CN103911190A - Multicomponent formula combined biological fuel oil and preparation method thereof - Google Patents
Multicomponent formula combined biological fuel oil and preparation method thereof Download PDFInfo
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Abstract
The invention provides multicomponent formula combined biological fuel oil and a preparation method thereof. Based on 100 parts by weight of the biodiesel, the multicomponent formula combined biological fuel oil comprises, in parts by weight, no more than 85 but larger than zero part of a methanol modified composite substance, 5-70 parts of oleic acid, 5-80 parts of methanol or ethanol or a mixture of methanol and ethanol, 1-8 parts of a surfactant and 1-15 parts of a modified additive; and 0-45 parts by weight of industrial purified water can be added according to specific application. The multicomponent biological fuel oil has the performances similar to those of petrochemical diesel oil and can be mixed with common petrochemical diesel oil according to a certain ratio for use, and the multicomponent biological fuel oil has the advantages of high fuel value, high flash point, low condensation point, low cold filter plugging point, low corrosivity, less discharge and low cost.
Description
Technical field
The present invention relates to fuel oil field, particularly relate to a kind of bio-fuel-oil of polynary formula combination and processing method of preparation thereof used.
Background technology
China's oil starvation weak breath, coal resources are relatively abundant, coal-based alcohol ether fuel source is wide, with advantage alcohol ether substitution of resources petroleum resources, or carry out petroleum replacing resource with alcohol ether class A fuel A and petroleum mixture, be conducive to ecotope, promote economic Sustainable development, and can create new growth engines.
A lot of countries once promoted ethanol petrol, and the addition of ethanol in petrochemical industry gasoline is generally 10～15%, but because ethanol is mainly derived from farm crop, its popularization is faced with the problems such as cost and grain security, therefore emphasis is promoted interpolation methyl alcohol in recent years.Methyl alcohol main source is the byproduct of Coal Chemical Industry or a lot of chemical industry, and does not fight for resource with grain farmer's industry, and when burning, carbon emission is low, and development methanol fuel oil has great importance for solving current energy scarcity.
The most in short supply on well-known market is diesel oil, the purposes of diesel oil is wide, consumption is large, the demand gap of China's oil fuel is mainly reflected on diesel oil, diesel oil becomes the product in short supply in the energy in short supply, and country also wants a large amount of finished diesel fuel of import every year in imported crude oil, methyl alcohol and diesel oil can be exchanged and uses with the easy application of propellant combination and with fossil diesel fuel, be the numerous experts' of industry technology dream, but not yet better solve so far.
Methyl alcohol (CH
3oH) be the simplest compound of structure in lower alcohol, polarity hydroxyl (OH) ratio in molecule is very large, oxygen level is up to 50%, have the advantages that combustionvelocity is fast, heat release is fast, thermo-efficiency is high, theory joins in petrochemical industry gasoline or petrifaction diesel can save petroleum resources in a large number, but present stage methyl alcohol still undesirable (addition general≤15%) of technology that be added on gasoline, the rarely seen technology successful example that is added on diesel oil.Methyl alcohol is typical hydrophilic compounds, and diesel oil belongs to the hydrocarbon macromolecular compound of typical oil phase, it is the mixture containing alkane, cycloalkanes or the aromatic hydrocarbons of 9 to 18 carbon atoms, under normal condition, methyl alcohol and diesel oil can not dissolve each other completely, there is the dissolving each other of methyl alcohol and diesel oil, flash-point is low, cetane value is low, with the known technical barrier such as the emulsification layering of water:
According to open source information, in the M15 methyl alcohol-diesel blended fuel of Germany's test use, the volume addition of solubility promoter is 15%, the volume addition of ignition improver is 1%, the cetane value of fuel can reach 45, because the price of solubility promoter and ignition improver is all very high, and consumption is too large, has limited its promoting the use of in the fuel of market.
Application number is that 201210200197.4 Chinese patent application discloses and a kind ofly mixes methanol-based fuel and the miscible technology of diesel oil by multielement additive, exist binder component complexity, flash-point and manufacturing process, cost performance to be difficult to the shortcoming of accepting or rejecting, for example, when methanol-based fuel adopts methyl alcohol and the simple mixture of oleic acid, flash-point is low, and adopts methyl alcohol modification complex body mixture to cause complex process, cost high.In the Chinese patent application that is 201010274919.1 at another part of application number, disclose a kind of methanol diesel-oil, its tensio-active agent adopts non-ionic polyoxyethylene ethers, and hydrophile-lipophile balance value is 3～6, and other auxiliary agents.These are filled a prescription all in the problem of dissolving each other that to a certain degree can solve methyl alcohol-diesel oil, but still exist the problems such as easy layering, mutual solubility and clarity deficiency, or the defect of the low aspect of cost performance.
Common methyl alcohol or ethanol modified fuel oil in the market, the defect that ubiquity calorific value is low; Conventionally described biofuel, mostly refers to and the mixture of Witconol 2301 or Witconol 2301 and petrifaction diesel has the defect that condensation point is high, cold filter clogging temperature is high, corrodibility is strong and cost performance is not enough.
Summary of the invention
The object of the invention is to: a kind of multi-element biologic fuel oil based on the multiple conventional biological raw materials such as methyl alcohol or ethanol, methyl alcohol modification complex body, oleic acid and petrifaction diesel mixture is provided, and visual concrete purposes is added pure water, can mix use with common petrifaction diesel by a certain percentage, there is the feature of burning abrasive or low-carbon (LC), to scheme realizing the largely technology application target of saving petroleum resources, reaching energy-saving and emission-reduction.
In order to realize this target, the present invention uses the colloid surface principles of chemistry, the technical barrier that has solved the modification of methyl alcohol or ethanol or its mixture and pure water and dissolved each other with the low cost of oleic acid, methyl alcohol modification complex body, can fully dissolve each other with petrifaction diesel in certain proportion scope, the biofuel oil that multiple starting material are dissolved each other is long stationary phase, is beneficial to transport deposit; By the emulsifying effect that helps of tensio-active agent, make biofuel oil and miscible diesel oil thereof form stable oily microcapsule structure again, effectively improve efficiency of combustion, reduce the object of carbon emission amount.
