Marine fuel blend

Abstract

This invention relates to a marine fuel blend having a thickness of 2-30 mm as measured at 50°C according to EN ISO 3104:2020. 2 The kinematic viscosity is 0.5-50 vol% of palm oil effluent sludge substrate.

Description

Technical Field

[0001] This invention relates to marine fuel blends and their uses. Background Technology

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

[0003] Palm oil sludge (also known as palm oil mill effluent oil (POME oil) or palm oil effluent sludge (PES)) is sludge produced as a byproduct of palm oil production. Today, it is considered a low-value waste product, but when it is further processed, the treated product can find other end uses, thereby increasing its value.

[0004] One treatment for PES is distillation, typically preceded by one or more purification processes. When the goal is to remove free fatty acids, the maximum distillation temperature is usually 260°C. Such distillation naturally also results in the removal of volatile organic compounds. Distillation is usually carried out under pressure (e.g., 3-5 mbar (absolute pressure)). Steam stripping is often used to enhance the removal of free fatty acids. The resulting products include palm oil effluent sludge bottom, thus representing the bottom fraction of a distillation column in the direct distillation of PES crude oil. It can also be referred to as refined palm oil mill effluent (refined POME). Distillation removes free fatty acids from the products, thereby reducing the total acid number (TAN).

[0005] Document WO 2012 / 108584 discloses a method for producing low-sulfur, environmentally friendly, high-viscosity biobunker C oil. This method utilizes a process where palm fruit is first subjected to temperature treatment, followed by pressing and refining to produce crude palm oil. This crude palm oil undergoes further refining to produce refined, bleached, and deodorized palm oil and palm oil byproducts. The liquid palm oil byproducts are then filtered and completely dissolved by adding an organic solvent. Water is then removed from the dissolved palm oil byproducts by contacting them with a dehydrating agent; impurities and organic solvents are removed from the dehydrated palm oil byproducts by centrifugation, thus completing the production of the refined palm oil byproducts. Finally, the refined palm oil byproducts are mixed with high-viscosity biobunker C oil to complete the production of the high-viscosity biobunker C oil.

[0006] The objective is to provide a use for palm oil effluent sludge substrate. Another objective is to provide alternative marine fuels and marine fuel blends. Yet another objective is to provide a marine fuel blend having less fossil-based components than conventional marine fuels, i.e., providing a marine fuel blend containing renewable components. Summary of the Invention

[0007] According to one aspect, a marine fuel blend is provided, having a thickness of 2-30 mm as measured at 50°C according to EN ISO 3104:2020. 2 The marine fuel blend has a kinematic viscosity of / s and includes 0.5-50 vol-% palm oil effluent sludge substrate. This marine fuel blend meets at least one category of ISO 8217:2017(E) for marine fuels. According to another aspect, the use of the marine fuel blend for reducing greenhouse gas emissions is provided. For the blend composition, depending on the volume % of the components, the reduction in GHG emissions is at least 9% (in terms of CO2) calculated according to European Parliament and Council Directive 2018 / 2001. 2eq / MJ (by measurement). According to another aspect, a method for manufacturing a marine fuel blend is provided, the marine fuel blend having a thickness of 2-30 mm² measured at 50°C according to EN ISO 3104:2020. 2 / s kinematic viscosity, including mixing a fossil-based component with 0.5-50 vol-% palm oil effluent sludge substrate, the resulting marine fuel blend meets at least one of the categories of ISO 8217:2017(E) for marine fuels. Attached Figure Description

[0008] Figure 1 The measured pour point and calculated pour point of some blends according to one embodiment are shown. Detailed Implementation

[0009] In this specification, weight percentage (wt-%) is calculated based on the total weight of the blend. Volume percentage (vol-%) is also calculated based on the total volume of the blend.

