CN103387857A - Nanometer fuel oil catalytic additive - Google Patents
Nanometer fuel oil catalytic additive Download PDFInfo
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- CN103387857A CN103387857A CN2013103570712A CN201310357071A CN103387857A CN 103387857 A CN103387857 A CN 103387857A CN 2013103570712 A CN2013103570712 A CN 2013103570712A CN 201310357071 A CN201310357071 A CN 201310357071A CN 103387857 A CN103387857 A CN 103387857A
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Abstract
The invention relates to a nanometer fuel oil catalytic additive which has good dispersity and lubricity, can be used for assisting the fuel oil to combust fully and is environmentally-friendly. The granular nanometer fuel oil catalytic additive comprises the following components in parts by weight: 1-10% of nanometer catalyst, 90-99% of xylogen and 0.1-1% of water. A preparation method of the nanometer fuel oil catalytic additive comprises the following steps of: mixing the nanometer catalyst, the soluble xylogen and water in parts by weight, and prilling through a screw extruder. A liquid nanometer fuel oil catalytic additive comprises 100 parts by weight of solvent, 0.5-1 part of nanometer catalyst, and 5-10 parts of xylogen. A preparation method of the liquid state nanometer fuel oil catalytic additive comprises the following steps of: mixing the nanometer catalyst, the soluble xylogen, the solvent, polyethylene glycol and other addition agents in parts by weight, and uniformly stirring and mixing in a speed of 60 rpm (revolutions per minute) at 20 DEG C till the liquid state nanometer fuel oil catalytic additive is in a stable state.
Description
Technical field
The present invention relates to a kind of fuel oil catalytic additive, specifically, is a kind of nano fuel catalytic additive.
Background technology
Along with the increase of recent year locomotive stock, the consumption of the oil fuel such as gasoline, diesel oil is day by day soaring, needs a large amount of Imported oils to meet domestic market demand, and the demand of exploitation economizing additive and alternative oil product is more and more urgent.Existing gasoline (or diesel oil) branched paraffin is few, octane value (cetane value) is low, easily produce the phenomenon of detonation of fuel and air mixed spontaneous combustion, cause fuel combustion insufficient, produce the nuisances such as carbon monoxide, nitrogen oxide and unburned hydrocarbon polymer, black smoke, influence ecological environment and human health; The solid matters such as coke that incomplete combustion produces also can be adsorbed on the bottom of throttling valve, form settling, reduce the suction of engine air, and affect exhaust emissions, make air and fuel ratio depart from suitable scope, further worsen engine internal combustion situation, in the work-ing life of reducing engine, increase fuel oil consumption.
In order to reach the purpose of fuel-economizing, minimizing carbon deposit, cleaning of off-gas, now developed many fuel oil additives, can reduce the generation of exhaust gas smoke, minimizing carbon deposit as economizing additive.The main purpose of fuel oil additive is combustion-supporting, minimizing carbon deposit, the protection engine.Existing fuel oil additive is mainly purification agent, octane promoter, pour point depressant of simple function etc., and market plane is mainly purification agent to the human consumer, to clean the carbon distribution function as main, even if there is its effect of other subsidiary functions also very limited, the oil-burning apparatus that even causes that has damages, technical barrier never is resolved, thus cause the public praise of additives industries market and acceptance very poor.
The fuel oil additive component is many, and production technique is more complicated, and production cost is high, and has individual compound to be difficult to obtain.simultaneously, now save energy, protection of the environment, minimizing are polluted and by many countries, paid attention to, its pollution problem of saving oily resource and solution exhaust emissions is the requirements of people to modern fuel oil for this reason, existing by add the active ingredient that excites fuel oil as catalyzer in fuel oil, but salts substances is ionic compound, can isolate metal positive ion and acid ion in solution, although the electrostatic attraction between ion and the ionic linkage that produces is relatively firm, but the high temperature of its generation is enough to have the energy of opening chemical bond when oil inflame, make it isolate metal ion and acid ion, and acid ion meeting attack metal parts, and when opening chemical bond, molecule absorbs energy always, therefore, use salts substances to have the work-ing life of certain energy waste and shortening working equipment as catalyzer, also have by adding when the nano metal ion particles activates fuel oil and reduce toxic ingredient in the fuel oil volatilization thing, but metal ion wherein still can cause wearing and tearing to working equipment, at the solution fuel oil, fully do not burn, solve the problem that reduces the working equipment injury in the time of protection of the environment.
