The field of invention relates to the latest technology in the development of a replacement synthetic lubricant to accommodate the dramatic reduction in sulfur content in Ultra-Low and Low Sulfur Diesel fuels.
Over the years diesel fuels have been subject to environmental pressures to have the lubrication factor (sulfur) dramatically reduced or eliminated. Sulfur has played a major role in the lubrication of mechanical parts within the fuel system of the diesel engines. Ultra-Low Diesel Fuel, which is limited to 15 PPM of sulfur, was proposed by the EPA as a new standard for the sulfur content in on-road diesel fuel sold in the United States since Oct. 15, 2006, except for California and rural Alaska. California has required this since Sep. 1, 2006 and rural Alaska will transition to all diesel to Ultra Low Sulfur diesel by 2010. The new regulation applies to all diesel fuel and diesel fuel additives and distillate fuels blended, and to diesel for on-road use, such as kerosene. By Dec. 1, 2010, all highway diesel will be Ultra-Low Sulfur Diesel. Non-road diesel will transition to 500-PPM sulfur in 2007 (Low sulfur diesel) and to Ultra-Low sulfur Diesel by 2010. Locomotives and marine diesel will also transition to 500 PPM of Sulfur in 2007, and to Ultra-Low sulfur diesel by 2012. Prior to October 1993, Sulfur Content in Diesel fuel was 5000 PPM allowing sufficient lubrication to moving parts such as fuel Pumps, Injectors and valves etc. With this dramatic reduction of Sulfur, necessary lubrication has diminished to the point of premature wear becoming a major problem in the diesel mechanical industry.
Disclosed herein is a diesel fuel lubricant as a replacement for sulfur lubrication in Ultra-Low and Low Sulfur Diesel fuels, the process for producing said lubricant, and the method of using said lubricant. This lubricant comprises alpha-olefins; low odor aromatic solvents; and at least one a base oil selected from the base oil group consisting of hydroisomerized high base oils and HT Severe Hydro-cracked Base Oils; as well as other ingredients. Also disclosed is a method for producing this lubricant.
The invention relates to the use of a replacement diesel fuel lubricant additive for Ultra-Low and Low Sulfur Diesel which that can be added to fuels to replace the dramatic loss of lubrication generally associated with higher sulfur content in diesel fuels. The product will have utility in all forms of diesel engines or turbines where sulfur was an integral component of internal lubrication. The invention has been submitted by confidential disclosure to the EPA and has received registration under 40CFR 79.23 in October 2007.
Previous diesel fuel additives relied on the concentrated dosage of sulfur in diesel fuels, which is now highly restricted by the United States Environmental Protection Agency and various foreign governments. With the new universal environmental standards, sulfur in diesel is limited to on-road application of 15-PPM. On certain marine and locomotive transports, a limited time allowance of 500-PPM is granted for change over to ultra-low sulfur diesel.
Primary Ingredients
The finished product (preferred embodiment of the invention) is a combination of:
The preferred blending Ratios for each component are shown as below. It is important to maintain a blend of component that fall within the following percentages. Note that in the event one or more of the ingredients shown below is omitted from the diesel fuel additive, the percentages by weight of the remaining ingredients are proportionately increased:
Alpha-Olefins: 5 to 30% by weight and preferably 7.0 to 25% by weight and more preferably 9.0 to 18% by weight. Most preferable is 11.0% by weight.
Low Odor Aromatic Solvents: 3.0 to 27% by weight and preferably 5.0 to 22% by weight and more preferably is 7.0 to 18% by weight. Most preferable is 15.0% by weight.
Hydroisomerized High-Base Oils and HT Severe Hydro-cracked Base Oils: 0.50 to 15 percent by weight and preferably 0.75 to 10% by weight and more preferably 2.0 to 8.0% by weight. Most preferable is 5.0% by weight.
