CN104341035A - Magnetic collagen modified cationic flocculant and preparation method thereof - Google Patents
Magnetic collagen modified cationic flocculant and preparation method thereof Download PDFInfo
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- CN104341035A CN104341035A CN201410435098.3A CN201410435098A CN104341035A CN 104341035 A CN104341035 A CN 104341035A CN 201410435098 A CN201410435098 A CN 201410435098A CN 104341035 A CN104341035 A CN 104341035A
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- 102000008186 Collagen Human genes 0.000 title claims abstract description 118
- 108010035532 Collagen Proteins 0.000 title claims abstract description 118
- 229920001436 collagen Polymers 0.000 title claims abstract description 79
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002699 waste material Substances 0.000 claims abstract description 29
- 239000011553 magnetic fluid Substances 0.000 claims abstract description 24
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 33
- 239000000413 hydrolysate Substances 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 12
- 208000001840 Dandruff Diseases 0.000 claims description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 8
- 239000004160 Ammonium persulphate Substances 0.000 claims description 7
- 239000004159 Potassium persulphate Substances 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000010985 leather Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 abstract description 41
- 230000000694 effects Effects 0.000 abstract description 22
- 238000000926 separation method Methods 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 13
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000000696 magnetic material Substances 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 description 39
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000000084 colloidal system Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 9
- 230000003311 flocculating effect Effects 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000008394 flocculating agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 230000017854 proteolysis Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000002435 tendon Anatomy 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a magnetic collagen modified cationic flocculant and a preparation method thereof. The magnetic collagen modified cationic flocculant is mainly prepared by combining a magnetic fluid with waste tanning collagen which is taken as a raw material. The magnetic collagen modified cationic flocculant has the beneficial effects that a magnetic material is applied to preparation of the flocculant, and a solid and liquid separation effect of a flocculation process is enhanced by the effect of a magnetic field, and thus the quality of water discharged after the flocculation process is improved, the water treatment running cost is lowered, and water content of floccules is reduced. Resource utilization of tanning wastes is realized, and pollutant emission caused by tanning is reduced. A magnetic collagen hydrolysis product is subjected to graft copolymerization and cationic modification, and a modified product has good flocculent properties. The magnetic collagen modified cationic flocculant is easy to degrade by microorganisms in environment, short in existence time in the environment and low in residual quantity.
Description
(1) technical field
The invention belongs to water conditioner preparation field, be specifically related to collagen-modified cationic flocculant of a kind of magnetic and preparation method thereof.
(2) background technology
Flocculation is time-honored water treatment method.At present, flocculence is widely used in productive life Water warfare, city domestic sewage and Industrial Wastewater Treatment, has significant impact to the operation condition of subsequent disposal operation, processing costs and final outflow water quality etc.
The process of flocculence process water and waste water, adds flocculation agent exactly in water body, makes colloid and the de-steady cohesion of suspended particle, by gravity settling effect, realizes the process of solid-liquid separation.Solid-liquid separation process in water and waste water flocculation treatment requires that colloid in water outlet, suspended particle concentration are low on the one hand; The sludge volume require on the other hand that solid-liquid interface fall off rate is fast, forming after colloid or suspended particle sedimentation is little.Flocculation agent acts on homodisperse colloid, suspended substance in water or waste water, makes it mutually assemble, and the flco that forming radius is large, solid is beneficial to gravity settling, realizes purification of water quality.Visible, the performance of flocculation agent directly affects the flocculation treatment effect of water or waste water.
The surface charge of colloid, suspended particle and volume are two principal elements affecting flocculating settling effect.Flocculation agent can in and colloid, suspended particle surface charge, weaken repulsive force between colloid, suspended particle, make colloid, suspended particle combines gradually, particle volume, density increase; Polymeric flocculant molecular weight and volume are comparatively large, with active group, are easily combined with colloidal solid, and the effects such as volume is swept, coprecipitation are caught in generation chemical bonding, net.The above-mentioned effect of flocculation agent makes colloid, suspended particle is easy to flocculating settling from water, thus realizes solid-liquid and be effectively separated.
