• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A fuel additive for use in Homogeneous Charge Compression Ignition engines, fuel cell systems, compression ignition engines, or jet engines, comprising cyclic organic compounds.
    公开号:SE0900656A1
    申请号:SE0900656
    申请日:2009-05-15
    公开日:2010-11-16
    发明作者:Per Hedemalm
    申请人:Sweden Green Tech Energy Ab；
    IPC主号:
    专利说明:

    15 20 25 30 2 is usually the first step in combustion, causing the polyaromatics to reappear in the exhaust gas. e) Fischer-Tropsch fuels. Such fuels contain mainly non-cyclic alkanes and have been shown to produce very low levels of toxic compounds (see for example WO 9805 740Al). However, non-cyclic alkanes have a low energy content, lower cold fate properties, low viscosity and high cetane number, which limits their range of use. t) The use of monocyclic alkanes in fuels has been described in patent EP 1452579A1. However, the present invention, which uses alkanes with oende your independent cyclic groups of a particular type, will provide a much higher density and a much higher energy content than when monocyclic alkanes are used, while maintaining a low toxicity and improving other important functional parameters.
    Chemical compounds similar to those of the present invention have been previously described for use in lubricating compounds in traction drives, see e.g.
    EP0208541A2. However, their non-obvious use in surface fuels has not been mentioned in connection with their use in power transmission lubricants and their environmental and functional benefits when used as fuel compounds have not been identified. 3. Summary of the Invention By using cyclic compounds of a specific type in the fuel, the energy content of the fuel will be high while maintaining the excellent combustion and functional properties. The cyclic compounds of the invention should contain at least two structural structures that do not share any atoms. Said cyclic compounds should preferably be linked together by a straight or branched chain containing at least three atoms.
    The atoms in the cyclic compounds of the invention should be selected from the group consisting of carbon, hydrogen, oxygen and nitrogen.
    The main advantages of the invention are: a) b) d) g) 3 By using the invention, energy densities have over 10% higher per kg of fuel than conventional ULSD diesel or conventional jet engine fuels (Jet Al, JP-8 etc) presented. This is an important advantage for land vehicles and a major advance for aircraft where the energy content per kg of fuel can be very important, both for military and commercial aircraft. By fully utilizing the invention, it may be possible to achieve up to 20-25% higher energy densities than conventional fuels.
    Flash points above 100 ° C are possible with appropriate application of the invention. This drastically reduces the risk of accidents and limits the effect of accidents should they nevertheless occur.
    Low toxicity and the high fl point make it possible not to label the fuel as dangerous goods when transporting and storing the fuel. This makes transport and storage of the fuel less expensive and less cumbersome because the drivers do not need any special training.
    Fully miscible and compatible with any type of conventional fuel, including but not limited to conventional diesel and kerosene / jet fuel, Fischer-tropsch fuels and fatty acid methyl esters (FAME). No changes or modifications to the engines or distribution systems are needed to use the new type of fuel, so it is a real adequate replacement for conventional fuels.
    The fuel manufactured according to the invention can be designed for a density above 800 kg / m3, which is the lower limit for complying with European standard EN590.
    The fuel can be easily synthesized using commercial raw materials and commercial catalysts.
    The fuel can be made from renewable raw materials, e.g. by polymerization of olefins or monocyclic compounds produced by the Fischer-Tropsch process. Description of a Preferred Embodiment of the Invention 10 15 20 25 30 4.1 Sample Preparation A sample was prepared as follows: 1. A mixture consisting essentially of C2-C6-1 alkenes (alpha-olefins) was polymerized in a lab reactor using a commercially available zeolite based polymerization catalyst, COD 900 obtained from Süd-Chernie AG, Lenbachplatz 6, Munich, Germany. The polymerized product from step 1 was hydrogenated in a lab reactor using a commercially available hydrogenation catalyst, TK-553 from Haldor-Topsoe, Nymoellevej 55, Kgs. Lyngby, Denmark. Five hundred ppm of a commercial lubricating additive from BASF AG was added to the fuel to provide good lubricating properties to the fuel.
