CN117046315B - Mixture with scale inhibition and slime control functions and preparation method thereof - Google Patents
Mixture with scale inhibition and slime control functions and preparation method thereof Download PDFInfo
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- CN117046315B CN117046315B CN202311323645.4A CN202311323645A CN117046315B CN 117046315 B CN117046315 B CN 117046315B CN 202311323645 A CN202311323645 A CN 202311323645A CN 117046315 B CN117046315 B CN 117046315B
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- mixture
- phosphonomethyl
- sulfonic acid
- acid copolymer
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- 239000000203 mixture Substances 0.000 title claims abstract description 93
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical class OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003814 drug Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000007800 oxidant agent Substances 0.000 claims description 21
- -1 phosphoenolpyruvate sodium salt Chemical class 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 14
- OIIANXCKEGUVFK-UHFFFAOYSA-N 2-(4-prop-2-enylpiperazin-1-yl)ethanol Chemical compound OCCN1CCN(CC=C)CC1 OIIANXCKEGUVFK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- 229930029653 phosphoenolpyruvate Natural products 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 150000007942 carboxylates Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 7
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- UUIVKBHZENILKB-UHFFFAOYSA-N 2,2-dibromo-2-cyanoacetamide Chemical compound NC(=O)C(Br)(Br)C#N UUIVKBHZENILKB-UHFFFAOYSA-N 0.000 claims description 2
- NESXXUAWVHXRGX-UHFFFAOYSA-M sodium;1-carboxyethenyl hydrogen phosphate Chemical compound [Na+].OP(O)(=O)OC(=C)C([O-])=O NESXXUAWVHXRGX-UHFFFAOYSA-M 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 20
- 230000002829 reductive effect Effects 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 43
- 230000000844 anti-bacterial effect Effects 0.000 description 29
- 239000000243 solution Substances 0.000 description 29
- 150000001408 amides Chemical class 0.000 description 24
- 239000003899 bactericide agent Substances 0.000 description 22
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 17
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 16
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 16
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 229910000975 Carbon steel Inorganic materials 0.000 description 13
- 239000010962 carbon steel Substances 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- DTBNBXWJWCWCIK-UHFFFAOYSA-N phosphoenolpyruvic acid Chemical compound OC(=O)C(=C)OP(O)(O)=O DTBNBXWJWCWCIK-UHFFFAOYSA-N 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 5
- 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 description 4
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 4
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 4
- 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 239000003139 biocide Substances 0.000 description 4
- 238000009285 membrane fouling Methods 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- YKLWRYOORWTCQQ-HKUMRIAESA-N phyllanthine Chemical class C1[C@@]23OC(=O)C=C2C=C[C@H]1N1CC[C@@H](OC)C[C@@H]13 YKLWRYOORWTCQQ-HKUMRIAESA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013642 negative control Substances 0.000 description 2
- 239000013641 positive control Substances 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009423 ventilation Methods 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
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a mixture with scale inhibition and slime control and a preparation method thereof, and relates to the technical field of water treatment medicaments. The mixture includes a modified sulfonic acid copolymer; the molecular weight of the modified sulfonic acid copolymer is 7000-20000; the modified sulfonic acid copolymer comprises a unit structure of a N- (phosphonomethyl) iminodiacetic acid derivative, and the chemical structure of the N- (phosphonomethyl) iminodiacetic acid derivative is shown as a formula I:I. the mixture product provided by the invention has better scale inhibition and online mud adhesion stripping effects, so that the running period of the system is prolonged, and the shutdown cleaning frequency of the system is reduced; and the corrosion inhibition performance and the dispersing capability of the mixture are obviously improved.
Description
Technical Field
The invention belongs to the technical field of water treatment medicaments, and particularly relates to a mixture with scale inhibition and slime control and a preparation method 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 water treatment process, the reverse osmosis membrane is used for a long time, a large amount of dirt deposition can occur, the phenomenon of membrane fouling and blocking can be caused, the permeation effect is reduced, and the reverse osmosis membrane is replaced in a short time when serious. Research and discussion on the cause of membrane fouling are carried out, and membrane fouling can be generally classified into inorganic scale and organic biological slime pollution. Inorganic scale is solved by adding a scale inhibitor, and organic biological slime pollution is generally solved by reducing the content of organic matters in water entering a membrane system through strengthening pretreatment of the system and preventing microorganism breeding or stopping washing by adding a bactericide subsequently.
The scale inhibitor, bactericide and cleaning agent which are commonly used at present are respectively added to solve the problems and risks existing in the existing system. Therefore, the comprehensive treatment agent for solving the pollution of inorganic scale and organic biological slime of a reverse osmosis system is very few, and the development of an agent with both scale inhibition and slime control is an urgent need in the current market.
