Patent name A diesel cetane number improver composition and a method for preparing diesel containing the same.
Technical field the present invention relates to a cetane number improver composition for diesel oil and diesel oil containing the same.
Background Art With the increase of diesel consumption, the requirements for diesel quality, especially cetane number, are getting higher and higher. Cetane number is an important index of diesel engine combustion performance, which has an influence on engine cold start, emission and combustion noise. According to the national diesel standard of China,
The cetane number of light diesel oil is not less than 45, and the cetane number of light diesel oil produced from intermediate crude oil or mixed with catalytic components is allowed to be not less than 40. The average value of diesel in the world is around 50, which is roughly equivalent to that in China. The main factor affecting the cetane number of diesel oil is the composition of diesel blending components. The cetane number of straight-run diesel oil is relatively high, which varies with crude oil. Under the same distillation range, the annual cetane number of straight-run diesel oil is as high as 63, while that of Liaohe straight-run diesel oil is only 43. The secondary processing capacity of diesel oil in China accounts for 60-70 wt% of the crude oil processing capacity, and the hexapod value of secondary processing diesel oil, especially heavy oil catalytic cracking diesel oil, is very low, generally only 30-40. With the increase of the proportion of processed heavy crude oil, the overall level of cetane number will show a downward trend. In the past, China's light diesel oil standard stipulated that the cylinder value of diesel oil 16 should not be less than 40 and 45, and most oil refining enterprises could reach this standard. However, since 2005, China has implemented a new diesel specification standard, which stipulates that the cetane number of diesel oil should reach 45 or even 50, so that the diesel oil of many oil refining enterprises can not meet this standard. Therefore, how to improve the cetane number of diesel oil has become an urgent problem faced by some refining enterprises. For some oil refining enterprises, it is necessary to adopt reasonable refining technology and measures to improve the cetane number of diesel oil. For example, the cetane number can be improved by hydrogenation, reforming and other processes. However, the processing cost through these processes is relatively high, which is uneconomical for some enterprises. It can't be solved by technology and measures.
At 5: 00, cetane number improver is needed to improve the cetane number of diesel oil to solve the quality problem of light diesel oil products. In other words, diesel improvers will be widely used.
At present, the additives used to improve the cetane number of diesel oil are nitrate additive and organic peroxide additive. Nitrate additive is a traditional cetane number improver, which has a good effect on improving cetane number of diesel oil. However, the use of nitrating agents, such as nitric acid or the mixture of sulfuric acid and nitric acid, in the production of such additives has caused certain environmental pollution. In addition, due to
Nitrification is a violent exothermic reaction, and explosions still occur in the production of such additives. suddenly
Danger. Organic peroxides, such as tert-butyl hydroperoxide, di-tert-butyl hydroperoxide, polyalkyl hydroperoxide, etc., can increase the unit value of 16 of diesel by L-3 units, and at the same time, these additives contain more oxygen elements, which is beneficial to promoting the combustion of diesel and improving the emission pollution of diesel engines.
American patent. 5,065,438+065,438+0,503 discloses Adi-tertiary alkyl peroxide as cetane number of diesel oil:
Modifier and a small amount of modified oxide can significantly improve the value of diesel oil 16 times.
Tert-butyl hydroperoxide, di-tert-butyl peroxide and polyalkyl peroxide can be mixed with diesel oil in any proportion, but the cetane number of diesel oil using such organic peroxide improvers will decrease with time, thus affecting the quality of diesel oil.
Summary of the invention
The invention aims to overcome the defect that the cetane number of diesel oil decreases with time when using organic peroxide cetane number improver in the prior art, and provide a diesel oil cetane number improver composition which can keep the cetane number of diesel oil stable without decreasing with time, and diesel oil containing the diesel oil cetane number improver composition.
The invention provides a diesel oil cetane number improver composition, which comprises an organic peroxide and an organic amine.
The invention also provides a diesel oil, which contains base oil and cetane number improver, wherein the cetane number improver is the diesel oil cetane number improver composition provided by the invention.
The cetane number improver composition for diesel oil provided by the invention effectively improves the cetane number of diesel oil and maintains its stability. It can obviously improve the cetane number and stability of diesel oil, and has a broad application prospect in China oil refining enterprises. The diesel oil cetane number improver composition can be used for light diesel oil, heavy diesel oil, Fischer-Tropsch diesel oil (GTL diesel oil) and fuel oil for boilers. The cetane number of diesel oil added with the diesel oil cetane number improver composition of the invention is improved and the cetane number is stable, thereby improving the combustion performance and increasing the engine power.
