CN106520235A - Preparation process of environment-friendly cetane number improver for diesel oil - Google Patents

Preparation process of environment-friendly cetane number improver for diesel oil Download PDF

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Publication number
CN106520235A
CN106520235A CN201611167308.0A CN201611167308A CN106520235A CN 106520235 A CN106520235 A CN 106520235A CN 201611167308 A CN201611167308 A CN 201611167308A CN 106520235 A CN106520235 A CN 106520235A
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Prior art keywords
cetane
diesel
environment
number improver
diesel cetane
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CN201611167308.0A
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Inventor
孙广军
孙禹
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Anyang Yutai Chemical Co Ltd
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Anyang Yutai Chemical Co Ltd
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Priority to CN201611167308.0A priority Critical patent/CN106520235A/en
Publication of CN106520235A publication Critical patent/CN106520235A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

The invention discloses a preparation process of an environment-friendly cetane number improver for diesel oil, and belongs to the field of diesel oil production. The cetane number improver for the diesel oil comprises the following components in percentage by mass: 76 percent to 90 percent of organic superoxide, 6 to 12 percent long carbon chain fat alkanes, 1 to 6 percent of oxalic acid isopentyl esters, and 2 to 6 percent of micro-nitrogen-containing compounds. By utilizing the improver, the product flashing point can be improved, the product stability is greatly improved, the product safety is improved, the risks brought by storage, transportation and use are eliminated, the stability of a cetane number for the diesel oil can be ensured, the exhaust gas emission of Nox of an engine is reduced, and the requirement of national standard is met.

