GB2261509A - Indicator systems for additives present in hydrocarbon fluid - Google Patents
Indicator systems for additives present in hydrocarbon fluid Download PDFInfo
- Publication number
- GB2261509A GB2261509A GB9223004A GB9223004A GB2261509A GB 2261509 A GB2261509 A GB 2261509A GB 9223004 A GB9223004 A GB 9223004A GB 9223004 A GB9223004 A GB 9223004A GB 2261509 A GB2261509 A GB 2261509A
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- GB
- United Kingdom
- Prior art keywords
- additive
- fuel
- indicator
- concentrate
- amount
- 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.)
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- 239000000654 additive Substances 0.000 title claims abstract description 110
- 239000012530 fluid Substances 0.000 title claims abstract description 53
- 239000004215 Carbon black (E152) Substances 0.000 title abstract 3
- 229930195733 hydrocarbon Natural products 0.000 title abstract 3
- 150000002430 hydrocarbons Chemical class 0.000 title abstract 3
- 230000000996 additive effect Effects 0.000 claims abstract description 85
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 239000000446 fuel Substances 0.000 claims abstract description 42
- 239000000314 lubricant Substances 0.000 claims abstract description 28
- 239000012141 concentrate Substances 0.000 claims abstract description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 30
- 239000002816 fuel additive Substances 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 150000002697 manganese compounds Chemical class 0.000 claims description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229960002317 succinimide Drugs 0.000 claims description 2
- KDZSOJJFEINEDS-UHFFFAOYSA-N C[Mn]C1C=CC=C1 Chemical compound C[Mn]C1C=CC=C1 KDZSOJJFEINEDS-UHFFFAOYSA-N 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- -1 i.e. Substances 0.000 description 17
- 239000002270 dispersing agent Substances 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920001079 Thiokol (polymer) Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical class C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- GGQRKYMKYMRZTF-UHFFFAOYSA-N 2,2,3,3-tetrakis(prop-1-enyl)butanedioic acid Chemical compound CC=CC(C=CC)(C(O)=O)C(C=CC)(C=CC)C(O)=O GGQRKYMKYMRZTF-UHFFFAOYSA-N 0.000 description 1
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- PFBBCIYIKJWDIN-BUHFOSPRSA-N 2-[(e)-tetradec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O PFBBCIYIKJWDIN-BUHFOSPRSA-N 0.000 description 1
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical group CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- RSPWVGZWUBNLQU-FOCLMDBBSA-N 3-[(e)-hexadec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCCCCCC\C=C\C1CC(=O)OC1=O RSPWVGZWUBNLQU-FOCLMDBBSA-N 0.000 description 1
- URVNZJUYUMEJFZ-UHFFFAOYSA-N 3-tetradec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC=CC1CC(=O)OC1=O URVNZJUYUMEJFZ-UHFFFAOYSA-N 0.000 description 1
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N Aspartic acid Chemical class OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- AAHZZGHPCKJNNZ-UHFFFAOYSA-N Hexadecenylsuccinicacid Chemical compound CCCCCCCCCCCCCCC=CC(C(O)=O)CC(O)=O AAHZZGHPCKJNNZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- RYSNDQDGZQEOAL-UHFFFAOYSA-N calcium;phenol Chemical class [Ca].OC1=CC=CC=C1 RYSNDQDGZQEOAL-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000009658 destructive testing Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 229940082615 organic nitrates used in cardiac disease Drugs 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Specific substances contained in the oils or fuels
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Presence of an additive in a hydrocarbon fluid e.g. fuel or lubricant is detected by mixing (i) the fuel or lubricant (ii) at least one additive, and (iii) at least one indicator for the additive in an amount less than an amount required to discolor the fuel or lubricant; and (b) analyzing said hydrocarbonaceous composition for the presence of said indicator. Additive is e.g. an octane improver and indicator is a blue whitener dye. A concentrate for addition to the hydrocarbon fluid comprises additive plus an indicator for the additive in amounts which do not discolor the fluid.
Description
ADDITIVE INDICATORS FOR HYDROCARBONACEOUS FLUIDS
This invention relates to methods and compositions for detecting the presence of additives in hydrocarbonaceous fluids such as fuels and lubricants.