Cetane Booster, Detergent, Cloud Point and wax Reducer Blend: 0.03 to 0.25% by weight and preferably 0.05 to 0.20% by weight and more preferably 0.09 to 0.17% by weight. Most preferable is 0.13% by weight.
Synthetic Calcium Sulfonates: 0.05 to 0.25% by weight, preferably 0.07 to 0.20% by weight and more preferably 0.10 to 0.18% by weight. Most preferable is 0.12% by weight.
Low Flash Mineral Spirits: 15 to 50% by weight and preferably 20 to 45% by weight and more preferably 25-39% by weight. Most preferable is 35% by weight.
Solvent Activated Dyes: 0.002 to 0.005 percent by weight and preferably 0.0025 to 0.004% by weight and more preferably 0.027 to 0.035% by weight. Most preferable is 0.003 percent by weight.
Pour Point Depressants or Cloud Point Depressants: 0.50 to 2% by weight and preferably 0.65 to 1.75% by weight and more preferably 0.75 to 1.35% by weight. Most preferable is 1% by weight.
Isomer Reformate: 0.50 to 5.0% by weight and preferably 0.75 to 4.0% by weight and more preferably 1.0 to 3.0% by weight. Most preferable is 2.0% by weight.
Dimethyl Ketones: 10 to 50% by weight and preferably 17 to 40% by weight and more preferably 24 to 36% by weight. Most preferable is 30%.
Preferred Sequence of Blending Components
The initial blend (primary blend) will require the Poly Alpha Olefins, the Low Aromatic Solvent and the Base Oil being blended until the liquid is a consistent amalgamation without any appearance of separation. Blending is based on speed of the agitator and temperature will dictate the amount of time for the blend to complete. The blending time range may vary from 4 to 6 hours. The ideal temperature for each component is between 22 to 30 degrees centigrade for ideal blending. While this is blending, a secondary blend for the Cetane Booster, Detergent and Cloud Point Reducer can be prepared in a smaller high speed enclosed blender, and then added to the main blend.
If the synthetic calcium sulfonates are employed (noting the recent U.S. law which could restrict their use in the U.S.), blending will require that the synthetic calcium sulfonates be blended with the mineral spirits in an approximate 50/50 ratio in the initial stage of the blend to produce a tertiary blend. (The mineral spirits used will be from the preferred percentage set forth earlier.) This tertiary blend, or the mineral spirits alone absent the synthetic calcium sulfonates, together with the balance of the ingredients, can be then added to the main blend and the agitator is run until the components appear to have thoroughly blended into a consistent liquid.
Preferred Blend Equipment
The Process sequence involves a series of blending and holding tanks where the product can be weighed and then pumped through control valves to maintain consistent flow and pressure. The blending should be performed in a enclosed tank to reduce product evaporation (loss) and prevent exposure to open spark. Blending equipment can be by a combination of high or low speed blending apparatus. Size or volume of tank is not critical to the blend.
Universal Use of Invention
The product has been put to experimental test in various on-road and off-road vehicles and has demonstrated that when added at 2 to 3 ounces per 10 gallons of either ultra-low and low sulfur diesels, reduced wear, increased mileage and reduced emissions have been experienced, as summarized below.
Testing Procedures
The latest method for testing wear with the Ultra-Low and Low Sulfur Diesel fuels is the High Frequency Reciprocating Rig (HFRR). ASTM-D 975. The fuel is subjected to wear test and must demonstrate a wear scar size of no more than 520 microns.
Test Results
Although all the diesel fuels tested exceeded the allowable wear by as much a 20 to 30 microns, the addition of the invention added to the Ultra-Low sulfur diesel (2.0 ounces per 10 gallons of diesel fuel) resulted in the wear scar being reduced by some 28 percent of the allowable scar size or approximately 375 microns.
This experimental testing has demonstrated the ability of the invention to dramatically reduce wear that is currently being experienced by diesel mechanical equipment. As further test ASTM standards are developed for Ultra-Low Sulfur diesel, further experimental tests will be conducted with the invention.
