CN103803722B - Non-phosphorus copolymer antiscale dispersant and preparation method thereof - Google Patents
Non-phosphorus copolymer antiscale dispersant and preparation method thereof Download PDFInfo
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- CN103803722B CN103803722B CN201210460356.4A CN201210460356A CN103803722B CN 103803722 B CN103803722 B CN 103803722B CN 201210460356 A CN201210460356 A CN 201210460356A CN 103803722 B CN103803722 B CN 103803722B
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 38
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 14
- 239000011574 phosphorus Substances 0.000 title abstract description 14
- 230000005764 inhibitory process Effects 0.000 claims abstract description 58
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 19
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 335
- 238000010438 heat treatment Methods 0.000 claims description 52
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 238000009835 boiling Methods 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 31
- 239000003153 chemical reaction reagent Substances 0.000 claims description 30
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 28
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 claims description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 21
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 21
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000005642 Oleic acid Substances 0.000 claims description 21
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 21
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 21
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 21
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 21
- 229960004488 linolenic acid Drugs 0.000 claims description 21
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 21
- 235000021313 oleic acid Nutrition 0.000 claims description 21
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 20
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 12
- 239000011976 maleic acid Substances 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 235000021342 arachidonic acid Nutrition 0.000 claims description 11
- 229940114079 arachidonic acid Drugs 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 230000002401 inhibitory effect Effects 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229960002969 oleic acid Drugs 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 60
- 230000000694 effects Effects 0.000 abstract description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000498 cooling water Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 7
- 239000001506 calcium phosphate Substances 0.000 abstract description 7
- 229910000389 calcium phosphate Inorganic materials 0.000 abstract description 7
- 235000011010 calcium phosphates Nutrition 0.000 abstract description 7
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 abstract description 7
- 150000003751 zinc Chemical class 0.000 abstract description 7
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 100
- 238000005303 weighing Methods 0.000 description 100
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 50
- 239000000243 solution Substances 0.000 description 28
- 238000010992 reflux Methods 0.000 description 26
- 239000011259 mixed solution Substances 0.000 description 25
- 238000002156 mixing Methods 0.000 description 25
- 230000000379 polymerizing effect Effects 0.000 description 25
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 25
- 235000010262 sodium metabisulphite Nutrition 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 229940001584 sodium metabisulfite Drugs 0.000 description 23
- 229910052742 iron Inorganic materials 0.000 description 12
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 10
- 235000020778 linoleic acid Nutrition 0.000 description 10
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- 239000012496 blank sample Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004457 water analysis Methods 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000668 effect on calcium Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
Abstract
The invention relates to a non-phosphorus copolymer antiscale dispersant and a preparation method thereof. The non-phosphorus copolymer antiscale dispersant is prepared by carrying out one-step polymerization on 5-15 wt% of C16-C24 unsaturated fatty acid, 15-25 wt% of C3-C8 unsaturated sulfonic acid and 60-80 wt% of C3-C8 carboxylic acid in an organic solvent under the initiation action of inorganic peroxide. The copolymer antiscale dispersant has certain surface activity and stripping property on the premise of having excellent calcium carbonate scale inhibition property, excellent calcium phosphate inhibition property and stable zinc salt property, and especially has better antiscale effect than common antiscale dispersants in a water body with higher oil content. The copolymer antiscale dispersant has the advantages of simple preparation method, low cost, low consumption and favorable antiscale and dispersion effects, is free of phosphorus, is green and environment-friendly, can be widely used in an industrial circulating cooling water system, and has higher economic benefit and social benefit.
Description
Technical Field
The invention relates to the field of circulating water treatment, and in particular relates to a phosphorus-free copolymer scale inhibition and dispersion agent and a preparation method thereof.
Background
With the scale of industrial production and the sharp increase of population, water resources are seriously deficient. The consumption of the circulating cooling water accounts for 60-70% of the industrial water, and the reasonable saving of the circulating cooling water is the most direct way for reducing the industrial water consumption. The main method for saving the circulating cooling water is to improve the recycling rate of the circulating cooling water, namely to increase the concentration factor, but the method can bring serious corrosion and scaling problems to a circulating water system, and puts higher requirements on a water treatment process. In order to ensure that a circulating water system can normally operate under the conditions of high hardness, high chloride ion concentration, high organic matter concentration and the like, the water treatment agent is very critical.
