CN116531953B - Scale inhibitor for membrane and preparation method and application thereof - Google Patents
Scale inhibitor for membrane and preparation method and application thereof Download PDFInfo
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- CN116531953B CN116531953B CN202310807684.5A CN202310807684A CN116531953B CN 116531953 B CN116531953 B CN 116531953B CN 202310807684 A CN202310807684 A CN 202310807684A CN 116531953 B CN116531953 B CN 116531953B
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- scale inhibitor
- acid
- scale
- carboxylic acid
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- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 102
- 239000012528 membrane Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 239000004793 Polystyrene Substances 0.000 claims abstract description 23
- 229920002223 polystyrene Polymers 0.000 claims abstract description 23
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 23
- TZBXHAADXXYJPG-UHFFFAOYSA-N N1=CC=CC=C1.C(CC)S(=O)(=O)OO Chemical compound N1=CC=CC=C1.C(CC)S(=O)(=O)OO TZBXHAADXXYJPG-UHFFFAOYSA-N 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002077 nanosphere Substances 0.000 claims abstract description 5
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims description 68
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 21
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 8
- 229920001444 polymaleic acid Polymers 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 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 5
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 3
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 3
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 53
- 238000005260 corrosion Methods 0.000 abstract description 26
- 230000007797 corrosion Effects 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 26
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 28
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 26
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 7
- 229910001424 calcium ion Inorganic materials 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000001506 calcium phosphate Substances 0.000 description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 description 6
- 235000011010 calcium phosphates Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 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 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000010962 carbon steel Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229930003944 flavone Natural products 0.000 description 4
- 150000002212 flavone derivatives Chemical class 0.000 description 4
- 235000011949 flavones Nutrition 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000003204 osmotic effect Effects 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000009285 membrane fouling Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000003436 Schotten-Baumann reaction Methods 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- IICHYVITRCPMBX-UHFFFAOYSA-N c1cc[nH+]cc1.CCC(O)S([O-])(=O)=O Chemical compound c1cc[nH+]cc1.CCC(O)S([O-])(=O)=O IICHYVITRCPMBX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000668 effect on calcium Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/08—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/167—Use of scale inhibitors
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a scale inhibitor for a membrane, a preparation method and application thereof, and relates to the technical field of water treatment chemicals. The scale inhibitor for the film at least comprises organic phosphonic acid and carboxylic acid polymer; the carboxylic acid polymer comprises carboxylic acid nanosphere polymer, and is obtained by grafting acrylic acid and modified monomers on the surface of a polystyrene core; the modified monomer is a chemical bonding product of methacryloyl chloride and pyridinium hydroxy propane sulfonate. The scale inhibitor prepared by the invention is compounded among the component compounds, plays a synergistic effect, and has a better scale inhibition effect; the corrosion inhibition capability is greatly improved, and a multi-effect of one agent is shown; meanwhile, the scale inhibition performance of the prepared scale inhibitor is longer and more effective, and the stable operation of a reverse osmosis membrane system can be better maintained.
Description
Technical Field
The invention belongs to the technical field of water treatment chemicals, and particularly relates to a scale inhibitor for a membrane, a preparation method and application thereof.
Background
Membrane separation technology has found wide application in the water treatment industry, where a large amount of impurities can be removed from water by membrane separation. For example, inorganic matters, metal ions, organic matters, colloid, even bacteria, viruses and the like, is a novel technology with high efficiency, low consumption and no pollution. The reverse osmosis membrane separation technology has the advantages of no phase change, componentization, simple flow, convenient operation, small occupied area, low investment, low power consumption and the like, and has wide application space in industrial water treatment. Membrane fouling is an important factor affecting the operating efficiency of the permeation system and the useful life of the membrane. In the process of treatment of the osmotic water, the osmotic membrane is used for a long time, a large amount of dirt is deposited, so that the membrane is blocked, the osmotic effect is reduced, and the reverse osmosis membrane is replaced in a short time when the osmotic effect is severe. Research and discussion on the cause of membrane fouling have been conducted, and membrane fouling can be classified into inorganic scale and organic scale pollution. The scale forms can be divided into particle scale and colloid scale or microorganism scale, the particle scale is solved by flocculating settling and filtering by adopting a flocculating agent, the microorganism scale is solved by adding a bactericide, and the inorganic scale is solved by adopting a scale inhibitor. The scale inhibitor with good performance can inhibit the formation of scale, prolong the service life of the permeable membrane, and reduce the operation cost of the permeable system.
The conventional corrosion and scale inhibitor generally consists of organic phosphine, copolymer, corrosion inhibitor and the like, and although the conventional medicament design means rarely relate to reverse osmosis inhibition mechanism research, so the selectivity of the corrosion and scale inhibitor for a reverse osmosis system is extremely low, and a reverse osmosis membrane has the characteristics of small pore diameter and easy fouling and blockage, so that a corrosion and scale inhibitor formula with uniqueness and proprietary needs to be selected. The method leads the current domestic reverse osmosis membrane chemicals to almost depend on import, no mature reverse osmosis special corrosion and scale inhibitor is sold in the market, and the development of the domestic reverse osmosis membrane corrosion and scale inhibitor is an urgent market demand.
