CN104130335A - High-substituted quaternary ammonium polysaccharide bioflocculant and preparation method thereof - Google Patents
High-substituted quaternary ammonium polysaccharide bioflocculant and preparation method thereof Download PDFInfo
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- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 39
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 quaternary ammonium polysaccharide Chemical class 0.000 title abstract 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 150000004676 glycans Chemical class 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical group CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006266 etherification reaction Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043276 diisopropanolamine Drugs 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 208000012839 conversion disease Diseases 0.000 abstract description 3
- 239000003245 coal Substances 0.000 abstract description 2
- 239000003651 drinking water Substances 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 238000004043 dyeing Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000003113 alkalizing effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 229920002472 Starch Polymers 0.000 description 9
- 239000008107 starch Substances 0.000 description 9
- 235000019698 starch Nutrition 0.000 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 description 8
- 229930006000 Sucrose Natural products 0.000 description 8
- 239000005720 sucrose Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005956 quaternization reaction Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 229920001503 Glucan Polymers 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000003311 flocculating effect Effects 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
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Abstract
The invention provides a high-substituted quaternary ammonium polysaccharide bioflocculant and a preparation method thereof. The preparation method comprises the following steps: alkalizing an aqueous solution of a raw material non-ionic bioflocculant in the presence of a certain amount of a catalyst at a certain water bath temperature through a wet process, slowly adding a certain amount of a dispersant in a dropwise manner, adding an etherifying agent, reacting for a period of time, precipitating, washing with water, washing with alcohol, drying, and grinding to prepare the quaternary ammonium polysaccharide bioflocculant with the substitution degree of 0.2-1.8. The method adopting the wet process has the advantages of good stability, simple operation, easy separation, high reaction conversion rate, high cost performance, and waste liquid recycling, and the quaternary ammonium polysaccharide bioflocculant has the advantages of non-toxicity, environmental protection, no secondary pollution and biodegradability, can be used for processing drinking water, printing and dyeing wastewater, coal washing water, mineral processing, oil refining wastewater, papermaking and chemical industry wastewater, and the like, and has substantial environmental and social benefits.
Description
Technical field
The invention belongs to water treatment flocculant technical field, particularly a kind of high degree of substitution quaternary ammonium type polysaccharide bioflocculant and preparation method thereof.
Background technology
In at present conventional water treatment flocculant, although poly-aluminium, Polyferric Sulfate, polyacrylamide etc. have good flocculating effect, but its bring the problems such as large, the corrosion pipeline of metal residual, sludge quantity and the monomer residue of polyacrylamide in water body, caused and both domestic and externally generally paid attention to.Since 20 century 70s, the states such as U.S., day, English and India have launched the development work of chemical modification natural organic high-molecular material, wherein contain polysaccharide, protein, glycoprotein or cellulosic biological flocculant and belong to natural macromolecular material because of it, produced by microbial metabolism, there is good flocculation sediment performance, and have safe, biodegradable, to features such as environment non-secondary pollutions, more and more come into one's own.
At present, modified natural polymer material mainly divides etherificate type, esterification type and graft copolymerization, and with the morning and in the majority of research of etherificate type, etherificate type product is that the hydroxyl containing in natural macromolecular material is combined and is produced by etherification reaction with etherifying agent, most widely used etherifying agent is mainly 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and 2 at present, 3-epoxypropyltrimethylchloride chloride, this etherifying agent has high reactivity, in high purity and reaction, by product is few, the features such as technological operation is simple, can with starch, Mierocrystalline cellulose, chitosan, the reactions such as guar gum, produce multiple product.The modified natural polymer flocculation agent that 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or 2,3-epoxypropyltrimethylchloride chloride and natural macromolecular material are synthesized by etherification technology makes some progress.Taking treated starch as example: the patent No. discloses a kind of high degree of substitution quaternary ammonium cationic starch flocculating agent and synthetic method thereof as the patent of invention of 200610166835.X, notification number is the technique that the patent of invention of CN1352196A discloses a kind of preparing quaternary ammonium cation starch by semi-dry method, the substitution value of industrial etherificate type starch used is generally lower than 0.2 at present, although the cationic starch ether performance of high substitution value is good, but more difficult preparation, reaction efficiency is lower, cost is higher, as Thomas Heinze has prepared the cationic starch ether that substitution value is 1.05, reaction efficiency is only 52%, while selecting the mol ratio of cationic starch and etherifying agent to be 1:10 when secondary etherificate, substitution value is up to 1.5, but reaction efficiency is only up to 10%, except preparation technology's factor, the Low-substituted Cationic Starch generating is because of sterically hindered and own positively charged, also having suppressed it occurs further to replace.
