oil-in-water emulsion

Abstract

This invention relates to oil-in-water (water-continuous) emulsions that can be used as fuels, particularly oil-in-water emulsions containing glycerol. The invention also relates to methods for their preparation and fuel compositions comprising such emulsions.

Description

Technical Field

[0001] This invention relates to oil-in-water (water-continuous) emulsions that can be used as fuels, particularly oil-in-water emulsions containing glycerol. The invention also relates to methods for their preparation and fuel compositions comprising such emulsions. Background Technology

[0002] Conventional heavy fuel oils are typically produced by blending viscous refinery residues with higher-value distillate fuels to provide the lower viscosity characteristics required for acceptable fuel handling and combustion performance. Direct use of high-viscosity refinery residues requires high-temperature storage and processing, which limits and hinders their potential applications and thus reduces their value. As an alternative to blending refinery residues for fuel oil production, residues from further processing (e.g., coking, hydrocracking, etc.) can be applied at refineries to produce additional distillate fuels. This strategy requires significant capital investment from refineries, produces some low-value products, generates unsellable byproducts, and leads to increased emissions (including greenhouse gases and acid gases), all of which limit the economic advantages of this approach. Furthermore, the combustion of conventional fuel oils is associated with major environmental problems, including black smoke, NOx, and other pollutants. x and SO x Emissions.

[0003] WO2017077302A2 discloses an oil-in-water emulsion comprising an oil phase, an aqueous phase, and a main surfactant. WO2018206963A1 discloses an oil-in-water emulsion comprising a polymer stabilizer selected from cationic polymers. WO2015175876A discusses glycerol / water-in-oil emulsions containing biodiesel. Summary of the Invention

[0004] This invention relates to oil-in-water emulsions, particularly for fuels used in thermal and power generation applications, such as marine fuels or fuel oils. Therefore, this invention provides an oil-in-water emulsion comprising an oil phase dispersed in an aqueous phase, the oil-in-water emulsion comprising:

[0005] 0.05 to 0.6 wt% of a surfactant selected from fatty alkylamines, ethoxylated fatty alkylamines, ethoxylated fatty alkyl monoamines, methylated fatty alkyl monoamines, methylated fatty alkylamines, and quaternary fatty alkyl amines or combinations thereof; and

[0006] 0.5 to 70 wt% glycerol;

[0007] Oil-in-water emulsions have the following characteristics:

[0008] Average droplet size (D[4,3]) ranging from 3 to 15 μm;

[0009] Droplets with a content of less than 3 wt% have a particle size greater than 125 μm; and

[0010] At 50℃ and 100s -1 The dynamic viscosity is up to 500 mPas, where the viscosity is in Malvern Kinexus TM Measurements were taken using the instrument.

[0011] On the other hand, a fuel composition is provided that comprises or consists of an oil-in-water emulsion as defined in the first aspect.

[0012] On the other hand, a method for preparing the oil-in-water emulsion fuel as defined in the first aspect is provided, the method comprising the following steps:

[0013] Heating the hydrocarbon-containing oil and optionally glycerol to form an oil phase;

[0014] Mix water, surfactant, and optionally glycerol to form an aqueous solution; and

[0015] Mix the oil phase and the aqueous solution under conditions sufficient to form an oil-in-water emulsion;

[0016] Glycerol can be present in the oil phase, the aqueous phase, or both the oil phase and the aqueous phase. Attached Figure Description

[0017] The present invention will now be described with reference to the accompanying drawings, in which:

[0018] Figure 1 A schematic diagram of a method for preparing an oil-in-water emulsion is shown, wherein glycerol is present in the aqueous phase, as described herein.

[0019] Figure 2 A schematic diagram of a method for producing an oil-in-water emulsion is shown, wherein glycerol is present in the oil phase, as described herein.

[0020] Figure 3 A schematic diagram of a method for producing an oil-in-water emulsion is shown, wherein glycerol is present in both the aqueous and oil phases, as described herein.

[0021] Figure 4 An example illustrating the droplet size distribution of oil-in-water emulsion fuel is shown.

[0022] Figure 5 A schematic diagram of a laboratory-scale colloid mill emulsification system used to produce test formulation samples is shown. Detailed Implementation

[0023] The oil-in-water emulsion according to the present invention is suitable for use as marine fuel, as well as fuel oil for thermal and power generation applications. Using the oil-in-water fuel emulsion according to the present invention can reduce nitrogen oxides (NOx). xIt reduces emissions of particulate matter (especially black smoke) and ash, as well as carbon dioxide (CO2) and sulfur dioxide (SO2), and can provide economic, environmental and operational advantages over known fuels.

[0024] As a first embodiment, the present invention provides an oil-in-water emulsion comprising an oil phase dispersed in an aqueous phase, the oil-in-water emulsion comprising:

[0025] 0.05 to 0.6 wt% of a surfactant selected from fatty alkylamines, ethoxylated fatty alkylamines, ethoxylated fatty alkyl monoamines, methylated fatty alkyl monoamines, methylated fatty alkylamines, and quaternary fatty alkyl amines or combinations thereof; and

[0026] 0.5 to 70 wt% glycerol;

[0027] Oil-in-water emulsions have the following characteristics:

[0028] Average droplet size (D[4,3]) ranging from 3 to 15 μm;

[0029] Droplets with a content of less than 3 wt% have a particle size greater than 125 μm;

[0030] At 50℃ and 100s -1 The dynamic viscosity is up to 500 mPas, where the viscosity is in Malvern Kinexus TM Measured by the instrument.

[0031] As a second embodiment, the present invention provides an oil-in-water emulsion according to the first aspect, wherein the oil phase comprises hydrocarbon residues derived from one or more of the following: processed heavy crude oil or natural bitumen; refinery atmospheric distillation; refinery vacuum distillation; refinery viscous cracking, thermal cracking or steam cracking; refinery catalytic cracking; refinery hydrotreating and hydrocracking; and deasphalting treatment; and / or the hydrocarbons are selected from those having the following chemical abstracts (Chemical... Hydrocarbon residues with the following CAS (Abstracts Service) registration numbers: 8052-42-4, 64741-45-3, 64741-56-6, 64741-67-9, 64741-75-9, 64741-80-6, 64742-07-0, 64742-78-5, 64742-85-4, 68748-13-7, 68783-13-1, 70913-85-8, 91995-23-2, or 92062-05-0 or combinations thereof.

[0032] As a third embodiment, the present invention provides an oil-in-water emulsion according to any of the foregoing aspects, comprising up to 70 wt% hydrocarbon residue, wherein the sum of the components in the emulsion does not exceed 100 wt%.

[0033] As a further embodiment, an oil-in-water emulsion according to any of the foregoing aspects is provided, comprising about 40 to about 60 wt% hydrocarbon residue, wherein the sum of the components in the emulsion does not exceed 100 wt%. For example, the oil-in-water emulsion may comprise about 40, about 50, or about 60 wt% hydrocarbon residue, wherein the sum of the components in the emulsion does not exceed 100 wt%.

[0034] As a further embodiment, an oil-in-water emulsion according to any of the foregoing aspects is provided, comprising up to 50 wt% hydrocarbon residue, wherein the sum of the components in the emulsion does not exceed 100 wt%.

[0035] As a further embodiment, an oil-in-water emulsion according to any of the foregoing aspects is provided, comprising 20 to 30 wt% hydrocarbon residue, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0036] As a further implementation, an oil-in-water emulsion according to any of the foregoing aspects is provided, wherein glycerol is derived from a renewable carbon source.

[0037] As used in this article, “renewable carbon source” or “biomass” refers to a carbon source derived from organic materials such as plants, trees, and crops. This term may include carbon sources from crops used specifically for energy purposes, or residues generated during crop processing for food or other products. Glycerol derived from renewable carbon sources can be produced from renewable plant crops such as rapeseed, canola, soybeans, or palm oil.

