CN105384874B - A kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant - Google Patents
A kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant Download PDFInfo
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- CN105384874B CN105384874B CN201510800694.1A CN201510800694A CN105384874B CN 105384874 B CN105384874 B CN 105384874B CN 201510800694 A CN201510800694 A CN 201510800694A CN 105384874 B CN105384874 B CN 105384874B
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- biological flocculant
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- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 49
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- -1 cationic polysaccharide Chemical class 0.000 title claims abstract description 31
- 239000000839 emulsion Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000004676 glycans Chemical class 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 125000002091 cationic group Chemical group 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 235000002639 sodium chloride Nutrition 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 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
- 239000000843 powder Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 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 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 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
- 239000002738 chelating agent Substances 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
- 239000007858 starting material Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- 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 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000010792 warming Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 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 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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 2
- 229960000583 acetic acid Drugs 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
- 150000001409 amidines Chemical class 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
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 108010042194 dextransucrase Proteins 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 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
- 230000004044 response Effects 0.000 claims description 2
- 239000011780 sodium chloride Substances 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
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 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
- 230000001954 sterilising effect Effects 0.000 claims description 2
- 238000004659 sterilization and disinfection Methods 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
- 239000003643 water by type Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- PSXRWZBTVAZNSF-UHFFFAOYSA-N hydron;quinoline;chloride Chemical compound Cl.N1=CC=CC2=CC=CC=C21 PSXRWZBTVAZNSF-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000007864 aqueous solution Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000003311 flocculating effect Effects 0.000 abstract description 2
- 239000010842 industrial wastewater Substances 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
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000011324 bead Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- 238000012688 inverse emulsion polymerization Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 210000000481 breast Anatomy 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
- 238000000227 grinding Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 102400000830 Saposin-B Human genes 0.000 description 2
- 101800001697 Saposin-B Proteins 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- IUPDXIXTYXNMFR-UHFFFAOYSA-N azane N,N-dimethylmethanamine hydrochloride Chemical compound [Cl-].[NH4+].CN(C)C IUPDXIXTYXNMFR-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- OYINQIKIQCNQOX-UHFFFAOYSA-M 2-hydroxybutyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCC(O)C[N+](C)(C)C OYINQIKIQCNQOX-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920002101 Chitin Polymers 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
- 229920001503 Glucan Polymers 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 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
- 230000033228 biological regulation Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification 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
- 239000012535 impurity Substances 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
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 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
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention relates to a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant：Using several unsaturated cationic monomers, self-aggregate or copolymer as stabilizer, non-ionic polysaccharide biological flocculant is auxiliary stabilizer, continuous phase is used as using the aqueous solution of inorganic salts, by certain technology controlling and process, make it that the cationic polysaccharide bioflocculation agent emulsion that radical polymerization forms the stable dispersion containing microcosmic polymer beads occur in the phase aqueous solution inside, wherein, solid content >=30%, the 10000mPa.s of apparent viscosity 300, average grain diameter≤10 μm, stability >=6 month.Product synthesis technique is simple, dissolubility is strong, degradable, flocculating effect is good, and non-secondary pollution, processing, sludge dewatering, paper industry available for municipal sewage and industrial wastewater are used as filter aid and retention agent, stifled and sewage disposal etc. is adjusted in oil field, have broad application prospects and the value of environmental protection.
Description
Technical field
The invention belongs to polysaccharide bioflocculant modified technique technical field, particularly a kind of water-in-water emulsion type cation
The preparation method of polysaccharide bioflocculant.