Disclosure of Invention
The invention aims to provide a scale inhibitor for a film, a preparation method and application thereof, wherein the scale inhibitor is compounded among all the component compounds to play a synergistic effect and has a better scale inhibition effect; the corrosion inhibition capability is greatly improved, and a multi-effect of one agent is shown; meanwhile, the scale inhibition performance of the prepared scale inhibitor is longer and more effective, and the stable operation of a reverse osmosis membrane system can be better maintained.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a scale inhibitor for a film, comprising at least an organic phosphonic acid, and a carboxylic acid polymer;
The carboxylic acid polymer comprises carboxylic acid nanosphere polymer, and is obtained by grafting acrylic acid and modified monomers on the surface of a polystyrene core; the modified monomer is a chemical bonding product of methacryloyl chloride and pyridinium hydroxy propane sulfonate. The novel carboxylic acid nanometer spherical polymer with a core-shell structure, regular morphology, uniform particle size and excellent dispersibility is successfully prepared through emulsion polymerization and photo-emulsion polymerization, and has more excellent scale inhibition capability. The reason for this may be that the chemical bonding product of methacryloyl chloride and pyridinium hydroxy propane sulfonate is used as a modification monomer to chemically modify the surface of the nanosphere, more active functional groups are introduced on the surface of the nanosphere, and the effect of electrostatic action and the like is beneficial to complexing metal ions such as calcium ions, magnesium ions and aluminum ions, and the metal ions are uniformly dispersed in water, so that the solubility of insoluble salts such as calcium carbonate and calcium sulfate in water is effectively increased; and the crystallization process of inorganic salt is effectively blocked by utilizing the space blocking effect of the chain structure, so that the generation and precipitation of the scale are inhibited, and a better scale inhibition effect is achieved; meanwhile, active functional groups on the surface of the metal can be adsorbed on the surface of the metal in a chemical adsorption mode and the like to form a protective adsorption film, so that corrosion of the surface of the metal is slowed down, and the corrosion inhibition capability of the scale inhibitor is enhanced. The synergistic effect is exerted by the compounding of the components of the scale inhibitor, the chelating property, the solubilizing capability, the lattice distortion and the electronegativity are fully exerted, and the scale inhibitor has better scale inhibition effect on various insoluble matters in water; and one agent has multiple effects, and can solve the problems of corrosion and scaling at the same time.
In a specific embodiment, the average particle size of the carboxylic acid polymer is 100 to 150nm.
In a specific embodiment, a method for preparing a carboxylic acid-based polymer comprises:
(1) Preparing a modified monomer by using pyridinium hydroxy propane sulfonate and methacryloyl chloride as raw materials through a Schotten-Baumann reaction;
(2) Preparing a polystyrene core coated with a photoinitiator by emulsion polymerization;
(3) Acrylic acid monomer and modifying monomer are grafted on the polystyrene core by ultraviolet light initiated free radical.
Further specifically, the preparation method of the carboxylic acid polymer comprises the following steps:
(1) Adding pyridinium hydroxy propane sulfonate into acetone for dissolution, adding a catalyst pyridine under the ice bath condition, then slowly dropwise adding an acetone solution of methacryloyl chloride by using a constant pressure dropping funnel, removing the ice bath after the dropwise adding is finished, continuing to react for 10-12 hours, and keeping out of light in the whole reaction process; removing the organic solvent by rotary evaporation, and purifying by silica gel column chromatography to obtain a modified monomer;
(2) Taking emulsifier SDS and initiator KPS, ultrasonically dissolving the emulsifier SDS and initiator KPS in deionized water, adding styrene, stirring, charging nitrogen for deoxidization, and then heating to 78-84 ℃ for reaction for 1-2 hours under the protection of nitrogen; then cooling to 68-72 ℃, slowly dropwise adding an acetone solution of a photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate, keeping stable and continuing to react for 0.5-1.5 h after the dropwise adding is finished, carrying out suction filtration, and dialyzing with deionized water of a dialysis bag to obtain polystyrene nuclear emulsion with the solid content of 2-4%;
(3) And adding acrylic acid monomer and modified monomer into the polystyrene nuclear emulsion, adding deionized water, and carrying out ultraviolet irradiation reaction for 2-3 hours under the protection of nitrogen, dialyzing by a dialysis bag, steaming in a rotary manner, and freeze-drying to obtain the carboxylic acid polymer.
In a specific embodiment, in the step (1), the solid-to-liquid ratio of pyridinium hydroxy propane sulfonate to acetone is 0.15-0.25 g/1 mL; the mass ratio of the catalyst pyridine to the pyridinium hydroxy propane sulfonate is 0.3-0.4:1; the concentration of the acetone solution of the methacryloyl chloride is 0.2-0.3 g/mL; the molar ratio of the pyridinium hydroxy propane sulfonate to the methacryloyl chloride is 1:1-1.1.
In a specific embodiment, in the step (2), the mass ratio of the emulsifier SDS to the initiator KPS is 1:2.5-3.5; the solid-to-liquid ratio of the emulsifier SDS to the deionized water is 0.5-1 mg:1mL; the mass ratio of the styrene to the emulsifier SDS is 45-55:1; the concentration of the acetone solution of the photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate is 8-12wt%; the addition amount of the photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate is 1-3wt% of styrene.
In the specific embodiment, in the step (3), the mass ratio of the polystyrene core emulsion to the acrylic monomer is 1:0.5-0.8; the molar ratio of the acrylic acid monomer to the modifying monomer is 1:0.3-0.5.
In a specific embodiment, the organic phosphonic acid is selected from one of diethylenetriamine pentamethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid, 2-phosphonate butane-1, 2, 4-tricarboxylic acid, hydroxyethylidene diphosphonic acid.
