AU2004298630B2 - Fuel for homogeneous charge compression ignition (HCCI) systems and a process for production of said fuel - Google Patents

Description

WO 2005/059063 PCT/ZA2004/000157 FUEL FOR HOMOGENEOUS CHARGE COMPRESSION IGNITION (HCCI) SYSTEMS AND A PROCESS FOR PRODUCTION OF SAID FUEL 5 Field of the Invention The invention relates to a fuel for Homogeneous Charge Compression Ignition (HCCI) systems and to a process for producing such a fuel. 10 Background to the Invention The HCCI engine is a relatively new concept under development by several institutions and companies. The principle of HCCI combustion is that a dilute, premixed, homogenous mixture of fuel and air reacts and burns volumetrically 15 throughout the cylinder as it is compressed by the piston. Combustion reactions start when the mixture reaches a sufficiently high temperature to autoignite. These reactions initiate at multiple locations simultaneously, proceed very quickly, and there is a complete absence of localized high-temperature regions or flame-fronts. 20 In essence, the HCCI combustion process seeks to combine the low nitrogen oxides' (NOx) exhaust emissions associated with the gasoline engine, with the high thermal efficiency associated with the diesel or compression ignition (CI) engine. In theory, HCCI offers the potential for sootless combustion and very low emissions of nitrogen oxides (NOx), together with an energy efficiency that can exceed that of the Cl engine. 25 Successful implementation of HCCI combustion would therefore increase the competitiveness of the internal combustion (IC) engine against emerging technologies such as fuel cells, thereby extending its lifespan. 30 Because HCCI is effectively an evolution of the IC engine, there are no external barriers to its implementation, and the gradual adoption of this technology may see it eventually being implemented in the majority of automotive IC engines, in one form or another. A 2001 report by the US Department of Energy to the US Congress speculated that, with successful R&D, passenger car HCC[ engines might be commercialised by 2010. Thus a need exists for a fuel for HCCI systems and engines. Throughout this specification, unless the context requires otherwise, the word 5 "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers. Each document, reference, patent application or patent cited in this text is expressly incorporated herein in their entirely by reference, which means that it should be read 10 and considered by the reader as part of this text. That the document, reference, patent application, or patent cited in this text is not repeated in this text is merely for reasons of conciseness. Reference to cited material or information contained in the text should not be understood as a concession that the material or information was part of the common general 15 knowledge or was known in Australia or any other country, Summary of the Invention According to one aspect of the invention, there is provided a HCCI fuel or fuel component, which fuel includes at least n-paraffins and iso-paraffins having from 7 to 14 carbon atoms, and which fuel has an ignition delay of less than 7 ms according to ASTM D6890, 20 which fuel has ASTM D86 distillation range from 90'C to 260 C The fuel may be substantially cyclo-paraffins free. Thus, the fuel may have less than 5 mass%, typically less than 1 mass% cyclo-paraffins. Moreover, it preferably contains less than 1 wt % of aromatic and negligible levels of sulphur. - 2/1 - In this specification, the ignition delay is measured using the ASTM Method D6890 in a constant volume combustion bomb, Ignition Quality Tester (IQTTM) The ignition delay of the fuel may be less than 5 ms. The ignition delay of the fuel may be between 2 and 5 ms. 5 The weight % of the n-paraffins may exceed that of any other single component in the fuel. The n-paraffins may be in excess of 25% by weight of the fuel The n-paraffins may be in excess of 50% by weight of the fuel. The n-paraffins may be in excess of 80% by weight of the fuel. - 2/2 - The n-paraffins may be in the order of 95% by weight of the fuel. The n-paraffins may be Fischer-Tropsch (FT) reaction derived n-paraffins. The iso-paraffins may be FT reaction derived iso-paraffins. The fuel may include olefins. 