CN104861115A - Preparation method of anionic glucan flocculating agent - Google Patents
Preparation method of anionic glucan flocculating agent Download PDFInfo
- Publication number
- CN104861115A CN104861115A CN201510070055.4A CN201510070055A CN104861115A CN 104861115 A CN104861115 A CN 104861115A CN 201510070055 A CN201510070055 A CN 201510070055A CN 104861115 A CN104861115 A CN 104861115A
- Authority
- CN
- China
- Prior art keywords
- solution
- dextran
- sucrose
- anionic
- glucan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a preparation method of an anionic glucan flocculating agent. The method comprises the following steps: 1, preparing a sucrose solution by adopting an acetic acid-sodium acetate buffering solution with the pH value of 5.0, adding dextransucrase to the sucrose solution, carrying out an enzymatic catalytic reaction, terminating the enzymatic catalytic reaction when the dynamic viscosity of the reaction solution reaches 8000-10000CPS in order to precipitate polymeric glucan, washing, and dissolving the washed polymeric glucan in water to obtain a polymeric glucan solution with the solid content of 5-10%; and 2, adding potassium persulfate and sodium bisulfite to the polymeric glucan solution as initiators, maintaining the temperature in a range of 50-70DEG C for 15-20min, adding a sodium acrylate solution as an anion monomer, carrying out a grafting copolymerization reaction, terminating the grafting copolymerization reaction, adopting ethanol to precipitate a crude grafted product, washing the crude grafted product by using ethanol, and re-dissolving the washed product in water to prepare the milky viscous liquid anionic glucan flocculating agent.
Description
Technical field
The present invention relates to biological flocculant field, particularly relate to a kind of preparation method of anionic dextran flocculation agent.
Background technology
Along with the develop rapidly of industry and the growth of population, increasing surface and ground water is subject to pollution in various degree, and water quality deterioration, shortage of water resources have been society huge difficult problems in the urgent need to address.In water treatment field, flocculation technique is a step operation of the maximum also most critical of application, and the height of flocculation efficiency depends primarily on the selection of flocculation agent kind.In the past few decades, inorganic flocculating agent (aluminium salt and molysite etc.) is widely used flocculating in operation with some organic polymers (as polyacrylamide) of synthesis, but result also in serious secondary pollution and new environmental problem.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of environmental protection non-harmful anionic dextran flocculation agent.
In order to solve the problem, the invention discloses a kind of preparation method of anionic dextran flocculation agent, described method comprises:
Acetic acid-sodium acetate buffer solution preparation sucrose solution of step 1, employing pH5.0, Sucrose:glucan alpha1-6-glucosyltransferase is added in described sucrose solution, at 26 ~ 28 DEG C, carry out enzymic catalytic reaction 24 ~ 28 hours, until the kinetic viscosity of reaction solution reaches 8000 ~ 10000CPS, stop described enzymic catalytic reaction, be settled out polymer dextran and wash rear soluble in water, obtaining the polymer dextran solution that solid content is 5 ~ 10%;
Under step 2, oxygen free condition, the Potassium Persulphate and sodium bisulfite that volumetric molar concentration ratio is (1:10) ~ (4:1) is added as initiator in described polymer dextran solution, be incubated 15 ~ 20min at 50 DEG C ~ 70 DEG C after, add sodium acrylate solution and carry out graft copolymerization 2 ~ 4 hours as anionic monomer, stop described graft copolymerization, alcohol settling is adopted to go out grafting crude product, multiple soluble in water after washing with alcohol, i.e. the anionic dextran flocculation agent of obtained oyster white thick liquid nano.
Preferably, described Sucrose:glucan alpha1-6-glucosyltransferase is by leuconostoc mesentroides and sour jujube spore mould mixed fungus fermentation gained.
Preferably, when adopting Sucrose:glucan alpha1-6-glucosyltransferase catalysing sucrose solution, the volumetric molar concentration of described sucrose is 0.2 ~ 1.0mol/L, the concentration of described Sucrose:glucan alpha1-6-glucosyltransferase is 0.5 ~ 3.0U/mL.
Preferably, the volumetric molar concentration of described Potassium Persulphate is 0.1 ~ 1.0mmol/L, and the volumetric molar concentration of described sodium bisulfite is 0.25 ~ 1.0mmol/L.
Preferably, described method also comprises:
The anionic dextran flocculation agent of described oyster white thick liquid nano is made lyophilized powder;
Or, through 45% ethanol repetitive scrubbing, dried overnight in 45 ~ 55 DEG C of baking ovens is placed on to prepared anionic dextran flocculation agent, obtains white dried solid particulate.
