CN103224824A - Additive for reducing diesel engine PM2.5 emission and application thereof - Google Patents
Additive for reducing diesel engine PM2.5 emission and application thereof Download PDFInfo
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- CN103224824A CN103224824A CN2013101584142A CN201310158414A CN103224824A CN 103224824 A CN103224824 A CN 103224824A CN 2013101584142 A CN2013101584142 A CN 2013101584142A CN 201310158414 A CN201310158414 A CN 201310158414A CN 103224824 A CN103224824 A CN 103224824A
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Abstract
The present invention relates to an additive for reducing diesel engine PM2.5 emission and an application thereof. The additive is a mixture of a peroxide and an azo compound, wherein the peroxide is a peroxide with a carbon number of 8-24, and is one or a plurality of materials selected from a tert-butyl peroxide, a peroxide organic ester, or a peroxide dicarbonate, and the azo compound is azobisisobutylnitrile, 2,2'-azobis(2,4-dimethyl)valeronitrile or isopropyl azodiformate. The application comprises: adding the additive to a diesel fuel, wherein the additive content is 300-3000 ppm relative to the diesel fuel content. With the present invention, diesel engine PM2.5 emission is significantly reduced; the additive-containing diesel fuel does not produce ash during burning so as not to provide wear for the diesel engine; a good match performance of the peroxide composition and the diesel fuel is provided; the peroxide has a mild reaction temperature; the process is simple; and the product and the diesel fuel are easily mixed so as to provide high practicality.
Description
Technical field
The invention belongs to the environmental protection field, be specifically related to a kind of additive that reduces diesel motor PM2.5 discharging.
Background technology
Along with the quickening of vehicle diesel oil trend in the world wide, the demand of diesel oil can be more and more big.PM2.5 mainly comes from motor vehicle in the topsoil, the PM2.5 overwhelming majority of automotive emission comes from diesel vehicle, the major cause that diesel engine discharged particle produces is because fuel combustion is inhomogeneous, part of fuel incomplete combustion, oxidation under the high temperature anoxia condition, cracking and form.Therefore countries in the world are more and more stricter to the restriction of diesel particulate emission, and for the requirement of the Abgasgesetz that reaches increasingly stringent, the technical measures of diesel particulate emission are all reduced in countries in the world at active development at present.
In the face of on a large scale, the long-time haze weather that occurs, the air contaminant treatment especially motor vehicle exhaust problem of administering is highlighted once more.PM2.5 is meant that diameter is less than or equal to 2.5 microns particulate matter in the atmosphere, is also referred to as and can goes into the lung particulate matter.The residue that discharges through burning in the processes such as its main source motor vehicle exhaust, industrial production also can cause great harm to HUMAN HEALTH.According to statistics, in Europe, PM2.5 causes 386000 people's death every year, and makes European Union member countries' average life expectancy reduce 8.6 months.PM2.5 is easy to the hazardous and noxious substances in the enriched air By, and can enter in the body along with people's breathing, even enters into alveolar and blood, causes various diseases.It still is the arch-criminal that visibility meter reduces, and according to the study, because the pollution of PM2.5, the visibility meter of the U.S. only is 30% of nature visibility meter; Particulate matter also has certain influence to weather, and it causes global cooling by directly influencing weather with indirect two kinds of approach.
Chinese patent CN102559336A relates to the agent of a kind of vehicle exhaust PM2.5 pollutant control, adopts methyl alcohol, ferrocene, butanols, nano lanthanum oxide, nano-cerium oxide, potassium permanganate, methyl isopropyl ether, aluminium acetylacetonate, the dodecyl alkenyl succinic acid, urea, different propionic aldehyde, polyene-based succimide, Manganse Dioxide, ethanol etc. are prepared from.
Chinese patent ZLO1814887.5 has proposed a kind of method of improving fuel at combustion unit internal combustion efficient and minimizing discharge, it is by with fuel dope, be at least aly to be coated with alkyl to complete the particulate state bright-coloured that acid joins be oxide compound, oxidation decorations especially, disperse realizes in fuel.
200480007843.9 of Chinese patent application have been described a kind of method that improves burning efficiency of internal combustion engine, promptly install the titanium dioxide decorations nano particle of the titanium dioxide decorations nano particle that adds the additive that acts as a fuel in the forward direction fuel or the metal that mixed at introducing fuel to the vehicle that comprises oil engine or other.
Chinese patent application CN101555423 discloses a kind of environmental-friendly and energy-saving catalytic combustion diesel oil, and by the CeO of diesel oil and high stable: the single dispersion of nanometer is mixed in proportion formulated at normal temperatures and pressures.
Chinese patent CN1465673 relates to a kind of multifunctional diesel oil, additive for heavy oil, and its composition is mixture, lipid acid cobalt, calcium naphthenate, polyisobutene succinimide, longer chain fatty acid of lipid acid cerium or lipid acid lanthanum or lipid acid cerium and lipid acid lanthanum etc.
Chinese patent CN1447848 relates to a kind of minimizing by diesel oil and fuel oil combustion granular material discharged additive that produces and the composition that contains described additive, and this additive is made of metal oxidation catalyst, organic nitrates and dispersion agent.
Chinese patent CN101439261 relates to a kind of emission of diesel engine cobalt oxide and cerium oxide catalyst for purifying particulate and preparation method, this catalyzer is the double oxide composite catalyst, especially support on nano ceric oxide by cobalt or the body of cobalt and cerium mutually mixed oxide form.
Chinese patent CN102732331A has related to a kind of petrochemical industry bio oil methyl alcohol synthetic (low PM2.5) diesel oil and preparation method thereof, comprises fatty acid ester of low-carbon alcohol, ammoniacal liquor, formations such as methyl alcohol and diesel oil.
Chinese patent CN1470618 relates to a kind of ashless diesel-dope and preparation method thereof and using method, by sorbitan monostearate, alkyl alcohol Soxylat A 25-7 and derivative, alkylphenol polyoxyethylene and derivative thereof, alcohol contract oxalic dialdehyde,, middle carbon alcohol, solvent oil forms, can improve the combustionproperty of diesel oil, keep the cylinder cleaning, reduce incomplete combustion, reduce the discharging of CO, NOx, HC and PM pollutent in the tail gas.
Above-mentioned these additives in use all can reduce the granular material discharged of diesel motor, owing to contain metallic element, as ferrocene, nano lanthanum oxide, nano-cerium oxide, potassium permanganate, aluminium acetylacetonate, Manganse Dioxide, these patent compounds can be produced certain ash content in combustion processes, and diesel motor is had certain wearing and tearing.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of additive that reduces diesel motor PM2.5 discharging, make the PM2.5 discharging of diesel motor that remarkable reduction be arranged, and can not produce ash content in combustion processes, whether diesel motor is worn and torn.
The additive of minimizing diesel motor PM2.5 discharging of the present invention, additive is the mixture of superoxide and azo-compound.
Rerum natura and structure from superoxide and azo-compound, with diesel motor diesel quality is required to combine consideration, because superoxide and azo-compound are under the condition of diesel motor work, can produce and a large amount of contain oxygen, contain nitrogen free radical, promote diesel combustion, reduce the generation of the PM2.5 of diesel motor, so this additive has good emission reduction effect on the diesel motor stand, can reduce the particle content in the diesel engine exhaust, especially the content of PM2.5 particulate matter.
Superoxide is the superoxide of carbonatoms between 8-24.
Superoxide is one or more in tert-butyl peroxide, peroxidation organic ester or the peroxy dicarbonate.
The molecular formula of tert-butyl peroxide is ((CH
3)
3COO)
2C (CH
3) R, R is the C1-C14 alkyl; The molecular formula of peroxidation organic ester is R
1COOOR
2, R
1, R
2Be the C1-C13 alkyl; The molecular formula of peroxy dicarbonate is R
3O (CO) OO (CO) OR
4, R
3, R
4Be the C1-C13 alkyl.
Tert-butyl peroxide is preferably a kind of in di-tert-butyl peroxide acetone, di-tert-butyl peroxide butanone, di-tert-butyl peroxide pentanone, diisobutyryl peroxide, peroxidation two (3,5, the 5-trimethyl acetyl) or the two lauroyl of peroxidation; The peroxidation organic ester is preferably peroxidation neodecanoic acid tertiary butyl ester, peroxidation trimethylacetic acid tertiary butyl ester, diethyl peroxide caproic acid tertiary butyl ester, peroxidation phenylformic acid tertiary butyl ester, di-t-butyl peroxide ester, peroxidation neodecanoic acid 2,4, a kind of in 4-trimethylammonium pentyl ester or the peroxidation neodecanoic acid isopropyl ester; Peroxy dicarbonate is preferably a kind of in two (2-oxyethyl group) ethyl esters of peroxy dicarbonate or two (2-ethyl) the own esters of peroxy dicarbonate.
Azo-compound is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azoformic acid isopropyl ester.
The weight ratio of superoxide and azo-compound is 1～100:1.
The Application of Additives of described minimizing diesel motor PM2.5 discharging is: additive is joined in the diesel oil, and additive is 300-3000ppm with respect to the content of diesel oil.Described diesel oil is commercially available No. 0 diesel oil ,-No. 10 diesel oil ,-No. 20 diesel oil or-No. 35 diesel oil.Have and reduce the granular material discharged of diesel motor or diesel vehicle preferably, especially reduce the effect of PM2.5 discharging.
In sum, the present invention has the following advantages:
(1) the present invention adopts additive, has overcome the limitation of conventional art, has developed brand-new additive utilisation technology route, makes the PM2.5 discharging of diesel motor that remarkable reduction be arranged.
(2) diesel oil that contains additive of the present invention can not produce ash content in combustion processes, and whether diesel motor is worn and torn.
(3) has good matching property between this additive and the diesel oil.And, the temperature of reaction gentleness of this superoxide, technology is simple, and product is easy to mix with diesel oil, has very high practicality.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
Get 2.97 kilograms in di-tert-butyl peroxide acetone, get 0.03 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 1 after mixing.
Embodiment 2
Get 1.96 kilograms of di-tert-butyl peroxide butanone, get 0.04 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 2 after mixing.
Embodiment 3
Get 0.9 kilogram of di-tert-butyl peroxide pentanone, get 0.1 kilogram of 2,2'-Azobis(2,4-dimethylvaleronitrile), join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 3 after mixing.
Embodiment 4
Get 0.15 kilogram in di-tert-butyl peroxide acetone, get 0.15 kilogram of 2,2'-Azobis(2,4-dimethylvaleronitrile), join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 4 after mixing.
Embodiment 5
Get 1.5 kilograms of peroxidation neodecanoic acid tertiary butyl ester, get 0.5 kilogram of azoformic acid isopropyl ester, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 5 after mixing.
Embodiment 6
Get 1.5 kilograms of peroxidation trimethylacetic acid tertiary butyl ester, get 0.5 kilogram of azoformic acid isopropyl ester, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 6 after mixing.
Embodiment 7
Get 1.5 kilograms of diethyl peroxide caproic acid tertiary butyl ester, get 0.5 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 7 after mixing.
Embodiment 8
Get 1.8 kilograms of peroxidation phenylformic acid tertiary butyl ester, get 0.2 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 8 after mixing.
Embodiment 9
Get 1.8 kilograms of di-t-butyl peroxide esters, get 0.2 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 9 after mixing.
Embodiment 10
Get peroxidation neodecanoic acid 2,4,1.5 kilograms of 4-trimethylammonium pentyl esters are got 0.5 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 10 after mixing.
Embodiment 11
Get 1.5 kilograms of peroxidation neodecanoic acid isopropyl esters, get 0.5 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 11 after mixing.
Embodiment 12
Get 1.5 kilograms of two (2-oxyethyl group) ethyl esters of peroxy dicarbonate, get 0.5 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 12 after mixing.
Embodiment 13
Get 1.5 kilograms of diisobutyryl peroxides, get 0.5 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 13 after mixing.
Embodiment 14
Get 1.5 kilograms of two (2-ethyl) own esters of peroxy dicarbonate, get 0.5 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 14 after mixing.
Embodiment 15
Get two (3,5, the 5-trimethyl acetyl) 1.5 kilograms of peroxidation, get 0.5 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 15 after mixing.
Embodiment 16
Get 1.5 kilograms of the two lauroyl of peroxidation, get 0.5 kilogram of Diisopropyl azodicarboxylate, join in 1000 kilograms of No. 0 diesel oil, obtain Dresel fuel compositions 16 after mixing.
Comparative Examples
The Dresel fuel compositions 1-16 that on the diesel motor test-bed, embodiment 1-16 is prepared and do not contain No. 0 diesel oil of superoxide additive and test according to GB/T18297-2001 " motor car engine method for testing performance " and GB/T17691-2005 " automobile-used compression-ignited, geseous fuel spark ignition engine and automobile exhaust pollutant discharge limit value and measuring method (Chinese III, IV, V stage) ", on the diesel motor stand, test, detect the granular material discharged data of diesel motor.Testing tool has electric eddy current dynamometer (GW160), Intelligent Fuel Consumption Instrument (FC2210), engine exhaust analytical system (MEXA7100), engine exhaust particulate matter analytical system (MDLT-1302TMA) and diesel motor (JX493ZLQ3).
Fixing diesel motor operating parameter in test, engine revolution is 1400r/min, loads to be 30kW, measures the particulate matter pollutent data in diesel motor exhaust this moment, sees Table 1.
Granular material discharged test result in table 1 diesel motor exhaust
| Sample | PM2.5/(g/kW·h) |
| No. 0 diesel oil | 1.93 |
| Dresel fuel compositions 1 | 0.62 |
| Dresel fuel compositions 2 | 0.75 |
| Dresel fuel compositions 3 | 0.93 |
| Dresel fuel compositions 4 | 1.17 |
| Dresel fuel compositions 5 | 0.79 |
| Dresel fuel compositions 6 | 0.77 |
| Dresel fuel compositions 7 | 0.72 |
| Dresel fuel compositions 8 | 0.69 |
| Dresel fuel compositions 9 | 0.78 |
| Dresel fuel compositions 10 | 0.83 |
| Dresel fuel compositions 11 | 0.92 |
| Dresel fuel compositions 12 | 0.63 |
| Dresel fuel compositions 13 | 0.71 |
| Dresel fuel compositions 14 | 0.75 |
| Dresel fuel compositions 15 | 0.79 |
| Dresel fuel compositions 16 | 0.88 |
As can be seen from Table 1: compare No. 0 diesel oil that does not contain the superoxide additive, the quantity discharged of the PM2.5 of the Dresel fuel compositions 1-16 that embodiment 1-16 prepares has remarkable reduction.
Claims (10)
1. one kind is reduced the additive that diesel motor PM2.5 discharges, and it is characterized in that: additive is the mixture of superoxide and azo-compound.
2. the additive of minimizing diesel motor PM2.5 discharging according to claim 1, it is characterized in that: superoxide is the superoxide of carbonatoms between 8-24.
3. the additive of minimizing diesel motor PM2.5 discharging according to claim 1, it is characterized in that: superoxide is one or more in tert-butyl peroxide, peroxidation organic ester or the peroxy dicarbonate.
4. the additive of minimizing diesel motor PM2.5 discharging according to claim 3 is characterized in that: the molecular formula of tert-butyl peroxide is ((CH
3)
3COO)
2C (CH
3) R, R is the C1-C14 alkyl; The molecular formula of peroxidation organic ester is R
1COOOR
2, R
1, R
2Be the C1-C13 alkyl; The molecular formula of peroxy dicarbonate is R
3O (CO) OO (CO) OR
4, R
3, R
4Be the C1-C13 alkyl.
