CN107540845A - A kind of preparation method of industrial gelatine graft copolymerization cationic flocculant - Google Patents
A kind of preparation method of industrial gelatine graft copolymerization cationic flocculant Download PDFInfo
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- CN107540845A CN107540845A CN201710398651.4A CN201710398651A CN107540845A CN 107540845 A CN107540845 A CN 107540845A CN 201710398651 A CN201710398651 A CN 201710398651A CN 107540845 A CN107540845 A CN 107540845A
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- cationic flocculant
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- industrial gelatine
- graft copolymerization
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Abstract
A kind of preparation method of industrial gelatine graft copolymerization cationic flocculant, industrial gelatine is dissolved in distilled water, is added complex enzyme and is hydrolyzed, collagen hydrolysate liquor is made;Under nitrogen protective condition, monomer is mixed with water, adjusts pH, collagen hydrolysate liquor made from addition after initiator for reaction certain time is added, continues reaction and obtain cationic flocculant.Obtained cationic flocculant crude product is precipitated through absolute ethyl alcohol, acetone washing, obtains cationic flocculant sterling.For the present invention to discard in leather the industrial gelatine extracted as raw material, yield is big, wide material sources, is readily biodegradable.Be advantageous to the recycling of Leather Solid Waste simultaneously, turn waste into wealth, with pollution treatment of giving up.
Description
Technical field
The invention belongs to flocculant preparation method technical field, is related to a kind of industrial gelatine graft copolymerization cationic flocculant
Preparation method, and in particular to a kind of preparation side of the industrial gelatine graft copolymerization cationic flocculant extracted from discarded leather
Method.
Background technology
China is leather industry big country, Animal Skin aboundresources, in leather making process, generally only has the raw hide less than 30%
It is changed into salable finished product skin, remaining is abandoned as discarded object mostly, is turned into solid pollutant, is caused to endanger to ecological environment
Evil.Discarded shavings can extract gelatin, using containing amino, carboxyl, hydroxyl isoreactivity on collagen molecules after gelatin hydrolysis
Group, good flocculating property can be obtained by graft modification.With the development of industrial and agricultural production, the demand of water is increasingly increased
Add.But due to entering water body containing some harmful substances in draining, cause natural water body that physics and change chemically occurs, make
Water quality is degenerated, available water resource is reduced.Therefore, it is sustainable restriction social economy has been turned into the problem that water pollution
An important factor for development.Water environment pollution not only hinders industrial and agricultural production, influences aquatic ecosystem, also directly or indirectly influences
People live and health.It is effectively treated for the industrial wastewater and trade effluent largely discharged, reaches discharge standard
Required with utilizing, be the particularly important approach for increasing water utilization rate, and preserved the ecological environment and human survival, promotion
The requisite measure of social progress.At present in lot of domestic and foreign method for treating water, flocculent precipitation is because its technique is simple, operation side
Just the advantages that, treatment effeciency is high and be widely used in industry and domestic water improvement and recycle.Flocculant extensively should
For metallurgy, petrochemical industry, papermaking, printing and dyeing, weaving, food, brewage and originally a variety of industries such as water and wastewater industry.In various flocculants,
Natural macromolecule flocculating agent has that dosage is few, and reaction is fast, efficiency high, decolourizes, the features such as being readily biodegradable, thus turns into one
The big water treatment agent for having development potentiality of kind.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, it is an object of the invention to provide a kind of industrial gelatine graft copolymerization sun from
The preparation method of sub- flocculant, flocculant being prepared by extracting industrial gelatine from discarded leather, its is nontoxic, environment-friendly,
Cost is cheap, and can realize Leather Solid Waste recycling.