Until now, it has been difficult to determine in the field whether or not any particular hydrocarbonaceous fluid contains an additive. Analysis techniques for the determination of the presence of such additives often time require the use of expensive analytical equipment or may involve destructive testing of the fluid.
Such analytical techniques are not suitable for field use to detect the presence of additives in hydrocarbonaceous fluids and are frequently quite costly. There is a need therefore for a simple, reliable method for detecting the presence of a wide variety of additives in hydrocarbonaceous fluids without the need for expensive analytical equipment or procedures.
It has now been discovered that additives in hydrocarbonaceous fluids can be detected by a method which comprises (a) forming a hydrocarbonaceous composition containing (i) fuel or lubricant, (ii) at least one additive, and (iii) at least one additive indicator dye in an amount less than an amount required to discolor the fuel or lubricant, and (b) analyzing the hydrocarbonaceous composition for the presence of the additive indicator.
In another embodiment, this invention provides a fuel composition comprising (a) fuel, (b) fuel additive, and (c) an amount of at least one additive indicator, which amount is less than the amount required to discolor the fuel composition.
In yet another embodiment, this invention provides a hydrocarbonaceous fluid additive concentrate comprising (a) additive, and (b) an amount of at least one additive indicator, which amount is less than the amount required to discolor a hydrocarbonaceous fluid containing the additive concentrate.
In a preferred embodiment, this invention provides a method for indicating the presence of additives in hydrocarbonaceous fluids which comprises: (a) forming a hydrocarbonaceous fluid composition by admixing (i) fuel or lubricant, (ii) one or more additives, and (iii) one or more additive indicators; (b) providing a field test method for detecting the presence of the additive indicator in the fluid composition; and (c) analyzing the fluid composition by the field method. It is highly desirable that the additive indicator used be essentially innocuous to the fluid composition; that the amount of additive indicator be less than the amount required to discolor the fluid composition; and that at least a portion of the additive indicator be readily removable from the fluid composition by the field method.
The method of this invention can be used with a wide variety of hydrocarbonaceous fluids such as fuels and lubricants for the determination of the presence of additives which may be added to such fluids. Hydrocarbonaceous fluids useful in the method and compositions of this invention include mineral and synthetic lubricants and base oils such as gear oils, hydraulic oils, automatic transmission fluids, brake fluids, and power steering fluids, and hydrocarbonaceous fuels such as fuels boiling in the gasoline boiling range, distillate fuels boiling in the diesel fuel range, jet fuels, marine fuels, and fuel oils.The particular fuel or lubricant used in the method and composition of this invention is not critical provided (1) the fuel or lubricant is not discolored by the additive indicator when the additive indicator is used in an amount which can be detected by the method of this invention and the amount is not sufficient to discolor the fuel or lubricant; (2) the additive indicator is sufficiently soluble in the fuel or lubricant; and (3) the fuel or lubricant is capable of being separated from the additive indicator by the method disclosed herein.
In a particularly preferred embodiment, the method and compositions of this invention are useful for detecting the presence of one or more additives in fuels. Such additives may be used to provide octane improvement, cetane improvement, induction system deposit control, octane requirement increase control, and emission control to a fuel. While this invention may be used to detect the presence of any one or more additives, fuel additives are generally formulated additives, i.e., additives which contain detergents, dispersants, antioxidants, demulsifiers, corrosion inhibitors, fuel stabilizers, dehazers, friction modifiers, and/or mixtures of any two or more of the foregoing. Hence the additive indicator may be used to detect the presence of an additive package in a fuel.
For lubricants, the methods and compositions of this invention may be used to detect the presence of antioxidants, corrosion inhibitors, antiwear extreme pressure agents, viscosity index improvers, dispersants, detergents, friction modifiers, pour point dispersants, antifoam agents, and/or mixtures of any two or more of the foregoing in the lubricant compositions. As used herein, the term "lubricant" contemplates both mineral and synthetic oleaginous fluids and base oils.
For the purposes of this invention, octane improvement additives may comprise one or more cyclomatic manganese compounds. Particularly preferred cyclomatic manganese compounds include cyclopentadienyl manganese tricarbonyl and methylcyclopentadienyl manganese tricarbonyl, and/or mixtures thereof. Cetane improvement additives include organic nitrates, peresters, and peroxyesters. Such octane and cetane improvers are well known to those skilled in the art.
Detergent/dispersant additives useful with the method and compositions of this invention include metal-containing detergents such as calcium phenols, magnesium phenates, calcium sulfonates, and magnesium sulfonates; and detergent dispersant compositions comprising the reaction product of (i) polyamine and (ii) at least one acyclic hydrocarbyl substituted succinic acylating agent. A particularly preferred detergent/dispersant for fuels comprises (a) a succinimide which is the reaction product of (i) polyamine and (ii) at least one acyclic hydrocarbyl substituted succinic acylating agent; (b) an unhydrotreated poly-a-olefin; and (c) optionally, a mineral oil having a viscosity index of less than 90.
Detergenr/dispersants useful with the compositions and methods of this invention are generally well known, hence no further description is deemed necessary.
Antioxidants useful as additives in combination with hydrocarbonaceous fluids include phenolic antioxidants, amine antioxidants, sulfurized phenolic compounds, and organic phosphites, among others. Particularly preferred for use in the practice of this invention are tertiary butyl phenols, such as 2,6-di-tertbutylphenol, 2,4,6-tri-tert-butylphenol, o-tert-butylphenol, and mixtures thereof.
A wide variety of demulsifiers are available for use in the practice of this invention, including, for example, polyoxyalkylene glycols, oxyalkylated phenolic resins, and like materials. Particularly preferred are mixtures of polyoxyalkylene glycols and oxyalkylated alkylphenolic resins, such as are available commercially from Petrolite Corporation under the TOLAD trademark.
Corrosion inhibitors useful with this invention include a wide variety of materials. Thus, use can be made of dimer and trimer acids, such as are produced from tall oil fatty acids, oleic acid, linoleic acid, or the like. Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humko Chemical Division of Witco Chemical Corporation and under the
EMPOL trademark by Emery Chemicals. Another useful type of corrosion inhibitor for use in the practice of this invention are the alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapro-penylsuccinic acid, tetrapropenylsuccinic anhydride, tetrade-cenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenyl-succinic acid, and hexadecenylsuccinic anhydride.Also useful are the half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols. Other suitable corrosion inhibitors include ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; imidazolines; and aminosuccinic acids or derivatives thereof.
Stabilizers which may be used with the method and compositions of this invention include pyrimidine, hexahydrotriazine compounds and derivatives thereof.
Other primary, secondary and tertiary amine compounds may also be used as stabilizing additives such as hydrocarbyl polyoxypropylene di(polyoxyethylene) amines; the condensation product of an alkanolamine and the reaction product of a terpene and a compound selected from an a,p-unsaturated polycarboxylic acid.
Dehazers useful as additives include one or more alkoxylated alcohols, one or more alkoxylated fatty amines, and/or mixtures thereof. Other dehazer additives include organosiloxanes, and the reaction product formed by reacting a phenolformaldehyde resin with an alpha-olefin epoxide and then reacting the product with an alkylene oxide such as ethylene oxide, propylene oxide, or combinations thereof.
Other additives which may be used include the antiwear/extreme pressure agents selected from phosphorus-containing ashless dispersants, boron containing ashless dispersants and phosphorus and boron-containing ashless dispersants.
Suitable viscosity index improvers include methacrylates, acrylates, styrene copolymers, and ethylene-propylene copolymers.
Also useful with the methods and compositions of this invention are friction modifiers such as aliphatic amines, or ethoxylated aliphatic gamines, aliphatic fatty acid amines, aliphatic carboxylic acids, aliphatic carboxylic esters, aliphatic carboxylic ester-amides, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, and aliphatic thiophosphates.
Additive indicators useful in the practice of this invention include a wide variety of solids and liquids which are essentially innocuous in their effect on the properties of the hydrocarbonaceous fluid containing an additive and the additive indicator, and which can readily be detected by the method disclosed herein. For example, if the hydrocarbonaceous fluid is a lubricant composition which is essentially devoid of metal-containing additive components, then the additive indicator used should also be essentially devoid of metal-containing components. By "essentially devoid" is meant that the lubricant composition contains, on a weight basis, no more than 100 parts per million of such metalcontaining components.
It is a key feature of the method and compositions of this invention that the amount of additive indicator be less than the amount necessary to discolor the hydrocarbonaceous fluid to which it is added. It is to be understood however, that such amount of additive indicator may in fact discolor the additive concentrate which may be preformulated to add to the hydrocarbonaceous fluids. However, when properly admixed with a hydrocarbonaceous fluid, it is most preferable that the additive concentrate containing the additive indicator not discolor the additized fluid.In order to determine if a hydrocarbonaceous fluid is discolored by an additive indicator used in accordance with this invention, a sample of unadditized fluid should be compared to a sample of additized fluid containing the additive indicator in ordinary light, e.g., sunlight, or room light, and there should be no noticeable difference in the coloration of each sample when viewed with the unaided eye.
Accordingly, the amount of additive indicator in the method and compositions of this invention is preferably less than 6 ppm based on the total weight of hydrocarbonaceous fluid, additive, and additive indicator composition.
A particularly preferred amount of additive indicator is 4 ppm or less based on the total weight of hydrocarbonaceous fluid, additive, and additive indicator composition. When added to an additive concentrate, the amount of additive indicator is typically less than 0.4 wt. percent based on the total weight of additive concentrate. Preferably, the amount of additive indicator in the concentrate is from 0.01 to 0.25 weight percent of the total weight of additive concentrate.
In another particularly preferred embodiment of this invention, the additive indicator is a liquid dye. The dye may be one or a mixture of dyes which are typically used for the coloration of hydrocarbonaceous fluids. Hence, the dye should be compatible with the fuel or lubricant to which it is added; i.e., should be miscible with the fuel or lubricant at least at a concentration which is below the concentration which discolors the fuel or lubricant. Suitable dyes include Blue
Whitener dye #7222, Automate Red #7111, and Fluorescent Yellow #7933, all of which are commercially available from Morton Thiokol, Inc.; and Mortrace SB (90-9397), commercially available from Morton International Specialty Co.
Particularly preferred is Blue Whitener dye #7222.
The additive indicator may be admixed with the hydrocarbonaceous fluid and additive in any order, or may be admixed with the additive -- which additive and additive indicator are then admixed with a hydrocarbonaceous fluid.
Commercially available equipment and well known blending techniques can be used to perform the blending of the fluid, additive, and indicator components.
To determine the presence of the additive indicator, and thus the presence of an additive in a hydrocarbonaceous fluid composition, the hydrocarbonaceous fluid may be analyzed using the following technique. If the hydrocarbonaceous fluid is a fuel containing the additive composition and an additive indicator, a quantity of the fuel is fed to a silicon absorption column. After removing substantially all of the fuel by vacuum, air or otherwise, and drying the column, the column is visually checked for discoloration of the silicon absorber.
A discoloration of the silicon absorbent attributable to the additive indicator indicates the presence of a fuel additive containing the additive indicator. For lubricants containing an additive component and additive indicator, or for highly polar fuels, it may be necessary to first dilute the lubricant or fuel in a suitable non-polar solvent prior to feeding the lubricant or fuel to the silicon adsorption column. Suitable non-polar solvents for diluting the lubricant or fuel composition include xylene, toluene, benzene, pentane, hexane, heptane, and petroleum ether.
The method of this invention is particularly suited for determination of the presence of additives in fuels and lubricants in the field where access to laboratory analytical instruments is difficult. The method and compositions of this invention are illustrated by the following non-limiting example.
Example
A fuel additive mixture containing 99.75 weight percent HiTec 4403 (Ethyl Corporation's induction valve deposit control additive) and 0.25 weight Blue
Whitener Dye #7222 (Morton Thiokol, Inc.) was prepared. This additive mixture was then admixed with gasoline so as to obtain a concentration of fuel additive of 300 ptb (pounds per thousand barrels). Once formed, 100 mL of the gasoline and additive mixture was dissolved in 300 mL of hexane and the resulting solution fed to a 60 cubic centimeter Varian MEGA BOND ELUT column with a silicon bonded phase, part number 1225-6034 having a single holed stopper in the open end of the column and a 700 mL collection flask placed under the other end of the column. The silicon column was prepared by wetting the silicon with hexane prior to passing the solution through the column. When the all of the additive mixture and gasoline had been fed through the column, the column was dried with several syringe volumes of air by inserting a syringe through the rubber stopper and injecting air into the column until all of the fuel was removed. The presence of a blue to green color on the dried silicon indicated the presence of the indicator dye in the mixture. In lieu of drying the column with air, the column may be purged with 30 to 40 mL of methylene chloride into a clear glass vessel. The presence of a blue to green color liquid in the vessel indicates the presence of the additive mixture containing the indicator dye.
Claims (10)
1. An additive concentrate comprising (a) additive, and (b) an amount of at least one additive indicator, which amount is less than the amount required to discolor a hydro-carbonaceous fluid containing said additive concentrate.
2. The concentrate of Claim 1 wherein said additive comprises a succinimide detergent.
3. The concentrate of Claim 1 wherein said additive is a fuel additive which comprises an octane improver.
4. The concentrate of Claim 3 wherein said octane improver is one or more cyclomatic manganese compounds.
5. The concentrate of Claim 4 wherein said cyclomatic manganese compound is methylcyclopentadienyl manganese tricarbonyI.
6. The concentrate of Claim 1 wherein said additive is a fuel additive which comprises a composition for control of induction system deposits.
7. The concentrate of Claim 6 wherein said induction system deposit control additive comprises (a) the reaction product of (i) polyamine and (ii) at least one acyclic hydrocarbyl substituted succinic acylating agent; (b) an unhydrotreated poly-a-olefin; and (c) optionally, a mineral oil having a viscosity index of less than 90 and/or one or more polyols.
8. The concentrate of Claim 1 wherein said additive indicator is a blue whitener dye.
9. A fuel composition comprising (a) fuel, (b) fuel additive, and (c) an amount of at least one additive indicator, which amount is less than the amount required to discolor said fuel composition.
10. A method for indicating the presence of additives in hydrocarbonaceous fluids which comprises:
(a) forming a hydrocarbonaceous fluid composition by admixing (i) fuel
or lubricant, (ii) one or more additives, and (iii) one or more additive
indicators;
(b) providing a field method for detecting the presence of said additive
indicator in said fluid composition; and
(c) analyzing said fluid composition by said field method wherein (1) the additive indicator is essentially innocuous to said fuel composition; (2) the amount of additive indicator is less than the amount required to discolor the fluid composition; and (3) at least a portion of said additive indicator is readily removable from the fluid composition by said field method.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79144691A | 1991-11-13 | 1991-11-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9223004D0 GB9223004D0 (en) | 1992-12-16 |
| GB2261509A true GB2261509A (en) | 1993-05-19 |
Family
ID=25153762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9223004A Withdrawn GB2261509A (en) | 1991-11-13 | 1992-11-03 | Indicator systems for additives present in hydrocarbon fluid |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2261509A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2280265A (en) * | 1993-07-21 | 1995-01-25 | Molecular Light Technology Lim | Monitoring bulk liquids for presence of an additive |
| WO2007014903A1 (en) * | 2005-08-03 | 2007-02-08 | Basf Se | Method for detecting a fuel additive component |
-
1992
- 1992-11-03 GB GB9223004A patent/GB2261509A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2280265A (en) * | 1993-07-21 | 1995-01-25 | Molecular Light Technology Lim | Monitoring bulk liquids for presence of an additive |
| GB2280265B (en) * | 1993-07-21 | 1997-06-04 | Molecular Light Technology Lim | Monitoring of chemical additives |
| WO2007014903A1 (en) * | 2005-08-03 | 2007-02-08 | Basf Se | Method for detecting a fuel additive component |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9223004D0 (en) | 1992-12-16 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |