temperature and get the water soluble organic polymer polymkeric substance.
8, method as claimed in claim 2, the pH that it is characterized in that the aqueous solution of telo merization is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash and the sodium bicarbonate aqueous solution.
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