The scale inhibiting dispersant is common water quality stabilizer for circular water treatment, and especially polycarboxylate scale inhibiting dispersant, which can prevent scale salt from depositing on metal surface, prevent particle (scale) from aggregating and depositing, maintain suspension state and reach double functions of inhibiting scale and dispersing.
Many patents related to polycarboxylate-type dirt dispersion agents in China, such as CN01123146 'low molecular weight (methyl) acrylic acid (salt) polymer and preparation method and application thereof', CN94194415.8 'unsaturated carboxylic acid copolymer and preparation method and application thereof' and the like, but with continuous development of industrial circulating cooling water treatment process, the complexity and the variability of the condition of a circulating water system are gradually deepened, and higher requirements are provided for the adaptability of water treatment agents. Especially, the frequent occurrence of material leakage leads oil substances to enter the circulating water, the indexes of COD, turbidity, oil content, suspended matters and the like of the circulating water are high, the common corrosion and scale inhibitor is difficult to play the normal effect, only the using amount of the corrosion and scale inhibitor can be increased, or frequent pollution discharge and replacement are carried out, the expense of circulating water treatment is greatly increased, and the repeatability of the circulating water treatment is also increased. In addition, most of the scale inhibition and dispersion agents which are disclosed and applied contain phosphorus, and the scale inhibition and dispersion agents can provide rich nutrition for bacteria and algae in water when entering a circulating water system, are easy to decompose, can increase the difficulty of sterilization and algae removal of the circulating water system, and influence the stable operation of the circulating water system.
Disclosure of Invention
In order to solve the problems, the invention provides a phosphorus-free copolymer scale inhibition and dispersion agent, which has better calcium carbonate scale inhibition performance, calcium phosphate scale inhibition performance, zinc salt stabilization performance, dispersion performance, surface activity and stripping performance in a water body with higher oil content, and particularly has better scale inhibition and dispersion effects under the guarantee of excellent surface activity when indexes such as COD (chemical oxygen demand), turbidity, oil content, suspended matters and the like of circulating water are higher and a common corrosion and scale inhibitor is difficult to play normal roles in a circulating water system with oil substance leakage, wherein the scale inhibition and dispersion effect of the phosphorus-free copolymer scale inhibition and dispersion agent exceeds that of the existing common scale inhibition and dispersion agent.
A preparation method of a phosphorus-free copolymer scale inhibition and dispersion agent comprises the following steps:
1) preparing a reagent:
dissolving unsaturated carboxylic acid and an inorganic reducing agent in an organic solution to form a reagent I; dissolving an inorganic oxidant in an organic solution to form a reagent II; dissolving unsaturated fatty acid and unsaturated sulfonic acid in an organic solution to form a reagent III;
2) polymerisation reaction
Adding a reagent II and a reagent III into a reagent I at the temperature of 45-65 ℃, heating until the solvent boils, and carrying out polymerization reaction on the reagent I, the reagent II and the reagent III at the boiling point temperature of the organic solvent for 1-5 h; wherein in the polymerization reaction, the addition amount of reactants is as follows:
5-15 wt% of unsaturated fatty acid;
15-25 wt% of unsaturated sulfonic acid;
60-80 wt% of unsaturated carboxylic acid;
the adding amount of sodium pyrosulfite is 8-14% of the total mass of unsaturated fatty acid, unsaturated sulfonic acid and unsaturated carboxylic acid;
the adding amount of the ammonium persulfate is 8-14% of the total mass of the unsaturated fatty acid, the unsaturated sulfonic acid and the unsaturated carboxylic acid
3) And cooling the product to obtain the phosphorus-free copolymer scale inhibition and dispersion agent.
The carbon number of the unsaturated fatty acid is 16-24; the carbon number of the unsaturated sulfonic acid is between 3 and 8; the number of carbon atoms of the unsaturated carboxylic acid is between 3 and 8.