Now widely used flocculation agent, is divided into inorganic and organic floculant according to composition; Low molecule and polymeric flocculant is divided into according to molecular weight; Negatively charged ion, positively charged ion, nonionic and amphoteric flocculating agent is divided into by electrically charged character after functional group's dissociation.
Inorganic flocculating agent mainly contains aluminium salt and molysite, and inorganic flocculating agent dosage is large, and settling velocity is slow, is replaced gradually by inorganic polymer flocculant.Inorganic polymer flocculant is also that molecular weight is generally 1 × 10 based on aluminium salt and molysite
5, poly-aluminium settling velocity is slow, have aluminium to remain, and Polyferric Sulfate easily makes that water is painted, alkalescence is strong.
The electrically charged active group of organic polymer coargulator is many, various structures, and the salt that coexisted, pH value and temperature affect little, and flocculation rate is fast, overcomes the shortcoming of inorganic flocculating agent.Organic synthesis flocculation agent is effective, but cost is high, not readily biodegradable.Conventional organic polymer coargulator polyacrylamide, although itself is without any toxicity, difficult degradation easily causes secondary pollution.Natural polymer and derivative biodegradable, degraded intermediate is to the mankind and environmentally friendly.But the flocculation activity of natural macromolecule flocculating agent is more weak, good flocculating effect can be obtained after suitable chemical modification.At present, the research trend of organic floculant is in the chemical modification of natural polymers.
In actual applications, in order to improve water or water treatment effect, when the flocs unit doing flocculation agent generation with molysite, aluminium salt is tiny, loose, when being unfavorable for sedimentation, normal add simultaneously there is absorption, the polymeric flocculant such as polyacrylamide of bridging action makes tiny, loose flco become thick and closely knit, improves flocculating settling effect.
Along with development that is theoretical to flocculating settling and flocculation agent Study on mechanism, cation polymeric flocculant more and more causes extensive concern.Cation polymeric flocculant has charge neutralization and adsorption bridging effect to water-borne glue body or particulate matter, thus makes the particulate in system take off surely, flocculate and contribute to sedimentation.
At present, be no matter the development of novel flocculant, or for water quality and for meet multiple flocculation agent that treatment effect requirement studies with the use of condition and method, be all theoretical according to gravity settling, realize solid-liquid separation under gravity.
The novel flocculant of exploitation excellent property, safety and environmental protection is the emphasis improving the research of water and waste water flocculation treatment effect.Up to now, novel flocculant research mainly concentrates on the aspects such as efficient, low dose, and realizing in rapid flocculation separation, the fragmentation of suppression flco, minimizing flco water ratio etc., the novel flocculant particularly not only relying on gravity settling to realize solid-liquid separation also compares shortcoming.
(3) summary of the invention
The present invention is in order to make up the deficiencies in the prior art, provide collagen-modified cationic flocculant of a kind of magnetic and preparation method thereof, the invention provides one with process hides waste collagen albumen for raw material, be combined with magnetic fluid, through proper method modification, prepare the method for the collagen-modified cationic flocculant of magnetic.High level conversion for tanning industry protein-based refuse have found a feasible approach.The action of a magnetic field is utilized to strengthen flocculation treatment solid-liquid separation effect.Preparation and application for flocculation agent provide new thinking and countermeasure.
The present invention is achieved through the following technical solutions:
The collagen-modified cationic flocculant of a kind of magnetic, its special character is: main with process hides waste collagen albumen for raw material, be combined with magnetic fluid and be prepared from.