[0038] As a further embodiment, an oil-in-water emulsion according to any of the foregoing aspects is provided, wherein glycerol is present in the oil phase.

[0039] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein glycerol is present in the aqueous phase.

[0040] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein glycerol is present in both the oil phase and the aqueous phase.

[0041] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion contains 20 to 70 wt% glycerol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0042] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion contains 30 to 70 wt% glycerol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0043] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion contains 40 to 70 wt% glycerol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0044] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion contains 10 to 60 wt% glycerol, wherein the total amount of all components in the emulsion does not exceed 100 wt%. For example, the oil-in-water emulsion may contain about 40, about 50, or about 60 wt% glycerol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0045] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion comprises about 0.5 to about 70 wt% of an oil selected from C1 to C2. 10 Alcohols in monohydric or dihydric alcohols, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0046] For example, an oil-in-water emulsion may contain about 1 to about 60 wt%, about 1 to about 50 wt%, about 1 to about 40 wt%, about 1 to about 30 wt%, or about 1 to about 25 wt% of an oil selected from C1 to C2. 10 Alcohols in monohydric or dihydric alcohols, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0047] In some embodiments, the oil-in-water emulsion may contain about 2 to about 25 wt% of an ingredient selected from C1 to C2. 10 Alcohols in monohydric or dihydric alcohols, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0048] In some embodiments, the alcohol is selected from methanol, ethanol, and butanol (e.g., 1-butanol, isobutanol, sec-butanol, or tert-butanol). As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein glycerol contributes less than 0.5 wt% to the fuel ash content.

[0049] The ash content of fuels is measured according to the method described in ASTM D 482-19 (Standard Test Method for Ash from Petroleum Products).

[0050] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion comprises one or more organic acids.

[0051] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion comprises one or more organic acids selected from methanesulfonic acid, formic acid, acetic acid, citric acid, benzoic acid, p-toluenesulfonic acid, and combinations thereof.

[0052] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion comprises one or more organic acids selected from methanesulfonic acid and formic acid.

[0053] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the pH of the emulsion and / or the aqueous phase is 2 to 6.

[0054] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the pH of the emulsion and / or the aqueous phase is 2 to 4.5; or 3 to 4.5.

[0055] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion further comprises a polymer stabilizer.

[0056] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion further comprises a polymer stabilizer selected from cationic polymers, said cationic polymers comprising at least one cationic monomer selected from: dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate quaternary ammonium salts, such as dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, and dimethylaminoethyl methacrylate methyl chloride quaternary salt. Salt), dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, and dimethylaminoethyl methacrylate hydrochloric acid salt;Alternatively, dialkylaminoalkylacrylamide or dialkylaminoalkylmethylacrylamide and their quaternary ammonium salts, such as acrylamide-1,4-propyltrimethylammonium chloride, dimethylaminopropylacrylamide methyl sulfate quaternary salt, dimethylaminopropylacrylamide methyl saulfate quaternary salt, dimethylaminopropylacrylamide sulfuric acid salt, dimethylaminopropylacrylamide hydrochloride salt, methacrylamidopropyltrimethylammonium chloride, and dimethylaminopropylmethacrylamide methyl sulfate quaternary salt. Salt), dimethylaminopropylmethacrylamide sulfate, dimethylaminopropylmethacrylamide hydrochloric acid salt, diethylaminoethylacrylate, diethylaminoethylmethacrylate, diallyldimethylammonium chloride, and diallyldimethylammonium chloride, and mixtures thereof.

[0057] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion further comprises one or more polymer stabilizers, wherein at least one polymer stabilizer is selected from alkyl hydroxyalkyl cellulose ethers, guar gum, starch and starch derivatives, hydroxyethyl cellulose and ethyl hydroxyethyl cellulose, and combinations thereof.

[0058] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, wherein the oil-in-water emulsion further comprises 0.03 to 0.08 wt% of a polymer stabilizer, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0059] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, comprising 20 to 30 wt% hydrocarbon residue and 40 to 70 wt% glycerol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0060] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, comprising 40 to 60 wt% hydrocarbon residue and 20 to 60 wt% glycerol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0061] As a further embodiment, an oil-in-water emulsion according to any of the foregoing embodiments is provided, comprising about 40 to about 60 wt% hydrocarbon residue; about 10 to 60 wt% glycerol; and about 1 to 30 wt% of a compound selected from C1 to C2. 10 An alcohol in the form of a monohydric alcohol or a dihydric alcohol, wherein the total amount of all components in the emulsion does not exceed 100 wt%. As a further embodiment, a fuel composition is provided comprising or consisting of an oil-in-water emulsion of any of the foregoing embodiments.

[0062] The fuel composition may be diesel fuel.

[0063] The fuel composition can be marine fuel.

[0064] The fuel composition may be fuel oil used for thermal and power generation applications.

[0065] As another embodiment, a method for preparing an oil-in-water emulsion fuel as defined in any of the foregoing embodiments is provided, the method comprising the following steps:

[0066] Heating the hydrocarbon-containing oil and optionally glycerol to form an oil phase;

[0067] Mix water, surfactant, and optional glycerol to form an aqueous solution; and

[0068] Mix the oil phase and the aqueous solution under conditions sufficient to form an oil-in-water emulsion;

[0069] Glycerol can be present in the oil phase, the aqueous phase, or both the oil phase and the aqueous phase.

[0070] The use of glycerol in the oil-in-water emulsion of this invention offers environmental and economic benefits. Advantages of this invention may include increased hydrocarbon residue derived from renewable carbon sources; increased aqueous phase density; improved lubricity; increased viscosity; reduced CO2 from non-renewable resources for the same energy content; reduced sulfur emissions; and reduced water content.

[0071] As used herein, the term "glycerol" refers to the compound propane-1,2,3-triol, also known as glycerine or glycerol. Glycerol can be derived from renewable or synthetic sources. Renewable resources include rapeseed, canola oil, soybean, and palm oil. Glycerol can also be produced through a saponification process (soap production). The purity of crude glycerol can be 60%–80%. Suitably, the glycerol used in emulsions as defined herein has a purity of 60% or higher; more preferably 70% or higher; more preferably 80% or higher; more preferably 90% or higher. More preferably, the glycerol used in emulsions as defined herein is substantially pure or contains only trace amounts of impurities.

[0072] Parameter measurement

[0073] The average droplet size distribution in the oil phase was determined using light scattering techniques with commercially available instruments, such as the Malvern Mastersizer. TM The instrument is used for measurement. The average droplet size is expressed as the average volume moment, denoted as the average D[4,3]. The average droplet size is suitably in the range of 3 to 15 μm, although preferably in the range of 5 to 10 μm.

[0074] Similar light scattering techniques and instruments can be used to determine the droplet size distribution and thus the weight percentage of droplets larger than 125 μm based on the volume equivalent sphere diameter. Suitably, the percentage of particles larger than 125 μm is less than 3 wt%. Preferably less than 2 wt%, more preferably less than 1 wt%. In an embodiment, less than 0.5 wt% can be achieved.

[0075] Using standard technologies and equipment such as Malvern Kinexus TM Dynamic viscosity is measured under controlled temperature and shear rate conditions. The value is expressed in mPas(cP) and measured at 50°C and 100 s⁻¹. -1The dynamic viscosity was determined at a shear rate of up to 500 mPas under these conditions. Suitably, this value is at most 500 mPas, more preferably at most 300 mPas, more preferably 50 to 300 mPas, and even more preferably 100 to 300 mPas. The dynamic viscosity can be measured after the oil-in-water emulsion is manufactured or after storage. The oil-in-water emulsion provided herein exhibits dynamic stability of up to 500 mPas at at least one test point under the above conditions, for example, after manufacture or after storage at 50°C for 3 weeks, preferably exhibiting this dynamic stability both after manufacture and after storage at 50°C for 3 weeks. Preferably, the oil-in-water emulsion, after manufacture or after storage at 50°C for 3 weeks, exhibits dynamic stability at 50°C and 100 s... -1 It exhibits dynamic stability up to 500 mPas.

