CN1597550A - Cation type polymer flocculating agent and its preparation method - Google Patents
Cation type polymer flocculating agent and its preparation method Download PDFInfo
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- CN1597550A CN1597550A CN 03133998 CN03133998A CN1597550A CN 1597550 A CN1597550 A CN 1597550A CN 03133998 CN03133998 CN 03133998 CN 03133998 A CN03133998 A CN 03133998A CN 1597550 A CN1597550 A CN 1597550A
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- persulfate
- dimethylaminoethyl methacrylate
- sulfite
- acrylamide
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Abstract
A high-molecular cationic flocculant is prepared from acrylamide, dimethylaminoethyl methylacrylate, hydrochloric acid and deionized water through polymerizing reaction in aqueous solution mode under the action of trigger.
Description
Technical Field
The invention relates to an organic flocculant and a preparation method thereof, in particular to a cationic polymeric flocculant and a preparation method thereof.
Background
The water treatment flocculation technology is characterized in that a flocculating agent is added into the wastewater, and COD, chromaticity, suspension and the like in the colloid, the suspended solid and the soluble organic matters in the water body are removed through the physical and chemical actions, so that the water quality of the wastewater is purified. At present, polyaluminium chloride is widely used, and the defects mainly comprise large dosage, large floc volume, slow settling speed, difficult dehydration, low efficiency, high treatment cost and the like.
In recent years, organic polymeric flocculants have been developed rapidly, have the advantages of multiple varieties, small dosage, less raw slag, easy solid-liquid separation, reduced equipment corrosion and the like, and have more and more important positions in the field of water treatment. For example, chinese patent CN1247838A discloses a cationic polymeric flocculant, which is a colloid of aminomethyl polyacrylamide obtained by mannich reaction using polyacrylamide, formaldehyde, and dimethylamine as main materials. The method has the defects of complex process, low effective content of the obtained flocculating agent and the like. Chinese patent CN1336391A discloses a cationic flocculant which is obtained by using inorganic ammonium salt, fatty aldehyde and dicyanodiamine as main materials and performing polycondensation reaction. The flocculant obtained by the method has the defects of low molecular weight, poor flocculation bridging capability and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a cationic polymeric flocculant which can effectively reduce the amount of raw slag when used for sewage treatment, can effectively remove gap water in slag during sludge treatment, and has good slag conglobation property, thereby improving the dehydration effect of sludge. The invention also provides a preparation method of the flocculant.
The cationic polymeric flocculant is a copolymer of a monomer quaternized by dimethylaminoethyl methacrylate and an acrylamide monomer:
the intrinsic viscosity is 500-1200 cm3Per g, cationThe degree is 1.0 to 4.5 mmol/g.
The preparation process of the cationic polymeric flocculant of the invention is as follows:
acrylamide monomer and dimethylaminoethyl methacrylate monomer are used as main raw materials, firstly, dimethylaminoethyl methacrylate monomer is quaternized, then, acrylamide, dimethylaminoethyl methacrylate quaternized monomer and deionized water are mixed according to a certain proportion, nitrogen is blown to remove dissolved oxygen, and finally, initiator is added to carry out polymerization reaction.
The quaternization reaction of the dimethylaminoethyl methacrylate monomer is to add hydrochloric acid into the dimethylaminoethyl methacrylate monomer, adjust the pH value to 2-9, preferably 4-8, and perform a violent exothermic reaction in a water bath or an ice-water bath or adopt other temperature control measures. The polymerization ratio (molar ratio) of acrylamide and dimethylaminoethyl methacrylate quaternized monomers is that the ratio of acrylamide to dimethylaminoethyl methacrylate is 10: 1-1: 10, and the optimal polymerization ratio is as follows: acrylamide and dimethylaminoethyl methacrylate are 8: 1-1: 8, and the total concentration of monomer polymerization is as follows: 0.5-1.5 mol/L, and the optimal polymerization concentration is as follows: 0.6-1.2 mol/L, and the reaction temperature of the polymerization is as follows: 20-90 ℃, and the optimal temperature is as follows: the polymerization reaction time is 1 to 15 hours, preferably 5 to 6 hours at 30 to 80 ℃. Different initiator systems are adopted for free radical polymerization reaction in the polymerization process, the initiator can adopt a redox initiation system consisting of persulfate or persulfate and sulfite, and the addition amount of the initiator is 10 percent of the total amount of the monomers-3～10-4The optimal addition amount is as follows: 5X 10-4～10-4mol/L, the ratio of persulfate to sulfite is as follows: the ratio of the persulfate to the sodium sulfite is 1: 0-1, wherein the persulfate can be one or more of potassium persulfate, ammonium persulfate, sodium persulfate and the like, and the sulfite can be one or more of sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, ammonium sulfite, ammonium bisulfite and the like.
