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
  • C10L1/28—Organic compounds containing silicon
  • C10L1/285—Organic compounds containing silicon 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
  • C10L1/16—Hydrocarbons
  • C10L1/1608—Well defined compounds, e.g. hexane, benzene
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • 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
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
• • 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
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1857—Aldehydes; Ketones
• • 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
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B3/00—Engines characterised by air compression and subsequent fuel addition
  • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

• This invention relates to foam control and is particularly concerned with controlling foaming in hydrocarbon liquids.
• U.S. Patent 5,192,336 discloses that bis-strearamides act as defoamers by remaining dispersed within hydrocarbon fuels. This is in contrast to silicone polyether defoamers of U.S. Patent 4,690,668 and U.S. Patent 3,233,986, which settle out over time because of their higher density relative to hydrocarbon fuel, often necessitating periodic agitation to re-disperse them. Silicone polyethers also tend to be more soluble or dispersible in water, which is a constant component of hydrocarbon fuels. In storage tanks, water tends to coalesce and forms a layer at the bottom of the tank. As the silicone polyether settles due to gravity effects and its hydrocarbon insolubility, eventual contact with the water layer can result in its ultimate absorbtion into that phase. Thus, it can be irreversibly removed from the fuel in its entirety.
• middle distillate fuels exhibit foaming during transfer operations, such as filling a vehicle's fuel tank at a service station.
• foaming occurs as the liquid is passed from one vessel to another.
• foam may develop at the surface of the fuel.
• the extent of foaming is sufficiently significant and persistent to require a reduction in the passage rate of the liquid fuel into the vessel. It is therefore desirable to provide means for controlling such foaming to permit sustained or higher rates of passage.
• U.S. Patent 3,233,986 deals with siloxane polyoxyalkylene block copolymers as antifoam agents and discloses a wide variety of such copolymers to reduce foaming of organic liquids.
• Organic liquids mentioned are various hydrocarbon fuels, e.g., kerosene, gasoline and diesel fuel.
• One copolymer therein comprises groups represented by the formula: wherein G3 is a member selected from hydrogen atom and monovalent hydrocarbon groups, G'' is an alkylene radical containing at least two carbon atoms, G' is a divalent hydrocarbon radical, G is a monovalent hydrocarbon radical, n has a value of at least two and c has a value from 0 to 2 inclusive.
• At least 60% by weight of the groups OG'' must be oxyethylene or oxypropylene groups, and other oxyalkylene groups may also be present.
• Each oxyalkylene block preferably contains from four to thirty OG'' groups. However, the number of oxyalkylene groups (OG'') and the average molecular weight of the copolymer attributable to the oxyalkylene blocks is not described therein as critical. Moreover, useful copolymers can contain siloxane blocks and oxyalkylene blocks in any relative amount.
• Organosilicone materials "density-matched" to the hydrocarbon medium act as defoamers in hydrocarbon fuel as described herein.
• our defoamers can be described as alkylmethylsiloxanes or crosslinked organopolysiloxane-polyoxyalkylenes. They are characterized by being slightly soluble or insoluble in water and hydrocarbon fuels. By changing the solvent and the method of dispersion, different particle size distributions of our alkylmethylsiloxanes or organopolysiloxane-polyoxyalkylenes are obtained.
• the present invention is directed to such formulations to reduce the tendency of hydrocarbon liquids to foam.
• Alkylmethylsiloxane mixtures comprising an alkylmethylsiloxane of the structure R II Me2SiO(Me2SiO) m (MeR I SiO) y SiMe2R II or R II Me2SiO(MeR I SiO) n SiMe2R II , wherein R I is the same or different alkyl of 2 to 100 carbon atoms, R II is methyl or R I , m is 1-499, n ⁇ 1 and m + n ⁇ 500.
• Our invention may also comprise mixtures of the aforesaid compositions.
• crosslinked organopolysiloxane-polyoxyalkylenes are selected from the group of: where:
• the aliphatic radicals represented by R1 include the C2 to C25 paraffin, olefin and acetylenic hydrocarbons.
• the paraffinic hydrocarbons are preferred, such as ethyl, propyl, hexyl, decyl, dodecyl, octadecyl and eicosyl.
• the organic groups represented by R' include C1 to C10 alkylene radicals such as methylene, dimethylene, trimethylene, pentamethylene and decamethylene; cycloalkylene radicals such as cyclohexylene; divalent aromatic radicals such as p-phenylene or o-phenylene; and oxygen containing radicals such as -COOCH2CH2OOC- and -CH2OCH2-.
