Marine Fuel Blends

Abstract

The present invention relates to a composition having a kinematic viscosity of 2 to 30 mm, measured at 50 ° C. according to EN ISO 3104:2020. 2 / s and for marine fuel blends containing 0.5 to 50 vol-% palm oil waste sludge bottoms.

Description

[Technical Field]

[0001] The present invention relates to marine fuel blends and uses of marine fuel blends.

[0002] Marine fuels have traditionally been based on fossil oils and are usually more viscous than the gasoline and diesel used in land-based vehicles. However, due to issues related to pollution and climate change, there is a need to provide marine fuels with, for example, a lower sulfur content. Another need is to reduce greenhouse gas (GHG) emissions. The International Maritime Organization (IMO) has a goal, in fact, to reduce total annual GHG emissions from international shipping by at least 50% by 2050 compared to 2008 levels. This goal could be achieved, for example, by improving the efficiency of motors and operations, but alternative fuels are also needed.

[0003] Palm oil sludge, also known as palm oil mill effluent (POME oil) or palm oil effluent sludge (PES), is a slurry that is a by-product of palm oil production. Although it is currently considered a low-value waste, further processing can find other end uses and increase the value of the treated product.

[0004] One type of PES processing involves distillation, which is usually preceded by one or more purification steps. When the goal is to remove free fatty acids, the maximum distillation temperature is typically 260°C. Naturally, such distillation also results in the removal of volatile organic compounds. Distillation is usually carried out under pressure (e.g., 3-5 mbar (absolute)). Steam stripping is often used to facilitate the removal of free fatty acids. The resulting products therefore include palm oil waste sludge bottoms, which are the distillation bottom fraction of the PES crude straight run. This is also known as refined palm oil mill effluent (refined POME). Distillation removes free fatty acids, resulting in a lower total acid number (TAN).

[0005] Patent Document 1 discloses a method for producing environmentally friendly biobunker C oil with a low sulfur content. In this method, palm fruits are first subjected to temperature treatment, followed by pressing and refining to obtain palm oil stock. This palm oil stock is then further refined to produce refined, bleached, and deodorized palm oil and palm oil by-products. This palm oil by-product liquid is then filtered and completely dissolved by adding an organic solvent. The dissolved palm oil by-product is then contacted with a moisture remover to remove moisture. Impurities are then removed from the dehydrated palm oil by-product by centrifugation, and the organic solvent is then removed to complete the production of refined palm oil by-products. Finally, the refined palm oil by-products and bunker C oil are mixed to complete the production of biobunker C oil.

[0006] It is an object of the present invention to provide a method for the production of palm oil waste sludge bottoms. Another object is to provide alternative marine fuels and marine fuel blends. Yet another object is to provide marine fuel blends that have less fossil-derived content than conventional marine fuels, i.e., to provide marine fuel blends that have renewable content therein. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2012 / 108584 Summary of the Invention

[0008] The present invention is defined by the features of the independent claims. Some specific embodiments are defined in the dependent claims. In one aspect, the kinematic viscosity measured at 50°C according to EN ISO 3104:2020 is between 2 and 30 mm 2A marine fuel blend is provided, comprising 0.5 to 50 vol-% palm oil waste sludge bottoms, wherein the marine fuel blend meets at least one of the categories of ISO 8217:2017(E) for marine fuels. In another aspect, a use of a marine fuel blend to reduce greenhouse gas emissions is provided. For blend components depending on the volume percentage of the components, the reduction in GHG emissions is at least 9% as CO2 eq / MJ calculated in accordance with Directive 2018 / 2001 of the European Parliament and of the Council. In a further aspect, a refined cashew nut shell liquid containing at least 50 wt-% cardanol has a kinematic viscosity of 2 to 30 mmHg, measured at 50°C in accordance with EN ISO 3104:2020. 2 / s, and comprising mixing a fossil-based component with 0.5 to 50 vol-% palm oil waste sludge bottoms, wherein the resulting marine fuel blend meets at least one of the categories of ISO 8217:2017(E) for marine fuels. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 shows calculated versus measured pour points for several blends in one embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0010] As used herein, weight percent (wt-%) is calculated based on the weight of the total blend, and volume percent (vol-%) is also calculated based on the volume of the total blend.

