CN101575132B - Dication polyacrylamide flocculating agent and preparation method thereof - Google Patents
Dication polyacrylamide flocculating agent and preparation method thereof Download PDFInfo
- Publication number
- CN101575132B CN101575132B CN2009101155225A CN200910115522A CN101575132B CN 101575132 B CN101575132 B CN 101575132B CN 2009101155225 A CN2009101155225 A CN 2009101155225A CN 200910115522 A CN200910115522 A CN 200910115522A CN 101575132 B CN101575132 B CN 101575132B
- Authority
- CN
- China
- Prior art keywords
- flocculating agent
- acrylamide
- dication
- preparation
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a dication polyacrylamide flocculating agent and preparation method thereof. More than two-thirds of structural units of flocculating agent copolymer are cationization acrylamide, and methyl carbonate quaternary amine ions are introduced into the copolymer. The flocculating agent of the invention has higher hydrophobic nature, favorable flocculation effect, acid resistance, alkali resistance and wide range of suitable pH value, and can be used for treating high concentration dyeing and desizing wastewater; and besides, the inventory rating of the flocculating agent is low, and therefore the use cost can be reduced. The preparation method of the invention simultaneously utilizes the two active groups, namely side-chain amido of acrylamide to generate methyl carbonate quaternary ammoniated cationic acrylamide monomer by Menez reaction, a main chain and trimethyl acyloxy ethide trimethyl ammonium chloride cationic monomer are copolymerized, and the method of environmentally friendly one pot boiling is adopted; and the operation is simple, the cost is low, and the obtained flocculating agent has favorable stability and flocculation effect.
Description
Technical field
The present invention relates to a kind of organic floculant and preparation method thereof, particularly a kind of cationic-type polyacrylamide flocculation agent and preparation method thereof.
Background technology
Composite waste at dyeing is handled, present widely used inorganic flocculating agent such as polymerize aluminum chloride, bodied ferric sulfate etc. and organic floculant such as polyacrylamide etc. all can only be handled lower concentration, the mixing dyeing waste water of low pH value, be unsuitable for handling the dyeing waste water (COD wherein contains organism such as a large amount of difficult carbohydrate of degrading, fat, protein, Mierocrystalline cellulose more than 20000mg/L) of high density.
The patent No. is " ZL03133998.0 ", the Chinese invention patent that name is called " a kind of cationic high-molecular flocculant and preparation method thereof " discloses a kind of flocculation agent, this flocculation agent be dimethylaminoethyl methacrylate after quaternary ammoniated monomer and the multipolymer of acrylamide monomer, this copolymer structure is as follows:
Acrylamide is widely used with a kind of monomer of flocculation agent, have two active groups of easy polymeric carbon carbon backbone chain and amide group side chain, yet this cationic polyacrylamide flocculant agent is that single to have used an active group of acrylamide be the main chain autohemagglutination, so wasted another active group, flocculating effect is limited, the use cost height; Simultaneously, because also there is an active group in this flocculation agent, poor stability is unsuitable for the processing of high-concentration printing and dyeing wastewater.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome the deficiencies in the prior art, to provide a kind of residue to have strong-hydrophobicity, and flocculating effect is good, and use cost is low, is applicable to the Dication polyacrylamide flocculating agent of handling high-concentration dye-printing desizing waste water.
The present invention also will provide a kind of preparation method of above-mentioned flocculation agent, and this method technology is simple, production cost is low, and the no three wastes produce, safety, environmental protection.
For solving above technical problem, a kind of technical scheme that the present invention takes is:
A kind of Dication polyacrylamide flocculating agent is the multipolymer of formula (I) expression:
In the formula (I), m
1, n and m
2Be 3-2*10
4Between integer, and m
1: n 〉=1, m
2: n 〉=1.