Summary of the invention
The objective of the invention is to obtain a kind of nano fuel catalytic additive, to overcome existing nano fuel catalytic additive environmental pollution and dispersed defect.
The present invention also provides a kind of preparation method of nano fuel catalytic additive.
A kind of nano fuel catalytic additive according to the present invention comprises particulate state nano fuel catalytic additive and liquid nano fuel oil catalytic additive.Particulate state nano fuel catalytic additive according to the present invention comprises the nanocatalyst of 1-10% by mass, and 90% to 99% soluble lignin.According to liquid nano fuel oil catalytic additive of the present invention, take solvent as 100 weight parts as reference, comprise by mass for the nanocatalyst between the 1-10 weight part, by mass the soluble lignin between the 5-10 weight part and by mass the molecular weight of 0.5-2 be 200～600 liquid no color or smell polyoxyethylene glycol.
Described a kind of nano fuel catalytic additive also comprises octane promoter, and described octane promoter is selected from methyl cyclopentyl-dialkyl-tricarbon manganium (MMT), methyl tertiary butyl ether (MTBE), tert amyl methyl ether(TAME) (TAME) etc.,
Described a kind of nano fuel catalytic additive also comprises oxidation inhibitor, and described oxidation inhibitor mainly is selected from phenol type antioxidant, amine type oxidation inhibitor and minute amine type oxidation inhibitor.
Described a kind of nano fuel catalytic additive also comprises metal passivator, and described metal passivator is selected from N, N '-two inferior bigcatkin willow-1, the alkyl phenate of 2-propylene diamine, compound organic amine etc.
The present invention, according to the acting principle of oil-burning apparatus, fundamentally solves the energy-conserving and emission-cutting technology problem.All to produce heat energy, heat energy is changed into the principle of kinetic energy through engine system again by oil inflame based on oil-burning apparatus, maintenance reparation, the performance boost of research engine, and catalysis fuel oil improving combustion efficiency two aspects, the oil inflame efficiency of nano fuel catalytic additive of the present invention is high, the engine transformation efficiency is high, has solved oil-burning apparatus maintenance and an energy-conserving and emission-cutting technology difficult problem.
Nano fuel catalytic additive effect of the present invention: by nanocatalyst and soluble lignin, make additive can gentle Safety Sweep carbon distribution, colloid and coking, increase the wearing and tearing of oil product oilness minimizing to oil nozzle and combustion system of engine, repair engine damage and gap and strengthen resistance to air loss lifting power, catalysis promoting fuel combustion rate stops carbon distribution regeneration, strengthens stability, the oxidation-resistance of oil product.
Embodiment
Below, the embodiment that the present invention relates to is described.In addition, the present invention, the embodiment that not the following describes, the restriction of embodiment.
Nanocatalyst
The nanocatalyst that the present invention uses is selected the nano-noble metal solid catalyst, nano transition metal oxides catalyzer, other nano-metal-oxide catalyzer.
Nanocatalyst is preferentially selected the nano-noble metal solid catalyst.
Precious metal in described nano-noble metal solid catalyst is Pt, Pd, Au nano-noble metal.
Transition metal oxide in described nano transition metal oxides catalyzer is TiO
2,, CeO
2, Mn
2O
3, the transition metal such as CuO steady oxide.
Other metals in described other nano-metal-oxide catalyzer are generally Al
2O
3
For nano particle, along with reducing of particle, its specific surface area significantly increases, and surface atom number shared ratio in whole Particle Cluster also greatly increases, and the increase of surface atom number causes the increase of surface atom coordination nonsaturation, thereby has produced
A large amount of outstanding keys and unsaturated link(age) etc.Surface step, gauffer and defect also increase thereupon, and this just makes nanoparticle have high surfactivity.
