CN104341035B - Collagen-modified cationic flocculant of a kind of magnetic and preparation method thereof - Google Patents
Collagen-modified cationic flocculant of a kind of magnetic and preparation method thereof Download PDFInfo
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- CN104341035B CN104341035B CN201410435098.3A CN201410435098A CN104341035B CN 104341035 B CN104341035 B CN 104341035B CN 201410435098 A CN201410435098 A CN 201410435098A CN 104341035 B CN104341035 B CN 104341035B
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- 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
Abstract
The present invention relates to collagen-modified cationic flocculant of a kind of magnetic and preparation method thereof, mainly, taking process hides waste collagen albumen as raw material, be combined and be prepared from magnetic fluid. Beneficial effect of the present invention: for flocculant preparation, utilize magnetic fields to strengthen the solid-liquid separation effect of flocculation treatment magnetic material, improve flocculation treatment effluent quality, reduce water treatment operating cost, reduce flco moisture content. Realize the recycling of tanning waste, reduced tanning production pollutant emission. Magnetic collagen hydrolysate is through graft copolymerization and cation modifying, and modified product has good flocculating property. The collagen-modified cationic flocculant of magnetic is easy to be degraded by microorganisms in environment, and in environment, life period is short, residual quantity is low.
Description
(1) technical field
The invention belongs to water treatment agent preparation field, be specifically related to the collagen-modified cationic flocculant of a kind of magnetic andIts preparation method.
(2) background technology
Flocculation is time-honored method for treating water. At present, flocculence is widely used in the purification of productive life water, city is rawSewage alive and Industrial Wastewater Treatment, operating condition, disposal cost and final outflow water quality etc. to subsequent treatment operation have aobviousThe impact of work.
Flocculence is processed the process of water and waste water, adds exactly flocculant in water body, makes colloid and suspended particle de-Steady cohesion, by gravitational settling effect, realizes the process of Separation of Solid and Liquid. Separation of Solid and Liquid process one in water and waste water flocculating processingAspect requires colloid in water outlet, suspended particle concentration low; Require on the other hand that solid liquid interface fall off rate is fast, colloid or suspensionThe sludge volume forming after composition granule sedimentation is little. Flocculant acts on homodisperse colloid, suspension in water or waste water, makes itMutually assemble, the flco that forming radius is large, solid, is beneficial to gravitational settling, realizes purification of water quality. Visible, the performance of flocculantDirectly affect the flocculation treatment effect of water or waste water.
The surface charge of colloid, suspended particle and volume are two principal elements that affect flocculating setting effect. FlocculationAgent can in and colloid, suspended particle surface charge, weaken repulsive force between colloid, suspended particle, make colloid, suspensionParticle is combination gradually, and particle volume, density increase; High polymer coagulant molecular weight and volume are larger, with active group, easily withColloidal solid combination, generation chemical bonding, net are caught the effects such as volume is swept, co-precipitation. The above-mentioned effect of flocculant makes colloid, suspensionComposition granule is easy to flocculating setting from water, effectively separates thereby realize solid-liquid.
Now widely used flocculant, is divided into inorganic and organic flocculant according to composition; Be divided into low point according to molecular weightSon and high polymer coagulant; Be divided into anion, cation, nonionic and both sexes flocculation by electrically charged character after functional group's dissociationAgent.
Inorganic flocculating agent mainly contains aluminium salt and molysite, and inorganic flocculating agent dosage is large, and sinking speed is slow, gradually by inorganic heightMolecular flocculant replaces. Inorganic polymer flocculant is also that molecular weight is generally 1 × 10 taking aluminium salt and molysite as main5, poly-aluminium is heavyReduction of speed degree is slow, have aluminium residual, and Polyferric Sulfate easily makes that water is painted, alkalescence is strong.
The electrically charged active group of organic polymer coargulator is many, and structure is various, and the salt that coexisted, pH value and temperature affectLittle, flocculation rate is fast, has overcome the shortcoming of inorganic flocculating agent. Organic synthesis flocculant is effective, but cost high, be difficult for biology and fallSeparate. Conventional organic polymer coargulator polyacrylamide, although itself is without any toxicity, difficult degradation easily causes secondary dirtDye. Natural polymer and derivative thereof are biodegradable, and degraded intermediate is to the mankind and environmentally friendly. But natural polymer flocculationThe flocculation activity of agent a little less than, after suitable chemical modification, can obtain good flocculating effect. At present, the research of organic flocculantTend to the chemical modification of natural polymers.