In specific embodiments, the scale inhibitor for a film further comprises an acrylic copolymer, polyepoxysuccinic acid, polymaleic acid.
In a specific embodiment, the scale inhibitor for the film comprises, by weight, 5-10 parts of organic phosphonic acid, 3-5 parts of acrylic acid copolymer, 3-5 parts of polyepoxysuccinic acid, 2-4 parts of carboxylic acid polymer, 2-5 parts of polymaleic acid, 1-3 parts of tetrasodium ethylenediamine tetraacetate, 0.2-1.5 parts of isothiazolinone, 0.5-1 part of sodium hydroxide and 60-80 parts of water.
Preferably, the polyepoxysuccinic acid is replaced by a modified polyepoxysuccinic acid, the modifier used in the modified polyepoxysuccinic acid comprising thiourea dioxide.
More preferably, the modifier further comprises 3-amino-5-mercapto-1, 2, 4-triazole. According to the invention, 3-amino-5-mercapto-1, 2, 4-triazole is adopted to modify polyepoxysuccinic acid, so that the scale inhibition performance of the modified polyepoxysuccinic acid is obviously improved, the inhibition effect of the modified polyepoxysuccinic acid on crystal nucleus generation is effectively improved, the nucleation induction period of calcium carbonate crystals is prolonged, and further the formation of calcium carbonate scale is effectively prevented; the anti-scaling agent is applied to the preparation process of the anti-scaling agent for the film, and is compounded in a synergistic way with other components, so that the anti-scaling capability of the anti-scaling agent can be further enhanced, the corrosion inhibition effect of the anti-scaling agent is improved, and the corrosion rates of carbon steel, flavone and stainless steel materials are further inhibited; meanwhile, the service life of the scale inhibitor can be effectively prolonged, and the long-time stable operation of the reverse osmosis membrane system device can be maintained. The reason for this may be that 3-amino-5-mercapto-1, 2, 4-triazole and thiourea dioxide are used to modify polyepoxysuccinic acid, and O, N and other atoms are introduced to form stable complexes with Ca 2+、Mg2+、Ba2+ and other metal ions in aqueous solution, so that the concentration of Ca 2+ plasma in the solution is effectively reduced, the possibility of separating out calcium carbonate, calcium sulfate and calcium phosphate scale is reduced, and an electric double layer structure is formed on the surface of calcium carbonate microcrystal through physical/chemical adsorption, so that electrostatic repulsion is generated between crystals, larger crystals are hindered from being formed, more excellent scale inhibition performance is shown, large scale scaling of salts on reverse osmosis membranes can be effectively controlled, further the cleaning frequency of reverse osmosis systems is obviously reduced, and normal operation is maintained.
The invention also discloses a preparation method of the modified polyepoxysuccinic acid, which comprises the following steps:
And (3) adding water into polyepoxysuccinic acid for dissolution, regulating the pH value to be neutral, adding thiourea dioxide and 3-amino-5-mercapto-1, 2, 4-triazole under the condition of 80-90 ℃ oil bath, reacting for 1-2 hours, decompressing, distilling, dialyzing in a dialysis bag, performing rotary evaporation and vacuum drying to obtain the modified polyepoxysuccinic acid.
In a specific embodiment, the solid-to-liquid ratio of polyepoxysuccinic acid to water is 0.02-0.03 g:1mL; the mass ratio of the polyepoxysuccinic acid to the thiourea dioxide is 1:0.4-0.6; the molar ratio of thiourea dioxide to 3-amino-5-mercapto-1, 2, 4-triazole is 1:0.2-0.4.
In a specific embodiment, the molecular weight of the modified polyepoxysuccinic acid is 500-700.
The invention also discloses a preparation method of the scale inhibitor for the membrane, which comprises the following steps: and uniformly mixing the raw materials according to the weight part ratio to obtain the scale inhibitor for the film.
The invention also discloses application of the scale inhibitor in water treatment based on a reverse osmosis membrane.
In particular embodiments, the water treatment comprises salt water treatment, reclaimed water treatment, or sea water treatment.
It is still another object of the present invention to provide a method for inhibiting the fouling of a reverse osmosis membrane by adding the above-described membrane scale inhibitor to a reverse osmosis system.
Compared with the prior art, the invention has the following beneficial effects:
The novel carboxylic acid nanometer spherical polymer is successfully prepared by emulsion polymerization and photo-emulsion polymerization, shows more excellent scale inhibition capability, can obviously enhance the scale inhibition effect of the scale inhibitor on calcium sulfate scale and calcium phosphate scale, has more excellent corrosion inhibition effect, and effectively prolongs the service life of the scale inhibitor when being applied to the preparation process of the scale inhibitor for the membrane. In addition, the 3-amino-5-mercapto-1, 2, 4-triazole is adopted to modify the polyepoxysuccinic acid to prepare the modified polyepoxysuccinic acid, the scale inhibition performance of the modified polyepoxysuccinic acid is obviously improved, the blocking effect of the modified polyepoxysuccinic acid on crystal nucleus generation is effectively improved, and the formation of calcium carbonate scale is effectively prevented; the anti-scaling agent is applied to the preparation process of the anti-scaling agent for the film, and is compounded in a synergistic way with other components, so that the anti-scaling capability of the anti-scaling agent can be further enhanced, the corrosion inhibition effect of the anti-scaling agent is improved, and the corrosion rates of carbon steel, flavone and stainless steel materials are further inhibited; meanwhile, the service life of the scale inhibitor can be effectively prolonged. The scale inhibitor for the membrane provided by the invention plays a synergistic effect through the compounding of the components, and the chelating property, the solubilizing capability, the lattice distortion and the electronegativity of the scale inhibitor are fully exerted, so that the scale inhibitor has a better scale inhibition effect on various insoluble matters in water; and one agent has multiple effects, and can solve the problems of corrosion and scaling at the same time.