The preparation method of the collagen-modified cationic flocculant of the magnetic described in a kind of basis, comprise the following steps: with process hides waste collagen albumen for raw material, through hydrolysis, in conjunction with obtaining the collagen-modified cationic flocculant of magnetic after magnetic fluid, graft copolymerization, cationization.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, comprises the following steps:
(1) process hides scrap leather bits hydrolysis:
Appropriate process hides scrap leather bits are joined in reactor, adds scurf quality 20-50 water doubly, be warming up to 60-100 DEG C, hydrolysis reaction, obtain collagen hydrolyzed solution;
(2) magnetic collagen hydrolysate preparation:
In above-mentioned collagen hydrolyzed solution, add collagen protein quality 30-60% tensio-active agent, at 40-70 DEG C of temperature, dispersed with stirring, adds the Fe of collagen protein quality 30-60% after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse, then slowly adds collagen protein quality 10-30 Virahol doubly under rapid stirring state, then ultrasonic disperse, adds glutaraldehyde water solution, rapid stirring, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate, wherein, glutaraldehyde quality is the 50-150% of scurf quality, suspension after Magneto separate, the solid of acquisition with washed with isopropyl alcohol for several times, for subsequent use after dry at 20-50 DEG C of temperature;
(3) graft copolymerization
Appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagen hydrolysate quality 30-70 water doubly, at 40-70 DEG C of temperature, be stirred to dissolving, take magnetic collagen hydrolysate quality 3-7 acrylamide doubly, add in above-mentioned reactor after dissolving by suitable quantity of water, temperature of reaction system controls at 70-100 DEG C, take acrylamide quality 1-3% initiator, dissolve by suitable quantity of water, react;
(4) cationization:
Above-mentioned reaction system is cooled to 40-70 DEG C, add the formaldehyde that molar weight is acrylamide molar weight 0.5-0.8, with aqueous sodium hydroxide solution adjust ph 8-10, reaction, add the dimethylamine identical with formaldehyde molar weight, continue reaction, add the concentrated hydrochloric acid identical with formaldehyde molar weight, reaction, obtains the collagen-modified cationic flocculant of magnetic.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (1), is warming up to 60-100 DEG C, adds the acid of scurf quality 1-5%, stirring reaction, and adjust ph is or close to 7, obtains collagen hydrolyzed solution.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (2), the mass concentration of glutaraldehyde water solution is 25%, and the addition of this glutaraldehyde water solution is collagen protein quality 2-6 times.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (2), in above-mentioned collagen hydrolyzed solution, add collagen protein quality 30-60% tensio-active agent, at 40-70 DEG C of temperature, dispersed with stirring 60-90 minute, adds the Fe of collagen protein quality 30-60% after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 5-15 minute, then slowly adds collagen protein quality 10-30 Virahol doubly under rapid stirring state, ultrasonic disperse 5-15 minute again, adding collagen protein quality 2-6 mass concentration is doubly the glutaraldehyde water solution of 25%, rapid stirring 60-90 minute, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate, suspension after Magneto separate, the solid of acquisition with washed with isopropyl alcohol for several times, for subsequent use after dry at 20-50 DEG C of temperature,
In step (3), appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagen hydrolysate quality 30-70 water doubly, at 40-70 DEG C of temperature, be stirred to dissolving.Take magnetic collagen hydrolysate quality 3-7 acrylamide doubly, add in above-mentioned reactor after dissolving by suitable quantity of water, temperature of reaction system controls at 70-100 DEG C.Take acrylamide quality 1-3% initiator, dissolve by suitable quantity of water, be slowly added drop-wise in above-mentioned reaction system in 60-90 minute, then react 30-60 minute.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (1), acid is the vitriol oil, concentrated hydrochloric acid and/or its mixture, is or close to 7 by aqueous sodium hydroxide solution adjust ph.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (1) and step (4), aqueous sodium hydroxide solution mass concentration is 20%.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (3), initiator is Potassium Persulphate, ammonium persulphate, Sulfothiorine-Potassium Persulphate initiator system, Sulfothiorine-ammonium persulphate initiator system, Sulfothiorine-hydrogen peroxide.
