KR910006965B1 - Method of regenerating deteriorated o/w type ultraheavy oil emulsion fuel - Google Patents

Abstract

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Description

Regeneration method of deteriorated O / W type super heavy oil emulsion fuel

1 and 2 are schematic diagrams of the playback apparatus used in Example 3, respectively.

* Explanation of symbols for main parts of the drawings

1: deteriorated emulsion 2: storage tank

3: stirrer 4: heater

5: pump 6, 6 ': additive

7, 7 ': static mixer 8, 8': line mixer

9: boiler

The present invention relates to a method for regenerating a degraded O / W type (oil-in-water type) super heavy oil emulsion fuel.

As fossil fuels that fall into the category of oil, coal and LNG, oil sands and bitumen have received extraordinary attention due to their high reserves. As for petroleum, asphalt, that is, residue after removing oil such as naphtha from petroleum through distillation or residue after heat treatment of asphalt are excessive. Such super heavy oil is an oily substance containing about 60 to 70% or more of a nonvolatile matter having a boiling point of 420 to 450 ° C or more, which is a vacuum distillation residue, and does not flow in itself or has a high viscosity of tens of thousands of cp or more. For this reason, they are very difficult fuels to deal with, because of the problem of clogging, handling and atomization when used as fuel without heating to 280 to 300 ° C. Recently, attempts have been made to reduce its viscosity to emulsify difficult heavy oil in water to have a viscosity similar to that of water.

In this case, surfactants are known to play an important role in keeping the emulsion fuel composed of super heavy oil emulsified in water in a stable state. Emulsions are thermodynamically unstable systems and break down over time. Likewise, in the case of the ultra-heavy emulsion fuel described above, the emulsion breaks down, i.e., deteriorates when stored for a long time or transported by ship. When this emulsion is actually combusted, many undesirable problems with combustion, such as a lot of unburnt, arise. Moreover, the deterioration of the emulsion lowers the fluidity and increases the viscosity to such an extent that it cannot be handled by the fluid, making it difficult to transport. For this reason, it is important to modify, i.e., regenerate, deteriorated super heavy oils into fuels having high flowability and low unburned fuel prior to combustion.

The inventors have found that in the regeneration of emulsion fuel of deteriorated super heavy oil, fuels suitable for combustion can be produced by the following two methods selected according to the degree of deterioration, thereby completing the present invention.

(1) Recycling method of O / W type super heavy oil emulsion fuel which is lightly deteriorated to be transportable and can be treated as a flowable liquid: having a HLB value of 2 to 16, preferably 10 to 14, and the following (i) 0.01 to 2 parts of the nonionic surfactant selected from the group consisting of (vii), preferably 0.1 to 1 part by 100 parts of the emulsion fuel, and add the resulting mixture to a high shear stirrer such as a line mixer. The emulsion fuel is regenerated by stirring to produce an O / W type super heavy oil emulsion fuel which can be sufficiently atomized at a high temperature, for example, 80 to 90 ° C., and has a small amount of unburnt. It is preferable to select the HLB value and the addition amount of the nonionic surfactant so that the emulsion fuel is changed to O / W type at the temperature during manufacture, storage, and transportation and W / O type at the atomization temperature from the viewpoint of improving the combustibility.

(i) alkylene oxide adducts of compounds having phenolic hydroxyl groups such as phenol, cresol, butylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, p-cumiphenol or bisphenol A, wherein oxidation Alkylene is ethylene oxide and / or propylene oxide, butylene oxide or styrene oxide.

(ii) alkylene oxide adducts of formalin condensates of compounds with phenolic hydroxyl groups such as alkylphenols, phenols, m-cresols, styrenated phenols or benzylated phenols, wherein the average degree of condensation is from 1.2 to 100, preferably Is 2 to 20 and the alkylene oxide is ethylene oxide and / or propylene oxide, butylene oxide or styrene oxide.

(iii) polyalkylene oxide adducts of compounds with monovalent active groups such as branched and / or straight chain aliphatic alcohols or aliphatic amines having from 2 to 50 carbon atoms, wherein alkylene oxide is ethylene oxide and / or propylene oxide, Butylene oxide or styrene oxide.

(iv) Blocks or random addition polymers of ethylene oxide with propylene oxide and / or butylene oxide or styrene oxide.

(v) polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, sugar, polyglycerol, ethylene glycol, polyethylene glycol, propylene glycol or polypropylene glycol, or polyhydric alcohols described above with 8 to 18 carbon atoms Alkylene oxide adducts of esters with fatty acids, wherein alkylene oxide is ethylene oxide and / or propylene oxide, butylene oxide or styrene oxide.

(vi) alkylene oxide adducts of polyamines having a plurality of active hydrogen atoms such as ethylenediamine, tetraethylenediamine or polyethyleneimine (molecular weight: 600 to 10,000), wherein alkylene oxide is ethylene oxide and / or propylene oxide, Butylene oxide or styrene oxide.

(vii) at least one selected from the group consisting of 1 mole of triglyceride oil and glycerin, trimethylolpropane, pentaerythritol, sorbitol, sugar, ethylene glycol, polyethylene glycols having a molecular weight of 1000 or less, polypropylene glycols having a molecular weight of 1000 or less Addition reaction product of alkylene oxide with one polyhydric alcohol and / or a mixture of 0.1 to 5 moles of water, wherein the alkylene oxide is ethylene oxide and / or propylene oxide, butylene oxide or styrene oxide. Among the nonionic surfactants described above, the most preferred surfactants and the next most preferred surfactants belong to the above-mentioned groups (vii) and (i), respectively.

(2) Regeneration method of O / W type super heavy oil emulsion fuel, which is difficult to transport due to high viscosity and cannot be handled as a fluid liquid: an anionic interface selected from the group consisting of the following surfactants (I) to (VII) 0.01 to 2 parts of the active agent, preferably 0.08 to 0.6 parts, are added to 100 parts of severely degraded O / W emulsion fuel, and stirred gently to lower the viscosity of the emulsion fuel, the HLB value is 2 to 16, and in relation to the method (1) Nonionic surfactants selected from the group consisting of one of the surfactants (i) to (vii) are added to the resulting mixture in an amount of 0.01 to 2 parts, preferably 0.1 to 1 part with respect to 100 parts of the emulsion fuel, and have high fluidity, For example, an emulsion fuel is prepared that can be sufficiently atomized at 80 to 90 ° C.

Alternatively, the method may be selected from the group consisting of the anionic surfactants selected from the group consisting of the following surfactants (I) to (VII) and the surfactants (i) to (vii) described above in connection with the method (1). The nonionic surfactant having a HLB value of 16 is 100: 10 to 100: 1000, preferably 100: 100 to 100: 400, and the total addition amount is 0.05 to 3 parts by weight ratio of the nonionic surfactant: anionic surfactant. Preferably 0.3 to 1.5 parts are added to 100 parts by weight of the emulsion fuel and the resulting mixture is stirred to regenerate the emulsion fuel which can be sufficiently atomized at high temperatures, for example 80 to 90 ° C., with excellent fluidity. Anionic surfactants primarily lower the viscosity of the emulsion fuel, while nonionic surfactants mainly prevent the emulsion particles from agglomerating into larger particles. It is preferable to select the HLB value and the amount of the nonionic surfactant so that the emulsion fuel is O / W type at the temperature during manufacture, storage and transportation and W / O type at the atomization temperature.

(I) formalin condensates of sulfonic acids or sulfonates of aromatic ring compounds such as naphthalene, alkylnaphthalene, alkylphenols or alkylbenzenes, wherein the average degree of condensation is from 1.2 to 100, preferably from 2 to 20, and the salts are ammonium, monoethanol Lower amines such as amines, diethanolamines, triethanolamines or triethylamines or salts of alkali or alkaline earth metals such as sodium, potassium, magnesium or calcium.

(II) formalin condensates of ligninsulfonic acid, salts of ligninsulfonic acid or derivatives thereof, and ligninsulfonic acids or sulfonic acids of aromatic compounds such as naphthalene or alkylnaphthalene, salts thereof, wherein the salts are ammonium, monoethanolamine, diethanol Amines such as amines, triethanolamine or triethylamine, or salts of alkali metals or alkaline earth metals such as sodium, potassium, calcium or magnesium, with an average condensation of 1.2 to 50, preferably 2 to 20.

(III) polystyrenesulfonic acid or salts thereof and copolymers of other copolymerizable monomers with styrenesulfonic acid and salts thereof wherein the molecular weight is from 500 to 500,000, preferably from 2,000 to 100,000 and the salts are ammonium, monoethanolamine, diethanolamine, triethanol Lower amines such as amines or triethylamine, or salts of alkali or alkaline earth metals such as sodium, potassium, calcium or magnesium.