[0076] Static stability was measured using the method defined in ASTM D6930-19 (Standard Test Method for Settlement and Storage Stability of Emulsified Asphalts).

[0077] The density of the glycerol-containing phase can be measured using any suitable method or instrument, such as an Anton Paar DMA 35 handheld densitometer. For example, the method defined in ISO 15212-1 can be used. Alternatively, the density of the glycerol-containing phase can be calculated based on the components within the glycerol-containing phase (e.g., using the density of the components and the volume shrinkage of the mixture).

[0078] oil phase

[0079] The oil phase of an emulsion contains hydrocarbons. Typically, oil is the source of heavy hydrocarbons, and its density may be slightly lower to significantly higher than water (e.g., 0.95 to 1.15 kg / m³ at 15°C). 3 Or 0.95 to 1.25 kg / m 3 Heavy hydrocarbons can have extremely high viscosity. For example, the viscosity can reach up to 300,000 centistokes (cSt) at 100°C. Residues or hydrocarbon sources with a viscosity of 7 cSt or higher at 25°C, or 10 cSt or higher at 100°C, can be used. Hydrocarbon sources with a viscosity of 180 cSt or higher, preferably 250 cSt or higher, at 25°C can also be used. Oil-phase hydrocarbons can be derived from many established processes, including:

[0080] Processed natural heavy crude oil or natural bitumen (usually after desanding, desalting, and dehydration);

[0081] Atmospheric distillation in oil refineries;

[0082] Vacuum distillation in oil refineries;

[0083] Refinery viscous cracking, thermal cracking, or steam cracking;

[0084] Catalytic cracking (thermal and catalytic) in oil refineries;

[0085] Refinery hydrotreating and hydrocracking;

[0086] Deasphalting treatment.

[0087] In one embodiment, the oil-in-water emulsion comprises an oil phase, which is a hydrocarbon residue, for example derived from refinery residues with a kinematic viscosity of up to 300,000 centistokes at 100°C, preferably above 200 centistokes at 100°C, and more preferably above 1,000 centistokes at 100°C. Table 1 provides examples of suitable hydrocarbon residues that can be used in the oil-in-water emulsions of the present invention.

[0088] Table 1: Examples of hydrocarbon residues

[0089]

[0090]

[0091]

[0092] Table 2 provides examples of usable hydrocarbon residues.

[0093] Table 2: Examples of hydrocarbon residues

[0094]

[0095] In some embodiments, the oil-in-water emulsion according to the invention may typically contain 20 wt% or more of an "oil" phase, such as hydrocarbon residue. In some embodiments, the emulsion may contain up to 70 wt% of an oil phase. In some embodiments, the emulsion may contain 20 to 30 wt% of an oil phase.

[0096] Aqueous phase

[0097] The water in the aqueous phase can come from a variety of sources. Table 3 provides examples of usable water specifications.

[0098] Table 3: Examples of water specifications for oil-in-water emulsion production

[0099] parameter value suspended solids Less than 10 mg / L, and filtered through a 35 μm filter. Chloride, mg / L Less than 50 Alkali metals, mg / l Less than 20 Alkaline earth metals, mg / l Less than 30 <![CDATA[Silicon in the form of SiO2, mg / l]]> Less than 40 pH 6.5 to 8 Total Hardness Maximum value 6°dH

[0100] Optionally, the water may be pretreated, for example by filtration and / or deionization. In some embodiments, the water content of the oil-in-water emulsion of the present invention may be trace to 40 wt%, typically in the range of 5 to 30 wt%. Preferably, the water content is in the range of 5 to 15 wt%.

[0101] Chemical additives

[0102] The oil-in-water emulsion of the present invention comprises a surfactant and glycerol. In some embodiments, the oil-in-water emulsion may additionally comprise one or more organic acids. In some embodiments, the oil-in-water emulsion may additionally comprise a polymer stabilizer. In some embodiments, the oil-in-water emulsion may additionally comprise a compound selected from C1 to C2. 10 Alcohols in monohydric or dihydric alcohols.

[0103] When preparing oil-in-water emulsions, chemical additives are typically added to the aqueous phase before mixing with the oil phase. Glycerin can be added to the oil phase, the aqueous phase, or both. C1 to C2... 10 Monohydric alcohols or dihydric alcohols are added to the oil phase or the aqueous phase, or to both the oil phase and the aqueous phase.

[0104] Chemical additives may be provided individually, or two or more additives may be provided in the form of pre-prepared chemical additive packages.

[0105] surfactants

[0106] The oil-in-water emulsion of the present invention comprises at least one surfactant, which is typically added to the aqueous phase before mixing with the oil phase when preparing the oil-in-water emulsion. In some embodiments, glycerol is present in the oil phase, and the surfactant may also be added to the oil phase.

[0107] The surfactant is present in an amount of 0.05 to 0.6 wt% of the oil-in-water emulsion. The purpose of the surfactant is to act as an emulsifier, stabilizing the oil droplets in the aqueous phase. Surfactants in the range of 0.05 to 0.5 wt%, for example, 0.08 to 0.4 wt%, can be used.

[0108] Multiple surfactants can be used. There can be one surfactant or a combination of one or more surfactants. At least one surfactant, optionally all surfactants, can be selected from one or more of the following:

[0109] According to the following formula, fatty alkylamines;

[0110] R a -[NH(CH2) m ] p -NH2

[0111] in;

[0112] R a It is an aliphatic group having 12 to 24 carbon atoms (preferably 12-14, 14-16, 16-18, 18-20, 20-22 or 22-24 carbon atoms).

[0113] m is the number 2 or 3.

[0114] p is a number from 0 to 3;

[0115] Ethoxylated fatty alkylamines according to the following formula;

[0116]

[0117] in;

[0118] R b It is an aliphatic group having 12 to 24 carbon atoms (preferably 12-14, 14-16, 16-18, 18-20, 20-22 or 22-24 carbon atoms).

[0119] m is the number 2 or 3.

[0120] p is the number 1 to 3.

[0121] n1, n2, and n3 are each independently a number in the range of 0 to 70, for example, 2 to 70, or 3 to 70. In one implementation, n1 + n2 + n3 is a number greater than 0 and at most 2^10. Each of n1, n2, and n3 may or may not be an integer.

[0122] Ethoxylated fatty alkyl monoamines according to the following formula;

[0123]

[0124] in;

[0125] R c It is an aliphatic group having 12 to 24 carbon atoms (preferably 12-14, 14-16, 16-18, 18-20, 20-22 or 22-24 carbon atoms).

[0126] m1 and m2 are each a number greater than 0 and at most 70, for example, 2 to 70, or 3 to 70. In one implementation, m1 + m2 is a number greater than 0 and at most 140. Each of m1 and m2 may or may not be an integer.

[0127] Methylated aliphatic alkyl monoamines according to the following formula;

[0128]

[0129] in;

[0130] Group R 1 R 2 and R 3 One or two of them are independently selected from aliphatic groups having 8 to 22 carbon atoms (preferably 8-10, 10-12, 12-14, 14-16, 16-18, 18-20 or 20-22 carbon atoms).

[0131] R 1 R 2 and R 3 The remaining group is methyl;

[0132] Methylated fatty alkylamines according to the following formula;

[0133]

[0134] in;

[0135] Group R 1 to R 5 One or two of them are independently selected from aliphatic groups having 8 to 22 carbon atoms (preferably 8-10, 10-12, 12-14, 14-16, 16-18, 18-20 or 20-22 carbon atoms).

[0136] R 1 to R 5 The remaining group is methyl.

[0137] n is an integer from 1 to 5.

