CN103382405B - Hexamine-containing additive capable of reducing PM2.5 emissions of diesel engines and application - Google Patents
Hexamine-containing additive capable of reducing PM2.5 emissions of diesel engines and application Download PDFInfo
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- CN103382405B CN103382405B CN201310312340.3A CN201310312340A CN103382405B CN 103382405 B CN103382405 B CN 103382405B CN 201310312340 A CN201310312340 A CN 201310312340A CN 103382405 B CN103382405 B CN 103382405B
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Abstract
The invention relates to a hexamine-containing additive capable of reducing PM2.5 emissions of diesel engines and an application of the additive. The additive comprises peroxide and hexamine. The number of carbon atoms of the peroxide is in a range of 8-24, and the peroxide is one or more of tert-butyl peroxide, organic ester peroxide or dicarbonate ester peroxide. The application comprises that the additive is added into diesel, and the relative quantity of the additive to the diesel is 300-3000ppm. By the aid of the additive, the PM2.5 emissions of the diesel engines are greatly reduced. Ash content is not produced during combustion of the diesel containing the additive, and the diesel engines are free from abrasions. The good coordination performance is achieved between the peroxide composition and the diesel. The reaction temperature of the peroxide is moderate, technologies are simple, products can be mixed with the diesel easily, and the additive is high in practicability.
Description
Technical field
The invention belongs to field of Environment Protection, be specifically related to a kind of additive containing vulkacit H and the application thereof that reduce diesel motor PM2.5 discharge.
Background technology
Along with the quickening of diesel oil of vehicle trend in world wide, the demand of diesel oil can be more and more large.In topsoil, PM2.5 mainly comes from motor vehicle, 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 uneven, part of fuel incomplete combustion, is oxidized, cracking and being formed under high temperature condition.Therefore countries in the world are more and more stricter to the restriction of diesel particulate emission, and in order to reach the requirement of the Abgasgesetz of increasingly stringent, the technical measures of diesel particulate emission are all reduced in current countries in the world at active development.
The haze weather occurred in the face of on a large scale, for a long time, the air contaminant treatment problem that especially motor vehicle exhaust is administered is highlighted again.PM2.5 refers to that in air, diameter is less than or equal to the particulate matter of 2.5 microns, also referred to as entering lung particulate matter.The residue of the discharge 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 dead 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 enriched air, and can enter in body along with the breathing of people, even enters into alveolar and blood, causes various disease.The arch-criminal that it or visibility meter reduce, according to the study, due to the pollution of PM2.5, the visibility meter of the U.S. is only 30% of nature visibility meter; Particulate matter also has a certain impact to weather, and it, by directly affecting weather with indirect two kinds of approach, causes global cooling.
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, dodecyl alkenyl succinic acid, urea, isopropyl aldehyde, polyene-based succimide, Manganse Dioxide, ethanol etc. are prepared from.
Chinese patent ZLO1814887.5 proposes and a kind ofly improves the method for fuel at combustion unit combustion efficiency and emissions reduction thing, it is by by fuel dope, namely at least one is coated with alkyl and completes the particulate state bright-coloured system oxide compound that acid joins, and be especially oxidized decorations, disperse realizes in fuel.
Chinese patent application 200480007843.9 describes a kind of method improving burning efficiency of internal combustion engine, namely introduce fuel to comprise in the vehicle of oil engine or other device forward direction fuel add as fuel dope titanium dioxide decorations nano particle or be doped with the titanium dioxide decorations nano particle of metal.
Chinese patent application CN101555423 discloses a kind of environmental-friendly and energy-saving catalytic combustion diesel oil, the CeO by diesel oil and high stable: nanometer single dispersing body 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 the mixture, lipid acid cobalt, calcium naphthenate, polyisobutene succinimide, longer chain fatty acid etc. of lipid acid cerium or lipid acid lanthanum or lipid acid cerium and lipid acid lanthanum.
Chinese patent CN1447848 relates to the granular material discharged additive that a kind of minimizing is produced by diesel oil and fuel oil combustion and the composition containing described additive, and this additive is made up 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 double oxide composite catalyst, especially supports on nano ceric oxide by cobalt or cobalt forms with the body phase mixed oxide of cerium.