Disclosure of Invention
The invention aims to provide a mixture with scale inhibition and slime control and a preparation method thereof, and the mixture product has better scale inhibition and online slime stripping effects, so that the system operation period is prolonged, and the system shutdown cleaning frequency is reduced; and the corrosion inhibition performance and the dispersing capability of the mixture are obviously improved.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a modified sulfonic acid copolymer with a molecular weight of 7000-20000; the modified sulfonic acid copolymer comprises a unit structure of a N- (phosphonomethyl) iminodiacetic acid derivative, and the chemical structure of the N- (phosphonomethyl) iminodiacetic acid derivative is shown as a formula I:
I. the invention adopts the N- (phosphonomethyl) iminodiacetic acid and the 1-allyl-4- (2-hydroxyethyl) -piperazine to react to prepare the N- (phosphonomethyl) iminodiacetic acid derivative, and is used as a polymerization monomer to be compounded and polymerized with other components to obtain the modified sulfonic acid copolymer, and the mixture with scale inhibition and slime stripping performance is prepared by application, so that the scale inhibition capability of the mixture can be effectively enhanced, and the scale inhibition rate of calcium carbonate scale and calcium sulfate scale is obviously improved; and the mixture shows better iron dispersion performance, and the corrosion inhibition performance is obviously enhanced.
In particular embodiments, the polymerized monomers of the modified sulfonic acid copolymer further include AA, AMPS, and sodium phosphoenolpyruvate.
The invention also discloses a preparation method of the modified sulfonic acid copolymer, which comprises the following steps: mixing acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, phosphoenolpyruvate and N- (phosphonomethyl) iminodiacetic acid derivatives, and polymerizing in the presence of ammonium persulfate to obtain the modified sulfonic acid copolymer.
Further specifically, the preparation method of the modified sulfonic acid copolymer comprises the following steps:
and adding isopropanol and distilled water into acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, phosphoenolpyruvate and N- (phosphonomethyl) iminodiacetic acid derivatives, uniformly stirring, heating to 80-90 ℃, slowly adding ammonium persulfate, finishing the addition within 1.5-2.5 h, performing constant temperature reaction for 1-3 h, cooling to room temperature, regulating pH to neutral, adding ethanol for precipitation and purification, performing vacuum filtration, and performing vacuum drying to obtain the modified sulfonic acid copolymer.
In a specific embodiment, the molar ratio of the acrylic acid to the 2-acrylamido-2-methylpropanesulfonic acid to the phosphoenolpyruvate to the N- (phosphonomethyl) iminodiacetic acid derivative is 1:0.6-0.8:0.8-1:0.4-0.6; the addition amount of ammonium persulfate is 12-15wt% of the total amount of the polymerization monomers; the addition amount of the isopropanol is 8-12wt% of the total amount of the polymerization monomers; the dosage ratio of the acrylic acid to the distilled water is 0.1-0.3 g:1mL.
The molecular weight of the modified sulfonic acid copolymer is 8000 to 20000.
Further, the N- (phosphonomethyl) iminodiacetic acid derivative comprises a product of a mixed reaction of N- (phosphonomethyl) iminodiacetic acid and 1-allyl-4- (2-hydroxyethyl) -piperazine.
The invention further provides a preparation method of the phyllanthine derivative, which comprises the following steps: and mixing N- (phosphonomethyl) iminodiacetic acid and 1-allyl-4- (2-hydroxyethyl) -piperazine, and carrying out esterification reaction in the presence of DCC and DMAP to obtain the N- (phosphonomethyl) iminodiacetic acid derivative.
Further specifically, the preparation method of the phyllanthine derivative comprises the following steps:
adding DMF into N- (phosphonomethyl) iminodiacetic acid, adding DCC and DMAP, activating for 0.5-1.5 h, adding 1-allyl-4- (2-hydroxyethyl) -piperazine, reacting for 5-8 h at room temperature, distilling under reduced pressure, diluting with diethyl ether, filtering, washing with 1-1.5M hydrochloric acid solution and 1-1.5M sodium hydroxide solution respectively, and purifying by column chromatography to obtain N- (phosphonomethyl) iminodiacetic acid derivatives.
In a specific embodiment, the solid-to-liquid ratio of N- (phosphonomethyl) iminodiacetic acid to DMF is 0.05-0.15 g:1mL; the molar ratio of DCC to N- (phosphonomethyl) iminodiacetic acid is 2.3-2.6:1; the molar ratio of DMAP to DCC is 0.25-0.35:1; the molar ratio of the 1-allyl-4- (2-hydroxyethyl) -piperazine to the N- (phosphonomethyl) iminodiacetic acid is 2-2.4:1.
A mixture, comprising: the modified sulfonic acid copolymer described above.
In particular embodiments, the mixture further comprises a carboxylate oxidizer, a non-oxidizer, a stabilizer, a solubilizing agent, and water. Furthermore, the mixture contains a non-oxidant and an oxidant, so that the biological slime can be effectively killed and controlled, and the bacteria are prevented from generating drug resistance.
In a specific embodiment, the carboxylate oxidizer is a halogen organic binder, preferably a chloramine compound.
In particular embodiments, the non-oxidizing agent comprises one or both of isothiazolinone or dibromocyanoacetamide.
In particular embodiments, the stabilizer comprises one or both of ethylene glycol and propylene glycol.
In particular embodiments, the solubilizing agent comprises sodium p-toluenesulfonate.
A mixture, comprising: the modified sulfonic acid copolymer comprises, by weight, 10-20 parts of a sulfonic acid copolymer or a modified sulfonic acid copolymer, 1-10 parts of a carboxylate oxidant, 0.5-5 parts of a non-oxidant, 0.5-1 part of a stabilizer, 0.5-1 part of a solubilizer and 60-88 parts of water.
In a specific embodiment, the sulfonic acid copolymer comprises AA, AMPS and phosphoenolpyruvate sodium polymerization products, and the molecular weight is 7000-10000.
When the water treatment agent is used on site, the water treatment agent is added into a pipeline inlet of a water system, and the concentration of the water treatment agent is 1-50 mg/L.
Further preferably, in the above mixture, an amide-based bactericide is used instead of a partial amount of a non-oxidizing agent; wherein the amide type bactericide comprises the product of the reaction of propyl methacrylate and sodium polysulfide reactant and then the reaction of the propyl methacrylate and sodium polysulfide reactant and 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridine-2-amine. The amide bactericide is prepared by reacting propyl methacrylate and sodium polysulfide reactant with 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridine-2-amine, has stronger bioactivity and obviously improves the antibacterial capacity. The anti-scale agent is applied to preparing a mixture with anti-scale and slime stripping properties, and is compounded with other components, so that the anti-scale property of the mixture can be further enhanced, the dispersing capability of ferric oxide is improved, and the corrosion inhibition capability of the mixture is further improved. Meanwhile, the mud stripping capability of the mixture can be effectively improved.
The preparation method of the amide bactericide further comprises the following steps:
s1: taking Na 2 S·9H 2 Mixing O and sulfur powder, adding water, and reacting to obtain sodium polysulfide solution;
s2: adding propyl methacrylate into sodium polysulfide solution, and sequentially adding sodium bicarbonate and Na 2 SO 3 Reacting under the condition to obtain an intermediate O;
s3: the intermediate O is taken to be mixed with 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridine-2-amine, and the amide bactericide is prepared by reaction under the condition of triethylamine.
Specifically, the preparation method of the amide bactericide comprises the following steps:
s1: taking Na 2 S·9H 2 Adding water into O and sulfur powder, heating to boiling and keeping for 10-20 min, carrying out suction filtration to obtain sodium polysulfide solution, and cooling for later use;
s2: adding 8-12wt% sodium bicarbonate solution into propyl methacrylate, cooling to 0-5 ℃, slowly adding sodium polysulfide solution, and finishing the addition within 1-2 hours; then heating to room temperature for reaction for 5-8 h, standing for layering to remove a water layer, and then adding Na with the concentration of 1-1.4M 2 SO 3 Continuously reacting the solution at 45-55 ℃ for 2-4, standing for layering to remove a water layer, washing an oil layer with water, extracting the separated water layer with ethyl acetate to obtain upper liquid, mixing the upper liquid with the oil layer, and distilling under reduced pressure to obtain an intermediate O;
s3: mixing 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridine-2-amine and triethylamine, cooling to 0-5 ℃, slowly adding an intermediate O, dropwise adding for 1-2 h, heating to room temperature for reaction for 24h, suction filtering, placing in air for a week, drying, and recrystallizing with absolute ethyl alcohol to obtain the amide bactericide.
In a specific embodiment, in step S1, na 2 S·9H 2 The mol ratio of O to sulfur powder is 1:3.8-4.2; na (Na) 2 S·9H 2 The solid-to-liquid ratio of O to water is 0.1-0.2 g:1mL.
In a specific embodiment, in the step S2, the dosage ratio of the propyl methacrylate to the sodium bicarbonate solution is 1-2 mmol:1mL; the molar ratio of sodium polysulfide to propyl methacrylate is 0.4-0.5:1; na (Na) 2 SO 3 The volume ratio of the solution to the sodium bicarbonate solution is 0.2-0.4:1.
In a specific embodiment, in step S3, the dosage ratio of 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridin-2-amine and triethylamine is 0.1 to 0.2mol:1mL; the mol ratio of the intermediate O to the 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridine-2-amine is 0.3-0.4:1.
The preparation method of the mixture comprises the following steps: the components are taken according to the weight parts and evenly mixed to obtain the mixture with the functions of scale inhibition and mud adhesion control.
The invention also discloses the application of the phyllanthine derivative in preparing a medicament with scale inhibition and slime control.
The invention also discloses application of the mixture in preparing a medicament with scale inhibition and slime control functions.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a mixture, and provides a feasible technical application product aiming at the technical problem of risk of inorganic scale and organic biological slime pollution in the daily operation process of a reverse osmosis system. The invention adopts the N- (phosphonomethyl) iminodiacetic acid and the 1-allyl-4- (2-hydroxyethyl) -piperazine to react to prepare the N- (phosphonomethyl) iminodiacetic acid derivative, and the N- (phosphonomethyl) iminodiacetic acid derivative is used as a polymerization monomer to be compounded and polymerized with other components to obtain the modified sulfonic acid copolymer, and the mixture with the scale inhibition and slime stripping performances is prepared by application, so that the scale inhibition capability of the mixture can be effectively enhanced, better iron dispersion performance is shown, and the corrosion inhibition performance is obviously enhanced. In addition, the amide bactericide is prepared by reacting propyl methacrylate and sodium polysulfide reactant with 5-bromo- [1,2,4] trithiazole [1,5-A ] pyridine-2-amine, has stronger antibacterial capability, is applied to preparing a mixture with scale inhibition and slime stripping performance, is compounded with other components, can further enhance the scale inhibition performance of the mixture, improves the dispersing capability of ferric oxide, and further improves the corrosion inhibition capability and slime stripping capability of the mixture. The product of the invention has the functions of scale inhibition and on-line mud sticking and stripping, reduces the adding cost, simplifies the on-site adding process, prolongs the running period of the system, reduces the shutdown cleaning frequency of the system, and has the advantages of convenient use, cost reduction, synergy and the like.
Therefore, the invention provides the mixture with the functions of scale inhibition and slime control and the preparation method thereof, and the mixture product has better functions of scale inhibition and online slime stripping, so that the running period of the system is prolonged, and the shutdown cleaning frequency of the system is reduced; and the corrosion inhibition performance and the dispersing capability of the mixture are obviously improved.
Drawings
FIG. 1 is an infrared test result of a sulfonic acid copolymer and a modified sulfonic acid copolymer prepared in the examples of the present invention;
FIG. 2 shows the results of an infrared test of an amide type bactericide prepared in the example of the present invention;
FIG. 3 shows the results of the iron oxide dispersion test in the test example of the present invention;
FIG. 4 shows the results of corrosion inhibition test in the test example of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following describes in detail various embodiments of the present invention with reference to the embodiments. However, those of ordinary skill in the art will understand that in various embodiments of the present invention, numerous technical details have been set forth in order to provide a better understanding of the present application. However, the technical solutions claimed in the present application can be implemented without these technical details and with various changes and modifications based on the following embodiments.
Example 1:
a mixture, comprising: 15 parts of modified sulfonic acid copolymer, 6 parts of carboxylate oxidant chloramine, 3 parts of non-oxidant isothiazolinone, 3.5 parts of stabilizer propylene glycol, 0.8 part of solubilizer sodium p-toluenesulfonate and 72 parts of water.
Preparation of modified sulfonic acid copolymer:
taking acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, phosphoenolpyruvate sodium salt and N- (phosphonomethyl) iminodiacetic acid derivatives (the molar ratio of the acrylic acid to the 2-acrylamido-2-methylpropanesulfonic acid, the phosphoenolpyruvate sodium salt to the N- (phosphonomethyl) iminodiacetic acid derivatives is 1:0.7:0.9:0.5), adding isopropanol (the addition amount is 10wt% of the total amount of the polymerized monomers) and distilled water (the addition amount of the acrylic acid to the distilled water is 0.2g:1 mL), heating to 88 ℃ after stirring uniformly, slowly adding ammonium persulfate (the addition amount is 13.5wt% of the total amount of the polymerized monomers), finishing the addition within 2h, then carrying out constant-temperature reaction for 2h, cooling to room temperature, regulating the pH to be neutral, adding ethanol for precipitation and purification, carrying out vacuum filtration, and carrying out vacuum drying to obtain the modified sulfonic acid copolymer with the molecular weight of 13600.
Preparation of the bis-glyphosate derivative:
adding DMF (solid-to-liquid ratio of 0.1g:1 mL) into N- (phosphonomethyl) iminodiacetic acid, adding DCC (mol ratio of 2.5: 1) and DMAP (mol ratio of 0.3: 1) into N- (phosphonomethyl) iminodiacetic acid, activating for 1h, adding 1-allyl-4- (2-hydroxyethyl) -piperazine (mol ratio of 2.2: 1) into N- (phosphonomethyl) iminodiacetic acid, reacting for 6.5h at room temperature, distilling under reduced pressure, diluting with diethyl ether, filtering, washing with 1M hydrochloric acid solution and 1M concentration sodium hydroxide solution respectively, purifying by column chromatography (eluent is diethyl ether/petroleum ether=1:2.5) to obtain N- (phosphonomethyl) iminodiacetic acid derivative, 1 H NMR（400 MHz，CDCl 3 ）：δ：5.91、5.20、5.14（6H，CH=CH 2 ），4.33（4H，O-CH 2 ），3.35、2.76（6H，-CH 2 ），3.00、2.95（8H，-CH 2 ），2.25~2.35（16H，-CH 2 ）。
the preparation method of the mixture comprises the following steps: the components are taken according to the weight parts and evenly mixed to obtain the mixture with the functions of scale inhibition and mud adhesion control.
Example 2:
a mixture different from example 1: 17 parts of modified sulfonic acid copolymer, 4 parts of carboxylate oxidant chloramine, 1.5 parts of non-oxidant isothiazolinone, 2.5 parts of stabilizer glycol, 0.6 part of solubilizer sodium p-toluenesulfonate and 65 parts of water.
The preparation of the modified sulfonic acid copolymer was different from that of example 1: the molar ratio of the acrylic acid to the 2-acrylamide-2-methylpropanesulfonic acid to the phosphoenolpyruvate to the N- (phosphonomethyl) iminodiacetic acid derivative is 1:0.65:0.82:0.57; the addition amount of ammonium persulfate is 12.8wt% of the total amount of the polymerization monomers; the amount of isopropanol added was 8.6wt% based on the total amount of the polymerized monomers.
The preparation of the bis-glyphosate derivative was the same as in example 1.
The preparation method of the above mixture was the same as in example 1.
Example 3:
a mixture different from example 1: 12 parts of modified sulfonic acid copolymer, 8 parts of carboxylate oxidant chloramine, 4 parts of non-oxidant isothiazolinone, 1 part of stabilizer propylene glycol, 0.5 part of solubilizer sodium p-toluenesulfonate and 60 parts of water.
The preparation of the modified sulfonic acid copolymer was different from that of example 1: the molar ratio of the acrylic acid to the 2-acrylamide-2-methylpropanesulfonic acid to the phosphoenolpyruvate to the N- (phosphonomethyl) iminodiacetic acid derivative is 1:0.75:0.95:0.4; the addition amount of ammonium persulfate is 14.3wt% of the total amount of the polymerization monomers; the amount of isopropanol added was 11.2wt% based on the total amount of the polymerized monomers.
The preparation of the bis-glyphosate derivative was the same as in example 1.
The preparation method of the above mixture was the same as in example 1.
Example 4:
a mixture different from example 1: the modified sulfonic acid copolymer comprises, by weight, 10 parts of modified sulfonic acid copolymer, 3 parts of carboxylate oxidant chloramine, 5 parts of non-oxidant isothiazolinone, 1 part of stabilizer propylene glycol, 1 part of solubilizer sodium p-toluenesulfonate and 85 parts of water.
The preparation of the modified sulfonic acid copolymer was different from that of example 1: the molar ratio of the acrylic acid to the 2-acrylamide-2-methylpropanesulfonic acid to the phosphoenolpyruvate to the N- (phosphonomethyl) iminodiacetic acid derivative is 1:0.8:0.8:0.6; the addition amount of ammonium persulfate is 13.6wt% of the total amount of the polymerization monomers; the amount of isopropanol added was 11.2wt% based on the total amount of the polymerized monomers.
The preparation of the bis-glyphosate derivative was the same as in example 1.
The preparation method of the above mixture was the same as in example 1.
Example 5:
a mixture different from example 1: the amide-based bactericide prepared in this example was used instead of 1/2 molar amount of isothiazolinone.
The modified sulfonic acid copolymer was prepared in the same manner as in example 1.
The preparation of the bis-glyphosate derivative was the same as in example 1.
The preparation method of the above mixture was the same as in example 1.
Preparation of amide bactericides:
s1: taking Na 2 S·9H 2 Adding water (Na) into O and sulfur powder (molar ratio of 1:4.1) 2 S·9H 2 The solid-to-liquid ratio of O to water was 0.14g:1 mL), heating to boiling and maintaining for 15min, filtering to obtain sodium polysulfide solution, and cooling for standby;
s2: adding 10wt% sodium bicarbonate solution into propyl methacrylate (the dosage ratio is 1.5mmol:1 mL), cooling to 3 ℃, slowly adding sodium polysulfide (the molar ratio of sodium polysulfide to propyl methacrylate is 0.44:1), and finishing the addition within 1.5 h; then the mixture is warmed to room temperature for reaction for 7 hours, and is stood for delamination to remove the water layer, then Na with the concentration of 1M is added 2 SO 3 Continuously reacting the solution (the volume ratio of the solution to the sodium bicarbonate solution is 0.3:1) for 3 hours at 50 ℃, standing for layering, removing a water layer, washing an oil layer with water, extracting the separated water layer with ethyl acetate to obtain an upper layer liquid, mixing the upper layer liquid with the oil layer, and distilling under reduced pressure to obtain an intermediate O;
s3: mixing 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridine-2-amine and triethylamine (the dosage ratio is 0.15mol:1 mL), cooling to 3 ℃, slowly adding an intermediate O (the molar ratio of the intermediate O to the 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridine-2-amine is 0.36:1), dropwise adding in 1.5h, heating to room temperature for reaction for 24h, suction filtering, placing in air for one week, drying, and recrystallizing with absolute ethyl alcohol to obtain the amide bactericide.
Example 6:
a mixture different from example 5: an equimolar amount of sulfonic acid copolymer was used instead of the modified sulfonic acid copolymer.
Preparation of sulfonic acid copolymer was different from the preparation of modified sulfonic acid copolymer in example 5: an equimolar amount of acrylic acid is used to replace the N- (phosphonomethyl) iminodiacetic acid derivative.
Example 7:
a mixture different from example 1: an equimolar amount of sulfonic acid copolymer was used instead of the modified sulfonic acid copolymer.
Preparation of sulfonic acid copolymer was different from the preparation of modified sulfonic acid copolymer in example 1: adopting equimolar amount of acrylic acid to replace the N- (phosphonomethyl) iminodiacetic acid derivative; the molecular weight of the sulfonic acid copolymer was 8740.
Example 8:
a mixture different from example 5: the amide type bactericide was prepared in this example.
The modified sulfonic acid copolymer was prepared as in example 5.
The preparation of the bis-glyphosate derivative was the same as in example 5.
The amide-based bactericide was prepared differently from example 5: an equimolar amount of gamma-phenoxyethoxypropylamine was used in place of 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridin-2-amine.
Example 9:
a mixture different from example 6: the amide type bactericide was prepared in this example.
The amide type bactericide was prepared differently from example 6: an equimolar amount of gamma-phenoxyethoxypropylamine was used in place of 5-bromo- [1,2,4] trithiazol [1,5-A ] pyridin-2-amine.
Test example 1:
infrared sign
The testing is carried out by adopting a Fourier infrared spectrometer, and the testing range is 500-4000 cm -1 。
The above test was conducted on the modified sulfonic acid copolymer prepared in example 1 and the sulfonic acid copolymer prepared in example 6, and the results are shown in fig. 1. From the analysis of the figures, it can be seen thatThe infrared test results of the sulfonic acid copolymer prepared in example 6 showed that the infrared spectrum of the modified sulfonic acid copolymer prepared in example 1 was at 1230cm -1 、1045cm -1 The intensity of the absorption peak of the nearby p= O, P-O bond was significantly enhanced, and the above results indicate that the modified sulfonic acid copolymer in example 6 was successfully produced.
The amide-based bactericide prepared in example 5 was subjected to the above test, and the results are shown in fig. 2. As can be seen from the analysis of the figure, 1670cm -1 、1550cm -1 Characteristic absorption peak of amide group existing nearby, 1581cm -1 、1480cm -1 、1410cm -1 The characteristic absorption peak of pyridine ring exists nearby, and the result shows that the amide bactericide is successfully prepared in the example 5.
Test example 2:
calcium carbonate scale inhibition performance test
The test method is carried out according to the standard specified in GB/T16632-2008 "method for measuring scale inhibition Performance of Water treatment agent" by calcium carbonate deposition method.
Calcium sulfate scale inhibition performance test
The testing method is carried out by adopting a static scale inhibition method, and specifically comprises the following steps: caCl is taken 2 50mL of standard solution, 25mL of borax standard solution and Na 2 SO 4 25mL of standard solution was mixed, a mixture test sample (15 mg/L added) was added, and the volume was set so that Ca was 2+ Concentration is 7100mg/L, SO 4 2- The concentration is 6800mg/L. Then placing the mixture in a water bath with constant temperature of 70 ℃ for 6 hours, cooling and filtering the mixture, taking 50mL of filtrate, adding 50mL of distilled water, 5mL of potassium hydroxide solution and 0.4g of carboxylic acid indicator, titrating the mixture with EDTA standard solution until the solution turns from purple red to light blue, stopping titration, and setting a blank control experiment. The calcium sulfate scale inhibition efficiency was calculated according to the following formula:
calcium sulfate scale inhibition efficiency/% = (V) 2 -V 0 )/ (V 1 -V 0 )×100%
Wherein V is 0 To avoid adding test sample, the volume of EDTA solution consumed by blank group when placed at normal temperature; v (V) 1 To add the test sample, the blank group consumed the volume of EDTA solution when heated for 6 hours; v (V) 2 To addThe test sample was entered and the experimental group consumed the volume of EDTA solution at 6h of heating.
The above-described test was performed on the mixtures provided in examples 1 to 9, and the results are shown in table 1:
TABLE 1 scale inhibition test results
| Sample of | Calcium carbonate scale inhibition/% | Calcium sulfate scale inhibition efficiency/% |
| Example 1 | 96.1 | 91.5 |
| Example 2 | 95.8 | 91.1 |
| Example 3 | 96.0 | 91.4 |
| Example 4 | 96.2 | 91.7 |
| Example 5 | 98.9 | 94.8 |
| Example 6 | 95.9 | 90.0 |
| Example 7 | 92.3 | 86.7 |
| Example 8 | 97.5 | 92.9 |
| Example 9 | 94.1 | 88.0 |
From the data analysis in table 1, the calcium carbonate scale inhibition rate and the calcium sulfate scale inhibition rate of the mixture provided in example 1 are obviously higher than those of example 7, which shows that the preparation of the N- (phosphonomethyl) iminodiacetic acid derivative by adopting the reaction of 1-allyl-4- (2-hydroxyethyl) -piperazine and N- (phosphonomethyl) iminodiacetic acid, and the compound polymerization of other components to obtain the modified sulfonic acid copolymer can further enhance the scale inhibition performance of the mixture, and the calcium carbonate scale inhibition performance and the calcium sulfate scale inhibition performance of the mixture can be obviously improved when the modified sulfonic acid copolymer is applied to the mixture. Example 5 is significantly better than example 1 and example 8, and example 6 is significantly better than example 7 and example 9, indicating that the use of propyl methacrylate in combination with sodium polysulfide reactant followed by reaction with 5-bromo- [1,2,4] trithiazol [1,5-a ] pyridin-2-amine to prepare an amide biocide, which can be used in a mixture preparation process, effectively improves the calcium carbonate scale and calcium sulfate scale inhibition capabilities of the mixture.
Test example 3:
determination of the dispersed iron oxide Properties
Preparing a calcium chloride solution and a ferrous sulfate solution, mixing the calcium chloride solution and the ferrous sulfate solution, ensuring that the concentration of calcium ions in the system is 150mg/L and the concentration of ferrous ions in the system is 10mg/L, then regulating the pH value to 9.0 by using a borax solution, adding a test sample (the concentration is 15 mg/L), stirring for 15min, and placing in a constant-temperature water bath at 50 ℃ for 5h; a blank control group was also set. The supernatant was taken to determine the light transmittance, and the lower the light transmittance, the better the ferric oxide dispersing ability was.
The above-described test was performed on the mixtures provided in examples 1 to 9, and the results are shown in fig. 3. From the analysis of the figure, the light transmittance of the mixture provided in example 1 is obviously lower than that of example 7, which shows that the preparation of the N- (phosphonomethyl) iminodiacetic acid derivative by adopting the reaction of 1-allyl-4- (2-hydroxyethyl) -piperazine and N- (phosphonomethyl) iminodiacetic acid, and the compound polymerization of other components to obtain the modified sulfonic acid copolymer can further enhance the capability of the mixture to disperse ferric oxide when being applied to the mixture. Example 5 is significantly better than examples 1 and 8 and example 6 is significantly better than examples 7 and 9, indicating that the use of propyl methacrylate in combination with sodium polysulfide reactant followed by reaction with 5-bromo- [1,2,4] trithiazol [1,5-a ] pyridin-2-amine to prepare an amide biocide can be used in a mixture preparation process to effectively enhance the ability of the mixture to disperse iron oxide.
Test example 4:
corrosion inhibition performance measurement
The test method is carried out with reference to the standard specified in GB/T8175-2000. The specific method is a rotary hanging piece corrosion method:
(1) Wiping a carbon steel hanging piece with filter paper, then sequentially placing the carbon steel hanging piece in acetone and absolute ethyl alcohol for soaking for 5min, then wiping the carbon steel surface with absorbent cotton, then wiping the carbon steel surface with the filter paper, placing the carbon steel hanging piece in a drying oven for drying for 4h, cooling to room temperature, and weighing the mass of each carbon steel piece;
(2) Preparing water for experiments according to the following table 2, placing the water into a beaker, and then adding a sample to be tested (the concentration is 15 mg/L); a blank control experiment was also set. Then placing the carbon steel hanging piece in a constant-temperature water bath at 45 ℃, placing the carbon steel hanging piece in an experimental group and a control group, wherein the distance between the upper end of the hanging piece and the liquid level of the beaker is more than 2cm, and meanwhile, the distance between the bottom of the hanging piece and the ventilation point is more than 3cm. Then starting a motor, wherein the rotation speed of the hanging piece is 90r/min, and timing at the same time;
table 2 Water quality index for experiment
| Index (I) | pH | Total hardness (mg/L) | Total alkalinity (mg/L) | Conductivity (mus/cm) | Ca2+（mg/L） |
| Numerical value | 7.85 | 200 | 180 | 890 | 160.30 |
(3) An appropriate amount of distilled water was added to the beaker every 3 hours during the test so that the liquid level was near the scale mark. Stopping the experiment after 72 hours, taking out the hanging piece, cleaning with water, removing rust by a brush, immersing in pickling solution for 30s, washing with distilled water, putting the carbon steel hanging piece into sodium hydroxide solution for 30s, taking out distilled water for cleaning, and wiping filter paper to dryness; finally, soaking the mixture in absolute ethyl alcohol for 3min, taking out the mixture, sucking the mixture by using filter paper, drying the mixture for 4h, and weighing the mixture by using an analytical balance.
The corrosion rate and corrosion inhibition rate were calculated according to the following formulas:
corrosion rate (mm/a) =87600 (m-m 0)/(sρt)
Corrosion inhibition rate/% = (blank test group corrosion rate a-hanging sheet group corrosion rate b)/blank test group corrosion rate a×100%
Wherein m represents the mass of the carbon steel hanging piece before the experiment, and g; m0 represents carbon steel after experimentThe mass of the hanging piece, g; s represents the area of the carbon steel hanging piece, cm 2 The method comprises the steps of carrying out a first treatment on the surface of the ρ represents density of carbon steel hanger, g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the t represents the experimental time, h.
The above-described test was performed on the mixtures provided in examples 1 to 9, and the results are shown in fig. 4. From the analysis of the figure, the corrosion inhibition rate of the mixture provided in the example 1 is obviously higher than that of the mixture provided in the example 7, which shows that the 1-allyl-4- (2-hydroxyethyl) -piperazine and the N- (phosphonomethyl) iminodiacetic acid are adopted to react to prepare the N- (phosphonomethyl) iminodiacetic acid derivative, and then the N- (phosphonomethyl) iminodiacetic acid derivative is compounded and polymerized with other components to obtain the modified sulfonic acid copolymer, so that the corrosion inhibition performance of the mixture can be further enhanced when the modified sulfonic acid copolymer is applied to the mixture. Example 5 is significantly better than example 1 and example 8, and example 6 is significantly better than example 7 and example 9, indicating that the use of propyl methacrylate in combination with sodium polysulfide reactant followed by reaction with 5-bromo- [1,2,4] trithiazol [1,5-a ] pyridin-2-amine to prepare an amide-based biocide can effectively enhance the corrosion inhibition properties of the mixture when applied in a mixture preparation process.
Example 5:
measuring the stripping performance of the biological slime:
50mL of biological slime is taken, 50mL of distilled water is added, shaking is carried out, 15mg/L of sample to be detected is added, and a blank control group is arranged. Then placing the mixture on a rotary instrument to rotate for 24 hours at a rotating speed of 150r/min, filtering the mixture by using filter paper, and then passing the mixture through a microporous filter membrane of 0.2 mu m to determine the protein concentration in the filtrate. Wherein, the greater the protein concentration, the better the stripping performance of the biological slime.
The method for measuring the protein concentration is carried out by adopting an ultraviolet-visible spectrophotometry, and specifically comprises the following steps: the absorbance at 260nm and 280nm was measured using an instrument and the protein content was calculated according to the following formula:
protein mass concentration (mg/L) =1.45a 280 -0.74A 260
The above-described test was performed on the mixtures provided in examples 1 to 9, and the results are shown in table 3:
TABLE 3 mud peel performance test results
| Sample of | Protein mass concentration (mg/L) |
| Example 1 | 131 |
| Example 2 | 129 |
| Example 3 | 134 |
| Example 4 | 130 |
| Example 5 | 166 |
| Example 6 | 164 |
| Example 7 | 128 |
| Example 8 | 147 |
| Example 9 | 145 |
From the analysis of the data in Table 3, the mass concentration of the protein after the mixture provided in example 1 is equivalent to that of example 7, which shows that the 1-allyl-4- (2-hydroxyethyl) -piperazine and N- (phosphonomethyl) iminodiacetic acid are adopted to react to prepare the N- (phosphonomethyl) iminodiacetic acid derivative, and then the N- (phosphonomethyl) iminodiacetic acid derivative is compounded and polymerized with other components to obtain the modified sulfonic acid copolymer, and the modified sulfonic acid copolymer is applied to the mixture, so that the slime stripping performance of the mixture is not negatively influenced. Example 5 is significantly better than examples 1 and 8 and example 6 is significantly better than examples 7 and 9, indicating that the use of propyl methacrylate in combination with sodium polysulfide reactant followed by reaction with 5-bromo- [1,2,4] trithiazol [1,5-a ] pyridin-2-amine to prepare an amide biocide can be used in the process of preparing the mixture to effectively enhance the slime stripping ability of the mixture.
Test example 6:
antibacterial property measurement
Test object: coli and staphylococcus aureus are all commercially available.
The specific test method comprises the following steps: taking a sterilized test tube, adding 2mL of liquid culture medium into the sterilized test tube by adopting a test tube double dilution method, and taking the inoculated test tube without adding a test sample as a positive control; and test tubes without test sample and without seed strain were set as negative controls. The initial concentration of the test sample is 1mg/mL, and the test sample is diluted twice in turn and uniformly mixed; then 200 mu L of bacterial suspension is added into the test tube, so that the final bacterial liquid concentration is 5 multiplied by 10 5 cfu/mL. Shake culturing for 24h, observing the bacterial growth (turbidity) of the positive control tube and the bacterial growth (transparency) of the negative control tube by naked eyes, and determining the minimum antibacterial concentration of the sample to be tested on the bacterial strain.
The above-described test was performed on the mixtures provided in examples 5 and 8, and the results are shown in table 4:
table 4 results of antibacterial property test
| Sample of | Minimum inhibitory concentration (mg/mL) of E.coli | Minimum inhibitory concentration (mg/mL) of Staphylococcus aureus |
| Example 5 | 0.0625 | 0.0625 |
| Example 8 | 0.1250 | 0.0625 |
As can be seen from the data analysis in Table 4, the minimum inhibitory concentration of the amide bactericide prepared in example 5 on Escherichia coli is obviously lower than that of example 8, which shows that the amide bactericide prepared by reacting propyl methacrylate with sodium polysulfide reactant and then reacting with 5-bromo- [1,2,4] trithiazole [1,5-A ] pyridin-2-amine shows better antibacterial activity, and especially the antibacterial effect on Escherichia coli is obviously improved.
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 (4)
1. A mixture, comprising: modified sulfonic acid copolymer, carboxylate oxidant, non-oxidant, stabilizer, solubilizer and water; the molecular weight of the modified sulfonic acid copolymer is 7000-20000, the modified sulfonic acid copolymer comprises a N- (phosphonomethyl) iminodiacetic acid derivative unit structure, and the preparation method of the modified sulfonic acid copolymer comprises the following steps: adding isopropanol and distilled water into acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, phosphoenolpyruvate sodium salt and N- (phosphonomethyl) iminodiacetic acid derivatives, uniformly stirring, heating to 80-90 ℃, slowly adding ammonium persulfate, after finishing the addition within 1.5-2.5 h, performing constant temperature reaction for 1-3 h, cooling to room temperature, regulating pH to neutral, adding ethanol for precipitation and purification, performing vacuum filtration, and performing vacuum drying to obtain a modified sulfonic acid copolymer;
wherein the molar ratio of the acrylic acid to the 2-acrylamido-2-methylpropanesulfonic acid to the phosphoenolpyruvic acid sodium salt to the N- (phosphonomethyl) iminodiacetic acid derivative is 1:0.6-0.8:0.8-1:0.4-0.6; the addition amount of ammonium persulfate is 12-15wt% of the total amount of the polymerization monomers; the addition amount of the isopropanol is 8-12wt% of the total amount of the polymerization monomers; the dosage ratio of the acrylic acid to the distilled water is 0.1-0.3 g:1mL;
the N- (phosphonomethyl) iminodiacetic acid derivative is a product prepared by mixing and reacting N- (phosphonomethyl) iminodiacetic acid and 1-allyl-4- (2-hydroxyethyl) -piperazine, and the chemical structure of the N- (phosphonomethyl) iminodiacetic acid derivative is shown as a formula I:I；
the non-oxidizing agent comprises one or two of isothiazolinone or dibromocyanoacetamide.
2. The mixture according to claim 1, wherein: the carboxylate oxidizer is a chloramine compound.
3. The mixture according to claim 1, wherein: the stabilizer is one or two of ethylene glycol and propylene glycol.
4. Use of the mixture of claim 1 for the preparation of a medicament having both scale inhibition and slime control.
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