The unsaturated fatty acid is at least one of oleic acid, linoleic acid, linolenic acid and arachidonic acid.
The unsaturated sulfonic acid is at least one selected from allyl sulfonic acid, styrene sulfonic acid and 2-acrylamide-2-methyl propane sulfonic acid.
The unsaturated carboxylic acid is at least one selected from acrylic acid, maleic acid and itaconic acid.
The organic solvent is alcohol or ketone with a boiling point of 70-90 ℃.
The alcohol is ethanol or isopropanol, and the ketone is butanone.
And the total adding time of the reagent II and the reagent III is controlled to be 1-3 h.
The inorganic reducing agent pyrosulfite or sulfite is preferably sodium pyrosulfite, potassium pyrosulfite, sodium sulfite or potassium sulfite.
The inorganic oxidant is persulfate, preferably ammonium persulfate, sodium persulfate or potassium persulfate.
The organic solvents in the reagent I, the reagent II and the reagent III are the same.
The copolymer scale inhibition and dispersion agent has a molecular weight range of 4000-12000, and the following functional groups in a molecular structure: -COOH, -SO3H. Carbon-carbon double bonds and long carbon chains;
the scale inhibition and dispersion agent comprises the following monomers in percentage by weight:
5-15 wt% of unsaturated fatty acid with 16-24 carbon atoms;
15-25 wt% of unsaturated sulfonic acid with 3-8 carbon atoms;
60-80 wt% of unsaturated carboxylic acid with 3-8 carbon atoms.
The application of the non-phosphorus copolymer scale inhibition and dispersion agent in a water body with higher oil content is characterized in that the dosage of the scale inhibition and dispersion agent is 6-30 mg/L calculated according to the effective concentration, and the performances of calcium carbonate scale inhibition, calcium phosphate scale inhibition, zinc salt stabilization and iron stabilization are higher than those of the conventional common scale inhibition and dispersion agent sold in the market.
Acrylic acid is the simplest unsaturated carboxylic acid, consisting of one vinyl group and one carboxyl group. The maleic acid is maleic acid, and has a double bond and two carboxyl groups in the molecule. The itaconic acid is known as methylene succinic acid and itaconic acid, and the molecule contains two active carboxyl groups and a double bond, and the double bond and the carboxyl group are in a conjugated relationship, so that the itaconic acid is very active in property. The unsaturated carboxylic acid is easy to perform combined reaction, addition reaction, functional group reaction and ester exchange reaction with a monomer with double bonds and carboxyl functional groups, is used for preparing polycyclic and heterocyclic compounds, can also be polymerized with other monomers with different numbers to perform various addition reactions, esterification reactions and polymerization reactions, and is an important raw material in the chemical synthesis industry. The molecules of the allyl sulfonic acid, the styrene sulfonic acid and the 2-acrylamide-2-methylpropanesulfonic acid all have unsaturated bonds and sulfonic acid groups, so that the allyl sulfonic acid, the styrene sulfonic acid and the 2-acrylamide-2-methylpropanesulfonic acid have good complexation, adsorption, biological activity, surface activity, hydrolytic stability and thermal stability, and are suitable for being used as comonomers. Unsaturated fatty acids are fatty acids whose carbon chain is not completely saturated with hydrogen atoms, i.e. contains one or more carbon-carbon double or triple bonds. Unsaturated fatty acid radicals are divided into monounsaturated fatty acids and polyunsaturated fatty acids according to the difference of the number of double bonds, wherein the monounsaturated fatty acids are oleic acid, and contain one double bond and one carboxyl; the polyunsaturated fatty acid is linoleic acid, which contains two double bonds and one carboxyl; linolenic acid, which contains three double bonds, one carboxyl group and arachidonic acid, four double bonds, one carboxyl group, etc. Isopropyl alcohol is also called dimethyl methanol or 2-propanol and is an isomer of n-propanol. Colorless and transparent liquid with an odor similar to the mixture of ethanol and acetone. Is dissolved in water, alcohol, ether, benzene, chloroform and other organic solvents and is an important chemical product and raw material. The boiling point of isopropanol at a pressure of 101.3kPa is 82.4 ℃. Unsaturated carboxylic acid, unsaturated sulfonic acid and unsaturated fatty acid all contain unsaturated bonds in the molecule, which makes the copolymerization reaction easy to occur. And because the molecular structure of the polymerized product contains a plurality of functional groups and long carbon chains, the performance of the polymerized product is diversified. The sulfonic group with strong polarity can improve the tolerance of calcium, has obvious scale inhibition effect on calcium phosphate, zinc scale and the like in water, and can improve the dispersibility of the copolymer. The long carbon chain with oleophylic effect can lead the polymer to have better calcium carbonate scale resistance, calcium phosphate scale resistance, zinc salt stability and dispersibility, and simultaneously have certain surface activity and stripping performance, and particularly in water with higher oil content, the scale inhibition effect is better than that of the common scale inhibition and dispersion agent. The copolymer scale inhibition and dispersion agent has the advantages of simple preparation method, low cost, small dosage, good scale inhibition and dispersion effect, no phosphorus, environmental protection, and high economic and social benefits, and can be widely used in industrial circulating cooling water systems.
