CN101381635B - Application of modified C5 in gasoline additives - Google Patents
Application of modified C5 in gasoline additives Download PDFInfo
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- CN101381635B CN101381635B CN2008102305920A CN200810230592A CN101381635B CN 101381635 B CN101381635 B CN 101381635B CN 2008102305920 A CN2008102305920 A CN 2008102305920A CN 200810230592 A CN200810230592 A CN 200810230592A CN 101381635 B CN101381635 B CN 101381635B
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Abstract
The invention provides application of modified carbon-5 in a gasoline additive, which belongs to the technical field of recycling gasoline side products and particularly discloses a method for treating light hydrocarbons taking carbon-5 as a main composition and application of the treated carbon-5 in the gasoline additive. When the modified carbon-5 is used, 50 to 80 percent of the additive according to the weight percentage is added in gasoline to produce composite gasoline, thereby not only partially replacing the gasoline fuel with tension in supply, but also improving the performance of the gasoline, ensuring that the gasoline is fully burnt and reducing the coking and carbon deposition in an engine and the emission of harmful matters; moreover, according to the inspection by the National Ethanol Gasoline Quality Surveillance Inspection Center, the composite gasoline meets the national standard.
Description
Technical field
The invention belongs to petroleum by-product reutilization technology field, be specifically related to carbon five and in gasoline dope, use.
Background technology
Liquid starting materials such as petroleum naphtha and light oil account for more than 90% in China's ethylene raw, and C5 fraction content is bigger after the cracking, reaches as high as more than 20% of ethylene yield.In recent years, along with the continuous expansion of China's ethylene production scale, the increase of heavy constituent in China's ethylene raw, the byproduct C5 fraction of ethylene unit also increase thereupon, and the productive rate of carbon five is increasing, and the comprehensive utilization of China's carbon five is more urgent.According to statistics, 90% fuel of China's cracking of ethylene byproduct C5 fraction at present as pyrolyzer and steam boiler, 3% is used to produce petroleum resin, 7% through hydrogenation as gasoline dope and cracking stock.This shows that the byproduct C5 fraction overwhelming majority of China's ethylene unit burns as ethane cracking furnace and steam boiler fuel, the cracking c_5 level of comprehensive utilization is extremely low.How to make good use of this part material, be related to the level of comprehensive utilization and the whole economic efficiency of China's ethylene unit.
The method that lighter hydrocarbons is processed into gasoline at present both at home and abroad mainly contains following several: 1, adopting zirconium halide is that catalyzer carries out catalytic reforming; 2, light normal paraffin is changed into the isomerization technique of corresponding isomeric hydrocarbon, the U.S. Shell Oil Co. (Shell oil company) have developed and have utilized C5 and C6 isomerization to produce high-octane oil refinery gasoline blending component.The raw material of this production technique can be directly to contain C5 and C6 or macromolecular slightly normal paraffin, monomethyl alkane, dimethyl alkane and a spot of naphthenic hydrocarbon, alkene and aromatic hydrocarbons etc. from refinery.Isomerization reaction is to carry out in the fixed-bed reactor of catalyzer are housed, and the catalyzer that is adopted must have makes normal alkane isomerization and the alkane cracking that makes greater than the C6 molecule.This class catalyzer is generally the silico-aluminate that is loaded with noble metal platinum or palladium, and isomerization product is mainly iso-pentane, 2,2-dimethylbutane, 2,3-dimethylbutane and low-octane hydro carbons and a small amount of C1～C4 light constituent; 3, gasoline octane rating improves technology, promptly adds new component one octane enhancing additive to improve gasoline octane rating in gasoline.
Preceding two kinds of methods investment is big, complex process, production cost height, is not suitable for China's actual conditions.The back is a kind of, and octane enhancing additive method equipment is few, technical process short by adding, and production cost is low, and is economical and practical.But this class gasoline all is that directly the various additives of interpolation are formulated in lighter hydrocarbons basically, and lighter hydrocarbons itself are not handled, the saturated vapor pressure that itself exists when being difficult to solve lighter hydrocarbons (is main component with carbon five) as gasoline or gasoline component fully is too high, easy coking produces the carbon distribution problem when being easy to generate vapour lock and burning, and this two large problems is the biggest obstacle that the restriction lighter hydrocarbons use as gasoline.Only lighter hydrocarbons are being carried out under the modification prerequisite of matter, adding various additives again and just can make carbon five really become the clean and effective vehicle fuel.
Summary of the invention
For this reason, it is the lighter hydrocarbons modification processing method of main component with carbon five that the object of the invention is to provide a kind of, and the carbon after the modification five is applied in the vehicle fuel, too high to overcome in the use gasoline saturated vapour pressure, easy coking produces the deficiency of carbon distribution when being easy to generate vapour lock and burning.
