WO2000012654A1 - Reformulated reduced pollution diesel fuel - Google Patents
Reformulated reduced pollution diesel fuel Download PDFInfo
- Publication number
- WO2000012654A1 WO2000012654A1 PCT/US1999/018622 US9918622W WO0012654A1 WO 2000012654 A1 WO2000012654 A1 WO 2000012654A1 US 9918622 W US9918622 W US 9918622W WO 0012654 A1 WO0012654 A1 WO 0012654A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fuel
- less
- diesel
- volume percent
- certified
- Prior art date
Links
Classifications
-
- 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
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
Definitions
- This invention relates to a reformulated diesel fuel meeting the requirements of ASTM D975-96a and providing significantly reduced emissions by comparison to a certified diesel fuel, certified under Section 2282, Title 13, California Code of Regulations.
- Section 2282 California Air Resources Board (“CARB”) has adopted Section 2282, Title 13, California Code of Regulations (“Section 2282") which limits the aromatic hydrocarbon content of diesel fuel sold or intended for sale as a motor vehicle fuel in California starting Oct. 1, 1993.
- Section 2282 establishes a basic California s nationwide aromatic hydrocarbon limit for vehicular diesel fuel of 10 percent by volume with a less stringent 20 percent standard for small refiners and a temporary 20 percent standard for independent refiners.
- Sections 2282(a)(1)(C) and 2282(g) allow diesel fuel producers and importers to comply with the regulation with a set of diesel fuel specifications of their choosing if they can demonstrate that the alternative specifications result in emission benefits at least equivalent to the emission benefits resulting from a 10 volume percent aromatic hydrocarbon standard (or, in the case of small refiners, the 20 percent aromatic hydrocarbon standard) reference fuel.
- Section 2282(g) identifies a test procedure for comparative testing of a candidate fuel and a reference fuel representative of a diesel fuel with 10 percent aromatic hydrocarbons (or 20 percent by volume for small refiners) as specified in Section 2282(g) involving back-to-back tests using a specified heavy-duty diesel engine and identifies the statistical methodology to be used in comparing the emissions of NO x , paniculate matter, and the soluble organic fraction of the particulate matter resulting from the two fuels, and establishes a process for certifying diesel fuel formulations that satisfy the regulatory criteria.
- the reference fuel is defined as shown in Table I.
- Section 2282(g)(1) requires that an applicant for certification submit to the Executive Officer of CARB for approval a proposed test protocol which includes detailed information on the entity proposed to conduct the tests, the test procedures, analytical test data on the candidate and reference fuels, the quality control and quality assurance procedures, and identification of any statistical outlier tests to be used.
- the same section also provides procedures for applicants to submit a certification application which includes the approved test protocol, all of the test data, a copy of the complete test log, and a demonstration that the candidate fuel meets the requirements for certification.
- an Executive Order certifying the diesel fuel formulation will be issued which assigns an identification name to the specific certified diesel fuel.
- the Order must specify that the certified diesel fuel formulation has the following specifications: (1) a sulfur content, a total aromatic hydrocarbon content, a polycyclic aromatic hydrocarbon content, and a nitrogen content not exceeding that of the candidate fuel; (2) a cetane number not less than that of the candidate fuel; and (3) presence of all additives that were contained in the candidate fuel in a concentration not less than in the candidate fuel, except for an additive demonstrated by the applicant to have the sole effect of increasing cetane number.
- Chevron D-4781, F-2 and G-2, and one Texaco fuel Upon observation of these fuels, it is noted that these fuels have aromatic contents varying from 15 weight percent up to 24.7 weight percent. These fuels also contain sulfur in amounts from less than 5 parts per million by weight (ppmw) up to 496 ppmw. The fuels also include polycyclic aromatics in an amount equal to from about 1.9 to about 8.6 weight percent. The nitrogen contents vary from 20 to 1050 ppmw and the minimum cetane number varies from about 50.7 up to about 59.
