CN101235094B - Method for producing flocculant, flocculant produced by the same method and application - Google Patents
Method for producing flocculant, flocculant produced by the same method and application Download PDFInfo
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- CN101235094B CN101235094B CN2008100469517A CN200810046951A CN101235094B CN 101235094 B CN101235094 B CN 101235094B CN 2008100469517 A CN2008100469517 A CN 2008100469517A CN 200810046951 A CN200810046951 A CN 200810046951A CN 101235094 B CN101235094 B CN 101235094B
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Abstract
The invention relates to a mechanical and chemical double modification method for producing quaternary ammonium cation modified starch, belonging to flocculant preparation technical field and starch modification technical field, while the quaternary ammonium cation modified starch can be used as flocculant for water treatment and waste water purification. The invention is characterized in that modifying starch and etherifying agent 2, 3-epoxypropyl trimethylammonium chloride, via mechanical force activation into quaternary ammonium cation starch, wherein the 2, 3-epoxypropyl trimethylammonium chloride and starch at the mol ratio of 0.2-0.7:1 are mixed uniformly, the agate abrading-ball of 1cm-0.6cm diameter and weight ratio of 1-5:1 is used as medium, the weight ratio of abrading-ball and material in a ball grinding tank is set as 1-5:1 to be grinded for 0.2-10h at 100-800r/min, the grinded materials are taken off to be arranged at 40-95 DEG C to be mixed and reacted for 0-5h to obtain modified starch crude product to be washed and purified by alcohol water solution to obtain quaternary ammonium cation modified starch. Compared with the prior art, the invention has simple process, non generation of three wastes and environment-friendly property.
Description
Technical field
The invention belongs to flocculation agent preparing technical field and starch conversion technical field, relate to a kind of by mechanical force and chemical modification, under alkali-free and dried preparation condition, produce the method for quaternary ammonium cation treated starch, the quaternary ammonium cation treated starch of producing with this method is as flocculation agent, and this flocculation agent can be in the application of water treatment during particularly purification of waste water is handled.
Background technology
China's starch resource is very abundant, cheap, starch is natural high molecular substance, have characteristics such as molecular weight distribution is wide, active group is many, structure variation because of it, often be used to cation modifying and prepare cationic starch, have the positively charged ion positive charge in the starch molecule after the modification, most electronegative fiber, micelle had affinity, be widely used in papermaking, mining, weaving, makeup and water treatment field, and, shown good prospects for application because of it is easy to biological degradation.Cationic starch is various in style, wherein tertiary amine-type cationic starch and quaternary ammonium cation starch are present main commodity, be to carry out etherification reaction by starch and the aminated compounds that has positive charge to synthesize, because the pH wide accommodation of quaternary ammonium cation starch, develop more rapidly and general, become the leading product in the current cationic starch.
The common method of preparation quaternary ammonium cation starch has wet method (Sableviciene D etc., Flocculation properties ofhigh-substituted cationic starches, Colloids and Surfaces A:Physicochemical and engineeringaspects, 2005,259:23-30), dry method (Khalil M I etc., Preparation of some cationic starches usingthe dry process, Starch/St
Rke, 1998,50 (6): 267-271) and semidrying (He Linhua etc., the technology of preparing quaternary ammonium cation starch by semi-dry method, Chinese patent: CN 1352196A, 2002; Zhang Xiaoyu etc., semidrying prepares the research of low degree of substitution cationic starch, food and biotechnology journal, 2005,24 (5): 94-97) three kinds.Wet method also claims the slurry method, be that starch is dispersed in water or other liquid mediums, be made into mass ratio and be 40～46% starch aqeous suspension, carry out etherification modified reaction with etherifying agent under moderate temperature (30～50 ℃) condition, the advantage of this technology is the reaction conditions gentleness, and production unit is simple, but reaction conversion ratio is lower than 40%, the aftertreatment difficulty, and have a large amount of unreacted etherifying agents during aftertreatment and starch runs off, cause serious waste water pollution problem.Dry method is under higher temperatures (60～120 ℃), and very a spot of water state (being lower than 20%) is finished reaction of degeneration, and this technology is solid state reaction, and technology is simple, does not have the three wastes substantially, and cost is lower, needn't carry out aftertreatment, but reaction conversion ratio has only 10～50%.Semidrying occurs after wet method and dry process, starch and cationics, alkaline catalysts are mixed together into aqueous starch fluid (20～30%), 60～100 ℃ of reactions, this technology has the advantage of dry process reaction, but under the high temperature, starch is easily gelatinization in buck, thereby this reaction pair mixes having relatively high expectations of stirring, and the degraded and cause side reaction easily in the pyritous buck of monomer reagent.Also studied in recent years with microwave accelerated reaction (Yue Shitai etc., microwave dry process of preparation of cationic starch, Chinese patent: CN89107080.X, 1991) etc. method prepares cationic starch, because microwave can shorten the reaction times, simplify the operation, have the environmental protection meaning, but the substitution value lower (less than 0.1) of the cationic starch of dry microwave preparation.
