CN103102459A - Preparation method of gelatin grafted acrylamide cation polymeric flocculant - Google Patents
Preparation method of gelatin grafted acrylamide cation polymeric flocculant Download PDFInfo
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- CN103102459A CN103102459A CN2013100171994A CN201310017199A CN103102459A CN 103102459 A CN103102459 A CN 103102459A CN 2013100171994 A CN2013100171994 A CN 2013100171994A CN 201310017199 A CN201310017199 A CN 201310017199A CN 103102459 A CN103102459 A CN 103102459A
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Abstract
The invention relates to a preparation method of a gelatin grafted acrylamide cation polymeric flocculant. Current flocculant in leather wastewater treatment is easy to cause secondary pollution to the environment. The method comprises the following steps of: firstly, adding dried gelatin into deionized water; uniformly stirring and adding a catalyst; reacting for 40-60 minutes in the presence of nitrogen; then, adding acrylamide; after reaction, preparing a grafted copolymer; and then, adding a glutaraldehyde liquor and a dimethylamine liquor into the grafted copolymer, stirring and reacting for 2-4.5 hours at 45-65 DEG C, and cooling and discharging to obtain the product. The gelatin grafted acrylamide cation polymeric flocculant prepared by the method provided by the invention is good in flocculating effect, quicker in sedimentation rate, low in cost and small in pollution, and can be completely biologically degraded.
Description
Technical field
The invention belongs to technical field of sewage, relate to a kind of preparation method of flocculation agent, specifically a kind of preparation method of gelatin graft acrylamide cation polymeric flocculant.
Background technology
Leather industry has also caused certain pollution to environment when producing tremendous economic and social benefit.In the process hides process, the Substance Transformation that raw material tare weight 20% is only arranged is finished product leather, rest part in the process hides process as cut open, cut, the solid waste such as mill and deburring bits are dropped.Contain the materials such as a large amount of COD, chromium and suspended substance in the sewage of while leather enterprise discharging.These are all to cause the with serious pollution important factor of leather industry.
The synthetic class organic polymer coargulator that uses during leather-making waste water is processed mainly comprises anionic with organic polymer coargulator non-ionic type, polyacrylamide and derivative, sodium polyacrylate, poly-sulphophenyl ethene, polyoxyethylene, urea-formaldehyde resin and polyvinyl alcohol etc. being arranged.
The residual toxicity one body problem of polyacrylamide series polymeric flocculant is not effectively solved at present yet.Similarly situation also is present in the preparation of urea-formaldehyde resin and polyvinyl alcohol, and this two classes flocculation agent belongs to the superpolymer of low relative molecular mass, the flocculating property relative mistake some.
The flocculation agent that present processing leather-making waste water adopts mostly is the organic synthesis polymeric flocculant, wherein uses to be the most widely the polyacrylamide series polymeric flocculant.Although it is larger that this class flocculation agent has a relative molecular mass, the constructional feature that the molecular chain active function groups is many, but there is fatal weakness, their great majority are little poison, affect HUMAN HEALTH, its residue is difficult for being biodegradable, and environment is caused secondary pollution, is restricting on the contrary the sustainable and healthy development of curriery.Therefore, on the basis of graft copolymer, utilizing the synthetic graft type polymeric flocculant of superiority condition of natural polymer raw material self, is a thinking that is worth exploration.
Summary of the invention
Purpose of the present invention provides a kind of preparation method of gelatin graft acrylamide cation polymeric flocculant for the deficiencies in the prior art.
