CN105384874A - Preparation method of water-in-water emulsion-type cation polysaccharide biological flocculant - Google Patents
Preparation method of water-in-water emulsion-type cation polysaccharide biological flocculant Download PDFInfo
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- CN105384874A CN105384874A CN201510800694.1A CN201510800694A CN105384874A CN 105384874 A CN105384874 A CN 105384874A CN 201510800694 A CN201510800694 A CN 201510800694A CN 105384874 A CN105384874 A CN 105384874A
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- polysaccharide biological
- water emulsion
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- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 48
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- -1 cation polysaccharide Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 150000004676 glycans Chemical class 0.000 claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 125000002091 cationic group Chemical group 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000004160 Ammonium persulphate Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 8
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 5
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000006392 deoxygenation reaction Methods 0.000 claims description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical group [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000003352 sequestering agent Substances 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- UFAGAQUHRODLFO-UHFFFAOYSA-M [Cl-].CC=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 Chemical compound [Cl-].CC=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 UFAGAQUHRODLFO-UHFFFAOYSA-M 0.000 claims description 3
- 150000001409 amidines Chemical class 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- MAZPIOPHRNWBNG-UHFFFAOYSA-N [Cl-].Cl[NH3+].[Na] Chemical compound [Cl-].Cl[NH3+].[Na] MAZPIOPHRNWBNG-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 2
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 2
- 230000002459 sustained effect Effects 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 12
- 150000001768 cations Chemical class 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000005189 flocculation Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 239000010802 sludge Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- 238000012688 inverse emulsion polymerization Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 210000000481 breast Anatomy 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 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 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000007795 chemical reaction product 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
- 108010042194 dextransucrase Proteins 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a preparation method of a water-in-water emulsion-type cation polysaccharide biological flocculant. The preparation method is characterized in that: an auto-polymer or a copolymer of several types of unsaturated cation monomers is used as a stabilizer, a non-ionic polysaccharide biological flocculant is used as an auxiliary stabilizer, an aqueous solution of inorganic salts is used as a continuous phase, and by virtue of certain technological control, free radical polymerization is performed in an internal phase aqueous solution to form stable and dispersed cation polysaccharide biological flocculant emulsion containing micro polymer particles, wherein the solid content is more than or equal to 30 percent, the appearance viscosity is 300 to 10000 mPa.s, the average particle size is less than or equal to 10 micrometers, and the stability is more than or equal to 6 months. The product is simple in synthetic process, high in solubility, degradable, good in flocculation effect and free from secondary pollution, can be used for treating urban sewage and industrial waste water and dehydrating sludge, can be used as a filter aid and a retention aid in the papermaking industry, can be used for plugging adjustment and sewage treatment in oil fields and the like and is wide in application prospect and high in environmental protection value.
Description
Technical field
The invention belongs to polysaccharide bioflocculant modified technique technical field, particularly a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant.
Background technology
If traditional aqueous solution polymerization mode control improper meeting because of heat transfer ununiformity and polymerization process in localized heat release, cause polymerization unevenly even can form gel, polymer yield obtained is on the whole low, molecular weight is lower, the apparent viscosity of high solids content product is very high, have impact on flocculating effect, also inconvenience is brought for post-processed or use.The inverse emulsion polymerization method occurred afterwards, because reaction conditions is gentle, system temperature is evenly easily controlled, side reaction is few, and the higher narrow distribution of the molecular weight product obtained, large arch dam and apparent viscosity is low, well the product of solving over is difficult to the problem of dissolving, substantially reduces the time of dispersing and dissolving, but needs to use a large amount of organic solvents and tensio-active agent in preparation process, not only increase production cost and potential safety hazard, and easily secondary pollution is caused to environment.