Therefore, the invention provides the scale inhibitor for the membrane, the preparation method and the application thereof, wherein the scale inhibitor is compounded among the component compounds, plays a synergistic effect and has a better scale inhibition effect; the corrosion inhibition capability is greatly improved, and a multi-effect of one agent is shown; meanwhile, the scale inhibition performance of the prepared scale inhibitor is longer and more effective, and the stable operation of a reverse osmosis membrane system can be better maintained.
Drawings
FIG. 1 shows the results of an IR spectrum test of a polystyrene core and a carboxylic acid polymer in example 1 of the present invention;
FIG. 2 shows the results of infrared spectrum testing of modified polyepoxysuccinic acid and polyepoxysuccinic acid of example 5 of the present invention;
FIG. 3 shows TEM test results of carboxylic acid-based polymer of example 1 of the present invention;
FIG. 4 shows the scale inhibition ability test results of the modified polyepoxysuccinic acid in the test example of the present invention;
FIG. 5 shows the results of the scale inhibition ability test of the scale inhibitor for a film in the test example of the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments:
The photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate used in the embodiment of the invention is prepared according to the prior art, and is synthesized by taking 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and methacryloyl chloride as raw materials through Schotten-Baumann reaction.
Example 1:
A scale inhibitor for a film comprising: 8 parts of diethylenetriamine pentamethylene phosphonic acid, 4 parts of acrylic acid copolymer, 4 parts of polyepoxysuccinic acid, 3 parts of carboxylic acid polymer, 3 parts of polymaleic acid, 2 parts of tetra sodium ethylene diamine tetraacetate, 1 part of isothiazolinone, 0.8 part of sodium hydroxide and 70 parts of water.
The preparation method of the scale inhibitor for the film comprises the following steps: and uniformly mixing the raw materials according to the parts by weight to obtain the scale inhibitor for the film.
Preparation of carboxylic acid polymer:
(1) Adding pyridinium hydroxy propane sulfonate into acetone for dissolution (solid-to-liquid ratio is 0.21g:1 mL), and adding a catalyst pyridine under ice bath condition, wherein the mass ratio of the catalyst pyridine to the pyridinium hydroxy propane sulfonate is 0.36:1; then, an acetone solution (concentration of 0.25 g/mL) of methacryloyl chloride was slowly added dropwise with a constant pressure dropping funnel, wherein the molar ratio of pyridinium hydroxy propane sulfonate to methacryloyl chloride was 1:1.05; removing ice bath after dripping, continuing to react for 12 hours, and keeping out light in the whole reaction process; the organic solvent was then removed by rotary evaporation and purified by column chromatography on silica gel (eluent chloroform: acetone=5:1, v/v) to give the modified monomer ,1H NMR(400 MHz, Acetone-d6) δ： 8.76、8.68、8.19 (5H, Py-H),6.52、6.33(2H, C=CH2), 5.40、5.15(m, 2H, -CH2), 4.74(m, 1H, -CH), 3.79、3.48(m, 2H, -CH2), 1.97(s, 3H, -CH3);
(2) Taking emulsifier SDS and initiator KPS, wherein the mass ratio is 1:3.1, dissolving in deionized water by ultrasonic (the solid-to-liquid ratio of the emulsifier SDS to the deionized water is 0.8mg:1 mL), adding styrene (the mass ratio of the emulsifier SDS to the emulsifier SDS is 50.5:1), stirring, charging nitrogen to remove oxygen, and then heating to 80 ℃ to react for 1.5h under the protection of nitrogen; then cooling to 70 ℃, slowly dropwise adding an acetone solution (the concentration is 10.2 wt%) of the photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate, wherein the adding amount of the photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate is 2.1wt% of styrene; after the dripping is finished, keeping stable and continuing to react for 1h, carrying out suction filtration, and dialyzing with deionized water by using a dialysis bag to obtain polystyrene nuclear emulsion, wherein the solid content is 3.2%;
(3) Adding acrylic acid monomer and modified monomer into polystyrene nuclear emulsion, adding deionized water, and under the protection of nitrogen, performing ultraviolet irradiation reaction for 2.5h, dialyzing with dialysis bag, steaming, and lyophilizing to obtain carboxylic acid polymer (average particle diameter is 136 nm); in a specific experimental process, the mass ratio of the polystyrene core emulsion to the acrylic monomer is 1:0.68; the molar ratio of acrylic monomer to modifying monomer was 1:0.41.
Example 2:
a scale inhibitor for a film comprising: according to the weight parts, 5 parts of hexamethylenediamine tetramethylene phosphonic acid, 5 parts of acrylic acid copolymer, 3 parts of polyepoxysuccinic acid, 2 parts of carboxylic acid polymer, 3 parts of polymaleic acid, 1 part of ethylene diamine tetraacetic acid tetrasodium, 0.2 part of isothiazolinone, 0.5 part of sodium hydroxide and 60 parts of water.
The scale inhibitor for a film was prepared in the same manner as in example 1.