For achieving the above object, the invention provides the bio-fuel-oil that a kind of polynary formula combination forms, based on 100 weight parts, comprising:
Methyl alcohol modification complex body is not more than 85 weight parts, and is not 0 weight part;
Oleic acid 5～70 weight parts;
Methyl alcohol or ethanol, or its mixture 5～80 weight parts;
Tensio-active agent 1～8 weight part;
Property-modifying additive 1～15 weight part;
Industrial pure water 0～45 weight part.
Described methyl alcohol modification complex body, at least comprise one or more in following material: the ester class (as diethyl carbonate, Witconol 2301) that ethers (for example t-butyl methyl ether), methyl alcohol and the sour condensation that methyl alcohol and alcohol condensation form forms, it adds the addition that can effectively reduce petrifaction diesel, saves industrial cost; But the source of methyl alcohol modification complex body is more complicated, its structural chain contains the abundance difference of saturated chain because of the difference of originating, when saturated chain abundance too Gao Shihui bring burning and exhausting to increase, affect low-temperature fluidity simultaneously, while specifically manufacture, can add as one sees fit.
Described oleic acid (chemical skeleton symbol CH
3(CH
2)
7cH=CH (CH
2)
7cOOH) be the unsaturated fatty acids containing 18 carbon atoms and 1 two key, it is a kind of important component that forms animal and plant grease, water insoluble, the source of oleic acid is more complicated equally, its structural chain contains the abundance difference of saturated chain because of the difference of originating, the oleic acid low-temperature fluidity that saturated chain abundance is too high is poor, specifically manufactures appropriate to the occasion selection containing the more product of unsaturated chain; Oleic acid both can be considered as the emulsifying agent of methyl alcohol or ethanol or its mixture, was again the multipolymer that is modified as " oleophylic ".
In described methyl alcohol and the mixture of ethanol, the ratio that methyl alcohol mixes with ethanol can be any.
In existing disclosed oil fuel technical literature, there is the system of dissolving each other taking methyl alcohol modification complex body as main body and petrifaction diesel, also there is the system of dissolving each other that is added into petrifaction diesel after using oleic acid to methyl alcohol or ethanol modification, the system of dissolving each other of rarely seen methyl alcohol modification complex body and oleic acid, methyl alcohol or ethanol.Experimental results show that, the latter is under Action of Surfactant, more easily form stable micelle phase interface, theory is thought, just because of methyl alcohol modification complex body is different from the space structure of oleic acid, methyl alcohol or ethanol, brought the space structure diversity of molecular cluster combination, likely formed more preferably compound isomer of burning behavior performance, this depends on selecting of tensio-active agent.
Described tensio-active agent comprises one or more of following material: sapn series emulsifying agent, twain series emulsifier, alkylsulphonic acid receive that series, thanomin, trolamine, Monoethanolamine MEA BASF, bromination hexadecyl sulfonic acid are received, dimethyl formamide, Xylo-Mucine, polyvinyl alcohol.Use different tensio-active agents different to final synthetic fuel oil proterties, various tensio-active agents respectively have its feature, hydrophile-lipophile balance value is each variant, even the tensio-active agent of same component, also can be because of content, different its hydrophile-lipophile balance values that affect of purity; The hydrophile-lipophile balance value of some tensio-active agents is higher, the dodecyl sodium sulfonate that for example alkylsulphonic acid is received in series is received, before use, the hydrophile-lipophile balance value of tensio-active agent should be adjusted to 10～14, be recommended in composite adjusting in described tensio-active agent, for example, use sapn series and twain series emulsifier to carry out composite adjusting.Use described tensio-active agent methyl alcohol or ethanol or its mixture, water and oleic acid can be formed to stable mixed system.Use other tensio-active agent also can play similar effect, but from the comparing check of over-all properties aspect, the tensio-active agent of other types, not as good as described tensio-active agent, can have impact to a certain degree to the over-all properties of product.
Described property-modifying additive, based on the property-modifying additive of 100 weight parts, comprising:
PH value buffer reagent 20～50 weight parts;
Isooctyl ester nitrate 5～20 weight parts;
Oxidation inhibitor 0.5～5 weight part;
Organic solvent 10～40 weight parts;
Functional modifier 0～40 weight part.
Wherein, the stability of the pH value that act as maintenance system of pH value buffer reagent, for the composite mixture of petroleum sodium sulfonate and barium mahogany sulfonate, wherein petroleum sodium sulfonate accounts for 10～40 weight parts, barium mahogany sulfonate accounts for 10～40 weight parts, and the weight of composite mixture is not less than 20 weight parts, is no more than 50 weight parts.Available pH buffer reagent must have following feature: be dissolved in organic solvent, and preferably liquid, corrosion-free to engine, and can not destroy the stability of methyl alcohol-oil phase emulsification system, have certain surge capability, all compound or its combinations with this feature all go for pH buffer reagent.For the present invention, the preferably combination of barium mahogany sulfonate and petroleum sodium sulfonate.Barium mahogany sulfonate (T701) and petroleum sodium sulfonate (T702) are the known rust preventive for metal surface of industry, in molecular structure, there is the sulfonic group of a strongly hydrophilic to connect mutually with alkyl, the pH value of the sulfuric acid of these two kinds of high fatty alcohols is 7-8, but under solution state due to common-ion effcet, the reversible quality of balance difference of dissociation, under enough concentration and suitable proportion, the desirable pH value of formation capable of being combined cushions rightly, and the petroleum sodium sulfonate in solution is that antacid composition, barium mahogany sulfonate are alkali resistant composition; Its buffering conjugation conformation model is: petroleum sodium sulfonate (R-SO
2o
-na
+) degree of ionization or ion(ic)activity stronger, under solution state, all dissociations go out Na
+and SO
2o
-; Barium mahogany sulfonate (R-SO
2o
-ba
++.