Mechanical force and chemical is the subject that research solid form, crystalline structure etc. when applying mechanical energy to solid matter changed and induced physics, chemical transformation.The chemical effect that solid matter takes place under mechanical force mainly contains: the chemical reaction between the variation of grain diameter and specific surface area, the variation of density, changes in crystal structure, mixture etc.The mechanical force and chemical effect makes material surface produce lattice distortion and defective, and surface free energy strengthens, cause chemical combination bond rupture and reorganization, can unsaturated link(age) and positively charged and negative electricity district occur at fresh fracture surface, the chemical reaction of evocating substance reaches the purpose of modification.Utilize the mechanical force and chemical method can synthesize general chemical process and heating means the structured material with property and the functional materials that can not obtain, at powder activation (Puclin T etc., Synthesis of alumina-nitride nanocomposites by successivereductionnitridation in mechanochemically activated reactions, Journal of Alloys and Compounds, 1998,266:283-292) with surface modification (Mak ó
Deng, Surface modification of mechanochemicallyactivated kaolinites by selective leaching.Journal of Colloid and Interface Science, 2006,294:62-370), toxic waste is handled (Rowlands S A etc., Destruction of toxic materials, Nature, 1994,367:223) etc. the aspect demonstrates the unique technique advantage.China Invention Announce utilize the grinding machine mechanochemical method to improve the physicochemical property (Chen Ling etc. of ative starch, utilize the method for grinding machine mechanochemical method treated starch, Chinese patent: CN1273491C, 2006), superfine modified lime carbonate (the Yang Mei etc. of dry process mechanical force and chemical, the method of the superfine modified lime carbonate of dry process mechanical force and chemical, Chinese patent: CN 1803937A, 2006), method (Luo Juhua with preparing high-purity mullite at low temperature by mechanochemical process, method with preparing high-purity mullite at low temperature by mechanochemical process, Chinese patent: CN 1699271A, 2005), low-temperature mechanical force chemical crosslinking modified alkyd resin (Lei Shaomin, a kind of preparation method of asynchronous low-temperature mechanical force chemical crosslinking modified alkyd resin, Chinese patent: CN 1908027A, 2007), show the chemical effect that solid matter takes place under mechanical force, excite modifying function, make the characteristic of material change, but carry out etherification reaction about utilizing the mechanical force and chemical effect to bring out starchy material, the application in water treatment does not appear in the newspapers and has preparation quaternary ammonium cation treated starch as yet as flocculation agent.
Summary of the invention
The production method that the purpose of this invention is to provide a kind of quaternary ammonium cation treated starch of efficient, environmental protection of using as flocculation agent, the flocculation agent of producing with this method and in the particularly application in the purification of waste water processing of water treatment.
The present invention is achieved in that
A kind of preparation method of flocculation agent, by mechanical force activating with starch and etherifying agent 2,3-epoxypropyl trimethylammonium chloride ammonium is modified as quaternary ammonium cation starch, wherein said 2,3-epoxypropyl trimethylammonium chloride ammonium and starch are 0.2～0.7 in molar ratio: 1 mixes, the mass ratio that with the diameter is 1cm and 0.6cm again is that 1～5: 1 agate abrading-ball is made medium, making the mass ratio of interior abrading-ball of ball grinder and material is 1～5: 1, under 100～800r/min, grind 0.2～10h, take out the material after grinding, place 40～95 ℃ of insulations and stirring reaction 0～5h, get the thick product of treated starch, with the thick product of aqueous ethanolic solution washing this treated starch of purifying, the step of described washing purifying is, be the thick product of treated starch to be distributed in 1: 3 in 70～90% the aqueous ethanolic solution by volume, stirring and dissolving 0～30min under the room temperature filters, filter residue is scattered in the described aqueous ethanolic solution again, repetitive scrubbing 2～6 times, dry under 30～50 ℃, obtain the pure product of quaternary ammonium cation treated starch.