Preferably, in described graft copolymerization, the volumetric molar concentration of described sodium acrylate is 0.05 ~ 0.20mol/L, and the volume ratio of described biopolymer dextran and described sodium acrylate is 1:1.
Preferably, adopt the acetic acid-sodium acetate buffer solution of described pH5.0 to be mixed with described sucrose solution that volumetric molar concentration is 0.2 ~ 1.0mol/L;
The described enzymic catalytic reaction of described termination comprises:
The mode of heating and thermal insulation is adopted to stop enzymic catalytic reaction;
Described be settled out polymer dextran and washing after step soluble in water comprise:
Go out polymer dextran with the alcohol settling of 95% after cooling, by the throw out washing with alcohol of 45%, be finally dissolved in distilled water.
Preferably, the described graft copolymerization of described termination comprises:
Described graft copolymerization is stopped by cooling;
Described employing alcohol settling goes out grafting crude product, after washing with alcohol, answer soluble in water comprising:
Adopt 95% alcohol settling to go out grafting crude product, after 45% ethanol repetitive scrubbing, redissolve in distilled water.
Compared with prior art, the present invention includes following advantage:
By the embodiment of the present invention, first adopt Sucrose:glucan alpha1-6-glucosyltransferase catalysing sucrose solution, obtained full-bodied biopolymer dextran solution; Then under anaerobic, in the redox initiation system that Potassium Persulphate and sodium bisulfite are formed, with gained biopolymer dextran for substrate, take sodium acrylate as anionic monomer, carry out graft copolymerization, obtain the anionic derivative of dextran, be anionic dextran flocculation agent.
Dextran is innovatively applied to field of Environment Protection by the embodiment of the present invention, the graft copolymerization of biopolymer is applied to the derivatize of dextran, the dextran graft product obtained, can as a kind of excellent biopolymer flocculation agent, for the treatment of all kinds of water pollution problems.
Compared with commercially available organic floculant, the flocculation agent safety non-toxic of the embodiment of the present invention is nuisanceless, without any composition environment being had to harm, achieves suitability for industrialized production and the application of green bio flocculation agent.Further, based on the basic skeleton structure of biopolymer, the derivative after grafting still can regenerate, and can biological degradation, meets the Ecological View of Sustainable development.Therefore, the hypotoxicity of this high affinity combination itself makes glucan derivative flocculation agent have very large application prospect in heavy metal environmental pollution.
In addition, the solution process step of the embodiment of the present invention is simple, preparation technology's cycle is short, and low in raw material price.
Through embody rule, the anionic dextran flocculation agent flocculation activity adopting the scheme of the embodiment of the present invention to prepare is high, and consumption is few, especially to the turbidity removal rate of aqueous suspension ofkaolin up to 99%, and can with other flocculation agents with the use of, process all kinds of water pollution problems.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of a kind of anionic dextran flocculation agent of the present invention;
Fig. 2 is the infrared spectrogram of anionic dextran flocculation agent in the example 1 of the embodiment of the present invention;
Fig. 3 is the X-ray crystallogram of anionic dextran flocculation agent lyophilized powder in the example 1 of the embodiment of the present invention.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, and below in conjunction with embodiment, the present invention is further detailed explanation.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
All there is the problem of contaminate environment in inorganic flocculating agent and organic floculant, and natural polymers belongs to renewable resources, possess these advantageous advantages such as easy to use, easy degraded, non-secondary pollution, but, most of natural high molecular substance surface charge is weak, molecular weight is not high enough, poorly water-soluble, therefore need to carry out chemically modified to biopolymer, the present invention proposes a kind of preparation method of anionic dextran flocculation agent.
With reference to Fig. 1, it illustrates the schema of the preparation method of a kind of anionic dextran flocculation agent described in the embodiment of the present invention, described method specifically can comprise:
Acetic acid-sodium acetate buffer solution preparation sucrose solution of step 101, employing pH5.0, Sucrose:glucan alpha1-6-glucosyltransferase is added in described sucrose solution, at 26 ~ 28 DEG C, carry out enzymic catalytic reaction 24 ~ 28 hours, until the kinetic viscosity of reaction solution reaches 8000 ~ 10000CPS, stop described enzymic catalytic reaction, be settled out polymer dextran and wash rear soluble in water, obtaining the polymer dextran solution that solid content is 5 ~ 10%.
