CN104130335B - 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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- CN104130335B CN104130335B CN201410352573.0A CN201410352573A CN104130335B CN 104130335 B CN104130335 B CN 104130335B CN 201410352573 A CN201410352573 A CN 201410352573A CN 104130335 B CN104130335 B CN 104130335B
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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 description 6
- 238000006467 substitution reaction Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 150000004676 glycans Chemical class 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 20
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 19
- 238000006266 etherification reaction Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 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
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 239000003426 co-catalyst Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- CSPHGSFZFWKVDL-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-trimethylazanium;chloride Chemical class [Cl-].C[N+](C)(C)CC(O)CCl CSPHGSFZFWKVDL-UHFFFAOYSA-M 0.000 claims description 5
- 108010042194 dextransucrase Proteins 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 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
- 230000001954 sterilising effect Effects 0.000 claims description 3
- 238000004659 sterilization and disinfection Methods 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 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
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims 2
- 229940043276 diisopropanolamine Drugs 0.000 claims 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000003651 drinking water Substances 0.000 abstract description 3
- 235000020188 drinking water Nutrition 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003245 coal Substances 0.000 abstract description 2
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 238000004043 dyeing Methods 0.000 abstract description 2
- 230000003113 alkalizing effect Effects 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
- 239000000243 solution Substances 0.000 description 15
- 229920002472 Starch Polymers 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000000463 material Substances 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
- 150000001412 amines Chemical class 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 230000000694 effects 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
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- 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
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000019426 modified starch Nutrition 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
- 239000013049 sediment Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 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
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 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
- 230000000368 destabilizing effect 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
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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
At present in conventional water treatment flocculant, although poly-aluminium, Polyferric Sulfate, polyacrylamide etc. have preferably flocculation effect
Really, but its metal residual, the monomer residue that sludge quantity is big, corrosion pipeline and polyacrylamide are in water body that bring etc. are all
Many problems, have caused most attention both domestic and external.Since 20 century 70s, the state such as U.S., day, English and India expands chemistry
The development work of modified natural high-molecular organic material, wherein the bioflocculation containing polysaccharide, protein, glycoprotein or cellulose
Agent belongs to natural macromolecular material because of it, by microbial metabolism produce, with good flocculation sediment performance, and with safety, can
It is biodegradable, to environment non-secondary pollution the features such as, be increasingly taken seriously.
At present, modified natural polymer material mainly divides etherificate type, esterification type and graft copolymerization, and grinding with etherificate type
Study carefully more early and in the majority, etherificate type product is that the hydroxyl that will contain in natural macromolecular material is combined with etherifying agent by etherification reaction
Produce, etherifying agent most widely used at present is mainly 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides and 2,3- glycidyl front three
Ammonium chloride, the etherifying agent has in high activity, high-purity and reaction the features such as accessory substance is few, technological operation is simple, can be with
Starch, cellulose, shitosan, guar gum etc. react, and produce multiple product.By 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides or
2,3- epoxypropyltrimethylchloride chlorides are wadded a quilt with cotton with natural macromolecular material by the modified natural polymer that etherification technology synthesizes
Solidifying agent has been achieved for certain progress.By taking modified starch as an example：The patent of invention of Patent No. 200610166835.X is disclosed
A kind of high degree of substitution quaternary ammonium cationic starch flocculating agent and its synthetic method, notification number for CN1352196A patent of invention
A kind of technique of preparing quaternary ammonium cation starch by semi-dry method is disclosed, at present the substitution value of industrial etherificate type starch used
Generally below 0.2, although the cationic starch ether performance of high substituted degree is good, more difficult preparation, reaction efficiency is relatively low, cost compared with
Height, such as Thomas Heinze are prepared for the cationic starch ether that substitution value is 1.05, and reaction efficiency is only 52%, secondary etherificate
When select the mol ratio of cationic starch and etherifying agent to be 1:When 10, substitution value is up to 1.5, but reaction efficiency is only up to
10%, in addition to preparation technology factor, the Low-substituted Cationic Starch of generation also presses down because sterically hindered and positively charged in itself
It is made and further replacement has occurred.
Etherification modified main employing dry and wet, although wherein dry method three wastes, process is simple, reaction time is short etc. excellent
Point, but reaction conversion ratio is low, high to equipment requirement, unstable product quality, and only minority producer adopts this method and is produced；It is wet
Method is the current main method for adopting, and is also the earliest method for adopting, and can obtain product, the reaction efficiency of higher conversion
High, equipment requirement is low, process is simple, but there are problems that the equipment costs such as the three wastes, rear washing and drying are difficult to process.
