PSF REFORMULATED FUEL REPORT OF REFORMULATED GASOLINE UTILIZING RAW FUEL FROM FCC REFINERY UNIT

Transcription

1 PSF REFORMULATED FUEL REPORT OF REFORMULATED GASOLINE UTILIZING RAW FUEL FROM FCC REFINERY UNIT INTRODUCTION In gasoline research speciation is a powerful tool to understand the combustion process and to physically observe the effects of varying gasoline and alternate fuel compositions. The objective of this rigorous test program which Concorde Technologies, has undertaken provides test data as to the merits of Permian Super Fuel (PSF). The research and testing to date provide excellent data as to the strengths of PSF in the market place. The Refinery gasoline selected for the most recent test is a fuel blend from the Fluid Catalytic Cracking Unit (FCC). This particular sample blend of FCC gasoline, which was tested, was taken downstream of the FCC Unit prior to the inlet to the Ethanolamine Unit. The sample set of gasoline does contain a trace amount of mercaptans sulfur compounds. It s important to understand the characteristics of FCC gasoline. Gasoline Refineries have struggled for years as what to do about detrimental sulfur compounds such as hydrogen sulfide and mercaptans. The current technology of choice to remove these sulfur species is utilizing an ethanolamine process. These sweeting units are located in all refineries located around the world. The major problem with the ethanolamine process is the fact that amine solutions in general remove valuable hydrocarbons from gasoline or diesel solutions. The removal of these hydrocarbons such as Butane, Ethane, and Propane, only to name a few, lowers the levels of octane points in the polished gasoline product. The key gasoline characteristics for a good gasoline product are volatility or in other words the gasoline s tendency to vaporize. The term volatility is important because, liquids and solids do not burn, only vapors burn. The dynamics of visually observing liquid burning, actually it is the invisible vapor above the surface that is burning. The absolute rule holds true in the combustion chamber of engine. Gasoline must be vaporized before it can burn, therefore, a gasoline blend is required to maintain its stability and as near a constant product as possible. The following test data on PSF FCC gasoline shows the unique qualities of the blend of this fuel. The attached test report contains test analysis, which will be identified by the following: DESCRIPTION MISC NUMBER PSF FCC Reformulated Fuel 274 FCC Control Sample 275 PSF FCC 20:1 Ratio 276 1

2 TEST DESCRIPTION AND CONCLUSIONS D Standard Test Method for Research Octane Number (RON) of Spark- Ignition Engine Fuel This laboratory test method covers the quantitative determination of the knock rating of liquid spark-ignition engine fuel in terms of Research Octane Number, except that this test method may not be applicable to fuel and fuel components that are primarily oxygenates. The sample fuel is tested using a standardized single cylinder, four-stroke cycle, variable compressions ratio, carbureted, CFR engine run in accordance with a defined set of operating conditions. The octane number scale is defined by the volumetric composition of primary reference fuel blends. The sample fuel knock intensity is compared to that of one or more primary reference fuel blends. The octane number of the primary reference fuel blend that matches the knock intensity of the sample fuel establishes the Research octane number. The octane number scale covers the range from 0 to 120 octane number but this test method has a working range from 40 to 120 Research octane number. Typical commercial fuels produced for spark-ignition engines rate in the 88 to 101 Research octane number range. Testing of gasoline blend stocks or other process stream materials can produce ratings at various levels throughout the Research octane number range. D Standard Test Method for Motor Octane Number (MON) of Spark- Ignition Engine Fuel The laboratory test method covers the quantitative determination of the knock rating of liquid spark-ignition engine fuel in terms of Motor Octane Number except, that this test method may not be applicable to fuel and fuel components that are primarily oxygenates. The sample fuel is tested in a standardized single cylinder, four-stroke cycle, variable compression ratio, carbureted, CFR engine run in accordance with a defined set of operating conditions. The octane number scale is defined by the volumetric composition of primary reference fuel blends. The sample fuel knock intensity is compared to that of one or more primary reference fuel blends. The octane number of primary reference fuel blend that matches the knock intensity of the sample fuel establishes the Motor octane number. The octane number scale covers the range from 0 to 120 octane number but this test method has a working range for 40 to 120 octane number. Typical commercial fuels produced for automotive spark-ignition engines rate in the 80 to 90 Motor octane number range. Typical commercial fuels produced for aviation spark-ignition engines rate in the 98 to 102 Motor octane number range. Testing of gasoline blend stocks or other process stream materials can produce ratings at various levels throughout the Motor octane number range. 2