To achieve these goals, the technical solution adopted by the present invention is:
A kind of preparation method of industrial gelatine graft copolymerization cationic flocculant, comprises the following steps:
Step 1:The industrial gelatine extracted in discarded leather is dissolved in distilled water, and adds complex enzyme, regulation pH is 7.5, temperature
Spend for 45 ~ 50 DEG C, being warming up to 95 DEG C after hydrolysis 1h inactivates enzyme, and the time is 5 ~ 10 min, and collagen hydrolysate liquor is made;
Step 2:Nitrogen intake is adjusted after the air being passed through in nitrogen discharge system causes system pressure constant and nothing in system
Air, under nitrogen protective condition, monomer is mixed with water, adjust pH, add initiator, initiator is configured to solution control with water
System is added dropwise simultaneously in 15 ~ 20 min, reacts 30 ~ 60min after complete;Then collagen hydrolysate liquor made from step 1, glue are added
The mass ratio of former protein hydrolyzate and monomer is 2:1~1:2,60 ~ 90min of stirring reaction at 40 ~ 60 DEG C;Cation wadding is made
Solidifying agent;
Step 3:Obtained cationic flocculant crude product is first precipitated with absolute ethyl alcohol, surname extraction is utilized by solvent of acetone
Device extracts, and 60 DEG C of dryings obtain cationic flocculant sterling in 24 hours;
Described monomer is acrylyl oxy-ethyl-trimethyl salmiac;
Described initiator is TBHP and sodium pyrosulfite;
Described complex enzyme is that neutral proteinase and trypsase are 1 in mass ratio:1 complex enzyme.
In described step one, industrial gelatine is 20 ~ 30g, and distilled water is 60 ~ 90mL, and complex enzyme is 0.4 ~ 0.6g.
In described step two, monomer is 20 ~ 25mL, and distilled water is 20~25mL.
PH is adjusted in described step two using NaOH adjustment controls between 7 ~ 8,40 ~ 45 DEG C of temperature.
Two kinds of materials of TBHP and sodium pyrosulfite in described initiator, are the 1 of monomer mass:
100~2:100, ratio 1:1.
The molecular mass of described cationic flocculant is 10000 ~ 1800000.
Compared with prior art, the beneficial effects of the invention are as follows:
To discard in leather the industrial gelatine extracted as raw material, yield is big, wide material sources, is readily biodegradable.On the one hand have
Beneficial to the recycling of Leather Solid Waste, turn waste into wealth, with pollution treatment of giving up;On the other hand can be provided for water treatment field newly
Flocculant.Compared with other flocculants, the cationic flocculant relative molecular mass that this method is prepared is higher, have compared with
Strong adsorption bridging performance, wider pH add scope, and the change to more turbidity, basicity, content of organics has relatively strong adapt to
Property, while also there is the characteristics of viscosity is low, dosage is few.
Brief description of the drawings
Fig. 1 is the gelatin hydrolysis liquid infared spectrum of embodiment;
Fig. 2 is the acrylyl oxy-ethyl-trimethyl salmiac homopolymer infared spectrum of embodiment;
Fig. 3 is the cationic flocculant sterling infared spectrum of embodiment.
Embodiment
The present invention is further discussed below with reference to embodiment.
Embodiment one:
A kind of preparation method of discarded leather industry Graft Copolymerization of Gelatin cationic flocculant, comprises the steps:
Step 1:20g industrial gelatines are weighed, 60mL water is added and is fully swelled, temperature 45 C is adjusted, pH 7.5, adds 0.2g pancreases
Protease, 0.2g neutral proteinases, it is warming up to 95 DEG C after hydrolyzing 1h and maintains 5min to inactivate enzyme, obtain collagen hydrolysate liquor;
Step 2:Acrylyl oxy-ethyl-trimethyl salmiac 20mL is taken, adds distilled water 20mL, is passed through nitrogen, pH is adjusted with NaOH
To 7.5,40 DEG C of temperature.Initiator TBHP and each 0.2g of sodium pyrosulfite are configured to solution control with 10mL water and existed
15 min are added dropwise simultaneously, react 30min after dripping;Then collagen hydrolysate liquor made from step 1, gelatin hydrolysis are added
The mass ratio of liquid and monomer is 2:1, the stirring reaction 60min at 40 DEG C.
Step 3:Obtained cationic flocculant crude product is precipitated through absolute ethyl alcohol, carried using acetone as solvent using Soxhlet
Take device to extract, remove homopolymer, 60 DEG C of dryings obtain cationic flocculant sterling in 24 hours.
