GB2116205A - Emulsifying agents - Google Patents
Emulsifying agents Download PDFInfo
- Publication number
- GB2116205A GB2116205A GB08236468A GB8236468A GB2116205A GB 2116205 A GB2116205 A GB 2116205A GB 08236468 A GB08236468 A GB 08236468A GB 8236468 A GB8236468 A GB 8236468A GB 2116205 A GB2116205 A GB 2116205A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight
- composition
- methanol
- ethanol
- emulsion
- 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.)
- Granted
Links
- 239000003995 emulsifying agent Substances 0.000 title claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 102
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 26
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 24
- 239000002283 diesel fuel Substances 0.000 claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 24
- 229920001400 block copolymer Polymers 0.000 claims abstract description 15
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 6
- 238000004945 emulsification Methods 0.000 claims abstract description 4
- 229920005862 polyol Polymers 0.000 claims abstract description 4
- 150000003077 polyols Chemical class 0.000 claims abstract description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract 2
- 239000000839 emulsion Substances 0.000 claims description 45
- 239000000446 fuel Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- -1 poly(12-hydroxystearic acid) Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 9
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of 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
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/34—Higher-molecular-weight carboxylic acid esters
-
- 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
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Surfactant compositions suitable for the emulsification of methanol or ethanol in hydrocarbon liquids, especially diesel oil, consist of a blend of (i) from 10% to 90% by weight of a block or graft copolymer in which one polymeric component is the residue of an oil-soluble complex monocarboxylic acid and another polymeric component is the residue of a water-soluble polyalkylene glycol or polyalkyleneoxy polyol and (ii) from 90% to 10% by weight of a conventional non-ionic, non-polymeric surfactant having an HLB value in the range 11.0 to 18.0.
Description
SPECIFICATION
Emulsifying agents
This invention relates to novel surfactant compositions which are useful in the production of emulsions of polar liquids in hydrocarbon liquids, in particular of emulsions of methanol and ethanol in hydrocarbon fuels such as diesel oil.
it has been widely proposed, as a way of extending the available reserves of fossil hydrocarbon fuels, to blend petrol or gasoline with minor proportions of ethanol or, to a lesser extent, methanol, these alcohols being in principle obtainable from renewable natural resources. It would likewise be desirable to blend methanol or ethanol with heavier hydrocarbon fuel fractions, such as diesel oil, gas oil and fuel oil, but, in contrast to the situation with petrol or gasoline where the dry alcohol blends are in most cases homogeneous and are therefore straightforward to prepare, problems are encountered in producing the blends with the heavier fractions.On the one hand, the limited miscibility of methanol or ethanol with these fractions means that surface-active additives are required in order to stabilise the blends as emulsions; on the other hand, the fact that both of these alcohols are soluble to some extent in the hydrocarbon liquids in question and vice versa, means that conventional surfactants are not very effective for this purpose.
According to published British Application No. 2,051,124A, an emulsion of 20% by weight of methanol, 79% by weight of diesel oil and 1% of emulsifier can be prepared when the emulsifier is a block or graft copolymer of the type having the general formula (A--COO),B, wherein m is an integer of at least 2, each polymer component A has a molecular weight of at least 500 and is the residue of an oil-soluble complex monocarboxylic acid, and where each polymer component B has a molecular weight of at least 500, and, if m is equal to 2, is the divalent residue of a water-soluble polyalkylene glycol and, if m is higher than 2, is a residue having the valency m of a water-soluble polyether polyol. The emulsion obtained has, however, only a limited stability.
According to published British Appin. No. 2,002,400A, blends of the above-mentioned block or graft copolymers with conventional surfactants, such as the condensate of nonylphenol with 4 molar proportions of ethylene oxide, are useful for the emulsification of water in hydrocarbon fuel oils and
Example 7 of the said application illustrates the case where methanol is additionally present in the disperse phase of the emulsion in order to confer greater stability of the emulsion towards low temperatures. However, in this case the methanol/water mixture contained 75% by weight of water.
We have now found that emulsions of much improved stability of methanol or ethanol, particularly in the heavier hydrocarbon fuel fractions, can be made more readily with the aid of a blend of a block copolymer as above described with a specified class of conventional surfactant distinguished from the conventional surfactants referred to in British Appln. 2,002,400A.
The present invention accordingly provides a surfactant composition suitable for the emulsification of methanol or ethanol in a hydrocarbon liquid, the composition being a blend of: (i) from 10% to 90% by weight of a block or graft copolymer having the general formula (A--COO),,-B, wherein m is an integer at least 2, wherein each polymeric component A has a molecular weight of at least 500 and is the residue of an oil-soluble complex monocarboxylic acid having the general structural formula
in which
R is hydrogen or a monovalent hydrocarbon or substituted hydrocarbon group;
R, is hydrogen or a monovalent C1 to C24 hydrocarbon group;
R2 is a divalent C, to C24 hydrocarbon group;
n is zero or 1;
p is an integer from zero up to 200; and wherein each polymeric component B has a molecular weight of at least 500 and, in the case where m is 2, is the divalent residue of a water-soluble polyalkylene glycol having the general formula
in which R3 is hydrogen or a Cg to C3 alkyl group; q is an integer from 10 up to 500; or in the case where m is greater than 2, is the residue of valency m of a water-soluble polyether polyol having the general formula
in which R3and m have their previous significance; r is zero or an integer from 1 to 500, provided that the total number of
units in the molecule is at least 10;
R4 is the residue of an organic compound containing in the molecule m hydrogen atoms reactive with an alkylene oxide; with (ii) from 90% to 10% by weight of a conventional non-ionic surfactant in which the oil-soluble component has a molecular weight below 500 and which has an HLB value in the range 11.0 to 18.0.
Block or graft copolymers as hereinabove defined are more fully described in the afore-mentioned
British Appln. No. 2,002,400A and reference may be made thereto for details of their composition and
the manner in which they may be prepared.
By a conventional non-ionic surfactant we mean a substance containing in the molecule at least
one non-ionic water-soluble component and at least one non-ionic oil-soluble (i.e. hydrocarbon-soluble)
component, wherein both components are at most oligomeric in character and, in particular, wherein
the hydrocarbon-soluble component has a molecular weight below 500, preferably below 350.
Preferably, the surfactant has an HLB value in the range 11.4 to 16.7.
"HLB" stands for "Hydrophile-Lipophile Balance" and is a measure of the relative proportions of
water-soluble and oil-soluble components in a surfactant: see Griffin, W.C., J. Soc. Cosmetic Chemists 1949, 1, 311 and "Emulsions: Theory and Practice", p.232 ff (P. Becher, Reinhold, 1 965). HLB values
for non-ionic surfactants can range from a minimum of zero to a maximum of 20.
In the blends of the block copolymers and conventional surfactants described in British Appln. No.
2,002,400A, none of the conventional surfactants shown has an HLB value greater than 10.9.
Preferred block or graft copolymers are those in which m in the above formula (I) has a value of 2
and the water-soluble polyalkylene glycol from which the polymeric component B is derived is a
polyethylene glycol of molecular weight in the range 1000 4000. It is further preferred that the
copolymer should contain from 20% to 50% by weight, especially from 30% to 45% by weight, of the
polyethylene glycol-derived polymeric component B; otherwise expressed, the copolymer shouid
preferably have an HLB value in the range 4 to 10, especially 6 to 9.
Preferred conventional surfactants are the ethylene oxide condensates of alcohols or phenols,
such as sorbitan monoleate or p-nonylphenol, the weight proportion of poly(oxyethylene) chains present
being such as to correspond to an HLB value in the range hereinabove defined.
The relative proportions, in the compositions of the invention, of the block or graft copolymer (i)
and the conventional surfactant (ii) may vary, within the broad ranges defined above, according to the particular nature of the two phases which are to be emulsified, but illustrations of individual constituents (i) and (ii) and of the compositions of blends thereof, are given for general guidance in
Tables I, II and Ill below.
TABLE I.
'A' Block 'B' Block Block HLB Copolymer Composition Wt. 96 Composition Wt. % Value Q Poly(12-hydroxy- 70 Polyethylene glycol 30 6.0 stearic acid) S 1 60 .. 40 8.0 T " 55 ii 45 9.0 TABLE II
Conventional HLB Surfactant Composition Value Sorbitan monooleate + 20 mols ethylene oxide 15.0 Sorbitan monostearate + 20 mols ethylene 14.9 oxide ill. Sorbitan monolaurate + 20 mols ethylene 16.7 oxide IV Nonyl phenol + 20 mols ethylene oxide 16.0 V Nonyl phenol + 15 mols ethylene oxide 15.0 VI C13-15 aliphatic alcohol + 9 mols ethylene 12.5 oxide VII Non-ionic surfactant G-1096 11.4 (Atlas Chemicals) VIII Non-ionic surfactant G-1288 16.0 (Atlas Chemicals) TABLE III
Blend Block Conventional No. Copolymer % by wt Surfactant % by wt 1 Q 80 1 20 2 Q 50 l 50 3 Q 20 l 80 4 S 80 III 20 5 S 66.7 l 33.3 6 S 50 l 50 7 S 50 II 50 8 S 50 lll 50 9 S 50 IV 50 10 S 50 V 50 11 S 50 VI 50 12 S 50 VII 50 13 S 50 Vl(l- 50 14 S 20 Ill 80 15 T 50 I 50 According to a further aspect of the present invention, there is provided an emulsion of methanol or ethanol in a liquid hydrocarbon fuel, the emulsion containing from 1% to 75% by weight of methanol or ethanol as the disperse phase and from 25% to 99% by weight of the hydrocarbon fuel as the continuous phase, and in addition, as emulsifying agent, from 1% to 100% by weight, based on the disperse phase, of a surfactant composition as hereinabove defined.From a practical point of view, particular interest centres around emulsions which contain from 5% to 60% of methanol or ethanol and from 40% to 95% of hydrocarbon fuel, since the fuel value of the emulsions falls off steadily with increasing alcohol content and the viscosity rises as the disperse phase volume increases.
Hydrocarbon fuels in which methanol or ethanol may be emulsified according to the invention include, for example, commercial grade diesel oil, '35 seconds' gas oil, No. 3. fuel oil, commercial grade '2-star' petrol and commercial grade mineral oil (having a viscosity of 60 centistokes at 400C).
Although the disperse phase of the emulsions may consist of essentially pure methanol or ethanol, emulsions of practical interest may be obtained according to the invention in which the methanol or ethanol contains up to 20% of its weight of water. In commercial application, water contents in the range 510% by weight may commonly be encountered.In general, where the water content of the methanol or ethanol is low, it is preferred to employ, as the block or graft copolymer constituent of the surfactant composition, a copolymer having an HLB value towards the upper end of the preferred range previously referred to, viz. a value in the region of 8-9; conversely, where the methanol or ethanol contains proportions of water approaching the maximum of 20%, it is preferred to use a block or graft copolymer having a lower HLB value, in the region of 6.
The proportion of the surfactant composition employed to the total amount of the emulsion will vary, within the broad range stated above, not only according to the nature and relative proportions of the two constituents of the surfactant blend but also according to whether it is methanol or ethanol that
is to be emulsified and according to the water content of the alcohol. In general, the higher the water content, the easier it becomes to emulsify the alcohol because of the greater degree of its immiscibility with the hydrocarbon. With methanol, or with ethanol containing 5% or more of water, stable emulsions are readily formed in diesel oil using a proportion of the surfactant composition in the range 1% to 20%, preferably 3% to 10% and more preferably in the region of 5%, by weight of the alcohol phase.However, with certain combinations, for example that of ethanol containing less than 5% of water with diesel oil, where the disperse phase has a significant but finite degree of miscibility with the continuous phase, it may be necessary tousle an amount of the surfactant composition which approaches the actual amount of the alcohol in the mixture, if stable products are to be obtained. These products differ from the other emulsions according to the invention, which are characteristically turbid and contain disperse phase droplets of a size in the region of 0.1 micron or more, in being only slightly hazy or even completely clear, like a solution.The physical state of the alcohol constituent in these cases is not completely elucidated, but it is evident that the average size of the disperse phase droplets must be very small, perhaps of the order of a few tens or hundreds of Angstram units only; for convenience these products may be referred to as "microemulsions".
The optimum surfactant composition for any particular system to be emulsified can, however,
readily be ascertained by simple experiment.
The emulsions according to the invention are conveniently produced by first dissolving or dispersing the selected emulsifier blend in the hydrocarbon liquid, with the aid of gentle heating where necessary. The alcohol phase is then added, initially under low speed mixing conditions and if necessary subsequently at high speed for a period of 1-2 minutes, ensuring that the temperature does not exceed a value at which significant evaporation of the alcohol phase occurs, e.g. about 400 C. The resulting emulsion is considered to be stable if no more than slight separation of either phase is detectable after 5 days' storage at ambient temperature, any separation being redispersible by gentle agitation.
There may, if desired, be present in the emulsions of the invention conventional fuel additives.
Thus, for example, there may be incorporated in the alcohol phase of a diesel oil emulsion a lubricant whereby seizing of the fuel injection pump of an engine powered by the emulsion may be prevented.
The invention is illustrated but not limited by the following Examples, in which parts, ratios and percentages are by weight.
EXAMPLES
General Procedure
The block or graft copolymer constituent and the conventional surfactant, as identified in detail below, were blended together and then dissolved or dispersed in the hydrocarbon liquid, with the assistance of mild heat where necessary (not exceeding a temperature of 500 C). The alcohol phase, as identified below, was then added to the hydrocarbon phase with low speed mixing, followed where
necessary by high speed mixing for 1-2 minutes.
EXAMPLE 1
"Microemulsion" of 99% ethanol in diesel oil
Diesel oil (80 parts), blend 12 (see Table lil) (20 parts), and 99% ethanol (20 parts) were mixed together with hand stirring. A stable, almost clear microemulsion was obtained.
EXAMPLE 2
Emulsions of 95% ethanol in diesel oil
95% Ethanol (20 parts) was added to diesel oil (79 parts) containing blend 11(1 part) according to the general procedure outlined above. A stable emulsion was obtained. Similar results were obtained when blend 11 was replaced by an equal weight of blend 7 or blend 9.
EXAMPLE 3
Emulsions of 90% ethanol in gas oil and diesel oil
(a) 90% Ethanol (20 parts) was added to 35" gas oil (79 parts) containing blend 2 (1 part), according to the general procedure. A stable emulsion was obtained.
(b) 90% Ethanol (20 parts) was added to diesel oil (79 parts) containing blend 6 (1 part). A stable emulsion was obtained.
EXAMPLE 4
Emulsions of 80% ethanol in diesel oil
80% Ethanol (20 parts) was emulsified with diesel oil (79 parts) containing blend 4 (1 part), following the general procedure. A stable emulsion was obtained. Similar results were obtained when blend 4 was replaced by an equal weight of blend 8 or blend 14.
EXAMPLE 5
Emulsions of 100% methanol in diesel oil
(a) Methanol (20 parts) was emulsified into diesel oil (79 parts) containing blend 5 (1 part), according to the general procedure. A stable emulsion was obtained. Similar results were obtained in replacing blend 5 by an equal weight of each of the following blends in turn: blend 8; blend 9; blend 11; blend 13; blend 15.
(b) Methanol (50 parts) was emulsified into diesel oil (47.5 parts) containing blend 2 (2.5 parts), according to the general procedure. A stable emulsion resulted.
EXAMPLE 6
Emulsion of 100% methanol in gas oil
Methanol (20 parts) was emulsified into 35" gas oil (79 parts) containing blend 10(1 part), following the general procedure. A stable emulsion was obtained.
EXAMPLE 7
Emulsions of 90% methanol in diesel oil
90% Methanol (20 parts) was emulsified into diesel oil (79 parts) containing blend 2 (1 part), according to the general procedure. A stable emulsion was obtained, and a similar result was given when blend 2 was replaced by an equal weight of blend 3.
EXAMPLE 8
Emulsion of 80% methanol in diesel oil
80% methanol (20 parts) was emulsified into diesel oil (79 parts) containing blend 1(1 part), following the general procedure. A stable emulsion resulted.
Claims (12)
1. A surfactant composition suitable for the emulsification of methanol or ethanol in a hydrocarbon liquid, the composition being a blend of:
(i) from 10% to 90% by weight of a block or graft copolymer having the general formula (A--COO),,-B, wherein m is an integer at least 2, wherein each polymeric component A has a molecular weight of at least 500 and is the residue of an oil-soluble complex monocarboxylic acid having the general structural formula
in which
R is hydrogen or a monovalent hydrocarbon or substituted hydrocarbon group; R1 is hydrogen or a monovalent C1 to C24 hydrocarbon group;
R2 is a divalent C1 to C24 hydrocarbon group;
n is zero or 1;
p is an integer from zero up to 200; and wherein each polymeric component B has a molecular weight of at least 500 and, in the case where m is 2, is the divalent residue of a water-soluble polyalkylene glycol having the general formula
in which
R3 is hydrogen or a C1 to C3 alkyl group;
q is an integer from 10 up to 500; or in the case where m is greater than 2, is the residue of valency m of a water-soluble polyether polyol having the general formula
in which
R3 and m have their previous significance;
r is zero or an integer from 1 to 500, provided that the total number of
units in the molecule is at least 10;
R4 is the residue of an organic compound containing in the molecule m hydrogen atoms reactive with an alkylene oxide; with (ii) from 90% to 10% by weight of a conventional non-ionic surfactant in which the oil-soluble component has a molecular weight below 500 and which has an HLB value in the range 11.0 to 18.0.
2. A composition as claimed in claim 1 wherein the oil-soluble component of the conventional surfactant has a molecular weight below 350.
3. A composition as claimed in claim 1 or claim 2, wherein the conventional surfactant has an HLB value in the range 11.4 to 16.7.
4. A composition as claimed in any one of claims 1 to 3, wherein the block or graft copolymer is one according to formula (I) where M has a value of 2 and the water-soluble polyalkylene glycol from which the polymeric component B is derived is a polyethylene glycol of molecular weight in the range 1000-4000.
5. A composition as claimed in any one of claims 1 to 4, wherein the copolymer contains from 20% to 50% by weight of the polyethylene glycol-derived polymeric component B, that is to say, the copolymer has an HLB value in the range 4 to 10.
6. A composition as claimed in claim 5, wherein the copolymer contains from 30% to 45% by weight of the polyethylene glycol-derived polymeric component B, that is to say, the copolymer has an
HLB value in the range 6 to 9.
7. A composition as claimed in any one of claims 1 to 6, wherein the polymeric component A of the block or graft copolymer is the residue of poly(12-hydroxystearic acid).
8. A composition as claimed in any one of claims 1 to 7, wherein the conventional surfactant is the ethylene oxide condensate of an alcohol or phenol.
9. A composition according to claim 1, substantially as herein before described with reference to the foregoing Examples.
10. An emulsion of methanol or ethanol in a liquid hydrocarbon fuel, the emulsion containing from 1% to 75% by weight of methanol or ethanol as the disperse phase and from 25% to 99% by weight of the hydrocarbon fuel as the continuous phase, and in addition, as emulsifying agent, from 1% to 100% by weight, based on the disperse phase, of a surfactant composition as claimed in any one of claims 1 to 9.
11. An emulsion as claimed in claim 10, containing from 5% to 60% of methanol or ethanol and from 40% to 95% of hydrocarbon fuel.
12. An emulsion as claimed in claim 10 or claim 11, wherein the hydrocarbon fuel is commercial grade diesel oil.
1 3. An emulsion as claimed in any one of claims 10 to 12, wherein the methanol or ethanol contains up to 20% of its weight of water.
1 4. An emulsion according to claim 10, substantially as herein before described, with reference to the foregoing Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08236468A GB2116205B (en) | 1982-01-14 | 1982-12-22 | Emulsifying agents |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8201043 | 1982-01-14 | ||
| GB08236468A GB2116205B (en) | 1982-01-14 | 1982-12-22 | Emulsifying agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2116205A true GB2116205A (en) | 1983-09-21 |
| GB2116205B GB2116205B (en) | 1985-01-30 |
Family
ID=26281715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08236468A Expired GB2116205B (en) | 1982-01-14 | 1982-12-22 | Emulsifying agents |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2116205B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678599A (en) * | 1983-10-27 | 1987-07-07 | Th. Goldschmidt Ag | Use of copolymers of polyoxyalkylene ethers of allyl and/or methallyl alcohol and vinyl esters as demulsifiers for water-containing crude oil |
| US5300255A (en) * | 1984-03-21 | 1994-04-05 | Imperial Chemical Industries, Plc. | Surfactant products of poly(hydroxyalkanecarboxylic acid) phosphate esters |
| US7642298B2 (en) | 2003-06-11 | 2010-01-05 | Ciba Specialty Chemicals Water Treatments Ltd. | Polymeric surfactant |
-
1982
- 1982-12-22 GB GB08236468A patent/GB2116205B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678599A (en) * | 1983-10-27 | 1987-07-07 | Th. Goldschmidt Ag | Use of copolymers of polyoxyalkylene ethers of allyl and/or methallyl alcohol and vinyl esters as demulsifiers for water-containing crude oil |
| US5300255A (en) * | 1984-03-21 | 1994-04-05 | Imperial Chemical Industries, Plc. | Surfactant products of poly(hydroxyalkanecarboxylic acid) phosphate esters |
| US5536445A (en) * | 1984-03-21 | 1996-07-16 | Zeneca Limted | Surfactant and dispersible or emulsifiable compositions employing surfactant |
| US7642298B2 (en) | 2003-06-11 | 2010-01-05 | Ciba Specialty Chemicals Water Treatments Ltd. | Polymeric surfactant |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2116205B (en) | 1985-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4504276A (en) | Emulsifying agents | |
| US4509950A (en) | Emulsifying agents | |
| US4203877A (en) | Block or graft copolymers and their use as surfactants | |
| US7419515B2 (en) | Multi-phase distillate fuel compositions and concentrates containing emulsified boric acid | |
| EP0004426B1 (en) | Surfactant compositions comprising a blend of two types of polyester and an emulsion of oil in water prepared therewith | |
| EP2343353B1 (en) | Uses of emulsifying agents in non-aqueous fuels and oils | |
| US4504275A (en) | Emulsifying agents | |
| CA2769545C (en) | Composition for preparing an emulsion | |
| CN103597028A (en) | Aqueous pour point depressant dispersion composition | |
| CN103597027A (en) | Method t0 make an aqueous pour point depressant dispersion composition | |
| GB2117398A (en) | Emulsifying agents | |
| AU2002246715B2 (en) | Stabilizer blends for alcohol in hydrocarbon fuel | |
| AU2002246715A1 (en) | Stabilizer blends for alcohol in hydrocarbon fuel | |
| US3639255A (en) | Process of dispersing oil slicks | |
| GB2116205A (en) | Emulsifying agents | |
| US5767192A (en) | Silicone foam control agents for hydrocarbon liquids | |
| JP5670459B2 (en) | Liquid fuel protection | |
| GB2115002A (en) | Emulsifying agents | |
| EP0505070B1 (en) | Motor fuel composition having enhanced water tolerance | |
| GB2234978A (en) | Fluorosilicone antifoam additive composition for use in crude oil separation | |
| US3951832A (en) | Stabilized polysiloxane-polyglycol foam inhibitors for mineral oils | |
| US12116541B2 (en) | Emulsifier package with a short-chained and optionally with a long-chained surfactant for fuel emulsion | |
| RU2153391C1 (en) | Emulsifier for reverse emulsions | |
| TW202225389A (en) | Emulsifier package with a branched and optionally with a propoxylated surfactant for fuel emulsion | |
| JPS63165488A (en) | Additive for powdered coal-oil mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19931222 |