In the prior art, a plurality of methods and products are related to preparation of polycarboxylate scale inhibition dispersants, most of the methods and products are polymerization reaction in aqueous solution, and most of monomers participating in polymerization are micromolecule unsaturated carboxylic acids with 3-10 carbon atoms. The invention uses the organic boiling point reflux polymerization technology to polymerize the insoluble macromolecular unsaturated fatty acid with the good water solubility micromolecular unsaturated carboxylic acid and unsaturated sulfonic acid, the method can lead the product to have a plurality of functional groups and long carbon chains at the same time, and the product has good calcium carbonate scale resistance, calcium phosphate scale resistance, zinc salt stability and dispersibility, and also has certain surface activity and stripping performance, especially in the water with high oil content, the scale inhibition effect is better than that of the common scale inhibition and dispersion agent. The copolymer scale inhibition and dispersion agent has the advantages of simple preparation method, low cost, small dosage, good scale inhibition and dispersion effect, no phosphorus, environmental protection, and high economic and social benefits, and can be widely used in industrial circulating cooling water systems.
Detailed Description
The following examples will help illustrate the invention without limiting its scope.
The evaluation method for the properties of the copolymer was as follows:
taking test raw water for resisting calcium carbonate scale, adding 30mg/L diesel oil, co-dissolving the raw water and the Ca in the raw water by using ultrasonic waves2+、HCO3 -Make up to 800mg/L (as CaCO)3Metering), adding 20mg/L (by effective concentration) copolymer scale inhibition and dispersion agent, keeping the temperature in a constant-temperature water bath at 80 +/-1 ℃ for 10h, cooling, sampling and analyzing the residual Ca in the water2+And simultaneously making blank samples, and calculating the scale inhibition rate.
The scale inhibition rate calculation formula is as follows: scale inhibition rate = (C-C)0)/(C1-C0)×100%
C measured Ca2+Concentration of (2)
C0Ca of blank sample2+Concentration of (2)
C1Ca in raw water2+Concentration of (2)
Taking test raw water for preventing calcium phosphate scale, adding 30mg/L diesel oil, co-dissolving with ultrasonic wave, and adding Ca in the raw water2+、HCO3 -Make up to 600mg/L (as CaCO)3Meter), PO4 3-Make up to 5mg/L (in PO)4Metering) forming test water, adding 12mg/L (by effective concentration) of copolymer scale inhibition and dispersion agent, and adding the copolymer scale inhibition and dispersion agent to 80 ±)Keeping the temperature in a constant-temperature water bath at 1 ℃ for 10 hours, sampling and analyzing the residual positive phosphorus content in the water after cooling, simultaneously making a blank sample, and calculating the scale inhibition rate.