Background technology
Can be because of the part in the inhomogeneities and polymerization process of heat transfer if traditional aqueous solution polymerization mode control is improper
Heat release, cause to polymerize uneven or even gel can be formed, obtained polymer yield is low on the whole, molecular weight is relatively low, large arch dam
The apparent viscosity of volume production thing is very high, have impact on flocculating effect, and inconvenience is also brought for post-processing or use.Occur afterwards
Inverse emulsion polymerization method, due to reaction condition is gentle, system temperature uniformly it is easily-controllable, side reaction is few, and obtained product point
Son measures higher narrow distribution, large arch dam and apparent viscosity is low, and the product of solving the problems, such as over is difficult to dissolve well, contracts significantly
The short time of dispersing and dissolving, but substantial amounts of organic solvent and surfactant are needed to use in preparation process, not only increase
Production cost and potential safety hazard, and secondary pollution easily is caused to environment.
At present, with polysaccharide bioflocculant attribute similar in natural macromolecular material, such as starch, cellulose, chitin,
Most of to use inverse emulsion polymerization and aqueous solution polymerization, Publication No. CN101665554A patent uses inverse emulsion polymerization
Mode prepare cationic starch graft copolymer flocculant, in its aqueous phase containing a certain proportion of starch, acrylamide and sun from
Sub- monomer, then the aqueous phase solution prepared is added in the oil phase dissolved with a certain amount of emulsifying agent, finally adds remaining propylene
Acid amides, this secondary mode for adding non-ionic monomer can overcome non-ionic monomer when once adding higher to a certain extent
Reactivity ratio caused by cationic monomer grafting rate it is low the problem of, but the secondary pollution of oil phase be present, and the cost of oil phase compared with
It is high.In addition, Publication No. CN1884324A patent mentions a kind of preparation of cation acrylamide copolymer water-in-water emulsion
Method, wherein described water-in-water emulsion polymerization has the advantages of inverse emulsion polymerization, solvent is water entirely, but because hydrophobic grouping
Presence, the product that obtain large arch dam is difficult to accomplish into breast and keeping and stablizes not stratified, to gather therefore, which employs the multistage
Merge addition auxiliary stabilizer (mainly polyalcohols material) to relax the contradiction between polymerization speed and speed of separating out, be easy to
Into breast, so as to improve active matter content and emulsion intercalation method, this polyalcohols material includes glycerine, polyethylene glycol, and
Polysaccharide such as modified tapioca starch, amylopectin, glucan or carbomethoxy cellulose, this method is because use continuous several times
Add the mode of monomer, the problems such as there is process slightly complicated.
As can be seen that there is problems, such as raising are solid for the method for traditional synthesizing water-solubility cationic polymer
While content product poor fluidity even gelation, indissoluble solution, exist organic solvent pollution or active matter content it is low, point
Son measures low the problem of can not avoiding simultaneously, and inconvenience is brought to follow-up processing or use.Water-in-water emulsion polymerization can be with
Solve above problems, but in terms of into breast and holding stability of emulsion, the control for process, which but shows, to be complicated.It
Preceding we use traditional polymerization successfully to realize the modification to polysaccharide bioflocculant, see patent
CN104130335A, CN104130351A, CN104327215A, we are still using polysaccharide bioflocculant as carrier now, lead to
The mode for crossing water-in-water emulsion dispersin polymerization obtains desired product.
The content of the invention
For overcome the deficiencies in the prior art, the invention provides a kind of water-in-water emulsion type cationic polysaccharide bioflocculation
The preparation method of agent, artificial synthesized and large-scale production the polysaccharide bioflocculant with HMW is used as base material,
By water-in-water emulsion dispersin polymerization technology, obtain with high solids content, without organic solvent and monomer conversion height, emulsion
The cationic polysaccharide bioflocculation agent emulsion that apparent viscosity is low and stability is strong.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant, is comprised the following steps：
It is 30-40wt% that unsaturated cationic monomer is dissolved in water and is diluted to concentration by [step 1], is warming up to 30-50 DEG C,
After logical nitrogen deoxygenation, initiator A is added, reacts 3-10h, obtains the polymer solution of cationic monomer as next step reaction
Stabilizer；
After [step 2] stirs stabilizer made from previous step and a certain amount of water, non-ionic polysaccharide life is added
After thing flocculant, cationic monomer, non-ionic monomer, inorganic salts, chelating agent stir, lead to nitrogen, be to slowly warm up to 30-60
DEG C, add initiator B, quick stirring 10-20min under 300-400r/min rotating speed, after add auxiliary while be slowly stirred
Stabilizer, sustained response 2-5h, take out, cooling, produce.
