CN114890525B - Preparation method and application of dextran-betaine cationic flocculant - Google Patents
Preparation method and application of dextran-betaine cationic flocculant Download PDFInfo
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- CN114890525B CN114890525B CN202210546609.3A CN202210546609A CN114890525B CN 114890525 B CN114890525 B CN 114890525B CN 202210546609 A CN202210546609 A CN 202210546609A CN 114890525 B CN114890525 B CN 114890525B
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- 229960003237 betaine Drugs 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920002307 Dextran Polymers 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012304 carboxyl activating agent Substances 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 230000032050 esterification Effects 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract 9
- 229930006000 Sucrose Natural products 0.000 claims description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 9
- 239000005720 sucrose Substances 0.000 claims description 9
- 108010042194 dextransucrase Proteins 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 108090000790 Enzymes Proteins 0.000 claims description 4
- 102000004190 Enzymes Human genes 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 2
- 229960003403 betaine hydrochloride Drugs 0.000 claims description 2
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940023579 anhydrous betaine Drugs 0.000 claims 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims 1
- 238000000855 fermentation Methods 0.000 abstract description 22
- 230000004151 fermentation Effects 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 15
- 150000004676 glycans Chemical class 0.000 abstract description 9
- 229920001282 polysaccharide Polymers 0.000 abstract description 9
- 239000005017 polysaccharide Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 1
- 229920005615 natural polymer Polymers 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 description 28
- 230000016615 flocculation Effects 0.000 description 28
- 230000000694 effects Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- 239000005995 Aluminium silicate Substances 0.000 description 9
- 235000012211 aluminium silicate Nutrition 0.000 description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 9
- 239000000725 suspension Substances 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- DGPUYHMCOANORE-UHFFFAOYSA-L calcium;acetic acid;diacetate Chemical compound [Ca+2].CC(O)=O.CC([O-])=O.CC([O-])=O DGPUYHMCOANORE-UHFFFAOYSA-L 0.000 description 3
- 241000186254 coryneform bacterium Species 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- PMMYEEVYMWASQN-DMTCNVIQSA-N Hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PMMYEEVYMWASQN-UHFFFAOYSA-N dl-hydroxyproline Natural products OC1C[NH2+]C(C([O-])=O)C1 PMMYEEVYMWASQN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229960002591 hydroxyproline Drugs 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005613 synthetic organic polymer Polymers 0.000 description 2
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- BWZHKRSSCFRVIE-UHFFFAOYSA-N 1-n,4-n-dimethyl-2h-pyridine-1,4-diamine Chemical compound CNN1CC=C(NC)C=C1 BWZHKRSSCFRVIE-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000186031 Corynebacteriaceae Species 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 102000003960 Ligases Human genes 0.000 description 1
- 108090000364 Ligases Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 101710184309 Probable sucrose-6-phosphate hydrolase Proteins 0.000 description 1
- 102400000472 Sucrase Human genes 0.000 description 1
- 101710112652 Sucrose-6-phosphate hydrolase Proteins 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229950010582 betaine anhydrous Drugs 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 235000011073 invertase Nutrition 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention provides a preparation method of a dextran-betaine cationic flocculant and application of the dextran-betaine cationic flocculant in pretreatment of fermentation broth. The preparation method comprises the following steps: dissolving dextran in dimethyl sulfoxide, adding betaine, carboxyl activating agent and esterification catalyst 4-dimethylaminopyridine into the mixed solution, controlling the reaction conditions to carry out esterification reaction, adding ethanol after the reaction is finished to obtain precipitate, fully washing with 80% ethanol, purifying, and drying to obtain white dry solid, namely the dextran-betaine cationic flocculant. The dextran-betaine cationic flocculant prepared by the method can be used for pretreatment of fermentation liquor, the flocculant is a natural polymer flocculant which is safe and nontoxic and is easy to biodegrade, and the formed flocculant can be used as feed after being filtered. The natural polysaccharide-based flocculant prepared by the method not only realizes the solid-liquid separation of fermentation liquor, but also realizes the fodder utilization of wastes.
Description
Technical Field
The invention relates to the field of polysaccharide-based flocculants, in particular to a preparation method and application of a dextran-betaine cationic flocculant.
