CN103911191A - Diesel oil additive and its preparation method - Google Patents
Diesel oil additive and its preparation method Download PDFInfo
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- CN103911191A CN103911191A CN201310007205.8A CN201310007205A CN103911191A CN 103911191 A CN103911191 A CN 103911191A CN 201310007205 A CN201310007205 A CN 201310007205A CN 103911191 A CN103911191 A CN 103911191A
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Abstract
The invention provides a multiple-component combined diesel oil additive and its preparing method, the diesel oil additive includes, on the basis of 100 parts by weight, 5 to 78 parts by weight of oleic acid; 5 to 88 parts by weight of methanol or ethanol or a mixture thereof; 1 to 31 parts by weight of a surface active agent; 1 to 42 parts by weight of a modified additive and 0 to 73 parts by weight of industrial water which is added according to the concrete application. New a multiple-component biodiesel can be obtained by adding of the additive into conventional fossil diesel, a methanol modified complex or their mixture, and the biodiesel has the advantages of high cetane number, high flash point, low condensation point, low cold filter plugging point, low corrosion, low emission and low cost.
Description
Technical field
The present invention relates to fuel oil field, particularly relate to a kind of procetane 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, the oil-based solvent of methyl alcohol modification need being got married solves the problem of dissolving each other, exist methyl alcohol and diesel oil to be difficult to fully to dissolve each other, 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 described biofuel in the market, on Witconol 2301 subjective basis, to add ignition dope to form mostly, there is the defect that condensation point is high, cold filter clogging temperature is high, corrodibility is strong and cost performance is not enough, be badly in need of a kind of improve its combustionproperty especially compression ignite performance, improve the additive of its comprehensive cost performance.
Summary of the invention
The object of the invention is to: a kind of diesel-dope based on the multiple conventional biological raw material such as methyl alcohol or ethanol, oleic acid and petroleum chemicals additive mixture is provided, and visual concrete purposes is added pure water, it can join by a certain percentage in common petrifaction diesel, methyl alcohol modification complex body or its mixture and use, 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 object, the present invention uses the colloid surface principles of chemistry, solve the modification of methyl alcohol or ethanol or its mixture and pure water and dissolved each other with oleic acid low cost, add the technical barrier that can keep good combustion proterties in diesel oil to larger proportion after modification, the oil fuel stable system phase that multiple starting material are dissolved each other is long, is beneficial to transport deposit; Especially by the compound action of tensio-active agent and property-modifying additive, make miscible diesel oil or biofuel oil form stable microcapsule structure, effectively reach the object of sufficient combustion, reduction carbon emission amount.
For achieving the above object, the invention provides the additive of the biofuel that a kind of polynary formula combination forms, based on 100 weight parts, comprising:
Oleic acid 5～78 weight parts;
Methyl alcohol or ethanol or its mixture 5～88 weight parts;
Tensio-active agent 1～31 weight part;
Property-modifying additive 1～42 weight part;
Industrial pure water is not more than 73 weight parts;
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, 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.
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
+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.
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 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 described diesel-dope 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) in the mixture obtaining to step 1), add property-modifying additive and oleic acid, make product.Oleic acid can add step by step, also can once add, and the order adding is also very flexible, such as adding oleic acid to make mixture become clear and bright in the mixture obtaining to step 1), afterwards by property-modifying additive and with step 2) mixture that obtains is fully uniformly mixed.
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 institute's blending fuel oil.Generally speaking, pure water uses properly the open flash point that can improve additive and institute's blending fuel oil thereof, bring " oxygen enrichment " tendency of oil fuel system inside simultaneously, be conducive to burn under atmospheric pressure state, need cautiously for the fuel oil additive in compressing ignition engine field, if the Grasping level of Surfactant is more shallow, can adds less and even not add pure water.
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.
Step 2) in concrete operations, because of 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, in the mixture preferably obtaining in step 1), substep adds oleic acid, to regulate the clarity of mixture and viscosity to the best as actual addition, for example first adding design flow 30～70%(is oleic acid total content) oleic acid, then react 3～10 minutes; In the time that mixture is muddy, within every 1～2 minute, add the oleic acid that accounts for methyl alcohol or ethanol or its mixture 1～3% weight ratio, until mixture change is clear and bright.Synthesis rate is had to the industrial production of requirement, be recommended in the interval mixing of same temperature, for example 30～40 DEG C of temperature ranges operations.