[0138] m is 2 or 3

[0139] Or, according to the following formula, methylated fatty alkylamines;

[0140]

[0141] in;

[0142] Group R 1 to R 7 One or two of them are each selected from aliphatic groups having 8 to 22 carbon atoms (preferably 8-10, 10-12, 12-14, 14-16, 16-18, 18-20 or 20-22 carbon atoms).

[0143] R 1 to R 7 The remaining group is methyl.

[0144] m is 2 or 3

[0145] y and z are integers from 0 to 4, and (y+z) is from 0 to 4;

[0146] Or, according to the following formula, methylated fatty alkylamines;

[0147]

[0148] in;

[0149] Group R 1 to R 7One or two of them are aliphatic groups containing 8 to 22 carbon atoms (preferably 8-10, 10-12, 12-14, 14-16, 16-18, 18-20 or 20-22 carbon atoms).

[0150] R 1 To R 7 The remaining group is methyl.

[0151] m is 2 or 3

[0152] t is between 0 and 3.

[0153] r and s are between 1 and 4, and (t+r+s) is between 2 and 5;

[0154] and;

[0155] According to the following formula, a fatty alkyl quaternary amine;

[0156]

[0157] in;

[0158] R 1 It is an aliphatic group having 12 to 24 carbon atoms (preferably 12-14, 14-16, 16-18, 18-20, 20-22 or 22-24 carbon atoms), such as -(CH2). y -CH3, optionally containing a carbonyl group adjacent to the nitrogen atom, i.e., -C(O)-(CH2). (y-1) -CH3, wherein y is 10 to 22 (preferably y is 10-12, 12-14, 14-16, 16-18, 18-20 or 20-22);

[0159] R 2 and R 3 Each time it is present, it is independently selected from H or an aliphatic group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms, more preferably 1 carbon atom);

[0160] R 4 Selected from H or C 1-4 Aliphatic groups;

[0161] m is 2 or 3;

[0162] t is 0 to 4

[0163] A is an anion;

[0164] n is the valence of the anion.

[0165] The aliphatic groups mentioned in the above formula include aliphatic groups containing carbonyl groups, which may be optionally substituted by one or more, for example, 1 to 3, substituents, which are independently selected from hydroxyl, C, and C groups. 1-3 Alkyl, C 1-3 Alkoxy or C 1-3 Hydroxyalkyl. Preferably, the aliphatic group has no substituents. Each aliphatic group may be saturated or may contain carbon-carbon double or triple bonds, for example, up to 6 double bonds, for example, up to 3 double bonds.

[0166] Preferably, R 1 Having formula C 14-20 H 24-41 or C(O)C 13-19 H 22-39 More preferably, R 1 Having formula C 14-20 H 24-41 .

[0167] Preferably, each R 2 and R 3 It is independently selected from CH3, H and CH2CH2OH.

[0168] Preferably, each R 4 It is independently selected from CH3 and H.

[0169] Examples of fatty alkylamines include:

[0170] According to the following formula, a quaternary fatty alkyl monoamine;

[0171]

[0172] in;

[0173] R d It is an aliphatic group having 12 to 24 carbon atoms (preferably 12-14, 14-16, 16-18, 18-20, 20-22 or 22-24 carbon atoms).

[0174] a is an anion;

[0175] and

[0176] According to the following formula, a quaternary fatty alkyl diamine;

[0177]

[0178] in;

[0179] R dIt is an aliphatic group having 12 to 24 carbon atoms (preferably 12-14, 14-16, 16-18, 18-20, 20-22 or 22-24 carbon atoms).

[0180] A is an anion.

[0181] n is the valence of the anion;

[0182] In the above text, anion A is preferably selected from those anions that bind more strongly to quaternary ammonium than carbonate. Examples include halides, particularly Cl-. - ; and organic anions, such as formate (HCOO) - Acetate (CH3COO) - ) and mesylate (CH3SO3) - ).

[0183] In the above text, the group "EO" stands for ethoxylate group (-CH2CH2O-). Ethoxylate groups (or polyether groups with more than one linked ethoxylate group) are usually H-terminated, i.e., -CH2CH2OH.

[0184] In the embodiments, the surfactant is selected from one or more fatty alkyl diamines, fatty alkyl triamines and fatty alkyl tetraamines, ethoxylated fatty alkyl monoamines, ethoxylated fatty alkyl diamines and ethoxylated fatty alkyl triamines, and fatty alkyl quaternary amines.

[0185] In a further embodiment, the surfactant is selected from one or more fatty alkyl diamines, fatty alkyl tetraamines, ethoxylated fatty alkyl diamines, and fatty alkyl quaternary ammoniums. Examples include fatty alkyl tripropylene tetraamines, such as tallow-based tripropylene tetraamine, fatty alkyl propylene diamine, and oleyl diamine ethoxylate.

[0186] The term "aliphatic alkyl" includes not only saturated groups (i.e., C14 groups) 12 To C 24 Alkyl, preferably C 12-14 C 14-16 C 16-18 C 18-20 C 20-22 Or C 22-24 It also includes partially unsaturated C. 12 To C 24 Group (i.e., C) 12 To C 24 Alkenyl, preferably C 12-14 C 14-16 C 16-18 C 18-20 C 20-22 Or C 22-24For example, having up to six C=C double bonds. Preferred aliphatic alkyl groups have no more than three double bonds. Examples of aliphatic alkyl groups include oleyl (C18, 1 double bond) and other groups associated with tallow, such as palmyl (C16, 0 double bonds), stearyl (C18, no double bonds), myristyl (C14, no double bonds), palm oilyl (C16, 1 double bond), linoleyl (C18, 2 double bonds), and linolenyl (C18, 3 double bonds). The term "aliphatic alkyl" includes both natural and synthetic alkyl groups; for example, synthetic alkyl groups may include C... 15 Or C 17 Examples of suitable aliphatic alkyl groups include C0. 12 C 13 C 14 C 15 C 16 C 17 and C 18 Groups, each of which may be fully saturated or may contain one or more double bonds.

[0187] Surfactants can be selected based on the overall composition of the aqueous phase, oil phase, and / or oil-in-water emulsion. For example, surfactants can be selected to ensure that the components of the aqueous or oil phase are soluble in each other. For example, surfactants can be selected to ensure the presence of C1 to C2 components. 10 The components of a monohydric alcohol or dihydric alcohol phase are soluble in each other.

[0188] alcohol

[0189] In some embodiments, the oil-in-water emulsion may contain components selected from C1 to C2. 10 An alcohol in the form of a monohydric alcohol or a dihydric alcohol. For example, the alcohol may be contained in an oil phase and / or an aqueous phase. For example, the alcohol may be contained in an aqueous phase. For example, the alcohol may be contained in an oil phase. For example, the alcohol may be contained in both an oil phase and an aqueous phase. Preferably, the alcohol is contained in an aqueous phase.

[0190] In some embodiments, the alcohol is contained in the glycerol-containing phase (i.e., the glycerol-containing phase contains the alcohol). The glycerol-containing phase is a phase containing glycerol (e.g., an oil phase or an aqueous phase).

[0191] It has been found that when an oil-in-water emulsion (e.g., in a glycerol-containing phase) contains C1 to C2... 10 When using monohydric or dihydric alcohols, a glycerol-containing phase with a particularly favorable density can be obtained. For example, a glycerol-containing phase with a density of about + / - 0.05 g / mL (e.g., + / - 0.05 g / mL) of hydrocarbon residue can be obtained. It has been found that such a glycerol-containing phase increases the stability of oil-in-water emulsions (e.g., for emulsion stratification or sedimentation).

[0192] When the term + / -0.05 g / mL is used, it means that the density of the glycerol-containing phase is +0.05 g / mL or -0.05 g / mL of the hydrocarbon residue density. This does not mean that the value of the glycerol-containing phase is within the range of + / -0.05 g / mL of the hydrocarbon residue.