As one of preferred steps, of the present invention 2,3-epoxypropyl trimethylammonium chloride ammonium and starch mol ratio are 0.3～0.6: 1, diameter is that the mass ratio of 1cm and 0.6cm is that 2～4: 1 agate abrading-ball is made medium, making the mass ratio of interior abrading-ball of ball grinder and material is 2～4: 1, under 300～500r/min, grind 1～8h, take out the material after grinding, place 70～90 ℃ of insulations and stirring reaction 1～4h.
Another one technical scheme as preferred steps, of the present invention 2, the mol ratio of 3-epoxypropyl trimethylammonium chloride ammonium and starch is 0.3～0.5: 1, the mass ratio that with the diameter is 1cm and 0.6cm is that 3～4: 1 agate abrading-ball is made medium, making the mass ratio of interior abrading-ball of ball grinder and material is 2～3: 1, under 400～500r/min, grind 3～6h, take out the material after grinding, place 80～90 ℃ of insulations and stirring reaction 2～3h.
A kind of flocculation agent, described flocculation agent is with starch and 2 with above-mentioned method, the quaternary ammonium cation starch that 3-epoxypropyl trimethylammonium chloride ammonium makes by modification, wherein said 2, the mol ratio of 3-epoxypropyl trimethylammonium chloride ammonium and starch is 0.2～0.7: 1.
The applicant proves that by a large amount of embodiment flocculation agent of the present invention can be applied to water purification and handle, thereby has promoted the application prospect of flocculation agent of the present invention greatly.
The present invention combines the advantage of mechanical force and chemical sex change and dry process and produces quaternary ammonium cation starch, compared with prior art has following advantage:
1, technology of the present invention is simple.Before the present invention, cationic modified starch generally adopts slurry method (wet method) to produce, its " three wastes " problem is outstanding, the aftertreatment difficulty, and waste water pollution problem is serious, the present invention is on the basis of dry method, in conjunction with ball grinding technique, realize the two modifications of machinery and chemistry, technology is simple, substantially do not have " three wastes ", needn't carry out aftertreatment.
2, Zhi Bei cationic starch substitution value height.The substitution value of the cationic starch of general dried preparation is 0.03～0.18, wet method be 0.02～0.10.Quaternary ammonium cation starch substitution value of the present invention is 0.30～0.40.
3, reaction efficiency height.The reaction efficiency of general dry process of preparation of cationic starch is below 55%, and the reaction conversion ratio of wet method is lower than 40%, and quaternary ammonium cation starch reactivity of the present invention reaches 75%～88%, thereby has improved the utilization ratio of etherifying agent, has reduced production cost.
4, reaction process need not the participation of alkali, does not have " three wastes ".General starch and etherifying agent 2,3-epoxypropyl trimethylammonium chloride ammonium needs to carry out etherification reaction under alkaline condition, complex process, wastewater treatment capacity is big, cause environmental pollution easily, quaternary ammonium cation treated starch of the present invention need not to add the participation of alkali when producing, get final product highly effective reaction under neutrallty condition, no post-processing step and nothing advantages such as " three wastes ".
Description of drawings
Fig. 1 is a techniqueflow chart of the present invention.
Fig. 2 is the X-ray diffractogram of W-Gum before and after the modification.
Fig. 3 is the scanning electron microscope picture before and after the W-Gum modification of the present invention:
Among the figure: Fig. 3 a is the scanning electron microscope picture of W-Gum before the mechanical activation modification of the present invention;
Fig. 3 b is the scanning electron microscope picture of W-Gum after the mechanical activation modification of the present invention;
Fig. 3 c is the scanning electron microscope picture of the quaternary ammonium cation treated starch for preparing after the mechanical activation modification of W-Gum of the present invention.
Fig. 4 is when to be quaternary ammonium cation treated starch of the present invention as flocculation agent handle the kaolin suspension liquid and the comparison of inorganic flocculating agent flocculating effect.
The relation of Fig. 5 water body pH and flocculating effect when to be quaternary ammonium cation treated starch of the present invention as flocculation agent handle the kaolin suspension liquid.
Fig. 6 is the relation of water temperature and flocculating effect when quaternary ammonium cation treated starch of the present invention is handled the kaolin suspension liquid as flocculation agent among the embodiment.
