Source: http://www.google.com/patents/US7981170?dq=6175559
Timestamp: 2017-04-30 20:18:04
Document Index: 294431096

Matched Legal Cases: ['§80', '§80', '§80', '§80', '§80', '§80', '§80', '§80', '§80', '§80', '§80']

Patent US7981170 - Gasoline-oxygenate blend and method of producing the same - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsBy controlling one or more properties of a gasoline-oxygenate blend, a gasoline-oxygenate blend may be blended to contain at least one alcohol that exhibits acceptable properties and characteristics. This blend and the preferred method of preparing this blend includes an alcohol, most preferably ethanol,...http://www.google.com/patents/US7981170?utm_source=gb-gplus-sharePatent US7981170 - Gasoline-oxygenate blend and method of producing the sameAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS7981170 B1Publication typeGrantApplication numberUS 09/556,852Publication dateJul 19, 2011Filing dateApr 21, 2000Priority dateApr 21, 2000Fee statusPaidAlso published asCA2406792A1, CN1214092C, CN1430664A, DE60103893D1, DE60103893T2, EP1287095A2, EP1287095B1, WO2001081513A2, WO2001081513A3Publication number09556852, 556852, US 7981170 B1, US 7981170B1, US-B1-7981170, US7981170 B1, US7981170B1InventorsCharles Arthur Lieder, Lloyd Elbert Funk, David Allen BarkerOriginal AssigneeShell Oil CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (26), Non-Patent Citations (12), Classifications (9), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetGasoline-oxygenate blend and method of producing the same
2. The blend of claim 1 wherein the blend has a 50% distillation point less than about 178° F.
3. The blend of claim 1 wherein the blend has a 10% distillation point less than about 123° F.
Gasolines are generally composed of a mixture of hydrocarbons, boiling at atmospheric pressure in a very narrow temperature range, e.g., 77° F. (25° C.) to 437° F. (225° C.). Gasolines are typically composed of mixtures of aromatics, olefins, and paraffins, although some gasolines may also contain such added non-hydrocarbons as alcohol (e.g., ethanol) or other oxygenates (e.g., methyl t-butyl ether (“MTBE”). Gasolines may also contain various additives, such as detergents, anti-icing agents, demulsifiers, corrosion inhibitors, dyes, deposit modifiers, and octane enhancers. The presence of oxygen in the fuel tends to raise the effective air-to-fuel ratio for combustion and fuel oxygen may effect catalyst efficiency. While the oxygen in ethanol can raise this air-to-fuel ratio which may increase combustion temperature, the lower temperature of combustion for ethanol mitigates this effect. The oxygen in ethanol also reduces carbon monoxide (“CO”) and volatile organic compound (“VOC”) emissions during high-emissions conditions in new vehicles and during all conditions for vehicles that do not have operational oxygen sensors or catalysts.
The present invention provides gasoline-oxygenate blends that produce a relatively low amount of gaseous pollutants with the reduction or elimination of MTBE as a fuel additive. The invention provides methods for producing gasoline-oxygenate blends having such desirable properties as overall emission performance such as: the reduction of Toxics, NOx, and VOCs; oxygen content; and requisite volatility characteristics including vapor pressure, and the 200° F. and 300° F. distillation fractions as discussed herein. This composition and its method of production offer a solution by including at least one alcohol while combating pollution, particularly in congested cities and the like, when large volumes of automotive fuel of the invention are combusted in a great number of automobiles in a relatively small geographical area.
In a preferred embodiment, the gasoline-oxygenate blend has a vapor pressure less than about 7.1 PSI and an alcohol content greater than about 5.8 volume percent. In another embodiment, this gasoline-oxygenate blend will have a 50% distillation point less than about 195° F., a 10% distillation point less than about 126° F., an oxygen weight percent that is greater than 1.8 weight percent, an anti-knock index greater than or equal to about 89, and/or the capability to reduce toxic air pollutants emissions by more than about 21.5% as calculated under the Complex Emissions Model (“Complex Model”) under 40 C.F.R. §80.45 (1999), more preferably more than about 30% for the appropriate location, season, and year. Though the present invention may substitute virtually any alcohol for MTBE, the inclusion of ethanol to reduce or replace MTBE is preferable.
In another embodiment, the gasoline-oxygenate blend has a vapor pressure less than about 7.2 PSI and an alcohol content greater than about 9.6 volume percent. This embodiment may also have a 50% distillation point less than about 178° F., a 10% distillation point less than about 123° F., an oxygen weight percent that is greater than 1.8 weight percent, an anti-knock index greater than about 89, and/or the capacity to reduce toxic air pollutants emissions by more than about 21.5%. In another embodiment, the gasoline-oxygenate blend has a vapor pressure less than about 7 PSI and an alcohol content greater than about 5.0 volume percent. This embodiment may also have a 50% distillation point less than about 250° F. and/or a 10% distillation point less than about 158° F.
fuel has evaporated ° C.(° F.)