-oSO
2-R) degree of ionization or ion(ic)activity relatively a little less than, in solution in the free trend of structure, mainly with R-SO
3ba
+and SO
2o
-form exist, Na in buffer reagent
+and SO
3h
-concentration larger; When the miscible system of oil fuel causes free state H because absorbing the oxidated factor such as occur becoming sour of airborne carbonic acid gas, ester class
+when total amount increases, SO
3h
-h+ in meeting and system is in conjunction with forming mahogany acid; Otherwise, when the miscible system of oil fuel is decomposed or other factors causes OH because of the residual amination salt of internal composition
-time more than needed, Na
+can the interior free OH of inhibition system
-and other negatively charged ion, thereby make the acid base equilibrium degree of oil fuel buffered soln in cushioning right conjugation protection domain, make the miscible system of oil fuel keep stable.
Described isooctyl ester nitrate (having another name called nitric acid 2-ethylhexyl ester or isooctyl ester nitrate), except can effectively improving the cetane value of diesel oil/methanol fuel oil/methanol diesel-oil, can also improve combustionproperty, shorten ignition time, reduce burning-point, improve locomotive thermal condition dynamic property.In polynary composite fuel oil, add the isooctyl ester nitrate of 0.1%-0.3%, generally can improve a cetane value 2-9 unit.
Described oxidation inhibitor is generally selected from 124 Triazole class (for example T406: 124 Triazole stearylamine salt, TTAS: methyl benzotriazazole sodium salt, N-nonyl oxygen methyl benzotriazole), thiadiazole (for example T561:2, two (alkyl dithio) thiadiazoles of 5-) and sulphur phosphorus type antioxygen corrosion inhibitor, the mainstream product of the oxidation inhibitor of this class sulfur-bearing, phosphorus is zinc dialkyl dithiophosphate (ZDDP), T504: sulfenyl phenolate etc.The oxidation inhibitor that the present invention adopts, not only be conceived to weaken some solubility promoter of concoct in basic fuel oil and additive formulations to copper or other corrosion of metal power, to weaken the corrosion strength of some solubility promoter to rubber in additive formulations simultaneously, and have the advantages that oil soluble is good, reductibility is strong, reach the object of effective this combined additive of raising preparation of fuels oil erosion resistance.The oxidation inhibitor that the present invention selects comprises a kind of or several combination in following a few class: amine type oxidation inhibitor (pentanoic that for example N-phenyl-a-naphthylamine or octyl group/butyl mixed alkyl replace); Phenol type antioxidant, for example T501:2,6-ditertbutylparacresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl phenol, T502: mixed type liquid shielding phenol, T5114,4: methylene-bis (2,6-di-tert-butylphenol), T512: phenolic ester type oxidation inhibitor etc.; Phenol amine type oxidation inhibitor, its main products for example 2,6-di-t-butyl-alpha, alpha-dimethyl amido p-cresol; Sulphur phosphorus type antioxygen corrosion inhibitor and dialkyl dithiocarbamate, use wherein a kind of or several oxidation inhibitor combination, do not limit relative proportion while being used in combination.
Described organic solvent should have following technical characterictic, as low in fusing point, good fluidity, does not destroy emulsification system, non-corrosiveness etc.; In the time that flash-point, solvent octane value or the cetane value of solvent is higher, the additive that preparation obtains has more advantage.Organic solvent can be selected from aromatic hydrocarbon solvent, ketones solvent, esters solvent, ether solvent, also can be selected from petroleum product solvent oil, as paraffin oil, diesel oil, but do not recommend to select the solvent that may pollute environment, the discharge that may produce oxynitride such as nitro kind solvent.Aromatic hydrocarbon solvent comprises toluene, dimethylbenzene and other solvents that contains aromatic ring structure; Ketones solvent comprises acetone, butanone and other ketone compounds; Esters solvent comprises the compounds such as ethyl acetate, methylcarbonate, original methyl carbonate, triethyl orthoformate; Ether solvent comprises t-butyl methyl ether, glycol dimethyl ether, and other have the ether of ether structure general formula.
Described functional modifier be this area common, the class additive that adds in order to improve bavin oil properties, it can need to add flexibly according to purposes.Such as tritolyl phosphate, claim again Tritolyl Phosphate, it has multiple isomer, all can be applied to the present invention, and effect is similar, such as T306, molecular formula C
21h
21o
4p, is typically used as softening agent, for example, for painting the snappiness that can increase paint film, also as synthetic rubber, polyester, polyolefine and flame retardant of plastic agent.T306 is dissolved in alcohol, benzene, ether, vegetables oil, the many organic solvents of mineral wet goods, and stability is strong, not volatile, can give the wear resistance that superpolymer is good, is also cited and makes gasoline and lubricated oil additives.Be anti-wear agent at the dominant role of combined additive of the present invention, serve as fire retardant simultaneously, wear-resistant, fire-retardant, raising flash-point are played to multiple action.Such as isopropylcarbinol is typically used as softening agent, synthetic rubber and synthetic drugs etc., be typically used as additive in petroleum industry again, the effect in additive formulations of the present invention, is not only and plays the part of hydrotropy and help the organic solvent of emulsification, and serve as multiple player; The combustion heat of for example isopropylcarbinol is 2667.7kJ/mol, and 107 DEG C of boiling points can be combustion-supporting, strengthen oil fuel explosive power, improve the combustion heat of composite fuel, can improve the clarity of biofuel oil simultaneously, the carbon distribution while reducing burning; The combination of isopropylcarbinol and isooctyl ester nitrate, can improve the cetane value of composite fuel significantly; The zero pour of isopropylcarbinol is-107 DEG C, with the combination of organic solvent, can effectively reduce condensation point and the cold filter clogging temperature of blended fuel.Again such as helping emulsifying dispersant, its function is that the component of this additive is effectively dispersed to concocted oil fuel, and can play and reduce carbon distribution, the effect of minimizing electrostatic accumulation prepared oil fuel, prior art is to the existing certain research of assistant for emulsifying agent, and the emulsifying dispersant that helps of the present invention, can be selected from such as, one in the derivative series product (T154A, T154B, T161A, T161B, T151, T155, T164A, T165A etc.) of succinate, polyolefinic succinimide acid polyhydroxy alkyl ester or polyisobutene, or wherein several combination; For example T161A be taking high-activity polyisobutene (molecular weight is as 2300) as raw material, the high molecular ashless dispersant that adopts hot adduction technique to prepare, there is dispersion and the solublization of good cigarette ash, greasy filth, can effectively suppress fuel oil viscosity and increase.In practical application, flexible addition of functions properties-correcting agent and be not limited to the property-modifying additive of mentioned kind as required.