In the scheme of the embodiment of the present invention, first adopt Sucrose:glucan alpha1-6-glucosyltransferase catalysing sucrose solution, obtained kinetic viscosity is the biopolymer dextran solution of 8000 ~ 10000CPS.Enzyme-catalyzed reaction condition is gentle, energy consumption is low, and the pH adopting acetic acid-sodium acetate strictly to control reaction solution is 5.0, and in order to ensure the purity of polymer dextran, needing to control the reaction times, making the kinetic viscosity of reaction solution at 8000 ~ 10000CPS.
Under step 102, oxygen free condition, the Potassium Persulphate and sodium bisulfite that volumetric molar concentration ratio is (1:10) ~ (4:1) is added as initiator in described polymer dextran solution, be incubated 15 ~ 20min at 50 DEG C ~ 70 DEG C after, add sodium acrylate solution and carry out graft copolymerization 2 ~ 4 hours as anionic monomer, stop described graft copolymerization, alcohol settling is adopted to go out grafting crude product, multiple soluble in water after washing with alcohol, i.e. the anionic dextran flocculation agent of obtained oyster white thick liquid nano.
The embodiment of the present invention is after obtained biopolymer dextran solution, further, in the redox initiation system that Potassium Persulphate and sodium bisulfite are formed, with above-mentioned gained biopolymer dextran for substrate, take sodium acrylate as anionic monomer, carry out graft copolymerization, obtain the anionic derivative of dextran, be anionic dextran flocculation agent.
Dextran is the polysaccharide of first suitability for industrialized production in the world, is formed by connecting, is the biopolymer that a class has important commercial value, is widely used in medicine, food and chemical field by glucose unit by α-1,6-glycosidic link and α-1,3-glycosidic link.Dextran is applied to field of Environment Protection by the present invention's innovation, the graft copolymerization of biopolymer is applied to the derivatize of dextran, the dextran graft product obtained has high avidity to metal ion (as silver, mercury, copper etc.), can as a kind of excellent biopolymer flocculation agent, for the treatment of all kinds of water pollution problems, further, the hypotoxicity of this high affinity combination itself makes glucan derivative have very large application prospect in heavy metal environmental pollution.
In flocculation operation, flocculation agent realizes the improvement of water quality mainly through two kinds of mechanism: one is charge neutrality effect, namely flocculating agent molecule ionic group (quaternary ammonium salt, carboxylate radical etc.) with opposite charges can the electrostatic double layer of impurity particle thing in shield water solution significantly, thus destroy the gathering between impurity particle thing; Another kind is adsorption bridging effect, when namely the biological flocculant of high molecular exists with water-soluble form, has large hydration particle diameter, different suspended particulates can be coupled together with the form of building bridge.But most of natural high molecular substance surface charge is weak, molecular weight is not high enough, poorly water-soluble, therefore need to carry out chemically modified to biopolymer.
Embodiment of the present invention innovation proposes to adopt graft copolymerization to carry out chemically modified to polymer dextran solution, to improve biopolymer flocculating properties, by graft copolymerization, the characteristic group in grafted monomer is introduced in biopolymer, increase the conformational freedom of biopolymer, thus improve its adsorption bridging and charge neutrality ability.Based on the basic skeleton structure of biopolymer, the derivative after grafting still can regenerate, and can biological degradation, meets the Ecological View of Sustainable development.Therefore, the hypotoxicity of this high affinity combination itself makes glucan derivative flocculation agent have very large application prospect in heavy metal environmental pollution.
In addition, the solution process step of the embodiment of the present invention is simple, preparation technology's cycle is short, and low in raw material price.
Through embody rule, the anionic dextran flocculation agent flocculation activity adopting the scheme of the embodiment of the present invention to prepare is high, and consumption is few, especially to the turbidity removal rate of aqueous suspension ofkaolin up to 99%, and can with other flocculation agents with the use of, process all kinds of water pollution problems.
In the embodiment of the present invention, preferably, described Sucrose:glucan alpha1-6-glucosyltransferase is by leuconostoc mesentroides and sour jujube spore mould mixed fungus fermentation gained, and mixed fungus fermentation raw material is simple, easy to operate, can produce the Sucrose:glucan alpha1-6-glucosyltransferase of the work of high enzyme, high stability.
In the embodiment of the present invention, preferably, when adopting Sucrose:glucan alpha1-6-glucosyltransferase catalysing sucrose solution, the height according to Sucrose:glucan alpha1-6-glucosyltransferase continues catalytic mechanism, and the volumetric molar concentration of described sucrose is preferably 0.2 ~ 1.0mol/L, the concentration of described Sucrose:glucan alpha1-6-glucosyltransferase is preferably 0.5 ~ 3.0U/mL.
