CN110921753B - Ternary graft copolymerization modified spirulina protein water quality clarifying agent and preparation method thereof - Google Patents
Ternary graft copolymerization modified spirulina protein water quality clarifying agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ternary graft copolymerization modified spirulina protein water quality clarifier, which comprises, by weight, 100-300 parts of spirulina proteolytic liquid, 75-120 parts of epoxy chloropropane, 50-80 parts of di-n-butylamine and 5-10 parts of diethylenetriamine, wherein environment-friendly bio-based spirulina protein is adopted, and the environment-friendly bio-type cation water quality clarifier is obtained by graft modification, has high positive charge density, has better removal and flocculation effects on oil, active dye and metal ions in sewage, has the advantages of high efficiency, no toxicity, convenient use, low price and the like, and can be widely applied to the field of water treatment; the invention also provides a preparation method of the ternary graft copolymerization modified spirulina protein water quality clarifier, which combines enzyme treatment and graft copolymerization reaction, and has the advantages of good grafting effect, excellent graft performance, easy reaction control and low production cost.
Description
Technical Field
The invention relates to a water quality clarifier, in particular to a ternary grafting copolymerization modified spirulina protein water quality clarifier and a preparation method thereof.
Background
Along with the accumulation of sewage discharge, the treatment of sewage and the development of a targeted water quality clarifier are urgent. In recent years, with the development of adsorption flocculation theory and chemical industry, water treatment agents develop rapidly in China from low molecules to high molecules, from inorganic to organic, and from single to composite to form a series of and diversified products. Although the traditional inorganic water treatment agent has low cost and easy operation, the water treatment effect is poor, and the residual concentration in the metal waste liquid is high; although the organic water treatment agent has better flocculation treatment capacity, the organic water treatment agent is easy to remain in water and is difficult to biodegrade; therefore, the biological water treatment agent with strong treatment capability and environmental friendliness has attracted more and more high attention from academia and the industry.
The chemical structure of the bio-based water quality clarifier has great flexibility, the influence of the charge density on the value is small, and high molecular weight can be obtained, so that the bio-based water quality clarifier is the water treatment medicament with the highest commercial value at present. The bio-based water clarifying agent can be divided into three categories according to the chemical composition, and the three categories are carbohydrate flocculants such as proteins, celluloses, polysaccharides and the like. The spirulina protein is an active protein, contains a large number of active groups such as amino, carboxyl and the like in the structure, has the characteristics of an ammonia compound and a carboxyl-containing compound, and has higher synthesis reaction activity. Therefore, the spirulina protein graft modification for synthesizing the water quality clarifier has theoretical feasibility.
Pollutants in sewage are usually negatively charged, the traditional neutral water quality clarifying agent cannot achieve an ideal treatment effect, and the cationic water quality clarifying agent can solve the problem according to charge neutralization, but the research on the cationic water quality clarifying agent is less at present in China, and the research has a larger difference compared with the foreign field, and particularly, the research and application of adopting graft copolymerization modified protein as a water treatment medicament are not reported at present. Therefore, the invention is based on natural bio-based spirulina protein, is prepared into the environment-friendly biological type cationic water clarifier by graft modification, and can be widely applied to the field of water treatment.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a ternary graft copolymerization modified spirulina protein water quality clarifier, which adopts spirulina protein to perform graft polymerization reaction through epoxy chloropropane, di-n-butylamine and diethylenetriamine to obtain an environment-friendly biological type cation water quality clarifier, has the advantages of high positive charge density, good oil removal and decoloration effects, small using amount, small sludge production amount, high efficiency, no toxicity, low manufacturing cost and the like, and can be widely applied to the field of water treatment;
the invention also aims to provide a preparation method of the ternary graft copolymerization modified spirulina protein water quality clarifier, which adopts enzyme treatment and graft copolymerization reaction, has good grafting reaction effect and easy control of reaction, can obtain the water quality clarifier with excellent comprehensive performance, and has low production cost.
