CN106587373A - Recyclable cationic chitosan type composite paint flocculant - Google Patents

Abstract

The invention discloses a recyclable cationic chitosan type composite paint flocculant. A preparation method of the recyclable cationic chitosan type composite paint flocculant includes the steps of firstly, separating and purifying strains; secondly, screening the strains; thirdly, performing fermental cultivation of the strains; fourthly, preparing composite magnetic microspheres. The prepared paint flocculant has the advantages that the paint flocculant has a good viscosity-removing and eliminating effect on paint, paint slag is nontoxic and odorless, and the paint flocculant is capable of being fast eliminated from circulating water, short in eliminating cycle, evident in effect, low in preparation cost, capable of achieving large-scale production and worthy of popularization.

Description

A kind of repeatable cationic chitosan type Compound paint flocculant for utilizing

Technical field

The present invention relates to Paint flocculant technical field, more particularly to a kind of repeatable cationic chitosan type for utilizing is multiple Close Paint flocculant.

Background technology

With the development of the industries such as automobile industry and furniture manufacturing industry, the consumption of spray paint is more and more, therefore has The coating cloud that much can not be coated on workpiece just becomes " cross and spray " coating, crosses discharge rate and reaches 25-60%.Containing big in these coating Amount volatile organic solvent, endanger the health of the mankind, but also the environment and air around severe contamination.Spraying is to apply Paint under pressure or centrifugal action, is uniformly dispersed into tiny particle, most by material by spray gun or dish-style atomizer Coating cloud particle is just applied to afterwards the process of body surface.The coating cloud for crossing spray normally enters recirculated water, by the tank of indoor and outdoor Take recirculated water out of outdoor, thus staff's body harm can be reduced, and water can be recycled." cross spray " coating by Just very big in the viscosity of itself, therefore will stick on the wall of tank, water pipe and water pump, Jing accumulates over a long period, will be formed compared with Big paint block causes line clogging, thus the operating efficiency of the circulatory system will be reduced.Mechanical curettage method, chemical agent absorption are solidifying Poly- partition method and biology say that solution etc. is the most frequently used several method of spray painting room processing cycle water, wherein being being widely used Learn coacervation.Due to the long-term addition of chemical type flocculating agent, content of organics in recirculated water is caused progressively to be accumulated, COD progressively rises Height, water quality is deteriorated therewith, causes the recirculated water replacement cycle to shorten, and the sediment in waste water resource, and circulation is too many, Solid waste amount is big, and processes method of the solid waste mainly by burning and fill now, therefore increased the pollution to environment, non- But the pollution problem of paint slag is fundamentally solved, the burden of environment is also add, therefore researches and develops green non-poisonous dirt The little flocculant of dye, not only can be greatly lowered solid waste amount, and can be with reduces cost.

Microbial flocculant is biodegradable by the safety non-toxic of output in various microorganism growth process Natural products, it can make the flocculation such as somatic cells in water, suspended particulate and colloidal particle, precipitation, with good ring Border compatibility.Yang Shuanshuan exists《Flocculation of the microbial flocculant to paint waste water is studied》Pass through a series of bolter in one text Choosing, obtains one plant of preferably flocculation bacterial strain FL-2, by carrying out single factor experiment to bacterial strain FL-2, it is determined that optimal condition of culture 30 DEG C, pH is 9, shaking speed is 160r/min, in the composition of culture medium charcoal source be glucose, mixed nitrogen be sodium nitrate, Ammonium chloride and urea, inorganic salts are magnesium sulfate, and good flocculating effect is reached when compounding with bacillusmusilaginosiengineering, but Effect when two kinds of microbial bacterias are compounded with inorganic flocculating agent is bad.A series of bacterium for above being obtained by separation screening steps Strain FL -2 have good flocculating effect, but from from Large-scale culture conditions, relatively costly, needs find and can substitute Charcoal source and the culture medium of nitrogen source culture, reduces cost, are advantageously implemented economic benefit, and control is needed when paint waste water is processed Amount and the addition sequence of compounding bacterial classification that system is added, cause complex steps, improve cost, can will by bio-immobilized technology Bacterial classification is fixed on carrier, is realized continuous operation, is reduced the purpose of production cost, reaches economic benefit and environmental benefit doulbe-sides' victory Effect.