The present invention with process hides waste collagen albumen for raw material, after hydrolysis, with Fe
3o
4magnetic fluid combines, through graft copolymerization and cationization, and the collagen-modified cationic flocculant of preparation magnetic.Feature of the present invention is preparation magnetic separation technique being used for flocculation agent, makes flocculation agent possess magnetic, by Magneto separate mode enhanced flocculation solid-liquid separation effect, improves flocculation treatment effluent quality, reduces water treatment running cost, reduce flco water ratio.
The present invention for magnetic flocculant prepared by raw material, takes full advantage of collagen protein resource with process hides waste collagen albumen, provides effective way, achieve the recycling of tanning waste for solving the discharge of process hides solid waste and piling up environmental pollution problem.
The present invention not only to consider to meet purification of water quality, sewage disposal to the requirement of flocculating effect, realize tanning waste recycling, also to consider to meet the requirement of degrading is easy to flocculation agent.Collagen hydrolysate is easy to be degraded by microorganisms in the environment, and lifetime is short in the environment, residual quantity is low.For improving the flocculating property of collagen hydrolysate, to combining Fe
3o
4the collagen hydrolysate of magnetic fluid has carried out graft copolymerization and cation modifying, makes the collagen-modified cationic flocculant of magnetic meet purification of water quality, sewage disposal to the demand of high-performance flocculation agent.
Beneficial effect of the present invention:
(1) magneticsubstance is used for flocculation agent preparation, utilizes the action of a magnetic field to strengthen the solid-liquid separation effect of flocculation treatment, improve flocculation treatment effluent quality, reduce water treatment running cost, reduce flco water ratio.
(2) achieve the recycling of tanning waste, decrease tanning production pollutant emission.
(3) magnetic collagen hydrolysate is through graft copolymerization and cation modifying, and modified product has good flocculating property.
(4) the collagen-modified cationic flocculant of magnetic is easy to be degraded by microorganisms in the environment, and lifetime is short in the environment, residual quantity is low.
(4) embodiment
In flocculation sediment, water or waste water contain not easily sedimentation under gravity, the separation of many little colloids, suspended substance, affect water or water treatment effect.If by colloid, suspended substance and magnetic flocculant effect, magnetic throw out moves on separator along magnetic line of force direction under magneticaction, thus realize colloid in water or waste water, suspended substance high efficiency separation, effectively improve flocculation removal effect.
In modern industry waste water and sanitary sewage, organic content is high, and organic matter particle surface is usually electronegative, and cation polymeric flocculant more easily makes de-steady, the flocculation of colloid electronegative in system, suspended substance, realizes solid-liquid separation.
Nature high molecular flocculant has renewable, substantially nontoxic, the easy biochemical degradation of raw material, does not cause secondary pollution, active group is many, be easy to adopt different methods to carry out the plurality of advantages such as modification as required, and nature high molecular flocculant preparation and application research is day by day in widespread attention.Protein molecule has various active group, and various structures, be suitable for the polymeric flocculant that different performance is prepared in modification.Collagen protein is present in the tissues such as the skin of animal, bone, cartilage and tendon, wide material sources; Containing functional groups such as-NH2 ,-COOH ,-OH in collagen protein partial hydrolystate molecule, be easy to carry out cation modifying.
Only have the collagen of 22%-30% to become leather in tanning industry, all the other are thrown away as solid waste in leather making process.According to statistics, China's tanning industry produces 1,400,000 tons of refuses based on collagen protein every year.Tanning waste is landfilled or natural degradation, serious environment pollution water body and soil, waste collagen protein resource in the environment.Therefore, collagen protein being converted into high added value or large Chemicals, is the only way solving China's tanning production solid waste pollution environment.Late 1920s, people begin one's study tanning waste process, recovery and utilization, and Chinese scholars has carried out extensive research in decades, obtains a large amount of achievements in research in fields such as food, feed, makeup, fertilizer and tanning agents.China natural resources utilizes the collagen protein in tanning waste to start from late 1980s, and mainly for the production of manufacture feed, fertilizer, gelatin etc., added value is low, is unfavorable for the popularization of tanning waste application technology as the second resource.