Optionally, can regulate by the ratio of final adjusting oleic acid and tensio-active agent the clarity of product, the batching source of wherein said property-modifying additive has compared with more options, its selection and step 2) the flash-point index of the mixture that obtains is relevant, in the time that diesel-dope of the present invention is used fuel oil intermediate as business, should avoid selecting low-flash material, such as toluene, methylcarbonate etc., to improve the security that stores and transport; Material in property-modifying additive can also be divided into two portions, high flash point material is in step 2) after sneak into, low-flash material be split as coordinate this additive use attached auxiliary agent, auxiliary agent adds in the time of mixture diesel oil again.When step 2) the mixture clarity deficiency that obtains or viscosity is when too large, can supplementary table surface-active agent or oleic acid, clear and bright by regulating the ratio of oleic acid and tensio-active agent to be adjusted to, viscosity meets the requirements.
In order to make the acidity of additive reach conventional diesel oil state scale value, can be to step 2) add petroleum sodium sulfonate or barium mahogany sulfonate or its mixture in the mixture that obtains, make its acidity 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, can fully dissolve each other with institute's mixture diesel oil is the prerequisite that described additive is successful, this technique effect can be tested by the Tyndall to institute's mixture diesel oil (Tyndall) phenomenon, known in industry, wavelength be the light of 400-700mm when the fuel oil 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.The Tyndall phenomenon of institute's mixture diesel oil is obvious, illustrates that the making of this additive reaches technical project target; Otherwise, can check out the additive 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 is split as after step 1) and step 2) after 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 additive, step 2) add again after completing the product stability of property-modifying additive 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 described diesel-dope is combustion-supporting 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.
The obvious technical superiority of this additive is to be fabricated to a kind of extensively applicable fuel oil intermediate, can be designed as high flash point commodity, stationary phase is long, be convenient to store and transport, when use, can make an addition to common petrifaction diesel with larger ratio, methyl alcohol modification complex body or both mixtures, described methyl alcohol modification complex body, at least comprise one or more in following material: the ethers (for example t-butyl methyl ether) that methyl alcohol and alcohol condensation form, the ester class that methyl alcohol and sour condensation form is (as diethyl carbonate, Witconol 2301), it adds the addition that can effectively reduce petrifaction diesel, save 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 the low-temperature fluidity of institute's mixture diesel oil simultaneously, while specifically manufacture, can add as one sees fit.
Use the multi-element biologic diesel oil that this additive makes to there are following several advantages:
1, dynamic property is strong: property-modifying additive is composite improves calorific value, strengthen the several important component of power, the multi-element biologic diesel cetane-number that has made to add additive and make is generally greater than 46, dynamic property strengthens compared with its like product, and leading indicator can reach or be 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, there is with the finished diesel fuel of same label mixture the scope of application being equal to, be applicable to the various different purposes such as stove, Industrial Stoves and diesel motor car, and without changing diesel motor;
4, 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 diesel 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 preferred preparation method of described diesel-dope 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) in the mixture obtaining to step 1), add oleic acid to make mixture become clear and bright;
3) to step 2) add property-modifying additive in the mixture that obtains, be fully uniformly mixed, make diesel-dope.
Optionally, in the diesel-dope obtaining to step 3), add petroleum sodium sulfonate or barium mahogany sulfonate, make the acidity of the diesel-dope finally obtaining be less than 7mg KOH/100mL.In addition the additive in step 3 also can add after step 1, or takes apart respectively and add after step 1 and step 2, and it does not affect the combustionproperty of the product making.
Embodiment 1,
Diesel-dope 1 comprises following component:
Oleic acid 35 weight parts;
Methyl alcohol 27 weight parts;
Tensio-active agent 6 weight parts
Property-modifying additive I12 weight part;
Industrial pure water 20 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Operation, finally obtains a brown oily liquids as stated above, records several the key technical indexes of user's care as shown in table 1a.
The physicochemical data of diesel-dope in table 1a embodiment 1
| Flash-point, DEG C | 33 |
| Density kg/m 3 | 873.6 |
| Viscosity, mm 2/s | 4.17 |
| Condensation point, DEG C | 0 |
| Cold filter clogging temperature, DEG C | 4 |
The part by weight mixture that this brown oily additive and conventional 0# petrifaction diesel and methyl alcohol modification complex body are pressed to 10:15:5, records several the key technical indexes that user is concerned about as shown in table 1b.
