Multicomponent diesel composition

Abstract

The invention discloses novel diesel fuel compositions including a renewable diesel component, a fossil diesel component and an oxygenate component, as well as methods for manufacture and use of a combination of a renewable diesel component, and an oxygenate component for reducing particulate matter emissions.

Claims

1. A fuel composition, comprising: a. a fossil diesel component; b. an oxygenate component in an amount from 10 vol-% to 40 vol-%, of a total fuel composition volume, wherein: i. said oxygenate has a molar mass from 128 to 300 g/mol, and ii. said oxygenate is of a structure:
R.sub.1—O—R.sub.2  (formula 1), in which formula R.sub.1 and R.sub.2 are same or different and selected from C.sub.1-C.sub.15 alkyl groups; and c. a renewable paraffinic diesel component in an amount from 10 vol-% to 30 vol-%, of the total fuel composition volume; wherein a sum amount of said oxygenate component and said renewable paraffinic diesel component is from 26 to 70 vol-%, of the total fuel composition volume.

2. The composition according to claim 1, wherein said oxygenate component is selected from symmetrical or asymmetrical straight chain monoethers, having a molar mass from 150 to 300 g/mol.

3. The composition according to claim 1, wherein an amount of the oxygenate component is about 20 vol-% of the total fuel composition volume.

4. The composition according to claim 1, wherein said oxygenate component is selected from a group consisting of: di-n-nonyl ether, di-n-decyl ether, di-n-octyl ether, di-n-heptyl ether, di-n-pentyl ether, di-n-hexyl ether, ethyl-dodecyl ether, ethyl-undecyl ether, ethyl-decyl ether, ethyl-octyl ether, propyl-dodecyl ether, propyl-undecyl ether, propyl-decyl ether, propyl-nonyl ether, propyl-octyl ether, propyl-heptyl ether, butyl-dodecyl ether, butyl-undecyl ether, butyl-nonyl ether, butyl-heptyl ether, butyl-hexyl ether, pentyl-dodecyl ether, pentyl-undecyl ether, pentyl-nonyl ether, pentyl-octyl ether, pentyl-heptyl ether, or pentyl-hexyl ether, ethyl-nonyl ether, butyl-dekyl ether, pentyl-dekyl ether, octyl-tert-butyl ether, dodecyl-tert-butyl ether, ethyl-hexyl-tert-butyl ether, di-ethylhexyl ether, and mixtures thereof.

5. The composition according to claim 1, wherein said oxygenate component is selected from symmetrical straight chain monoethers.

6. The composition according to claim 1, wherein said renewable paraffinic diesel component comprises: hydrocarbons produced from biomass by gasification of biomass to produce syngas and production of paraffins from said syngas by Fischer-Tropsch synthesis to obtain a paraffinic C.sub.9-C.sub.24 hydrocarbon fraction, hydrotreatment of vegetable oil, animal fat, fish fat, fish oil, algae oil, microbial oil and/or wood and/or other plant based oil as well as recyclable waste and/or residue or a combination thereof to obtain a paraffinic C.sub.9-C.sub.24 hydrocarbon fraction, optionally followed by isomerization, or a combination thereof.

7. The composition according to claim 1, wherein said renewable paraffinic diesel component comprises: hydrotreated vegetable oil, hydrotreated wood and/or other plant based oil, hydrotreated animal fat, hydrotreated fish fat and oil, hydrotreated algae oil, hydrotreated microbial oil, hydrotreated recyclable waste, hydrotreated recyclable residue, or a combination thereof.

8. The composition according to claim 1, wherein in said renewable paraffinic diesel component, an amount of the paraffinic C.sub.15-C.sub.18 hydrocarbons is selected to be at least 70 vol %.

9. The composition according to claim 1, wherein in said renewable paraffinic diesel component, an amount of the paraffinic component in a range of carbon number C.sub.3-C.sub.14 which is selected to be less than 25 vol %.

10. The composition according to claim 1, wherein in said renewable paraffinic diesel component, an amount of the paraffinic component in a range of carbon number C.sub.19-C.sub.24 is selected to be less than 25 vol %.