- CARB CARB specifications for the reference fuel are shown in Table 1 and contain certain distillation requirements
- the properties of the TF-1 and TF-3 fuels in Table 2 at column 3 have initial boiling points lower than permitted in the test fuel, Ten volume percent distillation temperatures lower than permitted in the test fuel, aromatics much higher than are permitted in the reference fuel, polycyclic aromatics much higher than permitted in the reference fuel, nitrogen much higher than permitted in the reference fuel and, in the TF-3, an end point higher than permitted in the test fuel. This serves to emphasize that the fuels which may be marketed under CARB certifications have little in common with the requirements for the reference fuel.
- a reformulated diesel fuel meeting the requirements of ASTM D 975-96a for a low-sulfur No. 2 diesel fuel and providing reduced emission benefits relative to a certified diesel fuel, certified under Section 2282, Title 13, California Code of Regulations, is provided.
- the reformulated diesel fuel contains less than 15 volume percent aromatics and has a natural cetane number of at least 55; a sulfur content less than 15 ppmw; a nitrogen content less than 10 ppmw; a polycyclic aromatics content no greater than 1.5 weight percent; at least about 14 weight percent hydrogen, and an initial boiling point of at least 350°F.
- the reformulated diesel fuel includes less than 12 volume percent aromatics and preferably less than 10 volume percent aromatics.
- the reformulated diesel fuel may be produced by a process comprising charging a diesel fuel range feedstock having a boiling range from about 250 to about 790 °F (ASTM D-2887) to a hydrotreating zone with added hydrogen in the presence of a hydrotreating catalyst at conditions effective to convert at least a portion of the organo-nitrogen and organo-sulfur compounds to hydrocarbons, ammonia and hydrogen sulfide, to produce a hydrotreater effluent stream; charging at least a portion of the hydrotreater effluent stream to a hydrocracking zone with added hydrogen in the presence of a hydrocracking catalyst at conditions sufficient to produce a hydrocracking zone effluent containing a gasoline range fraction and a diesel fuel range fraction and fractionating the hydrocracking zone effluent to separate the gasoline fraction and produce the diesel fuel product.
- the feedstock contains aromatics in an amount and of a type such that, after processing in the hydrotreating zone and in the hydrocracking zone, the aromatics content is reduced to the desired level in the resulting diesel fuel product.
- the sulfur content, polynuclear aromatics content, nitrogen content and material types are controlled in the feedstock so that after processing in the hydrotreating zone and in the hydrocracking zone, the contents of the sulfur, polynuclear aromatics and nitrogen are within the limits specified above for the reformulated diesel fuel.
- the reformulated diesel fuel is useful in a method for reducing pollution resulting from the combustion of a CARB certified diesel fuel in diesel-powered ground transportation vehicles and other diesel-powered equipment by fueling such vehicles and equipment with the reformulated diesel fuel.
- the Figure is a schematic diagram of a process suitable for the production of the diesel fuel of the present invention.
- a reformulated diesel fuel which meets the requirements of ASTM D975-96a for a low-sulfur number 2-D diesel fuel and provides significantly reduced emissions relative to a certified diesel fuel certified under Section 2282, Title 13, California Code of Regulations.
- the reformulated fuel has a natural cetane number of greater than 55, a sulfur content less than 15 ppmw, and a polycyclic aromatics content no greater than 1.5 weight percent.
- the fuel has an aromatics content less than about 15 volume percent, a nitrogen content less than about 10 ppmw and an initial boiling point of at least 350°F and preferably contains no cetane enhancer.
- Various cetane enhancers are commercially marketed and used to increase the cetane of diesel fuels.
- cetane improvers such as ethyl hexyl nitrate
- Nitrogen oxides which are generated upon the combustion of such nitrogen- containing cetane improvers are generally considered to be an undesirable environmental pollutant.
- Non-combusted cetane improvers in diesel emissions may constitute a toxic emission and contribute to the formation of particulates.
- the fuel of the present invention has a low sulfur content which is suitably less than 15 ppmw but is preferably less than 10 ppmw and desirably less than about 5 ppmw.
- the combustion of fuels containing sulfur compounds results in the production of undesirable particulate emissions.
- CARB has recently deterrnined that the particulates in diesel emissions are toxic. Sulfur also has a detrimental effect on diesel engine after-treatment devices such as catalytic converters. Accordingly, the sulfur content of the present fuel is low.
- the content of polycyclic aromatics in the present fuel is also very low.