3 Conclusion for D2699 and D2706 Utilizing the test method outlined for octane levels of FCC Gasoline the trend data indicates that PSF FCC Gasoline contains a level of Octane greater than 93.0 by wt. % This determination was validated by the following mathematical formula. # knocks / / second SWRI Chemist Supervisor visually observed that no excessive mechanical vibration was realized during the duration of the test. This observation is important to note because of the lubricity characteristics of the fuel sample we refer to as PSF. An open table discussion was held at the conclusion of the RON and MON test. The topic of the octane values were evaluated. The discussion was brought about as a result of the RON values. These values were consistently high. It was further discussed that the test results from ASTM D5599 revealed no detectable level of typical oxygenates. At this point in our discussion with SWRI, they explained that most recent historical data regarding oxygenates have indicated that such gasoline will lower a car s fuel economy by 2% to 3% because, oxygenates contain less energy to burn that conventional gasoline. D Standard Test Method for Lead In Gasoline By Atomic Absorption Spectroscopy This test method covers the determination of the total lead content of gasoline within the concentration range of to 0.10 g of lead/u.s. gal (2.5 to 25 mg/l). This test method compensates for variations in gasoline composition and is independent of lead alkyl type. The values given in grams per U.S. gallon are to be regarded as the standard in the United States. Note that in other countries, other units can be preferred. D Standard Test Method for Manganese In Gasoline By Atomic Absorption Spectroscopy This test method covers the determination of the total manganese content, present as methylcyclopentadienyl manganese tricarbony (MMT), of gasoline within the concentration range from to g of manganese/u.s. gas (0.25 to 30 mg/l). This test method is not applicable to gasoline containing highly cracked materials (greater than 20 Bromine Numbers). 3

4 The values of operating conditions are stated in SI units and are considered standard. The values in parentheses are the historical inch-pounds units. The standardized CFR engine measurements continue to be in inch-pound units only because of the extensive and expensive tooling that has been created for this equipment. D Standard Test Method For Phosphorus in Gasoline This test method covers the determination of phosphorus generally present as pentavalent phosphate esters or salts, or both, in gasoline. This test method is applicable for the determination of phosphorus in the range from 0.2 to 40 mg P/ Liter or to 0.15 g P/U.S. gal. The value given in acceptable SI units are to be regarded as the standard. D Standard Test Method for Sulfur in Petroleum Products by Wavelength Depressive X-ray Fluorescene Spectrometry This test method covers the determination of total sulfur in liquid petroleum products and in solid petroleum products that can be liquefied with moderate heating or dissolved in a suitable organic solvent. The applicable concentration range will vary to some extent with the instrumentation used and the nature of the sample. Optimum conditions will allow the direct determination of sulfur in essentially paraffinic samples at concentrations exceeding mass %. Methanol containing fuels M-85 and M-100 may be analyzed with an accompanying loss of sensitivity and precision because of the more absorbing matrix caused by the high oxygen content of these fuels. M-85 is 85% methanol 15% gasoline, and M-100 fuel is 100% methanol. Correction factors are applied to achieve these results. This test method also covers the determination of sulfur in crude oil. The preferred units are mass percent sulfur. Comments and discussion focused on any corrosive sulfur species. Any related sulfur are those conclusively not found to be a detriment to the combustibility process of the reformulated gasoline. Please refer to the compound list of these species: DECANETHIOL ETHYL SULFIDE BUTLY SULFIDE PHENYL SULFIDE PROPANETHIOL 2 - METHYL 1 - PROPANETHIOL THIOPHEN CARBON DISULFIDE 4