The scale inhibition rate calculation formula is as follows: scale inhibition rate = (C-C)0)/(C1-C0)×100%
C, actually measuring the content of the positive phosphorus
C0The positive phosphorus content of the blank
C1The content of phosphorus in raw water
Taking test raw water for zinc scale resistance, adding 30mg/L diesel oil, dissolving with ultrasonic wave, and adding Ca in the raw water2+、HCO3 -Make up to 600mg/L (as CaCO)3Meter), Zn2+Supplementing 5mg/L (calculated by Zn) to form test water, adding 12mg/L (calculated by effective concentration) copolymer scale inhibition and dispersion agent, preserving heat for 10 hours in a constant-temperature water bath at 80 +/-1 ℃, sampling and analyzing the content of residual zinc ions in the water after cooling, simultaneously preparing a blank sample, and calculating the scale inhibition rate.
The scale inhibition rate calculation formula is as follows: scale inhibition rate = (C-C)0)/(C1-C0)×100%
C, actually measuring the content of zinc ions
C0The zinc ion content of the blank
C1The zinc ion content in the raw water
Taking test raw water for iron scale inhibition performance, adding 30mg/L diesel oil, dissolving the raw water and the diesel oil together by ultrasonic waves, and adding Ca in the raw water2+、HCO3 -Make up to 600mg/L (as CaCO)3Calculated), the total iron is supplemented to 5mg/L (calculated by Fe) to form test water, 12mg/L (calculated by effective concentration) of copolymer scale inhibition dispersant is added, the temperature is kept for 10 hours in a constant-temperature water bath at 80 +/-1 ℃, a sample is taken after cooling to analyze the content of the residual iron ions in the water, meanwhile, a blank sample is made, and the scale inhibition rate is calculated.
Scale inhibition rate calculation formulaComprises the following steps: scale inhibition rate = (C-C)0)/(C1-C0)×100%
C, actually measuring the total iron content
C0Total iron content of blank
C1 Total iron content in raw Water
The effective content measuring method is to weigh 1.0000g of copolymer scale inhibiting dispersant on a ten-thousandth balance into an evaporation pan with constant weight at 105 +/-5 ℃, and then transfer the evaporation pan into a drying oven with 105 +/-5 ℃ to dry to constant weight.
The calculation formula of the effective content is as follows: effective content = (W)2-W1)×100/W0 %
W0: mass of copolymer dirt dispersion agent, g
W1: weight of evaporating dish and residue, g
W2: weight of clean evaporating dish, g
Effective concentration calculation method effective concentration = commodity concentration × effective content.
Analytical method Ca2+The concentration determination method refers to Ca in GB 6905.3-862+A method for measuring the concentration; PO (PO)4 3-The concentration determination method refers to PO in ISO6878/1 of determination of phosphorus in water by molybdate spectrophotometry4 3-A method for measuring the concentration; zn2+The concentration determination method refers to Zn in Zhongshimei cooling water analysis and test method Q/SH 3155, S08.004-20062+A method for measuring the concentration; the total iron determination method refers to a determination method of total iron concentration in Zhongshimei cooling water analysis and test method Q/SH 3155, S08.005-2006.
The quality of the test raw water is shown in Table 1.
TABLE 1 test Water quality
| Name (R) | Ca2+ | Total alkalinity | Cl- | SO4 2- | pH | Phosphorus (IV) | Zn2+ | Total iron | SiO2 |
| Regenerated water | 284 | 247 | 208 | 270 | 8.13 | 0.39 | 0.14 | 0.52 | 69 |
Note: pH valueNone unit, the rest units are mg/L, Ca2+Total alkalinity and total hardness are all as CaCO3In terms of positive phosphorus, PO4In terms of Zn2+The total iron, calculated as Zn and Fe, is as follows.
The following examples
Example 1
Weighing 70g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of oleic acid and 20g of allylsulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add a mixed solution of ammonium persulfate solution and oleic acid and allyl sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 2
Weighing 73g of maleic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 5g of linoleic acid and 22g of styrene sulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add a mixed solution of ammonium persulfate solution and linoleic acid and styrene sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 3
Weighing 67g of maleic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 15g of linoleic acid and 18g of styrene sulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add a mixed solution of ammonium persulfate solution and linoleic acid and styrene sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 4
Weighing 60g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 15g of linolenic acid and 25g of allylsulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and beginning to drop a mixed solution of ammonium persulfate solution, linolenic acid and allylsulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 5
Weighing 66g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 12g of linolenic acid and 22g of allylsulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and beginning to drop a mixed solution of ammonium persulfate solution, linolenic acid and allylsulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 6
Weighing 74g of maleic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 8g of linolenic acid and 18g of styrene sulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and beginning to drop ammonium persulfate solution and mixed solution of linolenic acid and styrene sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 7
Weighing 80g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 5g of linolenic acid and 15g of allylsulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and beginning to drop a mixed solution of ammonium persulfate solution, linolenic acid and allylsulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 8
Weighing 72g of itaconic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 12g of linolenic acid, 16g of 2-acrylamide-2-methylpropanesulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant pressure funnel II; heating to raise the temperature, and when the temperature is raised to 60 ℃, dropwise adding a mixed solution of an ammonium persulfate solution and linolenic acid and 2-acrylamide-2-methylpropanesulfonic acid; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 9
Weighing 68g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 24g of linolenic acid, 2-acrylamide-2-methylpropanesulfonic acid 8g, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant pressure funnel II; heating to raise the temperature, and when the temperature is raised to 60 ℃, dropwise adding a mixed solution of an ammonium persulfate solution and linolenic acid and 2-acrylamide-2-methylpropanesulfonic acid; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 10
Weighing 70g of maleic acid and 8g of sodium sulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 8g of sodium persulfate, dissolving the sodium persulfate in 40ml of isopropanol, and adding the sodium persulfate into a constant-pressure funnel I; weighing 10g of arachidonic acid and 20g of allylsulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add a mixed solution of ammonium persulfate solution and arachidonic acid and allylsulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 11
Weighing 70g of itaconic acid and 14g of potassium sulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant pressure dropping funnel and a thermometer; weighing 14g of potassium persulfate, dissolving the potassium persulfate in 40ml of isopropanol, and adding the potassium persulfate into a constant-pressure funnel I; weighing 10g of oleic acid and 20g of styrene sulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add an ammonium persulfate solution and a mixed solution of oleic acid and styrene sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 12
Weighing 70g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of linoleic acid and 20g of 2-acrylamide-2-methylpropanesulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add a mixed solution of ammonium persulfate solution and linoleic acid and 2-acrylamide-2-methylpropanesulfonic acid when the temperature is raised to 45 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 13
Weighing 70g of maleic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of linolenic acid and 20g of allylsulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and beginning to drop a mixed solution of ammonium persulfate solution, linolenic acid and allylsulfonic acid when the temperature is raised to 65 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 14
Weighing 70g of itaconic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of arachidonic acid and 20g of styrene sulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add an ammonium persulfate solution and a mixed solution of arachidonic acid and styrene sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 1 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 15
Weighing 70g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of oleic acid and 20g of 2-acrylamide-2-methylpropanesulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and when the temperature is raised to 60 ℃, dropwise adding a mixed solution of an ammonium persulfate solution and oleic acid and 2-acrylamide-2-methylpropanesulfonic acid; controlling the dropwise adding for 3 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 16
Weighing 70g of maleic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of linoleic acid and 20g of allylsulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add a mixed solution of ammonium persulfate solution and linoleic acid and allyl sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 1h at the boiling point of the isopropanol; cooling to obtain the product.
Example 17
Weighing 70g of itaconic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of linolenic acid and 20g of styrene sulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and beginning to drop ammonium persulfate solution and mixed solution of linolenic acid and styrene sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 5h at the boiling point of the isopropanol; cooling to obtain the product.
Example 18
Weighing 70g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 5g of oleic acid, 5g of arachidonic acid and 20g of 2-acrylamide-2-methylpropanesulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and when the temperature is raised to 60 ℃, dropwise adding a mixed solution of an ammonium persulfate solution, oleic acid, arachidonic acid and 2-acrylamide-2-methylpropanesulfonic acid; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 19
Weighing 35g of acrylic acid, 35g of maleic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of oleic acid and 20g of 2-acrylamide-2-methylpropanesulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and when the temperature is raised to 60 ℃, dropwise adding a mixed solution of an ammonium persulfate solution and oleic acid and 2-acrylamide-2-methylpropanesulfonic acid; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 20
Weighing 70g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of arachidonic acid, 10g of 2-acrylamide-2-methylpropanesulfonic acid and 10g of allylsulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and beginning to drop a mixed solution of ammonium persulfate solution, arachidonic acid, 2-acrylamide-2-methylpropanesulfonic acid and allylsulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 21
Weighing 70g of itaconic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 3g of oleic acid, 3g of linolenic acid, 4g of linoleic acid and 20g of allylsulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and when the temperature is raised to 60 ℃, dropwise adding a mixed solution of ammonium persulfate solution, oleic acid, linolenic acid, linoleic acid and allyl sulfonic acid; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 22
Weighing 25g of acrylic acid, 25g of maleic acid, 20g of itaconic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of oleic acid and 20g of styrene sulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add an ammonium persulfate solution and a mixed solution of oleic acid and styrene sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 23
Weighing 70g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of isopropanol, stirring to dissolve the isopropanol, and adding the isopropanol into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of isopropanol, and adding into a constant-pressure funnel I; weighing 10g of linoleic acid, 7g of allylsulfonic acid, 7g of styrene sulfonic acid and 6g of 2-acrylamide-2-methylpropanesulfonic acid, dissolving in 50ml of isopropanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and beginning to drop a mixed solution of ammonium persulfate solution, linoleic acid, allyl sulfonic acid, styrene sulfonic acid and 2-acrylamide-2-methylpropanesulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the isopropanol boils, and polymerizing for 3h at the boiling point of the isopropanol; cooling to obtain the product.
Example 24
Weighing 70g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of ethanol, stirring to dissolve the ethanol, and adding the mixture into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of ethanol, and adding into a constant-pressure funnel I; weighing 10g of oleic acid and 20g of allylsulfonic acid, dissolving in 50ml of ethanol, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add a mixed solution of ammonium persulfate solution and oleic acid and allyl sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the ethanol boils, and polymerizing for 3h at the boiling point of the ethanol; cooling to obtain the product.
Example 25
Weighing 70g of acrylic acid and 11g of sodium metabisulfite, weighing 110ml of butanone, stirring to dissolve the butanone, and adding the mixture into a four-neck flask provided with a stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermometer; weighing 11g of ammonium persulfate, dissolving in 40ml of butanone, and adding into a constant-pressure funnel I; weighing 10g of oleic acid and 20g of allylsulfonic acid, dissolving in 50ml of butanone, uniformly mixing, and adding into a constant-pressure funnel II; heating to raise the temperature, and starting to dropwise add a mixed solution of ammonium persulfate solution and oleic acid and allyl sulfonic acid when the temperature is raised to 60 ℃; controlling the dropwise adding for 2 h; after the dropwise addition, heating until the butanone is boiled, and polymerizing for 3h at the boiling point of the butanone; cooling to obtain the product.
Comparative example 1
Acrylic acid/hydroxypropyl acrylate copolymer (available from Tai and Water treatment Co., Ltd., Shandong, under the designation T225.
Comparative example 2
Acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer available from Hangzhou Tuo science and technology Inc. under the designation lov 166.
The scale inhibition performance in test water of examples and comparative examples is shown in table 2.
TABLE 2 Scale inhibition Performance of examples and comparative examples
The above examples and comparative examples demonstrate that the copolymer scale inhibiting and dispersing agent of the present invention has excellent CaCO inhibition3Scale, Ca3(PO4)2The scale, zinc salt and iron salt are stabilized, and the scale inhibition and dispersion effect is better than that of a common scale inhibition and dispersion agent in a water body with higher oil content because the scale, zinc salt and iron salt are stabilized.