Described industrial pure water is deionized water.For example, because containing many impurity in ortho-water (tap water, well water), salt and pH contained in it are different, though these impurity are micro-, can have a strong impact on the emulsion stabilizing effect of oil fuel long-term storage; The commercial run that pure water obtains is very ripe, and deionized water makes by electrodialyzer method, ion-exchanger method, reverse osmosis method with former water conventionally.The addition range of choice of pure water is relevant with the purposes of the oil fuel of made, in the time that the oil fuel of making is directly used in burning, should get below intermediate value to ensure the burning behavior of oil fuel in described span (0～45%), when the oil fuel of making is during by a certain percentage with conventional petrochemical industry fuel oil mixed firing, scope more than desirable intermediate value.
Industrial pure water described in the present invention fills a prescription, for example, by the active enhancing greatly of the physics and chemistry after high-energy processing (magnetic swashs resonance), can need to add flexibly according to purposes.In the oil fuel of polynary formula combination, the pure water adding when appropriateness can reach while fully dissolving each other in oil fuel system, experimental results show that its burning behavior is better, aspect technical project mechanism, can use the more just and more sound microexplosion theoretical explanation of current theoretical circles:
1, mechanism: under the effect of tensio-active agent and property-modifying additive, the microstructure of dissolving each other of methanol-water-oleic acid-methyl alcohol modification complex body is in a disguised form a kind of microemulsion of water-in-oil-type, when surface combustion, inner methyl alcohol and water sharply expand because of gasification volume, the immense pressure producing makes oil droplet explosion, thereby makes the further miniaturization of oil droplet, forms secondary-atomizing in combustion processes, make it to increase considerably with the contact area of air, improve efficiency of combustion.
2, accelerate combustion reaction: in the gasification of water-in-oil-type oil droplet explosion, OH group activity in multicomponent system strengthens greatly, carbon monoxide has obtained burning more completely, thereby accelerate the burning of oil fuel system coke that cracking forms, while having suppressed miscible fuel oil combustion, the generation of flue dust, reaches emission reduction effect.
Especially energy excitation is to metastable pure water for pure water, and it is the important proposition that theoretical circles are paid close attention in recent years that its space state distributes, and the combination of some Surfactants of breaking with the conventional idea is selected and is conducive to major technological breakthrough.As everyone knows, water molecules is made up of two hydrogen atoms and a Sauerstoffatom, and space is unsymmetric structure, and because hydrogen is flammable, comburant oxygen, splitting water molecule obtains the cheap energy and become the science dream of succession from generation to generation.One of the applicant proposes in patent of invention (ZL200410074446.5) application documents: be all a large amount of water molecules set to the analytic target of water so far, and subsistence logic of equal value leak of equal value whether in the microsystem of " enough little ".In recent years due to the particularly progress of data processing technique of micro-imaging, make fundamental research laboratory, various countries all can repeatedly observe the nano-scale structures of pure water, know so far: pure water is generally 13-18 molecular cluster structure, with the structure of its understanding macroscopic view water be H
2o can not show a candle to and is interpreted as nH
2o is more approaching true; Scientific circles progressively admit neodoxy: the water on macroeconomic significance is made up of water molecule cluster, and cluster size is directly linked to the physics-chem characteristic of water.
Technology Direct Electrolysis water is lost more than gain for energy cost at present, but water is miscible to multi-factor structure system by chemical process, more easily participates in the space structure restructuring approach of the micro-dispersion system of colloid by water molecules, acquisition water molecules bonding state conversion and process thereof and the cheap energy that produces.For the mechanism of water, theory is thought, being less than 94nm(nanometer) the cluster yardstick of the micro-dispersion system of colloid in, water molecules participates in fully dissolving each other forming the more complicated cluster of space structure under outside Conditioning, under the condition of high temperature, be the water molecules of unsymmetric structure, quite a few hydrogen atom can escape into free path in combustion processes and participate in reaction, " oxygen enrichment " tendency of having brought oil fuel system inside, makes it burning behavior better.The cluster space structure of multi-factor structure oil fuel forms, both relevant with main raw material selection and tensio-active agent, simultaneously also relevant to preparation method.
The preparation method of the bio-fuel-oil of described polynary formula combination comprises:
1) hydrophile-lipophile balance value of described tensio-active agent is adjusted to 10～14, rear and methyl alcohol or ethanol or its mixture and water fully mix, or palm off as deciliter even with methyl alcohol or ethanol or its mixture;
2) mixture, oleic acid, methyl alcohol modification complex body and the property-modifying additive that step 1) are obtained mix, and make bio-fuel-oil.
Wherein the addition sequence of oleic acid and property-modifying additive and feed way are flexible.Such as adding oleic acid in the mixture obtaining to step 1), then mix with methyl alcohol modification complex body; Or by after oleic acid and the mixing of methyl alcohol modification complex body, the mixture obtaining with step 1) mixes; Or add respectively oleic acid in the mixture obtaining to step 1) and methyl alcohol modification complex body, then two portions mixture is mixed.Fully be uniformly mixed with property-modifying additive more afterwards.
Step 2) in, in the time that the mixture clarity that obtains is not enough, can supplementary table surface-active agent or oleic acid, be adjusted to clear and bright by the ratio that regulates oleic acid and tensio-active agent.
Tensio-active agent described in step 1), in the time that the hydrophile-lipophile balance value of selecting single component is not in 10～14 scopes, two or more that adopt described tensio-active agent carry out composite adjusting.