In actual applications, in order to improve water or water treatment effect, when do the flocculation of flocculant generation with molysite, aluminium saltBody is tiny, loose, while being unfavorable for sedimentation, often adds the flocculating polymer such as polyacrylamide with absorption, bridging action simultaneouslyAgent makes tiny, loose flco become thick and closely knit, improves flocculating setting effect.
Along with the development of and flocculant Study on mechanism theoretical to flocculating setting, cation polymeric flocculant moreMore cause extensive concern. Cation polymeric flocculant is to water-borne glue body or particle has charging neutrality and adsorption bridging is doneWith, thereby make the particulate in system take off surely, flocculate and contribute to sedimentation.
At present, no matter be the development of novel flocculant, or treatment effect requirement study for water quality with for meetingThe condition that multiple flocculant is used in conjunction with and method, be all according to gravitational settling theory, under Action of Gravity Field, realizes Separation of Solid and Liquid.
The novel flocculant of exploitation function admirable, safety and environmental protection is the weight that improves water and the research of waste water flocculating treatment effectPoint. Up to now, the aspects such as that novel flocculant research mainly concentrates on is efficient, low dose, and separate, press down realizing rapid flocculationThe aspects such as flco fragmentation processed, minimizing flco moisture content, particularly not only rely on gravitational settling to realize the novel flocculation of Separation of Solid and LiquidAgent is also relatively short of.
(3) summary of the invention
The present invention is in order to make up the deficiencies in the prior art, provide the collagen-modified cationic flocculant of a kind of magnetic andIts preparation method, the invention provides one taking process hides waste collagen albumen as raw material, is combined with magnetic fluid, changes through proper methodProperty, prepares the method for the collagen-modified cationic flocculant of magnetic. For transforming, the high value of leather industry albumen base refuse findsA feasible approach. Utilize magnetic fields to strengthen flocculation treatment solid-liquid separation effect. For the preparation and application of flocculant are carriedNew thinking and method are supplied.
The present invention is achieved through the following technical solutions:
The collagen-modified cationic flocculant of a kind of magnetic, its special character is: mainly with process hides waste collagen albumenFor raw material, be combined and be prepared from magnetic fluid.
A preparation method for the collagen-modified cationic flocculant of magnetic described in basis, comprises the following steps: withProcess hides waste collagen albumen is raw material, through hydrolysis, obtain magnetic collagen after in conjunction with magnetic fluid, graft copolymerization, cationization and changeProperty cationic flocculant.
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, add scurf quality 20-50 water doubly, be warming up to 60-100DEG C, hydrolysis, obtains collagen hydrolyzate;
(2) magnetic collagen hydrolysate preparation:
In above-mentioned collagen hydrolyzate, add collagen quality 30-60% surfactant, 40-70 DEG C of temperatureUnder degree, dispersed with stirring, is cooled to the Fe that adds collagen quality 30-60% after room temperature3O4Magnetic fluid, ultrasonic dispersion, then existsUnder rapid stirring state, slowly add collagen quality 10-30 isopropyl alcohol doubly, more ultrasonic dispersion, add glutaraldehyde water-solubleLiquid, rapid stirring, makes Fe3O4The compound suspension of magnetic fluid and collagen hydrolysate, wherein, glutaraldehyde quality isThe 50-150% of scurf quality, suspension is after magnetic separates, and washed with isopropyl alcohol several for the solid of acquisition, at 20-50 DEG C of temperatureFor subsequent use after dry;
(3) graft copolymerization
Appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagen hydrolysate quality 30-The water of 70 times, at 40-70 DEG C of temperature, is stirred to dissolving, takes magnetic collagen hydrolysate quality 3-7 acryloyl doublyAmine, adds in above-mentioned reactor after dissolving by suitable quantity of water, and temperature of reaction system is controlled at 70-100 DEG C, takes acrylamide quality1-3% initator, dissolves by suitable quantity of water, reacts;
(4) cationization:
Above-mentioned reaction system is cooled to 40-70 DEG C, and adding mole is the formaldehyde of acrylamide mole 0.5-0.8,With sodium hydrate aqueous solution adjusting pH value 8-10, reaction, adds the dimethylamine identical with formaldehyde mole, continues reaction, addsThe concentrated hydrochloric acid identical with formaldehyde mole, 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 60-100DEG C, adding the acid of scurf quality 1-5%, stirring reaction, regulates pH value be or approach 7, obtains collagen hydrolyzate.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (2), glutaraldehyde water solutionMass concentration be 25%, the addition of this glutaraldehyde water solution be collagen quality 2-6 doubly.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (2), at above-mentioned collagenIn protein hydrolyzate, add collagen quality 30-60% surfactant, at 40-70 DEG C of temperature, dispersed with stirring 60-90 dividesClock, is cooled to the Fe that adds collagen quality 30-60% after room temperature3O4Magnetic fluid, ultrasonic dispersion 5-15 minute, then fastUnder stirring, slowly add collagen quality 10-30 isopropyl alcohol doubly, more ultrasonic dispersion 5-15 minute, add collagenThe glutaraldehyde water solution that quality 2-6 mass concentration is doubly 25%, rapid stirring 60-90 minute, makes Fe3O4Magnetic fluid and collagenThe compound suspension of protein hydrolysate, suspension is after magnetic separates, and washed with isopropyl alcohol several for the solid of acquisition, at 20-It is for subsequent use after dry at 50 DEG C of temperature,
In step (3), appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagen hydrolysateAmount 30-70 water doubly, at 40-70 DEG C of temperature, is stirred to dissolving. Take magnetic collagen hydrolysate quality 3-7 doublyAcrylamide, with suitable quantity of water dissolve after add in above-mentioned reactor, temperature of reaction system is controlled at 70-100 DEG C. Take propyleneAcid amides quality 1-3% initator, dissolves by suitable quantity of water, is slowly added drop-wise in above-mentioned reaction system, then reacts in 60-90 minute30-60 minute.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (1), acid be the concentrated sulfuric acid,Concentrated hydrochloric acid and/or its mixture, regulate pH value be or approach 7 with sodium hydrate aqueous solution.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (1) and step (4), hydrogenAqueous solution of sodium oxide mass concentration is 20%.
The preparation method of the collagen-modified cationic flocculant of magnetic of the present invention, in step (3), initator is over cureAcid potassium, ammonium persulfate, sodium thiosulfate-potassium peroxydisulfate initiator system, sodium thiosulfate-ammonium persulfate initiator system, sulfo-sulphurAcid sodium-hydrogen peroxide.
The present invention is taking process hides waste collagen albumen as raw material, after hydrolysis, with Fe3O4Magnetic fluid combination, through graft copolymerization and sun fromSonization, the collagen-modified cationic flocculant of preparation magnetic. Feature of the present invention is magnetic separation technique for flocculationThe preparation of agent, makes flocculant possess magnetic, by magnetic separate mode enhanced flocculation solid-liquid separation effect, improves flocculation treatment water outletWater quality, reduces water treatment operating cost, reduces flco moisture content.
The present invention prepares magnetic flocculant taking process hides waste collagen albumen as raw material, takes full advantage of collagen resource, forSolving the discharge of process hides solid waste and piling up environmental pollution problem provides effective way, has realized the resource profit of tanning wasteWith.
The present invention not only will consider to meet requirement to flocculating effect of purification of water quality, sewage disposal, realize tanning waste moneySourceization is utilized, and also will consider to meet the requirement that flocculant is easy to degraded. Collagen hydrolysate is easy to by micro-life in environmentThing degraded, in environment, life period is short, residual quantity is low. For improving the flocculating property of collagen hydrolysate, to combiningFe3O4The collagen hydrolysate of magnetic fluid has carried out graft copolymerization and cation modifying, makes the collagen-modified sun of magneticIonic flocculant meets purification of water quality, the demand of sewage disposal to high-performance flocculant.
Beneficial effect of the present invention:
(1) magnetic material is prepared for flocculant, utilized magnetic fields to strengthen the solid-liquid separation effect of flocculation treatment, carryHigh flocculation treatment effluent quality, reduces water treatment operating cost, reduces flco moisture content.
(2) realize the recycling of tanning waste, reduced tanning production pollutant emission.
(3) magnetic collagen hydrolysate is through graft copolymerization and cation modifying, and modified product has good waddingSolidifying performance.
(4) the collagen-modified cationic flocculant of magnetic is easy to be degraded by microorganisms in environment, in environment, existsTime is short, residual quantity is low.