5 The HCCI fuel may include oxygenates. The HCCI fuel may be substantially free of heteroatoms such a nitrogen, sulphur and oxygen. The HCCI fuel may be substantially sulphur free. The HCCI fuel may be substantially oxygenate free. 10 The fuel may include a lubricity improver or other fuel additives to make meeting product specifications possible. An aspect of the invention relates to the use of the fuel or fuel component as a blending component with conventional fuel. The invention extends to a process for preparing a HCCI fuel or fuel component, which 15 fuel or fuel component includes at least n-paraffins and iso-paraffins, which fuel has an ignition delay of less than 7 ms, said process including: a) hydrotreating at least a Condensate fraction of a Fischer-Tropsch (FT) synthesis reaction product, or a derivative thereof; b) hydroconverting a Wax fraction of the FT synthesis product or a derivative 20 thereof; - 3/1 c) fractionating in a single unit or in separate units, one or more of the hydrotreated Condensate fractions of step a) and the hydroconverted fraction of step b) to obtain the desired HCCI fuel or fuel component having 7 to 14 carbon atoms, and which fuel has an ASTM D86 distillation range from 90 C to 270 C; and 5 d) optionally, blending two or more of said components from step c) in a desired ratio to obtain the desired HCCI fuel. - 3/2 - WO 2005/059063 PCT/ZA2004/000157 4 The hydroconversion may be by way of hydrocracking. The properties of the fuel made according to the process may be as disclosed above 5 and elsewhere in the specification. The blending of step d) may be the blending of FT condensate derivative and hydroconverted FT wax derivative from 1:99 to 99:1 by volume 10 The table below gives a typical composition of the two fractions. Typical FT product after separation into two fractions (vol % distilled) FT Condensate FT Wax (< 270 0 C fraction) (> 270*C fraction) C5-1 600C 44 3 160-2704C 43 4 270-3700C 13 25 370-500C 40 > 5004C 28 The >1604C fraction, contains a considerable amount of hydrocarbon material, which 15 boils higher than the normal naphtha range. The 1600C to 2700C fraction may be regarded as a light diesel fuel. This means that all material heavier than 270'C needs to be converted into lighter materials by means of a catalytic process often referred to as hydroprocessing, for example, hydrocracking. 20 Catalysts for this step are typically of the bifunctional type; i.e. they contain sites active for cracking and for hydrogenation. Catalytic metals active for hydrogenation include group VIII noble metals, such as platinum or palladium, or a sulphided Group VIII base metals, e.g. nickel, cobalt, which may or may not include a sulphided Group VI metal, e.g. molybdenum. The support for the metals can be any refractory 25 oxide, such as silica, alumina, titania, zirconia, vanadia and other Group Il1, IV, V and VI oxides, alone or in combination with other refractory oxides Alternatively, the support can partly or totally consist of zeolite. 5 Specific Description and Examples The following table summarises the origin and carbon number ranges for the proposed fuels usable in HCCI engines: 10 - 5- Class Typical (LTFT) Composition Carbon Number range Feedstock CC-Ci C7-C14 C 0