At present, the natural macromolecular material close with polysaccharide bioflocculant attribute, as starch, Mierocrystalline cellulose, chitin etc., major part adopts inverse emulsion polymerization and aqueous solution polymerization, publication number is that the patent of CN101665554A adopts the mode of inverse emulsion polymerization to prepare cationic starch graft copolymer flocculant, containing a certain proportion of starch in its aqueous phase, acrylamide and cationic monomer, then the aqueous phase solution prepared is joined in the oil phase being dissolved with a certain amount of emulsifying agent, finally add remaining acrylamide, the mode that this secondary adds non-ionic monomer can overcome the higher reactivity ratio of non-ionic monomer when once adding and the low problem of the cationic monomer percentage of grafting caused to a certain extent, but there is the secondary pollution of oil phase, and the cost of oil phase is higher.In addition, publication number is the preparation method that the patent of CN1884324A mentions a kind of cation acrylamide copolymer water-in-water emulsion, wherein said water-in-water emulsion polymerization has the advantage of inverse emulsion polymerization, solvent is water entirely, but because the existence of hydrophobic grouping, the product obtaining large arch dam is just difficult to accomplish into breast and keeps stablizing not stratified, for this reason, which employs multistage polymerization and add auxiliary stabilizer (mainly polyalcohols material) and relax contradiction between polymerization velocity and speed of separating out, be convenient to into breast, thus improve active matter content and emulsion intercalation method, this polyalcohols material comprises glycerine, polyoxyethylene glycol, and polysaccharide is as modified tapioca starch, amylopectin, dextran or methoxycarbonyl Mierocrystalline cellulose, this method is because adopt continuous several times to add the mode of monomer, just there is the problems such as processing sequence slightly complicated.
Can find out, the method of traditional synthesizing water-solubility cationic polymers also exists problems, the poor fluidity of product even gelation while such as improving solid content, indissoluble solution, there is organic solvent pollution or the problem that active matter content is low, molecular weight is low etc. can not avoid simultaneously, bring inconvenience to follow-up process or use.Water-in-water emulsion polymerization can solve above problems, but in one-tenth breast and maintenance stability of emulsion, the control for processing sequence is aobvious complicated.We adopt traditional polymerization process successfully to achieve modification to polysaccharide bioflocculant before, see patent CN104130335A, CN104130351A, CN104327215A, now we are still carrier with polysaccharide bioflocculant, obtain desired product by the diffuse-aggregate mode of water-in-water emulsion.
Summary of the invention
In order to overcome the deficiencies in the prior art; the invention provides a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant; adopt synthetic and the polysaccharide bioflocculant with high molecular of large-scale production is base material; by water-in-water emulsion dispersion polymerization technology, obtain and there is high solids content, not containing organic solvent and monomer conversion is high, emulsion apparent viscosity is low and the cationic polysaccharide biofloculation agent emulsion that stability is strong.
The technical solution adopted for the present invention to solve the technical problems is:
A preparation method for water-in-water emulsion type cationic polysaccharide biological flocculant, comprises following steps:
Unsaturated cationic monomer is dissolved in water and is diluted to concentration by [step 1] is 30-40wt%, is warming up to 30-50 DEG C, after logical nitrogen deoxygenation, adds initiator A, reaction 3-10h, the stablizer that the polymers soln obtaining cationic monomer reacts as next step;
After stablizer obtained for previous step and a certain amount of water stir by [step 2], add non-ionic type polysaccharide bioflocculant, after cationic monomer, non-ionic monomer, inorganic salt, sequestrant stir, logical nitrogen, slowly be warming up to 30-60 DEG C, add initiator B, rapid stirring 10-20min under the rotating speed of 300-400r/min, auxiliary stabilizer is added while rear slowly stirring, sustained reaction 2-5h, takes out, cools, to obtain final product.
Preferably, described non-ionic type polysaccharide bioflocculant, cationic monomer and non-ionic monomer are total reaction material, and its solid masses accounts for the 10-40wt% of whole reaction system.
Preferably, molecular weight≤2,000,000 of described stablizer, and its solid dosage is 0.01-0.2 times of total reactant solid masses.
Preferably, described auxiliary stabilizer is nonionic polysaccharide biological flocculant powder, and its dosage is the 0.05-0.10wt% of total reactant.
Preferably, described cationic monomer is the several of any one or arbitrary proportion in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryloxyethyldimethyl benzyl ammonium chloride, acryloxyethyldimethyl benzyl ammonium chloride, methacryloyl hydroxypropyltrimonium chloride, acryloyl hydroxypropyltrimonium chloride, dimethyl diallyl ammonium chloride, the total dosage of its solid be the 0.5-5 of nonionic polysaccharide biological flocculant solid masses doubly.
