JP2016150334A - Emulsion breaking agent, and processing method of oil-containing aqueous solution - Google Patents
Emulsion breaking agent, and processing method of oil-containing aqueous solution Download PDFInfo
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- JP2016150334A JP2016150334A JP2015030981A JP2015030981A JP2016150334A JP 2016150334 A JP2016150334 A JP 2016150334A JP 2015030981 A JP2015030981 A JP 2015030981A JP 2015030981 A JP2015030981 A JP 2015030981A JP 2016150334 A JP2016150334 A JP 2016150334A
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- Prior art keywords
- oil
- polycation
- aqueous solution
- agent
- containing aqueous
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- 239000000839 emulsion Substances 0.000 title claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 20
- 238000003672 processing method Methods 0.000 title claims abstract description 5
- -1 aldehyde compound Chemical class 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003242 anti bacterial agent Substances 0.000 claims description 18
- 229920002873 Polyethylenimine Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 125000006353 oxyethylene group Chemical group 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229920006317 cationic polymer Polymers 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 18
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 2
- 239000000701 coagulant Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 239000012459 cleaning agent Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- VAZJLPXFVQHDFB-UHFFFAOYSA-N 1-(diaminomethylidene)-2-hexylguanidine Polymers CCCCCCN=C(N)N=C(N)N VAZJLPXFVQHDFB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920002413 Polyhexanide Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 108010039918 Polylysine Proteins 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 2
- 239000002173 cutting fluid Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940079826 hydrogen sulfite Drugs 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229920000656 polylysine Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- WEYSQARHSRZNTC-UHFFFAOYSA-N 1h-benzimidazol-2-ylcarbamic acid Chemical compound C1=CC=C2NC(NC(=O)O)=NC2=C1 WEYSQARHSRZNTC-UHFFFAOYSA-N 0.000 description 1
- NZUXRGMXFCTGBV-UHFFFAOYSA-N 2-(1,1,2,2-tetrachloroethylsulfanyl)-3a,4,5,7a-tetrahydroisoindole-1,3-dione Chemical compound C1CC=CC2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)C21 NZUXRGMXFCTGBV-UHFFFAOYSA-N 0.000 description 1
- LROZSPADHSXFJA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1O LROZSPADHSXFJA-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- NCKMMSIFQUPKCK-UHFFFAOYSA-N 2-benzyl-4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1CC1=CC=CC=C1 NCKMMSIFQUPKCK-UHFFFAOYSA-N 0.000 description 1
- DHVLDKHFGIVEIP-UHFFFAOYSA-N 2-bromo-2-(bromomethyl)pentanedinitrile Chemical compound BrCC(Br)(C#N)CCC#N DHVLDKHFGIVEIP-UHFFFAOYSA-N 0.000 description 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- HFOCAQPWSXBFFN-UHFFFAOYSA-N 2-methylsulfonylbenzaldehyde Chemical compound CS(=O)(=O)C1=CC=CC=C1C=O HFOCAQPWSXBFFN-UHFFFAOYSA-N 0.000 description 1
- YVEBRYGCUAUZSI-UHFFFAOYSA-N 3-iodohept-6-ynylcarbamic acid Chemical compound IC(CCNC(O)=O)CCC#C YVEBRYGCUAUZSI-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- IJALWSVNUBBQRA-UHFFFAOYSA-N 4-Isopropyl-3-methylphenol Chemical compound CC(C)C1=CC=C(O)C=C1C IJALWSVNUBBQRA-UHFFFAOYSA-N 0.000 description 1
- OSDLLIBGSJNGJE-UHFFFAOYSA-N 4-chloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Cl OSDLLIBGSJNGJE-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- GBKXRWNDORMHSG-UHFFFAOYSA-N 5-chloro-2,4,6-trifluorobenzene-1,3-dicarbonitrile Chemical compound FC1=C(Cl)C(F)=C(C#N)C(F)=C1C#N GBKXRWNDORMHSG-UHFFFAOYSA-N 0.000 description 1
- RQCLKJICDPMGDH-UHFFFAOYSA-N 7-(dichloromethyl)-2-fluoro-3-sulfanylideneisoindol-1-one Chemical compound S=C1N(F)C(=O)C2=C1C=CC=C2C(Cl)Cl RQCLKJICDPMGDH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical compound C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 108010053775 Nisin Proteins 0.000 description 1