In the embodiment of the present invention, preferably, the volumetric molar concentration of described Potassium Persulphate can be 0.1 ~ 1.0mmol/L, and the volumetric molar concentration of described sodium bisulfite can be 0.25 ~ 1.0mmol/.
Described anionic dextran flocculation agent can have three kinds of existence forms: oyster white thick liquid, white dried particle, white lyophilized powder.In the embodiment of the present invention, preferably, described method can also comprise: the anionic dextran flocculation agent of described oyster white thick liquid nano is made lyophilized powder; Or, through 45% ethanol repetitive scrubbing, dried overnight in 45 ~ 55 DEG C of baking ovens is placed on to prepared anionic dextran flocculation agent, obtains white dried solid particulate.
In the embodiment of the present invention, preferably, in described graft copolymerization, the volumetric molar concentration of described sodium acrylate is 0.05 ~ 0.20mol/L, the volume ratio of described biopolymer dextran and described sodium acrylate is 1:1, to prevent implode phenomenon, guarantees the high efficiency of graft copolymerization.
In the embodiment of the present invention, preferably, adopt the acetic acid-sodium acetate buffer solution of described pH5.0 to be mixed with described sucrose solution that volumetric molar concentration is 0.2 ~ 1.0mol/L.
In the embodiment of the present invention, preferably, the described enzymic catalytic reaction of described termination can comprise: adopt the mode of heating and thermal insulation to stop enzymic catalytic reaction, guarantee the complete deactivation of enzyme molecule.
In the embodiment of the present invention, preferably, the described graft copolymerization of described termination can comprise: logical overcooled mode can reduce free radical polymerization rate rapidly, and then stops described graft copolymerization.
In the embodiment of the present invention, preferably, described be settled out polymer dextran and washing after step soluble in water can comprise: cooling after with 95% alcohol settling go out polymer dextran, by throw out with 45% washing with alcohol, wash away low-molecular polysaccharide as far as possible, ensure the purity of polymer dextran, be finally dissolved in distilled water.
In the embodiment of the present invention, preferably, described employing alcohol settling goes out grafting crude product, soluble in water can comprising is answered: adopt 95% alcohol settling to go out grafting crude product after washing with alcohol, through 45% ethanol repetitive scrubbing, guarantee that low molecular homopolymer and other small-molecule substances are separated completely with product, finally precipitation is redissolved in distilled water.
For making those skilled in the art understand the present invention better, the preparation method of a kind of anionic dextran flocculation agent of the present invention is described below by way of multiple concrete example.
Example 1
First, adopt the sucrose solution of the acetic acid-sodium acetate buffer solution preparation 0.2mol/L of pH5.0, the Sucrose:glucan alpha1-6-glucosyltransferase of sucrose solution and 1.5U/mL is carried out catalyzed reaction 24 hours under 26 DEG C of stirring in water bath conditions, obtains the polymer dextran of 8000CPS; Then the dextran (about 100mL) obtained loaded in the 250mL tri-neck reaction flask with prolong conjunction mechanical stirring device (solid content is about 10%), 60 DEG C of stirrings make it to dissolve fully; Again the sodium bisulfite (as redox initiator system) of the Potassium Persulphate of 0.1mmol/L and 1.0mmol/L is slowly added in three-necked bottle, insulation 15min; Then 100mL 0.1mol/L sodium acrylate is added in three neck reaction flasks, 50 DEG C are stirred polyreaction 4 hours, last alcohol precipitation namely collecting precipitation obtains milky graft product, redissolve in distilled water in after precipitation being rinsed repeatedly with 45% ethanol and distilled water respectively simultaneously, obtain the anionic dextran flocculation agent of oyster white thick liquid nano.
Graft product obtained above is carried out kaolin active testing: first with tap water, kaolin is made into the suspension 200mL of 0.5%, after ultrasonic dissolution assisting 10min, leave standstill 10min, get a certain amount of supernatant liquor (real is turbid solution) and record OD
550=1.458, be designated as A
0; Then above-mentioned graft product is diluted to the solution that solid content is about 0.5%, and under whipping appts, add the anionic dextran flocculation agent that 400 μ L solid contents are 0.5%, leave standstill 10min after stirring 5min and observe settling of floccus phenomenon, then drawing a certain amount of supernatant liquor and record OD
550=0.028, be designated as A; Finally calculate flocculating rate F=(A
0-A) ÷ A
0× 100%=98.1%.