For realizing the object of the invention, technical scheme is as follows:
The present invention is a raw material based on the lighter hydrocarbons (carbon five) of pentane, at first by addition reaction, the carbon in the lighter hydrocarbons five is carried out modification, the detergency when improving carbon five burnings.Modification carbon five production methods: add cis-butenedioic anhydride in the reactor, after the heat fused, mix carbon five to wherein adding, react and heat release, add catalyzer, keeping temperature of reaction is 80 ~ 90 ℃, reacted 2-3 hour, with solid-liquid separation, to get product liquid and be the used modification carbon five of the present invention, its representative reactions is:
Catalyst system therefor is zinc chloride, aluminum chloride or skeleton nickel, and cis-butenedioic anhydride and carbon five mol ratios are 1:1.
Then modification carbon five and stablizer are mixed, the stablizer add-on is the 1-25 ‰ of modification carbon five weight, obtain a kind of can vast scale ground and marketable gasolines blended, reach the motor spirit auxiliary agent that GB requires, this fuel assistants is joined in the gasoline, make composite gasoline.
The stablizer major ingredient is:
Semen Maydis oil, Viscotrol C, plam oil biomass extract 1:1:1 mixed thing 15%,
C12-18 aliph polyols 59.9%,
Oxidation inhibitor: Tert. Butyl Hydroquinone 5% and di-sec-butyl-p-phenyl enediamine 10%
Octane promoter: Ethyl Tertisry Butyl Ether 5% and ferrocenyl coordination compound 5%,
Passivator 0.1%, each component by weight percentage.
Stablizer is divided into three groups when preparation, one group is that the biomass extract that will not be soluble in petrochemical industry oils earlier is dissolved in polyvalent alcohol; The 2nd, antioxidant and metal passivator are mixed; Three is octane promoter.Form branch with three then and add successively in the reactor, fully stirring promptly becomes the fuel assistants that has antiknock and reduce the vapour pressure comprehensive action.
The technology of the present invention main points are:
The lighter hydrocarbons that fractionate out in ethylene industry, diolefine, alkynes, cyclic hydrocarbon etc. have many isomer, the component complexity, at fuel oil for vehicles, must carry out technical finesse to lighter hydrocarbons (carbon five) based on pentane, make the lighter hydrocarbons after the processing really become the clean and effective vehicle fuel.In addition, higher at modification lighter hydrocarbons vapour pressure, octane value is on the low side, be prone to problems such as pinking, vapour lock, by a large amount of secular shaker tests, preferred be mixed with a kind of composite additive stable, antiknock that integrates, solved the object of the invention preferably by kind of chemical substance and bio-extract surplus ten.This additive formulations combination is not the simple performance sum of each component, but a kind of synergistic function.Its major cause is: each component octane value is higher in the prescription, has improved the oxidation-resistance of fuel, can effectively improve the combustion characteristic of engine internal fuel, and various composition self steam forces down, and can reduce the vapour pressure of modification carbon five effectively; In addition, various compositions and gasoline intermiscibility in the prescription are good, do not mix erosion, not stratified, do not absorb water, be the good mixture of a kind of intermiscibility.
Advantage of the present invention: (1) has solved the coking and the carbon distribution problem of engine well by the modification to carbon five.(2) prepared one package stabilizer, prevented the generation of engine vapour lock phenomenon, engine operates steadily, and fluctuation ratio is low than marketable gasolines.(3) owing to go into stablizer modification carbon slender acanthopanax, can mix use with marketable gasolines in vast scale ground, and dynamic property, economy, spatter property and low emission performance be better than marketable gasolines, not only improved the gasoline performance, and made gasoline combustion more abundant.(4) this adds auxiliary agent, can not produce waste vapour, waste water, waste residue in process of production, belongs to environment-friendly type technique.Abundant raw material, technology maturation, clean environment firendly, be easy to promote, popularize the fundamental state policy that meets national energy-saving and emission-reduction, significant for national energy security.Succeeding in developing of this project will farthest fully utilize the lighter hydrocarbons resource, replenish the gasoline vacancy, significantly reduce noxious gas emission in the vehicle exhaust simultaneously.
Embodiment
For the present invention is illustrated better, be exemplified below:
1, C 5 modified
In reactor, add cis-butenedioic anhydride 60kg, after the heat fused, mix carbon five to wherein adding, after the exothermic heat of reaction, add catalyzer zinc chloride 2g, keeping temperature of reaction is 80 ~ 90 ℃, react after 2-3 hour, solid-liquid separation is got product liquid and is the used modification carbon five of the present invention.
