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    • 专利摘要:
    RENEWABLE HYDROCARBON COMPOSITION This is a composition comprising 8 to 30% by weight of C4-12 linear alkanes, 5 to 50% by weight of C4-17 branched alkanes, 25 to 60% by weight of C5 ~ 12 1a cycloalkanes 25% by weight of C6-12 aromatic hydrocarbons, maximum 1% by weight of alkenes, and maximum 0.5% by weight in the total of oxygen-containing compounds; wherein the total amount of C4-12 alkanes is 40 to 80% by weight, and the total amount of C4-12 alkanes, CS-12 cycloalkanes and C6-12 aromatic hydrocarbons is at least 95% by weight; and wherein the amounts are based on the mass of the composition. Also provided is a method for the production of the composition comprising the step of hydroprocessing a biological raw material with the use of a catalyst and the step of fractioning the product of the step of hydroprocessing.
    公开号:BR112015024645B1
    申请号:R112015024645-1
    申请日:2014-03-24
    公开日:2020-11-17
    发明作者:Nousiainen Jaakko (Fi/Fi)；Rissanen Arto (Fi/Fi)；Laumola Heli (Fi/Fi)；Lindberg Teemu (Fi/Fi)
    申请人:Upm-Kymmene Corporation (Fi/Fi)；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [0001] The present invention relates to a hydrocarbon composition. More particularly, the present invention relates to a composition that contains a variety of hydrocarbons and is obtainable from a renewable biological raw material. The composition can be used as a fuel component. BACKGROUND OF THE INVENTION
    [0002] Fuels are conventionally produced by refining crude oil (petroleum). This typically involves the separation of several fractions of crude oil by distillation. Such a fraction is naphtha, which is a volatile liquid fraction distilled between the light gaseous components of the crude oil and the heavier kerosene fraction. Naphtha contains a mixture of hydrocarbons (linear alkanes, branched alkanes, cycloalkanes and aromatic hydrocarbons) that have a boiling point between about 30 ° C and about 200 ° C. The density of naphtha is typically 750 to 785 kg / m3.
    [0003] Naphtha has many uses, one of which is as an automotive fuel. Naphtha is also used as a lighter fluid and as a fuel for camping stoves.
    [0004] Renewable fuels derived from biological matter (“biofuels”) are gaining popularity as a more environmentally friendly alternative to fossil fuels. Examples of biofuels include biodiesel, which is typically produced by transesterification of triglycerides contained in vegetable oils (for example, soybean oil). This yields a mixture of alkyl fatty acid esters (for example, fatty acid methyl ester (FAME)). Biodiesel can also be produced from animal fats (eg tallow).
    [0005] An object of the present invention is to provide a renewable hydrocarbon composition that is useful as a fuel component. BRIEF DESCRIPTION OF THE INVENTION
    [0006] A first embodiment of the present invention is a composition comprising 8 to 30 wt% C4-12 linear alkanes, 5 to 50 wt% C4-12 branched alkanes, 25 to 60 wt% C5 cycloalkanes. 12, 1 to 25% by weight of Có.i2 aromatic hydrocarbons, maximum 1% by weight of alkenes, and maximum 0.5% by weight in the total of oxygen-containing compounds; where the total amount of C4.12 alkanes is 40 to 80% by weight, and the total amount of € 4-12 alkanes, C5.12 cycloalkanes and C & -12 aromatic hydrocarbons is at least 95% by weight; and where the amounts are based on the mass of the composition.
    [0007] The above composition has a high content of hydrocarbons and a low content of oxygen and compounds containing oxygen (oxygenates). In particular, the composition does not contain ester compounds or an insignificant amount of ester compounds. The composition also has good stability. The total hydrocarbon content is comparable to that of petroleum-derived fuels. This makes the composition highly suitable for use as an oil fuel replacement or a biofuel component to be mixed with an oil fuel. The composition is particularly suitable for use as a substitute for petroleum naphtha due to the carbon content and the amounts of the various hydrocarbons.
    [0008] A main feature of the composition of the invention is that it can be produced from a renewable biological raw material. More particularly, it is possible to produce the composition by subjecting a biological raw material (for example, crude pine oil) to hydroprocess (i.e., treatment with hydrogen gas) with the use of a catalyst. Hydroprocessing chemically alters the compounds in the raw material; heteroatoms (for example, sulfur and oxygen) can be removed from compounds in the raw material and unsaturated compounds can be hydrogenated.