Chinese patent CN102732331A relate to a kind of petrochemical industry bio oil methanol-fueled CLC (low PM2.5) diesel oil and preparation method thereof, comprises fatty acid ester of low-carbon alcohol, ammoniacal liquor, the formation 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 ethoxylates and derivative thereof, alkylphenol polyoxyethylene and derivative thereof, alcohol contract oxalic dialdehyde, middle carbon alcohol, solvent oil form, the combustionproperty of diesel oil can be improved, maintenance cylinder cleans, reduce incomplete combustion, reduce the discharge of CO, NOx, HC and PM pollutent in tail gas.
These additives above-mentioned in use all can reduce the granular material discharged of diesel motor, due to containing metallic element, as ferrocene, nano lanthanum oxide, nano-cerium oxide, potassium permanganate, aluminium acetylacetonate, Manganse Dioxide, these patents can produce certain ash content in combustion processes, have certain wearing and tearing to diesel motor.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of additive containing vulkacit H reducing diesel motor PM2.5 and discharge, the PM2.5 of diesel motor is discharged and has remarkable reduction, and can not ash content be produced in combustion processes, whether diesel motor is worn and torn.
The additive containing vulkacit H that minimizing diesel motor PM2.5 of the present invention discharges, additive is the mixture of superoxide and vulkacit H.
From physical property and the structure of superoxide and vulkacit H, require to combine consideration to diesel quality with diesel motor, because superoxide and vulkacit H are under the condition of diesel motor work, can produce a large amount of containing oxygen, containing 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 diesel engine machine frame, the particle content in diesel engine exhaust can be reduced, especially the content of PM2.5 particulate matter.
Wherein: superoxide is preferably the superoxide of carbonatoms between 8-24.
Superoxide is one or more in tert-butyl peroxide, peroxidation organic ester or peroxy dicarbonate.
The molecular formula of tert-butyl peroxide is ((CH
3)
3cOO)
2c (CH
3) R, R be C1-C14 alkyl; The molecular formula of peroxidation organic ester is R
1cOOOR
2, R
1, R
2for C1-C13 alkyl; The molecular formula of peroxy dicarbonate is R
3o (CO) OO (CO) OR
4, R
3, R
4for C1-C13 alkyl.
Tert-butyl peroxide is preferably the one in di-tert-butyl peroxide acetone, di-tert-butyl peroxide butanone, di-tert-butyl peroxide pentanone, diisobutyryl peroxide, peroxidation two (3,5,5-trimethyl acetyl) or the two lauroyl of peroxidation.
Peroxidation organic ester is preferably peroxidation neodecanoic acid tertiary butyl ester, peroxidation trimethylacetic acid tertiary butyl ester, diethyl peroxide caproic acid tertiary butyl ester, peroxybenzoate, di-t-butyl peroxide ester, peroxidation neodecanoic acid 2, one in 4,4-trimethylammonium pentyl ester or peroxidation neodecanoic acid isopropyl ester.
Peroxy dicarbonate is preferably the one in two (2-oxyethyl group) ethyl ester of peroxy dicarbonate or two (2-ethyl) the own ester of peroxy dicarbonate.
The weight ratio of superoxide and vulkacit H is 1 ~ 100:1.
Being applied as of the additive containing vulkacit H that described minimizing diesel motor PM2.5 discharges: joined by additive in diesel oil, additive is 300-3000ppm relative 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 preferably the granular material discharged of diesel motor or diesel vehicle, especially reduce the effect of PM2.5 discharge.
In sum, the present invention has the following advantages:
(1) the present invention adopts additive, overcomes the limitation of conventional art, develops brand-new additive application technological line, and the PM2.5 of diesel motor is discharged remarkable reduction.
(2) whether the diesel oil containing additive of the present invention can not produce ash content in combustion processes, wear and tear to diesel motor.
(3) between this additive and diesel oil, there is good matching property.Further, the temperature of reaction of this superoxide is gentle, and technique is simple, and product is easy to mix with diesel oil, has very high practicality.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
Get 2.97 kilograms, di-tert-butyl peroxide acetone, get vulkacit H 0.03 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 1.
Embodiment 2
Get di-tert-butyl peroxide butanone 1.96 kilograms, get vulkacit H 0.04 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 2.
Embodiment 3
Get di-tert-butyl peroxide pentanone 0.9 kilogram, get vulkacit H 0.1 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 3.