The content of the invention

The object of the invention is exactly to make up the defect of prior art, there is provided a kind of repeatable cationic chitosan for utilizing Type Compound paint flocculant.

The present invention is achieved by the following technical solutions：

A kind of repeatable cationic chitosan type Compound paint flocculant for utilizing, comprises the following steps：

（1）Strain separating is purified

The paint waste water for processing later stage is fitted in aseptic triangular flask, 4 DEG C of preservations are placed in, seed culture is based on into 121 DEG C Lower sterilizing, takes 100 μ L waste water and is inoculated in the seed culture medium of 100ml after cooling, in 37 DEG C of constant temperature Amplification Cultures 24h, then Nutrient solution is diluted to respectively 10-1,10-2,10-3,10-4,10-5,10-6 times, then the bacteria suspension coating by each after diluting On isolation medium, 37 DEG C of incubated 24h, good bacterium colony of choosing form completes initial gross separation, then will be singled out each Bacterium is inoculated in seed culture medium, 37 DEG C of incubated 24h, line is diluted and carried out to the nutrient solution of each bacterium and is isolated and purified, The purifying single bacterium colony for finally obtaining is stored on isolation medium；

（2）Bacteria selection

By step（1）The bacterium separated is inoculated in seed culture medium respectively with oese, at 30 DEG C, the condition of 160r/min Lower culture 72h, with the aqueous suspension ofkaolin of 4g/L the flocculating rate of bacterial classification is tested, and bacterial classification of the flocculating rate more than 50% is retained, and Repeatedly passed on, by the culture presevation for filtering out；

（3）The fermented and cultured of bacterial classification

A, beer waste water and sugaring fermentation waste water are centrifuged into respectively 20min under 5000rpm, suspended impurity are removed, wherein refining sugar Fermentation waste water total sugar content is 19.85g/L, and total nitrogen content is 3263.3mg/L, and beer waste water total sugar content is 196.1g/L, always Nitrogen content is 1796.8mg/L, then according to total sugar concentration 7g/L, charcoal source and nitrogen source compare 50:1 is diluted, and adds phosphoric acid Sodium dihydrogen and disodium hydrogen phosphate, wherein phosphate dihydrogen sodium concentration are 2g/L, and disodium hydrogen phosphate concentration is 5g/L, adds magnesium sulfate The pH for adjusting fermentation medium is 9, and autoclaving is standby；

B, by step（2）In be deposited in the producing strains bacterial classification on inclined-plane and be inoculated in fermentation medium, in 30 DEG C, 150r/min constant temperature 3h is cultivated on oscillator, makes each bacterial strain be in exponential phase, make bacterial classification suspension, be inoculated with according to the inoculum concentration of 5-10% In the fermentation medium prepared to 100ml steps a, under the conditions of being 160r/min in 30 DEG C, rotating speed 72h is cultivated；

C, zymotic fluid obtained in step b is placed on 4 DEG C of high speed freezing centrifuges in 8000r/min be centrifuged 30-40min, will To supernatant in add 2 times amount absolute ethyl alcohols stand 24h at 4 DEG C, then proceed under the conditions of 4 DEG C in 8000r/min Centrifugation 30-40min, by the precipitation for obtaining absolute ethyl alcohol cyclic washing, is placed in bag filter the 48h that dialyses, after freeze-drying Microbial flocculant；

(4) preparation of composite magnetic microballoon

D, by ferric chloride hexahydrate and Iron dichloride tetrahydrate according to ferric iron and ferrous iron mol ratio 1：1 mixing, electric stirring It is fully mixed, be slowly added dropwise while stirring at 30 DEG C 1mol/L NaOH until solution pH be 11, heating makes Its reaction temperature is controlled at 60 DEG C, is then added dropwise over oleic acid stirring reaction 1-1.5h, and reaction is cooled to room temperature after terminating, then With distilled water cyclic washing in neutrality, grind after vacuum drying standby；