The preparation of carboxylic acid polymers differs from example 1 in that:
the mass ratio of the catalyst pyridine to the pyridinium hydroxy propane sulfonate is 0.3:1; the concentration of the acetone solution of the methacryloyl chloride is 0.2g/mL; the molar ratio of the pyridinium hydroxy propane sulfonate to the methacryloyl chloride is 1:1;
The mass ratio of the emulsifier SDS to the initiator KPS is 1:2.5; the mass ratio of the styrene to the emulsifier SDS is 48:1; the concentration of the acetone solution of the photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate is 9wt%; the addition amount of the photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate is 1.2wt% of styrene;
the mass ratio of the polystyrene core emulsion to the acrylic monomer is 1:0.5; the molar ratio of the acrylic acid monomer to the modifying monomer is 1:0.3;
The average particle diameter of the carboxylic acid polymer was 109nm.
Example 3:
a scale inhibitor for a film comprising: 10 parts of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 3 parts of acrylic acid copolymer, 4 parts of polyepoxysuccinic acid, 4 parts of carboxylic acid polymer, 2 parts of polymaleic acid, 2 parts of tetrasodium ethylenediamine tetraacetate, 0.5 part of isothiazolinone, 1 part of sodium hydroxide and 76 parts of water.
The scale inhibitor for a film was prepared in the same manner as in example 1.
The preparation of carboxylic acid polymers differs from example 1 in that:
The mass ratio of the catalyst pyridine to the pyridinium hydroxy propane sulfonate is 0.4:1; the concentration of the acetone solution of the methacryloyl chloride is 0.3g/mL; the molar ratio of the pyridinium hydroxy propane sulfonate to the methacryloyl chloride is 1:1.1;
the mass ratio of the emulsifier SDS to the initiator KPS is 1:3.5; the mass ratio of the styrene to the emulsifier SDS is 55:1; the concentration of the photoinitiator 2- (p-2-hydroxy-2-methylpropionone) -hydroxyethyl methacrylate in acetone was 11.5wt%; the addition amount of the photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate is 2.6wt% of styrene;
The mass ratio of the polystyrene core emulsion to the acrylic monomer is 1:0.8; the molar ratio of the acrylic acid monomer to the modifying monomer is 1:0.5;
the average particle size of the carboxylic acid polymer was 142nm.
Example 4:
A scale inhibitor for a film comprising: the adhesive comprises, by weight, 7 parts of hydroxyethylidene diphosphonic acid, 5 parts of an acrylic copolymer, 3 parts of polyepoxysuccinic acid, 4 parts of a carboxylic acid polymer, 3 parts of polymaleic acid, 3 parts of tetrasodium ethylenediamine tetraacetate, 0.7 part of isothiazolinone, 1 part of sodium hydroxide and 72 parts of water.
The scale inhibitor for a film was prepared in the same manner as in example 1.
The preparation of carboxylic acid polymers differs from example 1 in that:
the mass ratio of the catalyst pyridine to the pyridinium hydroxy propane sulfonate is 0.33:1; the concentration of the acetone solution of the methacryloyl chloride is 0.23g/mL; the molar ratio of the pyridinium hydroxy propane sulfonate to the methacryloyl chloride is 1:1.08;
The mass ratio of the emulsifier SDS to the initiator KPS is 1:3.3; the mass ratio of the styrene to the emulsifier SDS is 47:1; the concentration of the photoinitiator 2- (p-2-hydroxy-2-methylpropionone) -hydroxyethyl methacrylate in acetone was 9.5wt%; the addition amount of the photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate is 1.8wt% of styrene;
The mass ratio of the polystyrene core emulsion to the acrylic monomer is 1:0.61; the molar ratio of the acrylic acid monomer to the modifying monomer is 1:0.37;
The average particle size of the carboxylic acid polymer was 122nm.
Example 5:
The scale inhibitor for a film is different from example 1 in that: the modified polyepoxysuccinic acid is replaced by the same molar amount of the polyepoxysuccinic acid.
The scale inhibitor for a film was prepared in the same manner as in example 1.
The carboxylic acid polymer was prepared in the same manner as in example 1.
Preparation of modified polyepoxysuccinic acid:
Adding water into polyepoxysuccinic acid for dissolution, wherein the solid-to-liquid ratio is 0.025 g/1 mL, regulating the pH to be neutral, adding thiourea dioxide and 3-amino-5-mercapto-1, 2, 4-triazole under the oil bath condition of 86 ℃ for reaction for 1.5h, carrying out reduced pressure distillation, dialyzing by a dialysis bag, carrying out rotary evaporation and vacuum drying to obtain modified polyepoxysuccinic acid, wherein the molecular weight is 618.4; the mass ratio of the polyepoxysuccinic acid to the thiourea dioxide is 1:0.52; the molar ratio of thiourea dioxide to 3-amino-5-mercapto-1, 2, 4-triazole is 1:0.32.
Example 6:
the scale inhibitor for a film is different from example 5 in that: modified polyepoxysuccinic acid was prepared in this example.
The scale inhibitor for a film was prepared in the same manner as in example 5.
The carboxylic acid polymer was prepared in the same manner as in example 5.
The preparation of the modified polyepoxysuccinic acid differs from example 5 in that:
the 3-amino-5-mercapto-1, 2, 4-triazole is replaced by thiourea dioxide with an equal molar weight.
Example 7:
the scale inhibitor for a film is different from example 5 in that: modified polyepoxysuccinic acid was prepared in this example.
The scale inhibitor for a film was prepared in the same manner as in example 5.