[0010] In the context of renewable fuel components, the term "renewable" refers to one or more organic compounds derived from any renewable source (i.e., not derived from any fossil-based source). Therefore, renewable fuel components are based on renewable sources and thus do not originate from or derive from any fossil-based material. Such components are characterized by a mandatory higher content of organic compounds than similar components derived from fossil sources. 14 C isotope content. The higher... 14 Carbon isotope content is an inherent characteristic that characterizes the components of renewable fuels and distinguishes them from fossil fuels. Therefore, in fuel blends, where a portion is based on fossil-based materials and a portion on renewable fuel components, the renewable components can be measured... 14 C activity is used to determine this. 14 C analysis (also known as carbon dating or radiocarbon dating) is an isotope-based method. 14 C and 12 The decay rate relative to C is an established method for determining the age of artifacts. This method can be used to determine the physical percentage of renewable material in biological / fossil mixtures, because renewable material is much younger than fossil material, and therefore these types of material contain very different... 14 C: 12 The C ratio. Therefore, the specific ratio of these isotopes can be used as a "tag" to identify renewable carbon compounds and distinguish them from non-renewable carbon compounds. While renewable components reflect the characteristics of the modern atmosphere... 14 C activity, but in fossil fuels (oil, coal) 14 The carbon content is very low. Therefore, the renewable portion of any material of interest is related to its... 14 The carbon content is proportional. Samples of the fuel blend can be analyzed after the reaction to determine the amount of renewable carbon in the fuel. This method is equally applicable to co-processed fuels or fuels produced from blended feedstocks. It is important to note that when using this method, it is not necessarily necessary to test the input materials, as the renewability of the fuel blend can be directly measured. Isotope ratios do not change during the chemical reaction. Therefore, isotope ratios can be used to identify renewable isoparaffinic alkane compositions, renewable hydrocarbons, renewable monomers, renewable polymers, and materials and products derived from said polymers, and to distinguish them from non-renewable materials. Bio-derived feedstocks refer to feedstocks that contain only renewable (i.e., modern or bio-based or bio-sourced) carbon. 14Materials with C content, which can be described in ASTM D6866 (2018) concerning... 14 C 13 C and / or 12 The isotopic distribution of carbon is determined using radiocarbon analysis. Other examples of suitable methods for analyzing carbon content from biological or renewable sources are DIN 51637 (2014) or EN 16640 (2017).

[0011] For the purposes of this invention, a carbon-containing material (such as a raw material or product) is considered to be of biological, renewable origin if it contains 90% or more of modern carbon (pMC) as measured using ASTM D6866 (e.g., 100% modern carbon).

[0012] In this specification, "ISO 8217:2017(E) Marine Fuel Categories" refers to the various categories (such as DMX, DMA, DFA, DMZ, RMA, RMG, RMD, RMG, etc.) listed in Tables 1 and 2 of this standard, as in "ISO-F-Category". Therefore, a marine fuel blend that meets at least one marine fuel category in ISO 8217:2017(E) is a marine fuel blend that meets all the requirements of a single category (such as RMG) and can be used in applications requiring the marine fuel to be classified as RMG.

[0013] According to one aspect of the invention, a marine fuel blend is provided having a thickness of 2-30 mm as measured at 50°C according to EN ISO 3104:2020. 2 The kinematic viscosity is / s, and includes 0.5-50 vol-% palm oil effluent sludge substrate. This marine fuel blend meets at least one of the categories of ISO 8217:2017(E) for marine fuels.

[0014] Therefore, the marine fuel blend includes a certain amount of palm oil effluent sludge substrate, also referred to herein as PES substrate. The marine fuel blend also meets at least one category of ISO 8217:2017(E) for marine fuels, which lists several different categories of marine fuels. Therefore, this marine fuel blend allows for the provision of decarbonized marine fuel blends to meet more stringent environmental requirements. It also provides a marine fuel blend that includes components unsuitable for the food industry or not intended for use in road or aviation fuels. The renewable components used in this marine fuel blend are gradeable and economical.

[0015] This marine fuel blend uses a PES substrate that is liquid at the blending or mixing temperature. In practice, it is not necessary to dissolve the PES substrate, and therefore no solvent specifically designed for PES substrates is required, as heating is sufficient to bring it to a stage where it can be mixed with other components. Therefore, this process and the resulting marine fuel blend are solvent-free, i.e., solvent-free.

[0016] The PES substrate used in this marine fuel blend is preferably manufactured as follows. First, the product from palm oil milling, namely crude palm oil mill effluent (POME) oil, is pretreated (i.e., purified by settling, degumming, and bleaching, or any combination thereof). This pretreatment reduces the amount of water, insoluble and soluble impurities in the material. Subsequently, the pretreated material is distilled, and free fatty acids are separated from the POME oil. The PES substrate used in this marine fuel blend is obtained as the bottom fraction of this distillation step, with a maximum cut point of 260°C. A particularly advantageous characteristic of this marine fuel blend is that, for some blends, the pour point is better (i.e., lower) than the expected calculated value.