[0193] In a preferred embodiment, the oil-in-water emulsion comprises a hydrocarbon residue, and the density of the glycerol phase is from +0.05 g / mL to about +0.5 g / mL or -0.05 g / mL to about -0.5 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase may be from +0.05 g / mL to about +0.46 g / mL or -0.05 g / mL to about -0.46 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase may be from +0.05 g / mL to about +0.3 g / mL or -0.05 g / mL to about -0.3 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase may be from +0.05 g / mL to about +0.2 g / mL or -0.05 g / mL to about -0.2 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase may be from +0.05 g / mL to about +0.1 g / mL or -0.05 g / mL to about -0.1 g / mL of the hydrocarbon residue. For example, the density of the glycerol-containing phase can be from +0.05 g / mL to about +0.08 g / mL or from -0.05 g / mL to about -0.08 g / mL of the hydrocarbon residue. In these embodiments, the density is measured at the storage temperature.

[0194] In a preferred embodiment, the oil-in-water emulsion comprises a hydrocarbon residue, and the density of the glycerol phase is from +0.05 g / mL to about +0.5 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from +0.05 g / mL to about +0.46 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from +0.05 g / mL to about +0.3 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from +0.05 g / mL to about +0.2 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from +0.05 g / mL to about +0.1 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from +0.05 g / mL to about +0.08 g / mL of the hydrocarbon residue. In these embodiments, the density is measured at the storage temperature.

[0195] In a preferred embodiment, the oil-in-water emulsion comprises a hydrocarbon residue, and the density of the glycerol phase is from -0.05 g / mL to about -0.5 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from -0.05 g / mL to about -0.46 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from -0.05 g / mL to about -0.3 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from -0.05 g / mL to about -0.2 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from -0.05 g / mL to about -0.1 g / mL of the hydrocarbon residue. For example, the density of the glycerol phase can be from -0.05 g / mL to about -0.08 g / mL of the hydrocarbon residue. In these embodiments, the density is measured at the storage temperature.

[0196] The storage temperature is between 20 and 40°C. Preferably, the storage temperature is 30°C.

[0197] The oil-in-water emulsion according to any of the foregoing embodiments may contain about 0.5 to about 70 wt% of an ingredient selected from C1 to C2. 10 An alcohol of monohydric or dihydric nature, wherein the total amount of all components in the emulsion does not exceed 100 wt%. For example, an oil-in-water emulsion may contain about 1 to about 60 wt%, about 1 to about 50 wt%, about 1 to about 40 wt%, about 1 to about 30 wt%, or about 1 to about 25 wt% of an alcohol selected from C1 to C2. 10 The emulsion contains a monohydric or dihydric alcohol, wherein the total amount of all components in the emulsion does not exceed 100 wt%. In some embodiments, the oil-in-water emulsion may contain about 2 to about 25 wt% of an alcohol selected from C1 to C2. 10 Alcohols of monohydric or dihydric composition, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0198] For example, an oil-in-water emulsion may contain about 2, about 10, about 15, about 20, or about 25 wt% of an oil selected from C1 to C2. 10 An alcohol of monohydric or dihydric alcohol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

[0199] In some implementations, C1 to C 10 Monohydric or dihydric alcohols are straight-chain or branched C1 to C2 alcohols. 10 The alcohol is a monohydric alcohol or a dihydric alcohol. In some embodiments, the alcohol is selected from C1 to C6 monohydric alcohols or dihydric alcohols. In some embodiments, the C1 to C6 monohydric alcohols or dihydric alcohols are straight-chain or branched C1 to C6 monohydric alcohols or dihydric alcohols. In some embodiments, the alcohol is selected from C1 to C4 monohydric alcohols or dihydric alcohols. In some embodiments, the C1 to C4 monohydric alcohols or dihydric alcohols are straight-chain or branched C1 to C4 monohydric alcohols or dihydric alcohols.

[0200] In some embodiments, the alcohol is selected from C1 to C2. 10Monohydric alcohols, C1 to C6 monohydric alcohols, or C1 to C4 monohydric alcohols. C1 to C4 monohydric alcohols can be methanol, ethanol, propanol, or butanol. For example, a dihydric alcohol can be ethylene glycol. For example, an alcohol can be selected from methanol, ethanol, or butanol (e.g., 1-butanol, isobutanol, sec-butanol, or tert-butanol).

[0201] In some implementations, C1 to C 10 A monohydric alcohol or dihydric alcohol can refer to two or more (e.g., two, three, or four) alcohols, each independently selected from C1 to C2. 10 Monohydric alcohol or dihydric alcohol.

[0202] In some embodiments, the oil-in-water emulsion according to any embodiment described herein may contain about 0.5 to about 70 wt% of a second alcohol, the second alcohol being independently selected from C1 to C2. 10 Monohydric alcohol or dihydric alcohol, provided that the oil-in-water emulsion contains C1 to C2 alcohols. 10 The total amount of monohydric or dihydric alcohols is about 1 to about 70 wt%, and the total amount of all components in the emulsion does not exceed 100 wt%. For example, an oil-in-water emulsion may contain a first alcohol (e.g., methanol) and a second alcohol (e.g., ethanol), provided that the C1 to C2 concentrations in the oil-in-water emulsion are within the range of C1 to C2. 10 The total amount of monohydric alcohols or dihydric alcohols is about 1 to about 70 wt%, and the total amount of all components in the emulsion does not exceed 100 wt%.

[0203] In some embodiments, the glycerol:alcohol ratio in the glycerol-containing phase is about 20:1 to about 1:5, for example, about 38:2 to about 1.5:2.5. In some embodiments, the glycerol:alcohol ratio in the glycerol-containing phase is about 38:2, about 3:10; about 2.5:1.5; about 2:2, or about 1.5:2.5.

[0204] In some embodiments, the density of the glycerol-containing phase is between 0.8 g / mL and about 1.3 g / mL (measured at 25°C using the method described in ISO 15212-1).

[0205] polymer stabilizers

[0206] In some embodiments, one or more polymeric stabilizers may be added to the aqueous phase during the preparation of the oil-in-water emulsion. Their content is preferably up to 0.25 wt% of the oil-in-water emulsion. In embodiments, they are present in a content ranging from 0.01 to 0.10 wt%.

[0207] Polymer stabilizers and flow improvers can be used to improve static stability during storage by compensating for the density difference between the residue and the aqueous phase. They can also alter the viscosity characteristics of emulsions.

[0208] Polymer stabilizers can form a weakly "gel-like" structure in the aqueous phase containing the additive. This helps improve the static stability of oil-in-water emulsions by keeping hydrocarbon residue droplets separated, preventing sedimentation under static storage conditions. The weak gel structure also imparts low resistance or yielding to applied stress, ensuring suitable low-viscosity characteristics of the emulsion, for example, during pumping and handling. This property is also recoverable; for example, once the oil-in-water emulsion fuel is pumped into the tank, it can regain its static stability. The polymer stabilizer helps achieve this by interacting with other additives in the formulation through entanglement and bonding mechanisms to form a gel-like molecular structure.

[0209] One or more polymer stabilizers and flow improvers may be present. At least one polymer stabilizer and flow improver is selected from polymers containing monomers, said monomers including dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate quaternary ammonium salts, or dialkylaminoalkylacrylamide or dialkylaminoalkylmethacrylamide and their quaternary ammonium salts.