Embodiment
Embodiment 1: the preparation of quaternary ammonium cation treated starch
Experiment material: commercial W-Gum, purchase in peak, Tianjin starch limited-liability company, or (method is referring to Guo Lei to adopt homemade W-Gum, Zhang Zhengmao, Hu Lili, Fu Guodong, Zhao Siming, the grinding dynamics research of water-soluble rice starch, Transactions of the Chinese Society of Agricultural Engineering, 2007,23 (1): 202-206), etherifying agent: 2,3-epoxypropyl trimethylammonium chloride ammonium, purchase in Shandong Dongying chemical inc, ethanol is the commercially available prod.
Concrete preparation process is as follows:
(1) extracting corn starch 32.5g (butt) adds 2,3-epoxypropyl trimethylammonium chloride ammonium 12.1g, mixing in agate jar;
(2) take by weighing agate abrading-ball (wherein the ball 75g of diameter 1cm, the ball 25g of diameter 0.6cm) 100g, put into ball grinder;
(3) ball grinder is put into the Ma Taozhong that draws of ball mill, added a cover, the setting rotating speed is 450r/min, per hour changes the sense of rotation of forward-oppositely and oppositely-forward, grinds 5h;
(4) mixture after will grinding is put stirring reaction 2.5h in 90 ℃ the water-bath, take out, fast cooling is pulverized with the stone roller alms bowl, and 1: 3 the proportioning of volume ratio of pressing material and ethanolic soln again is with this material of aqueous ethanolic solution dispersed with stirring of 80%, filtering and washing, repeated treatments 6 times is checked to free chloro ion concentration with Silver Nitrate to be lower than 9mg/L, and the precipitation of gained is placed glassware, in 50 ℃ of oven dry, promptly get the pure product of quaternary ammonium cation treated starch.
Adopt X-ray diffraction that the crystal property of the pure product of treated starch of above-mentioned steps acquisition is analyzed, obtain the X-diffracting spectrum (see figure 2) of the treated starch of ative starch and the present invention preparation.As shown in Figure 2, grind back starch crystalline structure and destroy, produce lattice distortion, crystal conversion, finally decrystallized.The crystalline structure of the quaternary ammonium cation treated starch of the starch preparation of employing grinding 5h is little with the preceding variation of reaction.
Adopt scanning electronic microscope that the pattern of starch granules is analyzed, obtain the scanning electron microscope picture (see figure 3) of the cationic starch of starch and preparation after corn ative starch, the mechanical activation modification.As shown in Figure 3, the particle of former W-Gum is the orange body structure, and the surface is more smooth.The corn starch granules of grinding 5h is broken, and shows to be laminar, and it is cellular uniformly that the quaternary ammonium cation starch of preparation becomes, and the product hole is more evenly distributed.
Compare with traditional cationic starch preparation method, the substitution value and the reaction efficiency of the cationic starch of different methods preparation see Table 1.
The substitution value and the reaction efficiency of the cationic starch of three kinds of method preparations of table 1
| The preparation method | Substitution value | Reaction efficiency/% |
| Slurry method (wet method) dry method method of the present invention | 0.033±0.000 0.259±0.002 0.300±0.001 | 4.69±0.03 37.17±0.24 75.06±0.13 |
Annotate: the preparation technology of slurry method is: starch, sodium hydroxide and etherifying agent monomer are mixing in 1.00: 0.04: 0.70 in molar ratio, react 7.4h down in 40 ℃, content of water in system 73%, reaction finishes the back and is neutralized to pH=7 with 0.1mol/L hydrochloric acid, use 80% ethanol sedimentation, washing is lower than 9mg/L to checking to free chloro ion concentration with Silver Nitrate, dries to moisture below 13% for 50 ℃.The preparation technology of dry method is: starch and etherifying agent monomer 1.00: 0.70 in molar ratio mix, and stir all under the room temperature, and in 90 ℃ of reaction 2.5h, the system moisture content is lower than 20%, and reaction finishes the back and presses slurry method technology washing monomer and drying.
As shown in Table 1, the substitution value of the quaternary ammonium cation treated starch of the present invention's preparation and the treated starch that reaction efficiency is much better than slurry method and dry production.The electric density of the quaternary ammonium cation treated starch that the present invention produces reaches 523.5umol/g, be better than reported method (Wu Zonghua etc., the electric density of colloid titration cationic starch, fine chemistry industry, 2001,18 (2): 98-102) Zhi Bei (215umol/g).The above results shows, mechanical force is ground the degree of crystallinity that reduces starch, makes the starch molecule group activation, and etherification reaction efficient improves greatly, improves the substitution value of ammonium, increases the electric density of cationic starch.