(IV) a polymer of dicyclopentadienesulfonic acid or a salt thereof, wherein the polymer has a molecular weight of 500 to 500,000, preferably 2,000 to 100,000, and the salt comprises ammonium, monoethanolamine, diethanolamine, triethanolamine or triethylamine Such as lower amines or salts of alkali or alkaline earth metals such as sodium, potassium, calcium or magnesium.

(V) copolymers of maleic anhydride and / or itaconic anhydride with other copolymerizable monomers and salts thereof, wherein the molecular weight is from 500 to 500,000, preferably from 1,500 to 100,000 and the salt is an alkali metal such as ammonium or sodium or potassium Is salt. Examples of copolymerizable monomers include olefins (ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, dekene, undekene, dodekene, tridekene, tetradekene, pentadecene, hexadekene), styrene, vinyl acetate , Acrylic acid esters, methacrylic acid and acrylic acid.

(VI) maleic acid-modified liquid polybutadiene or a salt thereof, wherein the liquid polybutadiene has a molecular weight of 500 to 200,000, preferably 1,000 to 50,000, and the degree of modification with maleic acid is water. To the extent necessary to dissolve in, preferably 40 to 70%, the salt is ammonium or a salt of an alkali metal such as sodium or potassium.

(VII) the following anionic surfactants having one or two hydrophilic groups in the molecule

(a) sulfates of alcohols having 4 to 18 carbon atoms, wherein the salt is a lower amine such as ammonium, monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali metal such as sodium, potassium, magnesium or calcium Or salts of alkaline earth metals.

(b) alkanes, alkenes, and / or alkylaryl-sulfonic acids having 4 to 18 carbon atoms, wherein the salts are lower amines such as ammonium, monoethanolamine, diethanolamine, triethanolamine, or triethylamine, or Salts of alkali or alkaline earth metals such as sodium, potassium, magnesium or calcium.

(c) sulfates or phosphates salts of compounds having at least one active hydrogen in the molecule and alkylene oxide adducts, wherein the salts are ammonium or salts of alkali metals such as sodium or potassium.

(d) sulfosuccinic acid salts which are esters of saturated or unsaturated fatty acids having 4 to 22 carbon atoms, wherein the salts are salts of ammonium, sodium or potassium.

(e) Alkyl diphenyl ether disulfonic acid or salts thereof, wherein the alkyl group has 8 to 18 carbon atoms and the salt is a salt of ammonium, sodium, potassium, magnesium or calcium.

(f) rosin acid or a salt thereof, wherein the salt is a salt of ammonium, sodium or potassium, and includes a toe oil blend acid and salt thereof consisting of a mixture of rosin acid and a higher fatty acid.

(g) Alkanes or alkenes fatty acids having 4 to 18 carbon atoms, wherein the salts are salts of ammonium, potassium or sodium.

Among the anionic surfactants described above, those of type (I) and (II) are preferable.

Surfactants of type (I) show slightly better performance.

There is no difference in performance as long as the degree of condensation is two or more in the surfactant of type (I).

For surfactants of type (II), modified lignin with carboxyl groups introduced instead of sulfonic acid groups showed slightly better performance. The HLB value of the nonionic surfactant is the same as that of the surfactant used in method (1). That is, 2 to 16, preferably 10 to 14. Among the nonionic surfactants, the best surfactants and the next best surfactants are of the type (vii) and (i) described above in connection with method (1), respectively.

In both the methods (1) and (2), any stirring means may be used. Moreover, you may use combining two or more types of stirrers. Particular preference is given to the use of high shear agitators. Examples include line mixers, fletching turbine blades, propeller wings, brumagin wings and paddle wings.

The oil referred to herein as "super heavy oil" includes the following oils that do not flow unless heated to high temperatures.

(1) petroleum derived asphalt and mixtures thereof with oils

(2) products of various treatments of petroleum-derived asphalt, intermediate products and residues and mixtures thereof with oils

(3) High kinematic oils or crude oils that do not flow at high temperatures

(4) petroleum-derived tar pitch and mixtures thereof

(5) bitumen

EXAMPLE

The invention will be explained with reference to the following examples. However, the present invention is not limited only to these examples.

Example 1

300 g of a lightly degraded O / W type ultra heavy oil emulsion fuel was added to an 800 ml SUS container, and the emulsion fuel was heated to 60 ° C. by impregnation in a heating bath. A predetermined amount of nonionic surfactant was added thereto. After reaching a constant temperature (60 ° C.), the mixture was stirred for 5 minutes at 300 rpm with a paddle blade. The mixture was subjected to high shear stirring at 6,000 rpm for 2 minutes with a TK homomixer to reemulsify the emulsion fuel and place in a thermostat at 60 ° C. and measure the viscosity. A portion of the reemulsified emulsion fuel was kept at 50 ° C. and removed from the thermostat to determine the percent passage of 100-mesh sieves.

The viscosity is Shibaura Systems Co. It was measured by model VS-AI Vismetron, No. 2 (rotator: 60 rpm) manufactured by Ltd., while the percent passage was about 10 g on 100 mm mesh 100-mesh stainless steel sieve in an atmosphere of 50 ° C. Ten minutes after the sample was placed, the remaining amount was measured to calculate the passage amount.

The results are shown in Table 1 and Table 2.

The lightly deteriorated emulsion fuel comprises 0.12 parts of lignin sulfonic acid and 0.48 parts of polyoxyethylene nonylphenyl ether (HLB value: 15.2) for Middle East petroleum-induced asphalt (infiltration 60-80) or Athabasca bitumen. (Softening temperature 12.5 ° C .: made in Canada) and the resulting mixture was stirred at 75 ° C. with a TK homomixer (with low viscosity stirring blades) manufactured by Tokushu Kogyo Koogyo Co., Ltd. to prepare an emulsion fuel. And stored at 50 ° C. for 1 month.

The performance is satisfactory in the order of?

TABLE 1

TABLE 2

Example 2

300 g of severely degraded O / W type ultra heavy oil emulsion fuel was added to an 800 ml SUS container, and the emulsion fuel was heated to 60 ° C. by impregnation in a heating bath. An amount of anionic surfactant was added thereto and the resulting mixture was stirred for 5 minutes at 300 rpm with a paddle blade. The mixture was further stirred at high shear for 2 minutes at 6,000 rpm with a TK homomixer. A predetermined amount of nonionic surfactant was added to the emulsion fuel, the mixture was stirred with a spatula, stirred again with a TK homomixer, and placed in a thermostat at 60 ° C. to measure the viscosity. A portion of the re-emulsified emulsion fuel was kept at 50 ° C. and removed from the thermostat to determine the percent passage of 100-mesh sieves. Viscosity was measured by Model VS-AI Vismetron, No. 2 (rotary speed: 60 rpm) manufactured by Shibaura Systems Co., Ltd., while the percent passage was 100 of 70 mm ψ in an atmosphere of 50 ° C. -It was measured by placing about 10 g of sample on the mesh stainless sieve and measuring the amount after 10 minutes to calculate the passage amount. The results are shown in Table 3 and Table 4. In the above test, anionic surfactants and nonionic surfactants were added separately. Next, a mixture of an anionic surfactant and a nonionic surfactant was added instead of the anionic surfactant, and the emulsion fuel was subjected to high shear stirring at 6,000 rpm for 2 minutes with a TK homomixer. The viscosity and the passage amount were measured under the same conditions as described above.

The severely degraded emulsion fuel described above comprises 1.0 parts of polyoxyethylene nonylphenyl ether (HLB value: 15.5) and 100 parts of Middle Eastern petroleum-induced asphalt (infiltration: 60-80) or Atavaska bitumen (softening temperature: 12.5). ℃: Canadian) and the resulting mixture was stirred at 75 ℃ by TK homomixer (with spot stirring blade) manufactured by Tokushu Kogyo Co., Ltd. to prepare emulsion fuel, and emulsion fuel Was stored at 50 ° C. for 1 month. The viscosity of the emulsion fuel was 500 cps immediately after preparation and 7,000 cps one month after preparation.

The performance is satisfactory in the order of?

TABLE 3

TABLE 4

Example 3

The degraded emulsion was regenerated on a pilot plant scale using the regeneration apparatus shown in FIG. 1 and FIG.

Regeneration using the regeneration device shown in FIG. 1 supplies a certain amount of the degraded emulsion 1 heated to 50 ° C. in the storage tank 2 through a circulation pump 5, and adds an additive 6, and a static mixer. The mixture was premixed with (7) and the emulsion was stirred under high shear with a line mixer (8).

In the regeneration apparatus shown in FIG. 2, the static mixers 7 and 7 'were connected in series to the line mixers 8 and 8' in both systems in order to add an additive in two stages 6 and 6 '.

In the example of regeneration, the regeneration apparatus shown in FIG. 1 reproduces the emulsion that has been lightly degraded (regeneration 1), and the regeneration of the severely degraded emulsion using the additives mixed in the regeneration apparatus shown in FIG. The regeneration apparatus shown in 2) and FIG. 2 includes regeneration by adding two types of additives separately (regeneration 3).

The mechanical conditions for this regeneration are shown in Table 5, while the description of the additives and the properties of the emulsion before and after regeneration are shown in Table 6.

As is apparent from the results shown in Table 6, as in Examples 1 and 2, sufficient effects were also recognized in the continuous regeneration of the emulsion deteriorated at the pilot plant scale.

TABLE 5

TABLE 6

Emulsion 909 (made by Gao Kaorui Co., Ltd.): polyoxyethylene nonylphenyl ether (HLB 12.4)

NSF: formalin condensate of sodium naphthalene sulfonate (condensation degree: 4.1)

Claims (7)

Non-ionic selected from the group consisting of the following surfactants (i) to (vii) with an HLB (hydrophilic-lipophilic balance) value of 2 to 16 in the method for regenerating deteriorated O / W type ultra heavy oil emulsion fuel A method characterized in that it is added to 100 parts by weight of an O / W type super heavy oil emulsion fuel which is capable of transporting 0.01 to 2 parts by weight of surfactant and is slightly degraded to be treated as a fluid liquid, and the resulting mixture is subjected to high shear stirring: (i) alkylene oxide adducts of compounds having phenolic hydroxyl groups such as phenol, cresol, butylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, p-cumylphenol or bisphenol A, wherein oxidation Alkylene is ethylene oxide and / or propylene oxide, butylene oxide or styrene oxide. (ii) alkylene oxide adducts of formalin condensates of compounds with phenolic hydroxyl groups such as alkylphenols, phenols, m-cresols, styrenated phenols or benzylated phenols, wherein the average condensation is from 1.2 to 100 and alkylene oxides Is ethylene oxide and / or propylene oxide, butylene oxide or styrene oxide. (iii) polyalkylene oxide adducts of compounds with monovalent active groups such as branched and / or straight chain aliphatic alcohols or aliphatic amines having from 2 to 50 carbon atoms, wherein alkylene oxide is ethylene oxide and / or propylene oxide, Butylene oxide or styrene oxide. (iv) block or random addition polymers of ethylene oxide with propylene oxide and / or butylene oxide or styrene oxide (v) polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, sugar, polyglycerol, ethylene glycol, polyethylene glycol, propylene glycol or polypropylene glycol, or polyhydric alcohols described above and 8 to 18 carbon atoms Alkylene oxide adducts of esters with aliphatic acids, wherein alkylene oxide is ethylene oxide and / or propylene oxide, butylene oxide or styrene oxide. (vi) alkylene oxide adducts of polyamines having a plurality of active hydrogen atoms such as ethylenediamine, tetraethylenediamine, or polyethyleneimine (molecular weight: 600 to 10,000), wherein alkylene oxide is ethylene oxide and / or propylene oxide, Butylene oxide or styrene oxide. (vii) a group consisting of 1 mole of triglyceride oil and glycerin, trimethylol propane, pentaerythritol, sorbitol, sugar, ethylene glycol, polyethylene glycol having a molecular weight of 1000 or less, propylene glycol and polypropylene glycol having a molecular weight of 1000 or less Addition reaction product of alkylene oxide with at least one polyhydric alcohol and / or a mixture of 0.1 to 5 moles of water, wherein the alkylene oxide is ethylene oxide and / or propylene oxide, butylene oxide or styrene oxide. In the method for regenerating a deteriorated O / W type ultra heavy oil emulsion fuel, 0.01 to 2 parts by weight of anionic surfactant selected from the group consisting of the following surfactants (I) to (VII) is difficult to transport due to high viscosity and is difficult to transport into a fluid liquid. 100 parts by weight of the O / W type super heavy oil emulsion fuel deteriorated so badly that it cannot be handled, and the resultant mixture is gently stirred to lower the viscosity of the emulsion fuel, and 0.01 to 2 parts by weight of the emulsion fuel described above. Parts by weight of the nonionic surfactant of claim 1 are added to the resulting mixture to prepare a highly fluid emulsion fuel; Anionic surfactants selected from the group consisting of the following surfactants (I) to (VII) and nonionic surfactants of claim 1; Adding a total amount of 0.05 to 3 parts by weight to 100 parts by weight of the above-mentioned emulsion with a weight ratio of the nonionic surfactant of 100: 10 to 100: 1000, and stirring the resulting mixture; (I) Gormalin condensates of sulfonic acids or sulfonates of aromatic ring compounds such as naphthalene, alkylnaphthalene, alkylphenols or alkylbenzenes, wherein the average degree of condensation is from 1.2 to 100, the salts are ammonium, monoethanolamine, diethanolamine, Triethanolamine, or lower amines such as triethylamine or salts of alkali metals or alkaline earth metals such as sodium, potassium, magnesium, or calcium. (II) formalin condensates of ligninsulfonic acid, salts of ligninsulfonic acid or derivatives thereof, and sulfonic acids of aromatic compounds such as ligninsulfonic acid with naphthalene or alkylnaphthalene, salts thereof, wherein the salts are ammonium, monoethanolamine, diethanolamine , Lower amines such as triethanolamine, or triethylamine, or salts of alkali metals or alkaline earth metals such as sodium, potassium, calcium or magnesium, with an average condensation of 1.2 to 50. (III) polystyrenesulfonic acid or salts thereof and copolymers of other copolymerizable monomers with styrenesulfonic acid and salts thereof, wherein the molecular weight is from 500 to 500,000 and the salts are ammonium, monoethanolamine, diethanolamine, triethanolamine or triethylamine Lower amines, or salts of alkali or alkaline earth metals such as sodium, potassium, calcium or magnesium. (IV) a polymer of dicyclopentadienesulfonic acid or a salt thereof, wherein the polymer has a molecular weight of 500 to 500,000, and the salt is a lower amine such as ammonium, monoethanolamine, diethanolamine, triethanolamine or triethylamine or sodium, potassium Salts of alkali metals or alkaline earth metals, such as calcium or magnesium. (V) copolymers of maleic anhydride and / or itaconic anhydride with other copolymerizable monomers and salts thereof, wherein the molecular weight is from 500 to 500,000 and the salts are ammonium or salts of alkali metals such as sodium or potassium. (VI) Maleic acid-modified liquid polybutadiene or a salt thereof, wherein the liquid polybutadiene has a molecular weight of 500 to 200,000 and the salt is an ammonium or a salt of an alkali metal such as sodium or potassium. (VII) the following anionic surfactants having one or two hydrophilic groups in the molecule (a) sulfates of alcohols having from 4 to 18 carbon atoms, wherein the salt is a lower amine such as ammonium, monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali metal such as sodium, potassium, magnesium or calcium Or salts of alkaline earth metals. (b) alkanes, alkenes, and / or alkylaryl-sulfonic acids having 4 to 18 carbon atoms, wherein the salts are lower amines such as ammonium monoethanolamine, diethanolamine, triethanolamine or triethylamine, or sodium; Salts of alkali or alkaline earth metals such as potassium, magnesium or calcium. (c) sulfates or phosphates of alkylene oxide adducts of compounds having at least one active hydrogen in the molecule and salts thereof, wherein the salts are ammonium or salts of alkali metals such as sodium or potassium. (d) sulfosuccinic acid salts which are esters of saturated or unsaturated fatty acids having 4 to 22 carbon atoms, wherein the salts are salts of ammonium, sodium or potassium. (e) Alkyl diphenyl ether disulfonic acid or salts thereof, wherein the alkyl group has 8 to 18 carbon atoms and the salt is a salt of ammonium, sodium, potassium, magnesium or calcium. (f) rosin acid or a salt thereof, wherein the salt is a salt of ammonium, sodium or potassium, and includes a toe oil blend acid and salt thereof consisting of a mixture of rosin acid and a higher fatty acid. (g) Alkanes or alkenes having 4 to 18 carbon atoms and their salts, wherein the salts are salts of ammonium, potassium or sodium. The method of claim 1 wherein the nonionic surfactant has an HLB value of 10-14. The method of claim 1 wherein the nonionic surfactant is selected from the group consisting of (vii) and (i). The method of claim 2, wherein the anionic surfactant is selected from the group consisting of (I) and (II). The method of claim 2 wherein the nonionic surfactant has an HLB value of 10-14. The method of claim 2 wherein the nonionic surfactant is selected from the group consisting of (vii) and (i).

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