The nano-noble metal solid catalyst shows very high activity and selectivity in catalyzed reaction, closely related with microtexture and the character of catalyzer.In general, the precious metal in nano-noble metal catalyst mainly exists with nano level form graininess.
Nano-noble metal is the highest active combustion catalysis material, has very high low-temperature catalytic burning active, the most representational is Pt metal, the catalytic activity of Pt nanoparticle is more much better than than bulk metal platinum, due to nanometer Pt particle because specific surface area is large, have small-size effect, quantum size effect, macro quanta tunnel effect etc., compare with platinum and demonstrate excellent catalytic performance, can be used for monomer polymerization, organic redox etc.
Described carrier nanometer catalyst is the compound catalyzer of nano-noble metal and other metal oxides.
Described carrier nanometer catalyst is selected nanometer Pt/Al
2O
3Catalyzer, nanometer Au/TiO2 catalyzer etc.
Carrier nanometer catalyst ratio nano precious metal solid catalyst has better catalytic activity.
For loaded catalyst, precious metal with nano level form particulate state high dispersive on carrier.For unsupported catalyst, precious metal exists with nano level form graininess or the nano level form metal cluster form of high dispersive.
The method for preparing carrier nanometer catalyst is the precipitator method, is about to aqueous metal salt and precipitation agent and adds respectively in stirred pot, generates the method for solid precipitation.
By adding nano metal or nano-metal-oxide, nano fuel catalytic additive of the present invention can have that burning facilitation effect, cigarette ash reduce effect, NOx reduces effect, simultaneously, nanocatalyst, also as carrier, helps dispersion and the dissolving of nano fuel catalytic additive in fuel.Can realize that fuel consumption reduces several percentage points.
Xylogen
Because of the monomer difference, xylogen can be divided into 3 types: the syringyl lignin (syringyllignin that is formed by Syringa oblata Lindl. base propane structure monomer polymerization, the S-xylogen), guaiacyl xylogen (the guaiacyllignin that is formed by guaiacyl propane structure monomer polymerization, the G-xylogen) and the p-hydroxy phenyl xylogen (hydroxy-phenyllignin, H-xylogen) that is formed by p-hydroxy phenyl propane structure monomer polymerization; Gymnosperm is mainly guaiacyl xylogen (G), and dicotyledons mainly contains guaiacyl-syringyl lignin (G-S), and monocotyledons is guaiacyl-Syringa oblata Lindl. base-p-hydroxy phenyl xylogen (G-S-H).Originally xylogen is insoluble to any solvent.
Condensation or degraded because having occurred in separating lignin, and many physical propertiess have changed, and dissolving properties also changes thereupon to some extent, thereby arranged dividing of soluble lignin and insoluble xylogen, and the former is amorphous structure, and latter is the morphological structure of raw fibre.
Nano fuel catalytic additive of the present invention is selected soluble lignin.
Available soluble lignin comprises: ethanol xylogen, alkali lignin, nitric acid xylogen, biological xylogen, phenol xylogen.
The preparation method of ethanol xylogen, alkali lignin, nitric acid xylogen, biological xylogen, phenol xylogen is by add ethanol, alkali, nitric acid, biology, phenol in the script xylogen, dissolves and obtains.
The effect of soluble lignin in the nano fuel catalytic additive:
1. xylogen is pure natural substance, is also simultaneously the abundantest organism of second in the world, renewable easy degraded, and the nano fuel catalytic additive does not pollute the environment while revealing.
2. soluble lignin contains many rings macromolecule organic of many negative electricity group, and metal ion is had stronger avidity.In the nano fuel catalytic additive, xylogen can adsorb nano metal or nano-metal-oxide., as the carrier of metallic catalyst, play dissemination.After loaded with nano metal or nano-metal-oxide, the reunion of xylogen and water-retaining capacity reduce.Xylogen after load can be stabilized in system.
3., by having added xylogen, reduced the wearing and tearing of metal catalyst particles to parts, can also effectively to carbon distribution, clear up simultaneously.
The present invention combines soluble lignin with nanocatalyst, described nanocatalyst is the carrier of xylogen, to improve the dispersion of xylogen in fuel oil, dissolve and to mix effect.