Show the infrared spectrogram of anionic dextran flocculation agent in the example 1 of the embodiment of the present invention with reference to figure 2, the collection of illustrative plates of contrast dextran and its derivative can be found out, after graft reaction, and the infrared absorption peak 1649cm of the Bound moisture of dextran itself
-1disappear, the substitute is the absorption peak 1721cm of carboxylic acid C=O structure
-1, illustrate that anionic monomer acrylic acid sodium and dextran are successfully made graft copolymerization;
The X-ray crystallogram of anionic dextran flocculation agent lyophilized powder in the example 1 of the embodiment of the present invention is shown with reference to figure 3, the crystallogram of contrast dextran and graft product can find, substrate dextran has 2 θ=15 °, 17 °, 18 °, 20 ° and the 2 θ=29 ° five kinds of absorption peaks located, demonstrate typical A-type X-ray diffraction pattern, and compose with the XRD figure of the graft product of sodium acrylate the broad peak only demonstrating dispersion, mean the reduction of degree of crystallinity, illustrate that the introducing of sodium acrylate monomers changes the ordered structure of dextran molecule inside simultaneously, show that dextran and anionic monomer acrylic acid sodium are successfully made graft copolymerization further.
Example 2
First, adopt the sucrose solution of the acetic acid-sodium acetate buffer solution preparation 0.5mol/L of pH5.0, the Sucrose:glucan alpha1-6-glucosyltransferase of sucrose solution and 0.5U/mL is carried out catalyzed reaction 28 hours under 26 DEG C of stirring in water bath conditions, obtains the polymer dextran of 9000CPS; Then the dextran (about 100mL) obtained loaded in the 250mL tri-neck reaction flask with prolong conjunction mechanical stirring device (solid content is about 5%), 60 DEG C of stirrings make it to dissolve fully; Again the sodium bisulfite (as redox initiation system) of the Potassium Persulphate of 1.0mmol/L and 0.25mmol/L is slowly added in three-necked bottle, insulation 18min; Then 100mL 0.2mol/L sodium acrylate is added in three neck reaction flasks, 65 DEG C are stirred polyreaction 3 hours, last alcohol precipitation namely collecting precipitation obtains milky graft product, redissolve in distilled water in after precipitation being rinsed repeatedly with 45% ethanol and distilled water respectively simultaneously, obtain the anionic dextran flocculation agent of oyster white thick liquid nano.
Graft product obtained above is carried out kaolin active testing: first with tap water, kaolin is made into the suspension 200mL of 0.5%, after ultrasonic dissolution assisting 10min, leave standstill 10min, get a certain amount of supernatant liquor (real is turbid solution) and record OD
550=1.508, be designated as A
0; Then above-mentioned graft product is diluted to the solution that solid content is about 0.5%, and under whipping appts, in aqueous suspension ofkaolin, add the anionic dextran flocculation agent that 400 μ L solid contents are 0.5%, leave standstill 10min after stirring 5min and observe settling of floccus phenomenon, then drawing a certain amount of supernatant liquor and record OD
550=0.018, be designated as A; Finally calculate flocculating rate F=(A
0-A) ÷ A
0× 100%=98.8%.
Example 3
First, adopt the sucrose solution of the acetic acid-sodium acetate buffer solution preparation 1.0mol/L of pH5.0, the Sucrose:glucan alpha1-6-glucosyltransferase of sucrose solution and 3.0U/mL is carried out catalyzed reaction 24 hours under 28 DEG C of stirring in water bath conditions, obtains the polymer dextran of 8500CPS; Then the dextran (about 100mL) obtained loaded in the 250mL tri-neck reaction flask with prolong conjunction mechanical stirring device (solid content is about 8%), 60 DEG C of stirrings make it to dissolve fully; Again the sodium bisulfite (as redox initiator system) of the Potassium Persulphate of 0.8mmol/L and 0.4mmol/L is slowly added in three-necked bottle, insulation 20min; Then 100mL 0.05mol/L sodium acrylate is added in three neck reaction flasks, 70 DEG C are stirred polyreaction 2 hours, last alcohol precipitation namely collecting precipitation obtains milky graft product, redissolve in distilled water in after precipitation being rinsed repeatedly with 45% ethanol and distilled water respectively simultaneously, obtain the anionic dextran flocculation agent of oyster white thick liquid nano.
Graft product obtained above is carried out kaolin active testing: first with tap water, kaolin is made into the suspension 200mL of 1%, after ultrasonic dissolution assisting 10min, leave standstill 10min, get a certain amount of supernatant liquor (real is turbid solution) and record OD
550=1.658, be designated as A
0; Then above-mentioned graft product is diluted to the solution that solid content is about 0.5%, and under whipping appts, in aqueous suspension ofkaolin, add 400 μ L 0.5% anionic dextran flocculation agents, leave standstill 10min after stirring 5min and observe settling of floccus phenomenon, then drawing a certain amount of supernatant liquor and record OD
550=0.066, be designated as A; Finally calculate flocculating rate F=(A
0-A) ÷ A
0× 100%=96%.