For improving water and waste water flocculation treatment efficiency, making up the deficiency that gravity settling effect is single, meeting the effluent quality requirement improved constantly; Recycling process hides waste collagen albumen simultaneously.Adopt proper method by Fe
3o
4magnetic fluid is combined with the protein modified material of process hides waste collagen prepares magnetic cation flocculation agent, give flocculation agent by magnetic, utilize the action of a magnetic field to strengthen the solid-liquid separation effect of flocculation treatment, improve flocculation treatment effluent quality, reduce water treatment running cost, reduce flco water ratio; The treatment of wastes with processes of wastes against one another, the high level conversion for process hides waste collagen albumen provides a feasible approach.
Embodiment 1
The preparation method of the collagen-modified cationic flocculant of magnetic of the present embodiment, comprising:
(1) process hides waste collagen proteolysis: appropriate process hides waste collagen albumen is joined in reactor, adds the water of scurf quality 20 times, be warming up to 60 DEG C, add the vitriol oil of collagen protein quality 1%, stirring reaction 60 minutes.Be 7 by the aqueous sodium hydroxide solution adjust ph that appropriate mass concentration is 20%.
(2) magnetic collagen hydrolysate mixture preparation: in above-mentioned collagen hydrolyzed solution, add collagen protein quality 30% Span-80 tensio-active agent, at 40 DEG C of temperature, dispersed with stirring 60 minutes.The Fe of collagen protein quality 30% is added after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 5 minutes, then slowly adds the Virahol of collagen protein quality 10 times under rapid stirring state, then ultrasonic disperse 5 minutes.The mass concentration adding collagen protein quality 2 times is the glutaraldehyde water solution of 25%, rapid stirring 60 minutes, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate.Suspension is after Magneto separate, and the solid washed with isopropyl alcohol several of acquisition, at 20 DEG C of temperature, drying is rear for subsequent use.
(3) graft copolymerization: join in reactor by appropriate magnetic collagen hydrolysate, adds the water of magnetic collagen hydrolysate quality 30 times, at 40 DEG C of temperature, is stirred to dissolving.Take the acrylamide of magnetic collagen hydrolysate quality 3 times, add in above-mentioned reactor after dissolving by suitable quantity of water, temperature of reaction system controls at 70 DEG C.Take acrylamide quality 1% Potassium Persulphate, dissolve by suitable quantity of water, be slowly added drop-wise in above-mentioned reaction system in 60 minutes, then react 30 minutes.
(4) cationization: above-mentioned reaction system is cooled to 40 DEG C, adds the formaldehyde that molar weight is acrylamide molar weight 0.5, is the aqueous sodium hydroxide solution adjust ph 8 of 20%, reacts 3 hours by mass concentration.Add the dimethylamine identical with formaldehyde molar weight, continue reaction 3 hours.Add the concentrated hydrochloric acid identical with formaldehyde molar weight, react 1 hour.Obtain the collagen-modified cationic flocculant of magnetic.
Embodiment 2
The preparation method of the collagen-modified cationic flocculant of magnetic of the present embodiment, comprising:
(1) process hides waste collagen proteolysis: appropriate process hides waste collagen albumen is joined in reactor, adds the water of collagen protein quality 50 times, be warming up to 100 DEG C, add the concentrated hydrochloric acid of scurf quality 3%, stirring reaction 90 minutes.Be 7 by the aqueous sodium hydroxide solution adjust ph that appropriate mass concentration is 20%.
(2) magnetic collagen hydrolysate mixture preparation: in above-mentioned collagen hydrolyzed solution, add collagen protein quality 60% cetyl trimethylammonium bromide tensio-active agent, at 70 DEG C of temperature, dispersed with stirring 90 minutes.The Fe of collagen protein quality 60% is added after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 15 minutes, then slowly adds the Virahol of scurf quality 30 times under rapid stirring state, then ultrasonic disperse 15 minutes.The mass concentration adding scurf quality 6 times is the glutaraldehyde water solution of 25%, rapid stirring 90 minutes, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate.Suspension is after Magneto separate, and the solid washed with isopropyl alcohol several of acquisition, at 50 DEG C of temperature, drying is rear for subsequent use.