    For comparison, a sample of conventional Swedish ultra-low-sulfur diesel (ULSD) was purchased at an OKQ8 petrol station in Gothenburg, Sweden, on 11 February 2009. 4.2 Sample characterization The two samples were characterized by gas chromatography with mass spectroscopy (GCMS) and pyrolysis-fold ionization mass spectroscopy (py-py .
    By GCMS, and by essentially following the method ASTM D2425-93, it was found that the amount of compounds containing 2 or more joined carbon rings, which is the sum of all di- and polyaromatics and di- and polyene fi eners, was below 1.0% in the sample according to the invention. The amount of compounds containing 2 or more joined carbon rings was approximately 24.0% in the ULSD sample.
    By py-FIMS, it was found that the amount of compounds of the invention containing two, three or four cyclohexane rings in the fuel was about 24.0% using the measurement method of Appendix 1. The amount of compounds of the invention in the ULSD test was 10 not measurable, in other words lower than 5.0%. The conclusion is thus that the fuel according to the invention contains approximately 23.0% cyclic compounds with separ your separate cyclic structures according to the invention (24.0% polycyclic compounds minus the maximum content of compounds containing two or fl your joined rings, 1.0%). The amount of C5-Cl2 oils was found to be about 5%.
    Measurements according to ASTM standards showed that the energy content per kg was approximately 10% higher for the fuel according to the invention in comparison with the ULSD test (see Table 1). However, since the content of cyclic compounds of the invention in the sample was only 23.0%, the full potential to increase the energy content should be at least 20% higher than conventional ULSD, if not higher. The cetane number was comparable.
    The cetane number was the same for both samples within the accuracy of the measurement (+/- 2 units).
    The flash point of the fuel according to the invention was above 100 ° C, which is the limit for the requirements for special storage of flammable products in Sweden, while the fl point of the ULSD sample was 73 ° C.
    The lubrication was better with fuel according to the invention, 350 against 390 um wear scars for the ULSD test.
    The density of the sample according to the invention was 802 kg / m 3, which is above the limit needed to meet EN590 standards (800 kg / ms).
    The Cold Flow Plugging Point (CFPP) was better for fuel according to the invention. However, it should be admitted that the CF PP of commercial ULSD fuel can vary, so the main conclusion that can be drawn is that the cold fate properties are at least as good for fuel according to the invention. 10 15 Ordinary Swedish ultra-low Fuel according to Method sulfur diesel (ULSD) invention Calorimetric calorific value 42.3 46.6 ASTM D240 (MJ / kg) Cetane number 54 53 ASTM D6l3 F lamp point (° C) 73 102 ASTM D93 Lubrication torque- 3 HFR ISO 12156-211998 abrasion scar (pm) Density (kg / mß) 817 soz ASTM 134052 Viscosity at 40 ° C (mmZ / s) 2.0 3.0 ISO 3104 Cold fl fate clogging point <-30 -27 ENl 16 (CFPP) (° C ) Table 1. Measurements on the two fuel samples according to the ASTM standard. 4.3 Measurements of emissions The environmental benefits of fuel according to the invention were demonstrated by running a Scania truck engine in a test bench using the ECE R49 combing cycle. 4.3.1. Measurements of regulated emissions The regulated emissions were the same for the two fuels as shown in Table 2. The small differences for NOx and soot emissions may not be statistically significant.
    Fuel according to ULSD Unit recovery Hydrocarbons (HC) 0.01 0.01 g / kWh NOx 2.7 2.8 g / kWh Soot 0.04 0.05 g / kWh CO 0.02 0.02 g / kWh Table 2 Comparison of regulated emissions between fuel according to the invention and ULSD fuel. The small differences for NOx and soot emissions may not be statistically significant. 10 15 20 25 30 4.3.2. Measurements of unregulated emissions Unregulated emissions were analyzed using naphthalene as an indicator substance.
    The reason for the choice is that naphthalene is the smallest polyaromatic substance and is usually present in relatively high concentrations in exhaust gases. Previous measurements have shown that measured emissions of naphthalene correspond well with the emissions of aromatics, aldehydes and heavier polyaromatics. It is therefore reasonable to use naphthalene as an indicator of unregulated emissions.