[0011] The term "renewable" in the context of a renewable fuel component refers to one or more organic compounds that are derived from any renewable source (i.e., not from any fossil-based source). Thus, a renewable fuel component is based on a renewable source and, as a result, does not originate from or is not derived from any fossil-based material. Such components have a higher carbon content compared to similar components derived from fossil sources. 14 C isotope content higher than 14 C isotope content is an intrinsic feature that characterizes a renewable fuel component and distinguishes it from fossil fuels. Thus, in a fuel blend where part of the blend is based partly on fossil-based materials and partly on renewable fuel components, the renewable component is 14 This can be determined by measuring C activity. 14 C analysis (also called carbon dating or radiocarbon analysis) 12 Isotopes compared to C 14 It is an established approach to date artifacts based on the decay rate of C. Renewable materials are not as old as fossil materials, so the type of material 14 C: 14 Because the biomass fractions contain very different ratios of C, this method can be used to determine the physical fraction of renewable materials in bio / fossil mixtures. The specific ratios of these isotopes can therefore be used as "tags" to identify and distinguish renewable carbon compounds from non-renewable carbon compounds. The renewable component is a key component of the modern atmosphere. 14 While it reflects C activity, in fossil fuels (oil, coal), 14 C is almost non-existent. Therefore, the renewable fraction of any material of interest is 14The carbon content is proportional to the carbon content. A sample of the fuel blend may be analyzed after the reaction to determine the amount of renewable carbon in the fuel. This approach would work equally well for co-processed fuels or fuels produced from mixed feedstocks. It should be noted that when using this method, it is not necessary to test the input feedstocks, as the renewable potential of the fuel blend can be measured directly. The isotope ratios do not change during the chemical reaction. Therefore, the isotope ratios can be used to identify renewable isomeric paraffin compositions, renewable hydrocarbons, renewable monomers, renewable polymers, and materials and products derived from said polymers, and to distinguish them from non-renewable materials. Biogenic feedstocks are defined as follows: 14 C. 13 C and / or 12 Renewable (i.e., modern or bio-based or bio-originating) carbon, which can be determined using radiocarbon analysis with an isotope distribution including C; 14 It refers to materials that have only C-containing components. Other examples of suitable methods for analyzing the content of carbon from biological or renewable sources are DIN 51637 (2014) or EN 16640 (2017).

[0012] For purposes of the present invention, a carbon-containing material, e.g., a feedstock or product, is considered to be of biological, i.e., renewable, origin, if it contains 90% or more modern carbon (pMC), e.g., 100% modern carbon, as measured by ASTM D6866.

[0013] As used herein, "category of ISO 8217:2017(E) for marine fuels" refers to the various categories listed as "category ISO-F-" in Tables 1 and 2 of that standard (e.g., DMX, DMA, DFA, DMZ, RMA, RMG, RMD, RMG, etc.). A marine fuel blend that meets at least one of the categories of ISO 8217:2017(E) for marine fuels is therefore a marine fuel blend that meets all the requirements of a single category, such as RMG, i.e., it can be used in applications where a marine fuel classified as RMG is required.

[0014] In one embodiment of the present invention, the kinematic viscosity measured at 50°C according to EN ISO 3104:2020 is 2 to 30 mm 2 / s, and a marine fuel blend comprising 0.5 to 50 vol-% palm oil waste sludge bottoms, wherein the marine fuel blend meets at least one of the categories of ISO 8217:2017(E) for marine fuels.

[0015] Thus, the marine fuel blend contains a certain amount of palm oil waste sludge bottoms, also referred to herein as PES bottoms. The marine fuel blend also meets at least one of the categories of ISO 8217:2017(E) for marine fuels, which describes several different marine fuel categories. Thus, the marine fuel blend of the present invention makes it possible to provide a decarbonized marine fuel blend to meet more stringent environmental requirements. It also provides a marine fuel blend containing ingredients that cannot be used in the food industry. The renewable ingredients used in the marine fuel blend of the present invention are scalable and economical.

[0016] The marine fuel blend of the present invention uses PES bottoms that are liquid at the blending or mixing temperature. In fact, it is not necessary to melt the PES bottoms, and therefore no specific solvent is required for the PES bottoms, since heating is sufficient to bring them to a stage where they can be mixed with the other components. Therefore, the process and the resulting marine fuel blend are solvent-free, i.e., solvent-free.

