US3880613A - Higher alkyl trimethyl ammonium salt liquid hydrocarbon compositions - Google Patents
Higher alkyl trimethyl ammonium salt liquid hydrocarbon compositions Download PDFInfo
- Publication number
- US3880613A US3880613A US224341A US22434172A US3880613A US 3880613 A US3880613 A US 3880613A US 224341 A US224341 A US 224341A US 22434172 A US22434172 A US 22434172A US 3880613 A US3880613 A US 3880613A
- Authority
- US
- United States
- Prior art keywords
- composition
- group
- trimethyl ammonium
- oil
- esters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 45
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 44
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 30
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims description 86
- 239000000654 additive Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 31
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- 230000015556 catabolic process Effects 0.000 claims abstract description 19
- 238000006731 degradation reaction Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 230000000996 additive effect Effects 0.000 claims description 26
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000446 fuel Substances 0.000 claims description 22
- 150000001298 alcohols Chemical class 0.000 claims description 20
- 230000000813 microbial effect Effects 0.000 claims description 19
- 239000003209 petroleum derivative Substances 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001805 chlorine compounds Chemical group 0.000 claims description 12
- 150000001450 anions Chemical group 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 7
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 claims description 7
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 7
- 229920001567 vinyl ester resin Polymers 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 239000004714 Polar ethylene copolymer Substances 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229920006112 polar polymer Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 100
- 230000000694 effects Effects 0.000 abstract description 30
- 238000010438 heat treatment Methods 0.000 abstract description 22
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 19
- 239000003599 detergent Substances 0.000 abstract description 9
- 230000002906 microbiologic effect Effects 0.000 abstract description 4
- 239000004599 antimicrobial Substances 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 94
- 238000012360 testing method Methods 0.000 description 41
- 150000001875 compounds Chemical class 0.000 description 28
- 229920001577 copolymer Polymers 0.000 description 27
- 230000001580 bacterial effect Effects 0.000 description 22
- 241000894006 Bacteria Species 0.000 description 16
- -1 fuels Chemical class 0.000 description 15
- 239000003899 bactericide agent Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 13
- 239000002283 diesel fuel Substances 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 12
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 11
- 239000002609 medium Substances 0.000 description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 229920005605 branched copolymer Polymers 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 5
- 235000019864 coconut oil Nutrition 0.000 description 5
- 239000003240 coconut oil Substances 0.000 description 5
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 5
- 230000003641 microbiacidal effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229940117958 vinyl acetate Drugs 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000006916 nutrient agar Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical class Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241001148470 aerobic bacillus Species 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 125000005131 dialkylammonium group Chemical group 0.000 description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 2
- 230000035899 viability Effects 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100264195 Caenorhabditis elegans app-1 gene Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241001517310 Eria Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000003946 cyclohexylamines Chemical class 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- QAWTYRYXDYHQNU-UHFFFAOYSA-N diazathiane Chemical compound NSN QAWTYRYXDYHQNU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229940059904 light mineral oil Drugs 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000002103 osmometry Methods 0.000 description 1
- 229940008118 paradyne Drugs 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
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Definitions
- Detergent range alkyl trimethyl ammonium chlorides of limited hydrocarbon solubility are especially useful as antihaze and/or antimicrobial agents for heating oils.
- the water solubility of the new oil additives unexpectedly facilitates their bactericidal effectiveness.
- antihaze activity of these additives is uniquely unaffected by polar oligomeric additives such as cold flow improvers and detergents also present in the oil products.
- This invention relates to liquid hydrocarbons containing minor amounts of surface active, higher alkyl trimethyl ammonium salts.
- this invention relates to hydrocarbon, oils, i.e., fuels, containing higher alkyl trimethyl ammonium salt additives.
- this invention relates to middle distillate fuels having higher alkyl trimethyl ammonium chlorides together with polar oligomeric additives.
- One useful aspect of the invention relates to the suppression of water-in-oil emulsion forming tendencies of liquid hydrocarbons by the use of minor amounts of said additives.
- the inhibition of haze formation in heating oils containing cold flow improver additives is of particular interest.
- Another useful aspect of the invention is the inhibition of microbiological deterioration, particularly of bacterial attack, of hydrocarbons.
- the higher dialkyl dimethyl ammonium salts are known oil soluble surfactants and microbiocides.
- U.S. Pat. Nos. 3,008,813 and 3,265,474 to .l. R. Siege] and U.S. Pat. 3,346,353 to B. R. Strickland and I... Berkowitz all describe hydrocarbon oils which contain higher dialkyl dimethyl ammonium salts, especially chlorides to improve their water tolerance.
- Other inventions involving similar compositions containing oil soluble quaternary ammonium salts are described in U.S. Pat. Nos. 3,033,665, 3,158,647 and 3,397,970.
- liquid hydrocarbon compositions containing higher monoalkyl trimethyl ammonium salts have highly unexpected useful properties. Although most of these monoalkyl salts such as the chlorides have a limited oil solubility, this does not adversely affect their usefulness. Surprisingly, oils containing these salts have properties which are absent in similar compositions containing the oil soluble salts of the prior art.
- monoalkyl trimethyl ammonium salts is particularly unique in hydrocarbons containing high molecular weight polar organic compounds.
- Such polymers in general facilitate the formation of water in oil emulsions, stabilize such emulsions and counteract the effect of antihaze agents.
- the additives of the present invention in contrast to quaternary ammonium salts having two or three higher alkyl groups, are effective in the presence of polar oligomers such as a low molecular weight ethylenevinyl acetate copolymer.
- This effectiveness of the salts of the present invention in the presence of such polymers is very important since such polymers are increasingly used, for example, to improve the cold flow properties of oils and to provide detergency to hydrocarbon systems.
- known antihaze agents often stabilize rather than break water in oil emulsions.
- emulsion stabilization results in water pickup from tank and ship bottoms.
- the hazy oil so obtained has an adverse appeal to the customer when contrasted with the clear oil he expects.
- the microbiocidal effect of monoalkyl trimethyl ammonium salts of low oil solubility in the present hydrocarbon compositions is surprisingly advantageous. This effect is associated with the preferential water solubility of such salts.
- Water solubility is important since the microbial degradation of oil, which is primarily due to bacterial activity, occurs at the water-oil interface. Since the amount of water, petroleum products are exposed to, is relatively small, preferential water solubility of our oil bactericides means concentration at their site of action rather than complete loss through selective extraction.
- liquid hydrocarbons containing minor amounts of surface active, C higher alkyl trimethyl ammonium salts have a surprising resistance to forming water in oil emulsions and to microbial degradation.
- the compositions of the present invention were distinguished over known hydrocarbon oil compositions containing higher dialkyl dimethyl ammonium salts by comparative evaluations of their antihaze and antibacterial properties.
- the present compositions were found to be particularly unique in retaining their haze resistance even in the presence of polar oligomeric additives, such as ethylene-vinyl acetate copolymers.
- the essential minor higher alkyl trimethyl ammonium salt components of the present compositions are characterized as follows: [R N (CI'I3)a] Q, wherein R is a C to C open chain aliphatic hydrocarbon group such as alkyl, alkenyl and alkynyl.
- the alkyl group may be interrupted by arylene groups such as phenylene, by amino, sulfide and oxide groups. As such the alkyl group may be branched or straight chain. A straight chain structure is preferred. Branching is preferably limited to methyl groups.
- the open chain alkyl group may have a saturated cyclic component such as cyclohexylene and cyclopentylene.
- the number of carbon atoms in the aliphatic group is preferably between Cg and C more preferably between C and C Salt mixtures having components with aliphatic groups of different carbon atoms are surprisingly advantageous.
- the aliphatic group is preferably saturated, i.e., an open chain alkyl radical such as shown by the formula [C H N (CH Cl".
- Preferred alkyl radicals have a completely non-branched straight chain structure or an alphamethyl substituted normal alkyl structure as shown by the following salt formula:
- n, m and l are numbers in accord with the number of carbons in the aliphatic group. These three formulae are of course related to the more general earlier formula.
- the R group of the earlier formula equals the C I-I Cl-I (Cl-l and the CH (CI-I ),,,CH(CI-I of the present formula. Accordingly, the preferable number ranges are 8 to 40 for n, 7 to 39 for m and 6 to 38 for l. In the case of unsubstituted normal alkyl groups, the most preferred number of carbon atoms is 14. However, it is surprisingly advantageously to employ a mixture of n-alkyl compounds derived from coconut oil. Similarly, the a-methyl branched product is preferably derived from a mixture of detergent range olefins.
- the higher alkyl group of the present salts is the hydrophobic part of a surfactant molecule.
- it is an oil soluble group; nevertheless its size, i.e., carbon number, is limited by a limited water solubility requirement for the overall molecule.
- this group must be large enough to assure some oil solubility.
- the water versus oil solubility ratios, i.e., coefficients, are very important in determining the demulsifying and bactericidal properties of the salts in hydrocarbon systems. The optimum properties for a practical use will, of course, also depend on the hydrocarbon, e.g. on its paraffinic versus aromatic character.
- the Q anion of the salts of the present invention includes negatively charged, nonradical species inorganic and organic in character.
- Inorganic anions include halides such as chloride, bromide, fluoride; phosphates such as polyphosphates; phosphite; sulfate and nitrite.
- Organic anions include carboxylates, having 1 to 30, preferably 1 to 18, carbon atoms, such as acetate, neotridecanoate, ethylenediamine tetraacetate; organic phosphate and phosphine anions such as C to C dialkyl dithiophosphate, phosphate, phosphite and phosphonate; C to C hydrocarbon sulfonate such as methanesulfonate, benzenesulfonate, tetrapropylenesulfonate; C to C alkyl sulfate such as methylsulfate.
- carboxylates having 1 to 30, preferably 1 to 18, carbon atoms, such as acetate, neotridecanoate, ethylenediamine tetraacetate
- organic phosphate and phosphine anions such as C to C dialkyl dithiophosphate, phosphate, phosphite and phosphonate
- Chloride anions are most preferred because of the ease of preparation of the chloride salts and their high effectiveness.
- the Q anion may be a complex anion formed by combining one of the simple anions such as the chloride with a metal salt or an acid such as boron fluoride or acetic acid. In general, monovalent anions are preferred.
- the ammonium salt component is usually present in the liquid hydrocarbon at a concentration of 0.0001 to 1 percent, preferably 0.0005 to 0.1 percent, most preferably, 0.00l to 0.004 percent.
- concentration of the salt is somewhat dependent on the major hydrocarbon component used and the properties desired. The above preferred concentrations are mainly recommended for heating oils resistant to water haze. Another important property of similar oil compositions is resistance to microbiological degradation. Other properties include reduced corrosivity, detergent action, etc.
- ammonium salts especially the higher n-alkyl trimethy] ammonium chlorides, are commercially available. Salts containing a mixture of alkyl groups are especially widely used because they can be manufactured from readily available agricultural products, such as coconut oil, tallow oil, soya oil. The preparation of such chlorides, their compositions and suppliers are described in the monograph on Cationic Surfactants cited hereinabove.
- the major hydrocarbon components of the present compositions are preferably hydrocarbon oils of natural origin such as crude petroleum and distillate fuels.
- the petroleum distillates have preferable boiling ranges between and 900F.
- Such products include gasolines, jet fuels, diesel fuels, heating oils, lubricating oil, transformer oils. Distillate fuels boiling in the range between about 250 and 750F. are particularly preferred.
- Heating oil and diesel fuel are specific choice hydrocarbons. They are described in ASTM Specifications D-396-48T and D-975-53-T. Most specifically, Grades 1 and 2 heating oils are used. Jet fuels are other specific examples. Typical aviation turbojet fuels are described by US. Military Specifications and referred to as JP-4, .IP-5, JP-6, etc.
- the polar oligomeric additives of the present compositions are optional minor components. Such additives are described in detail in US Pat. Nos. 3,008,813; 3,265,474; 3,346,353 and 3,397,970 which were referred to earlier. These additives preferably contain a major proportion of nonpolar hydrocarbon groups such as alkyl, alkylene, phenyl, naphthyl, and a major proportion of polar atoms such as oxygen and chlorine. The oxygen is preferably present in est'er groups.
- a preferred polar oligomer is the copolymer of ethylene and vinyl-acetate described by M. J. Wisotsky, A. E. Kober and I. A.
- Such polymers have a preferable molecular weight range of 400 to 20,000. Increasingly more preferred molecular weight ranges are from 500 to 10,000, from 500 to 5,000, from 1,000 to 3,000.
- polymeric additives are preferably employed in concentrations ranging from about 0.00l-to 2 percent, more preferably 0.001 to 0.15 percent, most preferably 0.005 to 0.05 percent.
- these polymers are mainly employed to secure the desired degree of fluidity at low tempertures.
- such additives have a polymethylene chain interrupted by aliphatic groups having substituents containing oxygen, chlorine and aromatic radicals.
- Such polymers can be preparedby copolymerizing a major amount of .etylene with minor amounts of an ethylenic monomer having substituents containing the above radicals.
- substituted ethylenes are vinyl esters of C -C monocarboxylic acids, acrylate, maleate and fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones.
- the copolymerization is usually catalyzed by free radical type chemical or irradiation initiators.
- compositions have a unique resistance to water haze formation and microbial degradation due to the presence of the higher alkyl trimethylammonium salt component.
- the haze behavior is usually determined in the Waring Blender Test, In this, five milliliters of water and.
- the rate of the breakup of the emulsion is measured spectrophotometrically.
- the amount of light transmitted through a sample from the top of the mixture is indirectly related to haze.
- the microbial degradation of hydrocarbons is mainly due to bacterial attack by gram negative organisms at water-oil interfaces. Certain bacteria readily metabolize straight chain hydrocarbons. These hydrocarbons are present in petroleum and hydrocarbon fuels. The higher the percentage of paraffinic hydrocarbons, the faster the microbial degradation. Fast microbial degradation is concurrent with a rapid increase of the number of bacteria in the water phase.
- the inhibition of microbial degradation is indirectly measured by determining the concentration of additives which will inhibit the multiplication of bacteria or kill the microorganisms. Usually, serial dilution tests are carried out using different additive concentrations. A known concentration of a bacterial culture is an aqueous nutrient medium which is overlayered with oil. Bacterial counts are made at various intervals after the inoculation.
- the abovedescribed higher alkyl trimethylammonium salts are surprisingly useful as demulsifiers for water in hydrocarbon systems particularly as antihaze agents for hydrocarbon fuels and petroleum crudes.
- such salts are useful antihaze agents in middle distillate fuels such as heating oil and diesel fuel.
- the said higher alkyl trimethyl ammonium salts are unexpectedly useful to prevent the microbial degradation of liquid hydrocarbons when in Contact with water.
- These salts are particularly effective bacteriostatic and bactericidal agents for petroleum and products derived therefrom such as distillate fuels. They are specifically useful as heating oil, diesel fuel, jet fuel and crude oil bactericides.
- the present invention provides methods for preventing and breaking water in oil emulsions especially haze in the systems described. It also provides a method for similarly preventing and inhibiting microbial, particularly bacterial, attack and deterioration.
- the present aliphatic hydrocarbyl trimethyl ammonium salts may be added to the liquid hydrocarbon as such or in the form of a concentrate solution in polar organic solvents.
- exemplary solvents are alcohols such as isopropanol, ethylene glycol; kettones such as methyl isobutyl ketone; esters such as ethyl acetate, tricresyl phosphate, etc.
- These salts may also be used in composite multipurpose formulations with other oil additives such as flow improvers, antioxidants, etc.
- EXAMPLES A. Effectiveness of Surface Active Quaternary Ammonium Compounds as Demulsifiers in the Waring Blender Test The antihaze effectiveness of various quaternary ammonium chlorides in oil was tested in a Waring Blender Test. In this test the oil was mixed with one percent water and a certain amount of the ammonium chloride in the blender at 10,000 rpm for 2 minutes to produce the test emulsions. The stability of the emulsions was then determined by a periodical measurement of their light transmittance. The light transmittance is directly related to the clarity of the resulting oil.
- the oil was a heating oil containing percent alkyl, 10 percent aryl and essentially no olefinic hydrogens by proton magnetic resonance (pmr) spectroscopy.
- the flow improver composition consisted of about 52 percent ethylene vinyl acetate copolymer and 48 percent light mineral oil.
- the copolymer had a number average molecular weight of about 2,605 by vapor phase osmometry. Its pmr spectrum showed a ratio of about 6.8 for the ethylene versus vinyl acetate derived structural units. For every one hundred methylene atoms in the backbone of the copolymer there were about 10-12 methyl branches.
- This copolymer was prepared by copolymerizing ethylene and vinyl acetate using an ethylene pressure of 950 psig at a temperature of about with di-tertiary butyl peroxide initiator.
- the C -a1kyl derivative is more effective than the C compound although the latter is more surface active.
- the higher dialkyl derivative in Group II, dicoco dimethyl ammonium chloride is an outstandingly effective demulsifier in the absence of the copolymer but an emulsion stabilizer in its presence.
- the compound of the third group i.e., the higher trialkyl methyl derivative has no significant beneficial action in the absence of the polar copolymer and an adverse effect in its presence.
- EXAMPLE 2 Effectiveness of Various Monoalkyl Trimethyl Ammonium Chlorides in thePresence and in the Absence of a Slightly Branched Ethylene Vinyl Acetate Copolymer
- a polar oligomer again an ethylene-vinyl acetate copolymer was used. This copolymer again had a molecular weight range in the 2,000s. Also, this copolymer had a high ethylene-vinyl acetate ratio, i.e., about 8. How ever, this polymer had only about 4 methyl branches per 100 methylene groups.
- this copolymer has more crystalline character and lower solubility. As such it is dissolved in a naphthenic solvent and employed as a concentrate.
- the other significant difference is the absence of crosslinking in this copolymer as opposed to the minor amount of gel in the cosequent to the mixing this control is almost completely clear just like most of the oils containing the test compounds.
- the demulsifying effect of the test compounds in this case is best observed shortly after mixing. The one hour data show that at the higher concentration all these quatemaries acted as effective demulsifiers (No.
- the sect-alkyl groups have the following composition: I)? Cu; 187: C l7'7r C I67: C r; I67: Cm; 14% Cm; I394 C 5% C polymer of the previous example. These differences are largely due to the lower temperature of polymerization of the present product, i.e., about C.
- the test data on compositions containing no quaternary additive show that, in contrast to the highly branched copolymer of Example 1 (No. 3), the slightly branched copolymer of Example 2 (No. 2) has no adverse effect on the emulsification tendency of the base oil (No. l).
- the transparency data of the first seven hours after the mixing show that the addition of the monoalkyl ammonium compounds helps to demulsify in the presence of both copolymers (Nos. 49).
- the dialkyl compound shows no beneficial effect in the presence of either of the copolymers (Nos. 1 1 and 12) although it is effective in their absence (No. In general, the effects are more pronounced and the differences are more significant in the presence of the highly branched copolymer.
- Oxidant Oxidant" Polymer ppm 0 l 5 7 24 l 3 17 29 73 2 2O 24 68 94 92 94 98 3 21 ll 59 67 74 79 89 4 21 9 48 71 74 79 87 5 21 20 20 63 95 96 97 I00 6 21 l5 6 30 39 43 41 61 7 21 15 20 24 62 81 84 92 88 8 21 15 7 34 69 61 57 77 9 21 I5 20 I2 45 64 7O 71 74 Used as a isopmpanol Solution Composed of light cracked oil and 25% virgin gas oil A mixture of methyl cyclohexyl amines Dieyclohexyl amine A multipurpose additive consisting of an acrylate copolymer which is described in Table V EXAMPLE Effectiveness of Monococo Trimethyl Ammonium Chloride as a Dehazing Agent in Various Heating Oils in the Presence of an Acrylate Copolymer As a hydrocarbon phase for
- monium chloride is further illustrated in various heat- As the water phase a P basal salt medium was used. ing oils. These oils also contained antioxidants and an Thi medium was similar to the one reported by E. .I. acrylate copolymer as a multipurpose additive.
- Table V. Iowa entitled Effect of Hydrocarbon Structure on The light transmittance data show that in each case Mechanisms of Microbial Alkane Metabolism, pubthe addition of the quaternary compound increased the lished by University Microfilms, Inc. as No. 66-7218 in transmittance, i.e., reduced haze. The difference in the Ann Arbor, Michigan.
- test compound was added as a 0.1 verse effect, however, is overcome by the addition of ml solution. Onto the top of the final water solution, the higher monoalkyl quaternary compound. 100 ml of the oil was layered.
- a multipurpose additive consisting of a 71 diluent solution of a copolymer of 52.671 di-C oxo alkyl fumarate, 26.8% di-C -alkyl fumarate 17.2% vinyl acetate,
- test bottles were closed with rubber stoppers and vented through a No. 18 gauge hypodermic needle. They were incubated for 7 days under stationary conditions on a laboratory bench at about 24C. Thereafter, 1 ml was withdrawn from the interface region of each bottle, using a 1 ml tuberculine syringe fitted with a No. 18 gauge needle. A 0.1 ml sample of each of 10' 10' and 10" dilutions were spread over a nutrient agar plate, which was subsequently incubated for 72 hours. Thereafter, the number of viable cells was determined and tabulated as shown in Table VI.
- the sharp reduction of viable cells by the application of the experimental and control compounds showed a generally high effectiveness.
- the lower cell count in the mixture containing 500 ppm monococo trimethyl ammonium chloride (No. 1) than in the similar mixture containing the dicoco compound (No. 2) indicates that the higher monoalkyl salts are surprisingly more effective than the higher dialkyl derivatives.
- the higher monoalkyl compound having a branched alkyl chain is more effective than the known oil bactericide control.
- the bacteria were from the Borregas Field, Kingsville, Texas.
- the test system was a 3.5 percent NaCl sulfate reducing broth bacteria culture containing 100,000 bacteria per milliliter. Different concentrations of the ammonium chlorides were added to vials containing the broth medium. The media were then inoculated. The vials were incubated at C. and observed at intervals for evidence of bacterial growth. The results are shown by Table VII.
- EXAMPLE 8 Effectiveness of Quaternary Higher Monoalkyl Versus Dialkyl Ammonium Chlorides as Crude Oil Bactericides against Aerobic Bacteria
- the comparative effectiveness of a pair of ammonium chlorides was determined against aerobic bacteria from Block 73, Louisiana.
- the test system was a 3.5 percent NaCl aerobic broth bacteria culture containing 100,000 bacteria per milliliter.
- the test procedure was the same as in the previous example. The results are shown by Table VIII.
- EXAMPLE 9 Effect of Higher n-Alkyl Trimethyl Ammonium Chlorides as Middle Distillate Bactericides
- the comparative bactericidal effectiveness of tri- 10 methyl ammonium chloridies having higher n-alkyl groups'of different chain length was investigated in a P basal salt medium overlayered with diesel fuel.
- test organisms two gram negative strains isolated from tank bottoms of a home oil heater were used (Nos. 1 and 2). l
- EXAMPLE 10 Effect of Straight Chain and Branched Higher Alkyl Trimethyl Ammonium Chloride as Middle Distillate Bactericides
- the comparative effectiveness of several higher 1- alkyl and 2-alkyl trimethyl ammonium chlorides was investigated using the test procedure described in the previous example. However, in this test only one gram negative bacterial strain was used. This strain was isolated from the heating oil tank bottoms of a home. The test mixtures were sampled after 24 and 48 hours. The results are shown in Table X.
- EXAMPLE 1 Effect of n-Dodecyl Trimethyl Ammonium Chloride as a Jet Fuel Bactericide The effect of various concentrations of n-dodecyl trimethyl ammonium chloride on the growth of various bacterial strains utilizing jet fuel was studied.
- the five bacterial isolates were routinely maintained on nutrient agar slants by weekly transfers.
- the above five cultures 24 hr. old slant cultures) were inoculated into culture tubes containing 7 ml of sterile nutrient broth and incubated at 30C. under stationary conditions for 24 hours. At the end of the incubation period, contents from each tube were transferred under sterile conditions into sterilized centrifuge tubes.
- the cells were harvested by centrifugation of 10,000 RPM for 15 minutes. The cells were washed by resuspending the pellet in 10 ml sterile P basal salts medium and recentrifuged. The washed cells were resuspended again in l ml of sterile medium.
- composition of claim 1 wherein the liquid hydrocarbon is crude petroleum or a petroleum distillate and the higher alkyl trimethyl ammonium salt is present at concentrations between abot 0.001 percent and 1 percent.
- composition of claim 2 wherein said higher alkyl trimethyl ammonium salt is a chloride in a concentration ranging from 0.00l to 0.004 percent by weight.
- composition of claim 3 wherein said ammonium chloride is present in a petroleum crude.
- composition of claim 5 wherein said petroleum distillate is a distillate fuel boiling in the range between about 250 and 750F.
- composition of claim 7 wherein said salt has an aliphatic R group of the formula C l-[ wherein n is 8 to 40.
- composition of claim 8 wherein the structure of the group C,,H is Cl-l (Ch and CH (CH CH(CH wherein m is 7 to 39 and l is 6 to 38.
- composition of claim 7 wherein said salt has the group Q, selected from the group consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate and phosphonate.
- composition of claim 10 wherein the group O is selected from the group of nonradical anions consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate, phosphonate.
- composition of claim 7 wherein the liquid hydrocarbon is crude petroleum or a petroleum distillate.
- composition of claim 13 wherein the petroleum distillate also contains a minor polar ethylene copolymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C, to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
- a minor polar ethylene copolymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C, to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
- a petroleum distillate composition boiling in the range between about 250 and 750F. having increased resistance to emulsion formation and microbial degradation containing from about 0.001 to 0.1 percent of a salt of the formula wherein n is 8 to 25, and from about 0.001 to 2 percent of a polar polymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones, in amounts sufficient to secure fluidity at low temperatures.
- composition of claim 7 wherein said salt is monococo trimethyl ammonium chloride.
- a crude petroleum or petroleum distillate composition containing as a minor component a surface active, water soluble, saturated, open chain higher alkyl trimethyl ammonium salt, said alkyl group containing a minimum of eight carbon atoms and a minor polar polymeric additive having a molecular weight range of about 400 to 20,000 and prepared by the copolymerization of ethylene and vinyl acetate, in amounts sufficient to increase its resistance to emulsion formation.
- composition of claim 2 wherein said petroleum also contains a minor polar ethylene copolymer additive having a molecular weight range of 400 to 20,000, said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C 1 to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
- a minor polar ethylene copolymer additive having a molecular weight range of 400 to 20,000, said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C 1 to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
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Abstract
Liquid hydrocarbons containing minor amounts of surface active, higher alkyl trimethyl ammonium salts are surprisingly resistant to forming water in oil emulsions and microbiological degradation. Detergent range alkyl trimethyl ammonium chlorides of limited hydrocarbon solubility are especially useful as antihaze and/or antimicrobial agents for heating oils. The water solubility of the new oil additives unexpectedly facilitates their bactericidal effectiveness. Furthermore, antihaze activity of these additives is uniquely unaffected by polar oligomeric additives such as cold flow improvers and detergents also present in the oil products.
Description
United States Patent [1 1 Oswald et al.
[ Apr. 29, 1975 HIGHER ALKYL TRIMETIIYL AMMONIUM SALT LIQUID I-IYDROCARBON COMPOSITIONS [76] Inventors: Alexis A. Oswald, 1809 Sunny Slope Dr., Mountainside, NJ. 07092; Jack Ryer, 61 Jensen St., East Brunswick, NJ. 08816; Raam R. Mohan, 1 12 Oakland St., Berkeley Heights, NJ. 07922 221 Filed: Feb. 7, 1972 21 App1.No.:224,34l
[521 US. Cl. 44/62; 44/66; 44/71; 44/72; 424/329 [51] Int. Cl C101 1/26 [58] Field of Search 44/71, 72, 62, 66; 424/329 [56] References Cited UNITED STATES PATENTS 2,295,505 9/1942 Shelton 424/329 2,786,797 3/1957 Lcderer 424/329 Primary ExaminerDaniel E. Wyman Assistant ExaminerY. H. Smith Attorney, Agent, or Firm-John Paul Corcoran [57] ABSTRACT Liquid hydrocarbons containing minor amounts of 7 surface active, higher alkyl trimethyl ammonium salts are surprisingly resistant to forming water in oil emulsions and microbiological degradation. Detergent range alkyl trimethyl ammonium chlorides of limited hydrocarbon solubility are especially useful as antihaze and/or antimicrobial agents for heating oils. The water solubility of the new oil additives unexpectedly facilitates their bactericidal effectiveness. Furthermore, antihaze activity of these additives is uniquely unaffected by polar oligomeric additives such as cold flow improvers and detergents also present in the oil products.
19 Claims, No Drawings HIGHER ALKYL TRIMETHYL AMMONIUM SALT LIQUID I-IYDROCARBON COMPOSITIONS FIELD OF THE INVENTION This invention relates to liquid hydrocarbons containing minor amounts of surface active, higher alkyl trimethyl ammonium salts. In one aspect, this invention relates to hydrocarbon, oils, i.e., fuels, containing higher alkyl trimethyl ammonium salt additives. In another aspect, this invention relates to middle distillate fuels having higher alkyl trimethyl ammonium chlorides together with polar oligomeric additives.
One useful aspect of the invention relates to the suppression of water-in-oil emulsion forming tendencies of liquid hydrocarbons by the use of minor amounts of said additives. In this respect, the inhibition of haze formation in heating oils containing cold flow improver additives is of particular interest. Another useful aspect of the invention is the inhibition of microbiological deterioration, particularly of bacterial attack, of hydrocarbons.
PRIOR ART Higher alkyl trimethyl ammonium salts, especially the chlorides, are known surfactants with high microbiocidal activity. Their synthesis and properties are described in considerable detail in a recent monograph entitled, Cationic Surfactants, edited by Eric .Iungermann, published by Marcel Dekker, Inc. in New York in 1970. However, to date such salts were considered as useful components mainly in systems containing a major amount of water. In contrast, the present invention describes compositions comprising such salts with major amounts of liquid hydrocarbons.
Unlike higher monoalkyl trimethyl ammonium salts, the higher dialkyl dimethyl ammonium salts are known oil soluble surfactants and microbiocides. For example, U.S. Pat. Nos. 3,008,813 and 3,265,474 to .l. R. Siege] and U.S. Pat. 3,346,353 to B. R. Strickland and I... Berkowitz all describe hydrocarbon oils which contain higher dialkyl dimethyl ammonium salts, especially chlorides to improve their water tolerance. Other inventions involving similar compositions containing oil soluble quaternary ammonium salts are described in U.S. Pat. Nos. 3,033,665, 3,158,647 and 3,397,970. There are also many general statements about the use fulness of quaternary ammonium salts in oil products. The latter invite experimentation with such salts in general. However, in toto the prior art teaches that in oil applications, the higher dialkyl rather than monoalkyl compounds are useful.
In the present invention, it was found, in contrast to the teaching of the prior art, that liquid hydrocarbon compositions containing higher monoalkyl trimethyl ammonium salts have highly unexpected useful properties. Although most of these monoalkyl salts such as the chlorides have a limited oil solubility, this does not adversely affect their usefulness. Surprisingly, oils containing these salts have properties which are absent in similar compositions containing the oil soluble salts of the prior art.
The effect of monoalkyl trimethyl ammonium salts is particularly unique in hydrocarbons containing high molecular weight polar organic compounds. Such polymers in general facilitate the formation of water in oil emulsions, stabilize such emulsions and counteract the effect of antihaze agents. It was surprisingly found that the additives of the present invention, in contrast to quaternary ammonium salts having two or three higher alkyl groups, are effective in the presence of polar oligomers such as a low molecular weight ethylenevinyl acetate copolymer. This effectiveness of the salts of the present invention in the presence of such polymers is very important since such polymers are increasingly used, for example, to improve the cold flow properties of oils and to provide detergency to hydrocarbon systems. In the presence of such polymers, known antihaze agents often stabilize rather than break water in oil emulsions. During the handling of fuels, emulsion stabilization results in water pickup from tank and ship bottoms. The hazy oil so obtained has an adverse appeal to the customer when contrasted with the clear oil he expects.
The microbiocidal effect of monoalkyl trimethyl ammonium salts of low oil solubility in the present hydrocarbon compositions is surprisingly advantageous. This effect is associated with the preferential water solubility of such salts. Water solubility is important since the microbial degradation of oil, which is primarily due to bacterial activity, occurs at the water-oil interface. Since the amount of water, petroleum products are exposed to, is relatively small, preferential water solubility of our oil bactericides means concentration at their site of action rather than complete loss through selective extraction.
SUMMARY OF THE INVENTION In the present invention it has been found that liquid hydrocarbons containing minor amounts of surface active, C higher alkyl trimethyl ammonium salts have a surprising resistance to forming water in oil emulsions and to microbial degradation. The compositions of the present invention were distinguished over known hydrocarbon oil compositions containing higher dialkyl dimethyl ammonium salts by comparative evaluations of their antihaze and antibacterial properties. The present compositions were found to be particularly unique in retaining their haze resistance even in the presence of polar oligomeric additives, such as ethylene-vinyl acetate copolymers.
The essential minor higher alkyl trimethyl ammonium salt components of the present compositions are characterized as follows: [R N (CI'I3)a] Q, wherein R is a C to C open chain aliphatic hydrocarbon group such as alkyl, alkenyl and alkynyl. The alkyl group may be interrupted by arylene groups such as phenylene, by amino, sulfide and oxide groups. As such the alkyl group may be branched or straight chain. A straight chain structure is preferred. Branching is preferably limited to methyl groups. The open chain alkyl group may have a saturated cyclic component such as cyclohexylene and cyclopentylene. The number of carbon atoms in the aliphatic group is preferably between Cg and C more preferably between C and C Salt mixtures having components with aliphatic groups of different carbon atoms are surprisingly advantageous.
The aliphatic group is preferably saturated, i.e., an open chain alkyl radical such as shown by the formula [C H N (CH Cl". Preferred alkyl radicals have a completely non-branched straight chain structure or an alphamethyl substituted normal alkyl structure as shown by the following salt formula:
and
wherein n, m and l are numbers in accord with the number of carbons in the aliphatic group. These three formulae are of course related to the more general earlier formula. The R group of the earlier formula equals the C I-I Cl-I (Cl-l and the CH (CI-I ),,,CH(CI-I of the present formula. Accordingly, the preferable number ranges are 8 to 40 for n, 7 to 39 for m and 6 to 38 for l. In the case of unsubstituted normal alkyl groups, the most preferred number of carbon atoms is 14. However, it is surprisingly advantageously to employ a mixture of n-alkyl compounds derived from coconut oil. Similarly, the a-methyl branched product is preferably derived from a mixture of detergent range olefins.
In general, the higher alkyl group of the present salts is the hydrophobic part of a surfactant molecule. As such it is an oil soluble group; nevertheless its size, i.e., carbon number, is limited by a limited water solubility requirement for the overall molecule. On the other hand, this group must be large enough to assure some oil solubility. The water versus oil solubility ratios, i.e., coefficients, are very important in determining the demulsifying and bactericidal properties of the salts in hydrocarbon systems. The optimum properties for a practical use will, of course, also depend on the hydrocarbon, e.g. on its paraffinic versus aromatic character.
The Q anion of the salts of the present invention includes negatively charged, nonradical species inorganic and organic in character. Inorganic anions include halides such as chloride, bromide, fluoride; phosphates such as polyphosphates; phosphite; sulfate and nitrite.
Organic anions include carboxylates, having 1 to 30, preferably 1 to 18, carbon atoms, such as acetate, neotridecanoate, ethylenediamine tetraacetate; organic phosphate and phosphine anions such as C to C dialkyl dithiophosphate, phosphate, phosphite and phosphonate; C to C hydrocarbon sulfonate such as methanesulfonate, benzenesulfonate, tetrapropylenesulfonate; C to C alkyl sulfate such as methylsulfate.
Chloride anions are most preferred because of the ease of preparation of the chloride salts and their high effectiveness. The Q anion may be a complex anion formed by combining one of the simple anions such as the chloride with a metal salt or an acid such as boron fluoride or acetic acid. In general, monovalent anions are preferred.
The ammonium salt component is usually present in the liquid hydrocarbon at a concentration of 0.0001 to 1 percent, preferably 0.0005 to 0.1 percent, most preferably, 0.00l to 0.004 percent. The preferred concentration of the salt is somewhat dependent on the major hydrocarbon component used and the properties desired. The above preferred concentrations are mainly recommended for heating oils resistant to water haze. Another important property of similar oil compositions is resistance to microbiological degradation. Other properties include reduced corrosivity, detergent action, etc.
Such ammonium salts especially the higher n-alkyl trimethy] ammonium chlorides, are commercially available. Salts containing a mixture of alkyl groups are especially widely used because they can be manufactured from readily available agricultural products, such as coconut oil, tallow oil, soya oil. The preparation of such chlorides, their compositions and suppliers are described in the monograph on Cationic Surfactants cited hereinabove.
The major hydrocarbon components of the present compositions are preferably hydrocarbon oils of natural origin such as crude petroleum and distillate fuels. The petroleum distillates have preferable boiling ranges between and 900F. Such products include gasolines, jet fuels, diesel fuels, heating oils, lubricating oil, transformer oils. Distillate fuels boiling in the range between about 250 and 750F. are particularly preferred. Heating oil and diesel fuel are specific choice hydrocarbons. They are described in ASTM Specifications D-396-48T and D-975-53-T. Most specifically, Grades 1 and 2 heating oils are used. Jet fuels are other specific examples. Typical aviation turbojet fuels are described by US. Military Specifications and referred to as JP-4, .IP-5, JP-6, etc.
The polar oligomeric additives of the present compositions are optional minor components. Such additives are described in detail in US Pat. Nos. 3,008,813; 3,265,474; 3,346,353 and 3,397,970 which were referred to earlier. These additives preferably contain a major proportion of nonpolar hydrocarbon groups such as alkyl, alkylene, phenyl, naphthyl, and a major proportion of polar atoms such as oxygen and chlorine. The oxygen is preferably present in est'er groups. A preferred polar oligomer is the copolymer of ethylene and vinyl-acetate described by M. J. Wisotsky, A. E. Kober and I. A. Zlochower in the Journal of Applied Polymer Science in Volume 15 on pages 1,737 to 1,742 in 1971. Such polymers have a preferable molecular weight range of 400 to 20,000. Increasingly more preferred molecular weight ranges are from 500 to 10,000, from 500 to 5,000, from 1,000 to 3,000.
These polymeric additives are preferably employed in concentrations ranging from about 0.00l-to 2 percent, more preferably 0.001 to 0.15 percent, most preferably 0.005 to 0.05 percent.
In middle distillaate fuels, these polymersare mainly employed to secure the desired degree of fluidity at low tempertures. In general, such additives have a polymethylene chain interrupted by aliphatic groups having substituents containing oxygen, chlorine and aromatic radicals. Such polymers can be preparedby copolymerizing a major amount of .etylene with minor amounts of an ethylenic monomer having substituents containing the above radicals. Such substituted ethylenes are vinyl esters of C -C monocarboxylic acids, acrylate, maleate and fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones. The copolymerization is usually catalyzed by free radical type chemical or irradiation initiators.
The claimed compositions have a unique resistance to water haze formation and microbial degradation due to the presence of the higher alkyl trimethylammonium salt component.
The haze behavior is usually determined in the Waring Blender Test, In this, five milliliters of water and.
500 milliliters of theliquid hydrocarbon composition, are mixed with a high speed rotational mixer for 2 minutes. The mixture is thenallowed to separate into a water and a hydrocarbon phase. Separation, i.e., the
rate of the breakup of the emulsion, is measured spectrophotometrically. The amount of light transmitted through a sample from the top of the mixture is indirectly related to haze.
The microbial degradation of hydrocarbons is mainly due to bacterial attack by gram negative organisms at water-oil interfaces. Certain bacteria readily metabolize straight chain hydrocarbons. These hydrocarbons are present in petroleum and hydrocarbon fuels. The higher the percentage of paraffinic hydrocarbons, the faster the microbial degradation. Fast microbial degradation is concurrent with a rapid increase of the number of bacteria in the water phase. The inhibition of microbial degradation is indirectly measured by determining the concentration of additives which will inhibit the multiplication of bacteria or kill the microorganisms. Usually, serial dilution tests are carried out using different additive concentrations. A known concentration of a bacterial culture is an aqueous nutrient medium which is overlayered with oil. Bacterial counts are made at various intervals after the inoculation.
It was found in the present invention, that the abovedescribed higher alkyl trimethylammonium saltsare surprisingly useful as demulsifiers for water in hydrocarbon systems particularly as antihaze agents for hydrocarbon fuels and petroleum crudes. Most specifically, such salts are useful antihaze agents in middle distillate fuels such as heating oil and diesel fuel.
It was also found that the said higher alkyl trimethyl ammonium salts are unexpectedly useful to prevent the microbial degradation of liquid hydrocarbons when in Contact with water. These salts are particularly effective bacteriostatic and bactericidal agents for petroleum and products derived therefrom such as distillate fuels. They are specifically useful as heating oil, diesel fuel, jet fuel and crude oil bactericides.
As such the present invention provides methods for preventing and breaking water in oil emulsions especially haze in the systems described. It also provides a method for similarly preventing and inhibiting microbial, particularly bacterial, attack and deterioration. When used in a process of dehazing oils and/or inhibiting their microbial deterioration, the present aliphatic hydrocarbyl trimethyl ammonium salts may be added to the liquid hydrocarbon as such or in the form of a concentrate solution in polar organic solvents. Exemplary solvents are alcohols such as isopropanol, ethylene glycol; kettones such as methyl isobutyl ketone; esters such as ethyl acetate, tricresyl phosphate, etc. These salts may also be used in composite multipurpose formulations with other oil additives such as flow improvers, antioxidants, etc.
EXAMPLES A. Effectiveness of Surface Active Quaternary Ammonium Compounds as Demulsifiers in the Waring Blender Test The antihaze effectiveness of various quaternary ammonium chlorides in oil was tested in a Waring Blender Test. In this test the oil was mixed with one percent water and a certain amount of the ammonium chloride in the blender at 10,000 rpm for 2 minutes to produce the test emulsions. The stability of the emulsions was then determined by a periodical measurement of their light transmittance. The light transmittance is directly related to the clarity of the resulting oil.
EXAMPLE 1 Comparison of the Effect of Various Types of Quaternary Ammonium Chlorides in the Presence and in the Absence of a Highly Branched Ethylene Vinyl Acetate Copolymer The haze behavior of an oil was tested in the presence and in the absence of a polar copolymer flow improver. Representative higher mono-, diand trialkyl derivatives of ammonium chlorides were used to determine the effect the type of surface active structure has on the haze behavior.
The oil was a heating oil containing percent alkyl, 10 percent aryl and essentially no olefinic hydrogens by proton magnetic resonance (pmr) spectroscopy.
The flow improver composition consisted of about 52 percent ethylene vinyl acetate copolymer and 48 percent light mineral oil. The copolymer had a number average molecular weight of about 2,605 by vapor phase osmometry. Its pmr spectrum showed a ratio of about 6.8 for the ethylene versus vinyl acetate derived structural units. For every one hundred methylene atoms in the backbone of the copolymer there were about 10-12 methyl branches. This copolymer was prepared by copolymerizing ethylene and vinyl acetate using an ethylene pressure of 950 psig at a temperature of about with di-tertiary butyl peroxide initiator.
The results of the Waring Blender Tests are shown in Table 1. Two sets of light transmittance values are tabulated. The first set of values were determined in tests using the base oil alone. The second set shows the behavior of the same base oil containing the polymer.
The data show that while the higher monoand dialkyl quaternary ammonium chlorides accelerate emulsion breaking in the absence of the flow improver, the higher diand trialkyl quaternary chlorides stabilize the emulsion when the polymeric additive is present. Only the higher alkyl trimethyl derivatives are effective demulsifiers in both presence and absence of the polar copolymer.
Of the two compounds of Group I in the Table the C -a1kyl derivative is more effective than the C compound although the latter is more surface active.
The higher dialkyl derivative in Group II, dicoco dimethyl ammonium chloride is an outstandingly effective demulsifier in the absence of the copolymer but an emulsion stabilizer in its presence.
The compound of the third group, i.e., the higher trialkyl methyl derivative has no significant beneficial action in the absence of the polar copolymer and an adverse effect in its presence.
In conclusion, these data show that certain water soluble higher alkyl trimethyl quaternary chlorides are effective demulsifiers for water in oil systems in the presence of oil soluble surfactants such as an ethylene-vinyl acetate copolymer.
TABLE I WARING BLENDER TEST OF OUATERNARY AMMONIUM CHLORIDES IN HEATING OIL WITHOUT AND WITH 0.04% PARADYNE 2O Quaternary Ammonium Light Transmittance of Oil After Hours,%
Chloride or R,N Cl Base Oil Base Oil Copolymer Group Type Structure of Cation ppm l 3 6 24 0 1 3 6 24 I Monoalkyl C H N*(CH; l0 I9 36 36 40 71 26 36 36 4] 74 20 ll 48 56 62 86 ll 38 52 53 94 C,,,H N (CH;,) l0 5 2I 24 44 3 l0 I8 24 5 3 2O 0 5 9 I4 53 3 3 6 15 43 II Dialkyl (Coco N(CH;,) I0 I3 65 67 72 88 I 2 2 2 9 24 I8 81 82 98 I 2 2 2 9 III Trialkyl (C,J-I N CH l0 3 I4 22 61 l l 2 9 20 3 I3 20 30 64 I I 2 3 10 IV (Control) (No Quaternary) 0 3 I5 22 29 71 2 3 5 8 l8 One percent water and 10 ppm of the test compound were added to 500 ml portions of the oil. The resulting compositions were then mixed in the blender at l0.000 rpm for 2 minutes. The solubility of the emulsions was determined by a periodical measurement of their light transmittance using a Bauseh and Lamb spectrophotometer.
" One ml of isopropanol was added to dissolve the quaternary ammonium compound. Dicoco dimethyl ammonium chloride. Although the average number of carbon atoms is about 12 in the higher alkyl chains. these chains consist of a mixture ol- 47% C 18% C 9% Cm. 8% C, I07 Cm. 5% C alkyl and 5% C, alkenyl groups which were derived from coconut oil.
EXAMPLE 2 Effectiveness of Various Monoalkyl Trimethyl Ammonium Chlorides in thePresence and in the Absence of a Slightly Branched Ethylene Vinyl Acetate Copolymer The haze behavior of an oil used in the previous example was tested in the presence of various monoalkyl trimethyl ammonium chlorides as demulsifiers. As a polar oligomer again an ethylene-vinyl acetate copolymer was used. This copolymer again had a molecular weight range in the 2,000s. Also, this copolymer had a high ethylene-vinyl acetate ratio, i.e., about 8. How ever, this polymer had only about 4 methyl branches per 100 methylene groups. As a consequence, this copolymer has more crystalline character and lower solubility. As such it is dissolved in a naphthenic solvent and employed as a concentrate. The other significant difference is the absence of crosslinking in this copolymer as opposed to the minor amount of gel in the cosequent to the mixing this control is almost completely clear just like most of the oils containing the test compounds. The demulsifying effect of the test compounds in this case is best observed shortly after mixing. The one hour data show that at the higher concentration all these quatemaries acted as effective demulsifiers (No.
booking at the relative effectiveness of the higher mono-n-alkyl compounds tested, it is interesting to observe that the monococo trimethyl ammonium chloride (No. 3) which contains a mixture of detergent range n-alkyl groups is more active than pure compounds of similar structure (Nos. 1 and 2). The sec-alkyl compounds consisting of mixtures of a-methyl branched alkyl trimethyl ammonium chlorides (Nos. 9 and 10) showed a behavior similar to their straight chain isomers (No. 3).
It seems that it is advantageous to use higher monoalkyl quatemaries containing a mixture of alkyl groups in the maximum activity range rather than a compound having a single alkyl group of optimum activity.
TABLE II EFFECT OF LONG CHAIN ALKYL TRIMETI-IYL AMMONIUM CHLORIDES ON THE HAZE BEHAVIOR OF HEATING OIL CONTAINING 0.04% LESS BRANCHED ETHYLENE-VINYL ACETATE COPOLYMER IN THE WARING BLENDER TEST 3 Light Transmittance of Heating Oil, In the Presence of Quaternary Chloride (ppm) After Standing (hr.)
Structure of Initial 1 Hr. 3 Hr. 7 Hr. 24 Hr. Sequence Quaternary Cation (ppm) (ppm) (ppm) (ppm) (ppm) No. in [R Q Cl l0 20 10 2O 10 20 I0 20 lo 20 1 nC.2H2,,N"(CH..) 6 53 63 89 2 nC H N*(CH I0 53 59 59 8l 3 CocoN (Cl-l;,), l4 7 44 59 48 46 76 90 100 4 iC N (CH 2 l0 4 48 7 68 8 73 22 95 5 iC, N (CH -fl3 8 36 62 41 67 42 74 97 6 (Control) No quaternary 2 6 25 35 91 Monococo trimethyl ammonium chloride having alkyl groups derived from coconut oil.(Table LC).
" Mixtures of homologous compounds of structure [C,,H,,, ,CH(CH )N(CH;,)] Cl- The Sec-alkyl groups have the following composition: 29? C 23% Cu; 23% C 24% C 2571 C 37: C
" The sect-alkyl groups have the following composition: I)? Cu; 187: C l7'7r C I67: C r; I67: Cm; 14% Cm; I394 C 5% C polymer of the previous example. These differences are largely due to the lower temperature of polymerization of the present product, i.e., about C.
The results of the Waring Blender Test in the presence of 0.04 percent of this copolymer are shown in Table II. The data show that the control base oil containing this less branched copolymer alone has a higher resistance to haze (No. 6). After 24 hours standing sub- EXAMPLE 3 Comparison of the Effect of Higher Monoand Di-Alkyl Ammonium Chlorides in the Presence of Two Ethylene Vinyl Acetate Copolymers Having Different Degrees of Branching The haze behavior of the oil used in the previous examples was tested in the presence of the slightly branched copolymer of Example 2 and the highly branched copolymer of Example 1. As demulsifiers de tergent range alkyl trimethyl ammonium chloride and dialkyl dimethyl ammonium chloride compounds were used. The results are shown by Table III.
The test data on compositions containing no quaternary additive (Nos. l-3) show that, in contrast to the highly branched copolymer of Example 1 (No. 3), the slightly branched copolymer of Example 2 (No. 2) has no adverse effect on the emulsification tendency of the base oil (No. l). The transparency data of the first seven hours after the mixing show that the addition of the monoalkyl ammonium compounds helps to demulsify in the presence of both copolymers (Nos. 49). In contrast, the dialkyl compound shows no beneficial effect in the presence of either of the copolymers (Nos. 1 1 and 12) although it is effective in their absence (No. In general, the effects are more pronounced and the differences are more significant in the presence of the highly branched copolymer.
TABLE III The C C monoalkyl derivatives of trimethyl ammonium chlorides were found to be effective in the previous examples as antihaze additives in the Waring Blender Test in oils containing various ethylene-vinyl acetate copolymer flow improvers. In the present example, the effectiveness of monococo trimethyl ammonium chloride was further examined in a heating oil in the presence of an acrylate copolymer as shown in Table IV. As shown by the Table, this oil contained cyclohexyl amine antioxidants and an acrylate copolymer multipurpose additive. The presence of the acrylate was of particular interest since it has an adverse effect on ha ze formation (No. l verus Nos. 6 and 8).
The data show that both the base oil (No. 1) and the oil containing dicyclohexyl amine (No. 4) are highly responsive to the quaternary antihaze additive (Nos. 2 and 5). The oils additionally containing the acrylate copolymer (Nos. 6 and 8) are also improved by the quaternary compound (Nos. 7 and 9). It is noted that after one hour the transparency readings become somewhat EFFECT OF TWO DIFFERENT ETHYLENE-VINYL ACETATE COPOLYMERS ON THE HAZE BEHAVIOR OF HEATING OIL CONTAINING HIGHER MONO- AND DIALKYL AMMONIUM CHLORIDES AS MEASUREDBY THE WARING BLENDER TEST Copolymer Quaternary Chloride Additive, 20 ppm 0.04% Structure of Quaternary Light Transmittance of Heating Oil Sequence of Example Cation (Hours After Mixing) No. No. Type [R O ]Cl Initial I 3 6(7) 24 I None 3 I5 22 29 71 2 2 None 3 2O 37 (48) 100 3 l 2 3 5 8 l8 4 None Mono- C H N CH 1 l 48 56 62 86 5 2 alkyl 10 53 59 (59) 81 6 I I 1 38 52 53 94 7" None Mono- Coc0N (CH IO 50 72 66 98 8 2 alkyl 7 59 7O 76 I00 9 l 22 53 58 78 l 0 None Di- (Coco N CH 24 1 8 8 l 82 98 1 l 2 alkyl 6 16 25 (34) 89 Monococo trimethyl ammonium chloride of Table ll Dicoco dimethyl ammonium chloride of Table I EXAMPLE 4 Effectiveness of Monococo Trimethyl Ammonium Chloride as a Dehazing Agent in the Presence and in the Absence of an Acrylate Copolymer overall the conclusion with regard to the effectiveness of the quaternary compound is very well supported.
TABLE IV Waring Blender Test of Monococo Trimethyl Ammonium Chloride as an Antihaze Additive in Heating Oils in the Presence of Cyclohexylamines and Acrylate copolymers Commercial Additives,ppm Quat. Light Transmittance of Oil, Sequence Anti- Anti- Polar Salt, (After Hours Standing Subsequent to Mixing) No. Oxidant Oxidant" Polymer ppm 0 l 5 7 24 l 3 17 29 73 2 2O 24 68 94 92 94 98 3 21 ll 59 67 74 79 89 4 21 9 48 71 74 79 87 5 21 20 20 63 95 96 97 I00 6 21 l5 6 30 39 43 41 61 7 21 15 20 24 62 81 84 92 88 8 21 15 7 34 69 61 57 77 9 21 I5 20 I2 45 64 7O 71 74 Used as a isopmpanol Solution Composed of light cracked oil and 25% virgin gas oil A mixture of methyl cyclohexyl amines Dieyclohexyl amine A multipurpose additive consisting of an acrylate copolymer which is described in Table V EXAMPLE Effectiveness of Monococo Trimethyl Ammonium Chloride as a Dehazing Agent in Various Heating Oils in the Presence of an Acrylate Copolymer As a hydrocarbon phase for utilization by these bacteria a petroleum middle distillate blend consisting of 73 percent diesel fuel and 27 percent water white kerosene was employed The diesel fuel component con- 5 tained about 80 percent paraffmic and 20 percent aro- In this example the effect of monococo trimethyl ammatic components. monium chloride is further illustrated in various heat- As the water phase a P basal salt medium was used. ing oils. These oils also contained antioxidants and an Thi medium was similar to the one reported by E. .I. acrylate copolymer as a multipurpose additive. The re- McKenna in a doctoral dissertation of the University of sults of the tests are shown by Table V. Iowa, entitled Effect of Hydrocarbon Structure on The light transmittance data show that in each case Mechanisms of Microbial Alkane Metabolism, pubthe addition of the quaternary compound increased the lished by University Microfilms, Inc. as No. 66-7218 in transmittance, i.e., reduced haze. The difference in the Ann Arbor, Michigan. haze behavior of the corresponding oils with and with- The tests used a high oil to water ratio to better simuout the quaternary additive is quite definite throughout late oil tank conditions'One hundred ml oil, 4 ml basal the 24 hour test period. salt medium and 1 ml aqueous suspension of the bacte- The table also provides some additional information rial inoculum in a 0.2 M phosphate buffer of pH 6.8 on the effect of the acrylate copolymer. This multipurwas used in each test. In each case, the aqueous phase, pose additive, when used in combination with cyclocontaining 700 X 10 viable organisms, was placed in hexylamine antioxidants, does again contribute to the aserum bottle of 2 in. diameter and 4 in. high. Then the haze problem like some other polar polymers do. Its addesired amount of test compound was added as a 0.1 verse effect, however, is overcome by the addition of ml solution. Onto the top of the final water solution, the higher monoalkyl quaternary compound. 100 ml of the oil was layered.
TABLE V WARING BLENDOR TEST OF MONOCOCO TRIMETHYL AMMONIUM CHLORIDE" AS AN ANTIHAZE ADDlTIVE IN VARIOUS HEATING OILS Commercial ppm Base Heating Oil: Anti Anti Polar Without Quaternary l 3 5 7 Light Transmittance of Oil After Hours,
With 20 ppm Quaternary Composition, Vol% Oxidant" Oxidant Polymer 0 24 0 24 Oil A": 3 19 3O 39 43 82 60% L. Cracked Cycle Oil 2l 7 46 59 67 63 92 20% H. Virgin Naphtha 21 6 29 43 51 56 91 20% Water Diesel Oil 2l l5 5 23 33 42 38 81 16 57 72 8O 79 95 21 15 4 ll 22 29 26 5O 2O 71 82 88 93 98 Oil B 9 28 48 52 6O 89 51% L. Cracked Cycle Oil 21 6 23 5O 58 61 86 I7% H. Virgin Naphtha 21 2 l l 23 23 27 55 17% Water White Diesel Oil 21 4 13 38 39 42 61 lo 27 43 4l 48 77 15% L. Virgin Gas Oil 2l 4 1O 37 38 26 59 29 64 83 84 84 100 Oil C: 3 18 33 43 43 73 75% L. Cracked Oil 21 6 34 48 58 61 86 Kerosene 21 8 53 7l 74 79 98 2l l5 5 38 53 53 4l 68 22 53 65 69 7l 89 21 15 5 53 69 54 58 73 1O 48 66 68 89 "Monococo trimethyl ammonium chloride of Table ll as a 50% isopropanol solution used at the 20 ppm active compound level;
Mixture of methyl cyclohexyl amines used as an antioxidant; Dicyclohexyl amine used as an antioxidant;
"A multipurpose additive consisting ofa 71 diluent solution of a copolymer of 52.671 di-C oxo alkyl fumarate, 26.8% di-C -alkyl fumarate 17.2% vinyl acetate,
3.41% hydroxyethyl methacrylate; "Cloud point l2F, aniline point 130F; 'Cloud point l()F aniline point l36.5F.
B. Effectiveness of Biologically Active Quaternary Ammonium Compounds as Oil Microbiocides in Bactericidal Tests The microbiocidal effectiveness of various quaternary ammonium chlorides was tested against various bacteria metabolizing hydrocarbons. These bacteria generally belonged to gram negative bacterial strains. Some of the bacteria were actually isolated from heating oil tank bottoms. All the bacteria utilized the paraffin components of uninhibited distillate fuels.
EXAMPLE 6 Effectiveness of Quaternary Higher Monoalkyl Verus Dialkyl Ammonium Chlorides as a Middle Distillate Bactericide The quaternary higher monoand dialkyl ammonium chlorides derived from coconut oil were compared for their bactericidal effectiveness against a mixture of three gram negative strains. These strains were isolated from two home oil heater tank bottoms.
The test bottles were closed with rubber stoppers and vented through a No. 18 gauge hypodermic needle. They were incubated for 7 days under stationary conditions on a laboratory bench at about 24C. Thereafter, 1 ml was withdrawn from the interface region of each bottle, using a 1 ml tuberculine syringe fitted with a No. 18 gauge needle. A 0.1 ml sample of each of 10' 10' and 10" dilutions were spread over a nutrient agar plate, which was subsequently incubated for 72 hours. Thereafter, the number of viable cells was determined and tabulated as shown in Table VI.
The sharp reduction of viable cells by the application of the experimental and control compounds showed a generally high effectiveness. The lower cell count in the mixture containing 500 ppm monococo trimethyl ammonium chloride (No. 1) than in the similar mixture containing the dicoco compound (No. 2) indicates that the higher monoalkyl salts are surprisingly more effective than the higher dialkyl derivatives. Similarly the higher monoalkyl compound having a branched alkyl chain is more effective than the known oil bactericide control.
I TABLE VI 2 EFFECTIVENESS OF HIGHER MONOALKYL AMMONIUM CHLORIDES AS PETROLELM BIOCIDES FOR GT1.
3 TANK BOTTOM APPLICATIONS IN A SIMULATED LABORATORY TEST 4 Number of Viable Cells x 10 in Solutions 5 Containing Various Bactericide 6 Quaternary Ammonium Chloride Experimental Bactericides Concentrations, ppm, after 7 [Jews Plus 72 7 Sequence Formula and Hours Incubation 8 No. Solution E loyed Composition 500 1,000
9 I [Coco-N"(CH ]Cl Monococo trimethyl ammonium 13,350 r 3 l0 chloride having n-alkyl groups ll 50% i-propanol as described in Table I 12 2 1:(Coco) N (CH ]Cl' Dicoco dimethyl ammonium 13,350 26 o 13 Control chloride having n-alkyl groups 14 757i. t-prnpanol as described in Table I I) 3 [C H2 +1CHN (Ci-I Alpha methyl branched n-alkyl 13,350 2 0 If; I ttiimethyl ammonium chloride 17 CH composed of a 1 to 1 mixture 18 of the two compositions des- 50% i-propanol Table III EXAMPLE 7 The effectiveness of several higher monoalkyl trimethyl ammonium chlorides was determined against sulfate reducing, anaerobic bacteria in comparative tests with a commercial higher dialkyl dimethyl ammonium chloride.
The bacteria were from the Borregas Field, Kingsville, Texas. The test system was a 3.5 percent NaCl sulfate reducing broth bacteria culture containing 100,000 bacteria per milliliter. Different concentrations of the ammonium chlorides were added to vials containing the broth medium. The media were then inoculated. The vials were incubated at C. and observed at intervals for evidence of bacterial growth. The results are shown by Table VII.
TABLE VII cribed under N0. 6 and 5 of The data show a complete growth inhibition for a minimum of 14 days by all the quaternary ammonium chlorides at the ppm concentration level. At 25 ppm the higher monoalkyl compounds still show a complete inhibition (Nos. 1 and 2). Surprisingly, the control higher dialkyl derivative (No. 3) shows no complete control.
EXAMPLE 8 Effectiveness of Quaternary Higher Monoalkyl Versus Dialkyl Ammonium Chlorides as Crude Oil Bactericides Against Aerobic Bacteria The comparative effectiveness of a pair of ammonium chlorides was determined against aerobic bacteria from Block 73, Louisiana. The test system was a 3.5 percent NaCl aerobic broth bacteria culture containing 100,000 bacteria per milliliter. The test procedure was the same as in the previous example. The results are shown by Table VIII.
EFFECTIVENESS OF HIGHER MONOALKYL TRIMETI-IYL AMMONIUM CHLORIDES AS OIL FIELD BACTERICIDES AGAINST ANAEROBIC BACTERIA Sequence Quaternary Ammonium Observation Growth or No Growth in the Presence of No. Chloride Tested Period, Days Various Concentrations (ppm) of Test Compounds 0 12.5 25 50 l [C H N (CH,,) Cl 4 7 14 2 I n zs a):iI II 4 7 14 3 [(Coco) N (CH Cl 4 Control 7 14 Composition as described in Example I.
TABLE VIII Quaternary Ammonium Chlorides as Oil Field Bactericides Against Aerobic Bacteria Growth(+) or No Growth in the Presence of Seq. Structure of Observation Various Concentrations No. Test Compound Period, Days (ppm) of Test Compound l ICHHZIDN+(CH.1)3]CI 1 7 14 2 [Coco) N (CH;,) ]Cl l Con- 7 trol 14 As described in Example I.
The data show that, surprisingly, about 50 ppm monoalkyl compound (No. l) was required for complete inhibition while 100 ppm dialkyl derivative (No. 2) was necessary for the same effect.
EXAMPLE 9 Effect of Higher n-Alkyl Trimethyl Ammonium Chlorides as Middle Distillate Bactericides The comparative bactericidal effectiveness of tri- 10 methyl ammonium chloridies having higher n-alkyl groups'of different chain length was investigated in a P basal salt medium overlayered with diesel fuel. As test organisms, two gram negative strains isolated from tank bottoms of a home oil heater were used (Nos. 1 and 2). l
Also employed were two other gram negative bacterial strains (Nos. 3 and 4) also utilizing diesel fuel. The organisms were grown in the presence of IO and 100 ppm of each salt. In each test, ml of basal salt medium overlayered with 0.1 ml. i.e., 1 percent of diesel fuel was used. After a 48 hour growth period, samples were streaked on nutrient agar plates and incubated for 48 hours at 30C..to determine the viability of the test organisms. The results are shown in Table IX.
The data show that all the quaternary ammonium chlorides examined show activity at the 100 ppm concentration level at least against one of the organisms employed. In these tests, the maximum activity was 7 shown by the n-hexadecyl derivative. However, the
data indicate that the optimum chain length is dependent on the bacterial strain used.
TABLE IX It should be noted that in commercial oil bactericide use, prevention of troublesome bacterial growth rather than total inhibition is sufficient. For this reason and due to the excess basal salt layer, the concentration of the salt additives may be smaller in field use than in these laboratory tests.
EXAMPLE 10 Effect of Straight Chain and Branched Higher Alkyl Trimethyl Ammonium Chloride as Middle Distillate Bactericides The comparative effectiveness of several higher 1- alkyl and 2-alkyl trimethyl ammonium chlorides was investigated using the test procedure described in the previous example. However, in this test only one gram negative bacterial strain was used. This strain was isolated from the heating oil tank bottoms of a home. The test mixtures were sampled after 24 and 48 hours. The results are shown in Table X.
The data show that in general, the mixtures of homologous alkyl compounds (Groups II and III) showed better inhibition than the pure alkyl compounds (Group I). Furthermore, the detergent range alkyl compounds (Nos. 3 and 5) were more active than those having even higher alkyl groups (Nos. 4 and 6). Interestingly, no difference was observed in the activity of the land 2- alkyl detergent range compounds (Nos. 3 and 5). Both the completely straight chain (No. 3) and the alpha methyl branched compounds completely inhibited bacterial growth for 48 hours at 20 ppm.
[Efiect of higher n-alkyl trimethyl ammonium chlorides on gram negative bacteria utilizing diesel fuel] Growth and no growth at various concentrations (p.p.m.) of salt Bacterial Bacterial Bacterial Bacterial isolate 1 isolate 2 isolate 3 isolate 4 Sequence R group of [RN+(CH3) 3101" number salt 0 100 10 100 10 100 10 100 1 n-Cn o 2 HC16H2B 3 I m 'Jo n-C1zH2a- Besides using 100 and 10 p.p.m., tests were also carried out in the presence of 1 p.p.m. of the salts.
However, at the latter concentration, no inhibition was observed.
TABLE X EFFECT OF HIGHER l-ALKYL AND Z-ALKYL TRIMETHYL AMMONIUM CHLORIDES ON GRAM NEGATIVE BACI'ERIA UTILIZING DIESEL FUEL Growth and No Growth at Various Concentrations (ppm) of Salt After 24 and 48 Hours Group Sequence R Groups of 20 ppm I00 ppm 500 ppm No. No. [RN (CH,,) ]CI Salt 24 48 24 48 24 48 l l a( 2)n 2 CH (CI-l n 3 (Coco") 4 (Soya Monococo trimethyl ammonium chloride as described in Table l. Soy-a tnmethyl ammonium chloride having primarily n-alkenyl groups of the following composition: C
EXAMPLE 1 1 Effect of n-Dodecyl Trimethyl Ammonium Chloride as a Jet Fuel Bactericide The effect of various concentrations of n-dodecyl trimethyl ammonium chloride on the growth of various bacterial strains utilizing jet fuel was studied.
Five contaminated jet fuel samples were used to isolate five bacterial strains by the spread plate technique. The isolated strains were further purified and then characterized. The cell morphology and the gram-stain characteristics of the strains are shown by Table XI.
The five bacterial isolates were routinely maintained on nutrient agar slants by weekly transfers. The above five cultures (24 hr. old slant cultures) were inoculated into culture tubes containing 7 ml of sterile nutrient broth and incubated at 30C. under stationary conditions for 24 hours. At the end of the incubation period, contents from each tube were transferred under sterile conditions into sterilized centrifuge tubes. The cells were harvested by centrifugation of 10,000 RPM for 15 minutes. The cells were washed by resuspending the pellet in 10 ml sterile P basal salts medium and recentrifuged. The washed cells were resuspended again in l ml of sterile medium. One ml from each suspension containing in the order of 10 cells/ml was used as the inoculum to each flask containing 9 ml of basal salts medium and the appropriate concentration of the inhibitors. Finally each flask was layered with ml of millipore filter sterilized jet fuel. The inoculated flasks were incubated for 40 hours on a New Brunswick rotary shaker maintained at 30C. and 250 RPM.
The growth in flasks was read at the end of seven days of incubation. At the end of 7 days of incubation, 0.01 ml of sample from each flask was streaked on nutrient agar plates and the plates were incubated overnight at 30C. to determine the viability of the test microorganisms. The results are shown by Table XIl. They indicate that, at 500 ppm, n-dodecyl trimethyl ammonium chloride completely inhibited for a week, the growth of all the bacterial strains.
TABLE Xl Morphological Characteristics of Jet Fuel Utilizing Microorganisms Effect of n-Dodccyl Trimcthyl Ammonium Chloride on Gram Negative Bacteria Utilizing Jet Fuel Bacterial Growth and No Growth of Strain Bacteria in the Presence of Test Compound No. Concentration of [C ;t(CH N+(CH Cl- 0 (Control) 10 50 100 500 What is claimed is:
l. A liquid hyrocarbon composition containing a surface active, water soluble, saturated open chain, higher alkyl trimethyl ammonium salt, said alkyl group containing a minimum of eight carbon atoms in amounts sufficient to increase its resistance to emulsion formation and/or microbial degradation.
2. The composition of claim 1 wherein the liquid hydrocarbon is crude petroleum or a petroleum distillate and the higher alkyl trimethyl ammonium salt is present at concentrations between abot 0.001 percent and 1 percent.
3. The composition of claim 2 wherein said higher alkyl trimethyl ammonium salt is a chloride in a concentration ranging from 0.00l to 0.004 percent by weight.
4. The composition of claim 3 wherein said ammonium chloride is present in a petroleum distillate.
5. The composition of claim 3 wherein said ammonium chloride is present in a petroleum crude.
6. The composition of claim 5 wherein said petroleum distillate is a distillate fuel boiling in the range between about 250 and 750F.
7. A liquid hydrocarbon composition containing a surface active, quaternary ammonium salt of the formula wherein R is a C to C saturated open chain aliphatic hydrocarbyl group and Q is an anion selected from the group consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate and phosphonate, in amounts sufficient to increase its resistance to emulsion formation and/or microbial degradation.
8. The composition of claim 7 wherein said salt has an aliphatic R group of the formula C l-[ wherein n is 8 to 40.
9. The composition of claim 8 wherein the structure of the group C,,H is Cl-l (Ch and CH (CH CH(CH wherein m is 7 to 39 and l is 6 to 38.
10. The composition of claim 7 wherein said salt has the group Q, selected from the group consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate and phosphonate.
11. The composition of claim 10 wherein the group O is selected from the group of nonradical anions consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate, phosphonate.
12. The composition of claim 11 wherein the anion Q is chloride.
13. The composition of claim 7 wherein the liquid hydrocarbon is crude petroleum or a petroleum distillate.
14. The composition of claim 13 wherein the petroleum distillate also contains a minor polar ethylene copolymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C, to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
15. A petroleum distillate composition boiling in the range between about 250 and 750F. having increased resistance to emulsion formation and microbial degradation containing from about 0.001 to 0.1 percent of a salt of the formula wherein n is 8 to 25, and from about 0.001 to 2 percent of a polar polymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones, in amounts sufficient to secure fluidity at low temperatures.
16. The composition of claim 7 wherein said salt is monococo trimethyl ammonium chloride.
17. A crude petroleum or petroleum distillate composition containing as a minor component a surface active, water soluble, saturated, open chain higher alkyl trimethyl ammonium salt, said alkyl group containing a minimum of eight carbon atoms and a minor polar polymeric additive having a molecular weight range of about 400 to 20,000 and prepared by the copolymerization of ethylene and vinyl acetate, in amounts sufficient to increase its resistance to emulsion formation.
18. A crude petroleum or petroleum distillate composition containing as a minor component in amounts up to 0.004 percent of a surface active, water soluble, saturated open chain, higher alkyl trimethyl ammonium :salt, said alkyl group containing a minimum of eight carbon atoms, whereby its resistance to microbial degradation and/or emulsion formation is increased.
19. The composition of claim 2 wherein said petroleum also contains a minor polar ethylene copolymer additive having a molecular weight range of 400 to 20,000, said additive being derived using comonomers selected from the group consisting of vinyl esters of C -C monocarboxylic acids, acrylate esters of C to C alcohols, maleate esters of C 1 to C alcohols, fumarate esters of C to C alcohols, vinyl chloride, C to C vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
0 P0-1050 v UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,880,613 Dated April 29, 1975 Inventor) Alexis A. Oswald, Jack. Ryer, Raam R. Mohan It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
I Top page, after the listing of inventors, please insert assignors to E550 Research and Engineering- Company,
a corporation of Delaware.
Q Signed and Scaled this third Day Of February 1976 [SEAL] Arrest:
RUTH C. MASON c. MARSHALL DANN ff Commissioner ofPatents and Trademarks o L .J
Claims (19)
1. A LIQUID HYDROCARBON COMPOSITION CONTANING A SURFACE ACTIVE, WATER SOLUBLE, SATURATED OPEN CHAIN, HIGHER ALKYL TRIMETHYL AMMONIUM SALT, SAID ALKYL GROUP CONTAINING A MINIMUM OF EIGHT CARBON ATOMS IN AMOUNTS SUFFICIENT TO INCREASE ITS RESISTANCE TO EMULSION FORMATION AND/OR MICROBIAL DEGRADATION.
2. The composition of claim 1 wherein the liquid hydrocarbon is crude petroleum or a petroleum distillate and the higher alkyl trimethyl ammonium salt is present at concentrations between abot 0.001 percent and 1 percent.
3. The composition of claim 2 wherein said higher alkyl trimethyl ammonium salt is a chloride in a concentration ranging from 0.001 to 0.004 percent by weight.
4. The composition of claim 3 wherein said ammonium chloride is present in a petroleum distillate.
5. The composition of claim 3 wherein said ammonium chloride is present in a petroleum crude.
6. The composition of claim 5 wherein said petroleum distillate is a distillate fuel boiling in the range between about 250* and 750*F.
7. A liquid hydrocarbon composition containing a surface active, quaternary ammonium salt of the formula (RN (CH3)3)Q , wherein R is a C8 to C40 saturated open chain aliphatic hydrocarbyl group and Q is an anion selected from the group consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate and phosphonate, in amounts sufficient to increase its resistance to emulsion formation and/or microbial degradation.
8. The composition of claim 7 wherein said salt has an aliphatic R group of the formula CnH2n 1 wherein n is 8 to 40.
9. The composition of claim 8 wherein the structure of the group CnH2n 1 is CH3(Ch2)m and CH3(CH2)1CH(CH3) wherein m is 7 to 39 and l is 6 to 38.
10. The composition of claim 7 wherein said salt has the group Q , seLected from the group consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate and phosphonate.
11. The composition of claim 10 wherein the group Q is selected from the group of nonradical anions consisting of halide, phosphate, phosphite, sulfate, nitrite, carboxylate, sulfonate, phosphonate.
12. The composition of claim 11 wherein the anion Q is chloride.
13. The composition of claim 7 wherein the liquid hydrocarbon is crude petroleum or a petroleum distillate.
14. The composition of claim 13 wherein the petroleum distillate also contains a minor polar ethylene copolymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C2-C18 monocarboxylic acids, acrylate esters of C1 to C18 alcohols, maleate esters of C1 to C18 alcohols, fumarate esters of C1 to C18 alcohols, vinyl chloride, C1 to C16 vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
15. A petroleum distillate composition boiling in the range between about 250* and 750*F. having increased resistance to emulsion formation and microbial degradation containing from about 0.001 to 0.1 percent of a salt of the formula (CnH2n 1 N (CH3)3)Cl wherein n is 8 to 25, and from about 0.001 to 2 percent of a polar polymer additive having a molecular weight range of about 400 to 20,000 said additive being derived using comonomers selected from the group consisting of vinyl esters of C2-C18 monocarboxylic acids, acrylate esters of C1 to C18 alcohols, maleate esters of C1 to C18 alcohols, fumarate esters of C1 to C18 alcohols, vinyl chloride, C1 to C16 vinyl ketones, in amounts sufficient to secure fluidity at low temperatures.
16. The composition of claim 7 wherein said salt is monococo trimethyl ammonium chloride.
17. A crude petroleum or petroleum distillate composition containing as a minor component a surface active, water soluble, saturated, open chain higher alkyl trimethyl ammonium salt, said alkyl group containing a minimum of eight carbon atoms and a minor polar polymeric additive having a molecular weight range of about 400 to 20,000 and prepared by the copolymerization of ethylene and vinyl acetate, in amounts sufficient to increase its resistance to emulsion formation.
18. A crude petroleum or petroleum distillate composition containing as a minor component in amounts up to 0.004 percent of a surface active, water soluble, saturated open chain, higher alkyl trimethyl ammonium salt, said alkyl group containing a minimum of eight carbon atoms, whereby its resistance to microbial degradation and/or emulsion formation is increased.
19. The composition of claim 2 wherein said petroleum also contains a minor polar ethylene copolymer additive having a molecular weight range of 400 to 20,000, said additive being derived using comonomers selected from the group consisting of vinyl esters of C2-C18 monocarboxylic acids, acrylate esters of C1 to C18 alcohols, maleate esters of C1 to C18 alcohols, fumarate esters of C1 to C18 alcohols, vinyl chloride, C1 to C16 vinyl ketones in amounts sufficient to secure fluidity at low temperatures.
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US224341A US3880613A (en) | 1972-02-07 | 1972-02-07 | Higher alkyl trimethyl ammonium salt liquid hydrocarbon compositions |
GB457873A GB1409019A (en) | 1972-02-07 | 1973-01-30 | Higher alkyl trimethyl ammonium salt liquid hydrocarbon compositions |
DE2305438A DE2305438A1 (en) | 1972-02-07 | 1973-02-03 | LIQUID HYDROCARBON MIXTURE WITH INCREASED RESISTANCE TO EMULSIONS AND / OR MICROBIOLOGICAL DEGRADATION |
IT20078/73A IT978851B (en) | 1972-02-07 | 1973-02-06 | QUID HYDROCARBON COMPOSITIONS CONTAINING HIGHER ALKYL TRIMETHYLAMONIUM SALTS |
CA163,044A CA1005341A (en) | 1972-02-07 | 1973-02-06 | Higher alkyl trimethyl ammonium salt liquid hydrocarbon compositions |
FR7304162A FR2171200B1 (en) | 1972-02-07 | 1973-02-06 | |
JP1482373A JPS5533760B2 (en) | 1972-02-07 | 1973-02-07 |
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US2295505A (en) * | 1939-08-02 | 1942-09-08 | Wm S Merrell Co | Composition of matter |
US2786797A (en) * | 1954-05-18 | 1957-03-26 | Hollingshead Corp | Corrosion-inhibited quaternary ammonium compositions |
US2975042A (en) * | 1955-09-29 | 1961-03-14 | Gulf Oil Corp | Fuel oil compositions containing antimicrobial agents |
US3093623A (en) * | 1960-01-05 | 1963-06-11 | Exxon Research Engineering Co | Process for the manufacture of improved pour depressants for middle distillates |
US3366673A (en) * | 1964-04-03 | 1968-01-30 | Millmaster Onyx Corp | Microbiologically active quaternary ammonium compounds |
US3567639A (en) * | 1966-06-01 | 1971-03-02 | Exxon Research Engineering Co | Hydrocarbon-containing compositions |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1150955A (en) * | 1956-05-23 | 1958-01-22 | Exxon Standard Sa | Additives against corrosion of equipment containing hydrocarbons |
US2951751A (en) * | 1958-07-30 | 1960-09-06 | Exxon Research Engineering Co | Hydrocarbon oils having improved electrical properties |
GB976720A (en) * | 1963-08-07 | 1964-12-02 | Socony Mobil Oil Co Inc | Quaternary ammonium naphthenates as fuel additives |
US3493354A (en) * | 1967-02-27 | 1970-02-03 | Monsanto Chemicals | Diesel fuel additive |
-
1972
- 1972-02-07 US US224341A patent/US3880613A/en not_active Expired - Lifetime
-
1973
- 1973-01-30 GB GB457873A patent/GB1409019A/en not_active Expired
- 1973-02-03 DE DE2305438A patent/DE2305438A1/en not_active Withdrawn
- 1973-02-06 IT IT20078/73A patent/IT978851B/en active
- 1973-02-06 CA CA163,044A patent/CA1005341A/en not_active Expired
- 1973-02-06 FR FR7304162A patent/FR2171200B1/fr not_active Expired
- 1973-02-07 JP JP1482373A patent/JPS5533760B2/ja not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2295505A (en) * | 1939-08-02 | 1942-09-08 | Wm S Merrell Co | Composition of matter |
US2786797A (en) * | 1954-05-18 | 1957-03-26 | Hollingshead Corp | Corrosion-inhibited quaternary ammonium compositions |
US2975042A (en) * | 1955-09-29 | 1961-03-14 | Gulf Oil Corp | Fuel oil compositions containing antimicrobial agents |
US3093623A (en) * | 1960-01-05 | 1963-06-11 | Exxon Research Engineering Co | Process for the manufacture of improved pour depressants for middle distillates |
US3366673A (en) * | 1964-04-03 | 1968-01-30 | Millmaster Onyx Corp | Microbiologically active quaternary ammonium compounds |
US3567639A (en) * | 1966-06-01 | 1971-03-02 | Exxon Research Engineering Co | Hydrocarbon-containing compositions |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4444790A (en) * | 1982-05-27 | 1984-04-24 | Millmaster Onyx Group, Inc. | Quaternary ammonium disinfectants |
US4450174A (en) * | 1982-05-27 | 1984-05-22 | Millmaster Onyx Group, Inc. | Decyl quaternary ammonium compounds |
US4605640A (en) * | 1985-05-29 | 1986-08-12 | The United States Of America As Represented By The Secretary Of Agriculture | Oil-absorbent cellulosic derivatives |
US5348561A (en) * | 1990-03-01 | 1994-09-20 | Exxon Chemical Patents Inc. | Fuel oil compositions |
US5545237A (en) * | 1994-07-08 | 1996-08-13 | Exxon Research And Engineering Company | Smoke reducing additive for two-cycle engine fuel mixture |
US20110224081A1 (en) * | 2002-05-31 | 2011-09-15 | Cjb Industries | Adjuvant for Pesticides |
US8481458B2 (en) | 2002-05-31 | 2013-07-09 | Cjb Industries | Adjuvant for pesticides |
US7476646B1 (en) * | 2004-09-27 | 2009-01-13 | Cjb Industries, Inc. | Agricultural promoters/active ingredients |
US20140238328A1 (en) * | 2012-11-02 | 2014-08-28 | Afton Chemical Corporation | Fuel additive for improved performance in direct fuel injected engines |
US9458400B2 (en) * | 2012-11-02 | 2016-10-04 | Afton Chemical Corporation | Fuel additive for improved performance in direct fuel injected engines |
WO2022101729A1 (en) * | 2020-11-16 | 2022-05-19 | Hindustan Petroleum Corporation Limited | Dewatering composition and implementations thereof |
Also Published As
Publication number | Publication date |
---|---|
FR2171200B1 (en) | 1979-01-12 |
IT978851B (en) | 1974-09-20 |
DE2305438A1 (en) | 1973-08-23 |
JPS5533760B2 (en) | 1980-09-02 |
FR2171200A1 (en) | 1973-09-21 |
JPS4891108A (en) | 1973-11-27 |
GB1409019A (en) | 1975-10-08 |
CA1005341A (en) | 1977-02-15 |
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