The concrete steps of the inventive method are as follows:
Step (1). graft copolymerization: dry gelatin is added in deionized water, stir, then add catalyzer, under the nitrogen protection condition, 35 ℃～55 ℃ were reacted 40～60 minutes, then add acrylamide, reacted 3～6 hours under 45 ℃～70 ℃, make graft copolymer; Add the dry gelatin of 50～150 grams, 2～20 gram catalyzer, 150～500 gram acrylamides in every liter of deionized water;
Described gelatin is the gelatin of 100～280 bloom;
As preferably, described gelatin is the gelatin of 250 bloom;
Described catalyzer is one or more in ceric ammonium nitrate, hydrogen peroxide, sodium bisulfite, persulphate; When being multiple, ratio be arbitrarily than;
Described catalyzer is that sodium bisulfite and persulphate are mixed by any ratio the mixture that forms;
Described persulphate is all persulphates;
Step (2). aminated reaction: glutaraldehyde solution and dimethylamine solution are added in the graft copolymer that makes, 45～65 ℃ of lower stirring reactions 2～4.5 hours, cooling discharging makes gelatin graft acrylamide cation polymeric flocculant;
The glutaraldehyde solution that adds in reaction system and the mass ratio of dry gelatin are 0.13～1:1, and the mass ratio of dimethylamine solution and dry gelatin is 0.13～1:1;
In described glutaraldehyde solution, the mass content of glutaraldehyde is 35～50%;
In described dimethylamine solution, the mass content of dimethylamine is 33～40%.
As preferably, in described glutaraldehyde solution, the mass content of glutaraldehyde is 45%, and in described dimethylamine solution, the mass content of dimethylamine is 40%.
The beneficial effect that the present invention has:
1. gelatin graft acrylamide cation polymeric flocculant of the present invention possesses following advantage: (1) consumption is few, and when flocculant addition was 1.5～4mg/L, flocculating effect was better; (2) flocculating effect is good, and flco forms soon, and particle is large, and subsidence rate is very fast; (3) cost is low; (4) pollute less.
2. the graft copolymerization polymeric flocculant has some good characteristic of natural high moleculer eompound and synthetic macromolecular compound concurrently, and this is mainly manifested in flocculation ability and strengthens, and molecular chain stability increases, and cationization such as more easily carries out at the aspect.Have a large amount of polar groups and surfactivity point on its molecular chain, therefore can produce flocculating effect by high molecular adsorption bridging or charge neutrality effect.Simultaneously himself fully biodegradable, have good " environmental acceptability ", therefore just meeting the requirement that present country advocates the environmental protection engineering.
Embodiment
Embodiment 1:
Step (1). graft copolymerization: the 100bloom gelatin of 50.0 gram dryings is joined in the 1L deionized water, stir, then add 2 gram ceric ammonium nitrates, under the nitrogen protection condition, 35 ℃ were reacted 60 minutes, add 150 gram acrylamides, reaction is 6 hours under 45 ℃, makes graft copolymer again;
Step (2). aminated reaction: be that 35% glutaraldehyde solution and 50.0 gram mass content are that 33% dimethylamine solution adds in the graft copolymer that makes with 50.0 gram mass content, 45 ℃ of lower stirring reactions 4.5 hours, cooling discharging makes gelatin graft acrylamide cation polymeric flocculant.
Embodiment 2:
Step (1). graft copolymerization: the 250bloom gelatin of 100 gram dryings is joined in the 1L deionized water, stir, then add 10 gram hydrogen peroxide, under the nitrogen protection condition, 50 ℃ were reacted 45 minutes, add 300 gram acrylamides, reaction is 4.5 hours under 57 ℃, makes graft copolymer again;
Step (2). aminated reaction: be that 50% glutaraldehyde solution and 13 gram mass content are that 40% dimethylamine solution adds in the graft copolymer that makes with 13 gram mass content, 55 ℃ of lower stirring reactions 3.5 hours, cooling discharging makes gelatin graft acrylamide cation polymeric flocculant.
Embodiment 3:
Step (1). graft copolymerization: the 280bloom gelatin of 150 gram dryings is joined in the 1L deionized water, stir, then add 20 gram sodium bisulfites, under the nitrogen protection condition, 55 ℃ were reacted 40 minutes, add 500 gram acrylamides, reaction is 3 hours under 70 ℃, makes graft copolymer again;
Step (2). aminated reaction: be that 45% glutaraldehyde solution and 75 gram mass content are that 37% dimethylamine solution adds in the graft copolymer that makes with 75 gram mass content, 65 ℃ of lower stirring reactions 2 hours, cooling discharging makes gelatin graft acrylamide cation polymeric flocculant.