[0017] The PES bottoms used in the marine fuel blends of the present invention are preferably produced as follows: The product from a palm oil mill, i.e., crude palm oil mill effluent (POME) oil, is first pretreated, i.e., refined by sedimentation, degumming, and bleaching, or any combination thereof. This pretreatment reduces the amount of water, insoluble, and soluble impurities in the feedstock. The pretreated feedstock is then distilled to separate the free fatty acids from the POME oil. The PES bottoms used in the marine fuel blends of the present invention are obtained as the bottom fraction of this distillation process and have a maximum cut point of 260°C. A particularly advantageous property of the marine fuel blends of the present invention is that they have a pour point that is better (i.e., lower) than expected (calculated) for the particular blend.

[0018] Therefore, the "crude POME" used in producing the PES bottoms of the present invention is a waste stream obtained at an earlier stage in the palm oil production process, different from the "palm raw oil" stream (after further refining and separation of the feed to refined palm oil and palm oil by-products) used in the above-mentioned Patent Document 1. Therefore, the "PES bottoms" of the present invention are a by-product of the palm oil production process, different from the "palm oil by-products" used in Patent Document 1.

[0019] The kinematic viscosity of marine fuel blends is measured at 50°C according to EN ISO 3104:2020 and is between 2 and 30 mm 2 / s, preferably 5 to 15 mm 2The kinematic viscosity is, for example, 2, 3, 4, 5, 7, 10, 12, 13, 15, 18, 20, 22 or 25 mm / s, measured at 50°C according to EN ISO 3104:2020. 2 / s to 5, 7, 10, 12, 13, 15, 18, 20, 22, 25, 27 or 30 mm 2 / s etc.

[0020] In one embodiment, the marine fuel blend has a pour point of at most 30°C, as measured by ASTM D5950-14(2020). The pour point may actually be lower than 0°C, and an upper limit of 30°C meets the requirements for marine fuel. In a preferred embodiment, the pour point is 15-30°C, more preferably 20-30°C, as measured by ASTM D5950-14(2020). Thus, the pour point may be, for example, from 1, 5, 10, 15, or 20°C, to 5, 10, 15, 20, 25, or 30°C, as measured by ASTM D5950-14(2020). As noted above, in some component combinations, the pour point is lower than the calculated value, as shown in the experimental section below.

[0021] In another embodiment, the marine fuel blend has an amount of aged sediments of less than 0.05 wt-% as measured by ISO 10307-2:2009. This amount meets the maximum 0.1 wt-% requirement cited in the marine fuel specification. The amount of aged sediments may be less than 0.04, 0.03, 0.02, or even 0.01 wt-%.

[0022] The marine fuel blend may also have an ash content of less than 0.04 wt-%, as measured by ISO 6245:2002. This ash content meets the requirements of marine fuel specifications. The ash content may be less than 0.03, 0.02, or even 0.01 wt-%.

[0023] The sulfur content of the marine fuel blend is preferably a maximum of 0.1 wt-%, as measured by ISO 8754:2003. This sulfur content meets the requirements for a Sulfur Emission Control Area (SECA Area). The sulfur content may be less than 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, or 0.03 wt-%, or even lower.

[0024] The marine fuel blend of the present invention comprises 0.5 to 50 vol-% palm oil refinery sludge bottoms, preferably 10 to 30 vol-% palm oil refinery sludge bottoms. Accordingly, the amount of PES bottoms in the blend can be from 0.5, 1, 3, 5, 7, 10, 12, 15, 18, 20, 25, 30, 35, or 40 vol-% to 1, 3, 5, 7, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, or 50 vol-%, calculated from the total volume of the marine fuel blend. In some embodiments, the amount of PES bottoms in the blend is from 12 vol-% to 50 vol-%, or from 18 vol-% to 46 vol-%.

[0025] The marine fuel blend may also contain other fuel components of renewable origin, such as fatty acid methyl esters (FAMEs). FAMEs are a type of fatty acid ester obtained by transesterification of fats with methanol, typically obtained by transesterification of vegetable oils. The amount of FAMEs is at most 10 vol-%. For example, the amount of FAMEs can be at most 9, 8, 7, 6, 5, 4, 3, 2, or 1 vol-% based on the total amount of the marine fuel blend.

[0026] The fossil portion of the marine fuel blend may include a distillate marine fuel or fuels, a residual marine fuel or fuels, or a mixture thereof. For example, the marine fuel blend may include 10 vol-% residual marine fuel and up to 50 vol-% PES bottoms, a residual of distillate marine fuel.

[0027] The composition of the marine fuel blend may be, for example, 90 vol-% residual marine fuel and 10 vol-% PES bottoms, or alternatively 80 vol-% residual marine fuel and 20 vol-% PES bottoms, or 83 vol-% residual marine fuel, 10 vol-% PES bottoms and 7 vol-% FAME.

[0028] Marine fuel blends may also contain co-processed components, i.e., components in which fossil-derived oils have been co-processed with renewable-derived field oils in conventional fossil fuel processing systems.

[0029] The marine fuel blend of the present invention may comprise any known marine fuel or mixture thereof, for example, it may comprise marine fuels defined by their properties in ISO 8217:2017(E), i.e. DMX, DMA, DFA, DMZ, DFZ, DMB, DFB, RMA, RMB, RMD, RME, RMG or RMK, such as RMG180, RMG380, RMG500 or RMG700 or RMK380, RMK500 or RMK700.

[0030] For example, marine fuels may be residual fuels, such as hydrocracked residual oil LCO (Light Cycle Oil, a diesel boiling range product from a fluid catalytic cracker) and / or RMG, which includes hydrocracked distillates. Fuels are typically available in a range of up to 700mm 2 / s and a kinematic viscosity of 991 kg / m 3 The hydrocracked residual oil content is typically in the range of 0-70 wt-%. The hydrocracked residual oil may also contain 0-100 wt-% hydrocracked deasphalted oil. In another example, the marine fuel may be RMB, which is also a residual fuel and may include distillate gas oil, including (hydrocracked) vacuum distillate. This typically has a kinematic viscosity of 30 cSt at 50°C and a maximum of 960 kg / m 3 It has a density of , a pour point of 30°C or less, and a boiling range of C6 to C43.

[0031] In another aspect, there is provided the use of a marine fuel blend to reduce greenhouse gas emissions by at least 4% as CO2 eq / MJ calculated in accordance with Directive 2018 / 2001 of the European Parliament and of the Council of December 11, 2018 on promoting the use of energy from renewable sources. Indeed, a reduction of at least 9% in GHG emissions is obtained in a blend containing 10 vol-% palm oil waste sludge bottoms. When 20 vol-% of this bottoms is used, the reduction in GHG emissions is 45% CO2 eq / MJ calculated in accordance with EU Directive 2018 / 2001. The use of the marine fuel blend of the present invention actually makes it possible to reduce GHG emissions due to the inclusion of renewable materials. Thus, the marine fuel blend of the present invention at least partially meets IMO requirements for greenhouse gas emission reduction, as described above.

[0032] In yet another embodiment, the kinematic viscosity measured at 50°C according to EN ISO 3104:2020 is 2 to 30 mm 2 A method for producing marine fuel of 0.5 to 50 vol-% palm oil waste sludge bottoms is provided, the method comprising mixing a fossil-based component with 0.5 to 50 vol-% palm oil waste sludge bottoms, the resulting marine fuel meeting at least one of the categories of ISO 8217:2017(E) for marine fuels. The palm oil waste sludge bottoms are as described above.

[0033] It is to be understood that the disclosed embodiments of the invention are not limited to the particular structures, process steps, or materials disclosed herein, but extend to equivalents thereof that would be recognized by one of ordinary skill in the relevant art. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0034] Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Numerous specific details are provided herein to provide a thorough understanding of embodiments of the present invention.

[0035] In this specification, the verbs "to comprise" and "to include" are used as open limitations which neither exclude nor require the presence of unreferred features. Features recited in dependent claims may be freely combined with each other unless expressly stated otherwise. Furthermore, it is to be understood that the use of "a" or "an", i.e., the singular, throughout this specification does not exclude the plural.

[0036] Experimental section Marine fuel blends of the present invention were tested at various compositions and the resulting blends were tested. The test results are shown in Tables 1 and 2.

[0037] The RMB used in the fuel blend is composed of heavy distillates and meets the ISO 8217:2020(E) marine grade specification for viscosity and residue.

[0038] The PES bottoms used was a straight run bottoms fraction from a crude PES with a maximum cut point of 260°C.

[0039] The FAME used met the EN 14214:2012+A2:2019 standard.