11. A method for producing a fuel composition having: a. a fossil diesel component; b. an oxygenate component in an amount from 10 vol-% to 40 vol-%, of a total fuel composition volume, wherein: i. said oxygenate has a molar mass from 128 to 300 g/mol, and ii. said oxygenate is of a structure:
R.sub.1—O—R.sub.2  (formula 1), in which formula R.sub.1 and R.sub.2 are same or different and selected from C.sub.1-C.sub.15 alkyl groups; and c. a renewable paraffinic diesel component in an amount from 10 vol-% to 30 vol-%, of the total fuel composition volume; and wherein a sum amount of said oxygenate component and said renewable paraffinic diesel component is from 26 to 70 vol-%, of the total fuel composition volume; and wherein the renewable paraffinic diesel component is produced from a renewable feedstock by a process selected from: d. hydrogenation or deoxygenation of vegetable oil, animal fat, fish fat, fish oil, algae oil, microbial oil and/or wood and/or other plant based oil as well as recyclable waste and/or residue or a combination thereof to obtain a paraffinic C.sub.9-C.sub.24 hydrocarbon fraction, which is optionally subjected to isomerization; or e. gasification of biomass to produce syngas and production of paraffins from said syngas by Fischer-Tropsch synthesis to obtain a paraffinic C.sub.9-C.sub.24 hydrocarbon fraction; or f. a combination thereof; and blending the renewable paraffinic diesel component thereby obtained, a monoether oxygenate component having molar mass from 128 to 300 g/mol, and a fossil diesel component.

12. A method according to claim 11, wherein the feedstock for renewable paraffinic diesel component comprises: vegetable oil, wood and/or other plant based oil, animal fat, fish fat and oil, algae oil, microbial oil, recyclable waste, recyclable residue, or a combination thereof.

13. A method for reducing particulate matter emissions, the method comprising: blending an oxygenate component and a renewable paraffinic diesel component as fuel blending components to fossil fuel for reducing particulate matter emissions, wherein a total fuel composition includes: a monoether oxygenate component having molar mass from 128 to 300 g/mol in an amount from 10 vol-% to 40 vol-%, and renewable diesel component in an amount from 10 vol-% to 30 vol-%, and a sum amount of said oxygenate component and said renewable paraffinic diesel component is from 26 to 70 vol-% of a total fuel composition weight.

14. The composition according to claim 1, wherein in said renewable paraffinic diesel component an amount of the paraffinic C.sub.15-C.sub.18 hydrocarbons is at least 80 vol-%.

15. The composition according to claim 2, wherein said oxygenate component is selected from a group consisting of: di-n-nonyl ether, di-n-decyl ether, di-n-octyl ether, di-n-heptyl ether, di-n-pentyl ether, di-n-hexyl ether, ethyl-dodecyl ether, ethyl-undecyl ether, ethyl-decyl ether, ethyl-octyl ether, propyl-dodecyl ether, propyl-undecyl ether, propyl-decyl ether, propyl-nonyl ether, propyl-octyl ether, propyl-heptyl ether, butyl-dodecyl ether, butyl-undecyl ether, butyl-nonyl ether, butyl-heptyl ether, butyl-hexyl ether, pentyl-dodecyl ether, pentyl-undecyl ether, pentyl-nonyl ether, pentyl-octyl ether, pentyl-heptyl ether, or pentyl-hexyl ether, ethyl-nonyl ether, butyl-dekyl ether, pentyl-dekyl ether, octyl-tert-butyl ether, dodecyl-tert-butyl ether, ethyl-hexyl-tert-butyl ether, di-ethylhexyl ether, and mixtures thereof.

16. The composition according to claim 1, wherein said oxygenate component comprises: di-n-pentyl ether.

17. The composition according to claim 2, wherein said renewable paraffinic diesel component comprises: hydrocarbons produced from biomass by gasification of biomass to produce syngas and production of paraffins from said syngas by Fischer-Tropsch synthesis to obtain a paraffinic C.sub.9-C.sub.24 hydrocarbon fraction, hydrotreatment of vegetable oil, animal fat, fish fat, fish oil, algae oil, microbial oil and/or wood and/or other plant based oil as well as recyclable waste and/or residue or a combination thereof to obtain a paraffinic C.sub.9-C.sub.24 hydrocarbon fraction, optionally followed by isomerization, or a combination thereof.

18. The composition according to claim 3, wherein said renewable paraffinic diesel component comprises: hydrotreated vegetable oil, hydrotreated wood and/or other plant based oil, hydrotreated animal fat, hydrotreated fish fat and oil, hydrotreated algae oil, hydrotreated microbial oil, hydrotreated recyclable waste, hydrotreated recyclable residue, or a combination thereof.

19. The composition according to claim 1, wherein in said renewable paraffinic diesel component, an amount of the paraffinic component in a range of carbon number C.sub.3-C.sub.14 is less than 20 vol-%, and an amount of the paraffinic components in a range of carbon number C.sub.19-C.sub.24 is less than 20 vol-%.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows emission results as compared to reference fuel for blends comprising different proportions of an oxygenate, renewable paraffinic diesel component and fossil diesel component calculated as an average for all measured points. Significant decrease of PM emissions was measured for fuels according to present claims.

DETAILED DESCRIPTION

(2) A fuel composition as used herein refers to diesel fuel complying with standards. The proportions of components are discussed here as percentages of the total fuel composition volume.

(3) In the context of fuel composition, the sum amount of the oxygenate component as defined in claim 1, and said renewable paraffinic diesel component is of special interest. In the context of diesel blends, they can be considered as the most relevant blend components to fossil diesel, the sum amount of which is from 26 to 70 vol-%, preferably from 30 vol-% to 50 vol-% of the total fuel composition volume.

(4) According to a preferable embodiment, in which the oxygenate component consists of ethers derived from renewable sources, i. e. biomass, the sum amount of said oxygenate and said renewable paraffinic diesel sets also the amount of renewable components or biocomponents of the total fuel composition, varying from 26 to 70 vol-%, preferably from 30 vol-% to 50 vol-% of the total fuel composition volume

(5) Parameters measured herein comprise both physical and chemical characteristics of diesel fuel as well as analyses relating to combustion in a diesel engine and emissions therefrom. Common emissions include unburned hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx) or particulate matter (PM). Emissions are regulated by variable standards depending on geographics, international agreements, engine types etc. Effects obtained herein are not dependent on a specific standard, but instead evidenced as decrease against a reference fuel for which experiments were conducted exactly the same manner.

(6) Renewable Paraffinic Diesel Component

(7) Renewable paraffinic diesel component refers here to paraffinic hydrocarbons, n-paraffins or a mixture of straight chain and branched paraffins, derived from biomass. Two approaches dominate, hydrotreating oils or fats of bio-origin or fuels made by Fischer-Tropsch synthesis of gasified biomass (BTL).

(8) It is noted that paraffins exist also in fossil diesel fuels which additionally contain significant amounts of aromatics and naphthenics. Renewable paraffinic diesel component is practically free of aromatics and has properties quite similar to GTL and BTL diesel fuels made by Fischer Tropsch synthesis from natural gas and gasified biomass.

(9) GTL

(10) Gas to liquid, GTL, is a Fischer-Tropsch derived fuel having a similar cloud point than a fuel derived by hydrotreating triglycerides, fatty acids or fatty acid derivatives. GTL is characterized by broad distribution of paraffinic hydrocarbons in the range C.sub.9-C.sub.24. GTL has typically a cetane number in the range 73-81.

(11) BTL

(12) When the synthesis gas used in Fischer-Tropsch process originates from gasification of biomass, the process may be referred to as “biomass to liquid”, “BTL”. Broad distribution of n-paraffinic hydrocarbons in the range C.sub.9-C.sub.24 is obtainable, even though selection of a fraction or fractions could be more specific. In an embodiment, product or a part of it may be subject to isomerization, wherein n-paraffins are at least partly converted to branched chain paraffins, i. e. isomerized.

(13) Hydrotreated Renewable Paraffinic Diesel Component

(14) The hydrotreated renewable paraffinic diesel component is obtainable by hydrotreating vegetable oil, animal fat, fish fat, fish oil, algae oil, microbial oil and/or wood and/or other plant based oil as well as recyclable waste and/or residue or a combination thereof. “Hydrotreated Vegetable Oil” or “Hydrogenated Vegetable Oil” was a common term used during last decade when only vegetable oils were used as feedstocks. Currently more and more of renewable paraffinic diesel is produced by hydrotreatment from waste and residue fat fractions coming from food, fish and slaughterhouse industries, as well as from non-food grade vegetable oil fractions.

(15) In an embodiment the renewable paraffinic diesel component comprises hydrotreated renewable diesel, or consists of hydrotreated renewable diesel. Hydrotreating typically produces bio based middle distillate fuels. The hydrotreated renewable diesels are distinct from “bio-diesel” which is a term reserved for the fatty acid methyl esters (FAME). Chemically hydrotreated vegetable oils are mixtures of paraffinic hydrocarbons and have a very low quantity of sulfur and aromatics. Cold properties of hydrotreated renewable paraffinic diesel can be improved to meet any local requirements, by increasing the amount of i-paraffins by controlling the process parameters or by additional catalytic processing.

(16) In an embodiment the renewable paraffinic diesel component in the fuel composition comprises hydrotreated vegetable oil, hydrotreated animal fat, hydrotreated fish fat, hydrotreated fish oil, hydrotreated algae oil, hydrotreated microbial oil, hydrotreated wood and/or other plant based oil, hydrotreated recyclable waste and/or residue or a combination thereof. In a preferred embodiment said renewable paraffinic diesel component consists of hydrotreated vegetable oil, hydrotreated wood and/or other plant based oil, hydrotreated animal fat, hydrotreated fish fat and oil, hydrotreated algae oil, hydrotreated microbial oil, hydrotreated recyclable waste, hydrotreated recyclable residue, or a combination thereof.

(17) In an embodiment in the hydrotreated renewable paraffinic diesel component the amount of the paraffinic components in the range of carbon number C.sub.15-C.sub.18 is at least 70 vol-%, more preferably more than 80 vol-%, most preferably more than 90 vol-%. When a hydrotreated renewable paraffinic diesel component having said paraffinic component profile is used, a fuel composition of increased cetane number is obtained.

(18) In an embodiment the amount of the paraffinic components in the hydrotreated renewable paraffinic diesel component in the range of carbon number C.sub.3-C.sub.14 is less than 25 vol-%, such as less than 20 vol-%, less than 10% vol-%, or less than 7 vol-%. Optionally in the hydrotreated renewable paraffinic diesel component the amount of the paraffinic components in the range of carbon number C.sub.19-C.sub.24 is less than 25 vol-%, such as less than 20 vol-%, less than 10 vol-%, or less than 5 vol-%.

(19) In an embodiment the renewable paraffinic diesel component consists of renewable paraffinic diesel component having a cetane number of at least 70, preferably at least 75. By using a renewable paraffinic diesel component having high cetane number, a smaller addition of renewable paraffinic diesel component and a monoether oxygenate having molar mass from 128 to 300 g/mol provides increased cetane number in a blend comprising a fossil diesel component and PM emission decrease.

(20) In an embodiment the content of the hydrotreated renewable paraffinic diesel component in the total fuel composition is in the range of 10-30 vol-%. In an embodiment the content of the hydrotreated renewable paraffinic diesel component in the fuel composition is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 vol-%.

(21) In an embodiment fatty acids or triglycerides are first hydrogenated to n-paraffins and n-paraffins are then at least partly converted to branched chain paraffins, i. e. isomerized.

(22) Monoether

(23) The ether component contributes to the fuel composition as an oxygenate. Generally oxygenates used in fuels include various alcohols, ethers, esters and carbonates. However, since hydrocarbons comprising oxygen is a very broad and versatile group of chemicals, different oxygenates contribute to different diesel properties and a trade-off to others is often unavoidable.

(24) To be compatible and soluble to diesel, the oxygenate is selected from monoethers having molar mass from 128 to 300 g/mol, preferably from 150 to 250 g/mol, and more preferably from 150 to 190 g/mol. This molar mass range provides best compatibility to diesels. Monoether refers to a compound comprising only one ether functionality. Said monoethers may be characterized by a formula R.sub.1—O—R.sub.2, wherein R.sub.1 and R.sub.2 are same or different and selected from straight chain or branched C.sub.1-C.sub.15 alkyls, also known as C.sub.1-C.sub.15 n-alkyls and i-alkyls respectively.

(25) Ethers suitable for present diesel composition comprise symmetrical or asymmetrical monoethers. In the context of the present fuel composition, the oxygenate component may comprise substantially one monoether or a mixture of monoethers within above definition.

(26) According to one embodiment, R.sub.1 and R.sub.2 are selected form straight chain C.sub.1-C.sub.15 alkyls, also known as C.sub.1-C.sub.15 n-alkyls. Straight chain ethers have ignition properties better than typical fossil diesel fuel as such. Straight chain ethers having total carbon number of at least 10 are known to have excellent properties as diesel components.

(27) Preferably the oxygenate herein used comprises one of straight chain symmetrical monoethers, wherein formula 1 is of form R.sub.1—O—R.sub.1. Such monoethers comprise compounds known to have high cetane number, such as di-n-pentyl-ether (DNPE), di-n-hexyl-ether (DNHE), di-n-heptyl-ether (DNHpE), di-n-octyl-ether (DNOE), di-n-nonyl-ether (DNNE) and di-n-decyl-ether (DNDE). Furthermore, production of symmetrical monoethers from one alcohol only provides advantages both as non-complexity and economics. DNPE was used as oxygenate in present experiments and provided unexpected decrease in NOx emissions as certain blend with fossil fuel and renewable diesel component. Symmetric monoethers of formula R.sub.1—O—R.sub.1 can be produced according to known methods. Typically symmetrical ethers may be prepared from their corresponding alcohols over acid catalysts. At high temperatures, reactions catalyzed by aluminium oxide are also known.

(28) Asymmetrical straight chain monoethers, i.e. ethers according to formula R.sub.1—O—R.sub.2, wherein R.sub.1 and R.sub.2 are both straight chain C.sub.1-C.sub.15 alkyls but different in carbon chain length, may be produced by well-known standard processes. A well-known example is the reaction of an alkyl halide with a sodium alkoxide, by Williamson ether synthesis. Suitable asymmetrical monoethers comprise those of high cetane number within molar mass range specified. Asymmetrical straight chain monoethers may be selected from compounds according to above specifications, such as ethyl-dodecyl ether, ethyl-undecyl ether, ethyl-decyl ether, ethyl-nonyl ether (ENE), ethyl-octyl ether, propyl-dodecyl ether, propyl-undecyl ether, propyl-decyl ether, propyl-nonyl ether, propyl-octyl ether, propyl-heptyl ether, butyl-dodecyl ether, butyl-undecyl ether, butyl-dekyl ether (BDE), butyl-nonyl ether, butyl-heptyl ether, butyl-hexyl ether, pentyl-dodecyl ether, pentyl-undecyl ether pentyl-decyl ether (PDE), pentyl-nonyl ether, pentyl-octyl ether, pentyl-heptyl ether, or pentyl-hexyl ether.

(29) Monoethers comprising straight carbon chain alkyls are preferred, since they provide better cetane number to blends than monoethers comprising a branched carbon chain.

(30) The oxygenate component may be selected from asymmetrical branched monoethers i.e. ethers according to formula R.sub.1—O—R.sub.2, wherein R.sub.1 and R.sub.2 are different C.sub.1-C.sub.15 alkyls and at least one of which is branched. Within the molar mass range from 128 to 300 g/mol, such ethers comprise among others, ethers comprising tert-butyl as one of the carbon chains, i.e. as R.sub.1 or R.sub.2, such as octyl-tert-butyl ether (OTBE), dodecyl-tert-butyl ether (DOTBE) and ethyl-hexyl-tert-butyl ether (EHTBE). Preferably the molar mass range is from 150 to 190 g/mol.

(31) According to another embodiment, the oxygenate component may be selected from symmetrical branched monoethers i.e. ethers according to formula R.sub.1—O—R.sub.2, wherein R.sub.1 and R.sub.2 are the same C.sub.1-C.sub.15 alkyls and branched. An example of branched symmetrical monoethers within range comprise i.e. di-ethylhexyl ether (DEHE).

(32) According to one embodiment, the oxygenate component of the composition comprises a renewable oxygenate, preferably the oxygenate component consists of a renewable oxygenate. Oxygenates may be produced by selecting the starting materials, typically alcohols, originating from biomass or biomass waste streams. When the oxygenate component is derived from biomass, it can be classified as renewal and thereby contributes to total share of renewal components in the composition. In such a case, sum of renewable components, i.e. sum of the renewable oxygenate and the renewable diesel is from 26 to 70 vol-% and preferably from 30 vol-% to 50 vol-% of the total fuel composition volume.

(33) Fossil Diesel Component

(34) The fossil diesel component means a component or composition, which is naturally occurring and derived from non-renewable sources. Examples of such non-renewable resources include petroleum oil/gas, shale oil/gas, natural gas or coal deposits, and the like, and combinations thereof, including any hydrocarbon-rich deposits that can be utilized from ground/underground sources. The term fossil also refers to recycling material of non-renewable sources.

(35) In an embodiment the fossil diesel component is fossil middle distillate, preferably fossil diesel. Diesel fuel in general is any liquid fuel suitable for use in diesel engines, where fuel ignition takes place without spark, as a result of compression of the inlet air mixture and then injection of fuel. The most common type of diesel fuel is a specific fractional distillate of fossil fuel, preferably petroleum fuel oil. Distillation characteristics define how fuel is evaporated when it is sprayed into the combustion chamber of a diesel engine. Standards (e.g. EN590) include information about typical distillation characteristics.

(36) To distinguish from alternative diesel fuels not derived from petroleum, petroleum-derived diesel is called herein as fossil diesel. It may also be called as e.g. petrodiesel, mineral diesel or petroleum distillate. Fossil diesel can comprise atmospheric or vacuum distillates. The distillate can comprise cracked gas oil or a blend of any proportion of straight run or thermally or catalytically cracked distillates. The distillate fuel can be subjected to further processing such as hydrogen-treatment or other processes to improve fuel properties. Typically fossil diesel comprise naphtenics about 10-50 weight %, monoaromatics about 5-30 weight %, other polyaromatics 0-8 weight % and paraffins about 10-50 weight %.

(37) The present diesel fuel composition comprises fossil diesel component from 30 vol-% to 74 vol-%. Use of a high fossil diesel component content is beneficial, because fossil diesels are well known and compatible with diesel engines. According to an embodiment the diesel fuel composition comprises fossil diesel component from 50 vol-% to 70 vol-% of the total fuel volume.

(38) Final fuel composition may contain refinery and performance additives such as lubricity, cold flow, antistatic and detergent additives.

EXAMPLES

(39) The following examples are provided to illustrate various aspects herein. They are not intended to be limiting.

Example 1. Combustion Experiments

(40) Method/Measurements

(41) Engine tests were performed with a single cylinder test engine. Four test fuels having the same components as different blend proportions were analyzed. Fossil EN 590 summer grade was used as reference fuel and represented the fossil diesel component in blends. The renewable paraffinic diesel and a monoether as oxygenate were further components. In the test procedure the test matrix was designed to combine two speeds and three loads per speed.

(42) For exhaust measurements, a single cylinder test engine with free valve lift and timing and fully adjustable injection parameters was used. Charge and exhaust pressure were also adjustable. Cylinder pressure, fuel consumption and four different emissions, CO, HC, NOx, and particulates were measured.

(43) Particulate mass (PM) emission measurements were performed according to ISO8178-1:2006.

(44) AVL SPC472 Smart Sampler was used for the measurements. Sample was taken from raw exhaust gas and diluted with a dilution factor of 6. Sampling time varied from 90 to 600 seconds depending on particulate concentration and pressure drop of the sample filter. Samples were collected on 47 mm TX40HI20-WW Pallflex filters. The filter flow was set to 1.3 g/s (60 nl/min) and the filter temperature was kept in between 42-50° C. Sample filters were weighed before and after the measurements in a climatic room in which the temperature and humidity were controlled. Minimum of 2 hours stabilisation time were used for the filters before weighing.

(45) The flow calibration of Smart Sampler was checked on daily basis and adjusted when needed. During the measurements campaign the need for adjustments was negligible. On each measurement point 2-3 samples were collected. The reference fuel was measured in the beginning and after the measurement period. Test matrix is given in table 1.

(46) TABLE-US-00001 TABLE 1 Parameters for test points studied. Charge In- Charge air Charge jection air mass temper- air back Injection pres- flow ature pressure timing sure Test point [kg/h] [Deg C.] [bar] [DBTDC] [bar] 1700 rpm 70% load 163 28 1.81 12 1400 1700 rpm 50% load 104 28 0.69 9 1399 1300 rpm 100% load 138 28 1.78 10 1200 1300 rpm 80% load 115 28 0.95 8 1200 1300 rpm 65% load 80 28 0.53 7 1200
Results

(47) The PM results measured with reference fuel are not presented alone, but used as reference level in FIG. 1 presenting overall performance of different blend compositions. The exact compositions shown in FIG. 1 are compiled in table 2. All compositions are not according to present claims but shown as reference. The final results have been calculated according to ISO8178-1:2006. Individual load/rpm points are not presented here. Instead, averages for each mixture are shown in FIG. 1.