The physicochemical data of table 1b embodiment 1 mixture multi-element biologic diesel oil
| Flash-point, DEG C | 33 |
| Density kg/m 3 | 857.6 |
| Viscosity, mm 2/s | 3.96 |
| Condensation point, DEG C | 1 |
| Cold filter clogging temperature, DEG C | 5 |
| Cetane value | 45.1 |
The brown oily liquids of the present embodiment mixture gained is used for to 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 diesel oil enough oxygen content that the present embodiment mixture makes, sufficient combustion, carbon emission is lower.
Embodiment 2
Diesel-dope 2 comprises following component:
Oleic acid 45 weight parts;
Methyl alcohol 32 weight parts;
Tensio-active agent 8 weight parts;
Property-modifying additive IV 15 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 additive in table 2 embodiment 2
| Flash-point, DEG C | 31 |
| Density kg/m 3 | 846.2 |
| Viscosity, mm 2/s | 3.86 |
| Condensation point, DEG C | -7 |
| Cold filter clogging temperature, DEG C | -2 |
| Cetane value | 46.1 |
The brown oily liquids of the present embodiment gained is added in diesel oil and (accounts for diesel oil volume ratio 30%) as additive, and for conventional diesel engine, compression ignite operating mode is stable, and soot emission is few.
Embodiment 3
Diesel-dope 3 comprises following component:
Oleic acid 32 weight parts;
Methyl alcohol 25 weight parts;
Tensio-active agent 5 weight parts;
Industrial pure water 30 weight parts;
Property-modifying additive I8 weight part.
Above-mentioned raw materials is totally 100 weight parts, by preceding method operation, obtains a brown oily liquids, adds in diesel oil and (adds the additive that accounts for diesel oil volume ratio 15%), and its burning behavior under normal pressure is similar to Example 1.
Embodiment 4
Diesel-dope 4 comprises following component:
Oleic acid 78 weight parts;
Methyl alcohol 3 weight parts, ethanol 2 weight parts;
Tensio-active agent 5 weight parts;
Property-modifying additive III7 weight part;
Industrial pure water 5 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Press preceding method operation, finally obtain a brown oily liquids, join in diesel oil by 40% weight ratio, can obtain equally diesel engine compression ignite operating mode effect similar to Example 2.
Embodiment 5
Diesel-dope 5 comprises following component:
Oleic acid 5 weight parts;
Ethanol 88 weight parts;
Tensio-active agent 3 weight parts;
Property-modifying additive IV 3 weight parts;
Industrial pure water 1 weight part.
Above-mentioned raw materials is totally 100 weight parts.Press preceding method operation, finally obtain a brown oily liquids, can be used for direct burning, join in diesel oil by 15% weight ratio, can obtain equally combustion efficacy similar to Example 1.
Embodiment 6
Diesel-dope 6 comprises following component:
Oleic acid 15 weight parts;
Methyl alcohol 17 weight parts;
Tensio-active agent 6 weight parts;
Property-modifying additive II42 weight part;
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, can be used for direct burning, join in diesel oil the burning behavior under normal pressure by 15% weight ratio similar to Example 1.
Embodiment 7
Diesel-dope 7 comprises following component:
Oleic acid 7 weight parts;
Methyl alcohol 5 weight parts;
Tensio-active agent 31 weight parts;
Property-modifying additive II11 weight part;
Industrial pure water 46 weight parts.
Above-mentioned raw materials is totally 100 weight parts, by preceding method operation, finally obtains a brown oily liquids, joins in diesel oil by 15% weight ratio, and its burning behavior is similar to Example 6.
Embodiment 8,
Diesel-dope 8 comprises following component:
Oleic acid 32 weight parts;
Methyl alcohol 30 weight parts;
Tensio-active agent 11 weight parts;
Property-modifying additive I16 weight part;
Industrial pure water 11 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Operation, finally obtains a brown oily liquids as stated above, joins in oleic acid methyl alcohol by 20% weight ratio, 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,
Diesel-dope 9 comprises following component:
Oleic acid 5 weight parts;
Methyl alcohol 5 weight parts;
Tensio-active agent 5 weight parts;
Property-modifying additive I12 weight part;
Industrial pure water 73 weight parts.
Above-mentioned raw materials is totally 100 weight parts.Operation, finally obtains a brown oily liquids as stated above, joins in oleic acid methyl alcohol by 10% weight ratio, and its burning behavior is similar to Example 1, similar to Example 2 for the compression ignite operating mode of conventional diesel engine.