[0040] The measurement method was as follows: Density at 15°C: ISO 12185:1996 Pour point: ASTM D5950-14(2020) Kinematic viscosity at 50°C: EN ISO 3104:2020, Method B Sulfur content of marine fuel blends and RMB: ISO 8754:2003 Sulfur content of FAME: Analysis is based on X-ray fluorescence analysis. Sulfur content of PES bottoms: ASTM D 7039-15(2013) Flash point: ISO 2719:2016, method A Flash Point of FAME: ASTMD 7236-16a (2016) Ash content: ISO 6245:2002 Carbon residue: ISO 10370:2014 Total Acid Number (TAN) for Marine Fuel Blends and RMB: ISO 6619:1988 Total Acid Number (TAN) of PES Bottoms and RMG: ASTM D664-2018 Total Acid Number (TAN) of RMB and FAME: ISO 660:2020 Total deposit amount: ISO 10307-1:2009 Total sediment volume over time: ISO 10307-2A:2009

[0041] Additionally, Table 1 shows the carbon aromaticity index (CCAI) calculated using the following formula:

number

[0042] In Table 1, the column entitled ISO 8217:2017 lists the requirements of said standard (ISO 8217:2017(E)) for marine fuels, with the exception of the pour point, which is shown as a maximum of 30.0°C ( * (marked). The maximum limit of 30.0°C on pour point is a requirement for certain R-grade marine fuels.

[0043] Table 2 shows the measured pour point versus the calculated pour point (as an arithmetic mean), which shows that combinations of at least 80 vol-% RMB and 20 vol-% PES have pour points 4°C lower than the calculated values. The same is shown in Figure 1.

[0044] In Figure 1, the horizontal axis represents the PES content in vol-%d and the vertical axis represents the pour point (°C). The dotted line represents the calculated value, while the solid line represents the measured result, i.e., the measured pour point.

[0045] [Table 1]

[0046] [Table 2]

[0047] Experiments using 10 or 20 vol% PES bottoms with RMB have shown that the resulting blends meet all but the most stringent pour point requirements of marine fuel specifications. Furthermore, blends with 20 vol% PES bottoms and 80 vol% RMB exhibited better-than-expected pour points. The lower-than-expected pour points allow the product to be handled under cooler conditions, which reduces energy consumption for heating, for example.

Claims

1. Kinematic viscosity measured at 50°C according to EN ISO 3104:2020 is 2 to 30 mm 2 / s, and 0.5 to 50 vol-% palm oil waste sludge bottoms, and Fossil-based ingredients and / or oils of fossil origin are co-processed with feeds of renewable origin in conventional fossil fuel processing systems wherein the marine fuel blend meets at least one of the categories of ISO 8217:2017(E) for marine fuels.

2. Kinematic viscosity measured at 50°C according to EN ISO 3104:2020 of 5 to 15 mm 2 2. A marine fuel blend according to claim 1, wherein:

3. 2. The marine fuel blend of claim 1, having a pour point of at most 30°C as measured by ASTM D5950-14(2020).

4. 4. The marine fuel blend of claim 3, having a pour point of 15 to 30°C as measured by ASTM D5950-14(2020).

5. 5. The marine fuel blend of claim 4, having a pour point of 20 to 30°C as measured by ASTM D5950-14(2020).

6. 2. The marine fuel blend of claim 1, having an amount of aged sediments of less than 0.05 wt-% as measured by ISO 10307-2:2009.

7. 2. The marine fuel blend of claim 1 having an ash content of less than 0.04 wt-% as measured by ISO 6245:2002.

8. 2. The marine fuel blend of claim 1, having a sulfur content, as measured by ISO 8754:2003, of maximum 0.1 wt-%.

9. 2. A marine fuel blend according to claim 1, comprising 10 to 30 vol-% palm oil waste sludge bottoms.

10. 10. The marine fuel blend of claim 1, further comprising fatty acid methyl esters.

11. A marine fuel blend according to claim 10, wherein the amount of fatty acid methyl esters is up to 10 vol-%.

12. 10. The marine fuel blend of claim 1, comprising a distillate marine fuel, a residual marine fuel, or a mixture thereof.

13. Kinematic viscosity measured at 50°C according to EN ISO 3104:2020 is 2 to 30 mm 2 1. A method for producing a marine fuel blend in which fossil-based components and / or oils of fossil origin have been co-processed with a feed of renewable origin in a conventional fossil fuel processing system, the method comprising mixing 0.5 to 50 vol-% palm oil waste sludge bottoms, the fossil-based components and / or oils of fossil origin having been co-processed with a feed of renewable origin in a conventional fossil fuel processing system, the method comprising mixing 0.5 to 50 vol-% palm oil waste sludge bottoms, the resulting marine fuel blend meeting at least one of the categories of ISO 8217:2017(E) for marine fuels.

Images