(3) graft copolymerization: join in reactor by appropriate magnetic collagen hydrolysate, adds the water of magnetic collagen hydrolysate quality 70 times, at 70 DEG C of temperature, is stirred to dissolving.Take the acrylamide of magnetic collagen hydrolysate quality 7 times, add in above-mentioned reactor after dissolving by suitable quantity of water, temperature of reaction system controls at 100 DEG C.Take acrylamide quality 3% Sulfothiorine, join in reaction system after dissolving by suitable quantity of water.Take the Potassium Persulphate identical with Sulfothiorine molar weight, dissolve by suitable quantity of water, be slowly added drop-wise in above-mentioned reaction system in 90 minutes, then react 60 minutes.
(4) cationization: above-mentioned reaction system is cooled to 70 DEG C, adds the formaldehyde that molar weight is acrylamide molar weight 0.8, is the aqueous sodium hydroxide solution adjust ph 10 of 20%, reacts 6 hours by mass concentration.Add the dimethylamine identical with formaldehyde molar weight, continue reaction 6 hours.Add the concentrated hydrochloric acid identical with formaldehyde molar weight, reaction 1-3 hour.Obtain the collagen-modified cationic flocculant of magnetic.
Embodiment 3
Initiator is ammonium persulphate, and other are identical with embodiment 1.
Embodiment 4
Initiator is Sulfothiorine and ammonium persulphate oxidation-reduction trigger system, and wherein, the mol ratio of Sulfothiorine and ammonium persulphate is 1:1, and other are identical with example 2.
Embodiment 5
Initiator is Sulfothiorine and hydrogen peroxide oxidation-reduction initiating system, and wherein, the mol ratio of Sulfothiorine and hydrogen peroxide is 1:1, and other are identical with example 2.
Embodiment 6
The preparation method of the collagen-modified cationic flocculant of magnetic of the present embodiment, comprising:
(1) process hides waste collagen proteolysis: appropriate process hides waste collagen albumen is joined in reactor, adds the water of scurf quality 35 times, be warming up to 80 DEG C, add the vitriol oil of collagen protein quality 2%, stirring reaction 75 minutes.Be 7 by the aqueous sodium hydroxide solution adjust ph that appropriate mass concentration is 30%.
(2) magnetic collagen hydrolysate mixture preparation: in above-mentioned collagen hydrolyzed solution, add collagen protein quality 45% Span80 tensio-active agent, at 55 DEG C of temperature, dispersed with stirring 75 minutes.The Fe of collagen protein quality 45% is added after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 10 minutes, then slowly adds the Virahol of collagen protein quality 20 times under rapid stirring state, then ultrasonic disperse 10 minutes.The mass concentration adding collagen protein quality 4 times is the glutaraldehyde water solution of 25%, rapid stirring 75 minutes, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate.Suspension is after Magneto separate, and the solid washed with isopropyl alcohol several of acquisition, at 35 DEG C of temperature, drying is rear for subsequent use.
(3) graft copolymerization: join in reactor by appropriate magnetic collagen hydrolysate, adds the water of magnetic collagen hydrolysate quality 50 times, at 55 DEG C of temperature, is stirred to dissolving.Take the acrylamide of magnetic collagen hydrolysate quality 5 times, add in above-mentioned reactor after dissolving by suitable quantity of water, temperature of reaction system controls at 85 DEG C.Take acrylamide quality 2% Potassium Persulphate, dissolve by suitable quantity of water, be slowly added drop-wise in above-mentioned reaction system in 75 minutes, then react 45 minutes.
