FUEL COMPOSITION OF DIESEL FUEL

Information

  • Patent Application
  • 20230053569
  • Publication Number
    20230053569
  • Date Filed
    October 20, 2022
    a year ago
  • Date Published
    February 23, 2023
    a year ago
  • Inventors
    • Aristov; Andrey Viacheslavovich
Abstract
The invention relates to a fuel composition based on a diesel fraction, having a sulphur content of less than 10 mg/kg with the boiling range of 180-360° C., characterized in that said fuel composition contains organic peroxides as ignition promoters, which are selected from the group: di-tert-butyl peroxide, 1,1-di-(tert-butylperoxy)cyclohexane, dicumyl peroxide, tert-butyl cumyl peroxide, isobutyl cumyl peroxide, n-butyl cumyl peroxide, isopropyl cumyl peroxide, ethyl cumyl peroxide and methyl cumyl peroxide, and contains an anti-wear additive based on carboxylic acids having the following ratio of components, wt %: 0.01-0.5 organic peroxide, 0.005-0.1 anti-wear additive, and up to 100 being the diesel fraction. The proposed diesel fuel composition allows producing diesel fuel which meets quality performance requirements.
Description
TECHNICAL FIELD

The invention relates to petroleum refining and petrochemistry, namely, to a diesel fuel composition.


BACKGROUND

Diesel fuel remains the most highly-demanded petroleum product both in the worldwide and in the Russian markets. It is mostly consumed by railway, water and road freight transportation, as well as by various electric generators, military and agricultural equipment.


Modern diesel fuel is a deeply hydroprocessed product having various additives, which provide the required environmental and operational properties.


A very important quality in the parameters of diesel fuel that characterizes its volatility is the cetane number, and its optimal value provides good starting properties of fuel, as well as a lesser amount of noxious emissions along with exhaust gases.


In order to enhance the ignition of diesel fuels, ignition promoters are used. Nowadays, additives based on 2-ethylhexyl nitrate are used as the ignition promoters in Russia. However, along with advantages, 2-ethylhexyl nitrate has a number of disadvantages: it is explosion-dangerous, may decompose upon explosion, accelerates the fuel oxidation, comprises nitrogen, corrosive relative to metals, and deteriorates antiwear properties of diesel fuel. It is known that in presence of the ignition promoter based on 2-ethylhexyl nitrate, the concentration of the antiwear additive must be increased in order to achieve the required fuel lubricity. Also, investigators note that the cetane numbers of diesel fuels are reduced in the process of their storage, which is explained by decomposition (by hydrolysis) of 2-ethylhexyl nitrate in the presence of water.


Abroad in view of the limitation of the nitrogen content in diesel fuel, the California Air Resources Board (CARB) implies a successive transition to output of diesel fuels with peroxides.


An additive for a low-sulfur diesel fuel is known in order to reduce the fuel consumption in a diesel engine, characterized in that it comprises peroxide in the amount of from 0.001 wt. % to 10 wt. %.


(Application WO 2016/174176 A1, 2016).


The additive disadvantage lies in an insufficient efficiency in terms of increase of lubricity the diesel fuel lubricity that does not allow the enhancement of this parameter up to the standard requirements.


(U.S. Pat. No. 5,314,511, 1994).


The composition disadvantage lies in a high sulfur content in the fuel composition being up to 500 mg/kg of sulfur, while nowadays, modern diesel fuels comprise up to 10 mg/kg of sulfur. When testing the obtained samples of the fuel composition, an influence of the additive onto the fuel consumption was studied and a toxicity of emissions was evaluated, i.e. environmental properties were evaluated, rather than operational ones.


The closest analogue of the suggested fuel composition is a diesel fuel formulation comprising an additive of premixed cyclohexyl nitrate or 2-ethylhexyl nitrate and peroxides selected from a group of: ditert-butyl peroxide, dicumyl peroxide, cumyl hydroperoxide under a mass ratio of said components from 3:1 to 1:3 in the amount of the additive of 0.1-0.5 wt. %.


(RU Patent No. 2451718, 2012).