Another technical scheme that the present invention takes is:
The preparation method of the flocculation agent of a kind of formula (I) expression is a starting raw material with acrylamide and trimethylammonium acrylyl oxy-ethyl ammonium chloride, comprises the steps:
(1), acrylamide and formaldehyde and dimethylamine generation Manny are reacted now, obtain containing the mixture of the acrylamide of N,N-DMAA and residual volume;
(2), in step (1) gained mixture, add methylcarbonate and react, obtain containing the mixture of the acrylamide of the cationic quaternary ammonium salt monomer of formula (II) expression and residual volume;
(3), the mixture of step (2) gained is mixed with trimethylammonium acrylyl oxy-ethyl ammonium chloride solution, add polymerizing catalyst then and carry out polyreaction, obtain described Dication polyacrylamide flocculating agent.
As preferred version of the present invention, step (1) is carried out in the following manner: at first prepare the aqueous solution of acrylamide, regulate its pH 8～9; Then under normal temperature, in the aqueous solution of acrylamide, add formaldehyde solution, finish, be warming up to 40～60 ℃, insulation reaction is 2～3 hours under this temperature, drips dimethylamine solution then, reacted 3～5 hours down in 40～60 ℃, finish reaction, obtain containing the mixture of the acrylamide of N,N-DMAA and residual volume.
The reaction of step (2) was preferably carried out 1～2 hour under 40 ℃～60 ℃.Polymerizing catalyst described in the step (3) is the mixture that Sodium Persulfate and sodium bisulfite 1: 0.9 by weight ratio～1.1 are formed, and the temperature of polyreaction is 50 ℃～70 ℃, and the reaction times is 4～6 hours.
Step (3) is preferably carried out as follows: at first with the mixture and the trimethylammonium acrylyl oxy-ethyl ammonium chloride solution thorough mixing of step (2) gained, be warming up to 50 ℃～70 ℃, the polymerizing catalyst that will be made into the aqueous solution then adds, reacted 4～6 hours, and finished reaction and promptly get described Dication polyacrylamide flocculating agent.Wherein, the preferable concentration of the aqueous solution of described polymerizing catalyst is 3%～8% (quality).
Because the utilization of technique scheme, the present invention compared with prior art has following advantage:
In the multipolymer as flocculation agent of the present invention, structural unit more than 2/3rds is the acrylamide of cationization, make flocculation agent have stronger hydrophobicity, flocculating effect is good, the methylcarbonate quaternary amine ion of introducing in the multipolymer, acidproof, alkaline-resisting, the pH scope that makes multipolymer be suitable for is wide, is suitable as the cationic polyacrylamide flocculant agent of handling high-concentration dye-printing desizing waste water, in addition, the charging capacity of flocculation agent is few, can reduce use cost.
Preparation method of the present invention utilizes two active groups of acrylamide simultaneously, be that the amide side chain base reacts the quaternary ammoniated cation acrylamide monomer of generation methylcarbonate now by Manny, and main chain and trimethylammonium acyl-oxygen ethyl-trimethyl salmiac cation monomer generation copolymerization, and " treating different things alike " method of employing environmental protection, simple to operate, cost is low, and the gained flocculation agent has advantages of excellent stability and flocculating effect.
Embodiment
Below the specific embodiment of the present invention is described, but be not limited to these embodiment.
Embodiment 1
Preparation method according to the Dication polyacrylamide flocculating agent of present embodiment comprises the steps:
(1), get the 71g acrylamide, make to be dissolved in the 100g distilled water to obtain acrylamide soln, this solution is joined in the four-hole boiling flask of 1L, regulate pH to 8～9 of acrylamide soln then with the aqueous sodium hydroxide solution of 1mol/L.
(2), at room temperature, the formaldehyde solution of 80g 38% time with 40 minutes is added drop-wise in the aforesaid propylene amide solution, heated solution to 50 ℃, react after 2.5 hours, in flask, drip the dimethylamine solution of 120g 40%, continue to react 2.5 hours down, add the methylcarbonate solution of 90g 98% again at 50 ℃, reacted 1.5 hours down at 50 ℃, obtain semi-finished product solution.