(4) detailed description of the invention
In flocculation sediment, water or waste water contain many little colloids, suspension is difficult for sedimentation under Action of Gravity Field, dividesFrom, affect water or water treatment effect. If by colloid, suspension and magnetic flocculant effect, magnetic flocculate is done at magnetic forceMove on separator along magnetic line of force direction with lower, efficiently separate thereby realize colloid, suspension in water or waste water, effectively improveFlocculation removal effect.
In modern industry waste water and sanitary sewage, the content of organic matter is high, and organic matter particle surface is conventionally electronegative, sun fromSub-high polymer coagulant more easily makes colloid electronegative in system, de-steady, the flocculation of suspension, realizes Separation of Solid and Liquid.
Nature high molecular flocculant has renewable, substantially nontoxic, the easy biochemical degradation of raw material, does not cause secondary dirtDye, active group is many, be easy to adopt as required distinct methods to carry out the plurality of advantages such as modification, nature high molecular flocculantPreparation and application research is day by day in widespread attention. Protein molecule has various active group, and structure is various, is suitable for changingProperty is prepared the high polymer coagulant of different performance. Collagen is present in the tissues such as skin, bone, cartilage and the tendon of animal,Wide material sources; Contain-NH2 ,-the COOH ,-functional groups such as OH in collagen partial hydrolystate molecule, be easy to carry out cationizationModification.
In leather industry, only have the collagen of 22%-30% to become leather, all the other are thrown away as solid waste in process hides process.According to statistics, China's leather industry is annual produces 1,400,000 tons taking collagen as main refuse. Tanning waste is landfilled or at environmentMiddle natural degradation, serious environment pollution water body and soil, waste collagen resource. Therefore, collagen is converted into high attachedValue added or large chemical products are the only ways that solve China's tanning production solid waste pollution environment. The twenties in 20th centuryEnd, people begin one's study tanning waste processing, recovery and utilization, Chinese scholars has been carried out extensive grinding in decadesStudy carefully, obtained a large amount of achievements in research in fields such as food, feed, cosmetics, fertilizer and tanning agents. China natural resources utilization systemCollagen in leather refuse starts from late 1980s, mainly for the production of manufacturing feed, fertilizer, gelatin etc., added valueLow, be unfavorable for the popularization of tanning waste application technology as the second resource.
For improving water and waste water flocculating treatment effeciency, make up the single deficiency of gravitational settling effect, meet and to improve constantlyEffluent quality requirement; Recycling process hides waste collagen albumen simultaneously. Adopt proper method by Fe3O4Magnetic fluid and process hides scrap rubberFormer protein modified material, in conjunction with preparing magnetic cation flocculant, is given flocculant by magnetic, utilizes magnetic fields to strengthen flocculationThe solid-liquid separation effect of processing, improves flocculation treatment effluent quality, reduces water treatment operating cost, reduces flco moisture content; WithGiving up, it is useless to control, for the feasible approach that provides is provided the high value of process hides waste collagen albumen.
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, add scurf matterMeasure the water of 20 times, be warming up to 60 DEG C, add the concentrated sulfuric acid of collagen quality 1%, stirring reaction 60 minutes. Dense by appropriate qualityDegree is that to regulate pH value be 7 for 20% sodium hydrate aqueous solution.
(2) magnetic collagen hydrolysate compound preparation: in above-mentioned collagen hydrolyzate, add collagen eggWhite matter amount 30%Span-80 surfactant, at 40 DEG C of temperature, dispersed with stirring 60 minutes. After being cooled to room temperature, add collagenThe Fe of albumen quality 30%3O4Magnetic fluid, ultrasonic dispersion 5 minutes then slowly adds collagenic protein under rapid stirring stateMeasure the isopropyl alcohol of 10 times, more ultrasonic dispersion 5 minutes. The glutaraldehyde that the mass concentration that adds 2 times of collagen quality is 25% is water-solubleLiquid, rapid stirring 60 minutes, makes Fe3O4The compound suspension of magnetic fluid and collagen hydrolysate. Suspension divides through magneticFrom rear, washed with isopropyl alcohol several for the solid of acquisition, dry rear for subsequent use at 20 DEG C of temperature.
(3) graft copolymerization: appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagenThe water that hydrolysate quality is 30 times, at 40 DEG C of temperature, is stirred to dissolving. Take third of 3 times of magnetic collagen hydrolysate qualityAlkene acid amides, adds in above-mentioned reactor after dissolving by suitable quantity of water, and temperature of reaction system is controlled at 70 DEG C. Take acrylamide quality1% potassium peroxydisulfate, dissolves by suitable quantity of water, is slowly added drop-wise in above-mentioned reaction system, then reacts 30 minutes in 60 minutes.