While adding pure water in step 1), preferred, the mass ratio of pure water and methyl alcohol or ethanol is 1:0.5～2.0, and the mass ratio of the methyl alcohol adding or ethanol or its mixture and oleic acid is 1:0.5～3.0; While not adding pure water in described step 1), preferred, the mass ratio of the methyl alcohol adding or ethanol or its mixture and oleic acid is 1:0.5～2.5.The add-on of pure water, should be used the particularly Grasping level of Surfactant of field depending on blended fuel, also needs to consider that pure water adds the impact of the physical and chemical index such as burning behavior and viscosity, proportion on oil fuel.Generally speaking, pure water uses properly the open flash point that can improve oil fuel, bring " oxygen enrichment " tendency of oil fuel system inside simultaneously, be conducive to burn under atmospheric pressure state, and need prudent for the oil fuel in compressing ignition engine field, if the Grasping level of Surfactant is more shallow, can adds less and even not add pure water.
The mixture that step 1) obtains need to form stable emulsification system by adding oleic acid, the method step 2) optional, oleic acid both can directly add after step 1), also can all mix the mixture interpolation that backward step 1) obtains with methyl alcohol modification complex body, preferably oleic acid is split as to two parts and after step 1), add and mixing with methyl alcohol modification complex body respectively; No matter oleic acid is after step 1), add or first mix with methyl alcohol modification complex body and add in the mixture that step 1) obtains again, and in the time that the addition of oleic acid is suitable, all can form clear and bright stabilising system at normal temperature.But in concrete operations, due to the source complexity of oleic acid, and its emulsifying capacity and envrionment temperature have relation, even same source oleic acid is by same procedure operation, also can affect because being subject to low temperature clarity and the stability of formed mixture, therefore preparation method of the invention process, is recommended in the interval mixing of same temperature, for example 30～40 DEG C of temperature ranges; Preferably oleic acid addition is split as after step 1) and in methyl alcohol modification complex body and is added respectively, oleic acid addition after step 1) is to regulate the clarity of mixture as target, obtain the first mixture, the surplus oleic acid that design load is added joins in methyl alcohol modification complex body, obtain the second mixture, then, the first mixture is mixed mutually with the second mixture, stir.
For the acidity that makes the final mixture forming reaches diesel oil state scale value, can add petroleum sodium sulfonate or barium mahogany sulfonate or its mixture to regulate, make the acidity of multi-element biologic fuel oil be less than 7mg KOH/100mL.
Described preparation method can mix at normal temperatures and pressures, also the pressurization of can heating helps reaction, described stirring or mixing comprise the shearing stirring that rotary stirring, periodicity or corner cut are random, and additional magnetic swashs, and resonance mixes or reaction pressure is mixed, in the time that use adds reaction pressure mixing, reaction pressure is no more than 25MPa.Conventional compressive reaction device is easily purchased on market, swash resonance device about magnetic, " a kind of liquid energy exciting device " (ZL200410074446.5) in existing detailed description in detail, this device comprises the liquid treatment chamber (waveguide cavity) with metal or the subsidiary formed material of wire netting, the n alternately arranging with m spacing along liquid in-out mouth passage in chamber is to permanent magnet (m >=0.2mm, n >=2), built-in or be disposed in cavity have >=1 tuning-points, can make the physics-chem characteristic that is subject to processing liquid as solubleness, oxygen level, perviousness, there is larger change in speed of reaction etc.
Be worth special instruction, fully dissolving each other is the successful prerequisite of multipropellant oil systems technology, this technique effect can be tested by Tyndall (Tyndall) phenomenon, known in industry, wavelength be the light of 400-700mm when the oil fuel system, can there is scattering if homodisperse colloidal particle diameter is less than lambda1-wavelength.Current experiment conclusion is: in the time of the particle dia≤94nm of dispersion system, the biquadratic that light intensity and wavelength are hit in scattering is inversely proportional to, and Tyndall phenomenon will be clearly; Otherwise, can check out the oil fuel system of made unsuccessful.
Above-mentioned preparation method is a kind of preferably recommendation, for the more deep personnel of this area research, can carry out equivalents to the adjusting of hydrophile-lipophile balance value by preferred surfactant and in mixing process completely; For example property-modifying additive is added after step 1), or join in the mixture of oleic acid and methyl alcohol modification complex body, even be split as some parts and in different mixing steps, add respectively, make mixture become clear and bright by supplementing the relative proportion of adjustment sheet surface-active agent and oleic acid.Though these preparation technologies that are equal to replacement also can operate, under different ambient temperature conditions, easily produce a small amount of isomer, affect combustionproperty or the outward appearance clarity of fuel oil; In the combination of multicomponent material,, adopt first by aqueous-phase material by tensio-active agent be converted into oil soluble mixture and then mutually mixed with oil phase thing after add the process sequence of property-modifying additive, stability and the outward appearance clarity of the product that obtains can be better.
In specific embodiment of the invention, different selection combinations and the combination process that feeds intake, under the similar prerequisite of final mixture steady state, may there is the contradiction of clarity and burning (comprising compression ignite) proterties, the latter is often relevant to the aobvious state degree of Tyndall phenomenon.The major function of oil fuel is burning (comprising compression ignite), in the time can'tting eat one's cake and have it, recommends the optimized formula of burning behavior and process for refining.
Use the conventional petrifaction diesel that is exactly like in appearance of the multi-element biologic fuel oil that makes of the inventive method, can be directly used in burning and compressing ignition engine uses, can also with larger proportion and petrifaction diesel or methanol diesel-oil, (methanol diesel-oil comprises the common on the market diesel oil that is added with methyl alcohol or carboxylate methyl ester herein, such as the Witconol 2301 diesel oil that is main body) dissolving each other to mix uses, and has following several technical superioritys:
1, dynamic property is strong: in combination formula, main material is C
14～C
18hydrocarbon polymer, property-modifying additive is composite improves calorific value, strengthen the several important component of power, make the multi-element biologic fuel oil cetane value making generally be greater than 46, dynamic property strengthens compared with its like product, and leading indicator reaches or is better than commercially available 0# diesel oil;
2, carbon discharge capacity is few: combined additive helps oil fuel and dissolve each other into the microcapsule structure of oily armored alcohol, noxious emission CO, NO while making to burn
x, HC content obviously reduces, emission smoke intensity fall exceedes 50%, environmentally friendly;
3, versatility is good: can replace ordinary diesel oil directly to use, can meet requirement and the steady running of engine, have with the finished diesel fuel of same label mixture the scope of application being equal to;
4, applied widely: be applicable to the various different purposes such as stove, Industrial Stoves and diesel motor car, and without changing diesel motor;
5, stationary phase is long: stationary phase >=6 month, adapt to store, transport and sell the required time of each link.