Embodiment two:
A kind of preparation method of discarded leather industry Graft Copolymerization of Gelatin cationic flocculant, comprises the steps:
Step 1:20g industrial gelatines are weighed, 60mL water is added and is fully swelled, temperature 45 C is adjusted, pH 7.5, adds 0.2g pancreases
Protease, 0.2g neutral proteinases, it is warming up to 95 DEG C after hydrolyzing 1h and maintains 5min to inactivate enzyme, obtain collagen hydrolysate liquor;
Step 2:Acrylyl oxy-ethyl-trimethyl salmiac 25mL is taken, adds distilled water 25mL, is passed through nitrogen, pH is adjusted with NaOH
To 7.5,40 DEG C of temperature.Initiator TBHP and each 0.25g of sodium pyrosulfite are configured to solution control with 10mL water
30min is reacted after 15 min are added dropwise, dripped simultaneously;Then collagen hydrolysate liquor made from step 1, gelatin water are added
The mass ratio for solving liquid and monomer is 2:1, the stirring reaction 90min at 50 DEG C.
Step 3:Obtained cationic flocculant crude product is precipitated through absolute ethyl alcohol, carried using acetone as solvent using Soxhlet
Take device to extract, remove homopolymer, 60 DEG C of dryings obtain cationic flocculant sterling in 24 hours.
Embodiment three:
A kind of preparation method of discarded leather industry Graft Copolymerization of Gelatin cationic flocculant, comprises the steps:
Step 1:20g industrial gelatines are weighed, 60mL water is added and is fully swelled, temperature 45 C is adjusted, pH 7.5, adds 0.2g pancreases
Protease, 0.2g neutral proteinases, it is warming up to 95 DEG C after hydrolyzing 1h and maintains 5min to inactivate enzyme, obtain collagen hydrolysate liquor;
Step 2:Acrylyl oxy-ethyl-trimethyl salmiac 25mL is taken, adds distilled water 25mL, is passed through nitrogen, pH is adjusted with NaOH
To 8,40 DEG C of temperature.Initiator TBHP and each 0.25g of sodium pyrosulfite are configured to solution control with 10mL water and existed
15 min are added dropwise simultaneously, react 30min after dripping;Then collagen hydrolysate liquor made from step 1, gelatin hydrolysis are added
The mass ratio of liquid and monomer is 1:1, the stirring reaction 60min at 60 DEG C.
Step 3:Obtained cationic flocculant crude product is precipitated through absolute ethyl alcohol, carried using acetone as solvent using Soxhlet
Take device to extract, remove homopolymer, 60 DEG C of dryings obtain cationic flocculant sterling in 24 hours.
Example IV:
A kind of preparation method of discarded leather industry Graft Copolymerization of Gelatin cationic flocculant, comprises the steps:
Step 1:30g industrial gelatines are weighed, 90mL water is added and is fully swelled, temperature 45 C is adjusted, pH 7.5, adds 0.3g pancreases
Protease, 0.3g neutral proteinases, it is warming up to 95 DEG C after hydrolyzing 1h and maintains 5min to inactivate enzyme, obtain collagen hydrolysate liquor;
Step 2:Acrylyl oxy-ethyl-trimethyl salmiac 20mL is taken, adds distilled water 20mL, is passed through nitrogen, pH is adjusted with NaOH
To 7.5,40 DEG C of temperature.Initiator TBHP and each 0.2g of sodium pyrosulfite are configured to solution control with 10mL water and existed
15 min are added dropwise simultaneously, react 30min after dripping;Then collagen hydrolysate liquor made from step 1, gelatin hydrolysis are added
The mass ratio of liquid and monomer is 2:1, the stirring reaction 60min at 40 DEG C.
Step 3:Obtained cationic flocculant crude product is precipitated through absolute ethyl alcohol, carried using acetone as solvent using Soxhlet
Take device to extract, remove homopolymer, 60 DEG C of dryings obtain cationic flocculant sterling in 24 hours.