Test used mixing carbon Wuyuan material and come from Central Plains ethene and Luoyang Petrochemical, the catalyst system therefor zinc chloride is the commercial catalyst.
2, the preparation of stablizer
(L9) screens best material proportion by orthogonal experimental design, result such as following table:
Various additives are industrial goods, and the C16-18 aliph polyols is purchased in last starfish sea group of enterprises, and passivator is the T1201 metal passivator, purchases in Zibo favour China chemical industry company limited.
From above test-results as can be seen, the content of biomass is the principal elements that influence vapour pressure, the biological quality of adding more steaminess press low more, when its content greater than 15% the time, vapour pressure can reach the requirement of GB quality of gasoline; The content of polyvalent alcohol and octane promoter then influences its octane value, when polyvalent alcohol content greater than 59%, uprising dose content greater than 10% or polyvalent alcohol content greater than 84%, uprising dose content greater than 5% the time octane value greater than 93.7.Take all factors into consideration various influence factors, the 9th group of experimental data is the optimal result in the Total Test.By this proportioning, choose the mixture of Semen Maydis oil, Viscotrol C, palm wet goods biomass extract respectively, aliph polyols, the ferrocenyl coordination compound, oxidation inhibitor, octane promoter, passivator are divided into three groups when preparation, one group will not be soluble in the biomass extract of petrochemical industry oils earlier, be dissolved in aliph polyols; Two groups mix three groups of octane promoters with antioxidant and metal passivator.Then three components are added in the reactor successively, fully stirring promptly becomes the one package stabilizer that has antiknock and reduce the vapour pressure comprehensive action.
3, the preparation of clean fuel oil auxiliary agent
The one package stabilizer for preparing is joined after the modification in the carbon five by 1-25 ‰ weight ratio, stirred 10 minutes, uniform mixing is made clean fuel oil auxiliary agent of the present invention.
In the practical application, the motor spirit performance has following requirement: 1, good anti-knocking property; 2, suitable vapo(u)rability; 3, good anti-oxidative stability; 4, good erosion resistance and certain environmental requirement.Clean fuel oil auxiliary agent of the present invention is made a service test.
(1), inspection after construction
Clean fuel oil auxiliary agent of the present invention is added in the 93# motor spirit with the 1:1 weight ratio, is mixed into new fuel oil for vehicles.Detect through national ethanol petrol quality surveillance inspection center, meet the national standard (GB17930-2006) of 93# gasoline fully.
(2), finished product internal combustion engine bench test
Country's mechanical industry I. C. engine oil product check evaluation center (being located at oil engine key lab of country of University Of Tianjin) makes clean fuel oil with clean fuel oil auxiliary agent of the present invention with the 93# gasoline that 50% weight ratio adds national standard, carried out engine rig test, the evaluation conclusion is as follows:
The 93# gasoline and the former 93# gasoline operation 50h front and back performance comparison that add fuel assistants of the present invention show: the 93# gasoline that adds fuel assistants of the present invention is behind operation 50h on the automobile, peak power and mean power, peak torque and average torque rate of descent are all few than 93# gasoline, and consumption minimization rate and average rate of fuel consumption rate of rise are identical with 93# gasoline.
93# gasoline and same motor speed characteristic contrast of 93# gasoline of adding fuel assistants of the present invention show: each point average fuel consumption rate all is better than and is equivalent to 93# gasoline on fuel assistants peak power, peak torque, mean power, average torque, consumption minimization rate, the external characteristics.
Stable comparative test result showed in 1 hour: fuel assistants operates steadily, and fluctuation ratio is little than 93# gasoline.
The 93# gasoline and the 93# gasoline discharging simultaneous test that add fuel assistants of the present invention show: the 93# gasoline HC and the C0 that add fuel assistants of the present invention decline to a great extent than 93# gasoline, and fuel assistants has bigger advantage on emission behavior.
The 93# gasoline that adds fuel assistants of the present invention shows with 93# gasoline cleanliness contrast evaluation: the interior oily detergency of cylinder of the present invention slightly is better than 93# gasoline, and valve deposits obviously shows and is less than 93# gasoline.
After adding the 93# gasoline operation 50h of fuel assistants of the present invention, the wearing and tearing of movement parts such as piston, piston ring, cylinder, cam are little, and are suitable with 93# gasoline.
The 93# gasoline colourity of adding fuel assistants of the present invention is bright, intermiscibility good, smell is little, shows good dynamic property, economy and low emission performance in engine uses.