- the polycyclic aromatics content is no greater than about 1.5 weight percent and is desirably from about 0.1 to about 1.45 weight percent. Even more desirably, the polycyclic aromatic content is less than 1.0 weight percent.
- the presence of polycyclic aromatic materials is considered to result in the emission of undesirable particulates and uncombusted hydrocarbons. Accordingly, the polycyclic aromatic content is low.
- the cetane number of the fuel is greater than 55. Desirable results are also achieved when the cetane number is greater than 56; 57; 58; 59; 60 or higher.
- the fuel desirably has an initial boiling point of at least about 350°F.
- the boiling point is from about 375 to about 390°F. It is desirable that the initial boiling point be sufficiently low so that good combustion is accomplished.
- the fuel desirably has a 10 volume percent boiling point of at least 430°F and preferably from about 430 to about 450°F.
- the fuel also desirably has a 90 volume percent boiling point of at least 590°F and desirably from about 590 to about 640°F and preferably from about 590 to about 610°F. It is desirable to have a substantial amount of higher boiling material in the fuel to provide suitable fuel efficiency when the fuel is combusted.
- the fuel of Claim 1 has an aromatics content less than 15 volume percent.
- the fuel of the present invention has an aromatics content less than about 10 volume percent.
- the other fuel composition criteria discussed previously are also desirably maintained with the fuels containing less than 10 volume percent aromatics.
- the fuel may contain less than 9 volume percent; 8 volume percent; 7 volume percent; 6 volume percent; 5 volume percent or less aromatics.
- the fuel of the present invention results in reductions of hydrocarbons, carbon monoxide and particulates emissions greater than 5 percent and normally greater than 10 percent by comparison to a certified fuel.
- the fuel also results in significant reductions in NO x emissions by comparison to a certified fuel.
- the fuel of the present invention may be readily formulated by those skilled in the art using refinery streams which contain suitable diesel fuel components with sufficiently low quantities of the materials discussed above.
- many of the fuels currently marketed as certified fuels in California contain substantial quantities of materials which are generally considered to be precursors to environmental pollutants in the emissions from diesel engines.
- various fuels are referred to.
- These fuels also contain 23.9 and 23.3 weight percent aromatics, respectively, 6.3 and 8.6 weight percent polycyclic aromatics, respectively, and 893 and 1050 ppmw nitrogen, respectively.
- the fuel of the present invention is designed to contain much lower quantities of these materials and to emit reduced quantities of pollutants, especially visible and odorous pollutants upon combustion.
- a diesel fuel range feedstream is charged to a hydrotreater 10.
- the feedstream is charged via a feedstream line 12.
- Hydrogen is supplied through a line 14 to a heater 16.
- the heated hydrogen is passed via a line 22 and the feedstream in line 12 is passed to hydrotreater 10.
- the feedstream in line 12 may be a blend of feedstocks mixed to achieve a feedstream having selected properties.
- a portion of the hydrogen may be added to the feedstream without heating via a line 14' if desired.
- the hydrogen may be introduced at a plurality of points along the length of hydrotreater 10, if desired.
- the feedstream desirably comprises a stream having diesel fuel properties including a boiling range from about 250 to about 790 °F.
- the feedstream is contacted with a suitable catalyst in hydrotreater 10 at an inlet pressure in the range of about 1450 to about 2100 psig and more preferably in the range of about 1700 to about 1800 psig at a temperature in the range of about 550 to about 700°F.
- the outlet temperature is typically in the range of about 680 to about 780°F.
- the catalyst in hydrotreater 10 is a gasoline-selective catalyst as described in S.I.R.
- hydrotreater effluent is passed via a line 20 to a hydrocracker 24. Additional heated hydrogen is added as required via a line 22' after heating in heater 16 or otherwise. As with hydrotreater 10, unheated hydrogen from a line 14' ' may be added as desired and the hydrogen may be optionally added at a plurality of locations along the length of hydrocracker 24.
- the operation of hydrocracker 24 is as described in S.I.R. H1553 and is considered to be known to those skilled in the art.
- the reactor effluent from hydrocracker 24 is recovered through a line 26 and passed to a high-pressure separator 28 where very light gases, such as hydrogen, are separated from the liquid stream and recovered via a line 30.