Embodiment 2: method of the present invention is to the application of the starch conversion of different sources
With glutinous rice, three river rice, surplus red rice (long-grained nonglutinous rice), conventional corn, Glutinous Semen Maydis, Ipomoea batatas, potato, bajiao banana taro and cassava is material, preparation method by embodiment 1 prepares treated starch of the present invention, and its substitution value, yield and reaction efficiency are shown in Table 2.
Substitution value, yield and the reaction efficiency (mean+SD) of table 2 different sources cationic starch
| Starch source | Positively charged ion nitrogen content/% | Substitution value | Reaction efficiency/% |
| The glutinous rice surplus red rice of three river rice (long-grained nonglutinous rice) conventional corn Glutinous Semen Maydis Ipomoea batatas potato bajiao banana taro cassava | 2.190±0.003 2.087±0.006 2.165±0.017 2.125±0.010 2.375±0.012 2.120±0.014 2.258±0.002 2.231±0.002 2.311±0.009 | 0.317±0.003 0.309±0.002 0.309±0.004 0.300±0.001 0.341±0.002 0.314±0.003 0.342±0.002 0.331±0.002 0.347±0.002 | 79.15±0.79 76.97±0.39 77.06±0.95 75.06±0.13 85.20±0.41 78.34±0.81 85.36±0.50 82.66±0.43 86.74±0.43 |
As shown in Table 2, by the substitution value of the quaternary ammonium cation treated starch of the present invention preparation all greater than 0.3, reaction efficiency is more than 75%.
Embodiment 3: the cationic modified starch of the present invention's preparation is as the application of flocculation agent in water treatment
In the present embodiment, the applicant uses the flocculation agent of the quaternary ammonium cation W-Gum of the present invention's preparation as water treatment, compares with traditional inorganic flocculating agent, the results are shown in Figure shown in 4-6 and the table 3.Fig. 4 is that the treated starch for preparing of the present invention is when handling kaolin suspension liquid (mass concentration is 1%) and the comparison of alum and polymerize aluminum chloride flocculating effect, wherein the optimum amount of quaternary ammonium cation treated starch, alum and the polymerize aluminum chloride of the present invention's preparation is distinguished 6mg/L, 833mg/L and 1000mg/L.Fig. 5 is the relation of treated starch of the present invention water body pH and flocculating effect when handling the kaolin suspension liquid.Fig. 6 is the relation of treated starch of the present invention water temperature and flocculating effect when handling the kaolin suspension liquid.Table 3 is cationic modified starch of the present invention and the fractal dimension of inorganic flocculating agent flocculation back alumen ustum and the comparison of precipitation volume.
The dissimilar flocculation agents of table 3 to the kaolin suspension liquid after the fractal dimension and the precipitation volume of alumen ustum
| The flocculation agent type | Fractal dimension D 2 | Fractal dimension D 3 | Settling volume/cm |
| Treated starch alum polymerize aluminum chloride of the present invention | 2.293 1.989 1.874 | 3.4396 2.9835 2.8111 | 1.65±0.05 3.45±0.35 6.70±0.70 |
Compare with inorganic flocculating agent, the treated starch of the present invention preparation shows excellent flocculating property during as flocculation agent, this flocculation agent is in sewage disposal, adding less, the pH use range is wide, the wide flocculation settling velocity of temperature optimum range is fast, suspension liquid clarity height, the fractal structure of flocs unit is closely knit, amount of sludge is few, biodegradable, non-secondary pollution are a kind of suitable green water treatment reagent.
Embodiment 4: different diameter and different ratios abrading-ball are to the influence of preparation treated starch of the present invention
Press the basic step of embodiment 1, at present embodiment, the applicant has compared the influence to preparation treated starch of the present invention of different diameter and different ratios abrading-ball, wherein abrading-ball is to add in the ball grinder in 2: 1,3: 1,4: 1 according to the mass ratio of big ball (1cm) and bead (0.6cm), after the grinding, insulation reaction, the washing purifying gets quaternary ammonium cation starch.
Embodiment 5: the abrading-ball of different proportionings and material are to the influence of preparation treated starch of the present invention
Press the basic preparation process of embodiment 1, design abrading-ball and material by mass ratio be added in 2: 1,3: 1,4: 1 grind in the ball grinder after, insulation reaction, the washing purifying gets quaternary ammonium cation starch.