5 ETHYL DISULFIDE 1-METHYL - 1- PROPANETHIOL PROPYL DISULFIDE ETHYL METHYL SULFIDE METHYL DISULFIDE BENZENETHIOL 2 METHYL - 2 PROPANETHIOL 1 BUTANETHIOL METHYL SULFIDE 2 ETHYLTHIOPHENE DIBENZOTHIOPHEN, WHITE ETHANETHIOL 3 METHYL THIOPHENE THIANAPHTHENE PROPYL SULFIDE ISOPROPYL DISULFIDE Conclusion for D Lead, D Manganese, D Phosphorus and D Sulfur During the rigorous process all tested elements on PSF were found to be detectable lower or Non detectable. The exception during these tests was found to be the sulfur species were not of a negative nature to the gasoline. The list provided of such species will, at a later date, be identified. It was further concluded that the unidentified species were not hydrogen sulfide or mercaptans. D Standard Test Method for Oxidation Stability of Gasoline (Induction Period Method) This test method covers the determination of the stability of gasoline in finished form only, under accelerated oxidation conditions. NOTE 1 this test method is not intended for determining the stability of gasoline components, particularly those with a high percentage of low boiling unsaturated compounds, as these may cause explosive conditions within the apparatus. However, because of the unknown nature of certain samples, the bomb assembly shall include a safety measurement of potential gum; refer to Test Method D873, or IP Test Method 138. The accepted SI unit of pressure is the kilo Pascal (kpa); pound per square inch (psi) values are provided in parentheses for information. Conclusion for ASTM D525-99A Oxidation Stability Tests have conclusively determined that the shelf life of the PSF gasoline exceeds the time threshold of 240 minutes (4 hours) the real time comparisons of 14 days in underground storage. It is important to note that no measured separation of the PSF Gasoline took place during the course of this test. The importance is to blend a fuel, which will maintain its structure overtime. Furthermore, the octane levels did not degrade with respect to time. 5

6 D Standard Test Method for Determination of Oxygenates in Gasoline by Gas Chromatography and Oxygen Selective Flame Ionization Detection The test method covers a gas chromatographic procedure for the quantitative determination of organic oxygenates compounds in gasoline having a final boiling point not greater than 220ºC and oxygenates having a boiling point limit of 130ºC. it is applicable when oxygenates are present in the 0.1 to 20 % by mass range. Conclusion for ASTM D , D 5188, and D 5291 The test conclusion indicated oxygen was not present in the various structures of the PSF Gasoline. To further investigate this possibility a second test was performed on the same sample set test # ASTM D 5291 which further concluded that oxygen was not present, the same sample set was also reviewed for any and all oxygenates (i.e. TAME, MTBE, and ETBE etc). The conclusion non-detectable. D Standard Test Method for Determination of Benzene and Toluene in Finished Motor and Aviation Gasoline by Gas Chromatography This test method provides for the determination of benzene and toluene in finished motor and aviation gasoline by gas chromatography. Benzene can be determined between the levels of 0.1 and 5 volume % and toluene can be determined between the levels of 2 and 20 volume %. Benzene is classified as a toxic material. A knowledge of the concentration of this compound can be an aid in evaluating the possible health hazard to persons handling and using the gasoline. This test method is not intended to evaluate such hazards. D Standard Test Method for Vapor-Liquid Ratio Temperature Determination of Fuels (Evacuated Chamber Method) This test method covers the determination of the temperature at which the vapor formed from a selected volume of volatile petroleum product saturated with air at 0 to 1ºC. (32 to 34ºF) producing a pressure of one atmosphere in an evacuated chamber of fixed volume. This test method is applicable to samples for which the determined temperature is between 36 and 80ºC (97 and 176ºF) and the vapor-liquid ratio is between 8 to 1 and 75 to 1. NOTE: When the vapor-liquid ratio is 20:1, the result is intended to be comparable to the results determined by Test Method D2533. NOTE 2 - This test method may also be applicable at pressures other than one atmosphere, but the stated precision may not apply. 6