While only certain preferred features of the invention have been illustrated and described, many modifications, changes and substitutions will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.
This application is a continuation of application U.S. Ser. No. 13/298,342 filed Nov. 17, 2011, now U.S. Pat. No. 8,491,676 issued Jul. 23, 2013. Said U.S. Ser. No. 13/298,342 is a continuation of application U.S. Ser. No. 12/747,227 filed Jun. 10, 2010, now U.S. Pat. No. 8,062,388 issued Nov. 22, 2011. Said U.S. Ser. No. 12/747,227 is a U.S. national stage application based on expired PCT/US07/88252 filed Dec. 19, 2007. Said U.S. Ser. No. 12/747,227 is also a continuation-in-part of U.S. Ser. No. 11/290,596 filed Dec. 1, 2005, now U.S. Pat. No. 7,745,382 issued Jun. 29, 2010. Said U.S. Ser. No. 11/290,596 claims priority benefit of expired provisional application U.S. 60/644,494 filed Jan. 18, 2005.
Number | Name | Date | Kind |
---|---|---|---|
3406419 | Young | Oct 1968 | A |
3984599 | Norton | Oct 1976 | A |
4127491 | Reick | Nov 1978 | A |
4131551 | Thompson et al. | Dec 1978 | A |
4218330 | Shubkin | Aug 1980 | A |
4224173 | Reick | Sep 1980 | A |
4228021 | Lenack | Oct 1980 | A |
4375418 | Zoleski et al. | Mar 1983 | A |
4443348 | Wright et al. | Apr 1984 | A |
4504404 | Schumacher et al. | Mar 1985 | A |
4534873 | Clark | Aug 1985 | A |
4844825 | Sloan | Jul 1989 | A |
4859359 | DeMatteo et al. | Aug 1989 | A |
4946510 | Kinnebrew et al. | Aug 1990 | A |
4956122 | Watts et al. | Sep 1990 | A |
5120358 | Pippett | Jun 1992 | A |
5136118 | Buchanan et al. | Aug 1992 | A |
5202040 | Sanderson et al. | Apr 1993 | A |
5332516 | Stephens | Jul 1994 | A |
5364994 | Scharf | Nov 1994 | A |
5431841 | Lockhart | Jul 1995 | A |
5631211 | Nakagawa et al. | May 1997 | A |
5672572 | Araik et al. | Sep 1997 | A |
5681797 | Lawate | Oct 1997 | A |
5741764 | Patel et al. | Apr 1998 | A |
5885942 | Zhang et al. | Mar 1999 | A |
5972853 | Boffa et al. | Oct 1999 | A |
6008164 | Aldrich et al. | Dec 1999 | A |
6046142 | Zilonis et al. | Apr 2000 | A |
6074993 | Waddoups et al. | Jun 2000 | A |
6143701 | Boffa | Nov 2000 | A |
6323162 | Yasunori et al. | Nov 2001 | B1 |
6413916 | Baumgart et al. | Jul 2002 | B1 |
6761645 | Weber | Jul 2004 | B1 |
6774091 | Dituro et al. | Aug 2004 | B2 |
6858567 | Akao | Feb 2005 | B2 |
6919300 | Dituro | Jul 2005 | B2 |
6962895 | Scharf et al. | Nov 2005 | B2 |
6992049 | Deckman et al. | Jan 2006 | B2 |
7018960 | Negoro et al. | Mar 2006 | B2 |
7022766 | Okada et al. | Apr 2006 | B2 |
7055534 | Goode et al. | Jun 2006 | B2 |
7109152 | Corby et al. | Sep 2006 | B1 |
7124728 | Carey et al. | Oct 2006 | B2 |
7745382 | Sloan | Jun 2010 | B2 |
7931704 | Sloan | Apr 2011 | B2 |
8022020 | Sloan | Sep 2011 | B2 |