To model this, the CAA lays out standards and appropriate Emission Models to calculate performance of gasoline blends. The following properties of the baseline fuels must be observed when blending gasolines. In addition to the properties discussed the following terms are included in the following table from the Complex Model of 40 C.F.R. §80.45 (1999). E200 is the fraction of the target fuel that evaporates (the distillation fraction) at 200° F. in terms of volume percent. E300 is the fraction of the target fuel that evaporates (the distillation fraction) at 300° F. in terms of volume percent.
TABLE 5 TOTAL BASELINE VOC, NOX AND TOXICS EMISSIONS Summer (mg/mile) Winter (mg/mile) Phase I Phase II Phase I Phase II Region Region Region Region Region Region Region Region Pollutant 1 2 1 2 1 2 1 2 NOx 660.0 660.0 1340.0 1340.0 750.0 750.0 1540.0 1540.0 VOC 1306.5 1215.1 1466.3 1399.1 660.0 660.0 1341.0 1341.0 Toxics 48.61 47.58 86.34 85.61 58.36 58.36 120.55 120.55 With these requirements, models, and standards in place, the following outlines how to meet these standards while reducing or eliminating the introduction of MTBE. In fact, the following demonstrates how to reduce Toxic Emissions (“ToxR”) by about 30% such that the Phase II Summer Emissions are from about 53.5 mg/mile to about 37.5 mg/mile using the calculations shown in 40 C.F.R. §80.45 (1999).
Of note, the percentage reduction of NOx, toxic pollutants, and VOCs shown in Tables 10 and 15 were calculated using the Complex Model that was in effect during the appropriate Phase. For example, the percentage reductions shown in Table 10, entitled “Additional Phase I Gasoline-Oxygenate Blend Properties,” show calculations based on the Complex Model Phase I as prescribed in 40 C.F.R. §80.45 (1999). Accordingly, Table 15, entitled “Additional Phase II Gasoline-Oxygenate Blend Properties,” shows the percentage reduction of NOx, toxic pollutants, and VOCs using the Complex Model Phase II as prescribed by Federal Regulations under 40 C.F.R. §80.45 (1999).
With respect to percentage reductions described herein, unless otherwise indicated, the Phase II Complex Model for determining the percentage reduction of NOx, toxic pollutants, and/or VOCs are to be calculated under the Phase II Complex Model as prescribed in 40 C.F.R. §80.45 (1999) unless otherwise indicated. Returning to the following Table 6, entitled “Phase I Neat Blend Recipes,” the following neat blends were formulated.
The Research Octane Number (“RON”) and the Motor Octane Number (“MON”) were collected using calibrated online analyzers using the testing procedures found in the Standard Text Method for Research and Motor Method Octane Ratings Using Online Analyzers, ASTM D 2885. The anti-knock index number or octane number (“(R+M)/2”) was established by averaging RON and MON. The DVPE was established by using an online testing method certified equivalent for the testing procedures found in The Standard Test Method for Vapor Pressure of Petroleum Products (Mini Method), ASTM D 5191 and is expressed in PSI. The 10% distillation temperature, the 50% distillation temperature, the 90% distillation temperature, the end point distillation temperate (“T10”, “T50”, “T90”, and “EP” respectively) and the 200° F. and the 300° F. distillation fractions (“E200” and “E300”, respectively) were collected using certified online procedures equivalent to the testing methods found in The Standard Specification for Automotive Spark-Ignition Engine Fuel, ASTM D 4814. With these testing procedures in mind, the neat blends had the following properties prior to the introduction of oxygenates.