Embodiment
To describe the preferred several embodiment of the present invention below, but the present invention is not limited to this.
First for the preparation of the property-modifying additive of multi-element biologic fuel oil, wherein
Property-modifying additive I, comprising:
PH value buffer reagent 20 weight parts, comprise each 10 weight parts of barium mahogany sulfonate and petroleum sodium sulfonate;
Isooctyl ester nitrate 20 weight parts;
Oxidation inhibitor 5 weight parts, are 124 Triazole compounds or amine oxygenant, and those skilled in the art can select as required flexibly;
Organic solvent 25 weight parts, comprise toluene 20 weight parts, acetone 5 weight parts;
Functional modifier 30 weight parts, comprise isopropylcarbinol 28 weight parts, and tritolyl phosphate 1.0 weight parts (optional) help emulsifying dispersant 1.0 weight parts (optional).
Property-modifying additive II, comprising:
PH value buffer reagent 50 weight parts, comprise each 25 weight parts of barium mahogany sulfonate and petroleum sodium sulfonate;
5 parts of isooctyl ester nitrates;
Oxidation inhibitor 0.5 weight part, selects T502;
Organic solvent 40 weight parts, comprise toluene 35 weight parts, ethylbenzene 5 weight parts;
Functional modifier 4.5 weight parts, comprise tritolyl phosphate 2 weight parts, succinate 0.5 weight part, isopropylcarbinol 2 weight parts.
Property-modifying additive III, comprising:
PH value buffer reagent 50 weight parts, comprise barium mahogany sulfonate 10 weight parts and petroleum sodium sulfonate 40 weight parts, depending on regulating the needs of potential of hydrogen, also both ratios can be inverted;
Isooctyl ester nitrate 6.0 weight parts;
Oxidation inhibitor 2.0 weight parts, select T502;
Organic solvent 40 weight parts, comprise toluene 35 weight parts, ethylbenzene 5 weight parts;
Functional modifier 2 weight parts, comprise tritolyl phosphate 1.5 weight parts, succinate 0.5 weight part.
Property-modifying additive IV, comprising:
PH value buffer reagent 30 weight parts, comprise barium mahogany sulfonate 14 weight parts and petroleum sodium sulfonate 16 weight parts;
Isooctyl ester nitrate 18 weight parts;
Oxidation inhibitor 2 weight parts, select T406;
Organic solvent 10 weight parts, select toluene;
Functional modifier 40 weight parts, comprise isopropylcarbinol 30 weight parts, tritolyl phosphate 5 weight parts, succinate 5 weight parts.
Property-modifying additive V, comprising:
PH value buffer reagent 50 weight parts, comprise barium mahogany sulfonate 28 weight parts and petroleum sodium sulfonate 22 weight parts;
Isooctyl ester nitrate 20 weight parts;
Oxidation inhibitor 5 weight parts, select TTAS, ZDDP, T504 equal proportion to mix;
Organic solvent 25 weight parts, the mixture of the 3:1:1 of selection toluene, ethyl acetate and t-butyl methyl ether.
Described property-modifying additive can, by raw material is directly mixed to get, also can be prepared as follows:
1) by the complete isooctyl ester nitrate that adds of organic solvent dissolution for oxidation inhibitor agent later;
2) add in the mixture in step 1) after pH value buffer reagent and functional modifier are mixed and make property-modifying additive.
Tensio-active agent, selects one or more combinations of following material: the serial emulsifying agent of sapn, twain series emulsifier, alkylsulphonic acid receive that series, thanomin, trolamine, Monoethanolamine MEA BASF, bromination hexadecyl sulfonic acid are received, dimethyl formamide, Xylo-Mucine, polyvinyl alcohol.Before using, the hydrophile-lipophile balance value of tensio-active agent is adjusted to 10～14, in the time that the one-component tensio-active agent of selecting does not meet hydrophile-lipophile balance value requirement, preferably adopts above-mentioned surfactant compound to be adjusted to 10～14.
The preparation method of multi-element biologic fuel oil is as follows:
1) hydrophile-lipophile balance value of described tensio-active agent is adjusted to 10～14, rear and methyl alcohol or ethanol or its mixture and water fully mix, or palm off as deciliter even with methyl alcohol or ethanol or its mixture;
2) mixture, oleic acid, methyl alcohol modification complex body and the property-modifying additive that step 1) are obtained mix, and make bio-fuel-oil.
Such as substep in the mixture obtaining to step 1) adds oleic acid, then mix with methyl alcohol modification complex body; Or by after oleic acid and the mixing of methyl alcohol modification complex body, the mixture obtaining with step 1) mixes; Or by adding respectively oleic acid in the mixture obtaining to methyl alcohol modification complex body and step 1), then two portions mixture is mixed.Add afterwards property-modifying additive, be fully uniformly mixed.
The preferred preparation method of multi-element biologic fuel oil is as follows:
1) hydrophile-lipophile balance value of tensio-active agent is adjusted to 10～14, rear and methyl alcohol or ethanol or its mixture and water fully mix, or palm off as deciliter even with methyl alcohol or ethanol or its mixture;
2) in the mixture obtaining to step 1), add oleic acid, make mixture become clear and bright, the oleic acid design addition after mixture change is clear and bright has surplus, joins in methyl alcohol modification complex body;
3) by step 2) there is the oleic acid of surplus to mix with methyl alcohol modification complex body;
4) by step 2) mixture that obtains with step 3) of the mixture that obtains mixes;
5) mixture obtaining to step 4) adds property-modifying additive, is fully uniformly mixed.
In preparation method, the addition of water and methyl alcohol modification complex body is 0 when different.
Optionally, in the mixture obtaining in step 5), selectivity adds petroleum sodium sulfonate or barium mahogany sulfonate or its composition, makes the acidity of the multi-element biologic fuel oil finally obtaining be less than 7mg KOH/100mL.