Example 4
First, adopt the sucrose solution of the acetic acid-sodium acetate buffer solution preparation 0.5mol/L of pH5.0, the Sucrose:glucan alpha1-6-glucosyltransferase of sucrose solution and 1.0U/mL is carried out catalyzed reaction 26 hours under 27 DEG C of stirring in water bath conditions, obtains the polymer dextran of 10000CPS; Then the dextran (about 100mL) obtained loaded in the 250mL tri-neck reaction flask with prolong conjunction mechanical stirring device (solid content is about 6%), 60 DEG C of stirrings make it to dissolve fully; Again the sodium bisulfite (as redox initiator system) of the Potassium Persulphate of 0.5mmol/L and 0.5mmol/L is slowly added in three-necked bottle, insulation 20min; Then 100mL 0.1mol/L sodium acrylate is added in three neck reaction flasks, 60 DEG C are stirred polyreaction 4 hours, last alcohol precipitation namely collecting precipitation obtains milky graft product, redissolve in distilled water in after precipitation being rinsed repeatedly with 45% ethanol and distilled water respectively simultaneously, obtain the anionic dextran flocculation agent of oyster white thick liquid nano.
Graft product obtained above is carried out kaolin active testing: first with tap water, kaolin is made into the suspension 200mL of 1%, after ultrasonic dissolution assisting 10min, leave standstill 10min, get a certain amount of supernatant liquor (real is turbid solution) and record OD
550=1.625, be designated as A
0; Then above-mentioned graft product is diluted to the solution that solid content is about 0.5%, and under whipping appts, in aqueous suspension ofkaolin, add 400 μ L 0.5% anionic dextran flocculation agents, leave standstill 10min after stirring 5min and observe settling of floccus phenomenon, then drawing a certain amount of supernatant liquor and record OD
550=0.016, be designated as A; Finally calculate flocculating rate F=(A
0-A) ÷ A
0× 100%=99%.
These are only the preferred embodiment cited by the present invention, and be not used to limit the scope of the invention, the equivalence that the those of ordinary skill in art uses the present invention to do is modified or change, all with belonging to scope of patent protection of the present invention.
For embodiment of the method, in order to simple description, therefore it is all expressed as a series of combination of actions, but those skilled in the art should know, the present invention is not by the restriction of described sequence of operation, because according to the present invention, some step can adopt other orders or carry out simultaneously.Secondly, those skilled in the art also should know, the embodiment described in specification sheets all belongs to preferred embodiment, and involved action and parts might not be that the present invention is necessary.
Above the preparation method of a kind of anionic dextran flocculation agent provided by the present invention is described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (8)
1. a preparation method for anionic dextran flocculation agent, is characterized in that, described method comprises:
Acetic acid-sodium acetate buffer solution preparation sucrose solution of step 1, employing pH5.0, Sucrose:glucan alpha1-6-glucosyltransferase is added in described sucrose solution, at 26 ~ 28 DEG C, carry out enzymic catalytic reaction 24 ~ 28 hours, until the kinetic viscosity of reaction solution reaches 8000 ~ 10000CPS, stop described enzymic catalytic reaction, be settled out polymer dextran and wash rear soluble in water, obtaining the polymer dextran solution that solid content is 5 ~ 10%;
Under step 2, oxygen free condition, the Potassium Persulphate and sodium bisulfite that volumetric molar concentration ratio is (1:10) ~ (4:1) is added as initiator in described polymer dextran solution, be incubated 15 ~ 20min at 50 DEG C ~ 70 DEG C after, add sodium acrylate solution and carry out graft copolymerization 2 ~ 4 hours as anionic monomer, stop described graft copolymerization, alcohol settling is adopted to go out grafting crude product, multiple soluble in water after washing with alcohol, i.e. the anionic dextran flocculation agent of obtained oyster white thick liquid nano.
2. method according to claim 1, is characterized in that, described Sucrose:glucan alpha1-6-glucosyltransferase is by leuconostoc mesentroides and sour jujube spore mould mixed fungus fermentation gained.
3. method according to claim 1, is characterized in that, when adopting Sucrose:glucan alpha1-6-glucosyltransferase catalysing sucrose solution, the volumetric molar concentration of described sucrose is 0.2 ~ 1.0mol/L, the concentration of described Sucrose:glucan alpha1-6-glucosyltransferase is 0.5 ~ 3.0U/mL.