Preferably, described non-ionic polysaccharide biological flocculant, cationic monomer and non-ionic monomer are total reactant
Matter, its solid masses account for the 10-40wt% of whole reaction system.
Preferably, the molecular weight of the stabilizer≤2,000,000, and its solid dosage is total reactant solid masses
0.01-0.2 times.
Preferably, the auxiliary stabilizer is nonionic polysaccharide biological flocculant powder, and its dosage is total reactant
0.05-0.10wt%.
Preferably, the cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl front three
Ammonium chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, acryloxyethyldimethyl benzyl ammonium chloride, methyl-prop
Any one in alkene acyl hydroxypropyltrimonium chloride, acryloyl hydroxypropyltrimonium chloride, dimethyl diallyl ammonium chloride
Or arbitrary proportion is several, the total dosage of its solid is 0.5-5 times of nonionic polysaccharide biological flocculant solid masses.
Preferably, the non-ionic monomer is acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N- isopropyls
Any one in base (methyl) acrylamide or N,N-DMAA, its dosage accounts for the 1- of overall reaction material
10wt%.
Preferably, the initiator A is ammonium persulfate/sodium hydrogensulfite, ammonium persulfate/triethanolamine, potassium peroxydisulfate/Asia
Any one in niter cake, potassium peroxydisulfate/triethanolamine, and the mass ratio of oxidant and reducing agent is 1: 0-1: 1, accounts for list
The 0.1-0.5wt ‰ of weight.
Preferably, the initiator B is initiator A or azo water soluble starter：Azo diisobutyl amidine hydrochloride
It is used cooperatively with the arbitrary proportion of azo dicyclohexyl formonitrile HCN hydrochloride, or initiator A and azo water soluble starter, always
Dosage is the 0.1-5wt ‰ of overall reaction material.
Preferably, the inorganic salts be ammonium sulfate, sodium sulphate, magnesium sulfate, aluminum sulfate, sodium chloride, ammonium chloride, sodium phosphate,
In disodium hydrogen phosphate, sodium dihydrogen phosphate, the ammonium salt of phosphate radical or hydrogen phosphate, sodium sulfocyanate, potassium rhodanide, ammonium thiocyanate extremely
Few one kind, addition account for the 10-40wt% of dispersion.
Preferably, the chelating agent includes disodium ethylene diamine tetraacetate and tetrasodium ethylenediamine tetraacetate, accounts for whole dispersion
The 0.1-0.5wt ‰ of system.
Preferably, the molecular weight of the non-ionic polysaccharide biological flocculant is 200-500 ten thousand, dynamic viscosity 2000-
4500cps。
Preferably, the preparation method of the non-ionic polysaccharide biological flocculant is as follows：
Compound concentration is 0.80mol/L 1000 milliliters of sucrose solution, then adds 0.5% calcium chloride solution inside
10 milliliters, the pH value of above-mentioned sucrose solution is then adjusted with 30% hac buffer in 5.2~5.4 scopes, then adds enzyme
Activity is 456IU/ml 17.5 milliliters of dextransucrase solution, after mixing, with 10% vinegar acid for adjusting pH value 5.2~5.4
Scope；The solution is placed in 20~22 DEG C of waters bath with thermostatic control, regulation stirring, fully reaction are until solution reaches required power
Viscosity, heat sterilization is finally carried out to reaction product, filtering and impurity removing, the non-ionic polysaccharide biology wadding is produced after purifying concentration
Solidifying agent.