7 This test method is applicable to both gasoline and gasoline-oxygenate blends. The values stated in SI units are to be regarded as the standard. The inch-pound units given in parentheses are provided for information only. X 3.4 Interim Guideline for Lubricity of Diesel Fuels (Reference to Data Points and Graphs attached) X The following guidelines are generally accepted and maybe used in the absence of a single test method and a single fuel lubricity value: Fuels having a SLBOCLE lubricity value below 2,000 grams will in all probability cause excessive wear in injection equipment while fuels with values above 3,100 grams should provide sufficient lubricity in all cases. If HFFR is used, values above 600 microns can cause excessive wear while values below 450 microns should protect injection equipment in all cases. More accurately, an industry accepted long-term durability pump test can be used to evaluate the lubricity of diesel fuel. A poor result in such a test indicates that the fuel has low lubricity and can cause excessive wear. The course of this test on the various samples did not measure metal wear exceeding 390 microns. The initial data point was achieved testing sales gasoline from the pump. This data point failed within nine minutes utilizing a reciprocating arm to exert the friction required for the test. The attached graphs are data points collected for each sample over a period of one hour and fifteen minutes. These graphs provide the information of specifically the friction, temperature, and the film during the test. As of to date, there has not been a gasoline test, which has not failed. SWRI Supervisor responsible for conducting this particular test, his comment during our meeting was, that he had never witnessed the success of this specific test on gasoline. He further commented that the PSF samples could easily set the standard for gasoline lubricity test in the future". PSF using the same type of reciprocating arm to exert the same friction required, the test LASTED FOR 74 MINUTES AND NEVER FAILED. Project Manager at SwRI, also commented that she had not witnessed this type of data for gasoline lubricity. 7

8 Permian Super Fuel (PSF) Lubricity Test By: Southwest Research Institute - San Antonio Texas Test No. 10 min. 20 min. 30 min. 40 min. 50 min. 60 min. 70 min. 75 min. Average Friction Test Film Test % % % % Temperature Test C C C C Notes: Set Temp: 25 deg. C. - Run time: 74 min. - Log Interval: 10 Sec. - Test load: 200 g - Frequency: 50 Hz - Stroke: 1000 um Test No. 257: PSF Service Station Ratio 20:1 - Unit SwRI Test No. 258: CONTROL Sample Raw FCC Gasoline/Refinery - Unit SwRI Test No. 259: PSF Raw Gasoline FCC Refinery - Unit SwRI Test No. 260: PSF Retail Pump Service Station - Unit SwRI The idea of how to understand the properties of PSF has been widely discussed at Southwest Research Institute. One particular point of discussion with SWRI has been to understand where the energy in PSF is originating from, as well as understanding the octane level. We have established that the boiling point of PSF is at 400ºF as compared to regular gasoline, which boils at 100ºF with this understanding in mind, we theorize that as the gasoline enters the combustion chamber under compression and the actual residence time with respect to ignition in being elongated. This effect 8

9 increases the life of gasoline under combustion. With more residence time the gasoline is allowed to burn longer and cleaner which reduces the emissions out of the engine. Further discussions were held with SWRI, with regards to PSF and its characteristics. PSF gasoline represented by the complete profile is what the engine must distribute, vaporize and burn. To predict cold start and warm-up drivability, a Drivability Index (DI) has been developed using the temperatures for the evaporated percentages of 10% (T 10 ), 50% (T 50 ) and 90% (T 90 ). DI = 1.5 (T 10 ) (T 50 ) + (T 90 ) The DI will vary with gasoline grades and season. The normal range has been established, between 850 to1300. Lower values of DI will generally result in better coldstart and warm up performance. The equation was developed using data for conventional gasoline such as PSF, which does not contain oxygenates. Gasolines, which contain one or more, oxygenates, this equation has not proven to be applicable. In conclusion all data collected from Southwest Research Institute is still being evaluated. As data becomes available it will be distributed promptly. The conclusion based on compiled data to date, conclusively provides the evidence that the residence time of the PSF product is providing additional energy during distribution in the engine. End of Report 9