Embodiment 4
Get 0.15 kilogram, di-tert-butyl peroxide acetone, get vulkacit H 0.15 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 4.
Embodiment 5
Get peroxidation neodecanoic acid tertiary butyl ester 1.8 kilograms, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 5.
Embodiment 6
Get peroxidation trimethylacetic acid tertiary butyl ester 1.5 kilograms, get vulkacit H 0.5 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 6.
Embodiment 7
Get diethyl peroxide caproic acid tertiary butyl ester 1.5 kilograms, get vulkacit H 0.5 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 7.
Embodiment 8
Get peroxybenzoate 1.8 kilograms, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 8.
Embodiment 9
Get di-t-butyl peroxide ester 1.8 kilograms, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 9.
Embodiment 10
Get peroxidation neodecanoic acid 2,4,4-trimethylammonium pentyl ester 1.8 kilograms, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 10.
Embodiment 11
Get peroxidation neodecanoic acid isopropyl ester 1.8 kilograms, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 11.
Embodiment 12
Get two (2-oxyethyl group) ethyl ester 1.8 kilograms of peroxy dicarbonate, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 12.
Embodiment 13
Get diisobutyryl peroxide 1.8 kilograms, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 13.
Embodiment 14
Get two (2-ethyl) the own ester 1.8 kilograms of peroxy dicarbonate, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 14.
Embodiment 15
Get two (3,5, the 5-trimethyl acetyl) 1.8 kilograms of peroxidation, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 15.
Embodiment 16
Get the two lauroyl 1.8 kilograms of peroxidation, get vulkacit H 0.2 kilogram, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 16.
Comparative example
Comparative example 1
Get tertbutyl peroxide 1.5 kilograms, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 17.
Comparative example 2
Get ditertiary butyl peroxide 2 kilograms, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 18.
Comparative example 3
Get 3 kilograms, di-tert-butyl peroxide acetone, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 19.
Comparative example 4
Get peroxidation neodecanoic acid tertiary butyl ester 2 kilograms, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 20.
Comparative example 5
Get diethyl peroxide caproic acid tertiary butyl ester 2 kilograms, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 21.
Comparative example 6
Get peroxybenzoate 2 kilograms, join in 1000 kilograms of No. 0 diesel oil, after mixing, obtain Dresel fuel compositions 22.
Test
The Dresel fuel compositions 1-16 that diesel motor test-bed prepares embodiment 1-16 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) " and do not contain Peroxide Additives No. 0 diesel oil and test, diesel engine machine frame is tested, detects 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).
Fix in test diesel motor operating parameter, engine revolution is 1400r/min, and load is 30kW, measures the Particulate Pollution thing data in now diesel motor exhaust, in 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 | 0.67 |
| Dresel fuel compositions 2 | 0.68 |
| Dresel fuel compositions 3 | 1.00 |
| Dresel fuel compositions 4 | 1.25 |
| Dresel fuel compositions 5 | 0.80 |
| Dresel fuel compositions 6 | 0.77 |
| Dresel fuel compositions 7 | 0.77 |
| Dresel fuel compositions 8 | 0.75 |
| Dresel fuel compositions 9 | 0.80 |
| Dresel fuel compositions 10 | 0.85 |
| Dresel fuel compositions 11 | 0.97 |
| Dresel fuel compositions 12 | 0.73 |
| Dresel fuel compositions 13 | 0.75 |
| Dresel fuel compositions 14 | 0.76 |
| Dresel fuel compositions 15 | 0.88 |
| Dresel fuel compositions 16 | 0.89 |
| Dresel fuel compositions 17 | 1.63 |
| Dresel fuel compositions 18 | 1.44 |
| Dresel fuel compositions 19 | 1.03 |
| Dresel fuel compositions 20 | 1.27 |
| Dresel fuel compositions 21 | 1.41 |
| Dresel fuel compositions 22 | 1.35 |
As can be seen from Table 1: compare not containing No. 0 diesel oil of Peroxide Additives, the quantity discharged of the PM2.5 of the Dresel fuel compositions 1-16 that embodiment 1-16 prepares has remarkable reduction., compare (comparative example 1 ~ comparative example 6) with existing superoxide, superoxide of the present invention has the effect better reducing diesel oil PM2.5 meanwhile.