[0210] Examples of such polymer stabilizers and flow improvers include cationic polymers comprising at least one cationic monomer selected from: dialkylaminoalkyl acrylates or dialkylaminoalkyl methacrylate quaternary ammonium salts, such as dimethylaminoethyl acrylate methyl chloride quaternary ammonium salt, dimethylaminoethyl acrylate methyl sulfate quaternary ammonium salt, dimethylaminoethyl acrylate benzyl chloride quaternary ammonium salt, dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, dimethylaminoethyl methacrylate methyl chloride quaternary ammonium salt, dimethylaminoethyl methacrylate methyl sulfate quaternary ammonium salt, dimethylaminoethyl methacrylate benzyl chloride quaternary ammonium salt, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate... Acrylamide hydrochloride, or dialkylaminoalkylacrylamide or dialkylaminoalkylmethylacrylamide and their quaternary ammonium salts, such as acrylamide propyltrimethylammonium chloride, dimethylaminopropylacrylamide methyl sulfate quaternary ammonium salt, dimethylaminopropylacrylamide methyl sulfate quaternary ammonium salt, dimethylaminopropylacrylamide sulfate, dimethylaminopropylacrylamide hydrochloride, methacrylamide propyltrimethylammonium chloride, dimethylaminopropylmethacrylamide methyl sulfate quaternary ammonium salt, dimethylaminopropylmethacrylamide sulfate, dimethylaminopropylmethacrylamide hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, diallyl dimethylammonium chloride and diallyl dimethylammonium chloride.

[0211] Additional polymer stabilizers and flow improvers may be selected from one or more alkyl hydroxyalkyl cellulose ethers (water-soluble), preferably containing alkyl groups and hydroxyalkyl groups (e.g., hydroxyethyl or hydroxypropyl) having 1-3 carbon atoms;

[0212] DS 烷基Within the range of 0.1 to 2.5;

[0213] MS 羟烷基 Within the range of 0.2 to 4.0;

[0214] The weight-average molecular weight is in the range of 100,000 to 2,000,000 Da (ideally 800,000 to 1,600,000 Da);

[0215] Examples include methyl ethyl hydroxyethyl cellulose ether (water-soluble), preferably having

[0216] DS 甲基 Within the range of 0.3 to 1.5;

[0217] DS 乙基 Within the range of 0.1 to 0.7;

[0218] MS 羟乙基 It is in the range of 0.2 to 3.0.

[0219] DS represents the degree of substitution of a specific component, and MS represents the molar degree of substitution of a specific component.

[0220] Further examples of additional polymer stabilizers include those where R (in the formulas shown below) is H, CH3, and / or [CH2CH2O] n H.

[0221]

[0222] Other examples of polymerization stabilizers and flow improvers include guar gum, starch and starch derivatives, hydroxyethyl cellulose and ethyl hydroxyethyl cellulose.

[0223] acid

[0224] Acid, namely Bronster Acids can be used to activate surfactants. In some embodiments, the pH of the oil-in-water emulsion and / or the aqueous phase is 2 to 6, more preferably 2 to 4.5, or 3 to 4.5.

[0225] Oil-in-water emulsions may contain one or more organic acids. The organic acids contain at least one CH bond, and examples include methanesulfonic acid, formic acid, acetic acid, citric acid, p-toluenesulfonic acid, and benzoic acid.

[0226] At least one organic acid (optionally all) is preferably selected from methanesulfonic acid, formic acid, acetic acid, citric acid, benzoic acid, and p-toluenesulfonic acid. Preferably, at least one acid (optionally all) is selected from formic acid and methanesulfonic acid.

[0227] Oil-in-water emulsions as fuel

[0228] In some embodiments, the oil-in-water emulsion fuel according to the present invention includes one, more, or all of the features defined in Table 4.

[0229] Table 4: Implementation schemes for oil-in-water emulsions suitable for use as fuel

[0230] Components Typical range (wt%)* hydrocarbon residue 20-70 water Trace amounts up to 40 surfactants 0.05 to 0.6 glycerin 0.5 to 70 polymer stabilizers 0 to 0.25 Total wt% 100wt%

[0231] *For each emulsion, the total is equal to 100 wt%.

[0232] To avoid ambiguity, the term "wt%" as used herein refers to the weight percentage of the active ingredient. For example, when the ingredient is a surfactant, the term wt% refers to the weight percentage of the active surfactant. Furthermore, when a range for each ingredient or active ingredient is given, the total amount of ingredients in the emulsion will not exceed 100 wt%. For example, in an oil-in-water emulsion using 70 wt% hydrocarbon residue, a smaller proportion of the glycerol component will be used, thus not exceeding the maximum value of 100 wt%. In an oil-in-water emulsion, when a higher amount of 70 wt% glycerol is used, a smaller proportion of hydrocarbon residue will be used.

[0233] In some embodiments, the oil-in-water emulsion may contain up to 70 wt% glycerol, up to 30 wt% hydrocarbon residue, and only trace amounts of water. In this embodiment, glycerol is equivalent to water in the aqueous phase.

[0234] In some embodiments, the oil-in-water emulsions listed in Table 4 may additionally contain one or more organic acids in an amount sufficient to achieve a pH of the emulsion and / or aqueous phase in the range of 2 to 6, preferably in the range of 2 to 4.5 or 3 to 4.5.

[0235] Preparation of oil-in-water emulsions. Oil-in-water emulsions can be prepared by: mixing water and one or more chemical additives to form an aqueous phase; heating a hydrocarbon-containing oil and optionally glycerol; and mixing the hydrocarbon-containing oil and the aqueous phase to form an oil-in-water emulsion.

[0236] Preferred chemical additives form an aqueous solution when mixed with water, although suspensions or emulsions are acceptable, provided they are thoroughly mixed with the hydrocarbon-containing oil phase to ensure the formation of a stable oil-in-water emulsion.

[0237] Examples of hydrocarbon-containing oils are as described above. It is preferable to heat them to a temperature sufficient to reduce their viscosity to below 500 centistokes (e.g., in the range of 100 to 500 centistokes or 200 to 500 centistokes).

[0238] Preferably, it is heated to a temperature such that when mixed with the aqueous phase, the resulting temperature at the oil-water interface will cause the viscosity of the oil phase to be less than 10,000 centistokes. This will depend on the heat capacity of the aqueous phase (with chemical additives) and the hydrocarbon-containing oil, as well as their relative concentrations.

[0239] The relationship between the temperature at the interface and the initial temperatures of the aqueous and oil phases can be expressed by the following equation:

[0240]

[0241] In the above equation:

[0242] T i = Oil / water interface temperature of an oil-in-water emulsion

[0243] T oil =Temperature of the oil phase before mixing (°C)

[0244] T aq =Temperature of the aqueous phase before mixing (°C)

[0245] C oil = Specific heat capacity of the oil phase (kJ / kg / ℃)

[0246] C aq = Specific heat capacity of aqueous phase (kJ / kg / ℃)

[0247] [oil] = the proportion of oil phase (wt%)

[0248] [aq] = Proportion of aqueous phase (wt%)

[0249] Before mixing, the oil phase (T) oil The optimal temperature range is one in which the viscosity of the hydrocarbon-containing oil is in the range of 200-500 centistokes. Although this depends on the source of the hydrocarbon, it is generally in the range of 110 to 230°C.

[0250] Temperature of the oil / water interface after mixing (T) i Preferably, the viscosity of the hydrocarbon-containing oil is less than 10,000 centistokes. This temperature is preferably below the boiling point of the aqueous phase, and is also the temperature at which the thermal and phase stability of the chemical additives are maintained. Typically, this temperature is in the range of 70 to 150°C, for example, 80 to 120°C.

[0251] Temperature of the aqueous phase before mixing (T) aq According to the above T i and T oil Choose the temperature requirement. It is usually in the range of 30 to 95°C, for example, 50 to 90°C, or 50 to 70°C.

[0252] Mixing to form an emulsion can be achieved using instruments and techniques known to the technician, such as high-shear mixing instruments.

[0253] In one embodiment, two separate and distinct emulsions are prepared and mixed to form a composite oil-in-water emulsion, which enables further control over the properties of the desired oil-in-water emulsion.