This composition disadvantage lies in a presence of the diesel fuel produced according to the GOST 305-82 that is characterized by an increased content of sulfuric compounds (up to 0.05 wt. %). Such diesel fuels have good lubricating properties and do not require adding of antiwear additives. Also, this fuel is produced to supply according to the state defense order only and for export. Also, the formulation of this fuel composition comprises nitrates that does not allow reduction of the content of nitrogen oxides in exhaust gases to the minimum.


SUMMARY

In one aspect of the invention, a fuel composition is provided, where the fuel composition based on a diesel fraction having a sulfur content of less than 10 mg/kg with boiling points in the range of 180-360° C., characterized in that it comprises ignition promoters such as organic peroxides selected from a group of: di-tert-butyl peroxide, 1,1-di(tert-butyl peroxy)cyclohexane, dicumyl peroxide, and an antiwear additive based on carboxylic acids having the following ratio of components, wt. %:

    • organic peroxide from 0.01 to 0.5,
    • antiwear additive from 0.005 to 0.1, diesel fraction up to 100.


In another aspect of the invention, a fuel composition is provided where the fuel composition is based on a diesel fraction having a sulfur content of less than 10 mg/kg with boiling points in the range of 180-360° C., characterized in that it comprises ignition promoters such as organic peroxides selected from a group of: tert-butyl cumyl peroxide, isobutyl cumyl peroxide, n-butyl cumyl peroxide, and an antiwear additive based on carboxylic acids having the following ratio of components, wt. %:

    • organic peroxide from 0.01 to 0.5,
    • antiwear additive from 0.005 to 0.1,
    • fraction up to 100.


In another aspect of the invention, a fuel composition is provided where the fuel composition is based on a diesel fraction having a sulfur content of less than 10 mg/kg with boiling points in the range of 180-360° C., characterized in that it comprises ignition promoters such as organic peroxides selected from a group of: isopropyl cumyl peroxide, ethyl cumyl peroxide, methyl cumyl peroxide, and an antiwear additive based on carboxylic acids having the following ratio of components, wt. %:

    • organic peroxide from 0.01 to 0.5,
    • antiwear additive from 0.005 to 0.1
    • diesel fraction up to 100.







DETAILED DESCRIPTION

A task of the invention is to create a fuel composition of a low-sulfur diesel fuel using organic peroxides as ignition promoters that could meet the requirements of GOST 32511-2013, GOST R 52368-2005, EN 590, GOST R 55475-2013, TR CU 013/2011.


The posed task is solved by the proposed diesel fuel composition including a diesel fraction with a sulfur content of less than 10 mg/kg with boiling points in the range of 180-360° C., characterized in that it comprises a synergistic combination of an organic peroxide as an ignition promoter (up to 0.5 wt. %) and an antiwear additive based on carboxylic acids (up to 0.1 wt. %).


In order to prepare a basic diesel fuel, the following components are used: ultra-low-sulfur (having the sulfur content of less than 10 mg/kg)=hydroprocessed diesel fraction and/or a hydrocracking diesel fraction with boiling points in the range of 180-360° C.


The proposed diesel fuel is prepared using a standard equipment by mixing components and additives until a homogeneous product is obtained.


Characteristics of the diesel fuel components, which are used in examples to support the proposed invention, are shown in Table 1.


As examples of the proposed invention, the diesel fuel compositions were prepared, with their test results stated in Tables 2, 3 and 4, wherein results of testing the diesel fuel comprising 2-ethylhexyl nitrate as the ignition promoter are provided for comparison.


The test results show that the diesel fuel samples comprising organic peroxide as the ignition promoter are highly competitive, in terms of an increment of the cetane numbers, with diesel fuels comprising 2-ethylhexyl nitrate as the ignition promoter.