-C

14 SR FT FT Condensate Paraffins, olefins and X X X ___________ oxygenates ____ __________ HT SR FT FT Condensate Mostly linear X X X I paraffins HX FT FT Wax Mostly iso-paraffins X X X GTL aT condensate Fully paraffinic X X X _______and Wax _______ Definitions - SR FT Straight Run Fischer-Tropsch - HT SR FT Hydrotreated Straight Run Fischer-Tropsch 5 - HX FT Hydrocracked Fischer-Tropsch - GTL Hydroconverted Product as expected from a Fischer-Tropsch Gas to-Liquid plant The fuel contains hydrocarbon species having from 7 to 14 carbon atoms and has been found to define unique characteristics with respect to vapour pressure and ignition delay. 10 Moreover, the criteria also made consideration to the highly paraffinic nature of the fuel as well as the high linearity of the hydrocarbon species. The C7 to C14 carbon number range has been found to exclude hydrocarbons like pentane or hexane that have high vapour pressures. Adequate volatility is important to establish a homogeneous gaseous charge in the combustion chamber, with enough 15 cetane character (propensity to auto-ignite) to effect the homogeneous ignition throughout the whole volume. Furthermore, the C7 to C14 carbon number range has been found to exclude hydrocarbons like n-hexadecane that conventionally has cetane number of 100. The - 6- WO 2005/059063 PCT/ZA2004/000157 7 cetane number of the HCCI fuel must not be too high and its ignition delay not too short to ensure controlled in-cylinder combustion. The inventors believe that the abovementioned twelve options cover almost all 5 practical options for FT-based synthetic HCCI fuels. The key quality requirements for these fuels are summarised in Table 1. 10 Table 1 Selected Quality Characteristics of Synthetic FT HCCI Fuels Desired Range Praccae Distillation Range 90-2700C ASTM D86 Density 0.65-0.78 kg/I ASTM D1298 Composition hydrocarbon GC-FID Ignition delay (IQT) 2-7 ms ASTM D6890-03 Cetane Number 25-75 ASTM D613-03a Aromatics content <1.0% wt ASTM D51-99 Sulfur content < 1 ppm wt ASTM D5453 Oxygen content <5000 ppm GC-TCD The ignition delay is a good indication of the elevated pressure, high temperature 15 autoignition characteristics of the fuel and can be correlated to the distillation range and cetane number of the fuel, which in turn relate to its chemical composition. The conditions at which the ignition delay is determined in the IQTM; at 22.4 bar air pressure and 565 0C, are comparable to the conditions that an HCCI fuel could experience in an HCCI engine, thus the ignition delay (ID) can be used as an 20 appropriate yardstick for HCCI fuel ignition quality. The implications are that fuels with a high propensity for autoignition under compression will have short ignition delays (-2-4 ms), while fuels with increased resistance against autoignition (equivalent to high octane spark ignition gasoline) will have longer ignition delays (-7-11 ms). 25 Since the resistance against autoignition is no different to a resistance against oxidation at the specific pressure and temperature conditions to which the fuel is exposed in an HCCI engine's combustion chamber, it follows that those sulphur (S) WO 2005/059063 PCT/ZA2004/000157 8 and nitrogen (N) heteroatoms present in crude oil derived HCCI fuel will act as oxidation inhibitors, leading to longer ignition delays and a lower propensity towards autoignition. 5 FT fuels are virtually sulphur free, with lower levels of nitrogen-containing compounds, and the absence of these naturally occurring anti-oxidants represent a benefit when FT fuels are applied in HCCI engines. This results in FT fuels outperforming conventional fuels in terms of their propensity to autoignite under HCCI conditions. 10 Process Scheme A generic block diagram flow scheme is included as figure 1. The process options for all four classes of HCCI fuels are shown in a simple format. The following table 2 summarises the basic processing for these fuels and feeds. 15 Table 2 Generic Requirement for FT Feedstock Processing Process Step Process Description Reference Distillation Atmospheric Distillation (1) = H 2 saturation of olefinic double bonds. Hydrotreatment * H 2 saturation of oxygen-containing hydrocarbons with formation of water US 6,475,375 - Other hydroconversion reactions = Cracking of heavy molecules (mostly paraffinic) ' Hydrocracking - H 2 saturation of olefinic double bonds. EP 1129155 * H 2 saturation of oxygen-containing hydrocarbons with formation of water - Other hydroconversion reactions 20 (1) There are many references for this unit operation. For example, refer to PA Schweitzer, Handbook of Separation Techniques for Chemical Engineers (McGraw Hill, 1979) or RH Perry and CH Chilton, Chemical Engineers' Handbook (McGraw-Hill, 5 th Edition, 1973) 25 The production of the synthetic HCCI fuel components can be achieved following at least four process configurations. The selection of one for a specific plant is an WO 2005/059063 PCT/ZA2004/000157 9 exercise in process synthesis that demands additional site and market specific information. A first group of HCCI fuels - named SR FT in this description - can be produced by 5 fractionation of a light synthetic FT hydrocarbon stream 10 in Distillation unit 1. The operation of this fractionation unit to the required product specification results in the group of products 11. A second group of HCCI fuels - named SR HT FT in this description - can be obtained 1,0 from a light synthetic FT hydrocarbon stream 10 which is first hydrogenated in hydrogenation unit 2 to saturate the olefinic double bonds and remove the oxygen from the oxygenate species. Then the hydrogenated products can be fractionated in fractionation unit 3 to the required specification, obtaining the group of products 13. 15 A third group of HCCI fuels - named HX FT in this description - can be obtained from a heavy synthetic FT hydrocarbon stream 14 which is hydrocracked in hydrocracking unit 4 to result in lighter saturated hydrocarbon species. Then the hydrocracked products can be fractionated in fractionation unit 5 to the required specification, obtaining the group of products 16. 20 An alternative to produce a fourth group of HCCI fuels - named GTL (GTL = gas to liquid) in this description - can be produced by direct blending of the hydrotreated and hydrocracked products described above. This can be done in an optimised way by using a common fractionator unit 6 to the required specification, obtaining the group of 25 products 18. It is also possible to blend the products 11 and 16, either by sharing a common fractionator or after fractionation to also obtain synthetic HCCI fuels. 30 In all of these process options there is co-production of non-HCCI hydrocarbon stream, both lighter and heavier than the designed HCCI synthetic products. The former can be described as a light naphtha and the latter as a heavy diesel stream. These can be used in fuel and non-fuel applications.