The carboxylic acid polymer was prepared in the same manner as in example 5.
The preparation of the modified polyepoxysuccinic acid differs from example 5 in that:
The thiourea dioxide is replaced by an equimolar amount of 3-amino-5-mercapto-1, 2, 4-triazole.
Example 8:
the scale inhibitor for a film is different from example 5 in that: the carboxylic acid polymer was prepared in this example.
The scale inhibitor for a film was prepared in the same manner as in example 5.
The preparation of carboxylic acid polymers differs from example 5 in that: an equimolar amount of acrylic acid was used instead of the modifying monomer.
The modified polyepoxysuccinic acid was prepared as in example 5.
Example 9:
the scale inhibitor for a film is different from example 1 in that: the carboxylic acid polymer was prepared in this example.
The scale inhibitor for a film was prepared in the same manner as in example 1.
The preparation of carboxylic acid polymers differs from example 1 in that: an equimolar amount of acrylic acid was used instead of the modifying monomer.
Test example 1:
Infrared sign
The testing is carried out by adopting a potassium bromide tabletting method and utilizing a Fourier transform infrared spectrometer, and the wavelength range is 4000-500 cm -1.
The polystyrene core and carboxylic acid polymer prepared in example 1 were subjected to the above test, and the results are shown in fig. 1. From the analysis in the figure, it is seen that, in comparison with the infrared spectrum of the polystyrene core, in the infrared test result of the carboxylic acid-based polymer, a characteristic absorption peak of c=o appears near 1709cm -1 and a characteristic absorption peak of the sulfonic acid group appears near 1185cm -1、610cm-1, indicating that the carboxylic acid-based polymer in example 1 was successfully produced.
The modified polyepoxysuccinic acid prepared in example 5 and polyepoxysuccinic acid were subjected to the above test, and the results are shown in FIG. 2. From the analysis in the figure, compared with the infrared spectrum curve of the polyepoxysuccinic acid, in the infrared spectrum of the modified polyepoxysuccinic acid, a characteristic absorption peak of C=O in the amide group appears near 1664cm -1, and a characteristic absorption peak of C-N bond appears near 1270cm -1; a characteristic absorption peak of s=o bond appears near 1160cm -1, a characteristic absorption peak of C-S bond appears near 1048cm -1, indicating successful preparation of polyepoxysuccinic acid in example 5.
TEM characterization
The carboxylic acid polymer prepared in example 1 was subjected to TEM test, and the scanning voltage was 200kV, and the result is shown in FIG. 3. From the analysis of the figure, the carboxylic acid polymer prepared in example 1 exhibited a more regular sphere and exhibited good dispersibility.
Test example 2:
Determination of Scale inhibition Capacity
The scale inhibition rate is measured by a static method: the experimental test method was carried out with reference to the standard specified in GB/T16632 and the standard application guidelines for water treatment agents. Experimental test conditions: c (Ca 2+) =400 mg/L (calculated as calcium carbonate), C (HCO 3 -) =800 mg/L (calculated as calcium carbonate), experimental temperature 60 ℃ for 10h. The Ca 2+ concentration in the solution was determined using EDTA. Finally, the static scale inhibition rate is calculated according to the following formula:
Static scale inhibition = (C 2-C1）/（C2-C0) ×100%
Wherein C 0 represents the content of calcium ions in the supernatant without adding the scale inhibitor, and mg/L; c 1 represents the content of calcium ions in the supernatant added with the scale inhibitor, and mg/L; c 2 represents the content of original calcium ions in the experimental water sample, and mg/L.
The modified polyepoxysuccinic acid prepared in examples 5 to 7 was subjected to the above test with an addition concentration of 3.5mg/L, and the results are shown in FIG. 4. From the analysis of the figure, the scale inhibition rate of the modified polyepoxysuccinic acid prepared in the example 5 is obviously higher than that of the example 6 and the example 7, and is better than that of the unmodified polyepoxysuccinic acid, and the effects of the example 6 and the example 7 are better than those of the unmodified polyepoxysuccinic acid, which shows that the scale inhibition capability of the modified polyepoxysuccinic acid can be effectively improved by modifying the polyepoxysuccinic acid by thiourea dioxide and/or 3-amino-5-mercapto-1, 2, 4-triazole, and the scale inhibition performance enhancement effect of the modified polyepoxysuccinic acid is better under the condition that thiourea dioxide and 3-amino-5-mercapto-1, 2, 4-triazole exist simultaneously.
Determination of the effect of nucleation on calcium carbonate crystals
The conductivity method is adopted for testing, and the specific steps are as follows: taking two dry beakers (500 mL) A and B, respectively adding a calcium chloride solution and a sodium bicarbonate solution with the same volume, adding a sample solution to be detected into the beaker A to enable the concentration of the sample solution to be 8mg/L, and adding no sample solution into the beaker B; the conductivity in the beakers was measured after 8min at the same temperature.
The modified polyepoxysuccinic acid prepared in examples 5 to 7 was subjected to the above test with an addition concentration of 3.5mg/L, and the results are shown in Table 1:
table 1 conductivity test results
From the data analysis in table 1, the conductivity of the modified polyepoxysuccinic acid prepared in example 5 is obviously lower than that of example 6 and example 7, and lower than that of unmodified polyepoxysuccinic acid, and the effects of example 6 and example 7 are better than those of unmodified polyepoxysuccinic acid, which shows that the modification of polyepoxysuccinic acid by thiourea dioxide and/or 3-amino-5-mercapto-1, 2, 4-triazole can effectively promote the inhibition of the modified polyepoxysuccinic acid on nucleation, prolong the nucleation induction period of calcium carbonate crystals, and further effectively prevent the formation of calcium carbonate scale; and the enhancement effect of the inhibition effect of the modified polyepoxysuccinic acid on the crystal nucleus generation is better under the condition that thiourea dioxide and 3-amino-5-mercapto-1, 2, 4-triazole exist simultaneously.