Embodiment 10,
Diesel-dope 10 comprises following component:
Oleic acid 66 weight parts;
Methyl alcohol 20 weight parts;
Tensio-active agent 1 weight part;
Property-modifying additive I1 weight part;
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, joins in oleic acid methyl alcohol by 10% weight ratio, and its burning behavior is similar to Example 1.
Embodiment 11,
Multi-element biologic diesel oil 1 comprises following component:
Additive 30 weight parts that embodiment 3 makes, 0# diesel oil 70 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 12,
Multi-element biologic diesel oil 2 comprises following component:
Additive 35 weight parts that embodiment 4 makes, Witconol 2301 35 weight parts, 0# diesel oil 30 weight parts.
Above-mentioned raw materials is totally 100 weight parts, is mixed to get a brown oily liquids, and its burning behavior is similar to Example 1, similar to Example 2 for the compression ignite operating mode of conventional diesel engine.
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 procetane, is characterized in that, based on the additive of 100 weight parts, comprising:
Oleic acid 5～78 weight parts;
Methyl alcohol or ethanol or its mixture 5～88 weight parts;
Tensio-active agent 1～31 weight part;
Property-modifying additive 1～42 weight part;
Industrial pure water is not more than 73 weight parts;
Described industrial pure water is deionized water.
2. additive 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. additive 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.
4. additive 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 biofuel 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.
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 diesel-dope 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) in the mixture obtaining to step 1), add oleic acid and property-modifying additive, make diesel-dope.
7. method according to claim 6, is characterized in that, described step 2) also comprise that ratio by regulating oleic acid and tensio-active agent regulates the clarity of product.
8. method according to claim 6, is characterized in that, described method also comprises in diesel-dope and adds petroleum sodium sulfonate, barium mahogany sulfonate or its mixture, 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. contain conventional petrifaction diesel, methyl alcohol modification complex body or its mixture of the arbitrary described diesel-dope of claim 1～5, described methyl alcohol modification complex body, at least comprises one or more of ester class that ethers, methyl alcohol and sour condensation that methyl alcohol and alcohol condensation form form.
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| CN105602637A (en) * | 2016-01-13 | 2016-05-25 | 山东联星能源集团有限公司 | Fuel gas assistant capable of reducing harmful substance in automobile exhaust |
| CN108485734A (en) * | 2018-04-12 | 2018-09-04 | 江门市优能新能源科技有限公司 | A kind of composite environment-friendly fuel-economizing decarbonizer |
| CN108546574A (en) * | 2018-05-15 | 2018-09-18 | 杨勇 | Biological alcohol-based fuel power heat value agent |
| CN108913230A (en) * | 2018-05-08 | 2018-11-30 | 桂林茂兴新能源科技有限公司 | Energy-saving discharge-reducing methanol diesel oil |
| CN108913231A (en) * | 2018-05-08 | 2018-11-30 | 桂林茂兴新能源科技有限公司 | A kind of methanol diesel for vehicle |
| CN109337725A (en) * | 2018-12-04 | 2019-02-15 | 苏州西姆提纳米科技有限公司 | A kind of diesel fuel additives and its application |
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| CN105602637A (en) * | 2016-01-13 | 2016-05-25 | 山东联星能源集团有限公司 | Fuel gas assistant capable of reducing harmful substance in automobile exhaust |
| CN108485734A (en) * | 2018-04-12 | 2018-09-04 | 江门市优能新能源科技有限公司 | A kind of composite environment-friendly fuel-economizing decarbonizer |
| CN108913230A (en) * | 2018-05-08 | 2018-11-30 | 桂林茂兴新能源科技有限公司 | Energy-saving discharge-reducing methanol diesel oil |
| CN108913231A (en) * | 2018-05-08 | 2018-11-30 | 桂林茂兴新能源科技有限公司 | A kind of methanol diesel for vehicle |
| CN108546574A (en) * | 2018-05-15 | 2018-09-18 | 杨勇 | Biological alcohol-based fuel power heat value agent |
| CN109337725A (en) * | 2018-12-04 | 2019-02-15 | 苏州西姆提纳米科技有限公司 | A kind of diesel fuel additives and its application |
| CN109456807A (en) * | 2019-01-04 | 2019-03-12 | 广东交通职业技术学院 | A kind of diesel fuel additives and its preparation method and application |
| CN109456807B (en) * | 2019-01-04 | 2021-02-19 | 广东交通职业技术学院 | Diesel oil additive and preparation method and application thereof |
| CN114672352A (en) * | 2022-03-25 | 2022-06-28 | 安徽速收宝网络科技有限公司 | Diesel vehicle power combustion cleaning agent |
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