Preferably, described non-ionic monomer is acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-sec.-propyl (methyl) acrylamide or N, any one in N-DMAA, its dosage accounts for the 1-10wt% of total reaction material.
Preferably, described initiator A is any one in ammonium persulphate/sodium bisulfite, ammonium persulphate/trolamine, Potassium Persulphate/sodium bisulfite, Potassium Persulphate/trolamine, and the mass ratio of oxygenant and reductive agent is 1: 0-1: 1, account for the 0.1-0.5wt ‰ of monomer mass.
Preferably, described initiator B is initiator A or azo water soluble starter: azo diisobutyl amidine hydrochloride and azo di-isopropyl imidazoline hydrochloride, or the arbitrary proportion of initiator A and azo water soluble starter with the use of, total dosage is the 0.1-5wt ‰ of total reaction material.
Preferably, described inorganic salt are at least one in the ammonium salt of ammonium sulfate, sodium sulfate, magnesium sulfate, Tai-Ace S 150, sodium-chlor, ammonium chloride, sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, phosphate radical or hydrogen phosphate, Sodium Thiocyanate 99, potassium sulfocyanate, ammonium thiocyanate, and addition accounts for the 10-40wt% of dispersion system.
Preferably, described sequestrant comprises disodium ethylene diamine tetraacetate and tetrasodium ethylenediamine tetraacetate, accounts for the 0.1-0.5wt ‰ of whole dispersion system.
Preferably, the molecular weight of described non-ionic type polysaccharide bioflocculant is 200-500 ten thousand, and kinetic viscosity is 2000-4500cps.
Preferably, the preparation method of described non-ionic type polysaccharide bioflocculant is as follows:
Compound concentration is the sucrose solution 1000 milliliters of 0.80mol/L, then the calcium chloride solution 10 milliliters of 0.5% is added inside, then regulate the pH value of above-mentioned sucrose solution in 5.2 ~ 5.4 scopes with 30% hac buffer, then the dextransucrase solution 17.5 milliliters that enzymic activity is 456IU/ml is added, after mixing, by 10% acetic acid adjust ph in 5.2 ~ 5.4 scopes; This solution is placed in 20 ~ 22 DEG C of waters bath with thermostatic control, regulates and stir, fully reaction is until solution reaches required kinetic viscosity, finally carries out heat sterilization to reaction product, filtering and impurity removing, namely obtains described non-ionic type polysaccharide bioflocculant after purified concentration.
Water-in-water emulsion type cationic polysaccharide biological flocculant of the present invention, with several unsaturated cationic monomer, unsaturated non-ionic monomer and existing non-ionic type polysaccharide bioflocculant are raw material, simultaneously with the self-aggregate of this several cation monomer or multipolymer for stablizer, non-ionic type polysaccharide bioflocculant is auxiliary stabilizer, using the aqueous solution of inorganic salt as external phase, by certain technology controlling and process, make it that radical polymerization occur in the interior phase aqueous solution and form the stable dispersion precursor emulsion containing microcosmic polymer beads, wherein, solid content >=30% of product, apparent viscosity 300-10000mPa.s, median size≤10 μm, stability >=6 month.
Product of the present invention is that white is to lurid emulsion, water-in-water emulsion polymerization technique is adopted to synthesize cationic polysaccharide biofloculation agent emulsion first, this technology effectively can overcome the problems of traditional product and technique existence, good fluidity, the effective solid content of final emulsion are high, molecular weight is high and stability is strong, dissolution rate is fast, easy to use, without harmful organic solvent during use, decrease synthesis cost and secondary pollution can not be caused to environment.
At present, like product is cationic polyacrylamide mainly, by comparison, present invention achieves the quantum jump to polysaccharide bioflocculant technical field of modification, this flocculation agent can provide the skeleton of graft copolymerization in the course of the polymerization process, makes product have comparatively regular molecular structure and higher molecular weight, degradable, nontoxicity, non-secondary pollution, this is that cationic polyacrylamide product does not have.Product of the present invention can be used for the process of municipal effluent and trade effluent, sludge dewatering, paper industry is used as flocculating aids and the fields such as stifled and sewage disposal are adjusted in retention aid, oil field, has broad application prospects and the value of environmental protection.
Embodiment
Below to a preferred embodiment of the present invention will be described in detail.