Test example 3:
Determination of scale inhibition ability of scale inhibitor
1) Determination of calcium phosphate scale resistance
The test method is carried out according to the standard specified in GB/T22626, and is determined by a spectrophotometer, and the experimental principle is as follows: the orthophosphate reacts with ammonium molybdate in an acidic environment to generate phosphomolybdic acid, and the phosphomolybdic acid is reduced into phosphomolybdic blue by ascorbic acid. Experimental test conditions: c (Ca 2+) =250 mg/L (calculated as calcium carbonate), C (PO 4 3-) =5 mg/L (calculated as PO 4 3-). The scale inhibition was calculated according to the following formula:
Scale inhibition = (a 1-A0）/（A2-A0) ×100%
Wherein A 0 represents absorbance after heating without adding scale inhibitor; a 1 represents absorbance after heating after adding the scale inhibitor; a 2 represents absorbance without adding scale inhibitor and without heating.
2) Calcium sulfate scale inhibition performance determination
Experimental test conditions: c (Ca 2+) =6800 mg/L (calculated as calcium sulfate), C (SO 4 2-) =7100 mg/L (calculated as Na 2SO4). The scale inhibition was calculated according to the following formula:
Scale inhibition = (C 2-C1）/（C2-C0) ×100%
Wherein C 0 represents the content of calcium ions in the supernatant without adding the scale inhibitor, and mg/L; c 1 represents the content of calcium ions in the supernatant added with the scale inhibitor, and mg/L; c 2 represents the content of original calcium ions in the experimental water sample, and mg/L.
The scale inhibitor for films prepared in examples 1 to 9 was subjected to the above test, and the addition amount was 4mg/L, and the results are shown in FIG. 5. From the graph analysis, the scale inhibitor prepared in the example 1 has significantly higher scale inhibition rate on calcium sulfate scale and calcium phosphate scale than that in the example 9, which shows that the chemical grafting modification is carried out on the surface of polystyrene core by using pyridinium hydroxy propane sulfonate to prepare carboxylic acid polymer, and the carboxylic acid polymer can effectively enhance the scale inhibition capability of the scale inhibitor and has more excellent scale inhibition effect on calcium sulfate scale and calcium phosphate scale when applied to the scale inhibitor. The scale inhibitor prepared in example 5 has significantly higher scale inhibition rate on calcium sulfate scale and calcium phosphate scale than in example 6 and example 7, and is better than in example 1, and the effects of example 6 and example 7 are better than those of example 1, which shows that the modified polyepoxysuccinic acid prepared by modifying polyepoxysuccinic acid with thiourea dioxide and/or 3-amino-5-mercapto-1, 2, 4-triazole is used in the scale inhibitor for films, can effectively improve the scale inhibition capability of the scale inhibitor, and has better enhancement effect on the scale inhibition performance of the scale inhibitor under the condition that thiourea dioxide and 3-amino-5-mercapto-1, 2, 4-triazole exist simultaneously.
Corrosion inhibition performance measurement
The test method is carried out by referring to the method specified in GB/T18175 test of corrosion inhibition performance of Water treatment agent-rotating hanging method, and the specific test conditions are as follows: the temperature is 45 ℃, the rotation speed is 75r/min, and the experimental time is 72h.
The scale inhibitor for films prepared in examples 1 to 9 was subjected to the above test, the addition amount was 4mg/L, and the results are shown in Table 2:
TABLE 2 Corrosion inhibition test results
From the data analysis in Table 2, the corrosion rates of the carbon steel, flavone and stainless steel materials using the scale inhibitor prepared in example 1 are obviously lower than those of example 9, which shows that the chemical grafting modification is carried out on the surface of the polystyrene core by using pyridinium hydroxy propane sulfonate to prepare carboxylic acid polymers, and the carboxylic acid polymers can effectively enhance the corrosion inhibition capability of the scale inhibitor when applied to the scale inhibitor. The corrosion rates of the carbon steel, the flavone and the stainless steel prepared in the example 1 are obviously lower than those of the example 6 and the example 7 and lower than those of the example 1, and the effects of the example 6 and the example 7 are better than those of the example 1, which shows that the thiourea dioxide and/or the 3-amino-5-mercapto-1, 2, 4-triazole is adopted to modify the polyepoxysuccinic acid, so that the modified polyepoxysuccinic acid is prepared and used in the scale inhibitor for the film, the corrosion inhibition capability of the scale inhibitor can be effectively improved, and the enhancement effect on the corrosion inhibition performance of the scale inhibitor is better under the condition that the thiourea dioxide and the 3-amino-5-mercapto-1, 2, 4-triazole exist simultaneously.
Device operation stability test
The conductivity of the water quality of the water inlet of a factory in a certain area is 3440 mu s/cm, the salt content is 2108mg/L, and the alkalinity is 315mg/L (calculated by calcium carbonate). Adding 4mg/L of scale inhibitor sample, and observing and recording the stable operation time of the reverse osmosis device.