Background
At present, industry rapidly develops, great convenience is brought to the life of substances of people, economic development is promoted, but great environmental problems are brought to the industrial development, wherein the pollution of industrial wastewater to the environment is more and more severe, the current method for treating wastewater mainly comprises a physical adsorption method, a flocculation method, a chemical method, a biological method and the like, wherein the flocculation method has the advantages of simple operation, excellent effect, short treatment period, low cost and the like, the flocculant used in the flocculation method is mainly divided into an inorganic flocculant (such as polyaluminium chloride, ferric sulfate and the like), a synthetic organic polymer flocculant (such as polyacrylamide) and a natural organic polymer flocculant (such as natural polysaccharide such as chitosan) and the like, the most widely used flocculant at present is an inorganic flocculant and a synthetic organic polymer flocculant, and the natural polysaccharide flocculant has remarkable advantages compared with other two flocculants, and has the advantages of wide source, no toxicity or harm, biodegradability, no secondary pollution and good biocompatibility. However, the natural polysaccharide has the defects of fewer flocculation active groups, poor flocculation effect and the like, so that the natural polysaccharide cannot be widely used, a great amount of flocculation active groups are introduced on a polysaccharide polymer chain by a common chemical modification method, the defects of a polysaccharide flocculant are overcome, and the flocculation effect is enhanced, so that the natural polysaccharide modified flocculant with environmental protection and excellent effect is prepared.
For the field of biological pharmacy, a fermentation method is often used for producing required medicines or medicinal raw materials, the pretreatment of fermentation liquor is firstly subjected to solid-liquid separation so as to separate thallus for fermentation and waste generated by metabolism, but the thallus particles are generally small, the viscosity of the fermentation liquor is high, and the solid-liquid separation is difficult to realize directly through filtration. Flocculation is commonly used for pretreatment, increasing suspended particles and improving the treatment performance of fermentation liquor. Although there is chinese patent application CN112920404 a-a method for preparing a dextran-polyamino acid cationic flocculant and its application-it is mentioned that it can be used for flocculation of escherichia coli culture solution, the amino acid only contains amino group, and the amino group needs to be protonated to carry positive charge, which necessarily affects its application effect.
Disclosure of Invention
The invention provides a preparation method and application of a dextran-betaine cationic flocculant. The preparation method of the dextran-betaine cationic flocculant comprises the following steps:
dissolving dextran in dimethyl sulfoxide, adding betaine, carboxyl activating agent and esterification catalyst 4-dimethylaminopyridine into the dextran solution, reacting for 6-48h at 25-80 ℃, adding absolute ethyl alcohol after the reaction is finished to obtain precipitate, washing and purifying with ethyl alcohol fully, and drying to obtain white dry solid, namely the dextran-betaine cationic flocculant; wherein, the reaction is preferably carried out at 25-50 ℃ for 12-24h; the washing is carried out fully by ethanol, and the concentration of the ethanol is more than 50%.
In the preparation method of the dextran-betaine cationic flocculant, preferably, the dextran is obtained by an enzyme catalytic reaction of dextran sucrase in a sucrose solution. The preparation method comprises the following steps: preparing sucrose solution by adopting acetic acid-calcium acetate buffer solution with pH value of 5.0-5.5, adding dextrorotatory sucrase into the sucrose solution for enzyme catalytic reaction, performing shaking table reaction at 100-500rpm at 20-28 ℃ until dynamic viscosity reaches 8000-10000CPS, stopping reaction about 20-30 hours, adopting ethanol to precipitate high molecular weight dextran, washing for 2-3 times, obtaining high molecular weight dextran solution if dissolved in water, and drying and grinding in a blast oven with constant temperature of 30-50 ℃ to obtain high molecular weight dextran solid powder with molecular weight of 100-800 ten thousand. Wherein, the molar concentration of the sucrose solution is preferably 0.55-0.75mol/L, which is prepared by adopting acetic acid-calcium acetate buffer solution with pH=5.0-5.5, and the concentration of the dextran sucrase is 5.0-6.0U/mL. Preferably, the concentration of the dextran solution is 10-60g/L. The dextran sucrase is a hydrolysis synthetase for synthesizing dextran by taking sucrose as a substrate, and can be produced by genetic engineering bacteria capable of high expression of dextran sucrase in Chinese patent CN101363009A or by mixed fermentation in Chinese patent CN 105132390A.
In the method for preparing the dextran-betaine cationic flocculant, preferably, at least one of betaine anhydrous betaine and betaine hydrochloride is selected.
In the preparation method of the dextran-betaine cationic flocculant, preferably, the carboxyl activating agent is at least one of dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-diisopropylcarbodiimide and N, N-carbodiimidazole.
In the preparation method of the dextran-betaine cationic flocculant, preferably, the molar ratio of betaine to dextran anhydroglucose units is 1-2:1.
in the preparation method of the dextran-betaine cationic flocculant, preferably, the molar ratio of the carboxyl activating agent to the betaine is 1-2:1.
in the preparation method of the dextran-betaine cationic flocculant, preferably, the dosage of the 4-dimethylaminopyridine is 5% of the mass of the betaine.
In the invention, high molecular dextran is prepared by catalyzing sucrose reaction with dextran sucrase, and betaine is grafted onto dextran molecular chain by esterification reaction between the high molecular dextran and betaine to obtain the cationic dextran-based flocculant. The invention innovatively applies two natural products of high molecular dextran and betaine to the field of flocculants, and utilizes the esterification reaction of the high molecular dextran and the betaine to carry out derivatization of the dextran, so that the obtained dextran-betaine cationic flocculant has high molecular weight and contains a large number of cationic active groups, and can be used as a biopolymer flocculant with good performance for removing impurity particles with negative charges in water.