Description

A kind of environment-friendly type diesel cetane-number improver preparation technology
Technical field
The present invention relates to a kind of cetane number improver preparation technology, more particularly to a kind of environment-friendly type diesel cetane-number changes Enter agent preparation technology, belong to diesel production field.
Background technology
Diesel-fuel cetane number is an important indicator for weighing diesel combustion performance, to engine cold-start and power, Exhaust emissions and combustion noise all have an impact, and are environmental protection, realize social sustainable development strategy, to exhaust emissions of diesel engine Sox、NOx, it is proposed that it is strict with, the high diesel oil hazardous emission of the Cetane number diesel oil low significantly lower than Cetane number.
The Cetane number of straight-run diesel oil typically in 50--70, the Cetane number of catalytic cracking diesel oil typically in 30--40, with The continuous increase of the catalyzed cracking processing disposal ability of domestic oil refining enterprises, overall diesel-fuel cetane number level is presented and declined Trend, existing diesel oil standard Cetane number are not less than 45, and five diesel oil standard Cetane number of state is not less than 51, while requiring diesel oil Sulfur content is less than 10ppm, and the micro detection of requirement of nitrogen, the diesel oil of many enterprises are difficult to meet existing diesel oil standard and state five Diesel oil standard, how to improve and reach five standard of state is that many oil refining enterprise compel and need the problem for solving, for improving diesel oil One of method of Cetane number be by the production technology such as being hydrogenated with or reforming improving diesel cetane-number, but hydrogenation or reform Production technology is costly, and production cost is also high, hence it is evident that affect the performance of enterprises；The two of method are changed by adding diesel cetane-number Enter agent to improve, it is general to add mix homogeneously just improve 2---9 unit of diesel cetane-number, with low cost, technique Simple advantage.Therefore, develop diesel cetane-number improver significant.
The diesel cetane-number improver that the country uses at present mainly has nitrate esters as traditional diesel cetane-number Modifier, improves diesel cetane-number effect substantially, and product stability is good, but contains nitrogen, and NOx exhaust emissions is serious, shadow Environment is rung, is polluted, five standard of state is not allowed, and market prospect gradually weakens.
Oxygen-containing class diesel cetane-number improver, due to comprising only C, H, O element burns in diesel oil fully, to environment friend It is good, reduce NOxDischarge, meet state five standard and require, therefore using oxygen-containing class modifier solving diesel product quality Problem is widely applied,
Foreign patent US011053 discloses a kind of two tertiary alkyl peroxide as diesel cetane-number improver, micro addition Diesel cetane-number can be significantly improved, but tert-butyl peroxide class is poor as diesel cetane-number improver stability, After adding diesel oil, its Cetane number declines over time, so as to affect diesel quality, while this kind of modifier flash-point is low, in reality Border uses, storage, and many risk factors are there are in transportation.
The content of the invention
Contain nitrogen, NO for current China Diesel standard cetane value modifierxExhaust emissions is serious, affects ring Border, pollutes in problem, foreign patent that diesel cetane-number improver flash-point is low, can reduce diesel quality, actually used, Storage, has a kind of a lot, environment-friendly type diesel cetane-number improvement of present invention offer in transportation Agent preparation technology, its objective is to improve diesel cetane-number, overcomes prior art using peroxide diesel fuel cetane The shortcoming that the Cetane number of the finished diesel fuel of value modifier declined with the time, improves the flash-point of product, eliminates storage, fortune Defeated, the danger of use, it is ensured that diesel-fuel cetane number stability reduces the NO of electromotorxExhaust emissions, meet National standard requirement.
The technical scheme is that：A kind of environment-friendly type diesel cetane-number improver, the diesel cetane-number are improved Agent includes organic peroxide, C16---C30 Long carbon chain fat alkane mixture, oxalic acid isoamyl esters, micro nitrogenous chemical combination Species composition, the mass percent of above-mentioned each constituents are respectively：
Organic peroxide class w/w is 76%---90%；
C16---C30 Long carbon chain fat alkane mixture w/w is 6%--12%；
Oxalic acid isoamyl esters w/w is 1%---6%；
Micro nitrogen-containing compound class w/w is 2%---6%.
Further, the organic peroxide class include di-tert-butyl peroxide, cyclohexane di-tert-butyl peroxide, two Any one organic peroxide or any several organic peroxies in tert-butyl hydroperoxide butane, peroxidized t-butyl perbenzoate The mixture of compound；
Further, the C16---C30 Long carbon chains fat alkane mixture includes C16, C18, C20, C25, C27, C30 alkane Class；
Further, the micro nitrogen-containing compound class includes any one in isooctyl ester nitrate, cyclohexyl nitrate, isoamyl nitrate Plant the mixture of micro nitrogen-containing compound class or any several micro nitrogen-containing compounds.
A kind of environment-friendly type diesel cetane-number improver preparation technology, including above-mentioned modifier material, the processing step It is as follows：
1）In 2000 liters of reactors equipped with high-order measuring tank, C16--- of metered mass percent w/w for 6%--12% C30 Long carbon chain fat alkane mixture；
2）By interlayer hot water heating to 30 35 ° of temperature in the kettle, mass percent w/w is sequentially added under stirring for 1%---6% Oxalic acid isoamyl esters, mass percent w/w for 2%---6% micro nitrogen-containing compound class；
3）20 minutes are stirred after all dissolving, 5 ° or so are cooled to, then is passed through lower addition mass percent w/w of nitrogen protection and be The organic peroxide class of 75%---90%；
4）Stirring had both obtained product in 20 minutes, went out kettle after chemical examination is qualified.