The scale inhibitor for films prepared in example 1 and examples 5 to 9 was subjected to the above test, and the results are shown in table 3:
TABLE 3 run stability test results
From the data analysis in Table 3, the scale inhibitor prepared in example 1 is used, and the reverse osmosis device stably operates and is obviously longer than that of example 9, which shows that the surface of the polystyrene core is subjected to chemical grafting modification by using pyridinium hydroxypropanesulfonate to prepare carboxylic acid polymers, and the carboxylic acid polymers are applied to the scale inhibitor, so that the service life of the scale inhibitor can be effectively prolonged. The scale inhibitor prepared in example 1 is used for stably operating a reverse osmosis device, is obviously longer than that of example 6 and example 7, is longer than that of example 1, and the effects of example 6 and example 7 are better than those of example 1, which shows that thiourea dioxide and/or 3-amino-5-mercapto-1, 2, 4-triazole are used for modifying polyepoxysuccinic acid, so that the modified polyepoxysuccinic acid is prepared, can effectively improve the service life of the scale inhibitor in the scale inhibitor for a membrane, and has better effect of enhancing the service life of the scale inhibitor in the presence of thiourea dioxide and 3-amino-5-mercapto-1, 2, 4-triazole.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A scale inhibitor for a film, comprising at least an organic phosphonic acid and a carboxylic acid polymer;
The carboxylic acid polymer comprises carboxylic acid nanosphere polymer, and is obtained by grafting acrylic acid and modified monomers on the surface of a polystyrene core; the modified monomer is a chemical bonding product of methacryloyl chloride and pyridinium hydroxy propane sulfonate;
the preparation method of the carboxylic acid polymer comprises the following steps:
(1) Adding pyridinium hydroxy propane sulfonate into acetone for dissolution, adding a catalyst pyridine under the ice bath condition, then slowly dropwise adding an acetone solution of methacryloyl chloride by using a constant pressure dropping funnel, removing the ice bath after the dropwise adding is finished, continuing to react for 10-12 hours, and keeping out of light in the whole reaction process; removing the organic solvent by rotary evaporation, and purifying by silica gel column chromatography to obtain a modified monomer;
(2) Taking emulsifier SDS and initiator KPS, ultrasonically dissolving the emulsifier SDS and initiator KPS in deionized water, adding styrene, stirring, charging nitrogen for deoxidization, and then heating to 78-84 ℃ for reaction for 1-2 hours under the protection of nitrogen; then cooling to 68-72 ℃, slowly dropwise adding an acetone solution of a photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate, keeping stable and continuing to react for 0.5-1.5 h after the dropwise adding is finished, carrying out suction filtration, and dialyzing with deionized water of a dialysis bag to obtain polystyrene nuclear emulsion with the solid content of 2-4%;
(3) Adding acrylic acid monomer and modified monomer into polystyrene nuclear emulsion, adding deionized water, and under the protection of nitrogen, performing ultraviolet irradiation reaction for 2-3 hours, dialyzing with a dialysis bag, performing rotary evaporation and freeze-drying to obtain carboxylic acid polymer;
wherein the molar ratio of the pyridinium hydroxy propane sulfonate to the methacryloyl chloride is 1:1-1.1; the addition amount of the photoinitiator 2- (p-2-hydroxy-2-methyl propiophenone) -hydroxyethyl methacrylate is 1-3wt% of styrene; the mass ratio of the polystyrene core emulsion to the acrylic monomer is 1:0.5-0.8; the molar ratio of the acrylic acid monomer to the modifying monomer is 1:0.3-0.5.
2. A scale inhibitor for a film according to claim 1, wherein: the average particle size of the carboxylic acid polymer is 100-150 nm.
3. A scale inhibitor for a film according to claim 1, wherein: the organic phosphonic acid is selected from one of diethylenetriamine pentamethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and hydroxyethylidene diphosphonic acid.
4. A scale inhibitor for a film according to claim 1, wherein: the scale inhibitor for the film further comprises an acrylic copolymer, polyepoxysuccinic acid and polymaleic acid.
5. A scale inhibitor for a film according to claim 1, wherein: the scale inhibitor for the film comprises, by weight, 5-10 parts of organic phosphonic acid, 3-5 parts of acrylic acid copolymer, 3-5 parts of polyepoxysuccinic acid, 2-4 parts of carboxylic acid polymer, 2-5 parts of polymaleic acid, 1-3 parts of tetrasodium ethylenediamine tetraacetate, 0.2-1.5 parts of isothiazolinone, 0.5-1 part of sodium hydroxide and 60-80 parts of water.
6. The scale inhibitor for a film according to claim 5, wherein: the polyepoxysuccinic acid is replaced by modified polyepoxysuccinic acid, and the modifier used by the modified polyepoxysuccinic acid comprises thiourea dioxide and/or 3-amino-5-mercapto-1, 2, 4-triazole; the molecular weight of the modified polyepoxysuccinic acid is 500-700.
7. The method for producing a scale inhibitor for a film according to claim 5, comprising: and uniformly mixing the raw materials according to the weight part ratio to obtain the scale inhibitor for the film.
8. Use of the scale inhibitor of claim 1 in reverse osmosis membrane-based water treatment.
9. The use according to claim 8, characterized in that: the water treatment includes a salt water treatment or a reclaimed water treatment.
10. A scale inhibiting method of a reverse osmosis membrane, comprising adding the scale inhibitor for a membrane according to any one of claims 1 to 6 to a reverse osmosis system.
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