Etherification modified main employing dry method and wet method, although wherein dry method is without the three wastes, the advantage such as technique is simple, reaction time is short, reaction conversion ratio is low, high to equipment requirements, unstable product quality, only has minority producer to adopt this method to produce; Wet method is the main method adopting at present, is also the method adopting the earliest, and product, the reaction efficiency that can obtain higher conversion are high, equipment requirements is low, technique is simple, but has the three wastes, rear washing and the equipment cost such as dry is large etc. that problem is difficult to process.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of high degree of substitution quaternary ammonium type polysaccharide bioflocculant and preparation method thereof, this flocculation agent is taking non-ionic type polysaccharide bioflocculant as raw material, this raw material is large-scale production and leading in the world, nontoxic, environment-friendly biodegradable, the present invention adopts wet processing, workable, technique is simple, reaction conditions gentleness, reaction conversion ratio is high, easily washing separates, consuming time short, waste liquid is also recycled, the product making is buff powder, nontoxic, solubility is strong, cheap, can be used for drinking water treatment, different sewage is had more to obvious flocculating effect simultaneously, there is significant environmental and social benefits.
The technical solution adopted for the present invention to solve the technical problems is: a kind of high degree of substitution quaternary ammonium type polysaccharide bioflocculant, and taking non-ionic type polysaccharide bioflocculant solution as raw material, a kind of quaternary ammonium type polysaccharide bioflocculant making, its molecular structure skeleton symbol is:
wherein Dx is non-ionic type polysaccharide bioflocculant, and its skeleton symbol is:
wherein n=10,000-310,000.Its position of substitution mainly occurs on C2, C3 or C4 position.
The preparation method of the raw material non-ionic type polysaccharide bioflocculant that the present invention adopts is the activator that adds Sucrose:glucan alpha1-6-glucosyltransferase in certain density sucrose solution, then regulate the pH value of this solution, after add Sucrose:glucan alpha1-6-glucosyltransferase solution, again regulate constant temperature stirring reaction for some time after pH, obtain the sterilizing of reaction product post-heating, filtration, removal of impurities, purifying and obtain the finished product after concentrated, it is a kind of Enzymology method of preparing polysaccharide bioflocculant described in CN101392280A that concrete preparation method is preferably patent announcement number, and its concrete preparation method is as follows:
The preferred kinetic viscosity of described non-ionic type polysaccharide bioflocculant is respectively 4500cPs, 11250cPs, 40100cPs and 65000cPs, comprises following making step:
(1), according to the requirement of above-mentioned polysaccharide bioflocculant kinetic viscosity, compound concentration is 1000 milliliters, 5000 milliliters, 100 liters and 1000 liters of the sucrose solutions of 0.80mol/L, 0.73mol/L, 0.58mol/L and 0.44mol/L accordingly respectively;
(2) in above-mentioned sucrose solution, add respectively calcium chloride solution, wherein concentration is in the solution of 0.80mol/L and 0.73mol/L, to add respectively 10 milliliters and 50 milliliters of 0.5% calcium chloride solutions; Concentration is in the solution of 0.58mol/L and 0.44mol/L, to add respectively 100 milliliters and 1000 milliliters of 5% calcium chloride solutions;
(3) regulate the pH value of above-mentioned sucrose solution in 5.2～5.4 scopes with 30% hac buffer;
(4) to adding respectively 17.5 milliliters of Sucrose:glucan alpha1-6-glucosyltransferase solution, 109.6 milliliters, 2500 milliliters and 29.2 liters in above-mentioned sucrose solution, the activity of enzyme is respectively 456IU/ml, 456IU/ml, 480IU/ml and 480IU/ml, after mixing, with 10% vinegar acid for adjusting pH value in 5.2～5.4 scopes;
(5) above-mentioned solution is placed in to water bath with thermostatic control, regulate and stir, fully reaction is until solution reaches desired kinetic viscosity, and the water bath with thermostatic control temperature corresponding to solution of above-mentioned 0.80mol/L, 0.73mol/L, 0.58mol/L and tetra-kinds of different concns of 0.44mol/L is respectively 20～22 DEG C, 22～24 DEG C, 24～26 DEG C, 24～26 DEG C;
(6) reaction product is carried out to heat sterilization, filtering and impurity removing, obtains described non-ionic type polysaccharide bioflocculant after purifying is concentrated.
A kind of preparation method of described high degree of substitution quaternary ammonium type polysaccharide bioflocculant, it is characterized in that: adopt wet processing, by adding catalyzer and promotor to carry out alkalinisation treatment in the non-ionic type polysaccharide bioflocculant solution that is 4～40% to mass concentration, a certain amount of dispersion agent of rear slowly dropping, stir, finally add etherifying agent reaction for some time, through precipitation, washing, alcohol wash, dry, grind and make the finished product.
Wherein, non-ionic type polysaccharide bioflocculant is 1:0.2～1:6 with the solid masses ratio of etherifying agent, the mass ratio of catalyzer and promotor is 1:0.1～1:3, the mol ratio of catalyzer and etherifying agent is 1:2～1:10, dispersion agent volume used accounts for 5～20% of water volume in reaction system, and the temperature of alkalization and etherification reaction is all 20～40 DEG C, and alkalization time is 10～60min, after dispersion agent adds, stir 0.5～1h, the etherificate time is 1～3h.
Described catalyzer is any one in sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, sodium carbonate, sodium bicarbonate.
Described promotor is any one in urea, Monoethanolamine MEA BASF, diethanolamine, trolamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, diglycolamine.
Described etherifying agent is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride (CTA), any one in 2,3-epoxypropyltrimethylchloride chloride (GTA).
Described dispersion agent is any one in methyl alcohol, ethanol, Virahol, acetone, ether.
The substitution value of described high degree of substitution quaternary ammonium type polysaccharide bioflocculant is 0.2-1.8, molecular weight 2,000,000-50,000,000.
Its reaction principle is as follows:
Remarkable advantage of the present invention is:
1. product appearance of the present invention is pale yellow powder, product is nontoxic, environmental protection, efficient, belong to the modified product of polysaccharide bioflocculant, at present the Biodegradable material such as such as modified starch series, modified-cellulose class of preparation all adopts dry method or semidrying preparation technology because of labile factors such as the facile hydrolysiss of etherifying agent, the product that the present invention adopts wet processing to prepare, not only good stability and simple to operate, easily separated, high without the three wastes, cost performance.
2. product of the present invention all has obvious flocculating effect to tap water and dyeing waste water, coal washing water, ore dressing, refinery water, papermaking and wastewater from chemical industry etc., and the problems that solved that metal residual, sludge quantity that the conventional in the market inorganic salt such as poly-aluminium, Polyferric Sulfate bring are large, corrosion pipeline and the monomer residue of polyacrylamide in water body etc. exist, its performance can compare favourably with it, and this series products has market outlook and good economic results in society widely.
3. product of the present invention carries out non-ionic type polysaccharide bioflocculant leading in the world quaternised modified, makes it have ultra-high molecular weight and high charge density, and this series products there is not yet report.
Embodiment
Below to a preferred embodiment of the present invention will be described in detail.
Embodiment 1
1. quaternization: get mass concentration and be 4% nonionic biological flocculant aqueous solution 200g in 500ml there-necked flask, start stirring, then add sodium carbonate solid 4.5g to add 9g urea after 30 DEG C of stirred in water bath are dissolved, continue to stir 10min.
2. etherification reaction: slowly stir 0.5h after the Virahol of dropping 20ml in 30 DEG C of water-baths in reaction system, be then evenly sprinkled into 16g2 in reaction system, 3-epoxypropyltrimethylchloride chloride (GTA), continues stirring reaction 2h.
3. product processing: take out reaction product, after precipitation with filter paper filtering, then washing, alcohol wash, dry, grind, make light yellow substitution value and be 1.60 quaternary ammonium type polysaccharide bioflocculant.
Embodiment 2
1. quaternization: get mass concentration and be 15% nonionic biological flocculant aqueous solution 200g in 500ml there-necked flask, start stirring, then add sodium oxide solid 8g, after 25 DEG C of stirred in water bath are dissolved, add 4g diglycolamine, continue stirring reaction 30min.
2. etherification reaction: slowly drip 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride (CTA) aqueous solution that 50g mass concentration is 60% in reaction system, then continue stirring reaction 2h.
3. product processing: the light yellow fluid that product is thickness, admittedly be 31% containing thing content, through washing, alcohol wash and dry and grind that to make light yellow substitution value be 0.23 quaternary ammonium type polysaccharide bioflocculant.
Embodiment 3
1. quaternization: get mass concentration and be 16.7% nonionic biological flocculant aqueous solution 200g in 500ml there-necked flask, start stirring, then add sodium hydrate solid 2.8g, after 30 DEG C of stirred in water bath are dissolved, add 2.8g trolamine, continue stirring reaction 10min.
2. etherification reaction: to the acetone that slowly adds 30ml in reaction system, after add 53.44g2,3-epoxypropyltrimethylchloride chloride (GTA), then continues stirring reaction 1.5h.
3. product processing: the brown color paste that product is thickness, admittedly be 35% containing thing content, through washing, alcohol wash and dry and grind that to make light yellow substitution value be 2.41 quaternary ammonium type polysaccharide bioflocculant.
Embodiment 4
1. quaternization: get mass concentration and be 15.3% nonionic biological flocculant aqueous solution 200g in 500ml there-necked flask, start stirring, then add sodium bicarbonate solid 8g, after 25 DEG C of stirred in water bath are dissolved, add 8g tri-isopropanolamine, rear continuation stirring reaction 60min.
2. etherification reaction: stir 20min to slowly dripping methyl alcohol 28.5ml in reaction system, then slowly adding 51g concentration is 60% 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride (CTA) aqueous solution, continues stirring reaction 3h.
3. product processing: the light yellow fluid that product is thickness, admittedly be 29.1% containing thing content, after precipitation with filter paper filtering, then washing, alcohol wash and dry grinding to make light yellow substitution value be 0.18 quaternary ammonium type polysaccharide bioflocculant.
Above-described is only the preferred embodiments of the present invention; institute is understood that; the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof; the protection domain being not intended to limit the present invention; all any amendments of making, be equal to replacement etc., within protection scope of the present invention all should be included within thought of the present invention and principle.
Claims (6)
1. a high degree of substitution quaternary ammonium type polysaccharide bioflocculant, is characterized in that: taking non-ionic type polysaccharide bioflocculant solution as raw material, the molecular structure skeleton symbol of the quaternary ammonium type polysaccharide bioflocculant making is:
wherein Dx is non-ionic type polysaccharide bioflocculant, and its skeleton symbol is:
wherein n=10,000-310,000.
2. the preparation method of a high degree of substitution quaternary ammonium type polysaccharide bioflocculant as claimed in claim 1, it is characterized in that: adopt wet processing, by adding catalyzer and promotor to carry out alkalinisation treatment in the non-ionic type biofloculation agent solution that is 4～40% to mass concentration, a certain amount of dispersion agent of rear slowly dropping, stir, finally add etherifying agent reaction for some time, through precipitation, washing, alcohol wash, dry, grind and make the finished product; Wherein non-ionic type polysaccharide bioflocculant is 1:0.2～1:6 with the solid masses ratio of etherifying agent, the mass ratio of catalyzer and promotor is 1:0.1～1:3, the mol ratio of catalyzer and etherifying agent is 1:2～1:10, dispersion agent volume used accounts for 5～20% of water volume in reaction system, the temperature of alkalization and etherification reaction is all 20～40 DEG C, alkalization time is 10～60min, after dispersion agent adds, stirs 0.5～1h, and the etherificate time is 1～3h.
3. the preparation method of a kind of high degree of substitution quaternary ammonium type polysaccharide bioflocculant according to claim 2, is characterized in that: described catalyzer is any one in sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, sodium carbonate, sodium bicarbonate.
4. the preparation method of a kind of high degree of substitution quaternary ammonium type polysaccharide bioflocculant according to claim 2, is characterized in that: described promotor is any one in urea, Monoethanolamine MEA BASF, diethanolamine, trolamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, diglycolamine.
5. the preparation method of a kind of high degree of substitution quaternary ammonium type polysaccharide bioflocculant according to claim 2, it is characterized in that: described etherifying agent is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride (CTA), any one in 2,3-epoxypropyltrimethylchloride chloride (GTA).
Described dispersion agent is any one in methyl alcohol, ethanol, Virahol, acetone, ether.
6. the preparation method of a kind of high degree of substitution quaternary ammonium type polysaccharide bioflocculant according to claim 2, is characterized in that: the substitution value of described high degree of substitution quaternary ammonium type polysaccharide bioflocculant is 0.2-1.8, molecular weight 2,000,000-50,000,000.
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