Energy and economic performance, and improve engine exhaust pollution, such as reducing nitrogen oxide emissions.
Detailed description
The invention provides a diesel oil cetane number improver composition, which comprises an organic peroxide, wherein the composition further comprises an organic amine. According to the diesel cetane number improver composition of the invention, a small amount of organic amine can achieve the purpose of the invention. However, it is preferred to use this composition.
The content of organic peroxide is 10-97% by weight, preferably 70-97% by weight, and further preferably 80-95% by weight; The content of organic amine is 3-90 wt%, preferably 3-30 wt%, and further preferably 5-20 wt%.
The organic peroxide will gradually decompose when it meets light, heat, organic matter and some metal ions, which affects the stability of this kind of diesel cetane improver in diesel oil and its effect of improving diesel cetane number. The diesel oil cetane number improver composition provided by the invention contains organic amine, which can avoid the decomposition of polyalkyl peroxide, thereby improving the stability of polyalkyl peroxide in diesel oil.
The organic amine may be selected from at least one of compound A represented by formula (I), compound B represented by formula (II) and compound C represented by formula (III).
7 See page 8(I) of the original document for the formula.
Wherein, R is alkoxy of C 1-c 12, preferably hydroxyl of D-C4, and the position of R 1 on the benzene ring can be 2, 3 or 4, that is, ortho, meta or para of the amide group; 1 12 is a pendant group of Crdo, preferably an alkyl group of CVC4;
㈡
Wherein R3 is hydrogen or crc4alkyl, preferably crc4alkyl. The position on the benzene ring can be 2, 3 or 4, that is, the ortho, meta or para position of the secondary amine group; R4 is alkyl of C 1-6, preferably alkyl of C 1-6;
R5 R
㈢
Wherein R5 is an alkyl group of CVC22, preferably c8-c18; R6 and R7 are each one of methyl, ethyl, propyl and butyl.
Preferably, the compound A can be N- acetoethoxyaniline; Compound b can be N- ethoxyaniline; Compound c can be tetradecyl dimethyl tertiary amine. Wherein, the chemical formula of N- acetoethoxyaniline is shown as formula (IV), the chemical formula of N- ethoxyaniline is shown as formula (V), and the chemical formula of tetradecyl dimethyl tertiary amine is shown as formula (VI).
The organic peroxide can be organic hydrogen peroxide, polycyclic peroxide, etc. Wherein, the polycyclic peroxide has a moiety shown in formula (VII)
See page 9 (VII) of the original document for the formula.
Wherein R8, R9 and R 1 are each one of methyl, ethyl, propyl and butyl.
Specifically, the polyalkyl peroxide can be one or more of 1, 1- di (tert-butyl peroxide) cyclohexane, 2,2-di (tert-butyl peroxide) butane and tert-butyl benzoate peroxide, wherein the chemical formula of U- di (tert-butyl peroxide) cyclohexane is shown in formula (VIII), and 2,2.
”\ ,〇〇C(CH3)3
/ 〇〇C(CH3)3
㈧
OCiC(CH3 & gt； 3 CH3CH2CCH3
OOC(CH3 & gt； three
㈨
Second year
calcium bicarbonate
(10)
The diesel cetane number improver composition provided by the invention can also include technicians in the field.
/become "
Known components for increasing cetane number of diesel oil, such as hexyl nitrate. Suitable examples of pestle nitrate include isooctyl nitrate and isoamyl nitrate. When the composition of the present invention also contains "alkane"
Based on the total amount of the composition, the content of organic peroxide is 15-80 wt%, the content of organic amine is 3-25 wt%, and the content of nitro ester is 15-80 wt%, wherein the content of organic peroxide is preferably 25-70 wt%. Because both alkyl nitrates and organic peroxides can improve the cetane number of diesel oil, when they are used together, they can not only exert their respective advantages, but also act synergistically, so that the composition contains more active oxygen elements than conventional peroxides, thus promoting the combustion of diesel oil and improving the cetane number of diesel oil more obviously.
The diesel cetane number improver composition provided by the invention can be prepared by the conventional preparation method of the diesel cetane number improver composition, except that the diesel cetane number improver composition is formed.
10 is the above-mentioned component described in the present invention.
The invention also provides a diesel oil, which contains base oil and cetane number improver, wherein the cetane number improver is the diesel oil cetane number improver composition provided by the invention.
Based on the total amount of diesel oil, the content of the cetane number improver composition is as follows
0.03-0.20 wt%, preferably 0.05-0. 16 wt%.