The specific chemical reaction formula is as follows:
1. quaternization of dimethylaminoethyl methacrylate monomers
2. Polymerisation reaction
The cationic polymeric flocculant has the intrinsic viscosity of 500-1200 cm3The cation degree is 1.0-4.5 mmol/g, the conversion rate is more than 92%, the reaction time is short, and the whole polymerization reaction can be completed within 5-6 hours.The cationic polymeric flocculant of the invention is a quaternary ammonium salt type organic polymeric flocculant. When the flocculant is used for treating sewage and sludge, the flocculant has the advantages of good flocculation effect, small quantity of slag, good effect of removing suspended matters (SS), COD and oil and the like. The flocculant of the invention can be widely used in the sewage and sludge treatment process in the industries of oil, petrifaction, chemical industry, light industry and the like.
Detailed Description
Example 1
Adding 15.7g of dimethylaminoethyl methacrylate into a 500ml four-neck flask provided with a stirrer, a thermometer, a feeding pipe and a nitrogen inlet and outlet, adding 1N HCl15ml, adjusting the pH value to 5.5, then adding 28.4g of acrylamide and 400ml of deionized water, uniformly mixing, introducing nitrogen to remove oxygen, adding 10-4mol/L of initiator potassium persulfate, and reacting in a water bath at 50 ℃ for 6 hours to obtain the flocculant-1.
Example 2
In a 500ml four-neck flask equipped with a stirrer, a thermometer, a charging tube and a nitrogen inlet and outlet, 37.68g of dimethylaminoethyl methacrylate, 1N HCl45ml are added, the pH value is adjusted to 4.0, 4.26g of acrylamide and 440ml of deionized water are added, after uniform mixing, nitrogen is introduced to remove oxygen, an initiator is added to remove oxygen, and the mixture is stirredAmmonium persulfate 5X 10-4mol/L, initiator sodium sulfite 2X 10-5And (3) reacting for 3 hours in a water bath at 35 ℃ and reacting for 2 hours in a water bath at 80 ℃ to obtain the flocculant-2.
Example 3
Adding 28.8g of dimethylaminoethyl methacrylate into a500ml four-neck flask provided with a stirrer, a thermometer, a feeding pipe and a nitrogen inlet and outlet, adding 1N HCl30ml, adjusting the pH value to 7.0, then adding 16.9g of acrylamide and 400ml of deionized water, mixing uniformly, introducing nitrogen to remove oxygen, adding an initiator ammonium persulfate 4 multiplied by 10, adding-4And (3) mol/L, reacting for 5.5 hours in a water bath at 45 ℃ to obtain the flocculant-3.
Example 4
In a 500ml four-neck flask equipped with a stirrer, a thermometer, a charging tube, and a nitrogen inlet/outlet, 9.6g of dimethylaminoethyl methacrylate, 1N HCl5ml were added to adjust the pH to 8.0, 38.6g of acrylamide and 440ml of deionized water were added, after mixing uniformly, nitrogen gas was introduced to remove oxygen, and 2X 10 potassium persulfate as an initiator was added-4mol/L, initiator sodium sulfite 1X 10-5And (3) reacting for 3 hours in a water bath at 25 ℃, and reacting for 1.5 hours in a water bath at 80 ℃ to obtain the flocculant-4.
Table one example to obtain flocculant product index
| Index (I) | Flocculating agent 1 | Flocculating agent 2 | Flocculating agent 3 | Flocculating agent 4 |
| Intrinsic viscosity cm3/g | 1050 | 560 | 820 | 1200 |
| Degree of cation mmol/g | 2.3 | 4.5 | 3.2 | 1.2 |
Example 5
The method is used for performing a demulsification and flocculation test on the wastewater of a certain oil production station of an oil field.