(4) cationization: above-mentioned reaction system is cooled to 40 DEG C, and adding mole is acrylamide mole 0.5The sodium hydrate aqueous solution that formaldehyde is 20% by mass concentration regulates pH value 8, reacts 3 hours. Add identical with formaldehyde moleDimethylamine, continue reaction 3 hours. Add the concentrated hydrochloric acid identical with formaldehyde mole, react 1 hour. Obtain magnetic collagen eggWhite modified cation flocculant.
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, add collagen eggThe water that white matter amount is 50 times, is warming up to 100 DEG C, adds the concentrated hydrochloric acid of scurf quality 3%, stirring reaction 90 minutes. Dense by appropriate qualityDegree is that to regulate pH value be 7 for 20% sodium hydrate aqueous solution.
(2) magnetic collagen hydrolysate compound preparation: in above-mentioned collagen hydrolyzate, add collagen eggWhite matter amount 60% softex kw surfactant, at 70 DEG C of temperature, dispersed with stirring 90 minutes. Be cooled to chamberAfter temperature, add the Fe of collagen quality 60%3O4Magnetic fluid, ultrasonic dispersion 15 minutes then slowly adds under rapid stirring stateEnter the isopropyl alcohol of 30 times of scurf quality, more ultrasonic dispersion 15 minutes. The mass concentration that adds 6 times of scurf quality is 25% penta 2The aldehyde aqueous solution, rapid stirring 90 minutes, makes Fe3O4The compound suspension of magnetic fluid and collagen hydrolysate. SuspensionAfter magnetic separates, washed with isopropyl alcohol several for the solid of acquisition, dry rear for subsequent use at 50 DEG C of temperature.
(3) graft copolymerization: appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagenThe water that hydrolysate quality is 70 times, at 70 DEG C of temperature, is stirred to dissolving. Take third of 7 times of magnetic collagen hydrolysate qualityAlkene acid amides, adds in above-mentioned reactor after dissolving by suitable quantity of water, and temperature of reaction system is controlled at 100 DEG C. Take acrylamide matterMeasure 3% sodium thiosulfate, after dissolving by suitable quantity of water, join in reaction system. Take the mistake identical with sodium thiosulfate molePotassium sulfate, dissolves by suitable quantity of water, is slowly added drop-wise in above-mentioned reaction system, then reacts 60 minutes in 90 minutes.
(4) cationization: above-mentioned reaction system is cooled to 70 DEG C, and adding mole is acrylamide mole 0.8The sodium hydrate aqueous solution that formaldehyde is 20% by mass concentration regulates pH value 10, reacts 6 hours. Add identical with formaldehyde moleDimethylamine, continue reaction 6 hours. Add the concentrated hydrochloric acid identical with formaldehyde mole, reaction 1-3 hour. Obtain magnetic collagenProtein modified cationic flocculant.
Embodiment 3
Initator is ammonium persulfate, and other are identical with embodiment 1.
Embodiment 4
Initator is sodium thiosulfate and ammonium persulfate oxidation-reduction trigger system, wherein, and sodium thiosulfate and persulfuric acidThe mol ratio of ammonium is 1:1, and other are identical with example 2.
Embodiment 5
Initator is sodium thiosulfate and hydrogen peroxide oxidation-reduction initiating system, wherein, and sodium thiosulfate and peroxidatingThe mol ratio of hydrogen 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, add scurf matterMeasure the water of 35 times, be warming up to 80 DEG C, add the concentrated sulfuric acid of collagen quality 2%, stirring reaction 75 minutes. Dense by appropriate qualityDegree is that to regulate pH value be 7 for 30% sodium hydrate aqueous solution.
(2) magnetic collagen hydrolysate compound preparation: in above-mentioned collagen hydrolyzate, add collagen eggWhite matter amount 45%Span80 surfactant, at 55 DEG C of temperature, dispersed with stirring 75 minutes. After being cooled to room temperature, add collagen eggThe Fe of white matter amount 45%3O4Magnetic fluid, ultrasonic dispersion 10 minutes then slowly adds collagen quality under rapid stirring stateThe isopropyl alcohol of 20 times, more ultrasonic dispersion 10 minutes. The glutaraldehyde that the mass concentration that adds 4 times of collagen quality is 25% is water-solubleLiquid, rapid stirring 75 minutes, makes Fe3O4The compound suspension of magnetic fluid and collagen hydrolysate. Suspension divides through magneticFrom rear, washed with isopropyl alcohol several for the solid of acquisition, dry rear for subsequent use at 35 DEG C of temperature.