E, glacial acetic acid is made into the acetic acid solution that volumetric concentration is 1.5% with distilled water diluting, be passed through nitrogen and add shitosan stirring Until being completely dissolved, the ammonium persulfate solution of 5mmol/L is then slowly added dropwise, it is ensured that completion of dropping in 15min, by acrylic amine It is added thereto after distillation water dissolves with 12 times of amounts, propylene phthalein amine is added after reaction 30-40min, it is slow after reaction 10-20min The micro- life for adding dimethyl diallyl ammonium chloride solution, the product of step d preparation and step c that mass fraction is 60% to prepare Thing flocculant, under agitation, controlling reaction temperature is 50 DEG C, reacts 2.5-3h, after reaction terminates, is cooled to room temperature i.e. Can.

The formulation ratio of described isolation medium is：Beef extract 3-4g/L, peptone 10-12g/L, sodium chloride 5-6g/ L, agar 15-20g/L, plus distilled water to 1000ml；PH value is adjusted to 7.0-7.2, sterilize 20min in 121 DEG C；Seed culture medium Recipe ratio is：Beef extract 3-4g/L, peptone 10-13g/L, sodium chloride 5-7g/L, plus distilled water to 1000ml, adjust pH value to 7-7.2, sterilize 20min in 121 DEG C.

The step（4）In each raw material be according to weight：Ferric chloride hexahydrate 12.1-12.8, oleic acid 0.4- 0.6th, shitosan 4.5-5.4, acrylamide 18-20, dimethyl diallyl ammonium chloride 4.5-5.4, ammonium persulfate 0.05- 0.07th, propylene phthalein amine 1.3-1.5, microbial flocculant 1.8-2.2, appropriate Iron dichloride tetrahydrate, 1mol/L NaOH are fitted Amount, appropriate glacial acetic acid, distillation appropriate amount of water.

It is an advantage of the invention that：The present invention from paint waste water screening, extracting and developing, be purified into microbial flocculant produce Raw bacterium, optimization culture improves its flocculation activity, and reduces the production of microbial flocculant using cheap substrate fermented and cultured Cost so as to can mass produce culture, and the resource to discarding reuses, with good economic benefit and Social benefit, environmental protection is that all many conditions when improving the single use of microbial flocculant or compounding use are limited, the present invention It is set to possess good absorption and magnetic behavior using the magnetic microsphere loading microorganisms flocculant for preparing, and it is easily separated, can Repetitive cycling is utilized, and by chemical coprecipitation nano ferriferrous oxide is prepared, and the magnetic ferroferric oxide surface of preparation has Hydrophily, insoluble in organic solvent, oleic acid one end is hydrophilic group, and the other end is lipophilic group, hydrophilic radical can with hydrophilic Property nano ferriferrous oxide particle surface be connected, be exposed to particle surface then for lipophilic group, reach oil loving purpose, and And define good clad on surface, it is to avoid and the reunion between magnetic particle, stability is improved, then by aqueous free radical Polymerisation is grafted to acrylamide, cationic monomer diallyldimethylammonChloride Chloride on shitosan, improves its cation Degree, increase molecular weight reduces cost, microbial flocculant is anionic, and modification of chitosan is cationic, by the oxygen of nanometer four Change three-iron and microbial flocculant is loaded on modification of chitosan, both compound, and can play the complementation of anion and cation flocculant Synergistic effect, improves flocculating effect, and Paint flocculant prepared by the present invention is to paint with good except viscous and scavenging action, paint The nontoxic odorless of slag, quickly can remove from recirculated water, and cycle of removing is short, effect is significant, and preparation cost is low, can give birth on a large scale Produce, be worthy to be popularized.