[0017] Therefore, the "crude POME" used to manufacture this PES substrate is an effluent stream obtained earlier in the palm oil milling process, which is different from the "crude palm oil" stream used in WO 2012 / 108584 mentioned above (after further refining and separation of feedstocks of refined palm oil and palm oil by-products). Therefore, this "PES substrate" is a palm oil milling process by-product, different from the "palm oil by-products" used in WO 2012 / 108584.

[0018] The kinematic viscosity of marine fuel blends, measured at 50°C according to EN ISO 3104:2020, is 2-30 mm. 2 / s, preferably 5-15 mm 2 / s. According to EN ISO 3104:2020, measured at 50°C, the kinematic viscosity can be, for example, 2 mm². 2 / s, 3mm 2 / s, 4 mm 2 / s, 5 mm 2 / s, 7 mm 2 / s, 10 mm 2 / s, 12 mm 2 / s, 13 mm 2 / s, 15 mm 2 / s, 18 mm 2 / s, 20mm 2 / s, 22 mm 2 / s or 25 mm 2 / s to 5 mm 2 / s, 7 mm 2 / s, 10 mm 2 / s, 12 mm 2 / s, 13 mm 2 / s, 15 mm 2 / s, 18mm 2 / s, 20 mm 2 / s, 22 mm 2 / s, 25 mm 2 / s, 27 mm 2 / s or 30 mm 2 / s.

[0019] According to one embodiment, the pour point of the marine fuel blend, measured according to ASTM D5950-14 (2020), is at most 30°C. In practice, the pour point may also be below 0°C, and the upper limit of 30°C meets the requirements for marine fuel. According to a preferred embodiment, the pour point, measured according to ASTM D5950-14 (2020), is 15-30°C, or more preferably 20-30°C. Therefore, the pour point measured according to ASTM D5950-14 (2020) can be, for example, 1°C, 5°C, 10°C, 15°C, or 20°C to 5°C, 10°C, 15°C, 20°C, 25°C, or 30°C. As mentioned above, for some component combinations, the pour point is lower than its calculated value, as shown in the experimental section below.

[0020] According to another embodiment, the marine fuel blend has an amount of aged deposits of less than 0.05 wt% as measured by ISO 10307-2:2009. This amount meets the requirement of a maximum of 0.1 wt% mentioned in the marine fuel standard. The amount of aged deposits can even be less than 0.04 wt%, 0.03 wt%, 0.02 wt%, or 0.01 wt% or lower.

[0021] Marine fuel blends can 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 standards. The ash content can even be less than 0.03 wt%, 0.02 wt%, or 0.01 wt%.

[0022] The sulfur content of marine fuel blends is preferably no more than 0.1 wt% as measured by ISO 8754:2003. This sulfur content meets the requirements of sulfur emission control areas (SECA areas). The sulfur content can even be less than 0.09 wt%, 0.08 wt%, 0.07 wt%, 0.06 wt%, 0.05 wt%, 0.04 wt%, or 0.03 wt%, or even lower.

[0023] This marine fuel blend contains 0.5-50 vol% palm oil effluent sludge substrate, preferably 10-30 vol% palm oil effluent sludge substrate. Therefore, the amount of PES substrate in the blend, calculated based on the total volume of the marine fuel blend, can be from 0.5 vol%, 1 vol%, 3 vol%, 5 vol%, 7 vol%, 10 vol%, 12 vol%, 15 vol%, 18 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol%, or 40 vol% to 1 vol%, 3 vol%, 5 vol%, 7 vol%, 10 vol%, 12 vol%, 15 vol%, 18 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol%, 40 vol%, 45 vol%, or 50 vol%. In some embodiments, the amount of PES substrate in the blend is 12 vol-% to 50 vol-%, or 18 vol-% to 46 vol-%.

[0024] Marine fuel blends may include other fuel components from renewable sources. For example, it may include fatty acid methyl esters (FAMEs). FAMEs are fatty acid esters obtained by transesterification of fats with methanol, typically from vegetable oils. The amount of FAMEs may be up to 10 vol-%. For example, based on the total volume of the marine fuel blend, the amount of FAMEs may be up to 9 vol-%, 8 vol-%, 7 vol-%, 6 vol-%, 5 vol-%, 4 vol-%, 3 vol-%, 2 vol-%, or 1 vol-%.