The combination of the additives' package in the formulation of the diesel fuel, where the package comprises an organic peroxide and the antiwear additive based on carboxylic acids, has a synergistic effect in terms of the lubricity of the fuel. Table 2 states experimental values of the corrected wear scar diameter according to the HFRR method for each diesel fuel sample. For comparison, the tables also state data regarding the lubricity of the diesel fuel samples, which comprise 2-ethylhexyl nitrate as an ignition promoter, while the formulation and concentration of the antiwear additive remain unchanged. Unexpectedly, it has been found that the peroxide additive in the package with the antiwear additive based on carboxylic acids does not negatively affect the lubricity of the diesel fuel as opposed to 2-ethylhexyl nitrate. The distinctive feature of the invention is the synergistic effect that is observed in case of the combined use of the organic peroxides as ignition promoters and the antiwear additive based on carboxylic acids in the diesel fuel (having the sulfur content of less than 10 mg/kg).


It is known that 2-ethylhexyl nitrate facilitates formation of resinous compounds in diesel fuels and acceleration of the fuel oxidation. The obtained data (Table 2) allow to conclude that the ignition promoters based on organic peroxides have less impact onto formation of a residue. This is advantageous as compared to the ignition promoters based on 2-ethylhexyl nitrate. The number of adsorption resins in fuels comprising ignition promoters based on organic peroxides and 2-ethylhexyl nitrate are commensurable and fall within limits of the method reproducibility.


The effective combination of the ignition promoters based on organic peroxides and the antiwear additive based on carboxylic acids may allow to reduce the concentration of the latter one. This is an advantage as compared to the ignition promoters based on 2-ethylhexyl nitrate, which, when they are used, make it necessary to increase the concentration of the antiwear additive in order to achieve the required lubricity.


Therefore, the proposed diesel fuel composition allows to produce the diesel fuel that meets the requirements of GOST 32511-2013, GOST R 52368-2005, EN 590, GOST R 55475-2013 and TR CU 013/2011 in terms of quality parameters.









TABLE 1







Main characteristics of the diesel fuel components










Hydroprocessed
Hydrocracking


Parameter
diesel fraction
diesel fraction












Cetane number, un.
46.2
55.7


Lubricity: the corrected parameter of
564
635


the wear scar diameter at 60° C., μm




Fractional formulation:
9.5
1.1


distilled up to 180° C., vol. %




distilled up to 360° C., vol. %
97.4
98.3


Overall sulfur content, mg/kg
<10
5.1









Tables 2, 3, 4-The component formulation of the samples of the proposed diesel fuel composition comprising the synergistic composition of the organic peroxide and the antiwear additive based on carboxylic acids, and results of its testing in comparison with the composition comprising 2-ethylhexyl nitrate.










TABLE 2








Content of the components, wt. %/number of sample/

















Component
1
2
2a
2b
3
3a
4
4a
4b
5





Hydroprocessed
99.97
99.77
99.47
99.5
99.77
99.7
99.77
99.77
99.47
99.77


diesel fraction












Hydrocracking












diesel fraction












Antiwear additive
0.03
0.03
0.03

0.03
0.1
0.005
0.03
0.03
0.03


Di-tert-butyl

0.2
0.5
0.5








peroxide












1,1-di




0.2
0.2






(tert-butyl












peroxy)cyclohexane












Dicumyl peroxide






0.01
0.2
0.3



2-ethylhexyl nitrate









0.2








Parameter
Parameter value

















Lubricity: the
398
356
328
359
359
332
425
348
325
405


corrected parameter












of the wear scar












diameter at












60° C., μm












Cetane number,
46.2
52.0
54.6
54.6
53.3
53.3
51.4
54.8
53.2 text missing or illegible when filed
53.2


in text missing or illegible when filed












Content of adsorption

692
765
698
805
867
769
785
803
744


resine, mg per












100 cm2 of the fuel












Overall residue mass,

0.300
0.400
0.375
0.675
0.725
0.725
0.700
0.675
0.750


ml/106 ml 2)






