One of the purposes of the invention is realized by adopting the following technical scheme:
a ternary graft copolymerization modified spirulina protein water clarifier comprises the following components in parts by weight:
preferably, the ternary graft copolymerization modified spirulina protein water clarifier comprises the following components in percentage by weight:
further, the mass ratio of the epichlorohydrin to the di-n-butylamine is (1-2): 1.
the spirulina protein enzymolysis liquid is obtained by sequentially hydrolyzing spirulina protein with alkaline protease and papain.
The second purpose of the invention can be achieved by adopting the following technical scheme:
the preparation method of the ternary grafting copolymerization modified spirulina protein water clarifier comprises the following steps:
enzyme pretreatment: treating spirulina dry powder with potassium chloride and lysozyme, performing negative pressure suction filtration to obtain spirulina protein crude extract, inactivating enzyme, and adjusting pH to neutral;
carrying out enzymolysis on spirulina protein: hydrolyzing the crude spirulina protein extract with alkaline protease, inactivating enzyme in high-temperature water bath, further hydrolyzing with papain, inactivating enzyme in high-temperature water bath, and centrifuging to obtain spirulina protein hydrolysate;
Graft copolymerization reaction: adding the spirulina protein enzymatic hydrolysate into a four-neck flask with a stirrer, a condenser pipe, a thermometer and a dropping funnel, adjusting the pH value to 3.5-4.5, slowly adding epoxy chloropropane, opening the condenser pipe for reflux, controlling the temperature to be 8-12 ℃, slowly dropwise adding di-n-butylamine under stirring, then heating to 60-70 ℃, slowly adding diethylenetriamine, continuously stirring, slowly heating to 75-85 ℃, reacting at constant temperature, and cooling to room temperature to obtain the ternary graft copolymerization modified spirulina protein water quality clarifier.
Further, the combined treatment conditions of the potassium chloride and the lysozyme are as follows: the temperature is 30 ℃, and the treatment time is 7-9 h.
The alkaline protease hydrolysis conditions are as follows: the hydrolysis time is 2-3h, the temperature is 52-58 ℃, the pH is 7.0, and the enzyme addition amount is 4000--1。
The hydrolysis conditions of the papain are as follows: the hydrolysis time is 3-4h, the temperature is 62-68 ℃, the pH is 6.5, and the enzyme adding amount is 30000--1。
Preferably, the graft copolymerization reaction comprises:
adding the spirulina protein enzymatic hydrolysate into a four-neck flask with a stirrer, a condenser pipe, a thermometer and a dropping funnel, adjusting the pH value to 4, slowly adding epoxy chloropropane, opening the condenser pipe for reflux, strictly controlling the temperature to be 10 ℃, slowly dropwise adding di-n-butylamine while stirring, then heating to 65 ℃, slowly adding diethylenetriamine, continuously stirring, slowly heating to 80 ℃, reacting at constant temperature for 5-7h, and cooling to room temperature to obtain the ternary graft copolymerization modified spirulina protein water quality clarifier.
Diethylenetriamine is used as a cross-linking agent to increase the molecular mass of the polymerization product. The use amount of the diethylenetriamine is increased, the polymerization reaction rate is improved, the polymerization degree is enhanced, but the excessive diethylenetriamine can cause the polymerization reaction to be too fast, the polymerization process is gelatinized, and the diethylenetriamine enters a chain termination stage too early, so that the situations that the solid content and the cationic degree are increased, but the adsorbability is reduced can occur. Therefore, the invention strictly controls the process of graft copolymerization reaction and comprehensively improves the solid content, cationic degree and adsorption performance of the water quality clarifier.
Further, the stirring speed of the stirrer is 50-60 r/min; the dripping speed of the di-n-butylamine is 4-5 g/min.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts natural spirulina as raw material, is energy-saving and environment-friendly and is easy to degrade; the spirulina protein molecule has amino and carboxyl at two ends and side chain containing great amount of active functional groups, such as phenolic hydroxyl, hydrophobic radical, etc. after the enzyme pre-treatment and double enzyme hydrolysis, the present invention can stretch the bent, folded and spiral polypeptide chain gradually to form loose peptide chain structure, so as to increase the motion resistance of the peptide chain molecule. In the stretched and loose polypeptide chains, more groups beneficial to grafting and complexing, such as hydroxyl, phenolic hydroxyl, carboxyl and the like, are exposed, and the graft copolymerization reaction with the di-n-butylamine and the epichlorohydrin is easier to be carried out, so that a graft copolymer with special performance is formed, the adsorption capacity is enhanced, and the processing capacity of the spirulina protein water quality clarifying agent is improved.
2. The invention combines the formula of the water quality clarifier and improves the preparation method, so that the obtained modified spirulina protein graft is more beneficial to clarification treatment of sewage in terms of branched chain composition, structure and length, and has high solid content, high cationic degree and strong adsorption performance.
3. The water quality clarifier of the invention has convenient use and low price, has better removal and flocculation effects on oil, reactive dye and metal ions in sewage, and provides a novel medicament for the effective treatment of sewage.
Drawings
FIG. 1 is a graph showing the effect of a water clarifier on the flocculation performance of oilfield wastewater according to examples 1-4 of the present invention;
FIG. 2 is a graph showing the adsorption performance of the water clarifiers of examples 1-4 and comparative example 1 of the present invention to Ni and Cr.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
A ternary graft copolymerization modified spirulina protein water clarifier comprises the following components in parts by weight:
wherein the mass ratio of the epichlorohydrin to the di-n-butylamine is (1-2): 1.
As a further preferable scheme, the mass ratio of the epichlorohydrin to the di-n-butylamine is 1.5: 1, since at this ratio, the degree of cationicity is highest, the higher the degree of cationicity, indicating that the higher the quaternary ammonium group content, the more positive charge, the higher the adsorptivity.
A preparation method of the ternary graft copolymerization modified spirulina protein water quality clarifying agent comprises the following steps:
enzyme pretreatment: diluting 10% spirulina dry powder with water, treating with potassium chloride and lysozyme at 30 deg.C for 7-9 hr, breaking cell wall to release spirulina protein, vacuum filtering to obtain spirulina protein crude extract, adjusting pH to 4.0 with 5% acetic acid, maintaining for 10min to inactivate enzyme, and adjusting pH to neutral;
the combined treatment method of the potassium chloride and the lysozyme comprises the following steps: preparing lysozyme into 2.0g/L potassium chloride-lysozyme mixed solution by using 0.1moL/L potassium chloride solution, and mixing the potassium chloride-lysozyme mixed solution with diluted spirulina dry powder for treatment.
Carrying out enzymolysis on spirulina protein: pouring the crude spirulina protein extract into a conical flask, and hydrolyzing the spirulina protein by using alkaline protease under the hydrolysis conditions of: the hydrolysis time is 2.5h, the temperature is 55 ℃, the pH is 7.0, and the enzyme addition amount is 4000-6000 U.g -1Inactivating enzyme in water bath at 85 deg.C for 20 min; then further hydrolyzing by papain under the following hydrolysis conditions: the hydrolysis time is 3-4h, the temperature is 62-68 ℃, the pH is 6.5, and the enzyme addition amount is 30000-80000 U.g-1Inactivating enzyme in water bath at 85 deg.C for 20min after hydrolysis, and centrifuging at 8000rpm for 20min to obtain Spirulina protease hydrolysate;
graft copolymerization reaction: adding the spirulina protein enzymatic hydrolysate into a four-neck flask with a stirrer, a condenser pipe, a thermometer and a dropping funnel, adjusting the pH value to 3.5-4.5, slowly adding epoxy chloropropane, opening the condenser pipe for reflux, controlling the temperature to be 8-12 ℃, slowly dropwise adding di-n-butylamine under stirring, then heating to 60-70 ℃, slowly adding diethylenetriamine, continuously stirring, slowly heating to 75-85 ℃, reacting at constant temperature for 5-7h, and cooling to room temperature to obtain the ternary graft copolymerization modified spirulina protein water quality clarifier.
Wherein the stirring speed of the stirrer is 50-60 r/min; the dropping speed of the di-n-butylamine is 4 to 5 g/min.
Example 1
A ternary graft copolymerization modified spirulina protein water clarifier comprises the following components in parts by weight:
the ternary graft copolymerization modified spirulina protein water clarifier of the embodiment is prepared by the following method:
Enzyme pretreatment: weighing 200g of spirulina dry powder, diluting with water by 10%, jointly treating 80g of potassium chloride-lysozyme mixed solution for 8h, breaking cell walls at 30 ℃ to release spirulina protein, and performing negative pressure suction filtration to obtain a spirulina protein crude extract. At the end of the pretreatment, the enzyme was deactivated by adjusting the pH to 4.0 with 5% acetic acid and maintaining for 10min, and finally the pH of the solution was adjusted back to neutral for use.
Double enzyme hydrolysis of spirulina protein: pouring 500mL of spirulina protein solution into a conical flask, hydrolyzing the spirulina protein by using alkaline protease firstly, wherein the hydrolysis conditions are as follows: the hydrolysis time is 2.5h, the temperature is 55 ℃, the pH is 7.0, and the enzyme addition amount is 4000 U.g-1And after hydrolysis, inactivating the enzyme in water bath at 85 ℃ for 20 min. Further hydrolyzing by papain under the following conditions: the hydrolysis time is 3.5h, the temperature is 65 ℃, the pH is 6.5, and the enzyme addition amount is 60000U g-1Inactivating enzyme in water bath at 85 deg.C for 20min after hydrolysis, and centrifuging at 8000rpm for 20min to obtain Spirulina protease hydrolysate.
Graft copolymerization reaction: adding 150 parts by weight of pre-spirulina protease hydrolysate into a four-neck flask with a stirrer (stirring speed of 50r/min), a condenser pipe, a thermometer and a dropping funnel, adjusting the pH to 4, firstly slowly adding 75 parts by weight of epoxy chloropropane, opening the condenser pipe for reflux, strictly controlling the temperature to be about 10 ℃, slowly dropwise adding 50 parts by weight of di-n-butylamine under stirring at a dropwise adding speed of 4g/min, heating to 65 ℃ after dropwise adding, then slowly adding 5 parts by weight of diethylenetriamine, continuously stirring, slowly heating to 80 ℃, reacting at constant temperature for 5 hours, and cooling to room temperature to obtain the ternary graft copolymerization modified spirulina protein water quality clarifier.
Example 2
A ternary graft copolymerization modified spirulina protein water quality clarifier comprises the following components in parts by weight:
the ternary graft copolymerization modified spirulina protein water clarifier of the embodiment is prepared according to the following method:
enzyme pretreatment: the same method as the enzymatic pretreatment of example 1.
Double enzyme hydrolysis of spirulina protein: pouring 500mL of spirulina protein solution into a conical flask, hydrolyzing the spirulina protein by using alkaline protease firstly, wherein the hydrolysis conditions are as follows: the hydrolysis time is 2.5h, the temperature is 55 deg.C, pH is 7.0, and the enzyme addition amount is 6000U g-1And after hydrolysis, inactivating the enzyme in water bath at 85 ℃ for 20 min. Further hydrolyzing by papain under the following conditions: the hydrolysis time is 3.5h, the temperature is 65 ℃, the pH is 6.5, and the enzyme addition amount is 30000 U.g-1Inactivating enzyme in water bath at 85 deg.C for 20min after hydrolysis, and centrifuging at 8000rpm for 20min to obtain Spirulina protease hydrolysate.
Graft copolymerization reaction: adding 200 parts by weight of spirulina protein enzymolysis liquid into a four-neck flask with a stirrer (the stirring speed is 55r/min), a condenser pipe, a thermometer and a dropping funnel, adjusting the pH to 4, firstly slowly adding 90 parts by weight of epoxy chloropropane, opening the condenser pipe for reflux, strictly controlling the temperature to be about 10 ℃, slowly dropwise adding 60 parts by weight of di-n-butylamine under stirring at the dropping speed of 4.5g/min, heating to 65 ℃ after the dropwise adding is finished, then slowly adding 8 parts by weight of diethylenetriamine, continuously stirring, slowly heating to 80 ℃, reacting at constant temperature for 7 hours, and cooling to room temperature to obtain the ternary graft copolymerization modified spirulina protein water quality clarifier.