8039424 | Sloan | Oct 2011 | B2 |
8062388 | Sloan | Nov 2011 | B2 |
8071513 | Sloan | Dec 2011 | B2 |
8071522 | Sloan | Dec 2011 | B2 |
8268022 | Sloan | Sep 2012 | B2 |
8334244 | Sloan | Dec 2012 | B2 |
8377861 | Sloan | Feb 2013 | B2 |
8415280 | Sloan | Apr 2013 | B2 |
8491676 | Sloan | Jul 2013 | B2 |
20030040444 | Garmier | Feb 2003 | A1 |
20030087769 | Dituro et al. | May 2003 | A1 |
20040014613 | Dituro et al. | Jan 2004 | A1 |
20040060229 | Todd et al. | Apr 2004 | A1 |
20040077506 | Arrowsmith et al. | Apr 2004 | A1 |
20060160708 | Sloan | Jul 2006 | A1 |
20080182769 | Sloan | Jul 2008 | A1 |
20080190014 | Volkel et al. | Aug 2008 | A1 |
20100269404 | Sloan | Oct 2010 | A1 |
20100273687 | Sloan | Oct 2010 | A1 |
20100273688 | Sloan | Oct 2010 | A1 |
20110009301 | Sloan | Jan 2011 | A1 |
20110015103 | Sloan | Jan 2011 | A1 |
20110197499 | Sloan | Aug 2011 | A1 |
20120035087 | Sloan | Feb 2012 | A1 |
20120060410 | Sloan | Mar 2012 | A1 |
20120077720 | Sloan | Mar 2012 | A1 |
20120077724 | Sloan | Mar 2012 | A1 |
20130157918 | Sloan | Jun 2013 | A1 |
20130178403 | Sloan | Jul 2013 | A1 |
Number | Date | Country |
---|---|---|
19723460 | Jan 1998 | DE |
0361180 | Apr 1990 | EP |
0837122 | Apr 1998 | EP |
1203803 | May 2002 | EP |
1736529 | Dec 2006 | EP |
2193080 | Jul 1972 | FR |
59204700 | Nov 1984 | JP |
07233001 | Sep 1995 | JP |
2001-271077 | Oct 2001 | JP |
9719153 | May 1997 | WO |
0234867 | May 2002 | WO |
03064571 | Aug 2003 | WO |
2006-015800 | Feb 2006 | WO |
2006100188 | Sep 2006 | WO |
2007004789 | Jan 2007 | WO |
2009078882 | Jun 2009 | WO |
2009079020 | Jun 2009 | WO |
2009085957 | Jul 2009 | WO |
2009085967 | Jul 2009 | WO |
2012-040153 | Mar 2012 | WO |
2012-040153 | Mar 2012 | WO |
Entry |
---|
Rudnick, Leslie R., Ed., Synthetic Mineral Oils and Bio Based Lubricants: Chemistry and Technology, Taylor & Francis (2006). |
Journal of Automotive Engineering, May 1, 2001, vol. 55, No. 5, pp. 67-72. |
Journal of Automotive Engineering, May 1, 2001, vol. 55, No. 5, pp. 67-72, English translation of: p. 70, last paragraph; Figures 6 and 7. |
Kioupis, L.I. ; Maginn, E.J., Molecular simulation of poly-(alpha)-olefin synthetic lubricants: Impact of molecular architecture on performance properties, Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical; Journal vol. 103; Journal Issue: 49; Dec. 9, 1999. |
Number | Date | Country | |
---|---|---|---|
20130298450 A1 | Nov 2013 | US |
Number | Date | Country | |
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60644494 | Jan 2005 | US |
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Parent | 13298342 | Nov 2011 | US |
Child | 13946074 | US | |
Parent | 12474227 | US | |
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Parent | 11290596 | Dec 2005 | US |
Child | 12474227 | US |