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The form of nano fuel catalytic additive
Nano fuel catalytic additive of the present invention can be particulate state and liquid state.
Particulate state:
Particulate state nano fuel catalytic additive of the present invention,, in weight part, preferably comprise the nanocatalyst of 1-10%, and 90% to 99% soluble lignin.If the content of nanocatalyst is greater than 10%, cost is too high, is not suitable for marketing.If the content of nanocatalyst, less than 1%, can reduce the catalytic efficiency of catalyzer.
Particulate state nano fuel catalytic additive of the present invention is a kind of mode of solid nano fuel oil catalytic additive, and is to be a granulated into coarse grained shape by the nano-catalytic immunomodulator compounds., about particle diameter, be preferably 0.1mm to 30mm, more preferably 1mm to 5mm.During less than 0.1mm, due to dust, the operation workability may be very poor when particle diameter.During greater than 30mm, due to the flocculation resistance that reduces, the dispersed and stability in fuel may reduce when particle diameter.
Can also add the water of 0.1%-1% in the present invention, to increase the bonding between nanocatalyst and soluble lignin.
?
Liquid:
Liquid nano fuel oil catalytic additive is that nanocatalyst and soluble lignin are dissolved in solvent, and described solvent includes but not limited to ethanol, white oil, gasoline, diesel oil.
Preferred white oil, the more preferably mixture of white oil and ethanol.
Following weight part is all take 100 parts of solvents as reference:
The content of nanocatalyst:
Because nano metal or nano-metal-oxide have very high activity, thus the addition of nano metal or nano-metal-oxide between the 0.5-1 weight part (take white oil 100 weight parts as with reference to).The catalytic efficiency that can reduce catalyzer is arranged lower than 0.5 weight part, and composition is too high higher than 1 weight part, also affects simultaneously the stability of system.
?
The content of soluble lignin:
Soluble lignin content between the 5-10 weight part,, lower than 5 weight parts, can't play the effect of loaded with nano catalyzer, can't not be worn by guard block.Higher than 10 weight parts, easily reunite between soluble lignin, soluble lignin is difficult for perfect combustion when burning.
Liquid nano fuel oil catalytic additive of the present invention can also comprise following material:
Polyoxyethylene glycol
Polyoxyethylene glycol (PEG),, also referred to as polyethylene oxide (PEO) or polyoxyethylene (POE), refer to oligomer or the polymkeric substance of oxyethane.Polyoxyethylene glycol is nontoxic, nonirritant, has good water-solublely, and with many organic matter components, good intermiscibility is arranged.The different in kind according to the relative molecular mass difference, from the no color or smell thick liquid to waxy solid.Be liquid under molecular weight 200～600 normal temperature, molecular weight just gradually becomes semi-solid 600 above persons, along with the increase of molecular weight, and the corresponding reduction of its wettability power.
It is 200～600 liquid no color or smell polyoxyethylene glycol that polyoxyethylene glycol of the present invention is selected molecular weight, and molecular weight is generally purer oligomer at the polyoxyethylene glycol of 200～600 scopes, dispersed than tool.
Be 200～600 liquid no color or smell polyoxyethylene glycol by comprising molecular weight, nano fuel catalytic additive of the present invention is diffusion rapidly, is dispersed in fuel oil, can make fuel combustion fully, reduce the effect of NOx, reduce the generation of carbon distribution etc.
Polyethyleneglycol content is (take white oil 100 weight parts as reference) between the 0.5-2 weight part,, lower than 0.5 weight part, can't play the effect of dispersing nanometer fuel oil catalytic additive, and fuel is burnt as much as possible fully., higher than 2 weight parts, can make polyoxyethylene glycol decompose volatilization.
Other auxiliary agents
Nano fuel catalytic additive of the present invention also comprises octane promoter, oxidation inhibitor, metal passivator.
Octane promoter is selected from methyl cyclopentyl-dialkyl-tricarbon manganium (MMT), methyl tertiary butyl ether (MTBE), tert amyl methyl ether(TAME) (TAME) etc.The consumption of octane promoter is 0.003 weight part (take white oil 100 weight parts as reference).