Embodiment five:
A kind of preparation method of discarded leather industry Graft Copolymerization of Gelatin cationic flocculant, comprises the steps:
Step 1:30g industrial gelatines are weighed, 90mL water is added and is fully swelled, temperature 45 C is adjusted, pH 7.5, adds 0.3g pancreases
Protease, 0.3g neutral proteinases, it is warming up to 95 DEG C after hydrolyzing 1h and maintains 5min to inactivate enzyme, obtain collagen hydrolysate liquor;
Step 2:Acrylyl oxy-ethyl-trimethyl salmiac 20mL is taken, adds distilled water 20mL, is passed through nitrogen, pH is adjusted with NaOH
To 8,40 DEG C of temperature.Initiator TBHP and each 0.2g of sodium pyrosulfite are configured to solution control 15 with 10mL water
Min is added dropwise simultaneously, reacts 30min after dripping;Then add step 1 made from collagen hydrolysate liquor, gelatin hydrolysis liquid with
The mass ratio of monomer is 1:2, the stirring reaction 90min at 40 DEG C.
Step 3:Obtained cationic flocculant crude product is precipitated through absolute ethyl alcohol, carried using acetone as solvent using Soxhlet
Take device to extract, remove homopolymer, 50 DEG C of dryings obtain cationic flocculant sterling in 24 hours.
Embodiment six:
A kind of preparation method of discarded leather industry Graft Copolymerization of Gelatin cationic flocculant, comprises the steps:
Step 1:30g industrial gelatines are weighed, 90mL water is added and is fully swelled, temperature 45 C is adjusted, pH 7.5, adds 0.3g pancreases
Protease, 0.3g neutral proteinases, it is warming up to 95 DEG C after reacting 1h and maintains 5min to inactivate enzyme, obtain collagen hydrolysate liquor;
Step 2:Acrylyl oxy-ethyl-trimethyl salmiac 25mL is taken, adds distilled water 25mL, is passed through nitrogen, pH is adjusted with NaOH
To 8,40 DEG C of temperature.Initiator TBHP and each 0.25g of sodium pyrosulfite are configured to solution control with 10mL water and existed
15 min are added dropwise simultaneously, react 30min after dripping;Then collagen hydrolysate liquor made from step 1, gelatin hydrolysis are added
The mass ratio of liquid and monomer is 1:1, the stirring reaction 90min at 60 DEG C.
Step 3:Obtained cationic flocculant crude product is precipitated through absolute ethyl alcohol, carried using acetone as solvent using Soxhlet
Take device to extract, remove homopolymer, 60 DEG C of dryings obtain cationic flocculant sterling in 24 hours.
Cationic flocculant infared spectrum is analyzed:
Contain cationic flocculant copolymer and acrylyl oxy-ethyl-trimethyl salmiac homopolymer, cation in flocculant crude product
Flocculant copolymer does not dissolve in acetone, and acrylyl oxy-ethyl-trimethyl salmiac copolymer is dissolved in acetone, by obtained cation
Flocculant crude product precipitates through absolute ethyl alcohol, is extracted, 60 DEG C of drying 24 hours, respectively must using apparatus,Soxhlet's using acetone as solvent
To cationic flocculant copolymer sterling, acrylyl oxy-ethyl-trimethyl salmiac homopolymer sterling.Take appropriate amounts of gelatin hydrolyzate
It is placed in surface plate and is dried 24 hours at 45 DEG C, obtained solid pure product mortar is finely ground standby.
Using FTIS using pellet technique respectively to collagen hydrolysate liquor, acryloyl-oxy
Ethyl-trimethyl salmiac homopolymer and cationic flocculant sterling are done from 400 ~ 4000cm-1Infrared scan, scanning times 32
It is secondary.Scanning spectra such as Fig. 1,2,3.
Analyze the general structure of gelatin and the structural formula of acrylyl oxy-ethyl-trimethyl salmiac homopolymer, it is known that flocculant
If structure in there is the structure of acid amides, can prove that collagen hydrolysate liquor is equal with acrylyl oxy-ethyl-trimethyl salmiac
Polymers is reacted.As shown in Figure 1 in gelatin hydrolysis liquid the absworption peak of carbonyl stretch acid amides in 1646cm-1, the N-H changes of solid-state
Shape acid amides is in 1519cm-1Appearance.Comparison diagram 3 is in 1655cm-1, 1500cm-1The respectively absworption peak and solid-state of carbonyl stretch acid amides
N-H deformation acid amides appearance, with Fig. 2 contrast acrylyl oxy-ethyl-trimethyl salmiac homopolymer in there is no the appearance, thus
The gelatin modified cationic flocculant of deducibility is successfully prepared.