    Emissions of naphthalene with standard ULSD were 0.27 mg / kWh, while emissions of naphthalene were 0.11 mg / kWh when fuel according to the invention was used, which is a decrease of approximately 60%. Aromatics, aldehydes and heavier polyaromatics can therefore also be expected to decrease by approximately 30-60%. 5. Discussion Although it was not possible here to determine exactly how the ring structures of the molecules were linked using the available analytical methods, it was possible by inference to determine that the ring structures were clearly separated by hydrocarbon chains.
    However, given the three-dimensional structure of the molecules of the invention, it is inevitable that only one or two molecules in the linking chain between the ring structures will make it difficult for the rings to move relative to each other, and they will suffer from so-called " sterically hindered ”behavior.
    Such a steric hindrance can probably result in a lower density and energy content per kg than molecules without such a steric hindrance. Therefore, the number of molecules in the chain that link the ring structures to each other should be 3 or fls. This also has the advantage that there will be a lower risk of the two rings joining together to form a toxic polycyclic compound during the combustion process. 10 6. Conclusions A new fuel formulation has been developed that can provide approximately 10-20% higher energy content per kg and more environmentally friendly properties compared to ultra-low sulfur diesel or kerosene of standard type. The regulated emissions are similar to the fuel according to the invention and ULSD fuel, while the unregulated toxic substances are expected to decrease by approximately 30-60% with the new fuel. The fuel according to the invention can be designed to meet the ENS 90 standard for diesel fuel, which is a density of over 800 kg / m3, and to fully meet the Jet Al standard and other standards for jet fuels. Due to the high energy content per liter, it is expected that the liquid fuel according to the invention will provide products that are very attractive for aircraft applications where the energy density per kg of fuel is very important. 10 15 9 Appendix 1. Measurements of cyclic compounds using py-F IMS The samples were analyzed using py-FIMS. It was assumed that the samples contained mainly carbon and hydrogen. Since a saturated hydrocarbon molecule containing a cyclic group will have exactly two hydrogen atoms less than the corresponding non-cyclic alkane, one can infer the content of compounds having 1, 2, 3 and 4 cyclic groups based on the molecular weight. A compound with two cyclic groups will have four hydrogen atoms smaller than the non-cyclic alkane etc.
    As an example, some of the py-FIMS data for the fuel according to the invention are shown in Table 3.
    Molecular weight (Dalton) Content weight% 311 0.17 312 0.04 313 0 314 0.02 315 0 316 0.13 317 0.02 318 0.59 319 0.15 320 1.49 321 0.35 322 1, 44 323 0.4 324 0.73 325 0.15 326 0.04 327 0 328 0.01 329 0 Table 3. py- FIMS data. Molecules with a weight of 324 Daltons correspond to a non-cyclic alkane C23H48 with a molecular weight of 23x12 + 48x1 = 324. Saturated alkanes containing a ring structure will therefore be found below 322 Daltons, alkanes having two ring structures below 320 Daltons, etc. A correction was made not to overestimate the amount of compounds of the invention: To account for some of the spread of data, half the sum of the values before and after the "top" is subtracted from the "top". This is the standard procedure for GCMS methods, often referred to as "baseline correction". Thus, with the peak at 322 Daltons (1.44%) as an example, half the sum of the 323 Dalton value (0.4%) and the 321 Dalton value (0.35%) was subtracted, giving a measurement result of 1, 06% for the 322-Dalton peak.
    This way of reasoning obviously presupposes that the sample consists mainly of carbon and hydrogen and has low levels of polyunsaturated compounds. For the present samples there was no doubt whether this was the case due to the raw materials and the known manufacturing processes, but for new and unknown samples the correctness of making this assumption can be confirmed by e.g. FTIR.
    Announcements Contributions from the following individuals and organizations are gratefully acknowledged: -Professor Emeritus Albin Czernichowski of ECP S.A.R.I., Orleans France, for assistance with data analysis.
    -Professor Peter Leinweber and Dr. André Schlichting from Steinbeis Transfer-Zentrum in Rostock Germany, for the sample analyzes and interpretation of data.