(3), get the 146g semi-finished product solution, the trimethylammonium acrylyl oxy-ethyl ammonium chloride solution of itself and 200g 79% is mixed, be heated to 60 ℃, added the polymerization catalyzed agent solution of 10 gram self-controls in per 20 minutes, add altogether 3 times, and keep mixing solutions under 60 ℃, and insulation reaction 5 hours, reaction finishes promptly to obtain described flocculation agent.Wherein, the self-control catalyst solution by persulfuric acid receive, sodium bisulfite and water mixes according to weight ratio at 1: 1: 58.
Embodiment 2
Preparation method according to the Dication polyacrylamide flocculating agent of present embodiment comprises the steps:
(1), get the 71g acrylamide, make to be dissolved in the 100g distilled water to obtain acrylamide soln, this solution is joined in the four-hole boiling flask of 1L, regulate the pH to 8-9 of acrylamide soln then with the aqueous sodium hydroxide solution of 1mol/L.
(2), at room temperature, the formaldehyde solution of 80g 38% time with 40 minutes is added drop-wise in the aforesaid propylene amide solution, heated solution to 50 ℃, react after 2.5 hours, in flask, drip the dimethylamine solution of 120g 40%, continue to react 2.5 hours down, add the methylcarbonate solution of 90g 98% again at 50 ℃, reacted 1.5 hours down at 50 ℃, obtain semi-finished product solution of the present invention.
(3), get the 146g semi-finished product solution, the trimethylammonium acrylyl oxy-ethyl ammonium chloride solution of itself and 190g 79% is mixed, be heated to 60 ℃, added 10 gram self-control catalyst solutions in per 20 minutes, add altogether 3 times, and keep mixing solutions under 60 ℃, and insulation reaction 5 hours, reaction finishes to such an extent that the strong colloid of water white thickness is described flocculation agent.Wherein, the self-control catalyst solution by persulfuric acid receive, sodium bisulfite and water mixes according to weight ratio at 1: 1: 58.
Embodiment 3
Preparation method according to the Dication polyacrylamide flocculating agent of present embodiment comprises the steps:
(1), get the 71g acrylamide, make to be dissolved in the 100g distilled water to obtain acrylamide soln, this solution is joined in the four-hole boiling flask of 1L, regulate the pH to 8-9 of acrylamide soln then with the aqueous sodium hydroxide solution of 1mol/L.
(2), at room temperature, the formaldehyde solution of 80g 38% time with 40 minutes is added drop-wise in the aforesaid propylene amide solution, heated solution to 50 ℃, react after 2.5 hours, in flask, drip the dimethylamine solution of 120g 40%, continue to react 2.5 hours down, add the methylcarbonate solution of 90g 98% again at 50 ℃, reacted 1.5 hours down at 50 ℃, obtain semi-finished product solution of the present invention.
(3), get the 146g semi-finished product solution, the trimethylammonium acrylyl oxy-ethyl ammonium chloride solution of itself and 210g 79% is mixed, be heated to 60 ℃, added 10 gram self-control catalyst solutions in per 20 minutes, add altogether 3 times, and keep mixing solutions under 60 ℃, and insulation reaction 5 hours, reaction finishes promptly to obtain described flocculation agent.Wherein, the self-control catalyst solution by persulfuric acid receive, sodium bisulfite and water mixes according to weight ratio at 1: 1: 58.
Flocculation agent to embodiment 1-3 characterizes, and wherein, molecular weight comes according to viscosity calculations, m
1, n and m
2Calculate according to actual experiment, the results are shown in Table 1.
The performance index of table 1 embodiment 1-3
Flocculation agent and the existing flocculation agent of embodiment 1-3 are handled high-concentration dye-printing desizing waste water, be the results are shown in Table 2.