Embodiment 1
Prepare stablizer-polymethyl acyloxyethyl trimethyl ammonia chloride aqueous ammonium: be the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 80% by massfraction, adding deionized water, to be diluted to concentration be 40%, with there-necked flask, pass into nitrogen, be slowly warming up to 40 DEG C, then add ammonium persulphate and sodium bisulfite that 0.2wt ‰ (accounting for monomer mass) mass ratio is 1: 1, control mixing speed 200r/min, after stirring 20min, be incubated 5h, purify after taking out, dry, grind.
This stablizer is added water and is mixed with the aqueous solution that concentration is 21%, get this solution of 32g in 500ml there-necked flask, then the polysaccharide bioflocculant that 100g mass concentration is 15% is added, 25g mass concentration is the dimethyl diallyl ammonium chloride solution of 60%, 3g acrylamide, 40g ammonium sulfate, 0.02g disodium ethylene diamine tetraacetate, start stirring, pass into nitrogen deoxygenation, when being slowly warming up to 50 DEG C, add the azo di-isopropyl imidazoline hydrochloride aqueous solution that 5ml concentration is 0.1mol/L, then under the rotating speed of 300r/min, 15min is stirred, add non-ionic type polysaccharide bioflocculant powder 0.02g, then slowly 5h is stirred.Take out, cooling, obtains emulsion-formulated products.
The solid content obtaining this product is after tested 42%, and apparent viscosity is 660mPa.s, median size 8.5 μm, stability > 6 months.
Embodiment 2
Prepare stablizer-Poly Dimethyl Diallyl Ammonium Chloride aqueous solution: be the dimethyl diallyl ammonium chloride of 60% by massfraction, adding deionized water, to be diluted to concentration be 30%, with there-necked flask, pass into nitrogen, be slowly warming up to 50 DEG C, then add the ammonium persulphate of 0.2wt ‰ (accounting for monomer mass), control mixing speed 200r/min, after stirring 10min, be incubated 10h, purify after taking out, dry, grind.
This stablizer is added water and is mixed with the aqueous solution that concentration is 15.6%, get this solution of 42.65g in 500ml there-necked flask, then the polysaccharide bioflocculant that 100g mass concentration is 15% is added, 18.75g mass concentration is the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride solution of 80%, 3.25g Methacrylamide, 35g ammonium sulfate, 0.1g disodium ethylene diamine tetraacetate, start stirring, pass into nitrogen deoxygenation, when being slowly warming up to 50 DEG C, add the azo diisobutyl amidine hydrochloride aqueous solution that 6ml concentration is 0.1mol/L, then under the rotating speed of 300r/min, 10min is stirred, add non-ionic type polysaccharide bioflocculant powder 0.03g, then slowly 4h is stirred.Take out, cooling, obtains emulsion-formulated products.
The solid content obtaining this product is after tested 37.5%, and apparent viscosity is 1100mPa.s, median size 3.5 μm, stability > 6 months.
Embodiment 3
Prepare stablizer-polymethyl acyloxyethyl dimethyl benzyl ammonium chloride aqueous solution: be the methylacryloxyethyldimethyl benzyl ammonium chloride of 60% by massfraction, adding deionized water, to be diluted to concentration be 30%, with there-necked flask, pass into nitrogen, be slowly warming up to 50 DEG C, then the ammonium persulphate of 0.5wt ‰ (accounting for monomer mass) is added, control mixing speed 200r/min, after stirring 20min, insulation, 5h, purifies after taking out, dries, grinds.
This stablizer is added water and is mixed with the aqueous solution that concentration is 5%, get this solution of 44.7g in 500ml there-necked flask, then the polysaccharide bioflocculant that 100g mass concentration is 15% is added, 15g mass concentration is the methacryloyl hydroxypropyltrimonium chloride solution of 50%, 0.25g acrylamide, 40g ammonium chloride, 0.02g disodium ethylene diamine tetraacetate, start stirring, pass into nitrogen deoxygenation, when being slowly warming up to 40 DEG C, add the aqueous solution that 1ml concentration is the ammonium persulphate of 0.1mol/L, 50 DEG C are warming up to after 1h, add the azo di-isopropyl imidazoline hydrochloride aqueous solution that 1.4ml concentration is 0.1mol/L, add non-ionic type polysaccharide bioflocculant powder 0.02g, then slowly 5h is stirred.Take out, cooling, obtains emulsion-formulated products.