[0025] The fossil fraction of a marine fuel blend may include one or more distillate marine fuels, one or more residual marine fuels, or mixtures thereof. For example, a marine fuel blend may include 10 vol-% residual marine fuel, up to 50 vol-% PES substrate, and the remainder distillate marine fuel.

[0026] The composition of the marine fuel blend can also be, for example, 90 vol-% residual marine fuel and 10 vol-% PES substrate. Alternatively, the composition can be 80 vol-% residual marine fuel and 20 vol-% PES substrate, or 83 vol-% residual marine fuel, 10 vol-% PES substrate and 7 vol-% FAME.

[0027] Marine fuel blends may also include co-processed components, which are components in conventional fossil fuel processing systems where fossil-derived oil has been co-processed with feedstock from renewable sources.

[0028] This marine fuel blend may include any known marine fuel or mixtures thereof. For example, it may include marine fuels as defined by their properties in ISO 8217:2017(E), namely 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.

[0029] For example, marine fuel can be RMG as a residual fuel, which includes hydrocracking residue, LCO (light cycle oil, a diesel boiling range product from a fluid catalytic cracking unit), and / or hydrocracking distillate. The maximum kinematic viscosity of the fuel at 50°C is typically 700 mm. 2 / s, and the maximum density is 991 kg / m³ 3 The content of hydrocracking residual oil is typically in the range of 0-70 wt%. Hydrocracking residual oil may also include 0-100 wt% hydrocracking deasphalted oil. According to another example, marine fuel can be RMB, also as a residual fuel, and may include distilled gas oil containing (hydrocracking) vacuum distillate. It typically has a kinematic viscosity of 30 cSt at 50°C and a maximum density of 960 kg / m³. 3 It has a pour point of 30°C or lower and a boiling range of C6-C43.

[0030] According to another aspect, a marine fuel blend is provided for reducing greenhouse gas emissions by at least 9% (in CO2) as calculated under Directive 2018 / 2001 of the European Parliament and the Council of 11 December 2018 on promoting the use of renewable energy sources. 2eq Applications (calculated as / MJ). For blends containing 10 vol-% palm oil effluent sludge substrate, GHG emissions were reduced by at least 9%. CO2 emissions were calculated according to EU Directive 2018 / 2001. 2eq / MJ, when using 20 vol% of this substrate, GHG emissions are reduced by 18%, and when using 50 vol% of the substrate, GHG emissions are reduced by 45%. Therefore, the use of this marine fuel blend can reduce GHG emissions because it includes renewable materials. Thus, as stated above, this marine fuel blend at least partially meets the IMO requirements for reducing greenhouse gas emissions.

[0031] According to another aspect, a method for manufacturing a marine fuel blend is provided, the marine fuel blend having a thickness of 2-30 mm as measured at 50°C according to EN ISO 3104:2020. 2 The method involves mixing a fossil-based component with 0.5-50 vol-% palm oil effluent sludge substrate, the resulting marine fuel blend satisfying at least one category of ISO 8217:2017(E) for marine fuels. The palm oil effluent sludge substrate is as described above.

[0032] It should be understood that the embodiments of the present invention disclosed herein are not limited to the specific structures, processes, or materials disclosed herein, but extend to equivalents that will be recognized by those skilled in the art. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0033] Furthermore, the described features, structures, or characteristics can be combined in any suitable manner in one or more embodiments. Numerous specific details are provided in the specification to provide a thorough understanding of embodiments of the invention.

[0034] In this document, the verbs “to include” and “to comprise” are used as open-ended restrictions, neither excluding nor requiring the presence of features not listed. Unless otherwise expressly stated, the features listed in the dependent claims are freely combinable. Furthermore, it should be understood that the use of “a” or “an” throughout the document, i.e., the singular form, does not exclude the plural.

[0035] Experimental Section

[0036] Fuel blends with different compositions for this ship were tested, and the properties of the resulting blends were also tested. The test results are given in Tables 1 and 2 below.

[0037] The RMB used in the fuel blend consists of heavy distillate and, based on viscosity, meets the residual marine grade specification ISO 8217:2020(E).