The base oil can be various diesel fractions with a boiling range of about 170-37(TC), including petroleum diesel, biodiesel and Fischer-Tropsch diesel.
The diesel oil of the present invention may also contain other additives that will not adversely affect the realization of the present invention, such as preservatives, rust inhibitors, detergents and dispersants, dyes, etc.
According to the diesel oil of the present invention, the diesel oil cetane number improver composition can be mixed with base oil to prepare diesel oil, or various components constituting the diesel oil cetane number improver composition can be directly mixed with base oil to prepare diesel oil. The mixing order of the components is not particularly limited.
The invention will be further illustrated by examples.
Example 1
This example is used to illustrate the cetane number improver composition for diesel oil, diesel oil containing the composition and its preparation method.
0.7 g of 1, 1- bis (tert-butyl peroxide) cyclohexene and 0. 1 g of N- ethoxyaniline were mixed to obtain the diesel cetane number improver composition of the invention.
All the above diesel fuel cetane number improver compositions were added to 1000g diesel fuel fraction (base oil a) with a boiling range of180-350.d egree. C. and a cetane number of 42.2, and uniformly mixed to obtain a diesel fuel sample containing 0.08 wt% of the above composition.
Comparative example 1
This comparative example illustrates the cetane number improver of diesel oil in the prior art and diesel oil containing the improver.
Ii and its preparation method.
A diesel sample was prepared according to the method described in Example 1, except that 0.8g of 1, 1- bis (tert-butyl peroxide) cyclohexene was used instead of 0.7g of 1, 1- bis (tert-butyl peroxide) cyclohexene and n-ethoxybenzene.
0. 1 g, a diesel sample containing 0.08 wt% 1. 1- bis (tert-butyl peroxide) cyclohexane was obtained. Example 2
This example is used to illustrate the cetane number improver composition for diesel oil, diesel oil containing the composition and its preparation method.
Add 2,2-di (tert-butyl peroxide) butyl 1.4g and N- acetyl-p-ethoxyaniline 0. 1g 1000 diesel fraction (base oil a) with boiling range of 180-350℃ and cetane number of 42.2.
Comparative example 2
This comparative example illustrates the cetane number improver of diesel oil in the prior art, diesel oil containing the improver and its preparation method.
A diesel sample was prepared according to the method described in Example 2, except that 2,2-di (tert-butylperoxide) butylstilbene 1.5g was used instead of 2,2-di (tert-butylperoxide) butylstilbene 1.4g and N- acetyl-p-ethoxyaniline 0.1g.
Example 3
This example is used to illustrate the cetane number improver composition for diesel oil, diesel oil containing the composition and its preparation method.
Add 1.0g of tert-butyl benzoate peroxide and 0.2g of tetradecyl dimethyl tertiary amine into 1000g of diesel oil fraction (base oil A) with boiling range of180-350 C and cetane number of 42.2, and mix evenly.
12, and a diesel sample with the total content of tert-butyl benzoate peroxide and tetradecyl dimethyl tertiary amine of 0. 12% by weight was obtained.
Comparative example 3
This comparative example illustrates the cetane number improver of diesel oil in the prior art, diesel oil containing the improver and its preparation method.
A diesel sample was prepared as described in Example 3, except that tert-benzoate peroxide was used.
Butyl ester 1.2g instead of tert-butyl benzoate 1.0g and 0.2g of tetradecyl dimethyl tertiary amine, a diesel sample containing 0. 12wt% tert-butyl benzoate was obtained.
Example 4
This example is used to illustrate the cetane number improver composition for diesel oil, diesel oil containing the composition and its preparation method.
Add 1.0g of tert-butyl benzoate peroxide and 0.2g of octyldimethyl tertiary amine into 1000g of diesel oil fraction (base oil A) with cetane number of 42.2 at 180-350℃, and mix evenly to obtain the total content of tert-butyl benzoate peroxide and octyldimethyl tertiary amine of 0.650.
Example 5
This example is used to illustrate the cetane number improver composition for diesel oil, diesel oil containing the composition and its preparation method.
0.5g of 1, 1- bis (tert-butyl peroxide) cyclohexane, 0. 1g of N- ethoxyaniline and 0.9g of isooctyl nitrate were mixed to obtain the diesel cetane number improver composition of the invention.
All of the above-mentioned diesel oil cetane number improver compositions were added into 170-370℃ and 1000g diesel oil fraction (base oil b) with a boiling range of 50. 1, and evenly mixed to obtain diesel oil containing 0. 15.
13 wt% of diesel oil sample with the above composition. Comparative example 4
This comparative example illustrates the diesel oil hexadecyl improver composition, diesel oil containing the composition and its preparation method in the prior art..