Water-in-water emulsion type cationic polysaccharide biological flocculant of the present invention, with several unsaturated cationic monomers, no
Saturation non-ionic monomer and existing non-ionic polysaccharide biological flocculant be raw material, at the same with this several cation monomer oneself
Aggressiveness or copolymer are stabilizer, and non-ionic polysaccharide biological flocculant is auxiliary stabilizer, using the aqueous solution of inorganic salts as
Continuous phase, by certain technology controlling and process, it is set radical polymerization occur in the phase aqueous solution inside to be formed to contain microcosmic polymer
The stable dispersion precursor emulsion of particle, wherein, solid content >=30% of product, apparent viscosity 300-10000mPa.s, average grain diameter
≤ 10 μm, stability >=6 month.
Product of the present invention, to lurid emulsion, has synthesized cation using water-in-water emulsion polymerization technique first to be white
Polysaccharide bioflocculant emulsion, the technology can effectively overcome problems existing for traditional product and technique, the stream of final emulsion
Dynamic property is good, effective solid content is high, molecular weight is high and stability is strong, and dissolution velocity is fast, easy to use, without harmful organic during use
Solvent, reduce synthesis cost and secondary pollution will not be caused to environment.
At present, like product is mainly PAMC, and by comparison, the present invention realizes to wad a quilt with cotton to polysaccharide biology
One quantum jump of solidifying agent technical field of modification, the flocculant can provide the skeleton of graft copolymerization in the course of the polymerization process so that product
Degradable with more regular molecular structure and higher molecular weight, non-toxic, non-secondary pollution, this is cation poly- third
Acrylamide product does not have.Product of the present invention can be used for the processing, sludge dewatering, papermaking row of municipal sewage and industrial wastewater
Industry is used as filter aid and retention agent, the fields such as stifled and sewage disposal are adjusted in 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 stabilizer-polymethyl acyloxyethyl trimethyl ammonia chloride aqueous ammonium：By the first that mass fraction is 80%
Base acrylyl oxy-ethyl-trimethyl salmiac, add deionized water and be diluted to concentration in 40%, with three-necked flask, to be passed through nitrogen
Gas, 40 DEG C are to slowly warm up to, then add ammonium persulfate and bisulfite that 0.2wt ‰ (accounting for monomer mass) mass ratio is 1: 1
Sodium, speed of agitator 200r/min is controlled, after stirring 20min, be incubated 5h, purified, dry after taking-up, grinding.
Add water to be configured to the aqueous solution that concentration is 21% stabilizer, take the 32g solution in 500ml three-necked flasks,
Then add 100g mass concentrations be 15% polysaccharide bioflocculant, 25g mass concentrations be 60% dimethyl diallyl
Ammonium chloride solution, 3g acrylamides, 40g ammonium sulfate, 0.02g disodium ethylene diamine tetraacetates, start stirring, are passed through nitrogen deoxygenation,
When being to slowly warm up to 50 DEG C, the azo dicyclohexyl formonitrile HCN hydrochloric acid saline solution that 5ml concentration is 0.1mol/L, Ran Hou are added
15min is stirred under 300r/min rotating speed, non-ionic polysaccharide biological flocculant powder 0.02g is added, is then slowly stirred 5h.
Take out, cooling, obtain emulsion-formulated products.
The solid content for obtaining the product after tested is 42%, apparent viscosity 660mPa.s, and 8.5 μm of average grain diameter is stable
Property ＞ 6 months.
Embodiment 2
Prepare stabilizer-PDDA aqueous solution：By the dimethyl diene that mass fraction is 60%
Propyl ammonium chloride, add deionized water and be diluted to concentration in 30%, with three-necked flask, to be passed through nitrogen, being to slowly warm up to 50 DEG C,
Then 0.2wt ‰ (accounting for monomer mass) ammonium persulfate is added, controls speed of agitator 200r/min, after stirring 10min, insulation
10h, purify, dry after taking-up, grinding.