    权利要求:
    Claims (9)
    [1]
    1. 5 10 15 20 25 30 Swedish Patent Application No. 0900656-0 Amended patent claims 2010-04-29 PATENT CLAIMS.
    [2]
    A surface fuel for use in homo recharge compression ignition engines, compression ignition engines and jet engines comprising more than about 5% of organic compounds comprising: - at least two ring structures having 4-9 atoms in each ring, the atoms being selected from hydrogen, carbon, oxygen and nitrogen , and wherein each ring is separated from each other by a saturated or unsaturated organic chain having at least 3 atoms, e.g. propylene. .
    [3]
    Liquid fuel according to claim 1, wherein the organic compounds have a molecular weight between 200 and 400 Daltons. .
    [4]
    Liquid fuel according to claims 1 to 2, wherein the organic compounds consist of hydrogen and carbon atoms. .
    [5]
    Liquid fuel according to claims 1 to 3, wherein the fuel has a density between 760 and 810 kg / m3. .
    [6]
    Liquid fuel according to any one of the preceding claims, wherein the content of molecules containing ring structures that share at least one atom in the fuel is less than 1%. Liquid fuel according to any one of the preceding claims, wherein the fuel comprises about 5% of C5-Cl2 olefins. .
    [7]
    Liquid fuel according to any one of the preceding claims, wherein the ring structures are saturated with VäÉCaÉOITIBI. .
    [8]
    Liquid fuel according to any one of the preceding claims, wherein the fuel has a melting point of at least 100 ° C.
    [9]
    Liquid fuel according to any one of the preceding claims, wherein the fuel is used in a homogeneous charge compression ignition engine, compression ignition engine, for example a diesel engine, or in a turbine engine. Summary 13 A new engine fuel is described which contains more than about 5.0% of compounds containing at least two ring structures per molecule, the ring structures not being bonded at any point. The ring structures are interconnected with branched or non-branched chains. The linking chains should preferably each contain 3 or more atoms. The compounds contain substances from the group of carbon, hydrogen, oxygen and nitrogen. Fuel according to the invention can contain approximately 10-20% more energy per kg than conventional diesel oil or kerosene. Fuel according to the invention produces considerably less toxic emissions than conventional low-sulfur diesel oil and also has excellent functional properties.
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    同族专利:
    公开号 | 公开日
    WO2010130841A2|2010-11-18|
    EP2430129A2|2012-03-21|
    WO2010130841A3|2011-07-21|
    SE534608C2|2011-10-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3105351A|1959-08-17|1963-10-01|Sinclair Research Inc|High energy fuel consisting of a mixture of bridged polycyclichydrocarbons and methods|
    US4556503A|1983-09-09|1985-12-03|Idemitsu Kosan Company Limited|Traction drive fluids|
    US4528414A|1983-11-15|1985-07-09|Union Carbide Corporation|Olefin oligomerization|
    EP0208541B1|1985-07-08|1991-12-04|Nippon Oil Co. Ltd.|Lubricant compositions|
    US5520710A|1993-09-29|1996-05-28|George A. Olah|Cleaner burning and cetane enhancing diesel fuel supplements|
    US5958370A|1997-12-11|1999-09-28|Chevron U.S.A. Inc.|Zeolite SSZ-39|
    EP1927644A3|2006-12-01|2008-09-24|C.E.-Technology Limited|Aircraft fuels based on synthetic hydrocarbons with a high percentage of isoparaffin and method for manufacturing aircraft fuels with alcohols|DE102016004684A1|2016-04-19|2017-10-19|Linde Aktiengesellschaft|Fuel for aerospace vehicles|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE0900656A|SE534608C2|2009-05-15|2009-05-15|A new liquid fuel with high energy content and reduced emissions|SE0900656A| SE534608C2|2009-05-15|2009-05-15|A new liquid fuel with high energy content and reduced emissions|
    PCT/EP2010/056747| WO2010130841A2|2009-05-15|2010-05-17|Fuel additive|
    EP20100719008| EP2430129A2|2009-05-15|2010-05-17|A fuel component comprising organic compounds containing at least two ring structures with 4-9 atoms in each ring|
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