Because main points of the present invention are the modification to raw material, proterties and the physicochemical data of the oil fuel therefore preparing according to above-mentioned several method are similar, and those skilled in the art can select flexibly according to practical situation.
Embodiment 1,
Multi-element biologic fuel oil 1 comprises following component:
Methyl alcohol modification complex body 40 weight parts;
Oleic acid 25 weight parts;
Methyl alcohol 15 weight parts;
Tensio-active agent 2.8 weight parts
Property-modifying additive I 5.2 weight parts;
Industrial pure water 12 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Operation, finally obtains a brown oily liquids as stated above, and several the key technical indexes that record user's care are as shown in table 1.
The physicochemical data of multi-element biologic fuel oil in table 1 embodiment 1
| Flash-point, DEG C | 30 |
| Density kg/m 3 | 864.9 |
| Viscosity, mm 2/s | 4.20 |
| Condensation point, DEG C | 0 |
| Cold filter clogging temperature, DEG C | 4 |
| Cetane value | 45.1 |
By the conventional petrifaction diesel that is exactly like in appearance of the brown oily liquids of the present embodiment gained, no matter be directly burn or use 3～5:1 weight ratio mixture 0# petrifaction diesel for burning, with respect to the burning behavior of 0# petrifaction diesel, air output can reduce over half relatively, can obviously differentiate from flame profile the multi-element biologic fuel oil enough oxygen content that the present embodiment makes, sufficient combustion, carbon emission is lower.
Embodiment 2
Multi-element biologic fuel oil 2 comprises following component:
Methyl alcohol modification complex body 50 weight parts;
Oleic acid 22 weight parts;
Methyl alcohol 17 weight parts;
Tensio-active agent 3 weight parts;
Property-modifying additive IV 8 weight parts.
Above-mentioned raw materials is totally 100 weight parts, and the present embodiment is not moisture.Operation, finally obtains a brown oily liquids as stated above, and several the key technical indexes that record user's care are as shown in table 2.
The physicochemical data of multi-element biologic fuel oil in table 2 embodiment 2
| Flash-point, DEG C | 27 |
| Density kg/m 3 | 846.1 |
| Viscosity, mm 2/s | 3.86 |
| Condensation point, DEG C | 1 |
| Cold filter clogging temperature, DEG C | 5 |
| Cetane value | 46.2 |
By the brown oily liquids of the present embodiment gained, for conventional diesel engine, compression ignite operating mode is stable.Can also use 1:1 part by weight and conventional petrifaction diesel mixture, use at conventional diesel engine.
Embodiment 3
Multi-element biologic fuel oil 3 comprises following component:
Methyl alcohol modification complex body 28 weight parts;
Oleic acid 27 weight parts;
Methyl alcohol 10 weight parts, ethanol 8 weight parts;
Tensio-active agent 5 weight parts;
Property-modifying additive III 8 weight parts;
Industrial pure water 14 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Press preceding method operation, finally obtain a brown oily liquids, can obtain equally combustion efficacy similar to Example 1.
Embodiment 4
Multi-element biologic fuel oil 4 comprises following component:
Methyl alcohol modification complex body 85 weight parts;
Oleic acid 6 weight parts;
Ethanol 5 weight parts;
Tensio-active agent 1 weight part;
Property-modifying additive IV 1 weight part;
Industrial pure water 2 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Press preceding method operation, finally obtain a brown oily liquids, can obtain equally combustion efficacy similar to Example 3.
Embodiment 5
Multi-element biologic fuel oil 5 comprises following component:
Methyl alcohol modification complex body 37 weight parts;
Oleic acid 19 weight parts;
Methyl alcohol 10 weight parts, ethanol 5 weight parts;
Tensio-active agent 5 weight parts;
Property-modifying additive II 4 weight parts;
Industrial pure water 20 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Press preceding method operation, finally obtain a brown oily liquids, its burning behavior under normal pressure is similar to Example 1.
Embodiment 6
Multi-element biologic fuel oil 6 comprises following component:
Methyl alcohol modification complex body 40 weight parts;
Oleic acid 12 weight parts;
Methyl alcohol 10 weight parts;
Tensio-active agent 4 weight parts;
Property-modifying additive II 9 weight parts;
Industrial pure water 25 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Press preceding method operation, finally obtain a brown oily liquids, itself and conventional petrifaction diesel are pressed 1:2 mixture, and successfully the burning behavior after igniting is similar to Example 6.Can also use 1:1 part by weight and conventional petrifaction diesel mixture, combustion efficacy is better.
Embodiment 7,
Multi-element biologic fuel oil 7 comprises following component:
Methyl alcohol modification complex body 20 weight parts;
Oleic acid 7 weight parts;
Methyl alcohol 5 weight parts;
Tensio-active agent 8 weight parts;
Property-modifying additive I 15 weight parts;
Industrial pure water 45 weight parts.
Above-mentioned raw materials is totally 100 weight parts, and operation, finally obtains a brown oily liquids as stated above, and by 1:4 part by weight and conventional petrifaction diesel mixture, its burning behavior is similar to Example 1.
Embodiment 8,
Multi-element biologic fuel oil 8 comprises following component:
Methyl alcohol modification complex body 50 weight parts;
Oleic acid 16 weight parts;
Methyl alcohol 10 weight parts;
Tensio-active agent 5 weight parts;
Property-modifying additive IV 9 weight parts;
Industrial pure water 10 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Operation, finally obtains a brown oily liquids as stated above, and its burning behavior is similar to Example 1, similar to Example 2 for the compression ignite operating mode of conventional diesel engine.
Embodiment 9,
Multi-element biologic fuel oil 9 comprises following component:
Methyl alcohol modification complex body 20 weight parts;
Oleic acid 30 weight parts;
Methyl alcohol 25 weight parts;
Tensio-active agent 5 weight parts;
Property-modifying additive IV 6 weight parts;
Industrial pure water 14 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Operation, finally obtains a brown oily liquids as stated above, and its burning behavior is similar to Example 1.