Embodiment 4:
Step (1). graft copolymerization: the 150bloom gelatin of 60 gram dryings is joined in the 1L deionized water, stir, then add 6 gram Sodium Persulfates, under the nitrogen protection condition, 40 ℃ were reacted 55 minutes, add 200 gram acrylamides, reaction is 5.5 hours under 50 ℃, makes graft copolymer again;
Step (2). aminated reaction: be that 40% glutaraldehyde solution and 48 gram mass content are that 35% dimethylamine solution adds in the graft copolymer that makes with 48 gram mass content, 50 ℃ of lower stirring reactions 4 hours, cooling discharging makes gelatin graft acrylamide cation polymeric flocculant.
Embodiment 5:
Step (1). graft copolymerization: the 200bloom gelatin of 80 gram dryings is joined in the 1L deionized water, stir, then add 15 gram Potassium Persulphates, under the nitrogen protection condition, 45 ℃ were reacted 50 minutes, add 250 gram acrylamides, reaction is 5 hours under 60 ℃, makes graft copolymer again;
Step (2). aminated reaction: be that 40% glutaraldehyde solution and 48 gram mass content are that 35% dimethylamine solution adds in the graft copolymer that makes with 48 gram mass content, 60 ℃ of lower stirring reactions 3 hours, cooling discharging makes gelatin graft acrylamide cation polymeric flocculant.
Embodiment 6:
Step (1). graft copolymerization: the 250bloom gelatin of 120 gram dryings is joined in the 1L deionized water, stir, then add 6 gram sodium bisulfites and 6 gram Sodium Persulfates, under the nitrogen protection condition, 48 ℃ were reacted 50 minutes, add 350 gram acrylamides, reaction is 4 hours under 65 ℃, makes graft copolymer again;
Step (2). aminated reaction: be that 45% glutaraldehyde solution and 48 gram mass content are that 40% dimethylamine solution adds in the graft copolymer that makes with 48 gram mass content, 60 ℃ of lower stirring reactions 3 hours, cooling discharging makes gelatin graft acrylamide cation polymeric flocculant.
Embodiment 7:
Step (1). graft copolymerization: the 230bloom gelatin of 140 gram dryings is joined in the 1L deionized water, stir, then add 8 gram hydrogen peroxide and 8 gram Sodium Persulfates, under the nitrogen protection condition, 52 ℃ were reacted 43 minutes, add 450 gram acrylamides, reaction is 3.5 hours under 65 ℃, makes graft copolymer again;
Step (2). aminated reaction: be that 48% glutaraldehyde solution and 28 gram mass content are that 38% dimethylamine solution adds in the graft copolymer that makes with 28 gram mass content, 63 ℃ of lower stirring reactions 2.5 hours, cooling discharging makes gelatin graft acrylamide cation polymeric flocculant.
Claims (6)
1. the preparation method of a gelatin graft acrylamide cation polymeric flocculant is characterized in that the method comprises the following steps:
Step (1). graft copolymerization: dry gelatin is added in deionized water, stir, then add catalyzer, under the nitrogen protection condition, 35 ℃～55 ℃ were reacted 40～60 minutes, then add acrylamide, reacted 3～6 hours under 45 ℃～70 ℃, make graft copolymer; Add the dry gelatin of 50～150 grams, 2～20 gram catalyzer, 150～500 gram acrylamides in every liter of deionized water;
Described catalyzer is one or more in ceric ammonium nitrate, hydrogen peroxide, sodium bisulfite, persulphate; When being multiple, ratio be arbitrarily than;
Step (2). aminated reaction: glutaraldehyde solution and dimethylamine solution are added in the graft copolymer that makes, 45～65 ℃ of lower stirring reactions 2～4.5 hours, cooling discharging makes gelatin graft acrylamide cation polymeric flocculant;
The glutaraldehyde solution that adds in reaction system and the mass ratio of dry gelatin are 0.13～1:1, and the mass ratio of dimethylamine solution and dry gelatin is 0.13～1:1.
2. the preparation method of a kind of gelatin graft acrylamide cation polymeric flocculant as claimed in claim 1, is characterized in that the gelatin described in step (1) is the gelatin of 100～280 bloom.