TABLE 7 PHASE I NEAT BLEND PROPERTIES DVPE T10 T50 T90 EP E200 E300 Blend RON MON (R + M)/2 PSI ° F. ° F. ° F. ° F. Vol. % Vol. % A 97.2 88.4 92.8 5.8 158.4 227.0 309.5 401.8 30.0 86.8 B 91.1 83.6 87.35 5.7 146.8 226.8 338.9 421.6 34.9 80.4 C 98.2 88.1 93.15 5.7 159.9 230.6 304.0 405.9 27.2 88.9 D 88 81 84.5 5.7 142.1 224.7 346.1 419.4 38.8 75.7 E 88.0 81.9 84.95 5.5 144.5 224.8 347.9 420.0 38.2 75.7 F 97.1 86.6 91.85 5.6 150.1 222.0 299.1 404.5 34.4 90.0 G 96.3 87.4 91.85 5.6 148.7 227.2 325.6 413.6 32.4 83.2 H 88.7 82.6 85.65 5.6 145.4 223.6 349.0 419.5 36.9 77.6 I 88.4 81.2 84.8 5.6 144.9 227.3 332.8 423.3 35.7 81.5 J 96.7 87.0 91.85 5.5 148.6 228.3 326.8 416.1 31.9 83.2 K 90.6 84.1 87.35 5.8 146.0 218.6 320.5 415.2 38.7 84.9 L 87.9 82.1 85 5.6 142.6 217.2 342.4 420.8 41.8 79.6 M 88.3 82.7 85.5 5.6 142.8 221.1 345.3 421.0 39.3 78.4 N 88.1 81.5 84.8 5.6 143.0 219.7 337.1 428.0 39.9 82.0 O 96.3 87.3 91.8 5.8 149.7 226.4 313.5 410.4 31.7 86.5 P 90.1 82.7 86.4 5.7 145.3 221.5 324.1 420.0 37.2 84.4 Q 89.4 82.5 85.95 5.7 145.4 227.2 341.0 424.1 36.3 79.4 R 87.9 80.9 84.4 5.8 143.6 225.5 336.9 415.5 38.0 78.9 S 96.2 87.4 91.8 5.7 151 215.1 279.8 373 37.7 92.2 T 88 80.9 84.5 5.7 145 228 339.8 417.7 36.2 77.9 U 95.9 87.6 91.8 5.6 150.1 223.6 318.1 416.3 33.5 85.0 V 87.9 82 85 5.8 146.4 224 342.2 416.7 37.2 77.7 W 96.5 87.4 91.9 5.8 146.1 227 324.2 400.7 34.4 83.3 X 88.6 83.4 86 5.7 146.2 223.3 352.8 420.3 35.8 78.5 Oxygenates were introduced via an oxygenate unit 14 in a line 52. As mentioned previously, the inclusion of oxygenates does not have to occur on the premises of the refinery. With regard to these blends, the oxygenate was added to the finished gasoline downstream of the gasoline blending process. To each of these blends, oxygenates were introduced such that the oxygenates of the blend comprised less than or equal to about ten (10) volume percent. Each of the gasoline-oxygenate blends contained denatured ethanol meeting the Standard Specification for Denatured Fuel Ethanol for Blending with Gasolines for Use as Automotive Spark-Ignition Engine Fuel ASTM D 4806 as the oxygenate.
Additionally, the percentage reduction of NOx (“NOxR”), toxic pollutants (“ToxR”), and VOCs (“VOCR”) were calculated using the Complex Model Phase I as prescribed by Federal Regulations, see, e.g., 40 C.F.R. §80.45 (1999), such that the positive value indicates the percentage amount that emissions were reduced. As before, the gasoline-oxygenate blend designations shown in Table 10 correspond to the gasoline-oxygenate blend designations in Tables 8-9. For example, the gasoline-oxygenate blend designation A1 corresponds to the gasoline-oxygenate blend designations shown in Tables 8-9 for gasoline-oxygenate blend A1. As previously discussed herein, each of these blend designation letters correspond to the neat blends shown in Table 6. The numerical designations following the letter designations are used to distinguish Phase I gasoline-oxygenate blends that have been prepared from the same neat blend. With these methods in mind, the following properties were found.
Additional properties of the Phase II gasoline-oxygenate blends were determined using ASTM Standards and Methods as discussed herein. Of note, the percentage reduction of NOx (“NOxR”), toxic pollutants (“ToxR”), and VOCs (“VOCR”) were calculated using the Complex Model Phase II as prescribed by Federal Regulations, see, e.g., 40 C.F.R. §80.45 (1999), such that the positive value indicates the percentage amount that emissions were reduced.
The blending of at least two hydrocarbon streams may produce gasoline-oxygenate blends having these desirable properties as well as low temperature and volatility. As the preferred embodiment shows, this gasoline-oxygenate blend successfully includes at least one alcohol, such as ethanol, while reducing pollution. With regard to the calculation of percentage of reduction of NOx, toxic pollutants, and/or VOCs, the mathematical models found in 40 C.F.R. §80.45 (1999) for Phase II Complex Model are currently more appropriate. Those skilled in the art will recognize that future regulations may alter, further restrict, or effectuate additional calculations for any of those properties including but not limited to the percentage reduction of these and other pollutants. Accordingly, nothing herein is intended to limit the scope of this disclosure or the claims.
Future regulations may even be more restrictive than the requirements outlined in the Complex Model Phase II, Region 1 presented in 40 C.F.R. §80.45 (1999). Those skilled in the art recognize the inventive concepts as disclosed and claimed herein are made with reference to the Complex Model Phase II presented in 40 C.F.R. §80.45 (1999), but that the inventive concepts as disclosed and claimed herein are equally applicable to future and possibly more restrictive regulations that may be promulgated.
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