All fuels in any of these four groups can be used as blends components for final HCCI fuels. Emissions Performance of the Synthetic FT HCCI Fuels There is wide acceptance to the fact that the synthetic FT fuels produce less noxious 5 emissions than conventional fuel. This point has been brought into the public domain several times - for example refer to "Processing of Fischer-Tropsch Syncrude and Benefits of Integrating its Products with Conventional Fuels" presented at the National Petrochemical & Refiners Association Annual Meeting held in March 2000 in San Antonio, Texas - paper AM-00-51. This document makes reference to both FT naphthas and FT 10 diesels. Typical Quality of Synthetic FT HCCI Fuels Table 3 contains the typical quality of synthetic FT HCCI fuels produced as described in accordance with the invention and generally conforming to the selected requirements. Table 4 shows a comparison between HT SR FT fuel and crude derived fuel. 15 Table 3 Typical Quality of Synthetic FT HCCI Fuels SR FT HT SRFT C10- C 1 0 Desired Range 7 -C 9

C

7

-C

14 C C 7 -C Q CrC 4 E DC 103- 103- 164- 90- 90- 165 Distillation Range 90-270 C 13 21 5 6 54 5 183 251 251 160 254 254 Density 0.65-0.78 kg/I 0.67 0.71 0.76 0.71 0.74 0.76 wt %_ 52.5 63.1 68.4 946 94.9 95.1 * i-paraffins wt % 0.4 1.6 2.2 5.4 5.1 4.9 Olefins wt % 38.5 26,5 20.5 0 0 0 * Oxygenates wt % 8.6 88 8.9 0 0 0 Ignition delay 2-7 ms 3.34 2.79 2.60 3.44 2.74 2.54 Cetane Number 30-70 60 76 83 58 77 86 Aromatics content <1.0% wt% <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Sulphur content < 1 ppm wt <1 <1 <1 <1 <1 <1 Oxygen content <5000 PPM 700 2000 2150 <80 <80 <80 -10- WO 2005/059063 PCT/ZA2004/000157 11 HX GTL Desired Range C-C9 C7-C14 010 C7-C9 C7-C14 014 IC14 C14 Distillation Range 90-270 0C 80-163 80-250 135- 90-163 90-250 155 250 250 Density 0.65-0.78 kg/I 0.68 0.72 0.74 0.69 0.72 0.75 Composition - n-paraffins wt % 46.0 30.7 26.6 57.5 41.0 38.0 - i-paraffins wt % 54.0 69.3 73.4 42.5 59.0 62.0 - Olefins wt % 0 0 0 0 0 0 - Oxygenates wt % 0 0 0 0 0 0 Ignition delay 2-7 ms 4.92 4.06 3.50 4.55 3.34 3.08

(IQT

TM

) Cetane Number 30-70 41 49 57 44 60 66 Aromatics content <1.0% wt % <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Sulphur content <1 ppm wt <1 <1 <1 <1 <1 <1 Oxygen content <5000 ppm <80 <80 <80 <80 <80 <80 (wt) I I WO 2005/059063 PCT/ZA2004/000157 12 Table 4 Comparison between equivalent synthetic FT Fuel for HCCI Fuels and Crude Derived Fuels HT SR FT Crude Derived Fuels Desired Range CrC 07 e0 CrC CrC1 C1o-C14 Distillation Range 90-270 C 90- 90- 165- 80-159 80-257 151-257 Dsiltio R05-27 160 254 245 Density 0.65-0.78 k 0.71 0.74 0.76 0.7329 0.7715 0.7961 Composition - n-paraffins wt % 94.6 94.9 95.1 28.2 23.8 24.7 - i-paraffins wt % 5.4 5.1 4.9 32.8 53.0 55.3 - Olefins wt % 0 0 0 0.4 0.4 0.5 - Oxygenates wt % 0 0 0 0 0 0 - Aromatics wt % 0 0 0 10.3 14.2 18 - Naphthenes wt % 0 0 0 28.3 8.6 1.5 Ignition delay 2-7 ms 3.44 2.74 2.54 6.17 5.22 4.79 Cetane Number 30-70 58 77 86 34.1 39.0 42.0 Sulphur content <1 ppm wt <1 <1 <1 50 50 50 5 Table 5 below presents an example of the quality characteristics of blends of the C7 C9 GTL HCCI fuel with an equivalent Petroleum fraction. The benefits of including synthetic FT fuel in conventional blends are quite evident. 10 Table 5 Quality of blends of the C7-C9 GTL HCCI fuel with an equivalent Petroleum fraction GTL Fuel Content 0% 25% 50% 75% 100% Density kg/I 0.733 0.722 0.711 0.700 0.690 Composition n-paraffins wt % 28.2 35.4 42.8 50.1 57.5 i-paraffins wt % 32.8 35.1 37.6 40.0 42.5 Olefins wt % 0.4 0.3 0.2 0.1 0.0 Oxygenates wt % 0.0 0.0 0.0 0.0 0.0 Aromatics wt % 10.3 7.8 5.2 2.6 0.0 Naphthenes wt% 28.3 21.3 14.2 7.1 0.0 Total wt % 100.0 99.9 100.0 99.9 100.0 Ignition delay (IQTTM) ms 6.17 5.75 5.22 4.75 4.55 Cetane Number 34.1 36.0 39.1 41.9 44.0 Sulphur content pm 50 38 25 13 <1 15