Specific embodiment

A kind of repeatable cationic chitosan type Compound paint flocculant for utilizing, comprises the following steps：

（1）Strain separating is purified

The paint waste water for processing later stage is fitted in aseptic triangular flask, 4 DEG C of preservations are placed in, seed culture is based on into 121 DEG C Lower sterilizing, takes 100 μ L waste water and is inoculated in the seed culture medium of 100ml after cooling, in 37 DEG C of constant temperature Amplification Cultures 24h, then Nutrient solution is diluted to respectively 10,10,10,10,10,10 times, then each bacteria suspension after diluting is coated into isolation medium On, 37 DEG C of incubated 24h, good bacterium colony completes initial gross separation to choose form, then each bacterium that will be singled out is inoculated in seed In culture medium, 37 DEG C of incubated 24h dilute to the nutrient solution of each bacterium and carry out line and isolate and purify, by what is finally obtained Purifying single bacterium colony is stored on isolation medium；

（2）Bacteria selection

By step（1）The bacterium separated is inoculated in seed culture medium respectively with oese, at 30 DEG C, the condition of 160r/min Lower culture 72h, with the aqueous suspension ofkaolin of 4g/L the flocculating rate of bacterial classification is tested, and bacterial classification of the flocculating rate more than 50% is retained, and Repeatedly passed on, by the culture presevation for filtering out；

（3）The fermented and cultured of bacterial classification

A, beer waste water and sugaring fermentation waste water are centrifuged into respectively 20min under 5000rpm, suspended impurity are removed, wherein refining sugar Fermentation waste water total sugar content is 19.85g/L, and total nitrogen content is 3263.3mg/L, and beer waste water total sugar content is 196.1g/L, always Nitrogen content is 1796.8mg/L, then according to total sugar concentration 7g/L, charcoal source and nitrogen source compare 50:1 is diluted, and adds phosphoric acid Sodium dihydrogen and disodium hydrogen phosphate, wherein phosphate dihydrogen sodium concentration are 2g/L, and disodium hydrogen phosphate concentration is 5g/L, adds magnesium sulfate The pH for adjusting fermentation medium is 9, and autoclaving is standby；

B, by step（2）In be deposited in the producing strains bacterial classification on inclined-plane and be inoculated in fermentation medium, in 30 DEG C, 150r/min constant temperature 3h is cultivated on oscillator, makes each bacterial strain be in exponential phase, make bacterial classification suspension, be inoculated into according to 5% inoculum concentration In fermentation medium prepared by 100ml steps a, under the conditions of being 160r/min in 30 DEG C, rotating speed 72h is cultivated；

C, zymotic fluid obtained in step b is placed on 4 DEG C of high speed freezing centrifuges in 8000r/min be centrifuged 30min, by what is obtained Add the absolute ethyl alcohol of 2 times of amounts to stand 24h at 4 DEG C in supernatant, then proceed to be centrifuged in 8000r/min under the conditions of 4 DEG C 30min, by the precipitation for obtaining absolute ethyl alcohol cyclic washing, is placed in bag filter the 48h that dialyses, and microorganism wadding is obtained after freeze-drying Solidifying agent；

(4) preparation of composite magnetic microballoon

D, by ferric chloride hexahydrate and Iron dichloride tetrahydrate according to ferric iron and ferrous iron mol ratio 1：1 mixing, electric stirring It is fully mixed, be slowly added dropwise while stirring at 30 DEG C 1mol/L NaOH until solution pH be 11, heating makes Its reaction temperature is controlled at 60 DEG C, is then added dropwise over oleic acid stirring reaction 1h, and reaction is cooled to room temperature after terminating, then with steaming Distilled water cyclic washing grinds standby in neutrality after vacuum drying；

E, glacial acetic acid is made into the acetic acid solution that volumetric concentration is 1.5% with distilled water diluting, be passed through nitrogen and add shitosan stirring Until being completely dissolved, the ammonium persulfate solution of 5mmol/L is then slowly added dropwise, it is ensured that completion of dropping in 15min, by acrylic amine It is added thereto after distillation water dissolves with 12 times of amounts, propylene phthalein amine is added after reaction 30min, after reaction 10min matter is slowly added to Amount fraction is the microbial flocculation of 60% dimethyl diallyl ammonium chloride solution, product prepared by step d and the preparation of step c Agent, under agitation, controlling reaction temperature is 50 DEG C, reacts 2.5h, after reaction terminates, is cooled to room temperature.