Claims (7)
1. reduce the additive containing vulkacit H that diesel motor PM2.5 discharges, it is characterized in that: additive is the mixture of superoxide and vulkacit H;
Superoxide is the superoxide of carbonatoms between 8-24;
Superoxide is one or more in tert-butyl peroxide, peroxidation organic ester or peroxy dicarbonate;
The weight ratio of superoxide and vulkacit H is 1 ~ 100:1.
2. the additive containing vulkacit H of minimizing diesel motor PM2.5 discharge according to claim 1, is characterized in that: the molecular formula of tert-butyl peroxide is ((CH
3)
3cOO)
2c (CH
3) R, R be C1-C14 alkyl; The molecular formula of peroxidation organic ester is R
1cOOOR
2, R
1, R
2for C1-C13 alkyl; The molecular formula of peroxy dicarbonate is R
3o (CO) OO (CO) OR
4, R
3, R
4for C1-C13 alkyl.
3. the additive containing vulkacit H of minimizing diesel motor PM2.5 discharge according to claim 2, 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) or the two lauroyl of peroxidation in one.
4. the additive containing vulkacit H of minimizing diesel motor PM2.5 discharge according to claim 2, it is characterized in that: peroxidation organic ester is peroxidation neodecanoic acid tertiary butyl ester, peroxidation trimethylacetic acid tertiary butyl ester, diethyl peroxide caproic acid tertiary butyl ester, peroxybenzoate, di-t-butyl peroxide ester, peroxidation neodecanoic acid 2, one in 4,4-trimethylammonium pentyl ester or peroxidation neodecanoic acid isopropyl ester.
5. the additive containing vulkacit H that discharges of minimizing diesel motor PM2.5 according to claim 2, is characterized in that: peroxy dicarbonate is the one in two (2-oxyethyl group) ethyl ester of peroxy dicarbonate or two (2-ethyl) the own ester of peroxy dicarbonate.
6. an application for the additive containing vulkacit H of the arbitrary described minimizing diesel motor PM2.5 discharge of claim 1-5, it is characterized in that: joined by additive in diesel oil, additive is 300-3000ppm relative to the content of diesel oil.
7. the application of the additive containing vulkacit H of minimizing diesel motor PM2.5 discharge according to claim 6, 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.
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|---|---|---|---|
| CN201310312340.3A CN103382405B (en) | 2013-05-02 | 2013-07-23 | Hexamine-containing additive capable of reducing PM2.5 emissions of diesel engines and application |
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|---|---|---|---|
| CN201310158340.2 | 2013-05-02 | ||
| CN2013101583402A CN103242917A (en) | 2013-05-02 | 2013-05-02 | Additive for reducing PM2.5 emission of diesel engine, and application of additive |
| CN2013101583402 | 2013-05-02 | ||
| CN201310312340.3A CN103382405B (en) | 2013-05-02 | 2013-07-23 | Hexamine-containing additive capable of reducing PM2.5 emissions of diesel engines and application |
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|---|---|
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| CN103382405B true CN103382405B (en) | 2015-07-15 |
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| CN201310312340.3A Active CN103382405B (en) | 2013-05-02 | 2013-07-23 | Hexamine-containing additive capable of reducing PM2.5 emissions of diesel engines and application |
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| CN1289645C (en) * | 2004-08-30 | 2006-12-13 | 何凤臣 | Fuel oil additive for gasoline engine and diesel oil engine |
| CN101353602A (en) * | 2008-08-29 | 2009-01-28 | 施孝豪 | Fuel additive |
| CN102041132A (en) * | 2011-01-14 | 2011-05-04 | 淄博正华助剂股份有限公司 | Improving agent for raising cetane number of diesel oil |
| CN102041117A (en) * | 2011-01-25 | 2011-05-04 | 刘俊 | Environment-friendly alcohol-based fuel additive and application thereof |
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| CN103242917A (en) | 2013-08-14 |
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Denomination of invention: Additives containing hexamethylene tetramine to reduce PM2.5 emissions from diesel engines and their applications Effective date of registration: 20220628 Granted publication date: 20150715 Pledgee: Qi commercial bank Limited by Share Ltd. Linzi branch Pledgor: ZIBO ZHENGHUA AUXILIARY Co.,Ltd. Registration number: Y2022980009180 |
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