3. the preparation method of a kind of gelatin graft acrylamide cation polymeric flocculant as claimed in claim 1, is characterized in that the gelatin described in step (1) is the gelatin of 250 bloom.
4. the preparation method of a kind of gelatin graft acrylamide cation polymeric flocculant as claimed in claim 1, is characterized in that the catalyzer described in step (1) is that sodium bisulfite and persulphate are mixed by any ratio the mixture that forms.
5. the preparation method of a kind of gelatin graft acrylamide cation polymeric flocculant as claimed in claim 1, the mass content that it is characterized in that glutaraldehyde in the glutaraldehyde solution described in step (2) is 35～50%, and in described dimethylamine solution, the mass content of dimethylamine is 33～40%.
6. the preparation method of a kind of gelatin graft acrylamide cation polymeric flocculant as claimed in claim 1, the mass content that it is characterized in that glutaraldehyde in the glutaraldehyde solution described in step (2) is 45%, and in dimethylamine solution, the mass content of dimethylamine is 40%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417666A (en) * | 2015-11-24 | 2016-03-23 | 宜兴市丰烨化学有限公司 | Acrylamide and glutaraldehyde flocculating agent and preparation method thereof |
| CN107459195A (en) * | 2017-08-18 | 2017-12-12 | 巢湖市俊业渔具有限公司 | A kind of fishing net modifying porcelain method |
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| CN1247838A (en) * | 1998-09-17 | 2000-03-22 | 吕广明 | Cationic high-molecular flocculant and its preparation |
| CN1519645A (en) * | 2003-02-06 | 2004-08-11 | ���Ῠ���ܴ�ع���ʽ���� | Silver-halide emulsion, its prepn. method, and silver-halide photograph material |
| EP1555997A1 (en) * | 2002-11-01 | 2005-07-27 | The Procter & Gamble Company | Polymeric assisted benefit agent delivery systems |
| US20070149694A1 (en) * | 2003-07-03 | 2007-06-28 | Venkataram Krishnan | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same |
| CN102020775A (en) * | 2010-11-26 | 2011-04-20 | 浙江工业大学 | Preparation method of modified gelatin |
| CN102329843A (en) * | 2011-08-05 | 2012-01-25 | 蚌埠丰原明胶有限公司 | Enzyme method for preparing gelatin |
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- 2013-01-17 CN CN201310017199.4A patent/CN103102459B/en not_active Expired - Fee Related
Patent Citations (7)
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| CN1247838A (en) * | 1998-09-17 | 2000-03-22 | 吕广明 | Cationic high-molecular flocculant and its preparation |
| EP1555997A1 (en) * | 2002-11-01 | 2005-07-27 | The Procter & Gamble Company | Polymeric assisted benefit agent delivery systems |
| CN1519645A (en) * | 2003-02-06 | 2004-08-11 | ���Ῠ���ܴ�ع���ʽ���� | Silver-halide emulsion, its prepn. method, and silver-halide photograph material |
| US20040157176A1 (en) * | 2003-02-06 | 2004-08-12 | Konica Minolta Holdings, Inc. | Silver halide emulsion, preparation method thereof and silver halide photographic material |
| US20070149694A1 (en) * | 2003-07-03 | 2007-06-28 | Venkataram Krishnan | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same |
| CN102020775A (en) * | 2010-11-26 | 2011-04-20 | 浙江工业大学 | Preparation method of modified gelatin |
| CN102329843A (en) * | 2011-08-05 | 2012-01-25 | 蚌埠丰原明胶有限公司 | Enzyme method for preparing gelatin |
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| 冷延国等: "明胶接枝丙烯酰胺的研究", 《高分子材料科学与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417666A (en) * | 2015-11-24 | 2016-03-23 | 宜兴市丰烨化学有限公司 | Acrylamide and glutaraldehyde flocculating agent and preparation method thereof |
| CN107459195A (en) * | 2017-08-18 | 2017-12-12 | 巢湖市俊业渔具有限公司 | A kind of fishing net modifying porcelain method |
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