The good effect that the technical program has is：By di-t-butyl peroxide is added in diesel cetane-number improver Mass percents w/ such as compound, cyclohexane di-tert-butyl peroxide, di-tert-butyl peroxide butane, peroxidized t-butyl perbenzoate Any one or a few mixture of the w for the organic peroxide apoplexy due to endogenous wind of 75%---90%, it is possible to increase engine power, carries High diesel cetane-number, improves combustibility, while reducing the discharge of NOx；By used in diesel cetane-number improver The C16---C30 Long carbon chain fat alkane mixture such as C16, C18, C20, C25, C27, C30 alkanes of 6--12%, can promote Organic peroxide class material improves flash-point, improves stability, and collaboration improves diesel cetane-number；By in diesel cetane-number Used in modifier, mass percent w/w is the oxalic acid isoamyl esters of 1---6%, can improve Cetane number, many containing oxygen element, changes Kind combustibility, while reducing NOxDischarge；By the isooctyl ester nitrate used in diesel cetane-number improver, nitric acid ring Mass percents w/w such as own ester, isoamyl nitrate for 2%---6% micro nitrogen-containing compound class any one or it is arbitrarily several Mixture, often adds one thousandth improve more than 3 units of diesel cetane-number, is the improvement of traditional diesel cetane-number Agent, can promote mutually to improve diesel cetane-number with organic peroxide class material, and can avoid organic peroxide class Substance decomposition, plays a part of organic peroxide stabilization class material.The present invention improve diesel cetane-number, overcome it is existing The shortcoming that technology is declined with the time using the Cetane number of the finished diesel fuel of peroxide diesel cetane-number improver, carries The high flash-point of product, eliminates the danger of storage, transport, use, it is ensured that diesel-fuel cetane number stability, subtracts The NO of electromotor is lackedxExhaust emissions, meet national standard requirement.
Specific embodiment
The raw material and its percentage by weight that the present invention is used is as follows by following proportions：
A：Organic peroxide class, di-tert-butyl peroxide, cyclohexane di-tert-butyl peroxide, di-tert-butyl peroxide fourth Any one or arbitrarily several mixture in alkane, peroxidized t-butyl perbenzoate, mass percent w/w is 76%---90%；
B：C16---C30 Long carbon chain fat alkane mixture, C16, C18, C20, C25, C27, C30 alkanes, mass percent W/w is 6--12%；
C：Oxalic acid isoamyl esters, 1---6%, such material improve Cetane number, many containing oxygen element, improve combustibility, while subtracting The discharge of few NOx；
D：The isooctyl ester nitrate of micro nitrogen-containing compound class, cyclohexyl nitrate, isoamyl nitrate etc. any one or it is arbitrarily several Mixture, mass percent w/w be 2%---6%, such material typically add one thousandth improve 3 lists of diesel cetane-number More than position, it is the modifier of traditional diesel cetane-number, but Nitrogen element, exhaust emissions NOx, environment is affected, dirt is caused Dye, it is impossible to meet Standard, but can be to promote mutually to improve diesel cetane-number with A classes material, and can avoid organic Peroxidic products decompose, and play a part of organic peroxide stabilization class material.
Embodiment of the present invention production technology is as follows：
In 2000 liters of reactors equipped with high-order measuring tank, metered C16---C30 Long carbon chains fat alkane compounding substances Long carbon chain fat alkanes of the amount percentage ratio w/w for 6%--12%, by interlayer hot water heating to 30 35 ° of temperature in the kettle, under stirring It is 1%---6% to sequentially add oxalic acid isoamyl esters mass percent w/w, and nitrogen-containing compound class mass percent w/w is 2%--- 6%, stirring is cooled to 5 ° or so in 20 minutes after all dissolving, and adds peroxide quality percentage in the case where nitrogen protection is passed through It is 76%---90% than w/w, stirs 20 minutes and both obtained product, after chemical examination is qualified, go out kettle.
Further illustrate with reference to embodiments：
As can be seen from the above table：
1. each component content given by the present invention is in the range of；
2. eight groups of example flash-points are all higher than 26 °, 12 ° of commercially available modifier flash-point；
3. it is higher than commercially available modifier that product of the present invention adds dosage 0.1% or 0.2% to improve Cetane number number.
Plus the relevant Data Comparison of the diesel stability after agent
Can be seen that by data above contrast：（1）In 90 days after product addition of the present invention, diesel cetane-number only has small change Change, with good stability, the like product of two factory of E, F adds 90 days diesel cetane-numbers of agent to reduce by 1 unit or so, at any time Between and reduce diesel cetane-number,（2）Use data of the product of the present invention in Shandong oil plant.
The technical program is by the di-tert-butyl peroxide used in diesel cetane-number improver, di-t-butyl peroxide Change mass percents w/w such as hexamethylene, di-tert-butyl peroxide butane, peroxidized t-butyl perbenzoate having for 76%---90% Any one or arbitrarily several mixture of machine peroxide apoplexy due to endogenous wind, it is possible to increase engine power, improves diesel fuel cetane Value, improves combustibility, while reducing NOxDischarge；By the C16 of the 6--12% used in diesel cetane-number improver, The C16---C30 Long carbon chain fat alkane mixture such as C18, C20, C25, C27, C30 alkanes, can promote organic peroxide Class material improves flash-point, improves stability, and collaboration improves diesel cetane-number；By used in diesel cetane-number improver Mass percent w/w is the oxalic acid isoamyl esters of 1---6%, can improve Cetane number, many containing oxygen element, improves combustibility, together When reduce NOxDischarge；By the isooctyl ester nitrate used in diesel cetane-number improver, cyclohexyl nitrate, nitric acid isoamyl The micro nitrogen-containing compound class of mass percents w/w%2---6% such as ester any one or arbitrarily several mixture, often adds thousand / mono- can improve more than 3 units of diesel cetane-number, be the modifier of traditional diesel cetane-number, can be with organic mistake Oxide-based material promotes mutually to improve diesel cetane-number, and can avoid organic peroxide class substance decomposition, plays steady Determine the effect of organic peroxide class material.The present invention improves diesel cetane-number, overcome prior art uses peroxidating The shortcoming that the Cetane number of the finished diesel fuel of species diesel cetane-number improver declined with the time, improves the flash-point of product, Eliminate the danger of storage, transport, use, it is ensured that diesel-fuel cetane number stability, reduce the NO of electromotorx Exhaust emissions, meet national standard requirement.