The content 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
Its preparation method, the flocculant with non-ionic polysaccharide biological flocculant as raw material, the large-scale production of this raw material and international neck
First, nontoxic, environment-friendly biodegradable, the present invention adopts wet processing, and workable, process is simple, reaction condition are gentle, anti-
High conversion rate, uncomplicated laundering is answered to separate, time-consuming short, waste liquid is also recycled, obtained product is buff powder, nontoxic, solvable
Property it is strong, it is cheap, can be used for drinking water treatment, while have more obvious flocculating effect to different sewage, with notable
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 bioflocculation
Agent, with non-ionic polysaccharide bioflocculation agent solution as raw material, a kind of obtained quaternary ammonium type polysaccharide bioflocculant, its molecule knot
Structure skeleton symbol is：Wherein Dx is non-ionic polysaccharide biological flocculant, and its skeleton symbol is：
Wherein n=10,000-310,000.It takes
Subrogate to put and occur mainly on C2, C3 or C4 position.
The preparation method of the raw material non-ionic polysaccharide biological flocculant that the present invention is adopted is molten to certain density sucrose
The activator of dextransucrase is added in liquid, the pH value of the solution is then adjusted, dextransucrase solution is added afterwards, again
Adjust constant temperature stirring reaction after pH for a period of time, to obtain being obtained final product after heat sterilization after product, filtration, removal of impurities, purified concentration
Final products, specific preparation method is preferably patent announcement number and prepares polysaccharide biology for the one kind described in CN101392280A
The Enzymology method of flocculant, its concrete preparation method is as follows：
The preferred dynamic viscosity of the non-ionic polysaccharide biological flocculant be respectively 4500cPs, 11250cPs,
40100cPs and 65000cPs, including following making step：
(1) according to the requirement of above-mentioned polysaccharide bioflocculant dynamic viscosity, respectively correspondingly compound concentration is 0.80mol/
1000 milliliters, 5000 milliliters, 100 liters and 1000 liters of the sucrose solution of L, 0.73mol/L, 0.58mol/L and 0.44mol/L；
(2) calcium chloride solution is separately added in above-mentioned sucrose solution, wherein concentration is 0.80mol/L and 0.73mol/L
Solution in be separately added into 0.5% 10 milliliters and 50 milliliters of calcium chloride solution；Concentration is 0.58mol/L's and 0.44mol/L
5% 100 milliliters and 1000 milliliters of calcium chloride solution is separately added in solution；
(3) with 30% hac buffer the pH value of above-mentioned sucrose solution is adjusted in 5.2～5.4 scopes；
(4) 17.5 milliliters of dextransucrase solution, 109.6 milliliters, 2500 millis are separately added into in above-mentioned sucrose solution
Rise and 29.2 liters, the activity of enzyme is respectively 456IU/ml, 456IU/ml, 480IU/ml and 480IU/ml, after mixing, uses 10% vinegar
Acid for adjusting pH value is in 5.2～5.4 scopes；
(5) above-mentioned solution is placed in water bath with thermostatic control, adjusts stirring, fully reaction until solution reaches required power
Viscosity, the corresponding constant temperature of solution of tetra- kinds of variable concentrations of above-mentioned 0.80mol/L, 0.73mol/L, 0.58mol/L and 0.44mol/L
Bath temperature is respectively 20～22 DEG C, 22～24 DEG C, 24～26 DEG C, 24～26 DEG C；
(6) heat sterilization is carried out to product, filtering and impurity removing obtains final product the non-ionic polysaccharide biological after purified concentration
Flocculant.
A kind of preparation method of the high degree of substitution quaternary ammonium type polysaccharide bioflocculant, it is characterised in that：Using wet method work
Skill, by adding catalyst and co-catalyst in the non-ionic polysaccharide bioflocculation agent solution that mass concentration is 4～40%
Carry out basification, after be slowly added dropwise a certain amount of dispersant, stir, be eventually adding etherifying agent reaction a period of time, Jing Guochen
Form sediment, wash, alcohol is washed, is dried, grind prepared final products.
Wherein, non-ionic polysaccharide biological flocculant and the solid masses ratio of etherifying agent are 1:0.2～1:6, catalyst with
The mass ratio of co-catalyst is 1:0.1～1:3, catalyst is 1 with the mol ratio of etherifying agent:2～1:10, dispersant volume used
Accounting 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, stirs 0.5～1h after dispersant addition, etherification time is 1～3h.
Described catalyst is any in NaOH, potassium hydroxide, sodium oxide molybdena, potassium oxide, sodium carbonate, sodium acid carbonate
It is a kind of.
Described co-catalyst is urea, monoethanolamine, diethanol amine, triethanolamine, monoisopropanolamine, diisopropanol
Any one in amine, triisopropanolamine, diglycolamine.
Described etherifying agent be 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (CTA), 2,3- epoxypropyltrimethylchloride chlorides
(GTA) any one in.
Described dispersant is any one in methyl alcohol, ethanol, isopropanol, acetone, ether.
The substitution value of the high degree of substitution quaternary ammonium type polysaccharide bioflocculant be 0.2-1.8, molecular weight 2,000,000-50,
000,000。
Its reaction principle is as follows：
The present invention remarkable advantage be：
1. product appearance of the present invention is pale yellow powder, and product is nontoxic, environmentally friendly, efficient, belongs to polysaccharide bioflocculant
The Biodegradable materials such as modified product, modified starch series, the modified cellulose class for preparing at present are because of etherifying agent
The destabilizing factors such as facile hydrolysis and adopt dry method or semidry method preparation technology, the present invention using wet processing prepare product, no
Only good stability and simple to operate, easily separated, three wastes, cost performance are high.
2. product of the present invention is useless to drinking water and dyeing waste water, coal washing water, ore dressing, refinery(waste) water, papermaking and chemical industry
Water etc. is respectively provided with obvious flocculating effect, and solves the metal that the inorganic salts such as poly-aluminium, Polyferric Sulfate conventional in the market bring
The problems of the presence such as residual, sludge quantity are big, the monomer residue of corrosion pipeline and polyacrylamide in water body, its performance
Can compare favourably with it, such product has extensive market prospects and good economic results in society.
3. product of the invention carries out non-ionic polysaccharide biological flocculant leading in the world quaternised modified so as to have
There are super high molecular weight and high charge density, there is not been reported for such product.
Specific embodiment
Below to a preferred embodiment of the present invention will be described in detail.
Embodiment 1
1. quaternization：Nonionic biological flocculant aqueous solution 200g that mass concentration is 4% is taken in 500ml there-necked flasks
In, stirring is started, it is subsequently adding sodium carbonate solid 4.5g and adds 9g urea after 30 DEG C of stirred in water bath dissolvings, continue to stir
10min。
2. etherification reaction：It is slowly added dropwise in reaction system in 30 DEG C of water-baths after the isopropanol of 20ml and stirs 0.5h, so
16g2 is uniformly sprinkled in backward reaction system, 3- epoxypropyltrimethylchloride chlorides (GTA) continue stirring reaction 2h.
3. product is processed：Product is taken out, is washed, is dried, is ground with filter paper filtration and then washing, alcohol after precipitation,
The quaternary ammonium type polysaccharide bioflocculant that light yellow substitution value is 1.60 is obtained.
Embodiment 2
1. quaternization：Take the nonionic biological flocculant aqueous solution 200g that mass concentration is 15% to burn for tri- mouthfuls in 500ml
In bottle, stirring is started, be subsequently adding sodium oxide molybdena solid 8g, after 25 DEG C of stirred in water bath dissolvings 4g diglycolamines are added, continued
Stirring reaction 30min.
2. etherification reaction：The chloro- 2- Hydroxyproyl Trimethyls of 3- that 50g mass concentrations are 60% are slowly added dropwise in reaction system
Ammonium chloride (CTA) aqueous solution, then proceedes to stirring reaction 2h.
3. product is processed：Product is sticky light yellow fluid, and Solid content content is 31%, wash through washing, alcohol and
Drying grinding is obtained the quaternary ammonium type polysaccharide bioflocculant that light yellow substitution value is 0.23.
Embodiment 3
1. quaternization：Nonionic biological flocculant aqueous solution 200g that mass concentration is 16.7% is taken in tri- mouthfuls of 500ml
In flask, stirring is started, be subsequently adding sodium hydrate solid 2.8g, after 30 DEG C of stirred in water bath dissolvings the ethanol of 2.8g tri- is added
Amine, continues stirring reaction 10min.
2. etherification reaction：The acetone of 30ml is slowly added to in reaction system, 53.44g2,3- glycidyl three are added afterwards
Ammonio methacrylate (GTA), then proceedes to stirring reaction 1.5h.