Add water to be configured to the aqueous solution that concentration is 15.6% stabilizer, take the 42.65g solution in tri- mouthfuls of burnings of 500ml
Bottle in, then add 100g mass concentrations be 15% polysaccharide bioflocculant, 18.75g mass concentrations be 80% methyl-prop
Alkene acyloxyethyl trimethyl ammonia chloride ammonium salt solution, 3.25g Methacrylamides, 35g ammonium sulfate, 0.1g disodium ethylene diamine tetraacetates,
Stirring is started, is passed through nitrogen deoxygenation, when being to slowly warm up to 50 DEG C, adds the azo diisobutyl amidine that 6ml concentration is 0.1mol/L
Hydrochloric acid saline solution, 10min is then stirred under 300r/min rotating speed, add non-ionic polysaccharide biological flocculant powder
0.03g, then it is slowly stirred 4h.Take out, cooling, obtain emulsion-formulated products.
The solid content for obtaining the product after tested is 37.5%, apparent viscosity 1100mPa.s, 3.5 μm of average grain diameter, surely
Qualitative ＞ 6 months.
Embodiment 3
Prepare stabilizer-polymethyl acyloxyethyl dimethyl benzyl ammonium chloride aqueous solution：It is 60% by mass fraction
Methylacryloxyethyldimethyl benzyl ammonium chloride, add deionized water and be diluted to concentration as in 30%, with three-necked flask,
Nitrogen is passed through, is to slowly warm up to 50 DEG C, then adds 0.5wt ‰ (accounting for monomer mass) ammonium persulfate, controls speed of agitator
200r/min, after stirring 20min, insulation, 5h, purify, dry after taking-up, grinding.
Add water to be configured to the aqueous solution that concentration is 5% stabilizer, take the 44.7g solution in 500ml three-necked flasks,
Then add 100g mass concentrations be 15% polysaccharide bioflocculant, 15g mass concentrations be 50% methacryl propyl group
Trimethyl ammonia chloride ammonium salt solution, 0.25g acrylamides, 40g ammonium chlorides, 0.02g disodium ethylene diamine tetraacetates, start stirring, are passed through
Nitrogen deoxygenation, when being to slowly warm up to 40 DEG C, the aqueous solution for the ammonium persulfate that 1ml concentration is 0.1mol/L is added, is warming up to after 1h
50 DEG C, the azo dicyclohexyl formonitrile HCN hydrochloric acid saline solution that 1.4ml concentration is 0.1mol/L is added, adds non-ionic polysaccharide
Biological flocculant powder 0.02g, is then slowly stirred 5h.Take out, cooling, obtain emulsion-formulated products.
The solid content for obtaining the product after tested is 32.5%, apparent viscosity 2300mPa.s, 6.0 μm of average grain diameter, surely
Qualitative ＞ 8 months.
Above-described is only the preferred embodiments of the present invention, should be understood that the explanation of above example is simply used
In help understand the present invention method and its core concept, the protection domain being not intended to limit the present invention, it is all the present invention
Any modification for being made within thought and principle, equivalent substitution etc., should be included in the scope of the protection.