- the liquid stream is recovered as a bottom stream 32 and passed to a low-pressure separator 34 where very light gases are separated via a line 36 with the bottom stream being recovered through a line 38 and passed to a fractionator 40.
- a light hydrocarbon stream is recovered through a line 42
- a lighter stream such as gasoline
- a heavier stream such as jet fuel
- the diesel product is recovered through a line 48 as the bottom stream.
- the operation of this process as described above is considered to be well- known to those skilled in the art.
- the fuel of the present invention is readily produced in such a process by adjusting the content of the feedstream to include aromatics, sulfur, nitrogen and polycyclic aromatics in an amount and of types such that, after treatment in the hydrotreater and hydrocracker, the amounts of these materials are reduced to the limits set forth above in the product diesel stream.
- the reformulated diesel fuel In addition to reducing the environmental pollutants introduced in the atmosphere upon combustion of the diesel fuel, the reformulated diesel fuel also provides these reductions with no reduction in fuel efficiency by comparison to a CARB certified diesel fuel.
- the reformulated diesel fuel of the present invention is delivered to a large number of distribution points over a wide geographic area and dispensed into diesel-powered vehicles so that a large number of diesel-powered vehicles are converted to use of the reformulated diesel fuel.
- the use of the reformulated diesel fuel in a large number of vehicles results in a greater reduction in pollution over a wide area.
- quantities greater than about 100,000 gallons are delivered on an average daily basis over a one- week period of time for dispensing into diesel-powered vehicles.
- the reference to the quantities of materials measured in the preceding discussion are made by reference to the standard test procedures referred to in the CARB specifications for the CARB test fuel.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA01002155A MXPA01002155A (en) | 1998-09-01 | 1999-08-17 | Reformulated reduced pollution diesel fuel. |
EP99941187A EP1115814A4 (en) | 1998-09-01 | 1999-08-17 | Reformulated reduced pollution diesel fuel |
AU54888/99A AU5488899A (en) | 1998-09-01 | 1999-08-17 | Reformulated reduced pollution diesel fuel |
CA002342610A CA2342610A1 (en) | 1998-09-01 | 1999-08-17 | Reformulated reduced pollution diesel fuel |
HK02100131.8A HK1039631A1 (en) | 1998-09-01 | 2002-01-09 | Reformulated reduced pollution diesel fuel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/145,189 US6461497B1 (en) | 1998-09-01 | 1998-09-01 | Reformulated reduced pollution diesel fuel |
US09/145,189 | 1998-09-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2000012654A1 true WO2000012654A1 (en) | 2000-03-09 |
WO2000012654A8 WO2000012654A8 (en) | 2000-06-08 |
Family
ID=22511989
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/018622 WO2000012654A1 (en) | 1998-09-01 | 1999-08-17 | Reformulated reduced pollution diesel fuel |
Country Status (7)
Country | Link |
---|---|
US (1) | US6461497B1 (en) |
EP (1) | EP1115814A4 (en) |
AU (1) | AU5488899A (en) |
CA (1) | CA2342610A1 (en) |
HK (1) | HK1039631A1 (en) |
MX (1) | MXPA01002155A (en) |
WO (1) | WO2000012654A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001083647A2 (en) * | 2000-05-02 | 2001-11-08 | Exxonmobil Research And Engineering Company | Wide cut fischer-tropsch diesel fuels |
EP1321504A3 (en) * | 2001-12-18 | 2003-10-22 | Ethyl Corporation | Extremely stable diesel fuel compositions |
WO2007024747A2 (en) * | 2005-08-22 | 2007-03-01 | Shell Internationale Research Maatschappij B.V. | A diesel fuel and a method of operating a diesel engine |
AU2003247996B2 (en) * | 2002-10-09 | 2009-10-08 | Chevron U.S.A. Inc. | Process for improving production of Fischer-Tropsch distillate fuels |