Table 2 flocculation agent is used to handle the effect of high-concentration dye-printing desizing waste water
| The medicament title | Dosage (g/L) | Settling time (min) | Keep alkali content (%) | Could reuse | Experimental phenomena |
| ?PAC(10％) | 200 | ?30 | 0.2 | Not | Alumen ustum is big, and is loose |
| Embodiment 1 | 150 | 5 | 0.85 | Can | Flco is agglomerating closely knit, and sedimentation is quick, and reuse water is clear. |
| Embodiment 2 | 170 | 10 | 0.80 | Can | Flco is agglomerating closely knit, and sedimentation is quick, and reuse water is turbid partially. |
| Embodiment 3 | 150 | 5 | 0.85 | Can | Flco is agglomerating closely knit, and sedimentation is quick, and reuse water is clear. |
As seen from Table 3, flocculation agent input amount of the present invention is few, and the settling time is short, and flocculating effect is good, and has kept the alkali content more than 80% in the waste water after handling, but reuse.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; can not limit protection scope of the present invention with this; all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (7)
1. Dication polyacrylamide flocculating agent is characterized in that: this flocculation agent is the multipolymer of formula (I) expression:
In the formula (I), m
1, n and m
2Be 3-2*10
4Between integer, and m
1: n 〉=1, m
2: n 〉=1.
2. the preparation method of a Dication polyacrylamide flocculating agent as claimed in claim 1, it is characterized in that: with acrylamide and trimethylammonium acrylyl oxy-ethyl ammonium chloride is starting raw material, comprises the steps:
(1), acrylamide and formaldehyde and dimethylamine generation Manny are reacted now, obtain containing the mixture of the acrylamide of N dimethylamine Methacrylamide and residual volume;
(2), in step (1) gained mixture, add methylcarbonate and react, obtain containing the mixture of the acrylamide of the cationic quaternary ammonium salt monomer of formula (II) expression and residual volume;
(3), the mixture of step (2) gained is mixed with trimethylammonium acrylyl oxy-ethyl ammonium chloride solution, add polymerizing catalyst then and carry out polyreaction, obtain described Dication polyacrylamide flocculating agent.
3. the preparation method of Dication polyacrylamide flocculating agent according to claim 2, it is characterized in that: the detailed process of step (1) is: at first prepare the aqueous solution of acrylamide, regulate its pH 8～9; Then under normal temperature, in the aqueous solution of acrylamide, add formaldehyde solution, finish, be warming up to 40～60 ℃, insulation reaction is 2～3 hours under this temperature, drips dimethylamine solution then, reacts 3～5 hours down in 40～60 ℃, finish reaction, obtain containing the mixture of the acrylamide of N dimethylamine Methacrylamide and residual volume.
4. the preparation method of Dication polyacrylamide flocculating agent according to claim 2, it is characterized in that: the temperature of the reaction of step (2) is 40 ℃～60 ℃, and the reaction times is 1～2 hour.
5. the preparation method of Dication polyacrylamide flocculating agent according to claim 2, it is characterized in that: described polymerizing catalyst is the mixture that Sodium Persulfate and sodium bisulfite 1: 0.9 by weight ratio～1.1 are formed, the temperature of polyreaction is 50 ℃～70 ℃, and the reaction times is 4～6 hours.
6. the preparation method of Dication polyacrylamide flocculating agent according to claim 5, it is characterized in that: the detailed process of step (3) is: at first with the mixture and the trimethylammonium acrylyl oxy-ethyl ammonium chloride solution thorough mixing of step (2) gained, be warming up to 50 ℃～70 ℃, the polymerizing catalyst that will be made into the aqueous solution then adds, reacted 4～6 hours, and finished reaction and promptly get described Dication polyacrylamide flocculating agent.
