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Additives for Cetane Improvement in Middle Distillate Fuels

a technology of additives and distillates, applied in the direction of fuel additives, liquid carbonaceous fuels, petroleum industry, etc., can solve the problems of self-accelerated decomposition, dangerous fire and explosive hazards,

Inactive Publication Date: 2010-12-30
BAKER HUGHES INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0008]Also provided in another non-limiting embodiment are methods for improving the cetane number of a middle distillate fuel by adding to the fuel an effective amount of an additive composition that includes a polymer component or combination of polymers that may be a polyolefin homopolymer or a random or block polyolefin copolymer and mixtures thereof, where the homopolymer or random copolymer has a weight average molecular weight ranging from about 200,000 to about 5,000,000. The polymer may be linear, branched or crosslinked. Again, the additive composition additionally contains a solvent such as an alcohol and also includes a free radical initiator component which may be an alkyl nitrate and / or a peroxide.

Problems solved by technology

However, most of these cetane improvers are thermally sensitive, that is, they can undergo self accelerated decomposition under thermal (elevated temperature) conditions.
Organic peroxides typically have self accelerated decomposition temperature (SADT) less than 80° C. Some other cetane improvers such as certain nitrite and azo compounds are even shock sensitive, which may pose a dangerous fire and explosive hazard in the field.

Method used

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  • Additives for Cetane Improvement in Middle Distillate Fuels
  • Additives for Cetane Improvement in Middle Distillate Fuels

Examples

Experimental program
Comparison scheme
Effect test

examples 1-18

[0025]Tables I through IV are compilations of experimental cetane number test results using the ASTM D613 test methodology in a Midwestern, Eastern, Western and CARB Diesel ultra-low sulfur diesel (ULSD) fuels. All tests were performed at Southwest Research Institute (SwRI) unless otherwise noted. The data show that in these ULSDs, the same level of cetane improvement may be achieved by replacing the relatively more expensive 2-EHN with an additive composition containing 0.2% of an about 2,000,000 Mw PIB homopolymer synergist. The results are plotted in FIG. 1.

TABLE ICetane Synergist Performance SummaryCetane Engine Test Results via ASTM D613 (Midwestern ULSD)Synergist2-EHNCetane NumberEx.Dosage, ppmDosage, ppmCetane #Improvement10044.8—20100048.23.4340060048.43.6450050048.33.5560040048.33.5

TABLE IICetane Synergist Performance SummaryCetane Engine Test Results via ASTM D613 (Eastern ULSD)Synergist2-EHNCetane NumberEx.Dosage, ppmDosage, ppmCetane #Improvement60047.7—70100049.61.98400...

examples 19-26

[0027]Examples 19-26 present the results of testing from the combination of diluted polymer synergist and 2-EHN which worked better than either additive used individually. In these comparisons, the solvent is believed to help improve the cetane number. The synergist was again 2,000,000 Mw PIB homopolymer. The fuels used were a ULSD and CARB Diesel. The results of Table VI are graphed in FIG. 2. FIG. 2 illustrates that with total 1000 ppm of either polymer synergist and solvent, 2-EHN and solvent, or polymer synergist and 2-EHN, the latter combination surprisingly gives the best results. The solvent was butanol.

TABLE VSynergistic Effect of 2-EHN and Cetane SynergistCetane Engine Test Results via ASTM D613 (Valero ULSD)2-EHNSynergistEx.Dosage, ppmDosage, ppmSolventCetane #1900—50.420050050047.121500050049.822500500—51.4

TABLE VISynergistic Effect of 2-EHN and Cetane SynergistCetane Engine Test Results via ASTM D613 (CARB Diesel)2-EHNSynergistEx.Dosage, ppmDosage, ppmSolventCetane #2300...

examples 27-29

[0028]During testing, all high molecular weight polymers ranging from about 900,000 to 2,100,000 only showed marginal performance when used alone for NOx reduction. It was surprisingly discovered that when about 2,000,000 Mw PIB polymer was used with 2-EHN that a clear synergistic effect was shown that gave a 6.2% NOx reduction as compared with only 0.1% reduction when only the 1% PIB mixture was used and only a 3.2% reduction when 2-EHN was used alone. The fuel used was a typical ULSD from a Valero refinery. The 1% PIB mixture was 1 vol % about 2,000,000 Mw PIB homopolymer, 5 vol % butanol and 94% Chevron heavy aromatic distillates. From previous experiments, adding about 5 to about 10% mineral oil may also help lower the NOx emissions. The results are shown in Table VII.

TABLE VIIHigh Molecular Weight PIB Alone, EHN Alone and PIB + EHNEHNEx.Treat RatePIB activeConc.% NOxNo.Sample(ppm)(ppm)(ppm)Red.27BPC91 (0.2% PIB2000400.1mixture)282-EHN50005003.229BPC121 (1% PIB20003.24006.2mixtu...

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Abstract

The cetane number of middle distillate fuels may be increased using an additive composition including a polymer that may be a homopolymer or copolymer of olefins, and the like, where the polymer has a weight average molecular weight ranging from about 200,000 to about 5,000,000. The additive composition also includes a free radical initiator component, which may be an alkyl nitrate such as 2-ethylhexylnitrate (2-EHN), and / or a peroxide, such as t-butyl peroxide. In one non-limiting embodiment the amount of polymer in the additive composition is greater than the free radical initiator component. A solvent is also present, which the solvent may include alcohol, an alkyl substituted phenol and / or a heavy aromatic distillate.

Description

CROSS-REFERENCE TO RELATED APPLICATION[0001]This application is a continuation-in-part application from U.S. Ser. No. 12 / 128,918 filed May 29, 2008, which is incorporated herein by reference, and which in turn claims the benefit of U.S. Provisional Patent Application No. 60 / 940,914 filed May 30, 2007.TECHNICAL FIELD[0002]The present invention relates to additives for middle distillate fuels, such as diesel, and more particularly relates, in one embodiment to methods for improving the cetane number of middle distillate fuels using chemical additives.TECHNICAL BACKGROUND[0003]Cetane number is a measurement of the combustion quality of middle distillate fuels during compression ignition. Middle distillate fuels include heating oil, diesel, kerosene, jet fuel and the like. It is a significant expression of middle distillate fuel quality among a number of other measurements that determine overall middle distillate fuel quality. The cetane number is a measure of a fuel's ignition delay; t...

Claims

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Application Information

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IPC IPC(8): C10L1/18C10L1/23
CPCC10L1/143C10L1/1616C10L1/1641C10L1/1811C10L1/1824C10L10/12C10L1/1832C10L1/1857C10L1/231C10L10/02C10L1/183
Inventor YANG, JIANZHONGZETLMEISL, MICHAEL J.BIGGERSTAFF, PAUL J.
Owner BAKER HUGHES INC
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