Claims (8)
1. A preparation method of a phosphorus-free copolymer scale inhibition and dispersion agent comprises the following steps:
1) preparing a reagent:
dissolving unsaturated carboxylic acid and an inorganic reducing agent in an organic solvent to form a reagent I; dissolving an inorganic oxidant in an organic solvent to form a reagent II; dissolving unsaturated fatty acid and unsaturated sulfonic acid in an organic solvent to form a reagent III;
2) polymerisation reaction
Adding a reagent II and a reagent III into a reagent I at the temperature of 45-65 ℃, heating until the solvent boils, and carrying out polymerization reaction on the reagent I, the reagent II and the reagent III at the boiling point temperature of the organic solvent for 1-5 h; wherein,
in the polymerization reaction, the addition amount of reactants is as follows:
5-15 wt% of unsaturated fatty acid;
15-25 wt% of unsaturated sulfonic acid;
60-80 wt% of unsaturated carboxylic acid;
the addition amount of the inorganic reducing agent is 8-14% of the total mass of the unsaturated fatty acid, the unsaturated sulfonic acid and the unsaturated carboxylic acid;
the addition amount of the inorganic oxidant is 8-14% of the total mass of the unsaturated fatty acid, the unsaturated sulfonic acid and the unsaturated carboxylic acid;
3) cooling the product to obtain the phosphorus-free copolymer scale inhibition and dispersion agent;
the carbon number of the unsaturated fatty acid is 16-24; the carbon number of the unsaturated sulfonic acid is between 3 and 8; the carbon number of the unsaturated carboxylic acid is between 3 and 8;
the copolymer scale inhibition and dispersion agent has a molecular weight range of 4000-12000, and a molecular structure containing-COOH and-SO3H. Carbon-carbon double bonds and long carbon chains;
the scale inhibition and dispersion agent comprises the following monomers in percentage by weight:
5-15 wt% of unsaturated fatty acid with 16-24 carbon atoms;
15-25 wt% of unsaturated sulfonic acid with 3-8 carbon atoms;
60-80 wt% of unsaturated carboxylic acid with 3-8 carbon atoms.
2. The method for preparing the phosphorus-free copolymer scale inhibiting and dispersing agent of claim 1, wherein the unsaturated fatty acid is at least one of oleic acid, linoleic acid, linolenic acid and arachidonic acid; the unsaturated sulfonic acid is selected from at least one of allyl sulfonic acid, styrene sulfonic acid and 2-acrylamide-2-methylpropanesulfonic acid; the unsaturated carboxylic acid is at least one selected from acrylic acid, maleic acid and itaconic acid.
3. The preparation method of the phosphorus-free copolymer scale inhibiting and dispersing agent of claim 1, wherein the organic solvent is alcohol or ketone with a boiling point of 70-90 ℃.
4. The method for preparing the phosphorus-free copolymer scale inhibiting and dispersing agent of claim 3, wherein the alcohol is ethanol or isopropanol; the ketone is butanone.
5. The preparation method of the phosphorus-free copolymer scale inhibiting and dispersing agent of claim 1, wherein the total adding time of the reagent II and the reagent III is controlled to be 1-3 h.
6. The method for preparing the phosphorus-free copolymer scale inhibiting and dispersing agent of claim 1, wherein the inorganic reducing agent is pyrosulfite or sulfite.
7. The method for preparing the phosphorus-free copolymer scale inhibiting and dispersing agent of claim 1, wherein the inorganic oxidant is persulfate.
8. The method for preparing the phosphorus-free copolymer dirt dispersion agent of claim 1, wherein the organic solvent in the reagent I, the reagent II and the reagent III is the same.
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| CN107512783A (en) * | 2016-06-17 | 2017-12-26 | 中国石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water |
| CN107601683A (en) * | 2016-07-12 | 2018-01-19 | 中国石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water |
| CN107686174A (en) * | 2016-08-05 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of composite scale-inhibiting corrosion inhibitor and its application and the processing method of recirculated cooling water |
| CN108726733A (en) * | 2018-07-13 | 2018-11-02 | 苏州新工环境工程技术有限公司 | Treatment of Phosphorus Containing Waste Water system and its processing method |
| CN113149862B (en) * | 2020-01-07 | 2022-11-04 | 中国石油天然气股份有限公司 | Scale inhibition and dispersion agent for acrylonitrile device and evaluation method thereof |
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