5. the additive of minimizing diesel motor PM2.5 discharging according to claim 4, it is characterized in that: tert-butyl peroxide is di-tert-butyl peroxide acetone, di-tert-butyl peroxide butanone, di-tert-butyl peroxide pentanone, diisobutyryl peroxide, peroxidation two (3,5,5-trimethyl acetyl) a kind of or in the two lauroyl of peroxidation.
6. the additive of minimizing diesel motor PM2.5 discharging according to claim 4, it is characterized in that: the peroxidation organic ester is peroxidation neodecanoic acid tertiary butyl ester, peroxidation trimethylacetic acid tertiary butyl ester, diethyl peroxide caproic acid tertiary butyl ester, peroxidation phenylformic acid tertiary butyl ester, di-t-butyl peroxide ester, peroxidation neodecanoic acid 2,4, a kind of in 4-trimethylammonium pentyl ester or the peroxidation neodecanoic acid isopropyl ester; Peroxy dicarbonate is a kind of in two (2-oxyethyl group) ethyl esters of peroxy dicarbonate or two (2-ethyl) the own esters of peroxy dicarbonate.
7. the additive of minimizing diesel motor PM2.5 discharging according to claim 1, it is characterized in that: azo-compound is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azoformic acid isopropyl ester.
8. the additive of minimizing diesel motor PM2.5 discharging according to claim 1, it is characterized in that: the weight ratio of superoxide and azo-compound is 1～100:1.
9. the Application of Additives of the arbitrary described minimizing diesel motor PM2.5 discharging of a claim 1-8, it is characterized in that: additive is joined in the diesel oil, and additive is 300-3000ppm with respect to the content of diesel oil.
10. the Application of Additives of minimizing diesel motor PM2.5 discharging according to claim 9, it is characterized in that: described diesel oil is commercially available No. 0 diesel oil ,-No. 10 diesel oil ,-No. 20 diesel oil or-No. 35 diesel oil.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101584142A CN103224824A (en) | 2013-05-02 | 2013-05-02 | Additive for reducing diesel engine PM2.5 emission and application thereof |
| CN201310310804.7A CN103361133B (en) | 2013-05-02 | 2013-07-23 | Azo compound containing additive for reducing PM2.5 emission of diesel engines and application of azo compound containing additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101584142A CN103224824A (en) | 2013-05-02 | 2013-05-02 | Additive for reducing diesel engine PM2.5 emission and application thereof |
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|---|---|
| CN103224824A true CN103224824A (en) | 2013-07-31 |
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ID=48835473
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|---|---|---|---|
| CN2013101584142A Pending CN103224824A (en) | 2013-05-02 | 2013-05-02 | Additive for reducing diesel engine PM2.5 emission and application thereof |
| CN201310310804.7A Active CN103361133B (en) | 2013-05-02 | 2013-07-23 | Azo compound containing additive for reducing PM2.5 emission of diesel engines and application of azo compound containing additive |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310310804.7A Active CN103361133B (en) | 2013-05-02 | 2013-07-23 | Azo compound containing additive for reducing PM2.5 emission of diesel engines and application of azo compound containing additive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016187798A1 (en) * | 2015-05-26 | 2016-12-01 | 高化学株式会社 | Vehicle fuel additive composition and use thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7332001B2 (en) * | 2003-10-02 | 2008-02-19 | Afton Chemical Corporation | Method of enhancing the operation of diesel fuel combustion systems |
| EP2032810B1 (en) * | 2006-05-18 | 2012-03-14 | Clean Diesel Technologies, Inc. | Improvements in diesel particulate control |
| JP5625641B2 (en) * | 2010-09-06 | 2014-11-19 | 信越化学工業株式会社 | Plastic substrate for automotive glazing |
-
2013
- 2013-05-02 CN CN2013101584142A patent/CN103224824A/en active Pending
- 2013-07-23 CN CN201310310804.7A patent/CN103361133B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016187798A1 (en) * | 2015-05-26 | 2016-12-01 | 高化学株式会社 | Vehicle fuel additive composition and use thereof |
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| Publication number | Publication date |
|---|---|
| CN103361133A (en) | 2013-10-23 |
| CN103361133B (en) | 2015-04-22 |
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Application publication date: 20130731 |