4. method according to claim 1, is characterized in that, the volumetric molar concentration of described Potassium Persulphate is 0.1 ~ 1.0mmol/L, and the volumetric molar concentration of described sodium bisulfite is 0.25 ~ 1.0mmol/L.
5. method according to claim 1, is characterized in that, described method also comprises:
The anionic dextran flocculation agent of described oyster white thick liquid nano is made lyophilized powder;
Or, through 45% ethanol repetitive scrubbing, dried overnight in 45 ~ 55 DEG C of baking ovens is placed on to prepared anionic dextran flocculation agent, obtains white dried solid particulate.
6. method according to claim 1, is characterized in that, in described graft copolymerization, the volumetric molar concentration of described sodium acrylate is 0.05 ~ 0.20mol/L, and the volume ratio of described biopolymer dextran and described sodium acrylate is 1:1.
7. method according to claim 1, is characterized in that:
Adopt the acetic acid-sodium acetate buffer solution of described pH5.0 to be mixed with described sucrose solution that volumetric molar concentration is 0.2 ~ 1.0mol/L;
The described enzymic catalytic reaction of described termination comprises:
The mode of heating and thermal insulation is adopted to stop enzymic catalytic reaction;
Described be settled out polymer dextran and washing after step soluble in water comprise:
Go out polymer dextran with the alcohol settling of 95% after cooling, by the throw out washing with alcohol of 45%, be finally dissolved in distilled water.
8. method according to claim 1, is characterized in that:
The described graft copolymerization of described termination comprises:
Described graft copolymerization is stopped by cooling;
Described employing alcohol settling goes out grafting crude product, after washing with alcohol, answer soluble in water comprising:
Adopt 95% alcohol settling to go out grafting crude product, after 45% ethanol repetitive scrubbing, redissolve in distilled water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510070055.4A CN104861115B (en) | 2015-02-10 | 2015-02-10 | A kind of preparation method of anionic glucan flocculant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510070055.4A CN104861115B (en) | 2015-02-10 | 2015-02-10 | A kind of preparation method of anionic glucan flocculant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104861115A true CN104861115A (en) | 2015-08-26 |
| CN104861115B CN104861115B (en) | 2017-09-15 |
Family
ID=53907338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510070055.4A Active CN104861115B (en) | 2015-02-10 | 2015-02-10 | A kind of preparation method of anionic glucan flocculant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104861115B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132390A (en) * | 2015-09-28 | 2015-12-09 | 合肥工业大学 | Method for preparing dextransucrase by using mixed fermentation |
| 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 |
| CN112920404A (en) * | 2021-01-29 | 2021-06-08 | 合肥工业大学 | Preparation method and application of dextran-polyamino acid cationic flocculant |
| CN114874445A (en) * | 2022-04-29 | 2022-08-09 | 合肥工业大学智能制造技术研究院 | Preparation method and application of dextran-polyaspartic acid anion flocculant |
| CN116134054A (en) * | 2020-06-04 | 2023-05-16 | 营养与生物科学美国4公司 | Dextran-alpha-glucan graft copolymer and derivatives thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005054316A1 (en) * | 2003-12-03 | 2005-06-16 | Toagosei Co., Ltd. | Process for producing water-soluble polymer |
| CN101392280A (en) * | 2007-09-18 | 2009-03-25 | 庄茅 | Enzymology method for preparing polysaccharide bioflocculant |
| US20110118168A1 (en) * | 2008-06-24 | 2011-05-19 | Cognis Ip Management Gmbh | Cleaning Composition Comprising Graft Copolymers |
| CN103834574A (en) * | 2014-01-03 | 2014-06-04 | 合肥工业大学 | Dextranase and application of same in preparation of low molecular dextran |
| CN104327215A (en) * | 2014-11-14 | 2015-02-04 | 威海汉邦生物环保科技有限公司 | Ultra-high molecular weight anion biological polysaccharide grafted copolymer and preparation method thereof |
-
2015
- 2015-02-10 CN CN201510070055.4A patent/CN104861115B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005054316A1 (en) * | 2003-12-03 | 2005-06-16 | Toagosei Co., Ltd. | Process for producing water-soluble polymer |
| CN101392280A (en) * | 2007-09-18 | 2009-03-25 | 庄茅 | Enzymology method for preparing polysaccharide bioflocculant |