[0254] Figure 1 , 2 Figures 3 and 4 provide schematic diagrams of non-limiting examples of methods for preparing oil-in-water emulsions. Figure 1 , 2 In section 3, the boxes labeled "glycerin" may include C1 to C1 in the implementation scheme. 10 Monohydric or dihydric alcohols, wherein the oil-in-water emulsion contains C1 to C2. 10 Monohydric alcohols or dihydric alcohols. That is, C1 to C2. 10 Monohydric alcohols or dihydric alcohols can be mixed with glycerol.

[0255] Figure 1 A schematic diagram of a non-limiting example of a method for preparing an oil-in-water emulsion is given, wherein glycerol is present in the aqueous phase. The designated region (1) represents the source of the hydrocarbon-containing oil used as the oil phase in the production of the oil-in-water emulsion.

[0256] The designated area (2) represents a suitable water source.

[0257] In a designated area (3), material from a hydrocarbon-containing oil source (1) can be cooled to a suitable temperature via a medium for storage as needed and further temperature control as required to achieve a viscosity of 250 to 500 centistokes for direct introduction into the emulsion preparation unit (4). Water (2) is first heated in a heat exchanger (5) (typically to the range of 50 to 90°C), which is also used to cool the final emulsion product (typically below 90°C) and to provide auxiliary cooling (typically below 60°C) to facilitate processing.

[0258] In zone (6), a polymer stabilizer is optionally mixed into the aqueous phase, followed by the addition of a surfactant, an organic acid (optional), and glycerol in zone (7). The chemical additives can be modified if desired to obtain an emulsified fuel with the required specifications and performance standards.

[0259] The chemical additives used (surfactants, optional organic acids, glycerol, optional C1 to C2) 10 The monohydric or dihydric alcohols and optionally polymer stabilizers are preferably free of any components or impurities that would negatively affect the use of the resulting emulsion as fuel. Therefore, preferably, they contribute no more than 50 ppm of halogenated compounds and no more than 100 ppm of alkali metals in the final emulsion fuel specification.

[0260] The aqueous phase is passed through a tank / container (8), which provides sufficient residence time for the acid to fully activate the surfactant. The aqueous phase and the hydrocarbon-containing oil phase are then introduced into a high-shear colloid mill (9), with its speed adjusted to ensure timely mixing of the components. One or more colloid mills (10) can be used in the manufacturing process, depending on the number of emulsion component streams with different desired properties (i.e., one for producing a single-component emulsion fuel, or two or more for producing a multi-component composite emulsion fuel). If more than one component is being produced, the different components can be mixed in the desired proportions via an in-line mixer (11) or downstream to obtain the correct properties of the final oil-in-water emulsion fuel. In this way, the final desired droplet size distribution, hydrocarbon / water ratio (i.e., energy density), and viscosity / rheological properties can be effectively controlled.

[0261] After production, emulsion fuel can be stored (12) for subsequent transportation and supply as fuel (13).

[0262] Figure 2 A schematic diagram of a non-limiting example of a method for preparing an oil-in-water emulsion is given, wherein glycerol is present in the oil phase.

[0263] In zone (14), glycerol and a surfactant are mixed with the residue source to form an oil phase. In zone (6), a polymer stabilizer is optionally mixed into the aqueous phase, followed by the addition of another surfactant and, optionally, an organic acid in zone (7). The process then proceeds as follows: Figure 1 The process is as described.

[0264] Figure 3 A schematic diagram of a non-limiting example of a method for preparing an oil-in-water emulsion is provided, wherein glycerol is present in both the aqueous and oil phases.

[0265] In zone (14), glycerol and a surfactant are mixed with the residue source to form an oil phase. In zone (6), an optional polymer stabilizer is mixed into the aqueous phase, followed by the addition of a surfactant, an optional organic acid, and glycerol in zone (7). The process then proceeds as follows. Figure 1 The process is as described.

[0266] Hydrocarbon residue assessment, formulation and emulsification processes

[0267] The formulation of oil-in-water emulsions can be optimized based on the properties of the hydrocarbon-containing oil (usually hydrocarbon residues, such as one of those listed in Table 1).

[0268] Chemical additives and their concentrations that can be used for different hydrocarbon residues can be optimized by technicians, preferably by selecting components to ensure compliance with any relevant operational, performance, or legal requirements.

[0269] To prepare a product containing additives (surfactants, optional organic acids, optional polymer stabilizers, glycerol, if present in an aqueous phase), the following procedure can be used:

[0270] A certain volume of water used to prepare the test formulation is heated to 50 to 70°C.

[0271] Add the required amount of polymer stabilizer (if used) to hot water and mix until completely dissolved.

[0272] If one or more organic acids are used, the pH of the solution is adjusted to 2 to 6, preferably 2 to 4.5, or within the range of 3 to 4.5.

[0273] During this preparation stage, a certain amount of surfactant and optional glycerol are added to mix the aqueous phase, while the pH is adjusted with another organic acid until the desired pH is reached. This mixing continues until all additives are dissolved and activated.

[0274] The aqueous phase is then transferred to a laboratory-scale colloid milling system, such as DENIMOTECH. TM The SEP-0.3R Emulsion Research Plant is capable of producing emulsions at a maximum capacity of 350 l / h. (See also...) Figure 4 Then a certain amount of residue material for evaluation is introduced into the system and heated to the required temperature (as described above).

[0275] The test emulsion can then be prepared using the following procedure;

[0276] Cooling water begins to flow to the system outlet heat exchanger.

[0277] The prepared aqueous phase was initially pumped through the system using a colloid mill.

[0278] Turn on the grinder and select an appropriate intermediate speed range (e.g., 9000 rpm for the SEP-0.3R system). Adjust the back pressure on the system to approximately 2 bar.

[0279] Once a stable flow rate and temperature are reached, the hydrocarbon residue pump starts at a low flow rate and steadily increases it until the desired flow rate is reached (e.g., to provide the final hydrocarbon residue content in the emulsion). The system back pressure is adjusted to maintain a level of approximately 2 bar. The water flow rate to the final heat exchanger is adjusted to ensure the emulsion flows at the system outlet at a temperature below 90°C.

[0280] Once the system reaches steady-state operation (i.e., steady-state operation in terms of flow rate, temperature, and pressure), a water-in-oil emulsion sample is taken for testing and analysis.

[0281] To stop production, stop pumping residue through the system and keep the aqueous phase flowing to flush the system.

[0282] For further evaluation and optimization, the operating procedures for the laboratory-scale colloid mill system will be the same, with adjustments made accordingly to the required process and formulation variables.

[0283] The principle of the production process for large-scale manufacturing of oil-in-water emulsion fuels using continuous online equipment is the same as described above.

[0284] Analysis of these test emulsion formulations provides an indication of the potential use of candidate hydrocarbon residues as feedstocks in the production of oil-in-water emulsion fuels using methods described with “generic” formulations and conditions. Based on the results of these tests, further formulation matrix testing can be conducted, if necessary, to fine-tune and optimize the residue’s response to emulsification and subsequent stability tests, focusing on specific aspects and variables.

[0285] The invention described above can be implemented in various embodiments, non-limiting examples of which are described below. Examples of oil-in-water emulsions were prepared using the methods described above. As mentioned above, the term "wt%" as used herein refers to the weight percentage of the active component. For example, when the component is a surfactant, the term wt% refers to the weight percentage of the active surfactant.

[0286]

[0287]

[0288] AF134 = Alkyldiamine ethoxylate

[0289] EM7000FQ = Ethyl, Methyl, Hydroxyethyl Cellulose

[0290] Formic acid (Formic acid)

[0291] NCV = Net Calorific Value

[0292] The surfactant is 100% active.

[0293] The data clearly show that the sulfur content of the oil-in-water emulsions of the examples is reduced compared to conventional emulsions A and B. The oil-in-water emulsions of this disclosure (Examples 1 to 5) exhibit a significant renewable carbon content of 7.8 wt% to 19.6 wt%, and also exhibit a renewable net calorific value (NCV) of 10% to 25%, while the NCV of conventional emulsions A and B is 0%.