Oxidation inhibitor is selected from 2,6-di-tertiary butyl methyl phenol (T501), N-phenyl-N '-secondary-butyl-p-phenylenediamine, 2, and 6-di-t-butyl-1-dimethyl p-cresol etc., the consumption of oxidation inhibitor are 0.002-0.004 weight part (take white oil 100 weight parts as reference).
Metal passivator is selected from N, N '-two inferior bigcatkin willow-1, the alkyl phenate of 2-propylene diamine, compound organic amine etc.The consumption of metal passivator is 0.005 weight part (take white oil 100 weight parts as reference).
The manufacture method of a kind of nano fuel catalytic additive of the present invention is:
Particulate state nano fuel catalytic additive
Nanocatalyst, soluble lignin, water are mixed by forming weight part, through the screw extrusion press extruding pelletization.
Liquid nano fuel oil catalytic additive
Nanocatalyst, soluble lignin, solvent, polyoxyethylene glycol and other auxiliary agents are mixed by forming weight part, and be uniformly mixed until liquid nano fuel oil catalytic additive is in steady state under 20 ℃ and 60rpm.
Specific embodiment
The test mode of the measurement of combustionvelocity is as follows:
By using differential thermal analysis system, diesel oil as the 10mg that will wherein add liquid nanometer fuel oil catalytic additive of the present invention, temperature rise rate with 100 ℃/min is heated to 500 ℃, and burning (ml represents that the carbon slag produces the quality of terminal), then remain on 500 ℃ of lower times, by quality minimizing curve calculation TG (thermogravimetric analysis) the carbon slag combustionvelocity constant of the carbon slag (m2 represents the quality of 95% point of ignition) that produces.Airshed is 100ml/min.Following formula is used for method of calculation.
TG carbon slag combustionvelocity constant=A * T * In (m1/m2)/τ ... (I)
A: constant
T: temperature
M1: the carbon slag produces the quality of terminal
The quality of m2:95% point of ignition
τ: (m2-m1) time
Particulate state nano fuel catalytic additive (embodiment 1-4)
The test mode of particulate state nano fuel catalytic additive stability test is as follows:
When stirring, prepare the nano fuel catalytic additive under 20 ℃ and 60rpm, and by measuring number of seconds, estimate until xylogen is dissolved in the dissolution rate in the A bunker A oil fully.Estimate the stability of the solution that obtains after the at room temperature standing week.
" very good " refers to dissolve fully,
" well " refers to almost dissolve,
" qualified " refers to can be observed a small amount of insoluble substance,
" bad " refers to can be observed very many insoluble substances.
Test result is shown in following table
The nano fuel catalytic additive component of above-described embodiment 1-4 is passed through the Screw Extrusion granulation.The nano fuel catalytic additive (namely 0.5%) that adds 1g in 200g diesel oil.Test in a manner mentioned above the TG carbon slag combustionvelocity constant of nano fuel catalytic additive of the present invention.
Liquid nano fuel oil catalytic additive (embodiment 5-10)
The test mode of liquid nano fuel oil catalytic additive stability test is as follows:
When stirring, by the composition shown in following table, prepare the nano fuel catalytic additive under 20 ℃ and 60rpm, and by measuring number of seconds, estimate until xylogen is dissolved in the dissolution rate in the A bunker A oil fully.Estimate the stability of the solution that obtains after the at room temperature standing week.
" very good " refers to dissolve fully,
" well " refers to almost dissolve,
" qualified " refers to can be observed a small amount of insoluble substance,
" bad " refers to can be observed very many insoluble substances.
Test result is shown in following table.
Said components is uniformly dispersed in dispersion agent after, add the nano fuel catalytic additive (namely 0.1%) of 0.2g in 200g diesel oil.Test in a manner mentioned above the TG carbon slag combustionvelocity constant of nano fuel catalytic additive of the present invention.
?
Liquid nano fuel oil catalytic additive embodiment 11-16
Test result is shown in following table.
Said components is uniformly dispersed in dispersion agent after, add the nano fuel catalytic additive (namely 0.1%) of 0.2g in 200g diesel oil.Test in a manner mentioned above the TG carbon slag combustionvelocity constant of nano fuel catalytic additive of the present invention.
After tested, the liquid nanometer fuel oil catalytic additive that soluble lignin combines with nanocatalyst is " well " and " very good " through the result that stability test goes out, therefore, can prove that liquid nanometer fuel oil catalytic additive of the present invention is very excellent aspect all of estimation of stability.Undertaken finding that nano fuel catalytic additive of the present invention can improve oil inflame efficiency after the test of TG carbon slag combustionvelocity constant by the fuel oil that adds nano fuel catalytic additive of the present invention.The nano fuel catalytic additive that soluble lignin combines with nanocatalyst is found after tested afterwards, the effect the when dispersiveness after described nano fuel catalytic additive use soluble lignin mixture, nano-catalytic agent composition, solvent mixture and efficiency of combustion all are better than a kind of soluble lignin of use, nanocatalyst, solvent.Nano fuel catalytic additive of the present invention when guaranteeing dispersion agent and improving the fuel combustion efficiency effect, also has the effect of environmental protection.
Claims (10)
1. a nano fuel catalytic additive, is characterized in that, described nano fuel catalytic additive, comprise nanocatalyst and soluble lignin.
2. a kind of nano fuel catalytic additive according to claim 1, it is characterized in that, described nanocatalyst is selected from one or several in nano-noble metal solid catalyst, nano transition metal oxides catalyzer, other nano-metal-oxide catalyzer, carrier nanometer catalyst.
3. a kind of nano fuel catalytic additive according to claim 1, is characterized in that described soluble lignin comprises: ethanol xylogen, alkali lignin, nitric acid xylogen, biological xylogen, phenol xylogen.
4. the described a kind of nano fuel catalytic additive of any one claim according to claim 1 to 3, is characterized in that described nano fuel catalytic additive, in weight part, comprises the nanocatalyst of 1-10% and the soluble lignin of 90-99%.
5. a kind of nano fuel catalytic additive according to claim 4, is characterized in that,, in weight part, also comprises the water of 0.1-1%.
6. the described a kind of nano fuel catalytic additive of any one claim according to claim 1 to 3, is characterized in that described nano fuel catalytic additive, in weight part, comprises following component and weight part
Nanocatalyst 0.5-1
Soluble lignin 5-10
Solvent 100.
7. a kind of nano fuel catalytic additive according to claim 6, is characterized in that, described solvent comprises ethanol, white oil, gasoline, diesel oil.
8. a kind of nano fuel catalytic additive according to claim 6, is characterized in that, described nano fuel catalytic additive can also comprise polyoxyethylene glycol.
9. make the method as the described a kind of nano fuel catalytic additive of any one claim in claim 1,2,3,5, it is characterized in that described manufacture method is for nanocatalyst, soluble lignin, water are mixed by forming weight part, through the screw extrusion press extruding pelletization.
10. make the method as the described a kind of nano fuel catalytic additive of any one claim in claim 6,7,8, it is characterized in that described manufacture method for nanocatalyst, soluble lignin, solvent are mixed by forming weight part, and be uniformly mixed until liquid nano fuel oil catalytic additive is in steady state under 20 ℃ and 60rpm.
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| CN106221833A (en) * | 2016-08-25 | 2016-12-14 | 桂林市味美园餐饮管理有限公司 | A kind of nanometer diesel fuel additives |
| CN106433821A (en) * | 2016-08-25 | 2017-02-22 | 桂林市味美园餐饮管理有限公司 | Nanometer gasoline additive |
| CN106520233A (en) * | 2016-08-25 | 2017-03-22 | 桂林市味美园餐饮管理有限公司 | Nano fuel oil additive |
| CN108707487A (en) * | 2018-05-23 | 2018-10-26 | 桐乡市五轮工贸有限公司 | A kind of new energy water and its processing method |
| CN112111307A (en) * | 2020-09-01 | 2020-12-22 | 姜跃跃 | Composite fuel oil additive and preparation method thereof |
| CN115717089A (en) * | 2022-11-14 | 2023-02-28 | 上海锱碳节能环保技术有限公司 | Method and system for improving fuel energy efficiency and fuel thereof |
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| CN103387857B (en) | 2015-07-15 |
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