Experimental result of treating oil extraction wastewater by using surfactant
| Medicament Name (R) | Amount of addition (mg/L) | Oil content (mg/L) | Oil removal rate ％ | Remarks for note | |
| Raw water | Discharging water | ||||
| PAC | 30.0 | 760 | - | - | Without breaking emulsion |
| PAC | 100.0 | 760 | 122 | 83.9 | Basic emulsion breaking |
| Flocculating agent 1 | 2.0 | 760 | 20.3 | 97.3 | Demulsification and water purification |
| Flocculating agent 2 | 4.5 | 760 | 33.8 | 95.5 | Demulsification and water purification |
| Flocculating agent 3 | 3.0 | 760 | 26.4 | 96.5 | Demulsification and water purification |
| Flocculating agent 4 | 1.5 | 760 | 16.6 | 97.8 | Demulsification and water purification |
Example 6
Taking oil-containing wastewater of a certain oil refinery to carry out a demulsification flocculation test.
Experimental results of treating wastewater of oil refinery
| Medicament Name (R) | Amount of addition (mg/L) | Oil content (mg/L) | Oil removal rate ％ | Remarks for note | |
| Raw water | Discharging water | ||||
| PAC | 15.0 | 117.5 | 38.6 | 67.1 | Slight demulsification |
| PAC | 20.0 | 117.5 | 29.4 | 75.0 | Demulsification |
| Flocculating agent 1 | 0.5 | 117.5 | 5.6 | 95.2 | Demulsification and water purification |
| Flocculating agent 2 | 0.5 | 117.5 | 10.5 | 91.1 | Demulsification and water purification |
| Flocculating agent 3 | 0.5 | 117.5 | 8.4 | 92.9 | Demulsification and water purification |
| Flocculating agent 4 | 0.5 | 117.5 | 3.8 | 96.8 | Demulsification and water purification |
Example 7
Taking oil-containing sludge of a certain oil refinery to carry out a demulsification flocculation test.
TABLE IV Experimental results on treating oil-containing sludge in oil refinery
| Medicament Name (R) | Amount of addition (mg/L) | The water content of the sludge is wt% | Backup note | |
| Raw sludge | Treated sludge | |||
| PAC | 2000 | 99.9 | 83.3 | Loosening mud cake |
| PAC | 3000 | 99.9 | 80.5 | Loosening mud cake |
| Flocculating agent 1 | 300 | 99.9 | 74.6 | Compacting mud cake |
| Flocculating agent 2 | 300 | 99.9 | 80.2 | Loosening mud cake |
| Flocculating agent 3 | 300 | 99.9 | 77.8 | The mud cake is more compact |
| Flocculating agent 4 | 300 | 99.9 | 72.7 | Compacting mud cake |
Claims (10)
1. A cationic polymeric flocculant is characterized in that the flocculant is a copolymer of monomers and acrylamide monomers after dimethylaminoethyl methacrylate is quaternized:
the intrinsic viscosity is 500-1200 cm3The cationic degree is 1.0 to 4.5 mmol/g.
2. A method for preparing the flocculating agent of claim 1, which is characterized by adopting the following processes: taking an acrylamide monomer and a dimethylaminoethyl methacrylate monomer as raw materials, firstly quaternizing the dimethylaminoethyl methacrylate monomer, then mixing the acrylamide, the dimethylaminoethyl methacrylate quaternization monomer and deionized water, blowing nitrogen to remove dissolved oxygen, and finally adding an initiator to carry out polymerization reaction.
3. The method according to claim 2, wherein the quaternization of the dimethylaminoethyl methacrylate monomer is carried out by adding hydrochloric acid into the dimethylaminoethyl methacrylate monomer and adjusting the pH value to 2-9.
4. A process according to claim 3, wherein the pH is from 4 to 8.
5. The method according to claim 2, wherein the polymerization molar ratio of the acrylamide and dimethylaminoethyl methacrylate quaternized monomers is 10: 1-1: 10, and the total concentration of the monomers is: 0.5-1.5 mol/L, and the reaction temperature of the polymerization is as follows: the polymerization reaction time is 1-15 hours at 20-90 ℃.
6. The method of claim 5, wherein the acrylamide and dimethylaminoethyl methacrylate are 8: 1 to 1: 8, and the total concentration of the monomers polymerized is: 0.6-1.2 mol/L, and the reaction temperature of the polymerization is as follows: the polymerization reaction time is 5-6 hours at 30-80 ℃.
7. The process according to claim 2, wherein the initiator added during the polymerization is a persulfate or a redox initiator system consisting of a persulfate and a sulfite.
8. The method according to claim 7, wherein the ratio of persulfate to sulfite is: the ratio of the persulfate to the sodium sulfite is 1: 0-1, wherein the persulfate is one or more of potassium persulfate, ammonium persulfate and sodium persulfate, and the sulfite is one or more of sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, ammonium sulfite and ammonium bisulfite.
9. A process according to claim 2 or 7, whereinthe initiator is added in an amount of 10% by weight based on the total amount of the monomers to be polymerized-3～10-4mol/L。
10. The process of claim 9 wherein said initiator is added in an amount of 5 x 10-4～10-4mol/L。
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| CN 03133998 CN1233569C (en) | 2003-09-15 | 2003-09-15 | Cation type polymer flocculating agent and its preparation method |
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| CN 03133998 CN1233569C (en) | 2003-09-15 | 2003-09-15 | Cation type polymer flocculating agent and its preparation method |
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| CN1597550A true CN1597550A (en) | 2005-03-23 |
| CN1233569C CN1233569C (en) | 2005-12-28 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453573C (en) * | 2007-03-02 | 2009-01-21 | 王旭东 | Positive ion organic high polymer coagulant and preparation method thereof |
| CN101575132B (en) * | 2009-06-11 | 2011-04-20 | 吴江市恒茂电子科技有限公司 | Dication polyacrylamide flocculating agent and preparation method thereof |
| CN102432750A (en) * | 2011-09-08 | 2012-05-02 | 华东理工大学 | Preparation method of amphoteric comb-shape polyacrylamide by synthesis of quaternary ammonium salt functional monomer |
| CN108912267A (en) * | 2018-06-11 | 2018-11-30 | 宁夏神耀科技有限责任公司 | The coal gasified black water processing preparation method of cationic polyacrylamide flocculant agent |
| CN109516607A (en) * | 2019-01-02 | 2019-03-26 | 江苏富淼科技股份有限公司 | A kind of sewage water treatment method |
| CN114426326A (en) * | 2020-09-21 | 2022-05-03 | 中国石油化工股份有限公司 | Oily sewage treatment flocculant and preparation method and application thereof |
| CN116135897A (en) * | 2021-11-18 | 2023-05-19 | 郑州大学 | Polyacrylamide copolymer, and preparation method and application thereof |
-
2003
- 2003-09-15 CN CN 03133998 patent/CN1233569C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453573C (en) * | 2007-03-02 | 2009-01-21 | 王旭东 | Positive ion organic high polymer coagulant and preparation method thereof |
| CN101575132B (en) * | 2009-06-11 | 2011-04-20 | 吴江市恒茂电子科技有限公司 | Dication polyacrylamide flocculating agent and preparation method thereof |
| CN102432750A (en) * | 2011-09-08 | 2012-05-02 | 华东理工大学 | Preparation method of amphoteric comb-shape polyacrylamide by synthesis of quaternary ammonium salt functional monomer |
| CN102432750B (en) * | 2011-09-08 | 2013-08-07 | 华东理工大学 | Preparation method of amphoteric comb-shape polyacrylamide by synthesis of quaternary ammonium salt functional monomer |
| CN108912267A (en) * | 2018-06-11 | 2018-11-30 | 宁夏神耀科技有限责任公司 | The coal gasified black water processing preparation method of cationic polyacrylamide flocculant agent |
| CN108912267B (en) * | 2018-06-11 | 2020-09-29 | 宁夏神耀科技有限责任公司 | Preparation method of cationic polyacrylamide flocculant for coal gasification black water treatment |
| CN109516607A (en) * | 2019-01-02 | 2019-03-26 | 江苏富淼科技股份有限公司 | A kind of sewage water treatment method |
| CN114426326A (en) * | 2020-09-21 | 2022-05-03 | 中国石油化工股份有限公司 | Oily sewage treatment flocculant and preparation method and application thereof |
| CN114426326B (en) * | 2020-09-21 | 2023-04-18 | 中国石油化工股份有限公司 | Oily sewage treatment flocculant and preparation method and application thereof |
| CN116135897A (en) * | 2021-11-18 | 2023-05-19 | 郑州大学 | Polyacrylamide copolymer, and preparation method and application thereof |
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| CN1233569C (en) | 2005-12-28 |
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