Claims (6)
1. a kind of preparation method of industrial gelatine graft copolymerization cationic flocculant, it is characterised in that comprise the following steps:
Step 1:The industrial gelatine extracted in discarded leather is dissolved in distilled water, and adds complex enzyme, regulation pH is 7.5, temperature
Spend for 45 ~ 50 DEG C, being warming up to 95 DEG C after hydrolysis 1h inactivates enzyme, and the time is 5 ~ 10 min, and collagen hydrolysate liquor is made;
Step 2:Nitrogen intake is adjusted after the air being passed through in nitrogen discharge system causes system pressure constant and nothing in system
Air, under nitrogen protective condition, monomer is mixed with water, adjust pH, add initiator, initiator is configured to solution control with water
System is added dropwise simultaneously in 15 ~ 20 min, reacts 30 ~ 60min after complete;Then collagen hydrolysate liquor made from step 1, glue are added
The mass ratio of former protein hydrolyzate and monomer is 2:1~1:2,60 ~ 90min of stirring reaction at 40 ~ 60 DEG C;Cation wadding is made
Solidifying agent;
Step 3:Obtained cationic flocculant crude product is first precipitated with absolute ethyl alcohol, surname extraction is utilized by solvent of acetone
Device extracts, and 60 DEG C of dryings obtain cationic flocculant sterling in 24 hours;
Described monomer is acrylyl oxy-ethyl-trimethyl salmiac;
Described initiator is TBHP and sodium pyrosulfite;
Described complex enzyme is that neutral proteinase and trypsase are 1 in mass ratio:1 complex enzyme.
2. a kind of preparation method of industrial gelatine graft copolymerization cationic flocculant according to claim 1, its feature exist
In in described step one, industrial gelatine is 20 ~ 30g, and distilled water is 60 ~ 90mL, and complex enzyme is 0.4 ~ 0.6g.
3. a kind of preparation method of industrial gelatine graft copolymerization cationic flocculant according to claim 1, its feature exist
In in described step two, monomer is 20 ~ 25mL, and distilled water is 20~25mL.
4. a kind of preparation method of industrial gelatine graft copolymerization cationic flocculant according to claim 1, its feature exist
In pH is adjusted using NaOH adjustment controls between 7 ~ 8 in the step 2,40 ~ 45 DEG C of temperature.
5. a kind of preparation method of industrial gelatine graft copolymerization cationic flocculant according to claim 1, its feature exist
In two kinds of materials of TBHP and sodium pyrosulfite in described initiator, are the 1 of monomer mass:100~2:
100, ratio 1:1.
6. a kind of preparation method of industrial gelatine graft copolymerization cationic flocculant according to claim 1, its feature exist
In the molecular mass of described cationic flocculant is 10000 ~ 1800000.
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Cited By (2)
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CN110921753A (en) * | 2019-11-04 | 2020-03-27 | 广州振清环保技术有限公司 | Ternary graft copolymerization modified spirulina protein water clarifying agent and preparation method thereof |
CN117110198A (en) * | 2023-08-28 | 2023-11-24 | 石家庄市长安育才建材有限公司 | Method for rapidly detecting type and content of flocculant in machine-made sand |
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CN110921753A (en) * | 2019-11-04 | 2020-03-27 | 广州振清环保技术有限公司 | Ternary graft copolymerization modified spirulina protein water clarifying agent and preparation method thereof |
CN117110198A (en) * | 2023-08-28 | 2023-11-24 | 石家庄市长安育才建材有限公司 | Method for rapidly detecting type and content of flocculant in machine-made sand |
CN117110198B (en) * | 2023-08-28 | 2024-04-12 | 石家庄市长安育才建材有限公司 | Method for rapidly detecting type and content of flocculant in machine-made sand |
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