• the terminal group represented by R'' includes radicals of C1 to C20, like acetyl, propionyl, butyryl, isobutyryl, lauroyl, myristoyl, and stearoyl 3-carboxypentadecanoyl; alkyl radicals of C1 to C10, such as methyl, ethyl, propyl, butyl, and decyl; and the hydrogen atom.
• the aliphatic radical represented by R''' includes any of the radicals illustrated for R and also includes the methyl radical.
• the cross-linking radical R2 represents the hydrogen atom and monovalent C1 to C3 aliphatic radicals such as methyl, ethyl and propyl.
• the cross-linking bond is not hydrolyzable, and that R' contains no hydrolyzable bonds.
• some cross-linking may accidentally occur where the polyoxyalkylene is hydroxy terminated at one end.
• the hydroxy group may react with a silicon hydride creating a polyoxyalkylene bridge between two silicon backbone molecules as shown below:
• the degree to which this cross-linking may occur in the reaction process is not readily predictable.
• the SiOC bond formed at the hydroxy end of the bridge is subject to hydrolysis, under the operating conditions described above.
• the preferred bridge bond of the organopolysiloxane-polyoxyalkylenes of the second aspect of the present invention is a saturated carbon-silicon bond which is not hydrolyzable and is highly stable.
• the organic or organosiloxane body R' of the cross-linking bridge is free of hydrolyzable bonds. Further, R' should not interfere with the organopolysiloxane-polyoxyalkylene formation in any way.
• Hydrocarbon fuels of particular interest in the present invention are diesel fuel and jet fuel.
• the hydrocarbon fuel is preferably a diesel fuel used in motor vehicles, e.g. cars, heavy vehicles, marine applications or aviation.
• diesel fuel means gas oil and fuel oil including those materials which are light domestic, heating oils and diesel fuel irrespective of whether they are intended for vehicular, heating or other uses. These materials are characterized as having a viscosity of not more than 115'' Redwood 1 at 38°C. and a boiling point in the range of 200°C. to 380°C. Particularly included are those hydrocarbon liquids having a viscosity of 30'' to 40'' Redwood at 38°C., including those having a viscosity at 20°C.
• these materials have a carbon residue (Conradson) of ⁇ 0.2% by weight, a water content of ⁇ 0.05% by weight, a sulphur content of ⁇ 1.0% by weight and a net calorific value within the range of 10100 to 10300 Kcal/Kg.
• jet fuel means kerosene and light oils or medium oils for example known as AVTUR fuel.
• AVTUR fuel is a medium oil distilling between 150° and 300°C. that distills at least 65% in volume at 250°C., has a flash point above 38°C., has a maximum aromatic content of 20% by volume, has been treated to have a kinematic viscosity of less than 15 mm2/s (cS) at -34°C. and has a freezing point not greater than -50°C.
• the present invention may also find limited use for controlling foaming of other hydrocarbon liquids; for example, residual fuel oils having a viscosity at 38°C. of greater than 115'' Redwood, light medium and heavy naphtha, vaporizing oils, motor oils and motor spirits.
• Our invention is particularly beneficial in the control of foaming of hydrocarbon liquids and especially diesel fuels, as they are pumped rapidly from one vessel to another in the presence of air and possibly in the presence of water. Such circumstances exist during transfer of materials though a supply pipe from one vessel to another, during separation of various grades of hydrocarbon liquids from crude oil or selected feedstocks, and during transfer from transportation tankers to fixed storage tanks.
• additive packages which contain corrosion inhibitors, anti-scaling agents, octane improvers, emulsifiers, detergents and their mixtures. These additives are known to improve overall engine performance. The types and quantities of these additives are well known to those skilled in the art.
• the organopolysiloxane-polyoxyalkylene polymers of this aspect are used in any desired quantity and are incorporated into the hydrocarbon liquid in any suitable manner.
• our copolymers are added to the hydrocarbon liquid in the form of a solution or dispersion.
• the preferred polymers are effective to reduce the tendency of hydrocarbon liquids to foam when used in quantities of 100 parts per million or less, for example in the range of 1 to 50 ppm by volume.
• the most preferred polymers are effective when used in quantities of from 1 to 29 ppm by volume.
• alkylmethylsiloxanes selected from: R II Me2SiO(Me2SiO) m (MeR I SiO) n SiMe2R II and R II Me2SiO(MeR I SiO) n SiMe2R II , wherein m is 1-499, n ⁇ 1, with m + n ⁇ 500, R I is the same or different alkyl group of 2-100 carbon atoms, and R II is methyl or R I .
• Exemplary alkylmethylsiloxanes include Me3SiO[Me(CH3(CH2) v )SiO]SiMe3, where v averages between 24 and 28, or v averages between 30 and 50.
• alkylmethylsiloxanes are density matched to the hydrocarbon liquid.
• density matched it is meant that the alkylmethylsiloxanes have a density roughly approximating the density of the hydrocarbon liquid.
• the density of most alkylmethylsiloxanes is within the range of the described hydrogen liquids, generally 0.8 to 0.9 g/cm3.
• cyclic alkylmethylsiloxane polymers can be produced by the reaction of a cyclic siloxane having Si-H functional units thereon (eg., [MeHSiO] a ) with a slight stoichiometric excess of an alkene in the presence of a platinum supported catalyst on carbon.
• a cyclic siloxane having Si-H functional units thereon eg., [MeHSiO] a
• linear alkylmethyl copolymers can be produced by the reaction of a linear siloxane having Si-H functionality in the chain such as (Me3SiO 0.5 )2(MeHSiO) z1 , in which z1 is 4-100, and a cyclic siloxane having (Me2SiO) z2 units, in which z2 is 3-6.
• the reaction product generally 10% cyclic and 90% linear
• Batch production of the alkylmethylsiloxanes is conducted by adding the reaction product to a non-agitated suspension of the catalyst in the alkene at 60°C.
• the preferred alkylmethylsiloxane is Me3SiO[Me(CH3(CH2) v )SiO]SiMe3, where v averages between 24 and 28, or v averages between 30 and 50.
• These antifoaming agents may be added directly to the hydrocarbon fuel, or may be predispersed in a predispersent liquid, such as the hydrocarbon fuel, xylene, toluene, naphtha or other aromatics; various ketones; ethers and other commonly used organic solvents.
• Sample A 90 g. of diesel fuel was weighed into a 473.2 ml (16 oz.) glass bottle. To this was added 10 ppm of Me3SiO[Me(CH3(CH2) v )SiO]SiMe3, where v averages between 30 and 50 (the "first antifoam agent"), predispersed as a 1% wt. solution in xylene.
• Sample B 90 g. of diesel fuel was weighed into a 473.2 ml (16 oz.) glass bottle, and to this was added 10 ppm of the first antifoam agent, predispersed as a 1% wt. solution in diesel fuel.
• Sample C 90 g. of diesel fuel was weighed into a 473.2 ml (16 oz.) glass bottle. To this was added 10 ppm of Me3SiO[Me(CH3(CH2) v )SiO]SiMe3, where v averages between 24 and 28 (the "second antifoam agent"), predispersed as a 1% wt. solution in xylene.
• Sample D 90 g. of diesel fuel was weighed into a 473.2 ml (16 oz.) glass bottle, and to this was added 10 ppm of the first antifoam agent, predispersed as a 1% wt. solution in diesel fuel.
• Table I has the results of the trials: TABLE I DAY 1 DAY 7 %Foam Volume Break Time %Foam Volume Break Time Sample A sec. + 18% 23 sec. + 23% 31 Sample B sec. + 18% 25 sec. + 21% 34 Sample C sec. + 26% 60 sec. + 19% 43 Sample D sec. + 28% 57 sec. + 21% 49 Control sec. (No Antifoam) + 27% 57 sec. + 25% 47
• Samples A and B reduce the break time by as much as 50% over the control (untreated diesel fuel). Samples A and B also showed a significant decrease in overall foam volume when compared to the control. Samples C and D also had improvement over the control.
• Sample B 90 g.
• Table II shows the results of the trials: TABLE II DAY 1 DAY 7 %Foam Volume Break Time %Foam Volume Break Time Sample A + 25% 34 sec. + 24% 41 sec. Sample B + 23% 43 sec. + 24% 48 sec. No Antifoam (control) + 27% 57 sec. + 25% 47 sec.
• Table II shows that the antifoam additive of Samples A and B reduce the break time by as much as 50% over untreated diesel fuel.

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Citations (11)

• 1994
  • 1994-11-14 EP EP19940308392 patent/EP0654525B1/fr not_active Expired - Lifetime
  • 1994-11-14 DE DE1994618152 patent/DE69418152T2/de not_active Expired - Fee Related

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