Example 3
A ternary graft copolymerization modified spirulina protein water clarifier comprises the following components in parts by weight:
the ternary graft copolymerization modified spirulina protein water clarifier of the embodiment is prepared by the following method:
enzyme pretreatment: the same method as the enzymatic pretreatment of example 1.
Double enzyme hydrolysis of spirulina protein: pouring 500mL of spirulina protein solution into a conical flask, hydrolyzing the spirulina protein by using alkaline protease firstly, wherein the hydrolysis conditions are as follows: the hydrolysis time is 2.5h, the temperature is 55 deg.C, the pH is 7.0, and the enzyme addition amount is 5000 U.g-1And after hydrolysis, inactivating the enzyme in water bath at 85 ℃ for 20 min. Further hydrolyzing by papain under the following conditions: the hydrolysis time is 3.5h, the temperature is 65 ℃, the pH is 6.5, and the enzyme addition amount is 80000 U.g-1Inactivating enzyme in water bath at 85 deg.C for 20min after hydrolysis, and centrifuging at 8000rpm for 20min to obtain Spirulina protease hydrolysate.
Graft copolymerization reaction: adding 300 parts by weight of spirulina protein enzymolysis liquid into a four-neck flask with a stirrer (stirring speed is 60r/min), a condenser pipe, a thermometer and a dropping funnel, adjusting the pH to 4, firstly slowly adding 120 parts by weight of epoxy chloropropane, opening the condenser pipe for backflow, strictly controlling the temperature to be about 10 ℃, slowly dropwise adding 80 parts by weight of di-n-butylamine under stirring, heating to 65 ℃ after dropwise adding at the speed of 5g/min, then slowly adding 10 parts by weight of diethylenetriamine, continuously stirring, slowly heating to 80 ℃, reacting at constant temperature for 6 hours, and cooling to room temperature to obtain the ternary graft copolymerization modified spirulina protein water quality clarifier.
Example 4
A ternary graft copolymerization modified spirulina protein water quality clarifier comprises the following components in parts by weight:
the ternary graft copolymerization modified spirulina protein water clarifier of the embodiment is prepared by the following method:
enzyme pretreatment: the same method as the enzymatic pretreatment of example 1.
Double enzyme hydrolysis of spirulina protein: pouring 500mL of spirulina protein solution into a conical flask, hydrolyzing the spirulina protein by using alkaline protease firstly, wherein the hydrolysis conditions are as follows: the hydrolysis time is 2.5h, the temperature is 55 deg.C, the pH is 7.0, and the enzyme addition amount is 5500U g-1And after hydrolysis, inactivating the enzyme in water bath at 85 ℃ for 20 min. Further hydrolyzing by papain under the following conditions: the hydrolysis time is 3.5h, the temperature is 65 deg.C, the pH is 6.5, and the enzyme addition amount is 68000 U.g-1Inactivating enzyme in water bath at 85 deg.C for 20min after hydrolysis, and centrifuging at 8000rpm for 20min to obtain Spirulina protease hydrolysate.
Graft copolymerization reaction: adding 250 parts by weight of spirulina protein enzymatic hydrolysate into a four-neck flask with a stirrer (stirring speed is 50r/min), a condenser pipe, a thermometer and a dropping funnel, adjusting the pH to 4, firstly slowly adding 105 parts by weight of epoxy chloropropane, opening the condenser pipe for reflux, strictly controlling the temperature to be about 10 ℃, slowly dropwise adding 75 parts by weight of di-n-butylamine under stirring at a dropwise adding speed of 4g/min, heating to 65 ℃ after dropwise adding, then slowly adding 7 parts by weight of diethylenetriamine, continuously stirring, slowly heating to 80 ℃, reacting at constant temperature for 7 hours, and cooling to room temperature to obtain the ternary graft copolymerization modified spirulina protein water quality clarifier.