7. the preparation method of Dication polyacrylamide flocculating agent according to claim 6, it is characterized in that: the mass percent concentration of the aqueous solution of described polymerizing catalyst is 3%～8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101155225A CN101575132B (en) | 2009-06-11 | 2009-06-11 | Dication polyacrylamide flocculating agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101155225A CN101575132B (en) | 2009-06-11 | 2009-06-11 | Dication polyacrylamide flocculating agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101575132A CN101575132A (en) | 2009-11-11 |
| CN101575132B true CN101575132B (en) | 2011-04-20 |
Family
ID=41270230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101155225A Expired - Fee Related CN101575132B (en) | 2009-06-11 | 2009-06-11 | Dication polyacrylamide flocculating agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101575132B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755001B (en) * | 2014-01-23 | 2015-04-29 | 中国海洋石油总公司 | Application of cationic polymer as flocculating agent |
| CN103772219B (en) * | 2014-01-23 | 2015-07-22 | 中国海洋石油总公司 | Multi-claw cationic functional monomer |
| CN103772604B (en) * | 2014-01-23 | 2015-12-09 | 中国海洋石油总公司 | A kind of cationic polymers |
| CN112239260A (en) * | 2019-07-18 | 2021-01-19 | 山东万和环保节能技术有限公司 | High-efficiency organic coagulant |
| CN112794945A (en) * | 2021-02-03 | 2021-05-14 | 中国海洋石油集团有限公司 | Reducible and degradable water clarifier and preparation method and application thereof |
| CN117228783B (en) * | 2023-09-07 | 2024-05-17 | 河海大学 | Magnetic ecological flocculation material, micro-polluted water treatment device and micro-polluted water treatment method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973639A (en) * | 1989-01-25 | 1990-11-27 | Hoechst Celanese Corporation | Polymerizable quaternary ammonium methyl carbonates |
| US5744563A (en) * | 1995-08-11 | 1998-04-28 | American Envirocare Inc | Mannich base copolymer and method for making it |
| CN1597550A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Cation type polymer flocculating agent and its preparation method |
-
2009
- 2009-06-11 CN CN2009101155225A patent/CN101575132B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973639A (en) * | 1989-01-25 | 1990-11-27 | Hoechst Celanese Corporation | Polymerizable quaternary ammonium methyl carbonates |
| US5744563A (en) * | 1995-08-11 | 1998-04-28 | American Envirocare Inc | Mannich base copolymer and method for making it |
| CN1597550A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Cation type polymer flocculating agent and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101575132A (en) | 2009-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101575132B (en) | Dication polyacrylamide flocculating agent and preparation method thereof | |
| CN107805292B (en) | Flocculating agent and preparation method thereof | |
| CN101613435B (en) | Hydrophobic group-containing cationic terpolymer and preparation method and application thereof | |
| CN102757119B (en) | Preparation method of composite type inorganic polymeric flocculating agent and application thereof | |
| CN101081883A (en) | Preparation method of poly dimethyl allyl ammonium chloride with high relative molecular mass | |
| CN101367573B (en) | Compound for wastewater treatment | |
| CN105198061A (en) | Flocculant composition and application thereof | |
| CN112794590A (en) | Shale gas well drilling waste oil-based mud curing material | |
| CN106008798A (en) | Method for preparing mico-crosslinking hydrophobically associating cation polyacrylamide flocculent | |
| CN107118301A (en) | A kind of hyperbranched amphiprotic polyacrylamide and preparation method thereof | |
| CN112624565B (en) | Polyhydroxy organic cation polymer sludge conditioner for deep dehydration of sludge and preparation method thereof | |
| CN104341554B (en) | Containing octadecyl hydrophobic group PDDA modified flocculant and synthetic method thereof | |
| CN113121002B (en) | Flocculating agent and preparation method and application thereof | |
| CN105481076A (en) | Tannin and chitosan-based environment-friendly water purifying agent and preparation method thereof | |
| CN102557217B (en) | Novel decolorizing agent and preparation method thereof | |
| CN107324466A (en) | Method is prepared in situ in a kind of river course water treatment coagulant | |
| CN115353185B (en) | Composite polyacrylamide flocculant and application thereof | |
| CN103539891A (en) | Amphoteric flocculant preparation method | |
| CN101618937B (en) | Hydrophobic cation polymeric flocculant preparation method | |
| CN103819612B (en) | A kind of preparation method of modified cation retention filtration adjuvant | |
| CN113354770A (en) | Liquid organic dehydrating agent and preparation method thereof | |
| CN1295257C (en) | Method for preparing high molecular weight cation type polyacrylamide | |
| CN101857294A (en) | Composite anionic and cationic starches/P(AM-DMC) flocculant and preparation method | |
| CN105504161B (en) | A kind of Anionic High-molecular Flocculant and preparation method thereof | |
| CN103342778A (en) | Composite salt-tolerant hydrophobic associated amphoteric flocculant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110420 Termination date: 20150611 |
|
| EXPY | Termination of patent right or utility model |