[0294]

[0295]

[0296] AF134 = Alkyldiamine ethoxylate

[0297] EM7000FQ = Ethyl, Methyl, Hydroxyethyl Cellulose

[0298] Formic acid (Formic acid)

[0299] NCV = Net Calorific Value

[0300] The surfactant is 100% active.

[0301] Similarly, it can be seen that even with a relatively low glycerol content of 6.5 wt%, a significant renewable carbon source of 2.5% is achieved, which is advantageous in terms of CO2 emissions. The sulfur content is also reduced compared to conventional emulsions.

[0302]

[0303] In each of Examples 7 through 12, the emulsion also contains 0.3 wt% AF134 (alkyl diamine ethoxylate). These examples also contain formic acid (pH 4), and the residue type is vacuum distillation residue.

[0304] The data clearly show that adding alcohol to an oil-in-water emulsion significantly increases the density of the glycerol-containing phase.

Claims

1. An oil-in-water emulsion, the oil-in-water emulsion comprising an oil phase dispersed in an aqueous phase, the oil-in-water emulsion comprising: 0.05 wt% to 0.6 wt% of a surfactant, said surfactant being selected from fatty alkylamines, ethoxylated fatty alkylamines, or combinations thereof; and 20wt% to 70wt% glycerol; The oil-in-water emulsion described therein has the following characteristics: Average droplet size (D[4,3]) from 3 μm to 15 μm; Droplets with a concentration below 3 wt% have a particle size greater than 125 μm; and At 50℃ and 100s -1 The dynamic viscosity is up to 500 mPas, where the viscosity is in Malvern Kinexus TM Measured by the instrument.

2. The oil-in-water emulsion according to claim 1, wherein the fatty alkylamine is selected from methylated fatty alkyl monoamines, fatty alkyl quaternary amines, or combinations thereof.

3. The oil-in-water emulsion according to claim 1, wherein the surfactant is selected from ethoxylated fatty alkyl monoamines, methylated fatty alkyl monoamines, or combinations thereof.

4. The oil-in-water emulsion according to claim 1, wherein the oil phase comprises hydrocarbon residues derived from one or more of the following: processed heavy crude oil or natural bitumen; refinery atmospheric distillation; refinery vacuum distillation; thermal cracking; refinery catalytic cracking; refinery hydrotreating and hydrocracking; and deasphalting treatment.

5. The oil-in-water emulsion according to claim 1, wherein the oil phase comprises hydrocarbon residues derived from one or more of the following: refinery viscous cracking and steam cracking.

6. The oil-in-water emulsion according to claim 1, wherein the oil phase comprises hydrocarbon residues derived from one or more of the following hydrocarbon residues having the following Chemical Abstracts Service (CAS) registration numbers: 8052-42-4, 64741-45-3, 64741-56-6, 64741-67-9, 64741-75-9, 64741-80-6, 64742-07-0, 64742-78-5, 64742-85-4, 68748-13-7, 68783-13-1, 70913-85-8, 91995-23-2 or 92062-05-0.

7. The oil-in-water emulsion according to any one of claims 1 to 6, comprising up to 70 wt% hydrocarbon residue, wherein the sum of the components in the emulsion does not exceed 100 wt%.

8. The oil-in-water emulsion according to claim 1, comprising 30 wt% to 70 wt% glycerol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

9. The oil-in-water emulsion according to claim 1, comprising 0.5 wt% to 70 wt% of an alcohol selected from C1 to C6. 10 Monohydric alcohol or dihydric alcohol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

10. The oil-in-water emulsion according to claim 9, wherein the alcohol is selected from methanol, ethanol and butanol.

11. The oil-in-water emulsion according to claim 1, wherein the contribution of glycerol to the ash content of the oil-in-water emulsion is less than 0.5 wt%.

12. The oil-in-water emulsion according to claim 1, wherein it comprises one or more organic acids.

13. The oil-in-water emulsion according to claim 1, comprising one or more organic acids selected from methanesulfonic acid, formic acid, acetic acid, citric acid, benzoic acid, p-toluenesulfonic acid, and combinations thereof.

14. The oil-in-water emulsion according to claim 1, wherein the pH of the emulsion and / or the aqueous phase is 2 to 6.

15. The oil-in-water emulsion according to claim 1, wherein the oil-in-water emulsion further comprises a polymer stabilizer.

16. The oil-in-water emulsion according to claim 15, wherein the polymer stabilizer is selected from: dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate quaternary ammonium salt, or mixtures thereof.

17. The oil-in-water emulsion according to claim 15, wherein the polymer stabilizer is selected from: dimethylaminoethyl acrylate methyl chloride quaternary ammonium salt, dimethylaminoethyl acrylate methyl sulfate quaternary ammonium salt, dimethylaminoethyl acrylate benzyl chloride quaternary ammonium salt, dimethylaminoethyl methacrylate methyl chloride quaternary ammonium salt, dimethylaminoethyl methacrylate methyl sulfate quaternary ammonium salt, dimethylaminoethyl methacrylate benzyl chloride quaternary ammonium salt, or mixtures thereof.

18. The oil-in-water emulsion according to claim 15, wherein the polymer stabilizer is selected from: dialkylaminoalkylacrylamide, dialkylaminoalkylmethylacrylamide, dialkylaminoalkylacrylamide quaternary ammonium salt, dialkylaminoalkylmethylacrylamide quaternary ammonium salt, or mixtures thereof.

19. The oil-in-water emulsion according to claim 15, wherein the polymer stabilizer is selected from: acrylamide propyltrimethylammonium chloride, dimethylaminopropylacrylamide methyl sulfate quaternary ammonium salt, dimethylaminopropylacrylamide methyl sulfate quaternary ammonium salt, methacrylamide propyltrimethylammonium chloride, dimethylaminopropylmethacrylamide methyl sulfate quaternary ammonium salt, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, diallyl dimethylammonium chloride, diallyl dimethylammonium chloride, or mixtures thereof.

20. The oil-in-water emulsion according to claim 1, wherein the oil-in-water emulsion comprises 0.03 wt% to 0.08 wt% of a polymer stabilizer, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

21. The oil-in-water emulsion according to claim 1, comprising 20 wt% to 30 wt% hydrocarbon residue and 40 wt% to 70 wt% glycerol, wherein the total amount of all components in the emulsion does not exceed 100 wt%.

22. A fuel composition comprising an oil-in-water emulsion as defined in any one of claims 1-20.

23. A fuel composition comprising an oil-in-water emulsion as defined in any one of claims 1-20.

24. The fuel composition according to claim 22 or 23, wherein the fuel composition is diesel fuel.

25. The fuel composition according to claim 22 or 23, wherein the fuel composition is marine fuel; or fuel oil for thermal and power generation applications.

26. A method for preparing an oil-in-water emulsion as defined in any one of claims 1-8, the method comprising the following steps: Heating the oil and glycerin to form an oil phase; Mix water and surfactant to form an aqueous solution; and Mix the oil phase and the aqueous solution under conditions sufficient to form an oil-in-water emulsion; Glycerol is present in the oil phase.

27. A method for preparing an oil-in-water emulsion as defined in any one of claims 1-8, the method comprising the following steps: Heating the oil to form an oil phase; Water, surfactant, and glycerol are mixed to form an aqueous solution; and Mix the oil phase and the aqueous solution under conditions sufficient to form an oil-in-water emulsion; Glycerol is present in the aqueous phase.

28. A method for preparing an oil-in-water emulsion as defined in any one of claims 1-8, the method comprising the following steps: Heat the oil and a portion of the glycerin to form an oil phase; Mix water, surfactant, and remaining glycerol to form an aqueous solution; and Mix the oil phase and the aqueous solution under conditions sufficient to form an oil-in-water emulsion; Glycerol exists in both the oil and aqueous phases.

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