Test example 1
Mixing oil field sewage with distilled water, stirring, standing for 3 hr, and collecting upper layer suspension (for removing flocculation and agglomeration)Larger particle size) is configured to have a certain turbidity of the oilfield effluent sample. Then, four equal portions of 200mL oilfield wastewater were taken, 0.5-5.0mg/100mL of the water clarificant of examples 1-4 was added, the pH was adjusted to 7, and 200rad min was applied-1Stirring rapidly for 1min at 50 rad.min-1Slowly stirring for 6min, stopping stirring, standing for a moment, and measuring the residual turbidity of the sample. The influence of different contents of the water clarifiers of examples 1-4 in the oilfield sewage on the flocculation performance is respectively examined, and the index for evaluating the flocculation performance is the flocculation rate. The calculation formula of the flocculation rate is shown as follows:
in the formula: e% -flocculation rate; n is a radical of0-turbidity of the oilfield wastewater suspension before adding the agent; n is a radical of1The turbidity of the suspension of the oilfield sewage after the medicament is added.
The test result is shown in figure 1, and as can be seen from figure 1, the flocculation rates of different water quality clarifiers increase with the increase of the dosage of the medicament, and when the dosage reaches a certain value, the dosage is continuously increased, and the flocculation rate is reduced; when the amount is too small, the adsorption bridging effect is not achieved during the flocculation process, but when the amount is too large, the colloidal particles are dispersed, so that the formed floccules are redispersed, and the flocculation effect is reduced. Under the condition of the same medicament feeding, the flocculation rates of different water quality clarifiers are different, which is probably because the lower the molecular weight is, the more difficult the bridge function is controlled to form flocs, so that the flocculant is protected, and part of particles cannot flocculate and settle in the supernatant of the solution; the larger the molecular weight is, the stronger the bridging action of the molecular chain is, the larger the formed floc is, the faster the sedimentation rate is and the enhanced flocculation effect is.
Comparative example 1
A spirulina protein water clarifying agent only contains spirulina protein enzymolysis liquid and is prepared by the following method:
enzyme pretreatment: the same enzymatic pretreatment method as in example 1, which is not described in detail herein;
double enzyme hydrolysis of spirulina protein: the same procedure as in example 1 for the double-enzyme hydrolysis of spirulina proteins will not be described in detail.
Test example 2
50mL of each of 1mmol/L Ni (II) and Cr (VI) solutions were added to a 250mL conical flask with a stopper, 0.03g of the water clarifiers of examples 1 to 3 and comparative example 1 was added thereto, the pH of the solution was adjusted to 6, and the mixture was shaken at a constant temperature of 25 ℃ for 4 hours and then filtered. Comparing the balance adsorption amounts of the spirulina protein enzymolysis liquid and the graft copolymer to Ni (II) and Cr (VI), and evaluating the adsorption performance as the balance adsorption amount (q)eMmol/g). Equilibrium adsorption capacity (q)eMmol/g) is shown in the formula:
qe＝V(C0-Ce)/m
in the formula: v is the volume of the solution, L; c0And CeThe concentrations of Ni (II) and Cr (VI) in the solution before adsorption and in adsorption equilibrium are mmol/L respectively; m is the mass of the adsorbent, g.
The test result is shown in fig. 2, and it can be seen from fig. 2 that the equilibrium adsorption capacity of the graft copolymer to Ni (ii) and Cr (vi) is higher than that of spirulina protein, probably because the positive charge of the adsorbent is increased after the introduction of the cationic group, the electrostatic effect is enhanced, and further more colloidal particles are adsorbed in the macromolecular branched chain of the graft copolymer, and more metal ion particles are present, so that the colloid is flocculated and settled, and then the bridging effect is generated, and the equilibrium adsorption capacity of Ni (ii) and Cr (vi) is greatly increased.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the scope of the present invention claimed in the present invention.