Embodiment 10,
Multi-element biologic fuel oil 10 comprises following component:
Methyl alcohol modification complex body 5 weight parts;
Oleic acid 70 weight parts;
Methyl alcohol 5 weight parts;
Tensio-active agent 5 weight parts;
Property-modifying additive IV 12 weight parts;
Industrial pure water 3 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Operation, finally obtains a brown oily liquids as stated above, and its burning behavior is similar to Example 1, similar to Example 2 for the compression ignite operating mode of conventional diesel engine.
Embodiment 11,
Multi-element biologic fuel oil 11 comprises following component:
Methyl alcohol modification complex body 5 weight parts;
Oleic acid 5 weight parts;
Methyl alcohol 80 weight parts;
Tensio-active agent 5 weight parts;
Property-modifying additive IV 3 weight parts;
Industrial pure water 2 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Operation, finally obtains a brown oily liquids as stated above, can be used for direct burning, also can use 1:3 part by weight and conventional petrifaction diesel mixture, and its burning behavior is similar to Example 1.
Embodiment 12,
Bio-fuel-oil 12 comprises following component:
Multi-element biologic fuel oil 8 and 0# diesel oil mix with arbitrary proportion within the scope of the weight ratio of 1:0.5～2, in the time mixing clarity deficiency, add described tensio-active agent to regulate, finally obtain a brown oily liquids, its burning behavior is similar to Example 1, similar to Example 2 for the compression ignite operating mode of conventional diesel engine.The 0# diesel oil of the present embodiment also can be replaced into market common low-grade catalytic diesel oil or methanol diesel-oil, can improve burning behavior.
Above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to embodiment, those of ordinary skill in the art is to be understood that, technical scheme of the present invention is modified or is equal to replacement, do not depart from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (10)
1. a bio-fuel-oil for polynary formula combination, is characterized in that, based on the bio-fuel-oil of 100 weight parts, comprising:
Methyl alcohol modification complex body is not more than 85 weight parts, and is not 0 weight part;
Oleic acid 5～70 weight parts;
Methyl alcohol or ethanol, or its mixture 5～80 weight parts;
Tensio-active agent 1～8 weight part;
Property-modifying additive 1～15 weight part;
Industrial pure water 0～45 weight part;
Described methyl alcohol modification complex body, at least comprises one or more in following material: the ester class that ethers, methyl alcohol and the sour condensation that methyl alcohol and alcohol condensation form forms; Described industrial pure water is deionized water.
2. bio-fuel-oil according to claim 1, it is characterized in that, described tensio-active agent comprises one or more of following material: sapn series emulsifying agent, twain series emulsifier, alkylsulphonic acid are received, diethanolamine, trolamine, Monoethanolamine MEA BASF, dimethyl formamide, Xylo-Mucine, polyvinyl alcohol.
3. bio-fuel-oil according to claim 1, it is characterized in that, when described industrial pure water content is not 0 weight part, the mass ratio of described industrial pure water and methyl alcohol or ethanol or its mixture is 1:0.5～2.0, and the mass ratio of described methyl alcohol or ethanol or its mixture and described oleic acid is 1:0.5～3.0; When described bio-fuel-oil does not comprise industrial pure water, the mass ratio of described methyl alcohol or ethanol or its mixture and described oleic acid is 1:0.5～2.5.
4. bio-fuel-oil according to claim 1, is characterized in that, described property-modifying additive comprises based on 100 weight parts:
PH value buffer reagent 20～50 weight parts;
Isooctyl ester nitrate 5～20 weight parts;
Oxidation inhibitor 0.5～5 weight part;
Organic solvent 10～40 weight parts;
Functional modifier 0～40 weight part;
Described pH value buffer reagent is the composite mixture of petroleum sodium sulfonate and barium mahogany sulfonate, described petroleum sodium sulfonate accounts for 10～40 weight parts, described barium mahogany sulfonate accounts for 10～40 weight parts, and the weight of described composite mixture is not less than 20 weight parts, is no more than 50 weight parts;
Described oxidation inhibitor comprises one or more in following material: amine type oxidation inhibitor, phenol type antioxidant, phenol amine type oxidation inhibitor, sulphur phosphorus type antioxygen corrosion inhibitor, dialkyl dithiocarbamate, 124 Triazole compounds and thiadiazole compound;
Described organic solvent comprises one or more in following solvent: aromatic hydrocarbon solvent, ketones solvent, esters solvent, ether solvent and petroleum product kind solvent oil, and described petroleum product kind solvent oil comprises paraffin oil, diesel oil;
Described functional modifier comprises one or more of following material: tritolyl phosphate 0～15 weight part, help emulsifying dispersant 0～5 weight part, isopropylcarbinol 0～30 weight part.
5. biofuel according to claim 1, is characterized in that, described industrial pure water uses magnetic to swash resonance and processes.
6. a method of preparing the arbitrary described polynary formula combination bio-fuel-oil of claim 1～5, comprising:
1) hydrophile-lipophile balance value of tensio-active agent is adjusted to 10～14, rear and methyl alcohol or ethanol or its mixture, and water fully mixes; Or fully mix with methyl alcohol or ethanol or its mixture;
2) mixture, oleic acid, methyl alcohol modification complex body and the property-modifying additive that step 1) are obtained mix, and make bio-fuel-oil.
7. method according to claim 6, is characterized in that, described step 2) also comprise that the ratio by regulating oleic acid and tensio-active agent regulates clarity.
8. method according to claim 6, is characterized in that, described method also comprises in the bio-fuel-oil making and adds petroleum sodium sulfonate or barium mahogany sulfonate, makes its acidity be less than 7mg KOH/100mL.
9. method according to claim 6, is characterized in that, described step 1) and step 2) in mixing adopt and mix under normal temperature and pressure or the pressurization of heating helps reaction; Described stirring or mixing comprise the shearing stirring that rotary stirring, periodicity or corner cut are random and additional magnetic swashs resonance mixing or reaction pressure is mixed; In the time that use adds reaction pressure mixing, reaction pressure is no more than 25MPa.
10. the arbitrary described bio-fuel-oil of claim 1～5 and petrifaction diesel or methanol diesel-oil mix the oil fuel making.
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