(48) TABLE-US-00002 TABLE 2 Compositions of blends tested and shown in figure 1. Renew- Fossil Distil- Distil- Lower Oxy- able diesel Density Viscosity Cetane lation lation heating Sample genate diesel 1 (15° C.) (40° C.) number IBP FBP value unit vol-% vol-% vol-% kg/m3 mm2/s ° C. ° C. MJ/kg standard EN ISO EN ISO ASTM EN ISO EN ISO ASTMD 12185 3104 D6890 3405 3405 4809 1 10 10 80 824.5 3.04 63.4 179.8 359.5 42.8 2 10 30 60 813.6 2.907 67.7 184.9 356.1 42.9 3 20 10 70 820.3 2.662 68.5 178.2 347.1 42.4 4 20 30 50 808.5 2.517 74.5 179.6 353.2 42.4 5 — 100 — 779.8 2.919 78.9 209.9 301.9 43.8

(49) FIG. 1 shows that unexpectedly heavy reductions in PM emissions were observed with mixtures comprising 20 vol-% of DNPE and 10 and 30 vol-% of renewable paraffinic diesel component in 70 and 50 vol-% of fossil diesel component respectively. Compared to fossil fuel, the most significant PM emission decrease was more than 20% for sample 3 comprising 20% of DNPE, 10% of renewable paraffinic diesel component and the rest fossil diesel component. Mixture of 10 vol-% DNPE, 10 vol-% renewable paraffinic diesel component and 80 vol-% of fossil diesel component (sample 1, not according to the present composition) showed increase in PM emissions, but surprisingly low NOx emissions.

(50) It is acknowledged also, that potential for further emission reductions by engine calibration may exist.

CONCLUSIONS

(51) The results showed DNPE as a straight chain, symmetrical monoether oxygenate lowering the particulate matter (PM) emissions. The renewable diesel component lowered both PM and NOx emissions. The surprising synergistic effect with blends comprising both oxygenate component and renewable diesel component lowering PM emissions considerably and at the same time, the NOx emissions were not increased, but remained almost at the same level as for the reference fossil diesel fuel.

(52) The blends (fuels 3 and 4) gave the best PM results with very low NOx-penalty. According to these tests higher renewable diesel component content would probably bring the NOx emission down to the reference level.

Example 2: Ether Testing

(53) Several monoethers, both symmetrical and asymmetrical were tested for their characteristics as mixtures containing oxygen from about 1 to 2 wt-% in fossil diesel. The fossil diesel used as both reference diesel and blend base varied slightly for different experiment series (fossil diesel 2 and 3). Both straight and branched chain ethers were studied. Depending on the carbon chain length, the desired oxygen content was achieved with different ether concentrations in diesel. Standard methods were applied and the results are compiled in tables 3 and 4 (symmetrical straight chain), table 5 (asymmetrical straight chain) and table 6 (asymmetrical branched).

(54) TABLE-US-00003 TABLE 3 Characteristics measured for ether-diesel mixtures for straight chain symmetrical monoethers according to the claimed composition. 89.3% 84.7% 69.3% 81.3% Fossil Fossil Fossil Fossil Fossil diesel 2 diesel 2 diesel 2 diesel 2 diesel 10.7 % 15.3% 30.7 % 18.7% ASTM 2 DNPE DNOE DNOE DNDE Density (15° C.) D4052 816.1 812.6 815.2 814.4 816.9 kg/m3 kV (15° C.) D445 2.62 2.35 2.79 3.06 3.26 mm2/s Cloud point ° C. D2500 −48 <−46 −41 −30 −9 Flash point ° C. D93 75 76 Distillation D86 174 189 195 199 181 IBP ° C. Distillation . 291 283 286 286 335 FBP ° C Cetane number D613 48 53.9 59.9 70 57.8 Oxyg. blend 104.7 125.8 119.7 100.4 cetane number bCN Oxygen (calc) 0 1 1 2 1 %-wt Carbon (calc) 85.9 84.8 84.8 83.8 84.8 %-wt Hydrogen 14.1 14 14 14 14 (calc) %-wt

(55) TABLE-US-00004 TABLE 4 Further straight chain symmetrical monoether characteristics and some values concerning ether-diesel mixture. Fossil 90% Fossil diesel 3 Method diesel 3 10% DNHE Density (15° C.) kg/m3 EN ISO12185 818.4 816.3 Cloud point ° C. ASTM D7689 −28.6 −29.5 Cetane number ASTM D6890 47.5 57 Oxyg. blend cetane 142 number bCN Oxygen (calc) %-wt 0 0.8