In the invention, the grafting monomer is derived from a natural quaternary ammonium alkaloid, namely betaine, which is a natural product widely existing in animals and plants, has no toxicity and can be biodegraded. Compared with amino acid, betaine has quaternary amine group with permanent positive charge, and amino acid only contains amino group, and the amino group needs to be protonated to carry positive charge, so that the betaine grafted dextran flocculant has better flocculation effect, wider application range and smaller influence of pH.
The modification method adopted by the invention is green and environment-friendly, mild in condition, simple in process steps, controllable in product quality, wide in raw material source, low in price and derived from natural products, and is truly green and environment-friendly, nontoxic and harmless. Compared with the inorganic and synthetic organic flocculant widely used at present, the prepared cation flocculant of the dextran-betaine is environment-friendly, nontoxic and harmless, safe and effective, biodegradable, has good biocompatibility, does not bring secondary pollution and does not cause harm to human bodies and the environment.
The dextran-betaine cationic flocculant prepared by the method has good application prospect in pretreatment of fermentation broth, can realize solid-liquid separation of the fermentation broth, can recover a large amount of organic nutrients, can be used as feed, and greatly increases economic benefit.
Drawings
FIG. 1 is a graph showing the flocculation property test effect of a dextran-betaine cationic flocculant kaolin suspension in application example 1 of the present invention: the left is a natural standing effect, and the right is a standing effect after flocculation;
FIG. 2 is a graph showing the results of a test of flocculation performance of a dextran-betaine cationic flocculant in a flocculated kaolin suspension in accordance with application example 1 of the present invention;
FIG. 3 is a diagram showing the effect of the dextran-betaine cationic flocculant in the fermentation broth of Corynebacterium floccus in application example 2 of the present invention: the left is a natural standing effect, and the right is a standing effect after flocculation;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing a sucrose solution with the concentration of 5.0U/mL by adopting an acetic acid-calcium acetate buffer solution with the pH value of=5.4, and adding a dextran sucrase solution into the sucrose solution with the concentration of 5.58 mol/L; enzyme catalytic reaction is carried out for 24 hours at 25 ℃ in a shaking table at 100 rpm; after the reaction is finished, precipitating a high molecular weight dextran product by using absolute ethyl alcohol, washing for 2 times, and then drying in a constant-temperature blast oven at 40 ℃; grinding after the high molecular weight dextran product is dried, and obtaining high molecular weight dextran solid powder.
Dissolving dextran in dimethyl sulfoxide, adding betaine, N' -diisopropyl carbodiimide and 4-dimethylaminopyridine into the dextran solution, wherein the molar ratio of the betaine to the dextran anhydroglucose unit is 1: the molar ratio of 1, N' -diisopropylcarbodiimide to betaine is 1:1, 4-dimethylaminopyridine accounting for 5 percent of the mass of betaine, reacting for 24 hours at 25-30 ℃, adding absolute ethyl alcohol after the reaction is finished to obtain precipitate, fully washing and purifying with 80 percent of alcohol, and drying to obtain white dry solid, namely the dextran-betaine cationic flocculant.
Performance test 1
The dextran-betaine cationic flocculant of example 1 of the present invention was subjected to flocculation performance test with a kaolin suspension: the dextran-betaine cationic flocculant powder is weighed and dissolved in distilled water to prepare the dextran-betaine cationic flocculant mother liquor with the concentration of 1 g/L. 0.50g of kaolin powder is weighed and stirred in 250mL of distilled water for 5min, and a kaolin suspension simulated waste water sample with the concentration of 2.0g/L is obtained. Adding a certain amount of dextran-betaine cationic flocculant mother liquor into kaolin suspension, rapidly stirring for 1min, slowly stirring for 2min, standing for 2min, taking supernatant, detecting absorbance value at 550nm, and calculating flocculation efficiency F% according to the following formula:
F％＝(F0-F1)/F0*100％
wherein F0 and F1 are absorbance values at 550nm of the kaolin suspension before and after flocculation, respectively.
FIG. 2 is a graph showing the results of a flocculation experiment of a kaolin suspension in simulating a waste water sample. The result shows that the maximum flocculation efficiency is increased gradually along with the increase of the dosage of the dextran-betaine cationic flocculant, the maximum flocculation efficiency is up to more than 98%, the kaolin suspension is rapidly destabilized when the dosage of the flocculant is 8mg/L, the maximum flocculation efficiency is reached, the flocculation efficiency tends to be stable along with the increase of the dosage, and the dextran-betaine cationic flocculant provided by the invention is kept at about 98%, so that the dextran-betaine cationic flocculant has excellent flocculation activity.