Claims (19)

1. A HCCI fuel or fuel component, which fuel includes at least n-paraffins and iso-paraffins having from 7 to 14 carbon atoms, and which fuel has an ignition delay of less than 7 ms, according to ASTM D6890, which fuel has ASTM D86 distillation range from 901C to 270 C.

2. A fuel or fuel component as claimed in claim 1, which fuel contains less than 1% wt of aromatic and negligible levels of sulphur, in an amount less than 1 ppm.

3. A fuel or fuel component as claimed in any one of the preceding claims, which fuel has an ignition delay of less than 5 ms.

4. A fuel or fuel component as claimed in any one of the preceding claims, which fuel has an ignition delay of between 2 and 5 me.

5. A fuel or fuel component as claimed in any one of the preceding claims, wherein the mass % of the n-paraffins exceeds that of any other single component in the fuel.

6. A fuel or fuel component as claimed in any one of the preceding claims, wherein the mass % of the n-paraffins is in excess of 25% by mass of the fuel

7. A fuel or fuel component as claimed in any one of the preceding claims, wherein the mass % of the n-paraffins is in excess of 50% by mass of the fuel.

8. A fuel or fuel component as claimed in any one of the preceding claims, wherein the mass % of the n-paraffins is in excess of 80% by mass of the fuel.

9. A fuel or fuel component as claimed in any one of the preceding claims, wherein the mass % of the n-paraffins is in the order of 95% by mass of the fuel. -13-

10. A fuel or fuel component as claimed in any one of the preceding claims, wherein the n-paraffins are Fischer-Tropsch (FT) reaction derived n-paraffins.

11. A fuel or fuel component as claimed in any one of the preceding claims, wherein the iso-paraffins are FT reaction derived iso-paraffins.

12. A fuel or fuel component as claimed in any one of the preceding claims, which fuel includes one or more of: olefins, lubricity improver, and oxygenates.

13. A fuel or fuel component as claimed in any one of claims I to 11, which fuel is substantially free of heteroatoms such as nitrogen, sulphur and oxygen.

14. Use of an HCCI fuel or fuel component as claimed in any one of claims I to 13 as a blending component with conventional fuel.

15. A process for preparing a HCCI fuel or fuel component, which fuel or fuel component includes at least n-paraffins and iso-paraffins, which fuel has an ignition delay of less than 7 rns, said process including: a) hydrotreating at least a Condensate fraction of a Fischer-Tropsch (FT) synthesis reaction product, or a derivative thereof; b) hydroconverting a Wax fraction of the FT synthesis product or a derivative thereof; c) fractionating in a single unit or in separate units, one or more of the hydrotreated Condensate fractions of step a) and the hydroconverted fraction of step b) to obtain the desired HCCI fuel or fuel component having 7 to 14 carbon atoms and which fuel has ASTIM D86 distillation range from 901C to 270 C; and d) optionally, blending two or more of said components from step c) in a desired ratio to obtain the desired HCCI fuel. -14-

16. A process as claimed in claim 15, wherein the hydroconversion is by way of hydrocracking.

17. A process as claimed in claim 15 or claim 16, wherein the blending of step d) is the blending of FT condensate derivative and hydroconverted FT wax derivative in a blending ratio of from 1:99 to 99:1 by volume.

18. A HCCI fuel or fuel component as claimed in claim 1, substantially as herein described and with reference to the examples.

19. A process as claimed in claim 15, substantially as herein described and illustrated. -15-