(3) product lubricating oil, detergency qualification test
Add of the present invention clean fuel oil auxiliary agent with 93# GB gasoline with the 1:1 weight ratio by national mechanical technology I. C. engine oil product check evaluation center, carry out test evaluation then, its evaluation conclusion is:
The oilness evaluation result shows: its lubricity index LTX=105, initial torque index IIX=100 is so the fuel assistants oilness is better than 93# gasoline.
The detergency evaluation result shows: detergency index D IX=102, skirt of piston paint film VIX=101 is so the fuel assistants detergency is better than 93# gasoline.
(4) the clean fuel oil auxiliary agent vehicle of the present invention application test that travels
Each 50% weight ratio of clean fuel oil auxiliary agent of the present invention and 93# GB gasoline mixes the back as vehicle fuel, car to more than 30 different brands of six units is tried out, the feedback opinion of unit on probation is consistent thinks that use above-mentioned raw materials vehicle starting, acceleration are soon, go up a slope energetically, under the situation of various speed per hours, there are not pinking, air-resistance phenomenon, do not have different sensations with using pure 93# gasoline, even be better than 93# gasoline.
Test sample is deposited and do not seen layering, mixed erosion phenomenon in 19 months yet, and is sparkling and crystal-clear bright.
Claims (1)
1. modification carbon five is used in gasoline dope, it is characterized in that, modification carbon five is added in the stablizer, and both are mixed, and the stablizer add-on is the 1-25 ‰ of modification carbon five weight, and the stablizer major ingredient is:
Semen Maydis oil, Viscotrol C, 1: 1: 1 mixed thing 15% of plam oil biomass extract,
C12-C18 aliph polyols 59.9%,
Oxidation inhibitor: Tert. Butyl Hydroquinone 5% and di-sec-butyl-p-phenyl enediamine 10%
Octane promoter: Ethyl Tertisry Butyl Ether 5% and ferrocenyl coordination compound 5%,
Passivator 0.1%, each component is by weight percentage;
Described modification carbon five has carried out following processing: add cis-butenedioic anhydride in reactor, after the heat fused, mix carbon five to wherein adding, after the exothermic heat of reaction, add catalyzer, keeping temperature of reaction is 80～90 ℃, reacted 2-3 hour, and, got product liquid and be modification carbon five solid-liquid separation; Catalyst system therefor is zinc chloride, aluminum chloride or skeleton nickel; Cis-butenedioic anhydride is 1: 1 with mixing carbon five mol ratios.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102305920A CN101381635B (en) | 2008-10-27 | 2008-10-27 | Application of modified C5 in gasoline additives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102305920A CN101381635B (en) | 2008-10-27 | 2008-10-27 | Application of modified C5 in gasoline additives |
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| Publication Number | Publication Date |
|---|---|
| CN101381635A CN101381635A (en) | 2009-03-11 |
| CN101381635B true CN101381635B (en) | 2011-12-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008102305920A Expired - Fee Related CN101381635B (en) | 2008-10-27 | 2008-10-27 | Application of modified C5 in gasoline additives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103525484B (en) * | 2013-09-30 | 2017-01-18 | 达州市东晶新能源研究所 | Formula and preparation method of novel PM (particulate matter) clean biological CHO motor gasoline |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1334322A (en) * | 2001-07-30 | 2002-02-06 | 李宇翔 | Environment-protecting energy-saving improver of lead-free gasoline |
| CN1530428A (en) * | 2003-03-10 | 2004-09-22 | 深圳市日研科技有限公司 | Motor light naphtholite and mixed fuel |
| CN1923980A (en) * | 2006-10-10 | 2007-03-07 | 北京中天醇能源技术有限公司 | Light hydrocarbon modifier and application thereof |
| CN1958746A (en) * | 2005-10-31 | 2007-05-09 | 鲁希诺 | Composite oil free from lead prepared by using finished product of gasoline, and carbon five |
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2008
- 2008-10-27 CN CN2008102305920A patent/CN101381635B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1334322A (en) * | 2001-07-30 | 2002-02-06 | 李宇翔 | Environment-protecting energy-saving improver of lead-free gasoline |
| CN1530428A (en) * | 2003-03-10 | 2004-09-22 | 深圳市日研科技有限公司 | Motor light naphtholite and mixed fuel |
| CN1958746A (en) * | 2005-10-31 | 2007-05-09 | 鲁希诺 | Composite oil free from lead prepared by using finished product of gasoline, and carbon five |
| CN1923980A (en) * | 2006-10-10 | 2007-03-07 | 北京中天醇能源技术有限公司 | Light hydrocarbon modifier and application thereof |
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| CN101381635A (en) | 2009-03-11 |
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