A diesel sample was prepared according to the method described in Example 5, except that 0.6g 1, 1- bis (tert-butylperoxy) cyclohexene and 0.9 g isooctyl nitrate were used to obtain a diesel sample containing 0. 15 wt% of a complexing agent.
Example 6
This example is used to illustrate the cetane number improver composition for diesel oil, diesel oil containing the composition and its preparation method.
0.9 g of 2,2-bis (tert-butyl peroxide) butane, 0.4 g of isooctyl nitrate and 0. 1 g of N- acetoethoxyaniline were added to 1000 g of diesel oil with a boiling range of 170-37(TC and cetane number of 50. 1).
Comparative example 5
This comparative example illustrates the cetane number improver composition of diesel oil in the prior art, diesel oil containing the composition and its preparation method.
A diesel sample was prepared according to the method described in Example 6, except that 0.5g of isooctyl nitrate was used instead of 0.4g of isooctyl nitrate and 0.1g of n-acetoethoxyaniline, and a diesel sample containing 0. 14wt% of complexing agent was obtained.
Example 7
This example is used to illustrate the diesel cetane number improver composition provided by the invention and the diesel oil containing the composition.
14 diesel oil and its preparation method.
0.3g of tert-butyl benzoate peroxide, 0.l of tetradecyl dimethyl tertiary amine and isoamyl nitrate.
0.3 g of ester was added to 1000 g of diesel fraction (base oil b) with a boiling range of170-370.degree. C. and a cetane number of 50. 1, and evenly mixed to obtain a diesel sample containing 0.07% by weight of the above composition.
Comparative example 6
This comparative example illustrates the cetane number improver composition of diesel oil in the prior art, diesel oil containing the composition and its preparation method.
A diesel sample was prepared according to the method described in Example 7, except that 0.35g of benzoic acid peroxide, 0.35g of tert-butyl ester and 0.3g of isoamyl nitrate were used instead of 0.3g of tert-butyl benzoate, 0. 1g of tetradecyl dimethyl tertiary amine and 0.3g of isoamyl nitrate, and a diesel sample containing 0.07% by weight of a complexing agent was obtained.
Example 8
This example is used to illustrate the cetane number improver composition for diesel oil, diesel oil containing the composition and its preparation method.
0.3 g of tert-butyl benzoate peroxide, 0. 1 g of octadecyl dimethyl tertiary amine and 0.3 g of isoamyl nitrate were added to 1000 g of diesel oil fraction (base oil b) with boiling range of 170-370℃ and cetane number of 50. 1 and mixed.
performance test
The cetane number of diesel oil samples prepared in the above example 1-8 and comparative example 1-6 were determined by GB/T 386-9 1, respectively, and the effect of diesel oil cetane number improver was evaluated. See table 1 for the results.
15 sample 16 foot value 16 foot added value
Base oil A42.2
Example 144.82.6
Comparative example 144.82.6
Example 245.93.7
Comparative example 245.83.6
Example 345.43.2
Comparative example 345.5 inches
Example 445, 33. 1
Base oil B50. 1
Example 555.55.4
Comparative example 455.55.4
Example 654.74.6
Comparative example 554.84.7
Example 752.72.6
Comparative example 652.72.6
Example 852.82.7
The results in table 1 show that the cetane number improver composition for diesel oil provided by the invention can effectively improve the cetane number of diesel oil. In addition, the cetane number of diesel samples using two cetane number improvers, namely, multiple groups of peroxide and alkyl nitrate, increased more significantly.
The cetane number of diesel oil samples prepared in Example 1-8 and Comparative Example 1-6 was measured by GB/T 386-9 1 method to evaluate the stability of diesel oil cetane number improver. Look at the results.
162。
Table 2
Samples on day 1 day, day 10, day 20 and day 30
Base oil A42.242
Example/kloc-0 144.844.844.844
Comparative example 144.843.543.5438+042.7
Example 245.945.945.945.8
Comparative example 245.845.444.743.6
Example 345.445.345.345.3
Comparative example 345.54544.343.5
Example 445.345.345.345.2
Base oil b 50.150.150.150.1
Example 555.555.455.355.3
Comparative example 455.555. 154.554.5
Example 654.754.654.654.6
Comparative Examples 554.854,253.553.2
Example 752.752.752.752.7
Comparative example 652.752.2 1.9438+0.7.
Example 852.852.852,752.7
The results in Table 2 show that the diesel sample using the diesel cetane improver containing organic amine provided by the invention shows good cetane stability, while the cetane number of the diesel sample without organic amine in the diesel cetane improver decreases with time.