Claims (5)

1. a kind of environment-friendly type diesel cetane-number improver, it is characterised in that：The diesel cetane-number improver includes organic Peroxide, C16---C30 Long carbon chain fat alkane mixture, oxalic acid isoamyl esters, micro nitrogen-containing compound constituents, on The mass percent for stating each constituents is respectively：
Organic peroxide class w/w is 76%---90%；
C16---C30 Long carbon chain fat alkane mixture w/w is 6%--12%；
Oxalic acid isoamyl esters w/w is 1%---6%；
Micro nitrogen-containing compound class w/w is 2%---6%.
2. a kind of environment-friendly type diesel cetane-number improver preparation technology according to claim 1, it is characterised in that：It is described Organic peroxide class includes di-tert-butyl peroxide, cyclohexane di-tert-butyl peroxide, di-tert-butyl peroxide butane, mistake The mixture of any one organic peroxide or any several organic peroxides in oxidation t-butyl perbenzoate.
3. a kind of environment-friendly type diesel cetane-number improver preparation technology according to claim 1, it is characterised in that：It is described C16---C30 Long carbon chain fat alkane mixture includes C16, C18, C20, C25, C27, C30 alkanes.
4. a kind of environment-friendly type diesel cetane-number improver preparation technology according to claim 1, it is characterised in that：It is described Micro nitrogen-containing compound class includes any one the micro nitrogenous chemical combination in isooctyl ester nitrate, cyclohexyl nitrate, isoamyl nitrate Species or the arbitrarily mixture of several micro nitrogen-containing compounds.
5. a kind of environment-friendly type diesel cetane-number improver preparation technology, including the modifier thing in above-mentioned 1-4 in any one Matter, it is characterised in that：The processing step is as follows：
1）In 2000 liters of reactors equipped with high-order measuring tank, C16--- of metered mass percent w/w for 6%--12% C30 Long carbon chain fat alkane mixture；
2）By interlayer hot water heating to 30 35 ° of temperature in the kettle, mass percent w/w is sequentially added under stirring for 1%---6% Oxalic acid isoamyl esters, mass percent w/w for 2%---6% micro nitrogen-containing compound class；
3）20 minutes are stirred after all dissolving, 5 ° or so are cooled to, then is passed through lower addition mass percent w/w of nitrogen protection and be The organic peroxide class of 75%---90%；
4）Stirring had both obtained product in 20 minutes, went out kettle after chemical examination is qualified.
CN201611167308.0A 2016-12-16 2016-12-16 Preparation process of environment-friendly cetane number improver for diesel oil Pending CN106520235A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5482518A (en) * 1994-11-18 1996-01-09 Exxon Research And Engineering Company Synergistic cetane improver composition comprising mixture of alkyl-nitrate and hydroperoxide quinone
JP2000119668A (en) * 1998-10-15 2000-04-25 Nippon Mitsubishi Oil Corp Gas oil compsition
CN102051248A (en) * 2009-11-10 2011-05-11 济南开发区星火科学技术研究院 Method for improving diesel fuel CN (Cetane Number)
CN102807904A (en) * 2012-08-30 2012-12-05 梁渠 Seed oil-compounded renewable diesel oil and compounding method thereof
CN103275775A (en) * 2013-06-25 2013-09-04 咸阳东庆石油化工有限公司 Harmonic ingredient of high-power clean diesel oil
CN103409177A (en) * 2013-08-29 2013-11-27 胡荣汉 Marine methanol fuel oil and preparation method thereof
CN104593106A (en) * 2015-01-22 2015-05-06 杨长江 High-cleanness diesel fuel additive and preparation method thereof
CN105296024A (en) * 2015-11-19 2016-02-03 深圳市广昌达实业有限公司 Multifunctional diesel oil cetane number improver and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5482518A (en) * 1994-11-18 1996-01-09 Exxon Research And Engineering Company Synergistic cetane improver composition comprising mixture of alkyl-nitrate and hydroperoxide quinone
JP2000119668A (en) * 1998-10-15 2000-04-25 Nippon Mitsubishi Oil Corp Gas oil compsition
CN102051248A (en) * 2009-11-10 2011-05-11 济南开发区星火科学技术研究院 Method for improving diesel fuel CN (Cetane Number)
CN102807904A (en) * 2012-08-30 2012-12-05 梁渠 Seed oil-compounded renewable diesel oil and compounding method thereof
CN103275775A (en) * 2013-06-25 2013-09-04 咸阳东庆石油化工有限公司 Harmonic ingredient of high-power clean diesel oil
CN103409177A (en) * 2013-08-29 2013-11-27 胡荣汉 Marine methanol fuel oil and preparation method thereof
CN104593106A (en) * 2015-01-22 2015-05-06 杨长江 High-cleanness diesel fuel additive and preparation method thereof
CN105296024A (en) * 2015-11-19 2016-02-03 深圳市广昌达实业有限公司 Multifunctional diesel oil cetane number improver and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"《汽油吸附脱硫（S Zorb）装置技术问答》" *

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Application publication date: 20170322