Embodiment 6: the application of the treated starch for preparing under the different technical parameters condition in water treatment
Step according to embodiment 1, with etherifying agent 2,3-epoxypropyl trimethylammonium chloride ammonium and starch are 0.2: 1.0 in molar ratio, 0.4: 1.0,0.7: 1.0 uniform mixing, then 100,300,400,600, the 800r/min rotating speed grinds 0.2 down, 0.5,1.0,2.5,5.0,10h, mixture takes out, in 40,50,60,70,80,85,90, react 1.0 under 95 ℃ the temperature, 1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0h, obtain the cationic modified starch of different technical parameters preparation, and the treated starch that obtains handled the kaolin suspension liquid as flocculation agent, effect sees Table 4.
The flocculating effect (mean+SD) of the cationic modified starch of table 4 different technical parameters preparation
| Etherifying agent: starch molmol -1 | Grind rotating speed r/min | Milling time h | Holding temperature ℃ | Reaction times h | Transmittance % |
| 0.2 0.4 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.4 0.4 0.4 0.4 0.4 0.4 | 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 100 300 450 600 800 450 450 450 450 450 450 | 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2.5 2.5 2.5 2.5 2.5 0.2 0.5 1.0 2.5 5.0 10.0 | 90 90 90 40 50 60 70 75 80 85 90 95 95 95 95 95 95 90 90 90 90 90 95 95 95 95 95 90 90 90 90 90 90 | 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 3.0 3.0 3.0 3.0 3.0 2.5 2.5 2.5 2.5 2.5 2.5 | 19.0±0.1 78.6±0.2 95.1±0.9 70.5±0.5 80.1±0.8 85.8±0.2 90.6±0.6 91.1±0.6 95.1±0.4 94.0±0.4 93.5±0.4 92.1±0.3 49.5±1.1 92.1±0.1 93.6±0.4 96.3±0.1 95.1±0.4 94.2±0.3 93.1±0.5 92.4±0.2 91.2±0.1 90.8±0.7 85.9±0.3 90.1±0.2 95.4±0.5 95.3±0.7 94.2±0.1 79.1±0.6 80.4±0.5 85.2±0.5 90.9±0.9 97.3±0.1 97.7±0.1 |
Claims (2)
1. the preparation method of a flocculation agent, it is characterized in that, by mechanical force activating with starch and etherifying agent 2,3-epoxypropyl trimethylammonium chloride ammonium is modified as quaternary ammonium cation starch, wherein said 2,3-epoxypropyl trimethylammonium chloride ammonium and starch are 0.3～0.6 in molar ratio: 1 mixes, the mass ratio that with the diameter is 1cm and 0.6cm again is that 2～4: 1 agate abrading-ball is made medium, making the mass ratio of interior abrading-ball of ball grinder and material is 2～4: 1, under 300～500r/min, grind 1～8h, take out the material after grinding, place 70～90 ℃ of insulations and stirring reaction 1～4h, get the thick product of treated starch, again with the thick product of the aqueous ethanolic solution washing described treated starch of purifying, remove described etherifying agent, obtain the quaternary ammonium cation treated starch.
2. preparation method according to claim 1, it is characterized in that, the step of described aqueous ethanolic solution washing purifying is, be the thick product of treated starch to be distributed in 1: 3 in 70～90% the aqueous ethanolic solution by volume, stirring and dissolving 0～30min under the room temperature filters, filter residue is scattered in the described aqueous ethanolic solution again, repetitive scrubbing 2～6 times, dry under 30～50 ℃, obtain the pure product of quaternary ammonium cation treated starch.
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| CN102807275B (en) * | 2012-07-16 | 2013-08-14 | 三明学院 | Modified cellulose wastewater treatment flocculating agent and preparation method thereof |
| CN107188976B (en) * | 2017-05-12 | 2019-10-01 | 威海晨源分子新材料有限公司 | Quaternary ammonium salt-modified starch demulsifier of branching type efficient cryogenic and preparation method thereof |
| CN115785295B (en) * | 2022-12-27 | 2023-11-24 | 大连理工大学 | Method for preparing high-substitution-degree cationic starch by mechanochemistry |
| CN117285027B (en) * | 2023-11-24 | 2024-02-02 | 成都锂能科技有限公司 | Crosslinked starch derived carbon sphere and preparation method and application thereof |
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| CN1887911A (en) * | 2006-07-28 | 2007-01-03 | 武汉科技学院 | Irradition initiating process for preparing cationic starch |
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