Requirements of











GOST 32511-











2013, GOST R














Content of the components, wt. %/number of sample/
52368-2005 and
















Component
6
7
8
8a
8
10
TR CU 013/2011




















Hydroprocessed











diesel fraction











Hydrocracking
99.97
99.77
99.77
99.7
99.77
99.77





diesel fraction











Antiwear additive
0.03
0.03
0.03
0.1
0.03
0.03





Di-tert-butyl

0.2









peroxide











1,1-di


0.2
0.2







(tert-butyl











peroxy)cyclohexane











Dicumyl peroxide




0.2






2-ethylhexyl nitrate





0.2














Parameter
Parameter value


















Lubricity: the
404
438
354
337
380
467
not more than 460

















corrected parameter











of the wear scar











diameter at











60° C., μm
























Cetane number,
55.7
64.7
62.2
62.2
63.2
62.2
not less than 51

















in text missing or illegible when filed
























Content of adsorption

333
263
328
236
116
not more than 2500 1)

















resine, mg per











100 cm2 of the fuel
























Overall residue mass,

0.450
0.550
0.650
0.575
0.625
not more than 2

















ml/106 ml 2)













Note:



1) Determined according to STO 11605031-056, the regulation is established within the MCO (MKO),




2) Determined according to STO 11605031-077-2013, the method is qualified, it is not included into the ND for diesel fuel




text missing or illegible when filed indicates data missing or illegible when filed















TABLE 3








Content of the components, wt. %/number of sample/

















Component
1
2
2a
2b
3
3a
4
4a
4b
5





Hydroprocessed
99.97
99.77
99.47
99.5
99.77
99.7
99.77
99.77
99.47
99.77


diesel fraction












Hydrocracking












diesel fraction












Antiwear additive
0.03
0.03
0.03

0.03
0.1
0.005
0.03
0.03
0.03


Tert-butyl cumyl

0.2
0.5
0.5








peroxide












Isobutyl cumyl




0.2
0.2






peroxide






0.01
0.2
0.5



2-ethylhexyl nitrate









0.2








Parameter
Parameter value

















Lubricity: the
398
356
328
559
359
332
425
346
325
405


corrected parameter












of the wear scar












diameter at












60° C., μm












Cetane number,
46.2
52.0
54.6
54.6
53.3
53.3
51.4
54.6
57.2
53.2


in text missing or illegible when filed












Content of adsorption

692
785 text missing or illegible when filed
698
805
867
769
785
803
744


resine, mg per












150 cm2 of the fuel












Overall residue mass,

0.305
0.400
0.375
0.675
0.725
0.725
0.700
0.675
0.750


ml/106 ml 2)






































Requirements of











GOST 32511-











2013, GOST R














Content of the components, wt. %/number of sample/
52368-2005 and
















Component
6
7
8
8a
9
10
TR CU 013/2011




















Hydroprocessed











diesel fraction
























Hydrocracking
99.97
99.77
99.77
99.7
99.77
99.77


















diesel fraction











Antiwear additive
0.03
0.03
0.03
0.1
0.03
0.03





Tert-butyl cumyl

0.2









peroxide











Isobutyl cumyl


0.2
0.2







peroxide




0.2






2-ethylhexyl nitrate





0.2














Parameter
Parameter value


















Lubricity: the
404
418
354
337
380
467
not more than 460

















corrected parameter











of the wear scar











diameter at











60° C., μm
























Cetane number,
55.7
64.7
62.2
62.2
63.2
62.2
not less than 51

















in text missing or illegible when filed
























Content of adsorption

133
263
328
236
120
not more than 2500 1)

















resine, mg per











150 cm2 of the fuel
























Overall residue mass,

0.450
0.550
0.630
0.575
0.625
not more than 2

















ml/106 ml 2)













Note:



1) Determined according to STO 11605031-056, the regulation is established within the MCO (MKO),




2) Determined according to STO 11605031-077-2013, the method is qualified, it is not included into the ND for diesel fuel




text missing or illegible when filed indicates data missing or illegible when filed















TABLE 4











Content of the components, wt. %/number of sample/


















Component
1
1a
2
2a
2b
2c
2d
3
3a
3b
3c





Hydroprocessed
99.97
99.77
99.77
98.87
99.5
99.07
99.77
99.77
99.7
99.4 
98.2 


diesel fraction













Hydrocracking













diesel fraction













Antiwear additive
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.3
0.1
0.3