Performance test 2
The dextran-betaine cationic flocculant powder is weighed and dissolved in distilled water to prepare the dextran-betaine cationic flocculant mother liquor with the concentration of 1 g/L. 100mg/L dextran-betaine cationic flocculant is added to a coryneform bacterium fermentation broth (hydroxyproline fermentation broth, shandong Jin Yang pharmaceutical Co., ltd.) while stirring, and after the addition, the mixture is stirred for 5min and then left to stand for 20min, so that the bacterial cells are almost completely settled. FIG. 3 is a diagram showing flocculation clarification effect of coryneform bacteria fermentation broth: the left is the effect before flocculation, almost completely turkish turbidity in the whole cup body, no layering, and the right is the effect after clarification by the product of the invention, namely layering, wherein turkish turbidity drops to the bottom of the cup, and the upper layer is obvious yellow clarified solution and occupies most part. Similarly, when the dextran-polyamino acid cationic flocculant prepared by the method of patent CN112920404a was used for flocculation test of the coryneform bacterium fermentation broth (hydroxyproline fermentation broth, shandong Jin Yang pharmaceutical industry limited), 100mg/L of the dextran-polyamino acid cationic flocculant was added to the coryneform bacterium fermentation broth while stirring, and after the addition was completed, stirring was continued for 5min, and after standing for 20min, there was no obvious flocculation phenomenon. Therefore, in the fermentation production, the thallus particles of the fermentation liquid are small, the viscosity of the fermentation liquid is high, and when the thallus for fermentation and waste generated by metabolism are separated by pretreatment, the dextran-betaine cationic flocculant has more remarkable flocculation effect than the dextran-polyamino acid cationic flocculant of the patent CN 112920404A.
Claims (10)
1. The preparation method of the dextran-betaine cationic flocculant comprises the steps of dissolving dextran in dimethyl sulfoxide, adding betaine, a carboxyl activating agent and an esterification catalyst 4-dimethylaminopyridine into the dextran solution, reacting for 12-24 hours at 25-50 ℃, adding absolute ethyl alcohol after the reaction is finished to obtain precipitate, fully washing and purifying with the ethyl alcohol, and drying to obtain white dry solids, namely the dextran-betaine cationic flocculant.
2. The use according to claim 1, characterized in that: the dextran is obtained by an enzyme catalyzed reaction of dextran sucrase in a sucrose solution.
3. The use according to claim 1, characterized in that: the betaine is at least one of anhydrous betaine and betaine hydrochloride.
4. The use according to claim 1, characterized in that: the carboxyl activating agent is at least one of dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-diisopropylcarbodiimide and N, N-carbonyl diimidazole.
5. The use according to claim 1, characterized in that: the mol ratio of betaine to dextran anhydroglucose units is 0.1-3:1.
6. the use according to claim 5, characterized in that: the mol ratio of betaine to dextran anhydroglucose units is 1-2:1.
7. the use according to claim 1, characterized in that: the molar ratio of the carboxyl activating agent to the betaine is 0.1-3:1.
8. the use according to claim 7, characterized in that: the mol ratio of the carboxyl activating agent to the betaine is 1-2:1.
9. the use according to claim 1, characterized in that: the dosage of the esterification catalyst 4-dimethylaminopyridine is 0-10% of the mass of betaine.
10. The use according to claim 9, characterized in that: the dosage of the esterification catalyst 4-dimethylaminopyridine is 4-6% of the mass of betaine.
Priority Applications (1)
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| WO2000015669A1 (en) * | 1998-09-15 | 2000-03-23 | Raisio Chemicals Ltd | New cationic starch, its preparation and use |
| JP2008200597A (en) * | 2007-02-20 | 2008-09-04 | Daiyanitorikkusu Kk | Amphoteric polymer flocculant and method for treating sludge by using the same |
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| CN110437378A (en) * | 2019-09-09 | 2019-11-12 | 安徽春霖环保科技有限公司 | Cationic dextran based polyalcohol, preparation and the application as flocculant |
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| WO2000015669A1 (en) * | 1998-09-15 | 2000-03-23 | Raisio Chemicals Ltd | New cationic starch, its preparation and use |
| JP2008200597A (en) * | 2007-02-20 | 2008-09-04 | Daiyanitorikkusu Kk | Amphoteric polymer flocculant and method for treating sludge by using the same |
| CN104130335A (en) * | 2014-07-23 | 2014-11-05 | 威海汉邦生物环保科技有限公司 | High-substituted quaternary ammonium polysaccharide bioflocculant and preparation method thereof |
| CN110437378A (en) * | 2019-09-09 | 2019-11-12 | 安徽春霖环保科技有限公司 | Cationic dextran based polyalcohol, preparation and the application as flocculant |
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