The formulation ratio of described isolation medium is：Beef extract 3g/L, peptone 10g/L, sodium chloride 5g/L, agar 15g/L, plus distilled water to 1000ml；PH value is adjusted to 7.0, sterilize 20min in 121 DEG C；Seed culture medium recipe ratio is：Beef Cream 3g/L, peptone 10g/L, sodium chloride 5g/L, plus distilled water to 1000ml, adjust pH value to 7, sterilize 20min in 121 DEG C.

The step（4）In each raw material be according to weight：Ferric chloride hexahydrate 12.1, oleic acid 0.4, shitosan 4.5th, acrylamide 18, dimethyl diallyl ammonium chloride 4.5, ammonium persulfate 0.05, propylene phthalein amine 1.3, microbial flocculant 1.8th, appropriate Iron dichloride tetrahydrate, 1mol/L Sodium hydroxide q. s, appropriate glacial acetic acid, distillation appropriate amount of water.

The validity of the performance of the Compound paint flocculant prepared in order to embody embodiment, configuration paint waste water enters Row performance verification, process is as follows：

100ml cold running waters are added in the open bottles equipped with magnetic stirring bar, it is 12 to adjust pH with the NaOH of 1mol/L, Turn on agitator adds the commercially available automotive paints of 6 drops, stands after stirring and obtains paint waste water, and concentration is about 30mg/L, to The Compound paint flocculant of waste water total amount mass fraction 0.3%, high-speed stirred 1min, observation knot after standing are added in paint waste water Really.It has been observed that：Bottle wall does not have obvious bur, and water quality is limpid, and the floccule of formation is compact in cellular and to bubble through the water column, Flocculating rate is 91.6%.

Claims (3)

1. a kind of repeatable cationic chitosan type Compound paint flocculant for utilizing, it is characterised in that comprise the following steps：

（1）Strain separating is purified

The paint waste water for processing later stage is fitted in aseptic triangular flask, 4 DEG C of preservations are placed in, seed culture is based on into 121 DEG C Lower sterilizing, takes 100 μ L waste water and is inoculated in the seed culture medium of 100ml after cooling, in 37 DEG C of constant temperature Amplification Cultures 24h, then Nutrient solution is diluted to respectively 10-1,10-2,10-3,10-4,10-5,10-6 times, then the bacteria suspension coating by each after diluting On isolation medium, 37 DEG C of incubated 24h, good bacterium colony of choosing form completes initial gross separation, then will be singled out each Bacterium is inoculated in seed culture medium, 37 DEG C of incubated 24h, line is diluted and carried out to the nutrient solution of each bacterium and is isolated and purified, The purifying single bacterium colony for finally obtaining is stored on isolation medium；

（2）Bacteria selection

By step（1）The bacterium separated is inoculated in seed culture medium respectively with oese, at 30 DEG C, the condition of 160r/min Lower culture 72h, with the aqueous suspension ofkaolin of 4g/L the flocculating rate of bacterial classification is tested, and bacterial classification of the flocculating rate more than 50% is retained, and Repeatedly passed on, by the culture presevation for filtering out；

（3）The fermented and cultured of bacterial classification

A, beer waste water and sugaring fermentation waste water are centrifuged into respectively 20min under 5000rpm, suspended impurity are removed, wherein refining sugar Fermentation waste water total sugar content is 19.85g/L, and total nitrogen content is 3263.3mg/L, and beer waste water total sugar content is 196.1g/L, always Nitrogen content is 1796.8mg/L, then according to total sugar concentration 7g/L, charcoal source and nitrogen source compare 50:1 is diluted, and adds phosphoric acid Sodium dihydrogen and disodium hydrogen phosphate, wherein phosphate dihydrogen sodium concentration are 2g/L, and disodium hydrogen phosphate concentration is 5g/L, adds magnesium sulfate The pH for adjusting fermentation medium is 9, and autoclaving is standby；