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EP1121401A1 (en) * | 1998-10-05 | 2001-08-08 | Sasol Technology (Proprietary) Limited | Biodegradable middle distillates and production thereof |
US7435335B1 (en) * | 1998-12-08 | 2008-10-14 | Exxonmobil Research And Engineering Company | Production of low sulfur distillates |
US20040140244A1 (en) * | 2000-05-30 | 2004-07-22 | Sughrue Edward L. | Desulfurization and sorbents for same |
US6550430B2 (en) * | 2001-02-27 | 2003-04-22 | Clint D. J. Gray | Method of operating a dual fuel internal |
DE60223059T2 (en) * | 2001-09-18 | 2008-07-17 | Southwest Research Institute, San Antonio | FUELS FOR HOMOGENALLY LOADED COMPACTION IGNITION MACHINES |
US7208078B2 (en) * | 2002-03-22 | 2007-04-24 | Exxonmobil Research And Engineering Company | Diesel fuel formulation for reduced emissions |
US7279018B2 (en) * | 2002-09-06 | 2007-10-09 | Fortum Oyj | Fuel composition for a diesel engine |
US7018524B2 (en) | 2003-02-06 | 2006-03-28 | The United States Of America As Represented By The United States Department Of Energy | Reformulated diesel fuel |
US20060201145A1 (en) * | 2005-03-08 | 2006-09-14 | Brady William J | Low emissions diesel system and method |
US20060218904A1 (en) * | 2005-03-08 | 2006-10-05 | Brady William J | Diesel emissions control system and method |
US10590360B2 (en) | 2015-12-28 | 2020-03-17 | Exxonmobil Research And Engineering Company | Bright stock production from deasphalted oil |
US10550335B2 (en) | 2015-12-28 | 2020-02-04 | Exxonmobil Research And Engineering Company | Fluxed deasphalter rock fuel oil blend component oils |
US10550341B2 (en) | 2015-12-28 | 2020-02-04 | Exxonmobil Research And Engineering Company | Sequential deasphalting for base stock production |
US10494579B2 (en) | 2016-04-26 | 2019-12-03 | Exxonmobil Research And Engineering Company | Naphthene-containing distillate stream compositions and uses thereof |
US11186789B2 (en) * | 2017-07-18 | 2021-11-30 | Hull Partners, Llc | Biodiesel fuel mixtures |
US11306266B2 (en) * | 2017-07-31 | 2022-04-19 | Hull Partners Llc | Biodiesel fuel mixtures |
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-
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- 1999-08-17 CA CA002342610A patent/CA2342610A1/en not_active Abandoned
- 1999-08-17 EP EP99941187A patent/EP1115814A4/en not_active Withdrawn
- 1999-08-17 MX MXPA01002155A patent/MXPA01002155A/en not_active IP Right Cessation
- 1999-08-17 AU AU54888/99A patent/AU5488899A/en not_active Abandoned
- 1999-08-17 WO PCT/US1999/018622 patent/WO2000012654A1/en active Application Filing
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2002
- 2002-01-09 HK HK02100131.8A patent/HK1039631A1/en unknown
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WO2001083647A2 (en) * | 2000-05-02 | 2001-11-08 | Exxonmobil Research And Engineering Company | Wide cut fischer-tropsch diesel fuels |
WO2001083647A3 (en) * | 2000-05-02 | 2002-03-07 | Exxonmobil Res & Eng Co | Wide cut fischer-tropsch diesel fuels |
US6833064B2 (en) * | 2000-05-02 | 2004-12-21 | Exxonmobil Research And Engineering Company | Wide cut Fischer Tropsch diesel fuels |
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WO2007024747A2 (en) * | 2005-08-22 | 2007-03-01 | Shell Internationale Research Maatschappij B.V. | A diesel fuel and a method of operating a diesel engine |
WO2007024747A3 (en) * | 2005-08-22 | 2007-06-14 | Shell Oil Co | A diesel fuel and a method of operating a diesel engine |
US8475647B2 (en) | 2005-08-22 | 2013-07-02 | Shell Oil Company | Diesel fuel and a method of operating a diesel engine |
Also Published As
Publication number | Publication date |
---|---|
CA2342610A1 (en) | 2000-03-09 |
EP1115814A4 (en) | 2004-11-17 |
WO2000012654A8 (en) | 2000-06-08 |
MXPA01002155A (en) | 2003-03-27 |
EP1115814A1 (en) | 2001-07-18 |
AU5488899A (en) | 2000-03-21 |
US6461497B1 (en) | 2002-10-08 |
HK1039631A1 (en) | 2002-05-03 |
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