SE534608C2 - A new liquid fuel with high energy content and reduced emissions - Google Patents

Abstract

A fuel additive for use in Homogeneous Charge Compression Ignition engines, fuel cell systems, compression ignition engines, or jet engines, comprising cyclic organic compounds.

Description

25 30 534 6GB 2 is usually the first step in combustion, causing the polyaromatics to reappear in the gases. 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 9805740A1). 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. f) The use of monocyclic alkane fuels has been described in patent EP 1452579Al. However, the present invention, which uses alkanes with ber 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 previously been 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 lubricants for power transmissions 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 according to the invention must contain at least two ring structures which do not share any atoms. Approximate cyclic compounds should preferably be linked together by a straight or branched chain containing at least three atoms.

The atoms in the cyclic compounds according to the invention must be selected from the group consisting of carbon, hydrogen, oxygen and nitrogen.

The main advantages of the invention are: 10 15 20 25 30 a) b) d) g) 534 B08 3 By using the invention, energy densities are 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 recovery, it may be possible to achieve up to 20-25% higher energy densities than conventional fuels.

Flash points above 100 ° C can be achieved 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 as 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, F ischer-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 really good replacement for conventional fuels.

The fuel manufactured according to the invention can be designed for a density above 800 kg / ma, 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 polymerizing olefins or monocyclic compounds made by the Fischer-Tropsch process. Description of a Preferred Embodiment of the Invention 10 15 20 25 30 534 608 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 by to use a commercially available zeolite-based polymerization catalyst, COD 900 obtained from Süd-Chemie 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 OKQS 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 fractionation mass spectroscopy. .

By GCMS, and by essentially following the method ASTM D2425-93, it was found that the amount of compounds containing 2 or fl joined carbon rings, which is the sum of all di- and polyaromatics and di- and polynaenes, was below 1.0% in the sample according to the invention. The amount of compounds containing 2 or more fused 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 approximately 24.0% using the measurement method of Appendix 1. The amount of compounds of the invention in the ULSD test was 534 608 5 not measurable, in other words lower than 5.0%. The conclusion is thus that the fuel according to the invention contains approximately 23.0% of cyclic compounds with their separate cyclic structures according to the invention (24.0% of polycyclic compounds minus the maximum content of compounds containing two or samman of their joined rings, 1.0%). The amount of C5-C12 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 according to 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 flash point of the ULSD test was 73 ° C.

The lubrication was better with fuel according to the invention, 350 against 390 μm 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 anwa standards (soc kg / mß).

The Cold Filter Plugging Point (CFPP) was better for fuel according to the invention. However, it should be admitted that the CFPP 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. 10 534 B08 6 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 D613 Flash point (° C) 73 102 ASTM D93 Lubrication power 390 350 ISO 12156-2: 1998 abrasion scar (pm) Density (kg / mt) 817 soz ASTM 04052 Viscosity at 40 ° C (mmz / s) 2.0 3.0 ISO 3104 Cold filter clogging point <-30 -27 ENl 16 (CFPP) (° C) Table 1. Measurements of 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 driving 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 30 534 608 4.3.2. Measurements of unregulated emissions Unregulated emissions were analyzed using the nañal as an indicator substance.

The reason for the choice is that the needle is the smallest polyaromatic substance, and it is usually present in relatively high concentrations in exhaust gases. Previous measurements have shown that measured emissions of na fi alen correspond well with the emissions of aromatics, aldehydes and heavier polyaromatics. It is therefore reasonable to use the needle as an indicator of unregulated emissions.

The emissions of the standard ULSD were 0.27 mg / kWh, while the emissions of naphthalene were 0.11 mg / kWh when fuel according to the invention was used, which is a reduction of about 60%. Aromatics, aldehydes and heavier polyaromatics can therefore also be expected to decrease by about 30-60%. 5. Discussion Although it was not possible here to determine exactly how the ring structures of the molecules were interconnected 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 hinder ”behavior.

Such a steric barrier can probably result in a lower density and energy content per kg than molecules without such a steric barrier. 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 gas to form a toxic polycyclic compound during the combustion process. 10 534 608 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 the standard type. The controlled 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 EN590 standard dry diesel fuel, which is a density of over 800 kg / m3, and to fully meet the Jet A1 standard and other standards for jet fuels. Due to the high energy content per kg, it is expected that the liquid fuel according to the invention will provide products that are very attractive vehicle plan applications where the energy density per kg of fuel is very important. 10 15 534 B08 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 purification 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% 31 1 0.17 312 0.04 313 0 314 0.02 31 5 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 recovered below 322 Daltons, alkanes having two ring structure nuns below 320 Daltons, etc. A correction was made so as not to overestimate the amount of compounds of the invention: To account for some of the dispersion of data, half the sum of the values before and e fi er “top” is subtracted from “top”. This is the standard procedure for GCMS methods, called "baseline conjugation". Thus, with the peak at 322 Daltons (1, 44%) as an example, half the sum of the 323 Daltons (0.4%) and 321 Daltons (0 35%) of, which gave 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 that 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.L., Orléans 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.

Claims (1)

1. 0 15 20 25 30 534 608 ll CLAIMS Patent protection is sought for the following:. A surface fuel which as a characteristic ingredient has more than about 5% of purifications having the following chemical structure: each molecule contains at least two ring structures with 4-9 atoms in each ring structure, the ring structures do not share atoms with each other, the ring structures are interconnected by one or more fl your chains of atoms which means that the shortest possible distance between the ring structures is preferably at least 3 atoms, the chains connecting the ring structures may be branched or unbranched, each ring structure may also have one or fl your other side chains, each of the side chains being branched or unbranched, the molecules consist of atoms selected from the group of carbon, oxygen, nitrogen and hydrogen. Liquid fuel according to claim 1 in which the compounds have a molecular weight between 200 and 400 Daltons. . Liquid fuel according to claim 2 in which the compounds consist of hydrogen and carbon atoms. Liquid fuel according to claim 3 having a density between 760 and 810 kg / m 3. Liquid fuel according to claim 4 having a polycyclic hydrocarbon content of less than 1% in which the polycyclic hydrocarbons contain at least two ring structures sharing at least one atom. Liquid fuel according to claim 5, which in addition to the ring-containing compounds also contains approximately 5.0-20.0% alkenes having 3 to 12 carbon atoms. Liquid fuel according to claim 6 in which the ring structures are saturated with hydrogen atoms. 534 608 12 A liquid fuel according to claim 6 which is intended for compression ignition engines (ie are diesel engines). Liquid fuel according to claim 6, which is intended for turbines. Liquid fuel according to claim 6 which is intended for high charge compression ignition engines (HCCI).