B, by step（2）In be deposited in the producing strains bacterial classification on inclined-plane and be inoculated in fermentation medium, in 30 DEG C, 150r/min constant temperature 3h is cultivated on oscillator, makes each bacterial strain be in exponential phase, make bacterial classification suspension, be inoculated with according to the inoculum concentration of 5-10% In the fermentation medium prepared to 100ml steps a, under the conditions of being 160r/min in 30 DEG C, rotating speed 72h is cultivated；

C, zymotic fluid obtained in step b is placed on 4 DEG C of high speed freezing centrifuges in 8000r/min be centrifuged 30-40min, will To supernatant in add 2 times amount absolute ethyl alcohols stand 24h at 4 DEG C, then proceed under the conditions of 4 DEG C in 8000r/min Centrifugation 30-40min, by the precipitation for obtaining absolute ethyl alcohol cyclic washing, is placed in bag filter the 48h that dialyses, after freeze-drying Microbial flocculant；

(4) preparation of composite magnetic microballoon

D, by ferric chloride hexahydrate and Iron dichloride tetrahydrate according to ferric iron and ferrous iron mol ratio 1：1 mixing, electric stirring It is fully mixed, be slowly added dropwise while stirring at 30 DEG C 1mol/L NaOH until solution pH be 11, heating makes Its reaction temperature is controlled at 60 DEG C, is then added dropwise over oleic acid stirring reaction 1-1.5h, and reaction is cooled to room temperature after terminating, then With distilled water cyclic washing in neutrality, grind after vacuum drying standby；

E, glacial acetic acid is made into the acetic acid solution that volumetric concentration is 1.5% with distilled water diluting, be passed through nitrogen and add shitosan stirring Until being completely dissolved, the ammonium persulfate solution of 5mmol/L is then slowly added dropwise, it is ensured that completion of dropping in 15min, by acrylic amine It is added thereto after distillation water dissolves with 12 times of amounts, propylene phthalein amine is added after reaction 30-40min, it is slow after reaction 10-20min The micro- life for adding dimethyl diallyl ammonium chloride solution, the product of step d preparation and step c that mass fraction is 60% to prepare Thing flocculant, under agitation, controlling reaction temperature is 50 DEG C, reacts 2.5-3h, after reaction terminates, is cooled to room temperature i.e. Can.

2. a kind of repeatable cationic chitosan type Compound paint flocculant for utilizing according to claim 1, its feature exists In the formulation ratio of described isolation medium is：Beef extract 3-4g/L, peptone 10-12g/L, sodium chloride 5-6g/L, agar 15-20g/L, plus distilled water to 1000ml；PH value is adjusted to 7.0-7.2, sterilize 20min in 121 DEG C；Seed culture medium recipe ratio For：Beef extract 3-4g/L, peptone 10-13g/L, sodium chloride 5-7g/L, plus distilled water to 1000ml, adjust pH value to 7-7.2, Sterilize 20min in 121 DEG C.

3. a kind of repeatable cationic chitosan type Compound paint flocculant for utilizing according to claim 1, its feature exists In the step（4）In each raw material be according to weight：Ferric chloride hexahydrate 12.1-12.8, oleic acid 0.4-0.6, shell gather Sugared 4.5-5.4, acrylamide 18-20, dimethyl diallyl ammonium chloride 4.5-5.4, ammonium persulfate 0.05-0.07, propylene phthalein Amine 1.3-1.5, microbial flocculant 1.8-2.2, appropriate Iron dichloride tetrahydrate, 1mol/L Sodium hydroxide q. s, glacial acetic acid are fitted Amount, distillation appropriate amount of water.