(4) cationization: above-mentioned reaction system is cooled to 55 DEG C, adds the formaldehyde that molar weight is acrylamide molar weight 0.6, is the aqueous sodium hydroxide solution adjust ph 9 of 30%, reacts 5 hours by mass concentration.Add the dimethylamine identical with formaldehyde molar weight, continue reaction 4 hours.Add the concentrated hydrochloric acid identical with formaldehyde molar weight, react 2 hours.Obtain the collagen-modified cationic flocculant of magnetic.
Embodiment 7
In step (1), add the vitriol oil of collagen protein quality 2%, add the concentrated hydrochloric acid of collagen protein quality 1%.
In step (2), the mass concentration adding collagen protein quality 4 times is the glutaraldehyde water solution of 32%.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.
The method for hydrolysis of collagen described in the present invention is the acid-hydrolysis method adopting concentrated hydrochloric acid, the vitriol oil; for the acid hydrolysis collagen adopting other kind; without departing from the inventive concept of the premise; the collagen-modified cationic flocculant of preparation magnetic, should be considered as belonging to protection scope of the present invention.
The method for hydrolysis of collagen described in the present invention is acid-hydrolysis method; employing alkaline process, enzyme process, enzyme process are combined with acid system, method is hydrolyzed collagen to enzyme process with alkaline process is combined etc.; without departing from the inventive concept of the premise; the collagen-modified cationic flocculant of preparation magnetic, should be considered as belonging to protection scope of the present invention.
Modified monomer described in the present invention is acrylamide; for other monomer of employing; the monomers such as such as methyl acrylate, butyl acrylate, vinylbenzene participate in graft copolymerization; without departing from the inventive concept of the premise; the collagen-modified cationic flocculant of preparation magnetic, should be considered as belonging to protection scope of the present invention.
Collagen described in the present invention derives from process hides solid waste; for the collagen taking from the generation of other production departments; without departing from the inventive concept of the premise, the collagen-modified cationic flocculant of preparation magnetic, should be considered as belonging to protection scope of the present invention.
Containing-NH in collagen hydrolysate molecule
2, the functional group such as-COOH ,-OH, be easy to and Fe
3o
4magnetic fluid combines, with acrylic amide graft copolymerization modification, preparation condition is gentle, simple to operate.
Adopt such scheme, take full advantage of industrial waste, achieve changing waste into resources and utilize; Magneticsubstance is used for the preparation of flocculation agent, utilizes the action of a magnetic field to strengthen the solid-liquid separation effect of flocculation treatment, improve flocculation treatment effluent quality, reduce water treatment running cost, reduce flco water ratio.
Claims (9)
1. the collagen-modified cationic flocculant of magnetic, is characterized in that: main with process hides waste collagen albumen for raw material, be combined with magnetic fluid and be prepared from.
2. the preparation method of the collagen-modified cationic flocculant of magnetic according to claim 1, it is characterized in that: comprise the following steps: with process hides waste collagen albumen for raw material, through hydrolysis, in conjunction with obtaining the collagen-modified cationic flocculant of magnetic after magnetic fluid, graft copolymerization, cationization.