- NVNLLIYOARQCIX-MSHCCFNRSA-N Nisin Chemical compound N1C(=O)[C@@H](CC(C)C)NC(=O)C(=C)NC(=O)[C@@H]([C@H](C)CC)NC(=O)[C@@H](NC(=O)C(=C/C)/NC(=O)[C@H](N)[C@H](C)CC)CSC[C@@H]1C(=O)N[C@@H]1C(=O)N2CCC[C@@H]2C(=O)NCC(=O)N[C@@H](C(=O)N[C@H](CCCCN)C(=O)N[C@@H]2C(NCC(=O)N[C@H](C)C(=O)N[C@H](CC(C)C)C(=O)N[C@H](CCSC)C(=O)NCC(=O)N[C@H](CS[C@@H]2C)C(=O)N[C@H](CC(N)=O)C(=O)N[C@H](CCSC)C(=O)N[C@H](CCCCN)C(=O)N[C@@H]2C(N[C@H](C)C(=O)N[C@@H]3C(=O)N[C@@H](C(N[C@H](CC=4NC=NC=4)C(=O)N[C@H](CS[C@@H]3C)C(=O)N[C@H](CO)C(=O)N[C@H]([C@H](C)CC)C(=O)N[C@H](CC=3NC=NC=3)C(=O)N[C@H](C(C)C)C(=O)NC(=C)C(=O)N[C@H](CCCCN)C(O)=O)=O)CS[C@@H]2C)=O)=O)CS[C@@H]1C NVNLLIYOARQCIX-MSHCCFNRSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 108010007568 Protamines Proteins 0.000 description 1
- 102000007327 Protamines Human genes 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- XDILZEPJCPEDLT-UHFFFAOYSA-N [Na].[O-][N+]1=CC=CC=C1S Chemical compound [Na].[O-][N+]1=CC=CC=C1S XDILZEPJCPEDLT-UHFFFAOYSA-N 0.000 description 1
- WPZSJJJTNREFSV-UHFFFAOYSA-N [Zn].[O-][N+]1=CC=CC=C1S Chemical compound [Zn].[O-][N+]1=CC=CC=C1S WPZSJJJTNREFSV-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229940109239 creatinine Drugs 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004995 haloalkylthio group Chemical group 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 229930182817 methionine Natural products 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000004309 nisin Substances 0.000 description 1
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- 150000002825 nitriles Chemical class 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000724 poly(L-arginine) polymer Polymers 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
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- 108010055896 polyornithine Proteins 0.000 description 1
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- 229920001184 polypeptide Polymers 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
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- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Description
本発明は、エマルション等の含油水溶液から油分を除去するエマルション破壊剤および含油水溶液の処理方法に関する。 The present invention relates to an emulsion breaker that removes oil from an oil-containing aqueous solution such as an emulsion, and a method for treating the oil-containing aqueous solution.
油は日常生活の様々な場所で使われ、油を含油する排水が多量に発生する。特に金属加工工場においては、鉱油、油脂、脂肪酸を含有する切削剤が使用され、金属加工後の洗浄剤に混入し、または直接排水に流れこんで廃棄される。これらの廃液はエマルション化しているので、これを廃棄または再利用するためにはエマルションを破壊する必要がある。しかし、非イオン界面活性剤により乳化されたエマルションは破壊することは困難である。 Oil is used in various places in daily life, and a large amount of wastewater containing oil is generated. In metal processing plants in particular, cutting agents containing mineral oil, fats and oils and fatty acids are used, mixed in cleaning agents after metal processing, or directly flowing into waste water and discarded. Since these waste liquids are emulsified, in order to discard or reuse them, it is necessary to break the emulsion. However, it is difficult to break an emulsion emulsified with a nonionic surfactant.
非イオン界面活性剤により乳化されたエマルションを破壊する目的で、非イオン界面活性剤の除去剤として、タンニン(特許文献1)、フェノール系縮合物(特許文献2)や芳香族スルホン酸の縮合物が開発されている。これらの非イオン界面活性剤除去剤は単独ではエマルションを破壊する能力はなく、通常は、硫酸バンド、ポリ塩化アルミニム等の無機凝集剤と併用する必要がある。この方法では、硫酸バンドやポリ塩化アルミニウムを添加して酸性とした後、消石灰を添加して中和することが必要であり、本格的な廃液処理設備を必要とする。また、これらの方法で含油廃液を処理した場合には、汚泥が沢山発生し、処理液中には高濃度の硫酸イオンや塩素イオンが存在する。 For the purpose of breaking an emulsion emulsified with a nonionic surfactant, a tannin (Patent Document 1), a phenol-based condensate (Patent Document 2) or an aromatic sulfonic acid condensate is used as a nonionic surfactant remover. Has been developed. These nonionic surfactant removing agents alone do not have the ability to break the emulsion, and usually need to be used in combination with an inorganic flocculant such as a sulfuric acid band or polyaluminum chloride. In this method, it is necessary to neutralize by adding slaked lime after adding a sulfuric acid band or polyaluminum chloride to make it acidic, and a full-scale waste liquid treatment facility is required. Further, when oil-containing waste liquid is treated by these methods, a large amount of sludge is generated, and high-concentration sulfate ions and chlorine ions are present in the treatment liquid.
近年、環境保護の観点から、排液の量を極力減少させ、水を再利用することが検討されている。硫酸イオンや塩素イオンは金属を腐食させるため、これらのイオンを高濃度で含有する廃液を金属加工用に再利用するためには、更に高度処理を必要とし、経済的に不利である。 In recent years, from the viewpoint of environmental protection, it has been studied to reduce the amount of drainage as much as possible and to reuse water. Since sulfate ions and chloride ions corrode metals, reusing a waste liquid containing these ions at high concentrations for metal processing is economically disadvantageous.
本発明の目的は、無機凝集剤を使用せず、簡便に用いることができるエマルション破壊剤と含油水溶液の処理方法を提供することである。 The objective of this invention is providing the processing method of the emulsion breaker and oil-containing aqueous solution which can be used simply, without using an inorganic flocculant.
本発明者は、上記課題を解決すべく鋭意研究を重ねたところ、特定の重縮合物とポリカチオンを組み合わせて用いると、無機凝集剤を用いなくともエマルションを破壊するこができることを見出した。本発明は、このような知見に基づき完成されたものであり、以下の様態の液状組成物を提供する。 The present inventor conducted extensive research to solve the above problems, and found that the emulsion can be broken without using an inorganic flocculant when a specific polycondensate and a polycation are used in combination. The present invention has been completed based on such findings, and provides a liquid composition having the following modes.
項1.(I)ビス(ヒドロキシフェニル)スルホン、及び低級アルデヒド化合物の重縮合物であってアルキルスルホン酸基を有する重縮合物、(II)ポリカチオンの2剤を組み合わせて使用する2剤型エマルション破壊剤。
項2. ポリカチオンが1分子中に2個以上のイミノ基、1分子中に2個以上のアンモニウム基、1分子中に2個以上のアミノ基のいずれかを有するカチオン性ポリマーである項1に記載の2剤型エマルション破壊剤。
項3. (II)がさらに抗菌剤を含有する項1または2に記載の2剤型エマルション破壊剤。
項4. ポリカチオンがポリ[オキシエチレン(ジメチルイミノ)エチレン(ジメチルイミノ)エチレンジクロライド]またはポリエチレンイミンであることを特徴とする項1〜3のいずれか1項に記載の2剤型エマルション破壊剤。
項5. 項1〜4に記載のエマルション破壊剤の(I)を含油水溶液に添加後、撹拌しながら(II)を添加し、静置後に含油凝集物を除去する含油水溶液の処理方法。
Item 1. (I) Bicondensation product of bis (hydroxyphenyl) sulfone and a lower aldehyde compound, which is a polycondensation product having an alkylsulfonic acid group, and (II) a polycation two-component emulsion breaker .
Item 2. Item 2. The polycation is a cationic polymer having any one of two or more imino groups in one molecule, two or more ammonium groups in one molecule, and two or more amino groups in one molecule. Two-part emulsion breaker.
Item 3. Item 3. The two-component emulsion breaker according to Item 1 or 2, wherein (II) further contains an antibacterial agent.
Item 4. Item 4. The two-component emulsion breaker according to any one of Items 1 to 3, wherein the polycation is poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] or polyethyleneimine.
Item 5. The processing method of the oil-containing aqueous solution which adds (II) of the emulsion breaking agent of claim | item 1-4 to oil-containing aqueous solution after stirring, adds (II), stirring, and removes an oil-containing aggregate after standing.
本発明においては、無機凝集剤を使用しないので汚泥が少なく、pH調整も不要のため処理工程を簡略化できる。しかも、排液処理による硫酸イオンや塩素イオン等の腐食性イオン濃度の上昇がないため処理液の再利用が可能である。 In the present invention, since an inorganic flocculant is not used, there is little sludge and no pH adjustment is required, so that the treatment process can be simplified. In addition, since the concentration of corrosive ions such as sulfate ions and chlorine ions does not increase due to the waste liquid treatment, the treatment liquid can be reused.
本発明のエマルション破壊剤は、(I)ビス(ヒドロキシフェニル)スルホン、及び低級アルデヒド化合物の重縮合物であってアルキルスルホン酸基を有する重縮合物を含む剤、(II)ポリカチオンを含む剤の2剤からなる。 The emulsion breaking agent of the present invention comprises (I) a bis (hydroxyphenyl) sulfone and a polycondensate of a lower aldehyde compound, which contains a polycondensate having an alkylsulfonic acid group, and (II) an agent containing a polycation. It consists of two agents.
(I)ビス(ヒドロキシフェニル)スルホン、及び低級アルデヒド化合物の重縮合物の水溶液(I) Aqueous solution of polycondensate of bis (hydroxyphenyl) sulfone and a lower aldehyde compound
本発明の重縮合物に用いるビス(ヒドロキシフェニル)スルホンとしては、例えば4,4´−ジヒドロキシジフェニルスルホン、2,4´−ジヒドロキシジフェニルスルホンなどを挙げることができるが、特に4,4´−ジヒドロキシジフェニルスルホンが好ましい。 Examples of the bis (hydroxyphenyl) sulfone used in the polycondensate of the present invention include 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, etc., and in particular, 4,4′-dihydroxysulfone. Diphenyl sulfone is preferred.
低級アルデヒドとしては、炭素数1〜3の脂肪族アルデヒドが好ましく、具体的にはホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒドを挙げることができる。特に、ホルムアルデヒドが好ましい。 As the lower aldehyde, an aliphatic aldehyde having 1 to 3 carbon atoms is preferable, and specific examples include formaldehyde, acetaldehyde, and propionaldehyde. In particular, formaldehyde is preferable.
本発明の重縮合物はビス(ヒドロキシフェニル)スルホン、低級アルデヒドおよび亜硫酸水素アルカリ金属塩または亜硫酸アルカリ金属塩をアルカリの存在下で加熱反応することにより得られる。前記反応は従来公知の方法で行えばよく、例えばビス(ヒドロキシフェニル)スルホン1モルに対して、低級アルデヒドを1〜4モル、亜硫酸水素アルカリ金属塩0.1〜0.7モルをアルカリの存在下で50℃〜140℃加熱すればよい。このようにして得られる重縮合物は低級アルキルスルホン酸基を有している。アルキルスルホン酸基はビス(ヒドロキシフェニル)スルホン1個に対して平均0.05〜3.0個有することが好ましく、0.05〜2.0個がより好ましい。 The polycondensate of the present invention can be obtained by subjecting bis (hydroxyphenyl) sulfone, a lower aldehyde, and an alkali metal hydrogen sulfite or alkali metal sulfite to a heat reaction in the presence of an alkali. The reaction may be carried out by a conventionally known method. For example, 1 mol of a lower aldehyde and 0.1 to 0.7 mol of an alkali metal hydrogen sulfite are present in the presence of an alkali with respect to 1 mol of bis (hydroxyphenyl) sulfone. What is necessary is just to heat 50 to 140 degreeC under. The polycondensate thus obtained has a lower alkyl sulfonic acid group. The alkylsulfonic acid group preferably has an average of 0.05 to 3.0, more preferably 0.05 to 2.0, per bis (hydroxyphenyl) sulfone.
重縮合物の中でも、ビス(ヒドロキシフェニル)スルホンモノメチルスルホン酸・ホルムアルデヒド重合物は性能が優れており、処理液のpHを殆ど変化させないので好適である。ビス(ヒドロキシフェニル)スルホンモノメチルスルホン酸・ホルムアルデヒド重合物はビスヒドロキシフェニル)スルホン、ホルムアルデヒド、亜硫酸ナトリウムを水酸化ナトリウムなどのアルカリ存在下で縮合反応させることにより得られる。 Among the polycondensates, a bis (hydroxyphenyl) sulfone monomethylsulfonic acid / formaldehyde polymer is preferable because it has excellent performance and hardly changes the pH of the treatment liquid. Bis (hydroxyphenyl) sulfone monomethylsulfonic acid / formaldehyde polymer is obtained by subjecting bishydroxyphenyl) sulfone, formaldehyde and sodium sulfite to a condensation reaction in the presence of an alkali such as sodium hydroxide.
本発明の重縮合物は市販品を使用してもよいし、前述の方法により製造して使用してもよい。重縮合物の分子量は通常500〜10000であり、好ましくは500〜2000である。 The polycondensate of the present invention may be a commercially available product, or may be produced by the method described above and used. The molecular weight of the polycondensate is usually 500 to 10,000, preferably 500 to 2,000.
(I)の残部は水であり、重縮合物を任意の濃度の水溶液にして使用すればよい。 The balance of (I) is water, and the polycondensate may be used in an aqueous solution having an arbitrary concentration.
重縮合物の作用時の濃度は、処理対象の含油水溶液に含まれる非イオン界面活性剤の種類および濃度によって異なるので限定できないが、一般的な防錆兼洗浄剤にエマルション型洗浄剤が混入した溶液の場合には、50〜10000ppm、好ましくは200〜2000ppmである。 The concentration at the time of action of the polycondensate varies depending on the type and concentration of the nonionic surfactant contained in the oil-containing aqueous solution to be treated. In the case of a solution, it is 50 to 10000 ppm, preferably 200 to 2000 ppm.
(II)ポリカチオン及び抗菌剤を含有する溶液(II) A solution containing a polycation and an antibacterial agent
本発明の含油水溶液処理剤に用いられるポリカチオンは、1分子中に2個以上のイミノ基、1分子中に2個以上のアンモニウム基、1分子中に2個以上のアミノ基のいずれかを有するカチオン性ポリマーであれば特に限定されるものではなく、ジメチルアミノエチルアクリレート系(DDA系)高分子凝集剤(例えば、アクリルアミドとN,N−ジメチルアミノエチルの共重合体、ポリジメチルアミノエチルアクリレート等)、ジメチルアミノエチルメタクリレート系(DAM系)高分子凝集剤(例えば、メタアクリルアミドとN,N−ジメチルアミノエチルの共重合体、ポリジメチルアミノエチルメタクリレート等)、アルキルアミノメタクリレート四級塩重合物、アルキルアミノアクリレート四級塩・アクリルアミド共重合物、アクリロニトリル・N−ビニルホルムアルデヒド共重合物、ジシアンジアミド系高分子凝集剤(例えば、ジシアンアミド・塩化アンモニウム・ホルムアルデヒド重合物等)、ポリ[オキシエチレン(ジメチルイミノ)エチレン(ジメチルイミノ)エチレンジクロライド]、ポリエチレンイミン、ポリビニルピロリドン、四級化ポリビニルピロリドン、ポリビニルアミン、ポリアリルアミン、ポリペプチド(例えば、ポリリジン、ポリアルギニン、ポリオルニチン、等)等が挙げられる。中でも、ポリ[オキシエチレン(ジメチルイミノ)エチレン(ジメチルイミノ)エチレンジクロライド]およびポリエチレンイミンは微生物を凝集して除去する効果があるので、特に好ましい。ポリカチオンは抗菌効果を有しており、本発明のエマルション破壊剤は処理液の生菌数を減少させる効果も有する。 The polycation used in the oil-containing aqueous solution treating agent of the present invention has any one of two or more imino groups in one molecule, two or more ammonium groups in one molecule, and two or more amino groups in one molecule. It is not particularly limited as long as it is a cationic polymer having dimethylaminoethyl acrylate (DDA) polymer flocculant (for example, a copolymer of acrylamide and N, N-dimethylaminoethyl, polydimethylaminoethyl acrylate) ), Dimethylaminoethyl methacrylate type (DAM type) polymer flocculant (for example, copolymer of methacrylamide and N, N-dimethylaminoethyl, polydimethylaminoethyl methacrylate, etc.), alkylamino methacrylate quaternary salt polymer , Alkylaminoacrylate quaternary salt / acrylamide copolymer, acrylo Tolyl / N-vinylformaldehyde copolymer, dicyandiamide polymer flocculant (eg, dicyanamide / ammonium chloride / formaldehyde polymer), poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride], polyethyleneimine, Examples include polyvinyl pyrrolidone, quaternized polyvinyl pyrrolidone, polyvinyl amine, polyallylamine, and polypeptides (eg, polylysine, polyarginine, polyornithine, etc.). Among them, poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] and polyethyleneimine are particularly preferable because they have an effect of aggregating and removing microorganisms. The polycation has an antibacterial effect, and the emulsion breaking agent of the present invention also has an effect of reducing the number of viable bacteria in the treatment liquid.
ポリカチオンの分子量は特に限定されないが、ポリ[オキシエチレン(ジメチルイミノ)エチレン(ジメチルイミノ)エチレンジクロライド]であれば例えば分子量3000〜10000の化合物を用いればよく、ポリエチレンイミンであれば例えば分子量300〜100000の化合物を用いればよい。 The molecular weight of the polycation is not particularly limited. For example, a compound having a molecular weight of 3000 to 10,000 may be used as long as it is poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride]. 100000 compounds may be used.
(II)はポリカチオンの他に抗菌剤を含有していてもよい。本発明に用いられる抗菌剤は特に限定されず、イソチアゾリン系抗菌剤(例えば、1,2−ベンゾイソチアゾリン−3−オン、2−メチル4−イソチアゾリン−3−オン、5−クロロ−2−メチル4−イソチアゾリン−3−オン、ピリジン系抗菌剤(例えば、2−クロロ−6クロロメチピリジン、2−ピリジンチオール−1―オキシドナトリウム、2−ピリジンチオール−1−オキシド亜鉛、等)、ニトリル系抗菌剤(例えば、4,5,6−テトラクロロイソフタロニトリル、5−クロロ−2,4,6−トリフロロイソフタロニトリル、等)、ベンゾイミダゾール系抗菌剤(例えば、1H−2−ベンズイミダゾールカルバミン酸メチル、1−ブチルカルバモイル−2−ベンズイミダゾールカルバミン酸メチル、等)、ハロアルキルチオ系抗菌剤(例えば、N−フロロジクロロメチルチオフタルイミド、N−1,1,2,2−テトラクロロエチルチオテトラヒロフタルイミド、等)、サルファイド系抗菌剤(例えば、ビス(ジメチルチオカルバモイル)ジサルファイド、等)、有機ヨード系抗菌剤(例えば、ジヨードメチル−p−トリルスルフォン、3―ヨード−プロパギルブチルカルバミン酸、4−クロロフェニル−3−ヨードプロパギルホルマール、等)、フェノール系抗菌剤(例えば、2−ベンジル−4−クロロフェノール、p−クロロフェノール、4−クロロ−3,5−ジメチルフェノール、3−メチル−4−イソプロピルフェノール、等)、ジフェニルエーテル系抗菌剤(例えば、トリクロサン、等)、ビグアナイド系抗菌剤(例えば、ポリヘキサメチレンビグアニジド、グルコン酸クロルヘキシジン、等)、有機臭素系抗菌剤(例えば、2−ブロモ−2−ニトロプロパン−1,3−ジオール、1,2−ジブロモ−2,4−ジシアノブタン)、第四級アンモニウム塩(例えば、塩化ベンザルコニウム、塩化ベンゼトニウム、ジデシルジメチルアンモニムクロライド、ハイジェニア、等)、銀系抗菌剤(例えば、ヒスチジン銀錯体、クレアチニン銀錯体、メチオニン銀錯体、等)、アルデヒド類(グルタルアルデヒド、ホルムアルデヒド、等)、金属イオン(例えば、銀イオン、銅イオン、等)、抗菌性ペプチド(例えば、ポリリジン、ナイシン、プロタミン、等)等が挙げられ、これらの中の1種または2種以上を用いる。 (II) may contain an antibacterial agent in addition to the polycation. The antibacterial agent used in the present invention is not particularly limited, and isothiazoline-based antibacterial agents (for example, 1,2-benzisothiazolin-3-one, 2-methyl 4-isothiazolin-3-one, 5-chloro-2-methyl 4 -Isothiazoline-3-one, pyridine antibacterial agent (for example, 2-chloro-6chloromethypyridine, 2-pyridinethiol-1-oxide sodium, 2-pyridinethiol-1-oxide zinc, etc.), nitrile antibacterial agent (For example, 4,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluoroisophthalonitrile, etc.), benzimidazole antibacterial agents (for example, 1H-2-benzimidazolecarbamic acid) Methyl, 1-butylcarbamoyl-2-benzimidazole carbamate methyl, etc.), haloalkylthio antibacterial (For example, N-fluorodichloromethylthiophthalimide, N-1,1,2,2-tetrachloroethylthiotetrahydrophthalimide, etc.), sulfide antibacterial agents (for example, bis (dimethylthiocarbamoyl) disulfide, etc.), organic iodine Antibacterial agents (for example, diiodomethyl-p-tolylsulfone, 3-iodo-propargylbutylcarbamic acid, 4-chlorophenyl-3-iodopropargyl formal, etc.), phenolic antibacterial agents (for example, 2-benzyl-4- Chlorophenol, p-chlorophenol, 4-chloro-3,5-dimethylphenol, 3-methyl-4-isopropylphenol, etc.), diphenyl ether antibacterial agent (eg, triclosan, etc.), biguanide antibacterial agent (eg, Polyhexamethylene biguanide, Chlorhexidine luconate, etc.), organic bromine antibacterial agents (for example, 2-bromo-2-nitropropane-1,3-diol, 1,2-dibromo-2,4-dicyanobutane), quaternary ammonium salts ( For example, benzalkonium chloride, benzethonium chloride, didecyldimethylammonium chloride, hygenia, etc.), silver antibacterial agents (eg, histidine silver complex, creatinine silver complex, methionine silver complex, etc.), aldehydes (glutaraldehyde, Formaldehyde, etc.), metal ions (eg, silver ions, copper ions, etc.), antibacterial peptides (eg, polylysine, nisin, protamine, etc.), etc., and one or more of these are used. .
中でも銀イオンはポリエチレンイミンと錯体を形成し、この銀錯体は塩素イオンが存在する条件下でも抗菌力を発揮するので、ポリカチオンとしてポリエチレンイミンを用いる場合には好適である。ポリエチレンイミン銀錯体は、ポリエチレンイミン溶液に酸化銀を添加して撹拌することにより調製される。銀イオンの作用時の濃度は、1〜100ppm、好ましくは10〜50ppmである。 Among them, silver ions form a complex with polyethyleneimine, and this silver complex exhibits antibacterial activity even in the presence of chlorine ions, and therefore is suitable when polyethyleneimine is used as a polycation. The polyethyleneimine silver complex is prepared by adding silver oxide to a polyethyleneimine solution and stirring. The concentration at the time of action of silver ions is 1 to 100 ppm, preferably 10 to 50 ppm.
ポリカチオンとしてポリ[オキシエチレン(ジメチルイミノ)エチレン(ジメチルイミノ)エチレンジクロライド]を用いる場合には、銀イオン以外の抗菌剤を用いる。例えば、ポリヘキサメチレンビグアニジドを用いる場合には、その使用時の濃度は10〜1000ppm、好ましくは50〜200ppmである。 When poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] is used as the polycation, an antibacterial agent other than silver ions is used. For example, when polyhexamethylene biguanide is used, the concentration at the time of use is 10 to 1000 ppm, preferably 50 to 200 ppm.
(II)の残部は水であり、ポリカチオンおよび抗菌剤の任意の濃度の水溶液として使用すればよい。 The balance of (II) is water and may be used as an aqueous solution of any concentration of polycation and antibacterial agent.
ポリカチオンの作用時の濃度は、含油水溶液に含まれる油分の量によって異なるので限定できないが、通常は10〜10000ppm、好ましくは100〜1000ppmである。この濃度はエマルションを処理するための使用時の濃度であり、凝集剤組成物はより高濃度の濃縮液であり、濃縮液を使用時に対象液に添加する。 The concentration at the time of the action of the polycation is not limited because it varies depending on the amount of oil contained in the oil-containing aqueous solution, but is usually 10 to 10,000 ppm, preferably 100 to 1000 ppm. This concentration is the concentration at the time of use for processing the emulsion, the flocculant composition is a concentrated solution having a higher concentration, and the concentrated solution is added to the target solution at the time of use.
(I)の重縮合物と(II)のポリカチオンの重量比は、(II)のポリカチオン1重量部に対して(I)の重縮合物が1〜5重量部、好ましくは2〜3重量部である。 The weight ratio of the polycondensate (I) to the polycation (II) is 1 to 5 parts by weight, preferably 2 to 3 parts by weight of the polycondensate (I) to 1 part by weight of the polycation (II). Parts by weight.
含油水溶液から油分を除去するためには、処理対象の含油水溶液に(I)を添加して撹拌しながら、(II)を添加する。その後室温で撹拌を5〜30分程度継続する。撹拌を止めて1時間〜数日静置すれば、非イオン界面活性剤と油分は凝集して沈降または浮上するので、濾過等により凝集物を除去する。
本発明の含油水溶液処理剤と、含油水溶液の処理方法は、主に金属加工工場の洗浄剤使用液や切削剤・研削剤使用液に適用される。
In order to remove oil from the oil-containing aqueous solution, (II) is added to the oil-containing aqueous solution to be treated while adding (I) and stirring. Thereafter, stirring is continued at room temperature for about 5 to 30 minutes. If the stirring is stopped and the mixture is allowed to stand for 1 hour to several days, the nonionic surfactant and the oil component aggregate and settle or float, so the aggregate is removed by filtration or the like.
The oil-containing aqueous solution treating agent and the method for treating an oil-containing aqueous solution of the present invention are mainly applied to a cleaning agent use liquid and a cutting agent / abrasive use liquid in a metal processing factory.
以下、本発明を実施例及び比較例を用いてより詳細に説明するが、本発明が実施例に限定されないことはいうまでもない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, it cannot be overemphasized that this invention is not limited to an Example.
ポリカチオンA剤
ビューサン77(バックマンラボラトリーズ株式会社製、ポリ[オキシエチレン(ジメチルイミノ)エチレン(ジメチルイミノ)エチレンジクロライド]60wt%溶液)を60倍量の水で希釈し、有効成分を1wt%含有する溶液を調製した。
Polycation A agent View Sun 77 (Buckman Laboratories, Inc., poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] 60 wt% solution) is diluted with 60 times the amount of water, and the active ingredient is 1 wt%. A containing solution was prepared.
ポリカチオンB剤
エポミンP−1000(純正化学株式会社製、分子量70000のポリエチレンイミンの30wt%水溶液)0.33gを蒸留水80gに溶解し、炭酸でpHを7.5に調整した後、蒸留水を加えて重量を100gにし、有効成分を1wt%含有する溶液を調整した。
Polycation B agent Epomin P-1000 (manufactured by Junsei Co., Ltd., 30 wt% aqueous solution of polyethyleneimine having a molecular weight of 70,000) was dissolved in 80 g of distilled water, and the pH was adjusted to 7.5 with carbonic acid. Was added to a weight of 100 g to prepare a solution containing 1 wt% of the active ingredient.
ポリカチオンC剤
エポミンP−1000 0.33gを蒸留水80gに溶解し、硝酸を添加してpHを9.5に調整した。この溶液に酸化銀0.11gを添加してスターラーで撹拌し、酸化銀が完全に溶解した後、蒸留水を加えて重量を100gに調整した。
0.33 g of polycation C agent Epomin P-1000 was dissolved in 80 g of distilled water, and nitric acid was added to adjust the pH to 9.5. To this solution, 0.11 g of silver oxide was added and stirred with a stirrer. After the silver oxide was completely dissolved, distilled water was added to adjust the weight to 100 g.
ポリカチオンD剤
ポリカチオンA剤に5wt%量のプロキセルIB(アーチ・ケミカルズ・ジャパン株式会社製、ポリヘキサメチレンビグアニド20wt%含有品)を添加した。
Polycation D agent A 5 wt% amount of Proxel IB (manufactured by Arch Chemicals Japan, Inc., containing 20 wt% polyhexamethylene biguanide) was added to the polycation A agent.
実施例1〜4、比較例1〜3
金属加工後用洗浄剤Aを水で希釈して3wt%溶液を調製した。一方、エマルション型切削油剤Xを水で希釈して10wt%溶液を調製した。洗浄剤希釈液99gと切削油剤の希釈液1gを混合し、大腸菌(IFO3301)、黄色ぶどう球菌(JCM20624)またはカンジダ・アルビカンス(JCM1542)を各菌数が106/mlとなるように接種した。
この溶液100gをビーカーに採り、スターラーで撹拌しながら、タキフロックL−2(多木化学株式会社製、ビス(ヒドロキシフェニル)スルホンモノメチルスルホン酸・ホルマリン重合物15wt%含有品)、以後L−2と表す)0.3ml、およびポリカチオンA剤、ポリカチオンB剤、ポリカチオンC剤またはポリカチオンD剤2mlを添加して、10分間撹拌した。これらの溶液を室温で一夜放置した後、濾過し、濾液のpH、濁度(650nmの吸光度)、菌数を測定した。結果を表1−1、1−2に示した。
Examples 1-4, Comparative Examples 1-3
The metalworking post-cleaning agent A was diluted with water to prepare a 3 wt% solution. On the other hand, emulsion type cutting fluid X was diluted with water to prepare a 10 wt% solution. 99 g of the cleaning agent dilution and 1 g of the cutting fluid dilution were mixed and inoculated with E. coli (IFO3301), Staphylococcus aureus (JCM20624) or Candida albicans (JCM1542) so that the number of each bacteria was 10 6 / ml.
While taking 100 g of this solution into a beaker and stirring with a stirrer, Takiflock L-2 (manufactured by Taki Chemical Co., Ltd., bis (hydroxyphenyl) sulfone monomethylsulfonic acid / formalin polymer containing 15 wt%), hereinafter referred to as L-2 0.3 ml) and 2 ml of polycation A agent, polycation B agent, polycation C agent or polycation D agent were added and stirred for 10 minutes. These solutions were allowed to stand overnight at room temperature and then filtered, and the pH, turbidity (absorbance at 650 nm), and the number of bacteria of the filtrate were measured. The results are shown in Tables 1-1 and 1-2.
実施例5〜7
C社、D社、E社の3社の金属加工工場で使用中の洗浄剤を入手した。これらの洗浄剤100mlにL−2 0.3mlと、ポリカチオンC剤3mlを添加して混合した。室温で一夜放置し、下の基準により液の性状を評価した。また、凝集処理前後の液0.1mlをSCD寒天培地に接種して30℃にて48時間培養し、寒天培地上のコロニー数から下の基準により抗菌性を評価した。結果を表2に示した。
(液の性状の評価)
〇:エマルションは完全に破壊し、フロックと透明な液に分かれている。
×:液の性状に変化がなく、乳濁したままである。
Examples 5-7
The cleaning agent in use in three metal processing factories of C company, D company, and E company was obtained. To 100 ml of these cleaning agents, 0.3 ml of L-2 and 3 ml of polycation C agent were added and mixed. The solution was allowed to stand overnight at room temperature, and the properties of the liquid were evaluated according to the following criteria. In addition, 0.1 ml of the solution before and after the aggregation treatment was inoculated on the SCD agar medium and cultured at 30 ° C. for 48 hours, and the antibacterial properties were evaluated based on the following criteria from the number of colonies on the agar medium. The results are shown in Table 2.
(Evaluation of liquid properties)
◯: The emulsion is completely broken and separated into floc and transparent liquid.
X: There is no change in the properties of the liquid and it remains milky.
表1−1、1−2および表2に示したように、本発明の破壊剤によりエマルションが破壊されて透明な液が得られた。また液のpHは処理前と殆ど変らず、生菌数の著しい減少が認められた。一方、(I)のみを添加した場合には、エマルションが破壊されず、生菌数も減少しなかった。また、(II)のみを添加した場合には生菌数の減少は認められたが、エマルションは完全には破壊されなかった。 As shown in Table 1-1, 1-2 and Table 2, the emulsion was broken by the breaker of the present invention, and a transparent liquid was obtained. Moreover, the pH of the solution was almost the same as that before the treatment, and a significant decrease in the number of viable bacteria was observed. On the other hand, when only (I) was added, the emulsion was not broken and the number of viable bacteria was not reduced. In addition, when only (II) was added, the number of viable bacteria was reduced, but the emulsion was not completely destroyed.
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JP2019089048A (en) * | 2017-11-16 | 2019-06-13 | 栗田工業株式会社 | Oil-water separation method of oil-containing scum, and oil-water separation agent |
JP2020116555A (en) * | 2019-01-28 | 2020-08-06 | 久保田 徹 | Functional water |
JP7587524B2 (en) | 2019-05-02 | 2024-11-20 | アンスティトゥート・ナシオナル・ドゥ・ラ・サンテ・エ・ドゥ・ラ・ルシャルシュ・メディカル・(インセルム) | Hyaluronic acid hydrogels with sustained antimicrobial activity |
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JP2019089048A (en) * | 2017-11-16 | 2019-06-13 | 栗田工業株式会社 | Oil-water separation method of oil-containing scum, and oil-water separation agent |
JP2020116555A (en) * | 2019-01-28 | 2020-08-06 | 久保田 徹 | Functional water |
WO2020158632A1 (en) * | 2019-01-28 | 2020-08-06 | 久保田 徹 | Functional water |
CN112203508A (en) * | 2019-01-28 | 2021-01-08 | 久保田徹 | Functional water |
EP3918915A4 (en) * | 2019-01-28 | 2022-05-11 | Toru Kubota | FUNCTIONAL WATER |
EP4541186A3 (en) * | 2019-01-28 | 2025-06-04 | Toru Kubota | Functional water |
JP7587524B2 (en) | 2019-05-02 | 2024-11-20 | アンスティトゥート・ナシオナル・ドゥ・ラ・サンテ・エ・ドゥ・ラ・ルシャルシュ・メディカル・(インセルム) | Hyaluronic acid hydrogels with sustained antimicrobial activity |
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