Claims (9)
1. a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant, it is characterised in that comprise the following steps：
It is 30-40wt% that unsaturated cationic monomer is dissolved in water and is diluted to concentration by [step 1], is warming up to 30-50 DEG C, leads to nitrogen
After gas deoxygenation, initiator A is added, reacts 3-10h, obtains stabilization of the polymer solution of cationic monomer as next step reaction
Agent；
After [step 2] stirs stabilizer made from previous step and a certain amount of water, non-ionic polysaccharide biology wadding is added
After solidifying agent, cationic monomer, non-ionic monomer, inorganic salts, chelating agent stir, lead to nitrogen, be to slowly warm up to 30-60 DEG C,
Add initiator B, quick stirring 10-20min under 300-400r/min rotating speed, after to add auxiliary while be slowly stirred stable
Agent, sustained response 2-5h, take out, cooling, produce；
Wherein, the auxiliary stabilizer is nonionic polysaccharide biological flocculant powder, and its dosage is the 0.05- of total reactant
0.10wt%；
The preparation method of the non-ionic polysaccharide biological flocculant is as follows：Compound concentration is 0.80mol/L sucrose solution
1000 milliliters, 0.5% 10 milliliters of calcium chloride solution is then added inside, is then adjusted with 30% hac buffer above-mentioned
The pH value of sucrose solution is in 5.2~5.4 scopes, the milli of dextransucrase solution 17.5 that then addition enzymatic activity is 456IU/ml
Rise, after mixing, with 10% vinegar acid for adjusting pH value in 5.2~5.4 scopes；The solution is placed in 20~22 DEG C of waters bath with thermostatic control, adjusted
Section stirring, fully reaction reach required dynamic viscosity up to solution, finally carry out heat sterilization to reaction product, cross and filter out
It is miscellaneous, produce the non-ionic polysaccharide biological flocculant after purifying concentration.
2. a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is special
Sign is：Described non-ionic polysaccharide biological flocculant, cationic monomer and non-ionic monomer is overall reaction material, its solid
Quality accounts for the 10-40wt% of whole reaction system.
3. a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is special
Sign is：The molecular weight of the non-ionic polysaccharide biological flocculant is 200-500 ten thousand, dynamic viscosity 2000-4500cps；
The molecular weight of the stabilizer≤2,000,000, and its solid dosage is 0.01-0.2 times of total reactant solid masses.
4. a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is special
Sign is：The cationic monomer be MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac,
Methylacryloxyethyldimethyl benzyl ammonium chloride, acryloxyethyldimethyl benzyl ammonium chloride, methacryl propyl group
Any one in trimethyl ammonium chloride, acryloyl hydroxypropyltrimonium chloride, dimethyl diallyl ammonium chloride or any ratio
Example it is several, the total dosage of its solid is 0.5-5 times of nonionic polysaccharide biological flocculant solid masses.
5. a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is special
Sign is：The non-ionic monomer is acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N- isopropyls (methyl)
Any one in acrylamide or N,N-DMAA, its dosage accounts for the 1-10wt% of overall reaction material.
6. a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is special
Sign is：The initiator A is ammonium persulfate/sodium hydrogensulfite, ammonium persulfate/triethanolamine, potassium peroxydisulfate/bisulfite
Any one in sodium, potassium peroxydisulfate/triethanolamine, and the mass ratio of oxidant and reducing agent is 1:0-1:1, account for monomer mass
0.1-0.5wt ‰.
7. a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is special
Sign is：The initiator B is initiator A or azo water soluble starter：Azo diisobutyl amidine hydrochloride and azo two
Isopropylimdazole quinoline hydrochloride, or the arbitrary proportion of initiator A and azo water soluble starter are used cooperatively, and total dosage is
The 0.1-5wt ‰ of overall reaction material.
8. a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is special
Sign is：The inorganic salts are ammonium sulfate, sodium sulphate, magnesium sulfate, aluminum sulfate, sodium chloride, ammonium chloride, sodium phosphate, phosphoric acid hydrogen two
At least one of sodium, sodium dihydrogen phosphate, the ammonium salt of phosphate radical or hydrogen phosphate, sodium sulfocyanate, potassium rhodanide, ammonium thiocyanate,
Addition accounts for the 10-40wt% of dispersion.
9. a kind of preparation method of water-in-water emulsion type cationic polysaccharide biological flocculant according to claim 1, it is special
Sign is：The chelating agent includes disodium ethylene diamine tetraacetate and tetrasodium ethylenediamine tetraacetate, accounts for the 0.1- of whole dispersion
0.5wt‰。
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