3. the preparation method of the collagen-modified cationic flocculant of magnetic according to claim 2, is characterized in that: comprise the following steps:
(1) process hides scrap leather bits hydrolysis:
Appropriate process hides scrap leather bits are joined in reactor, adds scurf quality 20-50 water doubly, be warming up to 60-100 DEG C, hydrolysis reaction, obtain collagen hydrolyzed solution;
(2) magnetic collagen hydrolysate preparation:
In above-mentioned collagen hydrolyzed solution, add collagen protein quality 30-60% tensio-active agent, at 40-70 DEG C of temperature, dispersed with stirring, adds the Fe of collagen protein quality 30-60% after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse, then slowly adds collagen protein quality 10-30 Virahol doubly under rapid stirring state, then ultrasonic disperse, adds glutaraldehyde water solution, rapid stirring, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate, wherein, glutaraldehyde quality is the 50-150% of scurf quality, suspension after Magneto separate, the solid of acquisition with washed with isopropyl alcohol for several times, for subsequent use after dry at 20-50 DEG C of temperature;
(3) graft copolymerization
Appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagen hydrolysate quality 30-70 water doubly, at 40-70 DEG C of temperature, be stirred to dissolving, take magnetic collagen hydrolysate quality 3-7 acrylamide doubly, add in above-mentioned reactor after dissolving by suitable quantity of water, temperature of reaction system controls at 70-100 DEG C, take acrylamide quality 1-3% initiator, dissolve by suitable quantity of water, react;
(4) cationization:
Above-mentioned reaction system is cooled to 40-70 DEG C, add the formaldehyde that molar weight is acrylamide molar weight 0.5-0.8, with aqueous sodium hydroxide solution adjust ph 8-10, reaction, add the dimethylamine identical with formaldehyde molar weight, continue reaction, add the concentrated hydrochloric acid identical with formaldehyde molar weight, reaction, obtains the collagen-modified cationic flocculant of magnetic.
4. the preparation method of the collagen-modified cationic flocculant of magnetic according to claim 3, is characterized in that: in step (1), be warming up to 60-100 DEG C, add the acid of scurf quality 1-5%, stirring reaction, adjust ph is or close to 7, obtains collagen hydrolyzed solution.
5. the preparation method of the collagen-modified cationic flocculant of the magnetic according to claim 3 or 4, is characterized in that: in step (2), and the mass concentration of glutaraldehyde water solution is 25%, and the addition of this glutaraldehyde water solution is collagen protein quality 2-6 times.
6. the preparation method of the collagen-modified cationic flocculant of the magnetic according to claim 3 or 4, it is characterized in that: in step (2), in above-mentioned collagen hydrolyzed solution, add collagen protein quality 30-60% tensio-active agent, at 40-70 DEG C of temperature, dispersed with stirring 60-90 minute, adds the Fe of collagen protein quality 30-60% after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 5-15 minute, then slowly adds collagen protein quality 10-30 Virahol doubly under rapid stirring state, ultrasonic disperse 5-15 minute again, adding collagen protein quality 2-6 mass concentration is doubly the glutaraldehyde water solution of 25%, rapid stirring 60-90 minute, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate, suspension after Magneto separate, the solid of acquisition with washed with isopropyl alcohol for several times, for subsequent use after dry at 20-50 DEG C of temperature,
In step (3), appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagen hydrolysate quality 30-70 water doubly, at 40-70 DEG C of temperature, be stirred to dissolving, take magnetic collagen hydrolysate quality 3-7 acrylamide doubly, add in above-mentioned reactor after dissolving by suitable quantity of water, temperature of reaction system controls at 70-100 DEG C, take acrylamide quality 1-3% initiator, dissolve by suitable quantity of water, be slowly added drop-wise in above-mentioned reaction system in 60-90 minute, then react 30-60 minute.
7. the preparation method of the collagen-modified cationic flocculant of the magnetic according to claim 3 or 4, it is characterized in that: in step (1), acid is the vitriol oil, concentrated hydrochloric acid and/or its mixture, is or close to 7 by aqueous sodium hydroxide solution adjust ph.
8. the preparation method of the collagen-modified cationic flocculant of the magnetic according to claim 3 or 4, is characterized in that: in step (1) and step (4), aqueous sodium hydroxide solution mass concentration is 20%.
9. the preparation method of the collagen-modified cationic flocculant of the magnetic according to claim 3 or 4, it is characterized in that: in step (3), initiator is Potassium Persulphate, ammonium persulphate, Sulfothiorine-Potassium Persulphate initiator system, Sulfothiorine-ammonium persulphate initiator system, Sulfothiorine-hydrogen peroxide.
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| CN109019825A (en) * | 2018-10-09 | 2018-12-18 | 宁波沸柴机器人科技有限公司 | A kind of efficient treating agent for papermaking wastewater and its preparation method and application |
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