As can be seen from the results in the above table 1 and table 2, the diesel cetane number improver provided by the invention does not
17 can not only effectively improve the cetane number of diesel oil, but also keep the cetane number of diesel oil unchanged for a long time, greatly improving the stability of cetane number of diesel oil.
claim of right
1. A diesel oil cetane number improver composition, which is characterized by containing organic peroxide and organic amine.
2. The composition according to claim 1, wherein the content of organic peroxide is 10-97 wt% and the content of organic amine is 3- 9 wt% based on the total amount of the composition.
3. The composition according to claim 2, wherein the content of organic peroxide is 70-97 wt% and the content of organic amine is 3-30 wt% based on the total amount of the composition.
4. The composition according to claim 3, wherein the content of organic peroxide is 80-95 wt% and the content of organic amine is 5-20 wt% based on the total amount of the composition.
5. The composition according to claim 1-4, wherein the organic amine is selected from at least one of compound A represented by formula (I), compound B represented by formula (II) and compound C represented by formula (III), wherein & is D-D alkoxy; The position on benzene ring is ortho, meta or para of amide group; R2 is a radical of Q-Qo; The molecular formula is shown on page 2 of the original document, in which R3 is hydrogen or c,-c. The position of R3 on benzene ring is ortho, meta or para of secondary amine; R4 is C 1-c8 alkyl; The formula is shown on page 3 (iii) of the original document, where Rs is an alkyl group of c8-C22; R6 and R7 are each one of methyl, ethyl, propyl and butyl.
6. The composition according to claim 5, wherein &: is an alkoxy group of D-C4, R2 is a pendant group of CrC4, and R3 is hydrogen or a pendant group of D-C4; It is C4 alkyl, and R5 is C8-C 18 alkyl.
7. The composition according to claim 5, wherein the compound A is N- acetoethoxyaniline; Compound b is N- ethoxyaniline; Compound c is tetradecyl dimethyl tertiary amine.
8. The composition according to claim 1-4, wherein the organic peroxide is a polyalkyl peroxide, and the polyalkyl peroxide has a partial formula shown in the formula. (VII), wherein R8, R9 and Ru) are each one of methyl, ethyl, propyl and butyl, and the formula is original.
9. The composition according to claim 8, wherein the polyhydroxy peroxide is one or more of 1, 1- bis (tert-butyl peroxide) cyclohexane, 2,2-bis (tert-butyl peroxide) butyl peroxide and tert-butyl benzoate.
10. The composition according to claim 1 or 2, wherein the composition further contains alkyl nitrate.
1 1. The composition according to claim 10, wherein the content of organic peroxide is 15-80 wt%, the content of organic amine is 3-25 wt%, and the content of nitro ester is 15-80 wt% based on the total amount of the composition.
12. The composition according to claim 1 1, wherein based on the total amount of the composition, the content of organic peroxide is 25-70wt%, the content of organic amine is 5-20wt%, and the content of alkyl nitrate is 25-65wt%.
13. The composition according to claim 10, wherein the alkyl nitrate is at least one of isooctyl nitrate and isoamyl nitrate.
14. A diesel oil contains base oil and a diesel cetane number improver, characterized in that the diesel cetane number improver is the diesel cetane number improver composition according to any one of claims 1- 13.
15. The diesel oil according to claim 14 is characterized in that the content of the diesel oil cetane number improver composition is 0.03-0.20 wt% of the total diesel oil.
Full text abstract
A diesel oil cetane number improver composition contains organic peroxide and organic amine. The invention also provides a diesel oil, and the cetane number improver used in the diesel oil is the diesel oil cetane number improver composition provided by the invention. The cetane number improver composition for diesel oil provided by the invention overcomes the defect that the cetane number of diesel oil decreases with time by using an organic peroxide cetane number improver, effectively improves the cetane number of diesel oil and maintains its stability. The diesel oil cetane number improver composition can be used for light diesel oil, heavy diesel oil, Fischer-Tropsch diesel oil and boiler fuel oil. The cetane number of diesel oil added with the cetane number improver composition of diesel oil is improved and stable, so that the combustion performance is improved, the power and economy of the engine are improved, and the tail gas emission pollution of the engine is improved.
The file number is c10l1012gk101469284sq200710304358.
Release date: July 20091; Date of application: February 27th, 2007; Priority date: February 27th, 2007.
Inventor, Shu Xingtian, Huang Applicant: China Petrochemical Company Limited; China Petrochemical Company Petrochemical Research Institute