(3) graft copolymerization: appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagenThe water that hydrolysate quality is 50 times, at 55 DEG C of temperature, is stirred to dissolving. Take third of 5 times of magnetic collagen hydrolysate qualityAlkene acid amides, adds in above-mentioned reactor after dissolving by suitable quantity of water, and temperature of reaction system is controlled at 85 DEG C. Take acrylamide quality2% potassium peroxydisulfate, dissolves by suitable quantity of water, is slowly added drop-wise in above-mentioned reaction system, then reacts 45 minutes in 75 minutes.
(4) cationization: above-mentioned reaction system is cooled to 55 DEG C, and adding mole is acrylamide mole 0.6The sodium hydrate aqueous solution that formaldehyde is 30% by mass concentration regulates pH value 9, reacts 5 hours. Add identical with formaldehyde moleDimethylamine, continue reaction 4 hours. Add the concentrated hydrochloric acid identical with formaldehyde mole, react 2 hours. Obtain magnetic collagen eggWhite modified cation flocculant.
Embodiment 7
In step (1), add the concentrated sulfuric acid of collagen quality 2%, add the concentrated hydrochloric acid of collagen quality 1%.
In step (2), the glutaraldehyde water solution that the mass concentration that adds 4 times of collagen quality is 32%.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assertSpecific 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 that adopts concentrated hydrochloric acid, the concentrated sulfuric acid, for employingThe acid hydrolysis collagen of other kind, without departing from the inventive concept of the premise, the collagen-modified sun of preparation magneticIonic flocculant, 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, for adopting alkaline process, enzyme process, enzyme process and acid systemThe method hydrolysis collagen such as be combined with alkaline process in conjunction with, enzyme process, without departing from the inventive concept of the premise, preparation magnetic glueFormer protein modified cationic flocculant, should be considered as belonging to protection scope of the present invention.
Modified monomer described in the present invention is acrylamide, for example, for adopting other monomer, methyl acrylate, acrylic acidThe monomer such as butyl ester, styrene participates in graft copolymerization, and without departing from the inventive concept of the premise, preparation magnetic is collagen-modifiedCationic flocculant, 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 skin of taking from other production divisions' generationsCollagen, without departing from the inventive concept of the premise, the collagen-modified cationic flocculant of preparation magnetic, should be considered as belonging to thisThe protection domain of invention.
Contain-NH in collagen hydrolysate molecule2,-the COOH ,-functional groups such as OH, be easy to and Fe3O4Magnetic fluidIn conjunction with, with acrylic amide graft copolymerization modification, preparation condition gentleness, simple to operate.
Adopt such scheme, take full advantage of industrial waste, realized changing waste into resources utilization; Magnetic material is used for to waddingThe preparation of solidifying agent, utilizes magnetic fields to strengthen the solid-liquid separation effect of flocculation treatment, improves flocculation treatment effluent quality, reduces waterTreatment operating costs, reduces flco moisture content.
Claims (8)
1. the collagen-modified cationic flocculant of magnetic, is characterized in that: mainly taking process hides waste collagen albumen as raw material,Be combined and be prepared from magnetic fluid,
The preparation method of the described collagen-modified cationic flocculant of magnetic, comprises the following steps: with process hides waste collagen eggWhite be raw material, and obtaining the collagen-modified cation of magnetic after through hydrolysis, in conjunction with magnetic fluid, graft copolymerization, cationization flocculatesAgent.