| US20110118168A1 (en) * | 2008-06-24 | 2011-05-19 | Cognis Ip Management Gmbh | Cleaning Composition Comprising Graft Copolymers |
| CN103834574A (en) * | 2014-01-03 | 2014-06-04 | 合肥工业大学 | Dextranase and application of same in preparation of low molecular dextran |
| CN104327215A (en) * | 2014-11-14 | 2015-02-04 | 威海汉邦生物环保科技有限公司 | Ultra-high molecular weight anion biological polysaccharide grafted copolymer and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132390A (en) * | 2015-09-28 | 2015-12-09 | 合肥工业大学 | Method for preparing dextransucrase by using mixed fermentation |
| CN105132390B (en) * | 2015-09-28 | 2018-05-01 | 合肥工业大学 | A kind of method that dextransucrase is prepared using mixed fungus fermentation |
| 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 |
| CN116134054A (en) * | 2020-06-04 | 2023-05-16 | 营养与生物科学美国4公司 | Dextran-alpha-glucan graft copolymer and derivatives thereof |
| CN112920404A (en) * | 2021-01-29 | 2021-06-08 | 合肥工业大学 | Preparation method and application of dextran-polyamino acid cationic flocculant |
| CN112920404B (en) * | 2021-01-29 | 2023-01-24 | 合肥工业大学 | Preparation method and application of dextran-polyamino acid cationic flocculant |
| CN114874445A (en) * | 2022-04-29 | 2022-08-09 | 合肥工业大学智能制造技术研究院 | Preparation method and application of dextran-polyaspartic acid anion flocculant |
| CN114874445B (en) * | 2022-04-29 | 2023-09-19 | 合肥工业大学智能制造技术研究院 | Preparation method and application of dextran-polyaspartic acid anionic flocculant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104861115B (en) | 2017-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104861115A (en) | Preparation method of anionic glucan flocculating agent | |
| Zou et al. | β-Cyclodextrin modified anionic and cationic acrylamide polymers for enhancing oil recovery | |
| Kang et al. | Cellulose derivatives and graft copolymers as blocks for functional materials | |
| Mittal et al. | Flocculation characteristics and biodegradation studies of Gum ghatti based hydrogels | |
| CN109553701B (en) | Preparation method of modified chitosan polymer | |
| Han et al. | Recyclable soluble–insoluble upper critical solution temperature-type poly (methacrylamide-co-acrylic acid)–cellulase biocatalyst for hydrolysis of cellulose into glucose | |
| CN103724455A (en) | Hyaluronic acid derivative and preparation method for hyaluronic acid hydrogel | |
| CN101397354A (en) | Hydrophobic modified cationic block polyacrylamide and synthesis method and application thereof | |
| CN104099317A (en) | Method for fixing pullulanase with chitosan magnetic nanoparticles | |
| CN101397351A (en) | Hydrophobic modified cationic polyacrylamide and synthesis method and application thereof | |
| CN104045778B (en) | Preparation method of star-like hybrid material with UCST and polyhedral oligomeric silsesquioxane (POSS) as core | |
| CN112898488B (en) | Polysaccharide modified salt-resistant resistance-reducing agent for shale gas fracturing fluid and preparation method thereof | |
| CN102321255A (en) | Ion type nano-composite hydrogel and preparation method thereof | |
| Yadav et al. | Synthesis of partially hydrolyzed graft copolymer (H-partially carboxymethylated guar gum-g-methacrylic acid): A superabsorbing material | |
| Luo et al. | Bacterial cellulose based superabsorbent production: A promising example for high value-added utilization of clay and biology resources | |
| Zhuang et al. | Using concanavalinA as a spacer for immobilization of E. coli onto magnetic nanoparticles | |
| CN102994489B (en) | Biotin-avidin system immobilized glucoamylase and preparation method thereof | |
| CN104829780A (en) | Preparation method for high-strength hydrogel with rapid response to both pH value and temperature | |
| Wang et al. | Synthesis and characterization of a cationic dextran-based flocculant and its application in bacterial sedimentation | |
| CN110437378A (en) | Cationic dextran based polyalcohol, preparation and the application as flocculant | |
| CN104387712A (en) | Nano composite carrier with superparamagnetism and preparation method thereof | |
| CN112553187A (en) | Polymer immobilized xylanase, preparation method and application thereof | |
| CN101816909A (en) | Preparation method of poly(phenylethylene-acrylic acid) magnetic polymer microsphere | |
| CN102250278B (en) | pH-sensitive renewable polymer for water-soluble immobilized cellulase as well as preparation method and application thereof | |
| CN101314626B (en) | Method for preparing cation polyacrylamide dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |