CA1127845A - Hydrocarbon-water fuels, slurries and other particulate mixtures - Google Patents
Hydrocarbon-water fuels, slurries and other particulate mixturesInfo
- Publication number
- CA1127845A CA1127845A CA297,387A CA297387A CA1127845A CA 1127845 A CA1127845 A CA 1127845A CA 297387 A CA297387 A CA 297387A CA 1127845 A CA1127845 A CA 1127845A
- Authority
- CA
- Canada
- Prior art keywords
- mixture
- molecular weight
- agent
- water
- high molecular
- 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
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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
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
-
- 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
- C10L1/328—Oil emulsions containing water or any other hydrophilic phase
-
- 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
- F02B2275/00—Other engines, components or details, not provided for in other groups of this subclass
- F02B2275/14—Direct injection into combustion chamber
Abstract
ABSTRACT OF THE DISCLOSURE
The first aspect of the invention involves stable emulsions of hydrocarbons and water using a combination of a low molecular weight agent and a high molecular weight material. In another aspect of the invention slurries are formed for fuel purposes utilizing coal particules with hydrocarbons and water and the aforesaid agent and material to achieve a stable combination. The invention further con-templates slurries of combustible or non-combustible materials with water alone or in conjunction with other liquids using the aforesaid agent and material.
The first aspect of the invention involves stable emulsions of hydrocarbons and water using a combination of a low molecular weight agent and a high molecular weight material. In another aspect of the invention slurries are formed for fuel purposes utilizing coal particules with hydrocarbons and water and the aforesaid agent and material to achieve a stable combination. The invention further con-templates slurries of combustible or non-combustible materials with water alone or in conjunction with other liquids using the aforesaid agent and material.
Description
SP~CIFICATION
Hydrocarbons and water mixtures have many potential uses, such as in internal combustion engines and as a fuel for heating purposes, either in themselves or combined with coal in acoal slurry, or when combined with combustible or non-combustible solids or even with water or oil as the sole liquid.
It is believed that emuls~ons oE hydrocarbons andwater have not come into general use because of the relative instabil-ity of emulsions involving agents in the fuel in economical quantities. However, the need for stable emul6ions of hydro-carbons and water has become even more important with the increasing price of fuel.
For many years it has been the practice to inject water into fuel systems for purposes of improving engine per-formance. It has also been recognized that water injection will enable combustion to occur at a lower temperature, thereby decreasing the formation of oxides of nitrogen, which are major pollutants.
In preparing satisfactory emulsions of hydrocarbons and watèr, it is necessary that the resulting~product have satisfactory properties for use in the internal combustion engine~ However, with heating uses, the fuel is normally fed into or atomized in a heating chamber. Moreover, it is neces-sary that any emulsion used as a heatin~ fuel have sufficient stability to retain its properties until the time comes for its use. It has been proposed to add coal to oil including crude ~~ 2 -oil, but such proposals have thus far proved unsuccessful be-cause of the inability to maintain the coal in a stable suspend-ed state in the oil for the usual passage of time between manu-facturers and comMercial use It is accordingly a principal object of the present invention to provide stable emulsions of hydrocarbons and water for general fuel use, either with an internal combustion engine, for heating purposes, for jet engines and turbines or general use. Also, contemplated are slurries, such as coal slurries which can be readily transported.
It has been recognized that hydrocarbon-water emul-sions can be formed using surfactants as disclosed in United States Patent No. 3 r 527,581. It has also been proposed to use blends of polyoxyethylene emulsifiers in a paper by Peters and Stebar entitled "Water-Gasoline Fuels-Their EfEect on Spark Ignition Engine Emissions and Performace" which was presented at the Society of ~utomotive Engineers, Inc., St. Louis, Mis-souri, on ~une 7--10, 1976. Such emulsions contain substantial aMounts oE water, but are either not stable over long periods oE time or require such high quantities of emulsifiers to achieve satisfactory stability as to be uneconomical.
Additional teachings of hydrocarbon-water emulsions for various purposes are disclosed in United States Patents Nos.3,206,410, 3,311,561, 3,346,494, 3,442,342, 3,355,394, 3,645,903 and 3,~76,391.
The emulsions of the present invention are preferably ~;~
water and qasoline, jet fuel, heating oil, diesel oil, crude oil, coal slurries and non-combustibles.
In accordance with the principles of the present invention, the suspended droplets and/or particles are relatively large and have a si~e usually in excess of about 1400 Angstroms.
Thus, the emulsions of the present invention are more properly termed macroemulsions and have a milky appearance or black when : ' ~
~, . .
coal is used. This is to be compared with microemulsions where-in the internal phase is present in a much smaller droplet and/
or particle size 50 that a microemulsion has a translucent or transparent appearance.
~ Jith the present invention the continuous phase is at times the hydrocarbon so that the emulsions are so-called water-in-oil emulsions. Other times the continuous phase is water so the emulsion is oil-in-water.
Where the water percentage is less than 30% by weight, it can be regarded as a low internal phase ratio. In the range oE 30% to 70% water by weight, it is present as a meduim inter- ~;
nal phase ratio and above 70% as a high internal phase ratio system, when water is the internal phase. ~`
On the the advanta~es offered b~7 the emulsions of the present invention is the ~reat stability over long periods OL^
time, usually well in excess of two months which satisfies usual storage and transportation requirements. Moreover, the viscosity of certain of the emulsions of the present invention i.s relatïve-ly low (about l cen-tipoise), although the sedimentation of an emulsion (and therefore its instability) increases as viscosi-ty is lowered. However, the present invention presents a sa-tis-factory balance of high stability and low viscosity. In other applications of the invention, high viscosity as well as high stability are afforded. Also, with the ~resent invention satis-factor~,7 vaporization is achieved under conditions of reasonably low viscosity and satisfactory stability.
Another characteristic of the invention is that it is usual to have water present in an amount of about l -to 20% volume with the upper limit reaching 4n% by volume or more.
The emulsions of the present invention are achieved by usin~ t'le combination of (1) a water or hydrocarbon soluble (iOlliC
or noionic) relatively low molecular weig1lt agen-t (r,~olecular weight in many instances oE the order oE lOOO) which is generally s a substance wherein one side or part of the molecular is hydrophillic and their other side lipophillic and (2) a high ~ erahl~
molesular weight material (of the order of 500, 000 or more) crably /1 ~that is swellable in water (cross-linked) and/or is water soluble (substan-tially non-cross-linked).
The combination of the agent and the high molecular weight material creates an extremely stable bond between the water and the hydrocarbon. At tlle same time, in many instances, the aforesaid co~bination achieves a low viscosity even where the water is present in excess of 25% by volume. It will be seen that the present invention alos contemplates the use of one or more agents or one or more hight molecular weight materials, or a combination of two of one material and one of the other, or vice versa, or two or more of each material.
~ he present invention is belleved to function satis-factorily with a wide range of: hydrocarbons and particularly various gasolines o.f hi~h or low octane and other well known ~uels. However, the present invention also applies to other hydrocarbons and other carbon containing materials such as coal 20 or even non-hvdrocarbons such as carbon or even inorganic mate- ;~
rials and incombustibles which may be introduced or dispersed in oil as a coal slurry with the dispersed particles being present in a size smaller than 60 mesh and preferably 200 to 325 mesh.
When the present invention is used in connection with oils for heatin~ purposes, it is demonstrated that many well known heat ing oils, such as ~1, #2 or #6 may be used in a water and oil emulsion with suspended coal and/or carbon particles or other particles, both combustile and non-combustile. Examples of non-combustiles are lime, chalk, alumina and o-thers.
Because the emlllsions prepared in accordance with the present invention are extremely stable, such emulsions are usuable in the same way as presently available furnace heating oil. Moreover, coal particules can be suspended and held sus-~27~
pended in the emulslon with coal present in as much as 50~
by weight and so~etimes in an even greater amount. Also, the presence of ~later in the emulsion may improve combustion per-formance because of the micro-explosions as discussed herein-after.
In some instances the coal can be suspended in water through the practice of the present invention with the use of little or no oil at all.
A very important consideration arising from the pre-sent invention ls that the presence of waterin the stable emul-sion serves to create micro-explosions of water when the emul-sion of the present invention is used in an internal combustion engine or in a heating system. Such micro-explosions arise from the superheating of the water in the emulsion. The effect achieved is the blowing of the oil particles apart throuyhout the hydrocarbon. It is believed that the aforesaid micro-explosions have the effect of substantially increasing the per-Eormance oF the combustion ~rocess.
In heating or use in a diesel engine the oil is nor-mally simply fed into or atomized in a heating chamber or inject-ed therein. Thus, the present invention has use for heating or diesel engine purposes and is especially attractive in the formation of stable coal slurries.
On agent used in connection ~ith the present invention is sold by the American Cynamid Comparly and is identified as product OT ln0. This agent is the sodium salt of dioctylsulfo-succinnic acid. A second agent usable in connection with the present invention is the sodium salt of decylbenzenesulfonic acid.
A third agent is Toximul MP (sulfonate/non-ionic blend) sold by the Stepan Co. ~his is calcium dodecyl benzene sulfonate and alkyl phenoxy polyoxyethylene ethanol. A fourth agent is Triton X45, sold by the ~ohm & HaAs Company, which is octyl,hen-oxypolyethoxy ethanol.
t~ ' _ 6 -Examples of hiyh molecular weigllt materials usable in the present invention are Carbopol 941 in the completely neutrali~ed form using sodium hydroxide, sodium carbonate, ammonia and other well known neutn^ali~ing agents, in stochio-metric amounts or otherwise. Carbopol ~1 is a high molecular weight polyacrylic acid as disclosed in U. S. Patent 2,798,053.
A second example of a high molecular weight material is an acrylamide/sodium acrylate identified as Dow XD 8992 as disclos-ed in U. ~. Patent 3,669,103 and is partially crosslin~ed.
A third example of a high molecular weight material is a hydroli~ed starch polyacrylonitrile graft copolymer as disclosed in U. S. Patent 3,935,099. A fourth example of a high molecular weight material is a high molecular weight polyoxyethy-lene coagulant of Union Carbide Corporation, where the molecular weight is in excess of five hundred thousand.
Yet another ad~antage of the present invention lies in the fact that relatively small amounts of the agent and high molecular weight materials are used. Indeed an effective amount of the agent can be as low as 3.7 grams per liter of ~asoline, down to as low as one gram per liter or slightly less.
In some instances it is desirable to combine two of the afore-mentioned high molecular weight materials such as the Carbopol 941 (in the form of the sodium salt or otherwise) and the Dow XD 8992 in formulating the stable emulsion of the present inven-tion.
The agent is added directly at times to the hydrocarbon with the high molecular weight material in aqueous solution or mixture then added to the hydrocarbon agent solution. In some instances, for example when using Triton X45, it is added to the water, rather than to the hydrocarbon because of the special solubility of Triton X45. This is followed by gentle mixing at room temperature immediately, or for some short period of time, usually not more than fifteen minutes -to achieve a white or QJe ~r~
27'~5 milky macroemulsion. The emulsions achieved through the present invention are so stable as to remain intact under short term centrifuge te~ts and temperature tests and storage tests for periods o F time of sixty days or more as required by indus-trv.
When used in a coal slurry, it is possible to use less liquid hydrocarbon or none at all because coal, carbon particles or other particulate heat giving material may be added to enhance the heat value of the emulsion. For example an emulsion produced in accordance with the invention for heat purposes is composed of 50% by weight coal, 40% by weight heating oil and 10% by weight water. ~lternatively, another coal slurry produced in accordance with this invention is composed of 50% by weight of water and 50% b~7 weight o.f coal, although the amount of coal can be even greater. Also, bituminous coal, liguite and solvent refined coal may be used.
It should be kept in mind that in formulating emulsions in accordance with the present inventi.on that the use of greater amounts of the hi~h molecular weight material generally allows the use of smaller amounts of the agent. This is important where the quantity of the high molecular weight material is less exPensive than the quantity of the agent. From the examples in the Specification of this Application it will be seen that relatively low quantities of both the high molecular weight material and the agent are used so that emulsions prepared in accordance with the invention are competitively priced. Thus, where the agent is present in relatively low levels, the high molecular weight material is effective to lower the amount of agent that is needed. ~Iowever, at higher levels of agent, it 30 tends to dominate the high molecular weight material to the ;
extent that in some cases the agent alone will produce a satis-factory, albeit extremely expensive emulsion.
I has also been observed that emulsions are more .
~Z~f~
rapidly formualted when the high molecular weight material is of the swellable type. ~loreover, with the increase of water in the internal phase, that is from low to medium or medium to high, viscosity will increase. Conversely, where the water is in the external phase, the increase of water will lower viscosity.
From the foregoing it can be seen that the emulsions of the present invention are more stable and are macroemulsions which give rise to micro-explosions when consumed, to achieve better engine and/or burning efficiency. Moreover, with the present invention, coal including bituminous coal, lignite and solvent refined coal and other combustible materials like carbon particles or non-combustible materials can be stabilized for a long period of time for transportation or storage.
Where desired the viscosity and volatility can be adjusted using suitahle materials or solvents, such as alcohols, like methyls, ethyl or isopropyl alcohol, ketones such as acetone, ethers, etc.
It is theorized that the high molecular weight material provides a generic matrix structure or has the effect of struc-turing the overall mixture in order to hold very tightly the ;
various components. While Applicants do not wish to be bound hy any particular theory, it is believed that the high molecular material of the present invention provides a matrix wherein the ~ ~`
water is usually latched onto the matrix with the agent acting as a hook between the water phase and the hydrocarbon phase.
Stated more broadly, the theory is that the present invention provides a matrix wherein the water has an affinity for the matrix with the agent having an affinity between the water 30 phase and the hydrocarbon phase. ~`
While in many instances the water is structured orfunctions as a matrix, the hydrocarbon can alos be structured, for instance through the use of aluminum salts of naphthenic . ~., , acids and coconut oil acids or a mixture of naphthenic acid and unsaturated acids with the agent and water. In many instances the agent is a surface active agent, although the invention is not limited to such a feature.
It is also contemplated that the agent be present in either the water or hydrocarbon phase or both.
It is also contemplated that other additives may be included, such as sodium chloride and other salts, the presence of which prevents the formation of a high internal phase ratio material.
Certain examples of the invention will now be provided for the sake of illustration and not by way of limitation. In these examples certain abbreviations have been used.
The low molecular wei~ht agent will have the Eollowing abbreviations:
Sl Am_rican Cyanamid Company OT-100 - sodium salt of dioctylsulfosuccinnic acid.
S2 _rco Chemica~ Compan~ - Ultrawet DS ~ sodium salt of decylbenzenesulfonic acid.
S3 Stepan C m any - Toximul MP - calcium dodecyl benzene sulfonate and alkyl phenoxy polyoxyethylene ethanol.
S4 _o m & Haas Company - Triton X45 - octylphenoxy-polyethoxy ethanol.
S5 mperial Chemica Company, Inc. (ICC U.S.) Arlacel C Sorbitan sesquioleate.
S6 _mperlal _hem cal _ompany, Inc. - Tween 40 poly-sorbate 40 (polyoxyethylene 20 Sorbitan mono palmitate).
S7 Proctor & Gamble (Ivory liquid detergent) U. S.
_ . ~
Patents 3,024,273, 3,179,598, 3,179,599 and 3,793, 233.
S8 Stepan Chemical - Ninate 401 - calcium dodecyl i (le /~ s benzene sulfonate S9 _tepan Che ical (Ninate 411 - alkylamine dodecyl benzene sulfonate (burns completely - contains no metal).
The high molecular weight material will have the Eollowing abbreviations:
Ql Dow Ch _lcal Company XD 8992 (1300 swellable poly (acrylamide/sodium acrylate) partially crosslinked as discussed in U.S. Patent 3,669 103.
02 General Mills Company SG-P 502S swellable hydro-__ _._. _ ~ _ _ --. -- ---lyzed starch polyacylonitrile graft copolymer asdisclosed in U.S. Patent 3,935,099.
03 B F Goodrich Carbo~ol 941 water soluble high-_ , _ _ _ . ... . _ _ molecular weight polyacrylic acid as disclosed in U.S. Patent 2,798,053 in the completely neutralized form using sodium hydroxide, sodium carbonate or ammonia or other bases in stochio-metric amounts or otherwise.
Q4 Union Carbide_Company - Polyox Coagulant (MWM 0 more than 500,000) polyoxyethylene ~5 Dow C em_ al_Company - Separan MG 700 partially hydrolized polyacrylamides as discussed in U.S.
Patent 3,825,069.
Also usable in the present invention are transporta-tion compositions which facilitate movements of the various emulsions, slurries, etc. through piping, pumps and pumping requirements by lowering pipe friction. The transportation agent is used in a pre-treatment step prior to pumping. One example is the use of Q4 as a pretreatment in the pipe or as incorporated in the Mixture. Also usable in the present inven-tion are transportation materials and agents selected from one or more of the S's and O's specified above but not limited there-to.
8~i In the following Examples the gasolines are:
(A) American Oil Co. (A~OCO) Premium (No lead) av. octane # = 95.7 H2O means distilled water.
(B) Same as above, but sub-regular (No lead~
average octane # = 88Ø
X~lPI,E I
75 parts by volume of Gasoline A containing 3.75 g/lit.
of OT-lOQ of American Cyanamide were shaken with 25 parts by volume of water, containing 0.7 g/lit. of Dow Chemical Company's DX-1300 and 0.5 g/lit. of -Ma~941-carbopolate of B.F. Goodrich Chemical Co. A
stable emulsion of gasoline/water was produced; on standing Eor one mon-th at room temperature no notice-ab]e separation took place; however, after 4.0 months a water layer, equalling 3.7 volume ~ of the total liquid appeared; after 9.0 months the separation of the aqueous layer was 5.6 volume ~ of the total liquid.
The fore~oing mixture was used as a fuel in a single cylinder internal combustion engine. Before use, viscosity was lowered by the addition of e~hyl alcohol (10% by volume). The engine operated satis-factorily under full load for an ex-tended period of time.
90 parts by volume of gasoline B containing 3.75 g of Ot-100 of American Cyanamide Co./lit. gasoline were shaken with 10 parts by volume of water containing 1.0 g/lit. of a water swellable polymer SGP~5025 of General Mills Chemcials, Inc. producing a stable milk-like emulsion of gasoline/wa-ter. There was no separa-tion of an aqueous layer after 30 days and after 100 days an aqueous lower layer approximately 0.5~ of the total liauid accumulated.
_XA~PLE 3 75 parts by volume of gasoline A containing 3.75 g/lit of gasoline of OT-100 were mixed and shaken with 25 parts by volume of water containing only 1.0 g/lit. solution of Na-9'~1-carbopolate. It formed a stable milk-like emulsion so that in 2 weeks no aqueous layer separated and after 100 days 3.3 volume percent of the total liquid separated.
Similar to Examples 1, 2 and 3 emulsions were pre-pared with the same agents and materials but using instead of gasoline a) Fuel Oil No. 1 b) Fuel Oil No. 2 c) ~et Engine Fuel J P 4 d) Angolan Crude Oil as is.
All of these four types formed stable emulsions, similarly to those of Examples 1, 2 and 3. ~;
20 EX~5PLE 5 50.0 parts by weight of No. 2 fuel oil, containing 3.75 g/lit. of OT-100 of American Cyanamide were mix-ed with 30.0 parts by weight of bituminous coal pass-ing a 325 mesh sieve, into a black asphalt-like liquid, after adding 1.65 parts by weight of isopro~yl alcohol to wet part of the coal powder. 20.0 parts by weight of water containing both 1 g/lit. of sodium 941 -carbopolate of B. F. Goodrich Chemical Co. and 1 g/lit.
XD-8992 of Dow Chemical Co. were mixed in by stirring and a 30% weight of coal. (20% weight water) (50%
fuel oil slurry produced). It exuded only 3 weight percent of fuel No. 2 after standing for 45 days at room temperature (_ 20 C) and after a temperature 7~
c~cle of 27 hours at - 12C and 4 hours at 85C to 100C to 85C.
EX~PLE 6 46 parts by weight of the same mesh coal as in Example 5 were mixed with 44-1~2 parts by weight Crude from Angola (light crude) containing 3.75 g/lit.
crude of American Cyanamide's OT-100. To this black liquid 10 parts by vol. of water containing the same ingredients and concentrations as in Example No. 5 above, were added and stirred with a stirrer to a homogenous black slurry of the composition: 46 w/o (weight percent) carbon - 9-1/2 w/o water - 44-1/2 w/o Gulf crude and which persists for long periods of time.
~XAMPLE 7 Speed up of invernsion a) To 20cc of H2O was added 80cc Gasoline B containing Sl (3 75 g/l Gasoline B) and mixed with gentle stirring in a magnet stirrer. The stirring sequence was 15 seconds stirring plus ~ seconds standin~ or manual swirling. After six such sequences the two separated layers rapidly formed a high internal phase ratio emulsion (gas in water), or an invert. ~ -`
b) Repeat (of a) except that 18cc of water solution containing Ql (0.63 g/l H20) was added to 73cc of Gasoline B with Sl (3.75 g/l gasoline). The emul-sion now formed in only two sequences of stirring.
c) Repeat (of a) except that 20cc of water solution of Q2 (1 g/l H2O) was added to 80cc Gasoline B
containing Sl (3.75 g/l gasoline). The emulsion now formed in only two se~uences of stirring.
EXAMPL~ 8 Change of viscosity and stability.
7~
a) For a 25cc water solution Q2 (1.0 g/l H2O) and 100 cc Gasoline s containing Sl (3.75 g/l gaso-line) the sequence of Example 7 c was followed.
The emulsion had a viscosity of about 3 centi-stokes and left a lower layer of .84cc in 6.0cc ~`
total in a centrifuge tube under about 200 x g for 5 minutesA
b) stirring of the sample in a) of four additional stirring sequences at about twice the stirring speed gave an emulsion viscosity of about 12 centi-stokes and a centrifuge lower layer (same centi-fuge conditions) of about 0.3cc, i.e. higher vis cosity and greater stability with increased rate of shear.
c) To a 20cc water solution of Q3 (1 g/l H2O) was added 80ec Gasoline B containing Sl (3.75 g/l gasoline). The stirrin~ sequence ko form an emul-sion o:F the inverted type took 10 sequenees oE the stirring rate of b) above plus 6 sequences of a combination of that of a) and b) above. ~ith four additional sequences of stlrring tafter inversion) at the speed of b) above the viseosity ~ -of the emulsion was about ~5 centistokes, with a centrifuge lower layer of about .48cc in 6cc total.
d) For the same composition as in c) above except that 20cc Q3 solution was replaced by lOcc Q2 solution and lOcc Q3 solution. A viscosity of 13 centistokes and a centrifuge lower layer of about .48cc in hcc total was obtained. The emul-sion was formed in only three sequences of the stlrring rate of b) above. This shows the syner-gistric effect of Q2 on rate of emulsion formation and Q3 on viscosi.ty.
e) To 25cc solution of 1:1 Ol and Q3 and one liter of water ~lg/l H20) each was added 75 cc Sl (3.75 g/l gasoline A). This solution was stirred at five times the stirring rate of Example 7 a) to produce an emulsion with a viscosity of about 50 centistokes and a centrifuge sedimenta-tion of about .12cc. This sample was allowed to stand in a flask and showed no appreciable separa-tion for three months, after which about O.lcc :
of water separated from about lOOcc of emulsion over an additional month. This correllates the short term stability centrifuge test with lony term stability, showing that both.v.iscosity and lower layer formation must be used bo establish : .
stability, for this emulsion. This shows that ::
the stability of d) about is yreater than c) above, for long term, because the viscosity is greater in d) although the centrifuge lower layer forma- : .
tion is the same. :
X~1PLE 9 -Addition of Q material improves stability a) A composition of 20cc H2O and 80cc gasoline s ., , :.
containing Sl (3.75 g/l) with stirring as in Example 8 b) gave an emulsi.on in 9 stirring sequences. Four more similar sti.rring sequences gave an emulsion with a viscosity of about 4 centistokes and a centrifuge lower layer of .54cc in 6cc.
h) ~his experiment is the same as a) above except that 2Cccwater solution of Q2 (lg/l H2O) replaced the 20cc H2O. A viscosity of about 8 centistokes and a centrifuge lower layer of .54cc in 6cc were ob-tained. This increase in viscosity with the O material shows increased stability over no use of 0 material as in a) abo~e. See remarks at end of Example 8 e).
_AMPLE 10 Q's have greates effect with low concentration of S's a) To 30cc ~l2O was added 120cc of gasoline ~ con-taining Sl (50 g/l) and following 2 sequences o:E
stirring as in Example 7 a) a low internal phase ratio (water in gasoline) was fo.rmed. With this composition a viscosity of about one centistoke and a zero centrifuge lower layer was obtained.*
b) Experiment a) above was repeated with 30cc water solution of Ql (1 g/l H2O) replacing the 30cc H2O.
The same type emu].sion with the same viscosity and lower layer were ob~ained as in a) above. This Example compared with Examples 7, 8 and 9 shows that Q's are most effective with low concentra- ~.
tions of S materials in producing high internal phase ratio emulsions and changing viscosity and thus stability~ * With this type emulsion zero centrifuge lower layer formation gave about a 1.5%
water layer in 7 days for long term stability.
_A PLE 11 Effect of alcohols, salts H2O/gasoline (Ratio) a) ~ composition of 20cc water solution Q2 (-34 g/l H2O) and 80cc gasoline B [S1 concentraLion grams/l gasoline b) with 3 minutes of uniterrupted magnetic stirring gave an emulsion with a viscosity of about 4 centistokes and centrifuge lower layer of about .7cc in 6cc.
b) With the same composition as in a) above plus l.Occ methanol, only 30 seconds were required ~.~`Z~ 5 to form an emulsion with a viscosity of about 3 centistokes and centrifuge lower layer of .9cc in 6cc.
c) ~ith the same composition as in a) except that ;
1.2 g of Sl was added to the gasoline and the concentration of Q2 was 1 g/l H20 an emulsion was produced in 60 seconds of uniterrupted stirring that gave a viscosity of about 7 centistokes and a centrifuge lower laver of about .14cc in 6cc.
d) l~ith the same composition as in c) above plus 1.0 cc methanol only 15 seconds was required to produce an emulsion with a viscosity of about 3 centistokes and a centrifuge lower layer of about .8cc ~
comparing a) with b) and c) with d) sho~s that methanol decreased the time of emulsification, de~
creases the emulsion viscosity, and decreases the ; ;
stability.
e) A composition of lOcc water solution Qa (.34 g/l H20) and 90cc gasoline B containing Sl (3.75 g/l) required five minutes of uninterrupted magnetic stirring to give an emulsion of with a viscosity -of about 16 centistokes and a centrifuge lower layer of about .3cc in 6cc.
f) The same composition as in a) was used with the addition of 0.55cc CaC12 (2g/lOOcc H20) and it ;~was not possible to produce an emulsion.
g) A composition of 30cc water solution Q2 (.34 g/l H20) and 70cc gasoline B containing Sl (3.75 g/l G25b) required 2 minutes of stirring to produce ~
an emulsion with a viscosity o about 3 centistokes - -and a centrifuge lower layer of about l.lcc in 6cc.
h) A composition of 20cc water solution Q2 (1 g/l H20) and lcc NaCl (2 g/lOOcc H20) and 80cc gasoline B containing (3.75 g/l) formed an emulsion, after 4 stirring sequences (as in Example 7 a).
This emulsion gave a viscosity of about 3 centri-fuge lower layer of about .19cc in 6cco i) Decreasing the quantity of Q2 in h) above to 18cc and increasing the quantity of NaCl to 2cc pre--vented the formation of an emulsion. Comparing e) with f) and h) with i) shows that sal-t con--centration can prevent a high internal phase ratio emulsion from forming. Comparing e) with g) shows that increased water phase gives an emulsion of this composition with decreased viscosity and stability.
EXA~PLE 12 Tests with Q4, S2, S3, S4, S9 a) A composition of 20cc water solution Q4 (1 g/l H20) and 80cc Sl. (3.75 g/l required 15 stirring sequences of the type in Example 7 a) and after an invert emulsion was formed 4 additional stir-ring sequences were added. This gave an emulsion with a viscosity o. about 10 centistokes and a and a centrifuge lower layer of about o33cc in 6cc.
b) The com~osition of a) above was changed for water phase to lOcc water solution Ql (1.5 g/l H2O) plus lOcc water solution 04 (1 g/l H2O)- `, The invert emulsion was now formed in 2 stirring sequences. The viscosity remained at 10 centi stokes and the centrifuge lower layer changed to ~ 42cc in 6cc. Comparing a) and b) shows similar synergistic effects to that obtained in Example 8 d).
c) A composition of 20cc water solution Q2 (l/g/l s~
H20) plus 80 cc gasoline B solution S2 (3.75 g/l) was stirred for 70 seconds in a magnetic stirrer at ahout .6 maximum stirring rate to produce an emulsion of the high internal phase ratio type. After an additional 30 seeonds of stirring the emulsion had a viseosity of about 8 centistokes and a centrifuge lower layer of about .8ee in 6ee. In the following example NaCl is `
used to prevent a high internal phase ratio emul- `
sion from forming, so that the following three examples are of the low internal phase ratio type - ~
(water in hydroearbon). In all eases maximum `
stirring speed of the magnetie stirrer was used. ~`
When a Waring blender was used it was found that the lower layer supernate interfaee (a:Eter eentri-fuge) eentrifuging was less apparent. In all eases the viseosity of the emulsion was about 1.0 eentistoke in the Eollowing three tests.
d) eomposition: 3cc NaCl-water solution (2g/lOOee H20) plus 14ee 01 water solution (1.5 g/l H20) plus 14ee ~3 water solution (1 ~ 2) plus 90ee gasoline solution ~ (3.75 g/l gas b) gave zero eentrifuge lower layer in 6ee and no water separa-tion in seven weeks on standing.
e) eomposition" 18ec H20 plus 5ee water solution Q2 (1 g/l X20) plus .75cc S4 as is plus 1.5ee S3 as is 72ee gasoline B gave same eentrifuge results as d) above.
f) composition: 3.5ce water solution Ql (1.5 g/l H20) plus 3.5ce water solution Q3 (1 g/l H20) plus l.Oee S4 plus 1.5cc S3 plus 87cc gasoline B gave a cen-trifuge lower layer of about .06ee in 6cc.
g) An invert emulsion was formed with lOee water solu~
.
tion Ol (1.5 g/l ~l2O) plus 90cc Angolan crude (containing 4 g Sl/l crude). Less than 3cc of H2O separated in 6 days.
h) A high internal phase ratio ma-terial was pre-pared with 9cc water solution ~l (1.5 g/l H2O) plus 50cc ~2 oil (with 4g Sl/l #2 oil) and stirring in a magnetic stirrer at l/5 and 3/5 full scale. ~ith the addition of an additional 40cc o #2 oil (with same concentration of Sl) the emulsion remained stable.
i) ~n emulsion of the type in h) above was made with 5cc water solution Ql (1.5 g/l H2O) plus 5cc water solution 03 (l g/l H2O) plus 40cc #2 oil (with .25g S9) and the same stirring sequence.
This emulsion was broken with the addition of 40cc more of #2 oil and stirr:ing. The emulsion was reformed with the further addition o~ .25 g of S9 with additional stirr:ing. This emulsion was stable, with no water separation, for more than l9 days.
j) A stable coal-oil-water slurry was prepared with 5cc water solution Ql (1.5 g/l H2O) plus 5cc water solution Q3 (1 g/l H2O) plus llcc #6 oil (vis-cosity of 126 Furol at about 120F) plus 0.5cc S9 plus 80 g Bituminous coal (-200 mesh, ~6 Illinois). Preparation was by hand for the firs-t `
60 g fo coal and was stirred (600 r.p.m.) for the 80 grams of coal, with a glass stirrer, while the material was elevated in temperature to about ;~;
130F, for 14 minutes of stirring. The slurry was then placed in a soll plastic syringe for sectioning at a later date, to determine settling.
EX~MPLE 13 . ' `' a) Ten cc of H2O was mixed with 100 cc of # 6 oil (126 Furol at 120~F) with a glass stirrer at about 600 r.p.m. for 5 minutes. When 60cc of this oil (no water) is passed through a reference funnel at 23C it took 30 seconds to obtain a thin filamen-t of oil and an additional 30 seconds before the end of the pour. With the water addi-tion the oil drained from the side of a glass graduate at 23C, in about 1.0 hour.
b) A composition and procedure described in a) above was followed except that -the lOcc of H2O was -replaced by a water solution of 1 to 1 Ql and Q3, with a concentration of 1.5 g/l H2O for Q3, plus about .3 g of S9. The funnel test gave 25 seconds to filament and an additional 30 seconds to end of pour. The separation from the walls of the glass container took about 1.0 seconds (at 23C);
for about 90~ oE the poured material. Parts a) and b) demonstrate that the addition of Q and S
materials change the pour ability of #6 oil, radi~ ~ `
cally.
EXA~IPL~ 14 composition of 3cc H2O plus a 7cc H2O solution of Ql (1.5 Ol/l H2O) plus 91.5 cc of gasoline B
plus 0.5cc S9, was formed in a Waring blender ~ `
operating at 1/2 full speed for 5 minutes. This ;` `
composition and procedure produced a very stable ;
lo~ internal phase ratio emulsior of water in gasoline. Less than O.lcc in 90cc of a viscous !
water layer was deposited at the bottom of the containing cylinder. `
~lthough the present invention has been disclosed with emphasis upon hydrocarbon and water mixtures with coal or com-bustibles or non-combustibles or as involving water or coal or oil and coal, it is contemplated that the agent and the high molecular weight material will achieve stable mixtures involving other materials or facilitate the transportation thereof.
Also, even the hydrocarbon water mixture or other mixtures of the present invention can be readily transported or held in stable condition for purposes of the combustion in the classical sense. For instance, the product of the inven- .
tion can be used in the petrochemical industry where the mix-ture can be separated into components and such components utilized for their chemical or other value.
I~ithout Eurther elaboration the :Eoregoing will so fully illustrate our invention that others may, by applying current or future knowledge, readily adapt the same ~or use under various conditions of service.
Hydrocarbons and water mixtures have many potential uses, such as in internal combustion engines and as a fuel for heating purposes, either in themselves or combined with coal in acoal slurry, or when combined with combustible or non-combustible solids or even with water or oil as the sole liquid.
It is believed that emuls~ons oE hydrocarbons andwater have not come into general use because of the relative instabil-ity of emulsions involving agents in the fuel in economical quantities. However, the need for stable emul6ions of hydro-carbons and water has become even more important with the increasing price of fuel.
For many years it has been the practice to inject water into fuel systems for purposes of improving engine per-formance. It has also been recognized that water injection will enable combustion to occur at a lower temperature, thereby decreasing the formation of oxides of nitrogen, which are major pollutants.
In preparing satisfactory emulsions of hydrocarbons and watèr, it is necessary that the resulting~product have satisfactory properties for use in the internal combustion engine~ However, with heating uses, the fuel is normally fed into or atomized in a heating chamber. Moreover, it is neces-sary that any emulsion used as a heatin~ fuel have sufficient stability to retain its properties until the time comes for its use. It has been proposed to add coal to oil including crude ~~ 2 -oil, but such proposals have thus far proved unsuccessful be-cause of the inability to maintain the coal in a stable suspend-ed state in the oil for the usual passage of time between manu-facturers and comMercial use It is accordingly a principal object of the present invention to provide stable emulsions of hydrocarbons and water for general fuel use, either with an internal combustion engine, for heating purposes, for jet engines and turbines or general use. Also, contemplated are slurries, such as coal slurries which can be readily transported.
It has been recognized that hydrocarbon-water emul-sions can be formed using surfactants as disclosed in United States Patent No. 3 r 527,581. It has also been proposed to use blends of polyoxyethylene emulsifiers in a paper by Peters and Stebar entitled "Water-Gasoline Fuels-Their EfEect on Spark Ignition Engine Emissions and Performace" which was presented at the Society of ~utomotive Engineers, Inc., St. Louis, Mis-souri, on ~une 7--10, 1976. Such emulsions contain substantial aMounts oE water, but are either not stable over long periods oE time or require such high quantities of emulsifiers to achieve satisfactory stability as to be uneconomical.
Additional teachings of hydrocarbon-water emulsions for various purposes are disclosed in United States Patents Nos.3,206,410, 3,311,561, 3,346,494, 3,442,342, 3,355,394, 3,645,903 and 3,~76,391.
The emulsions of the present invention are preferably ~;~
water and qasoline, jet fuel, heating oil, diesel oil, crude oil, coal slurries and non-combustibles.
In accordance with the principles of the present invention, the suspended droplets and/or particles are relatively large and have a si~e usually in excess of about 1400 Angstroms.
Thus, the emulsions of the present invention are more properly termed macroemulsions and have a milky appearance or black when : ' ~
~, . .
coal is used. This is to be compared with microemulsions where-in the internal phase is present in a much smaller droplet and/
or particle size 50 that a microemulsion has a translucent or transparent appearance.
~ Jith the present invention the continuous phase is at times the hydrocarbon so that the emulsions are so-called water-in-oil emulsions. Other times the continuous phase is water so the emulsion is oil-in-water.
Where the water percentage is less than 30% by weight, it can be regarded as a low internal phase ratio. In the range oE 30% to 70% water by weight, it is present as a meduim inter- ~;
nal phase ratio and above 70% as a high internal phase ratio system, when water is the internal phase. ~`
On the the advanta~es offered b~7 the emulsions of the present invention is the ~reat stability over long periods OL^
time, usually well in excess of two months which satisfies usual storage and transportation requirements. Moreover, the viscosity of certain of the emulsions of the present invention i.s relatïve-ly low (about l cen-tipoise), although the sedimentation of an emulsion (and therefore its instability) increases as viscosi-ty is lowered. However, the present invention presents a sa-tis-factory balance of high stability and low viscosity. In other applications of the invention, high viscosity as well as high stability are afforded. Also, with the ~resent invention satis-factor~,7 vaporization is achieved under conditions of reasonably low viscosity and satisfactory stability.
Another characteristic of the invention is that it is usual to have water present in an amount of about l -to 20% volume with the upper limit reaching 4n% by volume or more.
The emulsions of the present invention are achieved by usin~ t'le combination of (1) a water or hydrocarbon soluble (iOlliC
or noionic) relatively low molecular weig1lt agen-t (r,~olecular weight in many instances oE the order oE lOOO) which is generally s a substance wherein one side or part of the molecular is hydrophillic and their other side lipophillic and (2) a high ~ erahl~
molesular weight material (of the order of 500, 000 or more) crably /1 ~that is swellable in water (cross-linked) and/or is water soluble (substan-tially non-cross-linked).
The combination of the agent and the high molecular weight material creates an extremely stable bond between the water and the hydrocarbon. At tlle same time, in many instances, the aforesaid co~bination achieves a low viscosity even where the water is present in excess of 25% by volume. It will be seen that the present invention alos contemplates the use of one or more agents or one or more hight molecular weight materials, or a combination of two of one material and one of the other, or vice versa, or two or more of each material.
~ he present invention is belleved to function satis-factorily with a wide range of: hydrocarbons and particularly various gasolines o.f hi~h or low octane and other well known ~uels. However, the present invention also applies to other hydrocarbons and other carbon containing materials such as coal 20 or even non-hvdrocarbons such as carbon or even inorganic mate- ;~
rials and incombustibles which may be introduced or dispersed in oil as a coal slurry with the dispersed particles being present in a size smaller than 60 mesh and preferably 200 to 325 mesh.
When the present invention is used in connection with oils for heatin~ purposes, it is demonstrated that many well known heat ing oils, such as ~1, #2 or #6 may be used in a water and oil emulsion with suspended coal and/or carbon particles or other particles, both combustile and non-combustile. Examples of non-combustiles are lime, chalk, alumina and o-thers.
Because the emlllsions prepared in accordance with the present invention are extremely stable, such emulsions are usuable in the same way as presently available furnace heating oil. Moreover, coal particules can be suspended and held sus-~27~
pended in the emulslon with coal present in as much as 50~
by weight and so~etimes in an even greater amount. Also, the presence of ~later in the emulsion may improve combustion per-formance because of the micro-explosions as discussed herein-after.
In some instances the coal can be suspended in water through the practice of the present invention with the use of little or no oil at all.
A very important consideration arising from the pre-sent invention ls that the presence of waterin the stable emul-sion serves to create micro-explosions of water when the emul-sion of the present invention is used in an internal combustion engine or in a heating system. Such micro-explosions arise from the superheating of the water in the emulsion. The effect achieved is the blowing of the oil particles apart throuyhout the hydrocarbon. It is believed that the aforesaid micro-explosions have the effect of substantially increasing the per-Eormance oF the combustion ~rocess.
In heating or use in a diesel engine the oil is nor-mally simply fed into or atomized in a heating chamber or inject-ed therein. Thus, the present invention has use for heating or diesel engine purposes and is especially attractive in the formation of stable coal slurries.
On agent used in connection ~ith the present invention is sold by the American Cynamid Comparly and is identified as product OT ln0. This agent is the sodium salt of dioctylsulfo-succinnic acid. A second agent usable in connection with the present invention is the sodium salt of decylbenzenesulfonic acid.
A third agent is Toximul MP (sulfonate/non-ionic blend) sold by the Stepan Co. ~his is calcium dodecyl benzene sulfonate and alkyl phenoxy polyoxyethylene ethanol. A fourth agent is Triton X45, sold by the ~ohm & HaAs Company, which is octyl,hen-oxypolyethoxy ethanol.
t~ ' _ 6 -Examples of hiyh molecular weigllt materials usable in the present invention are Carbopol 941 in the completely neutrali~ed form using sodium hydroxide, sodium carbonate, ammonia and other well known neutn^ali~ing agents, in stochio-metric amounts or otherwise. Carbopol ~1 is a high molecular weight polyacrylic acid as disclosed in U. S. Patent 2,798,053.
A second example of a high molecular weight material is an acrylamide/sodium acrylate identified as Dow XD 8992 as disclos-ed in U. ~. Patent 3,669,103 and is partially crosslin~ed.
A third example of a high molecular weight material is a hydroli~ed starch polyacrylonitrile graft copolymer as disclosed in U. S. Patent 3,935,099. A fourth example of a high molecular weight material is a high molecular weight polyoxyethy-lene coagulant of Union Carbide Corporation, where the molecular weight is in excess of five hundred thousand.
Yet another ad~antage of the present invention lies in the fact that relatively small amounts of the agent and high molecular weight materials are used. Indeed an effective amount of the agent can be as low as 3.7 grams per liter of ~asoline, down to as low as one gram per liter or slightly less.
In some instances it is desirable to combine two of the afore-mentioned high molecular weight materials such as the Carbopol 941 (in the form of the sodium salt or otherwise) and the Dow XD 8992 in formulating the stable emulsion of the present inven-tion.
The agent is added directly at times to the hydrocarbon with the high molecular weight material in aqueous solution or mixture then added to the hydrocarbon agent solution. In some instances, for example when using Triton X45, it is added to the water, rather than to the hydrocarbon because of the special solubility of Triton X45. This is followed by gentle mixing at room temperature immediately, or for some short period of time, usually not more than fifteen minutes -to achieve a white or QJe ~r~
27'~5 milky macroemulsion. The emulsions achieved through the present invention are so stable as to remain intact under short term centrifuge te~ts and temperature tests and storage tests for periods o F time of sixty days or more as required by indus-trv.
When used in a coal slurry, it is possible to use less liquid hydrocarbon or none at all because coal, carbon particles or other particulate heat giving material may be added to enhance the heat value of the emulsion. For example an emulsion produced in accordance with the invention for heat purposes is composed of 50% by weight coal, 40% by weight heating oil and 10% by weight water. ~lternatively, another coal slurry produced in accordance with this invention is composed of 50% by weight of water and 50% b~7 weight o.f coal, although the amount of coal can be even greater. Also, bituminous coal, liguite and solvent refined coal may be used.
It should be kept in mind that in formulating emulsions in accordance with the present inventi.on that the use of greater amounts of the hi~h molecular weight material generally allows the use of smaller amounts of the agent. This is important where the quantity of the high molecular weight material is less exPensive than the quantity of the agent. From the examples in the Specification of this Application it will be seen that relatively low quantities of both the high molecular weight material and the agent are used so that emulsions prepared in accordance with the invention are competitively priced. Thus, where the agent is present in relatively low levels, the high molecular weight material is effective to lower the amount of agent that is needed. ~Iowever, at higher levels of agent, it 30 tends to dominate the high molecular weight material to the ;
extent that in some cases the agent alone will produce a satis-factory, albeit extremely expensive emulsion.
I has also been observed that emulsions are more .
~Z~f~
rapidly formualted when the high molecular weight material is of the swellable type. ~loreover, with the increase of water in the internal phase, that is from low to medium or medium to high, viscosity will increase. Conversely, where the water is in the external phase, the increase of water will lower viscosity.
From the foregoing it can be seen that the emulsions of the present invention are more stable and are macroemulsions which give rise to micro-explosions when consumed, to achieve better engine and/or burning efficiency. Moreover, with the present invention, coal including bituminous coal, lignite and solvent refined coal and other combustible materials like carbon particles or non-combustible materials can be stabilized for a long period of time for transportation or storage.
Where desired the viscosity and volatility can be adjusted using suitahle materials or solvents, such as alcohols, like methyls, ethyl or isopropyl alcohol, ketones such as acetone, ethers, etc.
It is theorized that the high molecular weight material provides a generic matrix structure or has the effect of struc-turing the overall mixture in order to hold very tightly the ;
various components. While Applicants do not wish to be bound hy any particular theory, it is believed that the high molecular material of the present invention provides a matrix wherein the ~ ~`
water is usually latched onto the matrix with the agent acting as a hook between the water phase and the hydrocarbon phase.
Stated more broadly, the theory is that the present invention provides a matrix wherein the water has an affinity for the matrix with the agent having an affinity between the water 30 phase and the hydrocarbon phase. ~`
While in many instances the water is structured orfunctions as a matrix, the hydrocarbon can alos be structured, for instance through the use of aluminum salts of naphthenic . ~., , acids and coconut oil acids or a mixture of naphthenic acid and unsaturated acids with the agent and water. In many instances the agent is a surface active agent, although the invention is not limited to such a feature.
It is also contemplated that the agent be present in either the water or hydrocarbon phase or both.
It is also contemplated that other additives may be included, such as sodium chloride and other salts, the presence of which prevents the formation of a high internal phase ratio material.
Certain examples of the invention will now be provided for the sake of illustration and not by way of limitation. In these examples certain abbreviations have been used.
The low molecular wei~ht agent will have the Eollowing abbreviations:
Sl Am_rican Cyanamid Company OT-100 - sodium salt of dioctylsulfosuccinnic acid.
S2 _rco Chemica~ Compan~ - Ultrawet DS ~ sodium salt of decylbenzenesulfonic acid.
S3 Stepan C m any - Toximul MP - calcium dodecyl benzene sulfonate and alkyl phenoxy polyoxyethylene ethanol.
S4 _o m & Haas Company - Triton X45 - octylphenoxy-polyethoxy ethanol.
S5 mperial Chemica Company, Inc. (ICC U.S.) Arlacel C Sorbitan sesquioleate.
S6 _mperlal _hem cal _ompany, Inc. - Tween 40 poly-sorbate 40 (polyoxyethylene 20 Sorbitan mono palmitate).
S7 Proctor & Gamble (Ivory liquid detergent) U. S.
_ . ~
Patents 3,024,273, 3,179,598, 3,179,599 and 3,793, 233.
S8 Stepan Chemical - Ninate 401 - calcium dodecyl i (le /~ s benzene sulfonate S9 _tepan Che ical (Ninate 411 - alkylamine dodecyl benzene sulfonate (burns completely - contains no metal).
The high molecular weight material will have the Eollowing abbreviations:
Ql Dow Ch _lcal Company XD 8992 (1300 swellable poly (acrylamide/sodium acrylate) partially crosslinked as discussed in U.S. Patent 3,669 103.
02 General Mills Company SG-P 502S swellable hydro-__ _._. _ ~ _ _ --. -- ---lyzed starch polyacylonitrile graft copolymer asdisclosed in U.S. Patent 3,935,099.
03 B F Goodrich Carbo~ol 941 water soluble high-_ , _ _ _ . ... . _ _ molecular weight polyacrylic acid as disclosed in U.S. Patent 2,798,053 in the completely neutralized form using sodium hydroxide, sodium carbonate or ammonia or other bases in stochio-metric amounts or otherwise.
Q4 Union Carbide_Company - Polyox Coagulant (MWM 0 more than 500,000) polyoxyethylene ~5 Dow C em_ al_Company - Separan MG 700 partially hydrolized polyacrylamides as discussed in U.S.
Patent 3,825,069.
Also usable in the present invention are transporta-tion compositions which facilitate movements of the various emulsions, slurries, etc. through piping, pumps and pumping requirements by lowering pipe friction. The transportation agent is used in a pre-treatment step prior to pumping. One example is the use of Q4 as a pretreatment in the pipe or as incorporated in the Mixture. Also usable in the present inven-tion are transportation materials and agents selected from one or more of the S's and O's specified above but not limited there-to.
8~i In the following Examples the gasolines are:
(A) American Oil Co. (A~OCO) Premium (No lead) av. octane # = 95.7 H2O means distilled water.
(B) Same as above, but sub-regular (No lead~
average octane # = 88Ø
X~lPI,E I
75 parts by volume of Gasoline A containing 3.75 g/lit.
of OT-lOQ of American Cyanamide were shaken with 25 parts by volume of water, containing 0.7 g/lit. of Dow Chemical Company's DX-1300 and 0.5 g/lit. of -Ma~941-carbopolate of B.F. Goodrich Chemical Co. A
stable emulsion of gasoline/water was produced; on standing Eor one mon-th at room temperature no notice-ab]e separation took place; however, after 4.0 months a water layer, equalling 3.7 volume ~ of the total liquid appeared; after 9.0 months the separation of the aqueous layer was 5.6 volume ~ of the total liquid.
The fore~oing mixture was used as a fuel in a single cylinder internal combustion engine. Before use, viscosity was lowered by the addition of e~hyl alcohol (10% by volume). The engine operated satis-factorily under full load for an ex-tended period of time.
90 parts by volume of gasoline B containing 3.75 g of Ot-100 of American Cyanamide Co./lit. gasoline were shaken with 10 parts by volume of water containing 1.0 g/lit. of a water swellable polymer SGP~5025 of General Mills Chemcials, Inc. producing a stable milk-like emulsion of gasoline/wa-ter. There was no separa-tion of an aqueous layer after 30 days and after 100 days an aqueous lower layer approximately 0.5~ of the total liauid accumulated.
_XA~PLE 3 75 parts by volume of gasoline A containing 3.75 g/lit of gasoline of OT-100 were mixed and shaken with 25 parts by volume of water containing only 1.0 g/lit. solution of Na-9'~1-carbopolate. It formed a stable milk-like emulsion so that in 2 weeks no aqueous layer separated and after 100 days 3.3 volume percent of the total liquid separated.
Similar to Examples 1, 2 and 3 emulsions were pre-pared with the same agents and materials but using instead of gasoline a) Fuel Oil No. 1 b) Fuel Oil No. 2 c) ~et Engine Fuel J P 4 d) Angolan Crude Oil as is.
All of these four types formed stable emulsions, similarly to those of Examples 1, 2 and 3. ~;
20 EX~5PLE 5 50.0 parts by weight of No. 2 fuel oil, containing 3.75 g/lit. of OT-100 of American Cyanamide were mix-ed with 30.0 parts by weight of bituminous coal pass-ing a 325 mesh sieve, into a black asphalt-like liquid, after adding 1.65 parts by weight of isopro~yl alcohol to wet part of the coal powder. 20.0 parts by weight of water containing both 1 g/lit. of sodium 941 -carbopolate of B. F. Goodrich Chemical Co. and 1 g/lit.
XD-8992 of Dow Chemical Co. were mixed in by stirring and a 30% weight of coal. (20% weight water) (50%
fuel oil slurry produced). It exuded only 3 weight percent of fuel No. 2 after standing for 45 days at room temperature (_ 20 C) and after a temperature 7~
c~cle of 27 hours at - 12C and 4 hours at 85C to 100C to 85C.
EX~PLE 6 46 parts by weight of the same mesh coal as in Example 5 were mixed with 44-1~2 parts by weight Crude from Angola (light crude) containing 3.75 g/lit.
crude of American Cyanamide's OT-100. To this black liquid 10 parts by vol. of water containing the same ingredients and concentrations as in Example No. 5 above, were added and stirred with a stirrer to a homogenous black slurry of the composition: 46 w/o (weight percent) carbon - 9-1/2 w/o water - 44-1/2 w/o Gulf crude and which persists for long periods of time.
~XAMPLE 7 Speed up of invernsion a) To 20cc of H2O was added 80cc Gasoline B containing Sl (3 75 g/l Gasoline B) and mixed with gentle stirring in a magnet stirrer. The stirring sequence was 15 seconds stirring plus ~ seconds standin~ or manual swirling. After six such sequences the two separated layers rapidly formed a high internal phase ratio emulsion (gas in water), or an invert. ~ -`
b) Repeat (of a) except that 18cc of water solution containing Ql (0.63 g/l H20) was added to 73cc of Gasoline B with Sl (3.75 g/l gasoline). The emul-sion now formed in only two sequences of stirring.
c) Repeat (of a) except that 20cc of water solution of Q2 (1 g/l H2O) was added to 80cc Gasoline B
containing Sl (3.75 g/l gasoline). The emulsion now formed in only two se~uences of stirring.
EXAMPL~ 8 Change of viscosity and stability.
7~
a) For a 25cc water solution Q2 (1.0 g/l H2O) and 100 cc Gasoline s containing Sl (3.75 g/l gaso-line) the sequence of Example 7 c was followed.
The emulsion had a viscosity of about 3 centi-stokes and left a lower layer of .84cc in 6.0cc ~`
total in a centrifuge tube under about 200 x g for 5 minutesA
b) stirring of the sample in a) of four additional stirring sequences at about twice the stirring speed gave an emulsion viscosity of about 12 centi-stokes and a centrifuge lower layer (same centi-fuge conditions) of about 0.3cc, i.e. higher vis cosity and greater stability with increased rate of shear.
c) To a 20cc water solution of Q3 (1 g/l H2O) was added 80ec Gasoline B containing Sl (3.75 g/l gasoline). The stirrin~ sequence ko form an emul-sion o:F the inverted type took 10 sequenees oE the stirring rate of b) above plus 6 sequences of a combination of that of a) and b) above. ~ith four additional sequences of stlrring tafter inversion) at the speed of b) above the viseosity ~ -of the emulsion was about ~5 centistokes, with a centrifuge lower layer of about .48cc in 6cc total.
d) For the same composition as in c) above except that 20cc Q3 solution was replaced by lOcc Q2 solution and lOcc Q3 solution. A viscosity of 13 centistokes and a centrifuge lower layer of about .48cc in hcc total was obtained. The emul-sion was formed in only three sequences of the stlrring rate of b) above. This shows the syner-gistric effect of Q2 on rate of emulsion formation and Q3 on viscosi.ty.
e) To 25cc solution of 1:1 Ol and Q3 and one liter of water ~lg/l H20) each was added 75 cc Sl (3.75 g/l gasoline A). This solution was stirred at five times the stirring rate of Example 7 a) to produce an emulsion with a viscosity of about 50 centistokes and a centrifuge sedimenta-tion of about .12cc. This sample was allowed to stand in a flask and showed no appreciable separa-tion for three months, after which about O.lcc :
of water separated from about lOOcc of emulsion over an additional month. This correllates the short term stability centrifuge test with lony term stability, showing that both.v.iscosity and lower layer formation must be used bo establish : .
stability, for this emulsion. This shows that ::
the stability of d) about is yreater than c) above, for long term, because the viscosity is greater in d) although the centrifuge lower layer forma- : .
tion is the same. :
X~1PLE 9 -Addition of Q material improves stability a) A composition of 20cc H2O and 80cc gasoline s ., , :.
containing Sl (3.75 g/l) with stirring as in Example 8 b) gave an emulsi.on in 9 stirring sequences. Four more similar sti.rring sequences gave an emulsion with a viscosity of about 4 centistokes and a centrifuge lower layer of .54cc in 6cc.
h) ~his experiment is the same as a) above except that 2Cccwater solution of Q2 (lg/l H2O) replaced the 20cc H2O. A viscosity of about 8 centistokes and a centrifuge lower layer of .54cc in 6cc were ob-tained. This increase in viscosity with the O material shows increased stability over no use of 0 material as in a) abo~e. See remarks at end of Example 8 e).
_AMPLE 10 Q's have greates effect with low concentration of S's a) To 30cc ~l2O was added 120cc of gasoline ~ con-taining Sl (50 g/l) and following 2 sequences o:E
stirring as in Example 7 a) a low internal phase ratio (water in gasoline) was fo.rmed. With this composition a viscosity of about one centistoke and a zero centrifuge lower layer was obtained.*
b) Experiment a) above was repeated with 30cc water solution of Ql (1 g/l H2O) replacing the 30cc H2O.
The same type emu].sion with the same viscosity and lower layer were ob~ained as in a) above. This Example compared with Examples 7, 8 and 9 shows that Q's are most effective with low concentra- ~.
tions of S materials in producing high internal phase ratio emulsions and changing viscosity and thus stability~ * With this type emulsion zero centrifuge lower layer formation gave about a 1.5%
water layer in 7 days for long term stability.
_A PLE 11 Effect of alcohols, salts H2O/gasoline (Ratio) a) ~ composition of 20cc water solution Q2 (-34 g/l H2O) and 80cc gasoline B [S1 concentraLion grams/l gasoline b) with 3 minutes of uniterrupted magnetic stirring gave an emulsion with a viscosity of about 4 centistokes and centrifuge lower layer of about .7cc in 6cc.
b) With the same composition as in a) above plus l.Occ methanol, only 30 seconds were required ~.~`Z~ 5 to form an emulsion with a viscosity of about 3 centistokes and centrifuge lower layer of .9cc in 6cc.
c) ~ith the same composition as in a) except that ;
1.2 g of Sl was added to the gasoline and the concentration of Q2 was 1 g/l H20 an emulsion was produced in 60 seconds of uniterrupted stirring that gave a viscosity of about 7 centistokes and a centrifuge lower laver of about .14cc in 6cc.
d) l~ith the same composition as in c) above plus 1.0 cc methanol only 15 seconds was required to produce an emulsion with a viscosity of about 3 centistokes and a centrifuge lower layer of about .8cc ~
comparing a) with b) and c) with d) sho~s that methanol decreased the time of emulsification, de~
creases the emulsion viscosity, and decreases the ; ;
stability.
e) A composition of lOcc water solution Qa (.34 g/l H20) and 90cc gasoline B containing Sl (3.75 g/l) required five minutes of uninterrupted magnetic stirring to give an emulsion of with a viscosity -of about 16 centistokes and a centrifuge lower layer of about .3cc in 6cc.
f) The same composition as in a) was used with the addition of 0.55cc CaC12 (2g/lOOcc H20) and it ;~was not possible to produce an emulsion.
g) A composition of 30cc water solution Q2 (.34 g/l H20) and 70cc gasoline B containing Sl (3.75 g/l G25b) required 2 minutes of stirring to produce ~
an emulsion with a viscosity o about 3 centistokes - -and a centrifuge lower layer of about l.lcc in 6cc.
h) A composition of 20cc water solution Q2 (1 g/l H20) and lcc NaCl (2 g/lOOcc H20) and 80cc gasoline B containing (3.75 g/l) formed an emulsion, after 4 stirring sequences (as in Example 7 a).
This emulsion gave a viscosity of about 3 centri-fuge lower layer of about .19cc in 6cco i) Decreasing the quantity of Q2 in h) above to 18cc and increasing the quantity of NaCl to 2cc pre--vented the formation of an emulsion. Comparing e) with f) and h) with i) shows that sal-t con--centration can prevent a high internal phase ratio emulsion from forming. Comparing e) with g) shows that increased water phase gives an emulsion of this composition with decreased viscosity and stability.
EXA~PLE 12 Tests with Q4, S2, S3, S4, S9 a) A composition of 20cc water solution Q4 (1 g/l H20) and 80cc Sl. (3.75 g/l required 15 stirring sequences of the type in Example 7 a) and after an invert emulsion was formed 4 additional stir-ring sequences were added. This gave an emulsion with a viscosity o. about 10 centistokes and a and a centrifuge lower layer of about o33cc in 6cc.
b) The com~osition of a) above was changed for water phase to lOcc water solution Ql (1.5 g/l H2O) plus lOcc water solution 04 (1 g/l H2O)- `, The invert emulsion was now formed in 2 stirring sequences. The viscosity remained at 10 centi stokes and the centrifuge lower layer changed to ~ 42cc in 6cc. Comparing a) and b) shows similar synergistic effects to that obtained in Example 8 d).
c) A composition of 20cc water solution Q2 (l/g/l s~
H20) plus 80 cc gasoline B solution S2 (3.75 g/l) was stirred for 70 seconds in a magnetic stirrer at ahout .6 maximum stirring rate to produce an emulsion of the high internal phase ratio type. After an additional 30 seeonds of stirring the emulsion had a viseosity of about 8 centistokes and a centrifuge lower layer of about .8ee in 6ee. In the following example NaCl is `
used to prevent a high internal phase ratio emul- `
sion from forming, so that the following three examples are of the low internal phase ratio type - ~
(water in hydroearbon). In all eases maximum `
stirring speed of the magnetie stirrer was used. ~`
When a Waring blender was used it was found that the lower layer supernate interfaee (a:Eter eentri-fuge) eentrifuging was less apparent. In all eases the viseosity of the emulsion was about 1.0 eentistoke in the Eollowing three tests.
d) eomposition: 3cc NaCl-water solution (2g/lOOee H20) plus 14ee 01 water solution (1.5 g/l H20) plus 14ee ~3 water solution (1 ~ 2) plus 90ee gasoline solution ~ (3.75 g/l gas b) gave zero eentrifuge lower layer in 6ee and no water separa-tion in seven weeks on standing.
e) eomposition" 18ec H20 plus 5ee water solution Q2 (1 g/l X20) plus .75cc S4 as is plus 1.5ee S3 as is 72ee gasoline B gave same eentrifuge results as d) above.
f) composition: 3.5ce water solution Ql (1.5 g/l H20) plus 3.5ce water solution Q3 (1 g/l H20) plus l.Oee S4 plus 1.5cc S3 plus 87cc gasoline B gave a cen-trifuge lower layer of about .06ee in 6cc.
g) An invert emulsion was formed with lOee water solu~
.
tion Ol (1.5 g/l ~l2O) plus 90cc Angolan crude (containing 4 g Sl/l crude). Less than 3cc of H2O separated in 6 days.
h) A high internal phase ratio ma-terial was pre-pared with 9cc water solution ~l (1.5 g/l H2O) plus 50cc ~2 oil (with 4g Sl/l #2 oil) and stirring in a magnetic stirrer at l/5 and 3/5 full scale. ~ith the addition of an additional 40cc o #2 oil (with same concentration of Sl) the emulsion remained stable.
i) ~n emulsion of the type in h) above was made with 5cc water solution Ql (1.5 g/l H2O) plus 5cc water solution 03 (l g/l H2O) plus 40cc #2 oil (with .25g S9) and the same stirring sequence.
This emulsion was broken with the addition of 40cc more of #2 oil and stirr:ing. The emulsion was reformed with the further addition o~ .25 g of S9 with additional stirr:ing. This emulsion was stable, with no water separation, for more than l9 days.
j) A stable coal-oil-water slurry was prepared with 5cc water solution Ql (1.5 g/l H2O) plus 5cc water solution Q3 (1 g/l H2O) plus llcc #6 oil (vis-cosity of 126 Furol at about 120F) plus 0.5cc S9 plus 80 g Bituminous coal (-200 mesh, ~6 Illinois). Preparation was by hand for the firs-t `
60 g fo coal and was stirred (600 r.p.m.) for the 80 grams of coal, with a glass stirrer, while the material was elevated in temperature to about ;~;
130F, for 14 minutes of stirring. The slurry was then placed in a soll plastic syringe for sectioning at a later date, to determine settling.
EX~MPLE 13 . ' `' a) Ten cc of H2O was mixed with 100 cc of # 6 oil (126 Furol at 120~F) with a glass stirrer at about 600 r.p.m. for 5 minutes. When 60cc of this oil (no water) is passed through a reference funnel at 23C it took 30 seconds to obtain a thin filamen-t of oil and an additional 30 seconds before the end of the pour. With the water addi-tion the oil drained from the side of a glass graduate at 23C, in about 1.0 hour.
b) A composition and procedure described in a) above was followed except that -the lOcc of H2O was -replaced by a water solution of 1 to 1 Ql and Q3, with a concentration of 1.5 g/l H2O for Q3, plus about .3 g of S9. The funnel test gave 25 seconds to filament and an additional 30 seconds to end of pour. The separation from the walls of the glass container took about 1.0 seconds (at 23C);
for about 90~ oE the poured material. Parts a) and b) demonstrate that the addition of Q and S
materials change the pour ability of #6 oil, radi~ ~ `
cally.
EXA~IPL~ 14 composition of 3cc H2O plus a 7cc H2O solution of Ql (1.5 Ol/l H2O) plus 91.5 cc of gasoline B
plus 0.5cc S9, was formed in a Waring blender ~ `
operating at 1/2 full speed for 5 minutes. This ;` `
composition and procedure produced a very stable ;
lo~ internal phase ratio emulsior of water in gasoline. Less than O.lcc in 90cc of a viscous !
water layer was deposited at the bottom of the containing cylinder. `
~lthough the present invention has been disclosed with emphasis upon hydrocarbon and water mixtures with coal or com-bustibles or non-combustibles or as involving water or coal or oil and coal, it is contemplated that the agent and the high molecular weight material will achieve stable mixtures involving other materials or facilitate the transportation thereof.
Also, even the hydrocarbon water mixture or other mixtures of the present invention can be readily transported or held in stable condition for purposes of the combustion in the classical sense. For instance, the product of the inven- .
tion can be used in the petrochemical industry where the mix-ture can be separated into components and such components utilized for their chemical or other value.
I~ithout Eurther elaboration the :Eoregoing will so fully illustrate our invention that others may, by applying current or future knowledge, readily adapt the same ~or use under various conditions of service.
Claims (25)
1. In a mixture of a hydrocarbon and water, the improvement comprising achieving a very stable mixture of a relatively low molecular weight hydrophillic - lipophillic agent and a high molecular weight material with at least one of said agent and material having an affinity between the water and the hydrocarbon.
2. The mixture of Claim 1 wherein the hydrocarbon is a liquid.
3. The mixture of Claim 2 wherein the hydrocarbon is gasoline.
4. The mixture of Claim 2 wherein the hydrocarbon is heating oil.
5. The mixture of Claim 2 with the further addition of coal.
6. The mixture of Claim 2 with the further addition of lignite.
7. The mixture of Claim 2 wherein the hydrocarbon is crude oil.
8. The mixture of Claim 2 used as a pour point depressant.
9. The mixture of Claim 2 used for transportation purposes.
10. The mixture of Claim 2 wherein the agent is sodium salt of dioctylsulfosuccinnic acid.
11. The mixture of Claim 2 wherein the agent is sodium salt of decylbenzenesulfonic acid.
12. The mixture of Claim 2 wherein the agent is calcium dodecyl benzene sulfonate and alkyl phenoxy polyoxyethylene ethanol.
13. The mixture of Claim 2 wherein the agent is octylphenoxypolyethoxy ethanol.
14. The mixture of Claim 2 wherein the agent is alkylamine dodecyl benzene sulfonate.
15. The mixture of Claim 2 wherein the high molecular weight material is swellable poly (acrylamide/sodium acrylate) partially crosslinked.
16. The mixture of Claim 2 wherein the high molecular weight material is swellable hydrolyzed starch polyacrylonitrile graft copolymer.
17. The mixture of Claim 2 wherein the high molecular weight material is water soluble high molecular weight polyacrylic acid in the completely neutralized form.
18. The mixture of Claim 2 wherein the high molecular weight material is polyoxyethylene having a molecular weight in excess of 500,000.
19. The mixture of Claim 2 wherein the agent is sodium salt of dioctylsulfosuccinnic acid and the high molecular weight material is a mixture of swellable poly (acrylamide/sodium acrylate) partially crosslinked and water soluble high molecular weight polyacrylic acid in the completely neutralized form.
20. The mixture of Claim 19 with the further addition of coal.
21. The mixture of Claim 2 wherein the agent is sodium salt of dioctylsufosuccinnic acid and the high molecular weight material is a mixture of swellable hydrolyzed starch polyacrylonitrile graft copolymer.
22. The mixture of Claim 2 wherein the agent is sodium salt of dioctylsulfosuccinnic acid and the high molecular weight material is a mixture of water soluble high molecular weight polyacrylic acid in the completely neutralized form.
23. The mixture of Claim 1,wherein the molecular weight of said material is at least 500,000.
24. The mixture of Claim 23, wherein said relatively low molecular weight agent has a molecular weight between 225 and 10,000.
25. The mixture of Claim 24, wherein said relatively low molecular weight agent has a molecular weight between 272 and 690.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77127277A | 1977-02-23 | 1977-02-23 | |
| US771,272 | 1977-02-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127845A true CA1127845A (en) | 1982-07-20 |
Family
ID=25091276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA297,387A Expired CA1127845A (en) | 1977-02-23 | 1978-02-21 | Hydrocarbon-water fuels, slurries and other particulate mixtures |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1127845A (en) |
| GB (1) | GB1601174A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4966235A (en) * | 1988-07-14 | 1990-10-30 | Canadian Occidental Petroleum Ltd. | In situ application of high temperature resistant surfactants to produce water continuous emulsions for improved crude recovery |
| US4978365A (en) * | 1986-11-24 | 1990-12-18 | Canadian Occidental Petroleum Ltd. | Preparation of improved stable crude oil transport emulsions |
| US4983319A (en) * | 1986-11-24 | 1991-01-08 | Canadian Occidental Petroleum Ltd. | Preparation of low-viscosity improved stable crude oil transport emulsions |
| US5083613A (en) * | 1989-02-14 | 1992-01-28 | Canadian Occidental Petroleum, Ltd. | Process for producing bitumen |
| US5156652A (en) * | 1986-12-05 | 1992-10-20 | Canadian Occidental Petroleum Ltd. | Low-temperature pipeline emulsion transportation enhancement |
| US5263848A (en) * | 1986-11-24 | 1993-11-23 | Canadian Occidental Petroleum, Ltd. | Preparation of oil-in-aqueous phase emulsion and removing contaminants by burning |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4358293A (en) * | 1981-01-29 | 1982-11-09 | Gulf & Western Manufacturing Co. | Coal-aqueous mixtures |
| ES8609441A1 (en) * | 1984-06-27 | 1986-09-01 | Epoch International | Fuel compositions. |
| FR2571735B1 (en) * | 1984-10-17 | 1987-03-20 | Elf France | SELF-LUBRICATING FUEL COMPOSITION BASED ON COAL AND A HYDROCARBON FRACTION |
| JPH06145677A (en) * | 1992-10-30 | 1994-05-27 | Kao Corp | Super heavy oil emulsion fuel |
| US6419714B2 (en) * | 1999-07-07 | 2002-07-16 | The Lubrizol Corporation | Emulsifier for an acqueous hydrocarbon fuel |
| EA200200691A1 (en) * | 2001-08-24 | 2003-02-27 | Альберт Васильевич Болотов | MODIFIER OF COMBUSTIBLE MIXTURE (IGU) |
| EA200200690A1 (en) * | 2001-09-14 | 2003-04-24 | Альберт Васильевич Болотов | FUEL COMPOSITION FOR HEAT ENGINE AND METHOD FOR ITS PREPARATION (OPTIONS) |
| EA200200693A1 (en) * | 2001-10-17 | 2003-04-24 | Альберт Васильевич Болотов | LIQUID HYDROCARBON FUEL |
-
1978
- 1978-02-21 CA CA297,387A patent/CA1127845A/en not_active Expired
- 1978-02-22 GB GB702578A patent/GB1601174A/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4978365A (en) * | 1986-11-24 | 1990-12-18 | Canadian Occidental Petroleum Ltd. | Preparation of improved stable crude oil transport emulsions |
| US4983319A (en) * | 1986-11-24 | 1991-01-08 | Canadian Occidental Petroleum Ltd. | Preparation of low-viscosity improved stable crude oil transport emulsions |
| US5263848A (en) * | 1986-11-24 | 1993-11-23 | Canadian Occidental Petroleum, Ltd. | Preparation of oil-in-aqueous phase emulsion and removing contaminants by burning |
| US5156652A (en) * | 1986-12-05 | 1992-10-20 | Canadian Occidental Petroleum Ltd. | Low-temperature pipeline emulsion transportation enhancement |
| US4966235A (en) * | 1988-07-14 | 1990-10-30 | Canadian Occidental Petroleum Ltd. | In situ application of high temperature resistant surfactants to produce water continuous emulsions for improved crude recovery |
| US5083613A (en) * | 1989-02-14 | 1992-01-28 | Canadian Occidental Petroleum, Ltd. | Process for producing bitumen |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1601174A (en) | 1981-10-28 |
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