3. product is processed：Product is sticky brown color paste, and Solid content content is 35%, through washing, alcohol wash with
And drying grinding is obtained the quaternary ammonium type polysaccharide bioflocculant that light yellow substitution value is 2.41.
Embodiment 4
1. quaternization：Nonionic biological flocculant aqueous solution 200g that mass concentration is 15.3% is taken in tri- mouthfuls of 500ml
In flask, stirring is started, be subsequently adding sodium bicarbonate solid 8g, after 25 DEG C of stirred in water bath dissolvings the isopropanols of 8g tri- are added
Amine, continues afterwards stirring reaction 60min.
2. etherification reaction：Methyl alcohol 28.5ml stirring 20min are slowly added dropwise in reaction system, 51g is then slowly added into dense
3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (CTA) aqueous solution for 60% is spent, continues stirring reaction 3h.
3. product is processed：Product is sticky light yellow fluid, and Solid content content is 29.1%, and filter paper is used after precipitation
Filter and then wash, alcohol is washed and dried grinding and the quaternary ammonium type polysaccharide bioflocculant that light yellow substitution value is 0.18 is obtained.
Above-described is only the preferred embodiments of the present invention, and the explanation that should be understood that above example is simply used
In helping understand the method for the present invention and its core concept, the protection domain being not intended to limit the present invention is all the present invention's
Any modification, equivalent for being made within thought and principle etc., should be included within the scope of the present invention.
Claims (5)
1. a kind of preparation method of high degree of substitution quaternary ammonium type polysaccharide bioflocculant, with non-ionic polysaccharide bioflocculation agent solution
For raw material, it is characterised in that：Using wet processing, by molten to the nonionic biological flocculant that mass concentration is 4～40%
Add catalyst and co-catalyst to carry out basification in liquid, after be slowly added dropwise a certain amount of dispersant, stir, be eventually adding ether
Agent reaction a period of time, wash, be dried, grinding prepared final products through precipitation, washing, alcohol；Wherein non-ionic polysaccharide life
Thing flocculant is 1 with the solid masses ratio of etherifying agent:0.2～1:6, catalyst is 1 with the mass ratio of co-catalyst:0.1～1:
3, catalyst is 1 with the mol ratio of etherifying agent:2～1:10, dispersant volume used account for water volume in reaction system 5～
20%, alkalize and the temperature of etherification reaction is all 20～40 DEG C, alkalization time is 10～60min, and after dispersant addition 0.5 is stirred
～1h, etherification time is 1～3h；
Wherein, the preparation method of the non-ionic polysaccharide biological flocculant raw material is added in certain density sucrose solution
The activator of dextransucrase, then adjusts the pH value of the solution, and dextransucrase solution is added afterwards, adjusts again after pH
Constant temperature stirring reaction for a period of time, obtains being obtained final product after heat sterilization after product, filtration, removal of impurities, purified concentration；
The molecular structure skeleton symbol of obtained quaternary ammonium type polysaccharide bioflocculant is：Wherein
Dx is non-ionic polysaccharide biological flocculant, and its skeleton symbol is：
Wherein n=10,000-310,000.
2. a kind of preparation method of high degree of substitution quaternary ammonium type polysaccharide bioflocculant according to claim 1, its feature exists
In：Described catalyst is any one in NaOH, potassium hydroxide, sodium oxide molybdena, potassium oxide, sodium carbonate, sodium acid carbonate.
3. a kind of preparation method of high degree of substitution quaternary ammonium type polysaccharide bioflocculant according to claim 1, its feature exists
In：Described co-catalyst is urea, monoethanolamine, diethanol amine, triethanolamine, monoisopropanolamine, diisopropanolamine (DIPA), three different
Any one in Propanolamine, diglycolamine.
4. a kind of preparation method of high degree of substitution quaternary ammonium type polysaccharide bioflocculant according to claim 1, its feature exists
In：Described etherifying agent be 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (CTA), 2,3- epoxypropyltrimethylchloride chlorides (GTA)
In any one；Described dispersant is any one in methyl alcohol, ethanol, isopropanol, acetone, ether.
5. a kind of preparation method of high degree of substitution quaternary ammonium type polysaccharide bioflocculant according to claim 1, its feature exists
In：The substitution value of the high degree of substitution quaternary ammonium type polysaccharide bioflocculant be 0.2-1.8, molecular weight 2,000,000-50,000,
000。
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| CN114890525B (en) * | 2022-05-19 | 2024-01-23 | 合肥工业大学 | Preparation method and application of dextran-betaine cationic flocculant |
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