Isopropyl cumyl

0.2











peroxide













Ethyl cumyl





0.3
0.2






peroxide













Methyl cumyl









0.3
0.3


peroxide













2-ethylhexyl













acetate text missing or illegible when filed



















Parameter
Parameter value


















Lubricity: the
398
372
356
328
328 text missing or illegible when filed
382
363
350
323
262   
354   


corrected













parameter













of the wear scar













diameter at













60° C., μm













Cetane number,
46.2
35.5
52.9
34.6
34.6
58.6
35.3
35.3
35.3
33.5 
33.1 


in text missing or illegible when filed













Content of

708
602
705
695
732
728
800
867
832   
836   


adsorption













resine, mg per













150 cm2 of the













fuel













Overall residue

0.350
0.300
0.400
0.375
0.425
0.400
0.635
0.720
 0.625
 0.700


mass, ml/106 ml 2)









































Requirements of












GOST 32511-














Content of the components, wt. %/number of sample/
2013, GOST R



























52368-2005 and

















Component
4
4a
4b
4c
5
9
10
TR CU 013/2011





















Hydroprocessed
98.77
99.77
99.87
99.49
99.77







diesel fraction












Hydrocracking





99.77
99.77





diesel fraction












Antiwear additive
0.005
0.03
0.03
0.03
0.03
0.03
0.03





Isopropyl cumyl



0.5








peroxide












Ethyl cumyl












peroxide












Methyl cumyl












peroxide












2-ethylhexyl




0.2

0.2





acetate text missing or illegible when filed




















Parameter
Parameter value


















Lubricity: the
425
336
325
353
405
380
407
not more



corrected







than 460


















parameter












of the wear scar












diameter at












60° C., μm


























Cetane number,
11.4
34.0
57.2
56.3
87.1 text missing or illegible when filed
63.3
83.2
not less than 51


















in text missing or illegible when filed


























Content of
749
785
805
792
346
256
110
not more than



adsorption







2500 1)



resine, mg per


























150 cm2 of the












fuel


























Overall residue
0.725
0.700
0.675
0.725
0.750
0.525 text missing or illegible when filed
0.623 text missing or illegible when filed
not more than 2


















mass, ml/106 ml 2)














Note:



1) Determined according to STO 11605031-056, the regulation is established within the MCO (MKO),




2) Determined according to STO 11605031-077-2013, the method is qualified, it is not included into the ND for diesel fuel




text missing or illegible when filed indicates data missing or illegible when filed






Claims
  • 1. A fuel composition based on a diesel fraction having a sulfur content of less than 10 mg/kg with boiling points in the range of 180-360° C., comprising as ignition promoters organic peroxides selected from a group of: di-tert-butyl peroxide, 1,1-di(tert-butyl peroxy)cyclohexane, dicumyl peroxide, and an antiwear additive based on carboxylic acids having the following ratio of components, wt. %: organic peroxide from 0.01 to 0.5;antiwear additive from 0.005 to 0.1; anddiesel fraction up to 100.
  • 2. A fuel composition based on a diesel fraction having a sulfur content of less than 10 mg/kg with boiling points in the range of 180-360° C., comprising as ignition promoters organic peroxides selected from a group of: tert-butyl cumyl peroxide, isobutyl cumyl peroxide, n-butyl cumyl peroxide, and an antiwear additive based on carboxylic acids having the following ratio of components, wt. %: organic peroxide from 0.01 to 0.5;antiwear additive from 0.005 to 0.1; anddiesel fraction up to 100.
Priority Claims (2)
Number Date Country Kind
2019101618 Jan 2019 RU national
2019112856 Apr 2019 RU national
CROSS-REFERENCE TO RELATED APPLICATION

This application is a Continuation of US national stage patent application Ser. No. 17/290,424 filed on Apr. 30, 2021, under 35 U.S.C. § 371, of International Patent Application No. PCT/RU2020/000021, filed Jan. 17, 2020, which claims priority to Russian Patent Application 2019112856, filed Apr. 26, 2019 and Russian Patent Application 2019101618, filed Jan. 22, 2019, which are incorporated herein by reference in their entirety.

Continuations (1)
Number Date Country
Parent 17290424 Apr 2021 US
Child 17969764 US