(56) TABLE-US-00005 TABLE 5 Characteristics measured for ether-diesel mixtures for straight chain asymmetrical monoethers according to the claimed composition. 88.3% 86.0% 86.0% Fossil Fossil Fossil Fossil diesel 2 diesel 2 diesel 2 diesel 11.7% 14.0% 14.0% ASTM 2 ENE BDE PDE Density (15° C.) D4052 816.1 813.3 814.7 814.6 kg/m3 kV (15° C.) D445  2.62 2.44 2.73 2.83 mm2/s Cloud point ° C. D2500 −48 <−46 <−45 −47 Flash point° C. D93  75 76 Distillation D86  174 194 205 197 IBP° C. Distillation 291 285 286 284 FBP° C. Cetane number D613  48 53.4 56 56.3 Oxyg. blend 94.1 105.1 107.3 cetane number bCN Oxygen (calc) 0 1.1 1 2 %-wt Carbon (calc) 85.9 84.8 84.8 84.8 %-wt Hydrogen (calc) 14.1 14 14 14 %-wt

(57) All compounds mentioned here were soluble in diesel fuel. During cold storage, (about −18° C.), no crystallization or phase separation was observed with any of said ethers studied. These results together with parameters in tables 2 and 3, indicate that with these ethers, similar emission results may be achieved as achieved in example 1 for compositions comprising fossil diesel, renewable diesel and a symmetrical, straight chain monoether, DNPE. It can be deduced that monoethers having molar mass within range from 128 to 300 g/mol such as symmetrical DNOE, DNDE, unsymmetrical ENE, BDE, and PDE, perform similarly to DNPE in diesel blends.

(58) TABLE-US-00006 TABLE 6 Characteristics measured for ether-diesel mixtures for branched chain asymmetrical monoethers according to the claimed composition, method and use. 88.0% 76.0% 76.0% 84.7% Fossil Fossil Fossil Fossil Fossil diesel 2 diesel 2 diesel 2 diesel 2 diesel 12.0% 24.0% 24.0% 15.3% ASTM 2 EHTBE EHTBE OTBE DOTBE Density (15° C.) D4052 816.1 813.6 810.9 810.4 814.9 kg/m3 kV (15° C.) D445 2.62 2.55 2.43 2.56 2.96 mm2/s Cloud point ° C. D2500 −48 <−45 <−45 <−45 <−45 Flash point ° C. D93 75 71 72 74 74 Distillation D86 174 178 170 186 182 IBP ° C. Distillation 291 286 285 286 287 FBP ° C. Cetane number D613 48 45.3 44.3 48.3 52.1 Oxyg. blend 25.5 32.6 49.3 74.8 cetane number bCN Oxygen (calc) 0 1 2 2 1 %-wt Carbon (calc) 85.9 84.8 83.8 83.8 84.8 %-wt Hydrogen (calc) 14.1 14 14 14 14 %-wt

(59) Since several ethers listed in the above tables have cetane number greater than that of diesel, they contribute to increase in cetane number of claimed compositions. As another advantage, it can be concluded that with such ethers lower blend ratio of components contributing to cetane number are required in compositions according to present compositions in order to meet cetane number target. In addition to meeting cetane number requirements in EN590 and ASTM D975, it is especially beneficial in producing premium diesel grades with higher cetane number. Based on this reasoning, the oxygenate component is preferable selected from the group of DNPE, DNOE, DNDE, BDE, DNHE, and PDE.

(60) As summary, ethers tested for their desirable blend characteristics comprised di-n-dekyl ether, di-n-octyl ether, di-n-pentyl ether, di-n-hexyl ether, ethyl-nonyl ether, butyl-dekyl ether, pentyl-dekyl ether, octyl-tert-butyl ether, dodecyl-tert-butyl ether, ethyl-hexyl-tert-butyl ether.

(61) The foregoing description has provided by way of non-limiting examples of particular implementations and embodiments, a full and informative description of the best mode presently contemplated by the inventors for carrying out the present composition and method thereof. It is however clear to a person skilled in the art that the disclosure is not restricted to details of the embodiments presented above, but that it can be implemented in other embodiments using equivalent means without deviating from the characteristics of the present composition and method thereof.

(62) Furthermore, some of the features of the above-disclosed embodiments may be used to advantage without the corresponding use of other features. As such, the foregoing description should be considered as merely illustrative of the principles of the present present composition and method thereof, and not in limitation thereof. Hence, the scope is only restricted by the appended patent claims.