Claims (8)
1. A preparation method of a ternary grafting copolymerization modified spirulina protein water quality clarifier is characterized in that,
the ternary graft copolymerization modified spirulina protein water quality clarifier comprises the following components in parts by weight:
100-300 parts of spirulina protease hydrolysate;
75-120 parts of epoxy chloropropane;
50-80 parts of di-n-butylamine;
5-10 parts of diethylenetriamine;
the preparation method of the ternary grafting copolymerization modified spirulina protein water clarifier comprises the following steps:
enzyme pretreatment: jointly treating spirulina dry powder with potassium chloride and lysozyme, performing negative pressure suction filtration to obtain a spirulina protein crude extract, inactivating enzyme, and adjusting pH to be neutral for later use;
carrying out enzymolysis on spirulina protein: hydrolyzing the crude spirulina protein extract with alkaline protease, inactivating enzyme in high-temperature water bath, further hydrolyzing with papain, inactivating enzyme in high-temperature water bath, and centrifuging to obtain spirulina protein hydrolysate;
Graft copolymerization reaction: adding the spirulina protein enzymatic hydrolysate into a four-neck flask with a stirrer, a condenser pipe, a thermometer and a dropping funnel, adjusting the pH value to 3.5-4.5, slowly adding epoxy chloropropane, opening the condenser pipe for reflux, controlling the temperature to be 8-12 ℃, slowly dropwise adding di-n-butylamine under stirring, then heating to 60-70 ℃, slowly adding diethylenetriamine, continuously stirring, slowly heating to 75-85 ℃, reacting at constant temperature, and cooling to room temperature to obtain the ternary graft copolymerization modified spirulina protein water quality clarifier.
2. The preparation method of the ternary graft copolymerization modified spirulina protein water clarifier of claim 1, which comprises the following components by weight:
200 parts of spirulina protease hydrolysate;
90 parts of epoxy chloropropane;
60 parts of di-n-butylamine;
8 parts of diethylenetriamine.
3. The preparation method of the ternary grafting copolymerization modified spirulina protein water clarifier of claim 1, wherein the mass ratio of the epichlorohydrin to the di-n-butylamine is (1-2): 1.
4. the preparation method of the ternary graft copolymerization modified spirulina protein water clarifier of claim 1, wherein the potassium chloride and lysozyme are processed under the following conditions: the temperature is 30 ℃, and the treatment time is 7-9 h.
5. The preparation method of the ternary graft copolymerization modified spirulina protein water quality clarifier of claim 1, wherein the alkaline protease hydrolysis conditions are: the hydrolysis time is 2-3 h, the temperature is 52-58 ℃, the pH is 7.0, and the enzyme addition amount is 4000-6000 U.g-1。
6. The preparation method of the ternary graft copolymerization modified spirulina protein water clarifier of claim 1, wherein the papain hydrolysis conditions are as follows: the hydrolysis time is 3-4 h, the temperature is 62-68 ℃, the pH is 6.5, and the enzyme addition amount is 30000-80000 U.g-1。
7. The preparation method of the ternary graft copolymerization modified spirulina protein water clarifier of claim 1, wherein the graft copolymerization reaction comprises:
adding the spirulina protein enzymatic hydrolysate into a four-neck flask with a stirrer, a condenser pipe, a thermometer and a dropping funnel, adjusting the pH value to 4, slowly adding epoxy chloropropane, opening the condenser pipe for reflux, strictly controlling the temperature to be 10 ℃, slowly adding di-n-butylamine while stirring, then heating to 65 ℃, slowly adding diethylenetriamine, continuing stirring, slowly heating to 80 ℃, reacting at constant temperature for 5-7h, and cooling to room temperature to obtain the ternary graft copolymerization modified spirulina protein water quality clarifier.
8. The preparation method of the ternary graft copolymerization modified spirulina protein water clarifier of claim 7, wherein the stirring speed of the stirrer is 50-60 r/min; the dripping speed of the di-n-butylamine is 4-5 g/min.
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| CN106379983B (en) * | 2016-08-08 | 2019-07-19 | 四川大学 | A kind of collagen flocculant and preparation method thereof without chemical modification |
| CN107540845A (en) * | 2017-05-31 | 2018-01-05 | 陕西科技大学 | A kind of preparation method of industrial gelatine graft copolymerization cationic flocculant |
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