2. the preparation method of the collagen-modified cationic flocculant of magnetic according to claim 1, is characterized in that: bagDraw together following steps:
(1) process hides scrap leather bits hydrolysis:
Appropriate process hides scrap leather bits are joined in reactor, add scurf quality 20-50 water doubly, be warming up to 60-100 DEG C, waterSeparate reaction, obtain collagen hydrolyzate;
(2) magnetic collagen hydrolysate preparation:
In above-mentioned collagen hydrolyzate, add collagen quality 30-60% surfactant, 40-70 DEG C of temperatureUnder, dispersed with stirring, is cooled to the Fe that adds collagen quality 30-60% after room temperature3O4Magnetic fluid, ultrasonic dispersion, then soonUnder speed stirring, slowly add collagen quality 10-30 isopropyl alcohol doubly, more ultrasonic dispersion, add glutaraldehyde water solution,Rapid stirring, makes Fe3O4The compound suspension of magnetic fluid and collagen hydrolysate, wherein, glutaraldehyde quality is scurfThe 50-150% of quality, suspension is after magnetic separates, and washed with isopropyl alcohol several for the solid of acquisition is dried at 20-50 DEG C of temperatureFor subsequent use afterwards;
(3) graft copolymerization
Appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagen hydrolysate quality 30-70 doublyWater, at 40-70 DEG C of temperature, be stirred to dissolving, take magnetic collagen hydrolysate quality 3-7 acrylamide doubly, useSuitable quantity of water adds in above-mentioned reactor after dissolving, and temperature of reaction system is controlled at 70-100 DEG C, takes acrylamide quality 1-3%Initator, dissolves by suitable quantity of water, reacts;
(4) cationization:
Above-mentioned reaction system is cooled to 40-70 DEG C, and adding mole is the formaldehyde of acrylamide mole 0.5-0.8, uses hydrogenAqueous solution of sodium oxide regulates pH value 8-10, and reaction, adds the dimethylamine identical with formaldehyde mole, continues reaction, adds and firstThe concentrated hydrochloric acid that aldehyde mole is identical, reaction, obtains the collagen-modified cationic flocculant of magnetic.
3. the preparation method of the collagen-modified cationic flocculant of magnetic according to claim 2, is characterized in that: stepSuddenly in (1), be warming up to 60-100 DEG C, add the acid of scurf quality 1-5%, stirring reaction, regulating pH value is 7, obtains collagen eggWhite hydrolyzate.
4. the preparation method of the collagen-modified cationic flocculant of magnetic according to claim 2, is characterized in that: stepSuddenly in (2), the mass concentration of glutaraldehyde water solution is 25%, and the addition of this glutaraldehyde water solution is collagen quality 2-6Doubly.
5. the preparation method of the collagen-modified cationic flocculant of magnetic according to claim 2, is characterized in that: stepSuddenly in (2), in above-mentioned collagen hydrolyzate, add collagen quality 30-60% surfactant, 40-70 DEG C of temperatureUnder degree, dispersed with stirring 60-90 minute, is cooled to the Fe that adds collagen quality 30-60% after room temperature3O4Magnetic fluid, ultrasonic pointLoose 5-15 minute then slowly adds collagen quality 10-30 isopropyl alcohol doubly under rapid stirring state, more ultrasonic dispersion5-15 minute, adds the glutaraldehyde water solution that collagen quality 2-6 mass concentration is doubly 25%, and rapid stirring 60-90 dividesClock, makes Fe3O4The compound suspension of magnetic fluid and collagen hydrolysate, suspension through magnetic separate after, the solid of acquisitionWith washed with isopropyl alcohol several, dry rear for subsequent use at 20-50 DEG C of temperature,
In step (3), appropriate magnetic collagen hydrolysate is joined in reactor, add magnetic collagen hydrolysate matterAmount 30-70 water doubly, at 40-70 DEG C of temperature, is stirred to dissolving, take magnetic collagen hydrolysate quality 3-7 doubly thirdAlkene acid amides, adds in above-mentioned reactor after dissolving by suitable quantity of water, and temperature of reaction system is controlled at 70-100 DEG C, takes acrylamideQuality 1-3% initator, dissolves by suitable quantity of water, is slowly added drop-wise in above-mentioned reaction system, then reacts 30-60 in 60-90 minuteMinute.
6. the preparation method of the collagen-modified cationic flocculant of magnetic according to claim 3, is characterized in that: stepSuddenly in (1), acid is the concentrated sulfuric acid, concentrated hydrochloric acid and/or its mixture, and regulating pH value with sodium hydrate aqueous solution is 7.
7. the preparation method of the collagen-modified cationic flocculant of magnetic according to claim 6, is characterized in that: stepSuddenly in (1) and step (4), sodium hydrate aqueous solution mass concentration is 20%.
8. according to the preparation method of the collagen-modified cationic flocculant of magnetic described in claim 2 or 5, its feature existsIn: in step (3), initator is potassium peroxydisulfate, ammonium persulfate, sodium thiosulfate-potassium peroxydisulfate initiator system, thiosulfuric acidSodium-ammonium persulfate initiator system, sodium thiosulfate-hydrogen peroxide.
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