The solid content obtaining this product is after tested 32.5%, and apparent viscosity is 2300mPa.s, median size 6.0 μm, stability > 8 months.
Above-describedly be only the preferred embodiments of the present invention; be understood that; the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; the protection domain be not intended to limit the present invention; all any amendments, equivalent replacement etc. made within thought of the present invention and principle, all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for water-in-water emulsion type cationic polysaccharide biological flocculant, is characterized in that comprising following steps:
Unsaturated cationic monomer is dissolved in water and is diluted to concentration by [step 1] is 30-40wt%, is warming up to 30-50 DEG C, after logical nitrogen deoxygenation, adds initiator A, reaction 3-10h, the stablizer that the polymers soln obtaining cationic monomer reacts as next step;
After stablizer obtained for previous step and a certain amount of water stir by [step 2], add non-ionic type polysaccharide bioflocculant, after cationic monomer, non-ionic monomer, inorganic salt, sequestrant stir, logical nitrogen, slowly be warming up to 30-60 DEG C, add initiator B, rapid stirring 10-20min under the rotating speed of 300-400r/min, auxiliary stabilizer is added while rear slowly stirring, sustained reaction 2-5h, takes out, cools, to obtain final product.
2. the preparation method of a kind of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is characterized in that: described non-ionic type polysaccharide bioflocculant, cationic monomer and non-ionic monomer are total reaction material, and its solid masses accounts for the 10-40wt% of whole reaction system.
3. the preparation method of a kind of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, is characterized in that: the molecular weight of described non-ionic type polysaccharide bioflocculant is 200-500 ten thousand, and kinetic viscosity is 2000-4500cps;
Molecular weight≤2,000,000 of described stablizer, and its solid dosage is 0.01-0.2 times of total reactant solid masses.
4. the preparation method of a kind of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, is characterized in that: described auxiliary stabilizer is nonionic polysaccharide biological flocculant powder, and its dosage is the 0.05-0.10wt% of total reactant.
5. the preparation method of a kind of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is characterized in that: described cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryloxyethyldimethyl benzyl ammonium chloride, acryloxyethyldimethyl benzyl ammonium chloride, methacryloyl hydroxypropyltrimonium chloride, acryloyl hydroxypropyltrimonium chloride, any one or arbitrary proportion in dimethyl diallyl ammonium chloride several, the total dosage of its solid is 0.5-5 times of nonionic polysaccharide biological flocculant solid masses.
6. the preparation method of a kind of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is characterized in that: described non-ionic monomer is acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-sec.-propyl (methyl) acrylamide or N, any one in N-DMAA, its dosage accounts for the 1-10wt% of total reaction material.
7. the preparation method of a kind of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is characterized in that: described initiator A is any one in ammonium persulphate/sodium bisulfite, ammonium persulphate/trolamine, Potassium Persulphate/sodium bisulfite, Potassium Persulphate/trolamine, and the mass ratio of oxygenant and reductive agent is 1: 0-1: 1, account for the 0.1-0.5wt ‰ of monomer mass.
8. the preparation method of a kind of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is characterized in that: described initiator B is initiator A or azo water soluble starter: azo diisobutyl amidine hydrochloride and azo di-isopropyl imidazoline hydrochloride, or the arbitrary proportion of initiator A and azo water soluble starter with the use of, total dosage is the 0.1-5wt ‰ of total reaction material.
9. the preparation method of a kind of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is characterized in that: described inorganic salt are at least one in the ammonium salt of ammonium sulfate, sodium sulfate, magnesium sulfate, Tai-Ace S 150, sodium-chlor, ammonium chloride, sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, phosphate radical or hydrogen phosphate, Sodium Thiocyanate 99, potassium sulfocyanate, ammonium thiocyanate, and addition accounts for the 10-40wt% of dispersion system.
10. the preparation method of a kind of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, is characterized in that: described sequestrant comprises disodium ethylene diamine tetraacetate and tetrasodium ethylenediamine tetraacetate, accounts for the 0.1-0.5wt ‰ of whole dispersion system.
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