[0038] The PES substrate used was a straight-run substrate fraction of crude PES with a maximum fractionation point of 260°C.

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

[0040] The measurement method is as follows:

[0041] Density at 15°C: ISO 12185:1996

[0042] Pour point: ASTM D5950-14 (2020)

[0043] Kinematic viscosity at 50°C: EN ISO 3104:2020, Method B

[0044] Sulfur content of marine fuel blends and RMB: ISO 8754:2003

[0045] Sulfur content of FAME: Analysis was based on XRF technology.

[0046] Sulfur content of PES substrate: ASTM D 7039-15 (2013)

[0047] Flash point: ISO 2719:2016, Method A.

[0048] Flash point of FAME: ASTM D 7236-16a (2016)

[0049] Ash content: ISO 6245:2002

[0050] Carbon residue: ISO 10370:2014

[0051] Total acid number (TAN) of marine fuel blends and RMB: ISO 6619:1988

[0052] Total acid number (TAN) of PES substrate and FAME: ISO 660:2020

[0053] Total sediment content: ISO 10307-1:2009

[0054] Total aged sediment content: ISO 10307-2A:2009

[0055] In addition, Table 1 presents the calculated carbon aromaticity index (CCAI), calculated using the following equation:

[0056]

[0057] in

[0058] Density at D=15°C (kg / m³) 3 )

[0059] V = kinematic viscosity (mm) 2 / s)

[0060] t = Viscosity temperature (°C)

[0061] In Table 1, the column titled ISO 8217 lists the requirements for marine fuels as stated in the standard (ISO 8217:2017(E)), excluding pour point, where the maximum value is expressed as 30.0 °C (and marked with...). The maximum limit of 30.0 °C for the pour point is a requirement for certain R-class marine fuels.

[0062] Table 2 shows the measured and calculated pour points (as arithmetic mean). It can be seen that, at least for the combination of 80 vol% RMB and 20 vol% PES substrate, it has a pour point 4 °C lower than the calculated value. Figure 1 The same situation is shown.

[0063] exist Figure 1 In the graph, the horizontal axis shows the PES content (in vol-%), and the vertical axis shows the pour point (in °C). The shaded line represents the calculated value, while the solid line represents the measured pour point.

[0064]

[0065] Table 1

[0066]

[0067] Table 2

[0068] Based on experiments, blends produced when 10 vol-% or 20 vol-% PES substrate is used with RMB meet marine fuel standards, except for the most stringent pour point limits. Furthermore, for blends with 20 vol-% PES substrate and 80 vol-% RMB, better-than-expected pour point values ​​have been measured. For example, lower-than-expected pour points allow for processing the product under cooler conditions with reduced heating energy consumption.

Claims

1. A marine fuel blend having a cross-sectional area of ​​2-30 mm as measured at 50°C according to EN ISO 3104:2020. 2 kinematic viscosity per second, and including 0.5-50 vol-% palm oil effluent sludge substrate, and Components based on fossils and / or components in which fossil-derived oils are co-processed with feed from renewable sources. The marine fuel blends meet at least one of the categories of ISO 8217:2017(E) for marine fuels.

2. The marine fuel blend according to claim 1, wherein the kinematic viscosity, measured at 50°C according to EN ISO 3104:2020, is 5-15 mm. 2 / s.

3. The marine fuel blend according to any one of the preceding claims has a pour point of up to 30°C as measured by ASTM D5950-14 (2020).

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

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

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

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

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

9. The marine fuel blend according to claim 1, comprising 10-30 vol-% palm oil effluent sludge substrate.

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

11. The marine fuel blend according to claim 10, wherein the amount of fatty acid methyl ester is at most 10 vol-.

12. The marine fuel blend according to claim 1, comprising distillate marine fuel, residual marine fuel, or mixtures thereof.

13. A method for manufacturing a marine fuel blend, said marine fuel blend having a thickness of 2-30 mm as measured at 50°C according to EN ISO 3104:2020. 2 / s kinematic viscosity, the method comprising mixing a fossil-based component and / or a component wherein fossil-derived oil is co-treated with a feed from a renewable source with 0.5-50 vol-% palm oil effluent sludge substrate, the resulting marine fuel blend satisfying at least one of the categories of ISO 8217:2017(E) for marine fuels.

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