    [0009] Another embodiment of the invention is a method for producing a composition, as defined above, the method comprising the step of hydroprocessing a biological raw material with the use of one or more catalysts and fractionating the hydroprocessed product. As mentioned above, the ability to produce the composition of the invention from a biological raw material allows the composition to be used as a renewable fuel component.
    [0010] An additional embodiment of the invention is the use of a composition, as defined above, as a fuel or a fuel component. The composition is suitable for use as a biofuel on its own or as a renewable fuel component due to its high hydrocarbon content and low oxygen content.
    [0011] Another additional embodiment of the invention is a fuel blend comprising a composition as defined above. As already mentioned, the composition is compatible with petroleum fuels, particularly petroleum naphtha and petroleum gasoline. The composition can also be mixed with non-hydrocarbons, such as ethanol, which can be produced by a biological process. In this way, it is possible to produce a fuel that contains a high proportion of renewable components. BRIEF DESCRIPTION OF THE DRAWINGS
    [0012] Figure 1: Schematic diagram illustrating a hydroprocessing reactor suitable for use in the production method of the present invention. DETAILED DESCRIPTION
    [0013] In this application, the terms "understand", "understand (understood)", "contain" and "contains (contained)", in the context of one or more components of the composition, cover the case where the components mentioned are the components of the composition, as well as the case in which other components are present. When the composition is defined as containing a certain amount of a compound defined in generic terms (for example, linear alkanes 04-12), the definition of a subset of compounds (for example, C5.9 linear alkanes) or a specific compound ( for example, n-hexane) which is included in the generic class means that the subset of compounds or the specific compound is present in said amount and other compounds (for example, linear Cs alkanes) within the generic class may or may not be contained in the composition .
    [0014] The composition of the invention is described in detail below. Unless otherwise specified, all amounts are in% by weight based on the mass of the composition.
    [0015] The composition comprises 8 to 30% by weight of C4.12 linear alkanes. The content of C4.12 linear alkanes is preferably 10 to 20% by weight, more preferably 12 to 18% by weight. Linear alkanes are preferably C5.10 linear alkanes, more preferably C5-9 linear alkanes, that is, the composition preferably comprises 8 to 30% by weight of C5.10 linear alkanes, more preferably , 8 to 30% by weight of C5-9 linear alkanes.
    [0016] In one embodiment, the composition contains 10 to 20% by weight of C5.10 linear alkanes. In another embodiment, the composition contains 10 to 20% by weight of C5.9 linear alkanes. In an additional embodiment, the composition contains 12 to 18% by weight of linear C1-10 alkanes. In yet another embodiment, the composition contains 12 to 18% by weight of C5-9 linear alkanes.
    [0017] The composition comprises 5 to 50% by weight of branched alkanes C4.12. The content of branched C4-12 alkanes is preferably 20 to 40% by weight, more preferably 30 to 40% by weight from the point of view of the cold flow properties of the composition. The branched alkanes are preferably C5.11 branched alkanes, more preferably C5.10 branched alkanes. 40% by mass of branched alkanes C5.11- In another embodiment, the composition contains 20 to 40% by mass of branched alkanes Cs-10- In an additional embodiment, the composition contains 30 to 40% by mass of branched C5 alkanes. 11. In yet another embodiment, the composition contains 30 to 40 wt.% Of branched alkanes C5.10.
    [0018] In one embodiment, the composition contains 20 to 40% was a mass of branched alkanes C5.11. In another embodiment, the composition contains 20 to 40% by weight of C5-10 branched alkanes. In an additional embodiment, the composition contains 30 to 40% by weight of C5-11 branched alkanes. In yet another embodiment, the composition contains 30 to 40% by weight of branched C5.10 alkanes.
    [0019] The composition comprises 25 to 60% by weight of C5.12 cycloalkanes. The C5.12 cycloalkane content is preferably 30 to 50% by weight, more preferably 35 to 45% by weight. Cycloalkanes are preferably C1-10 cycloalkanes, more preferably CÓ-9 cycloalkanes.
    [0020] In one embodiment, the composition contains 30 to 50% by weight of cycloalkanes CÓ-IO- In another embodiment, the composition contains 30 to 50% by weight of cycloalkanes CÔ-9- In an additional embodiment, the composition contains 35 to 45% by mass of cycloalkanes C6.io- In yet another embodiment, the composition contains 35 to 45% by weight of cycloalkanes CÓ-9-
    [0021] The composition comprises 1 to 25% by weight of C6-i2 aromatic hydrocarbons. The Có-n aromatic hydrocarbon content is preferably 2 to 15% by weight, more preferably 5 to 10% by weight. Aromatic hydrocarbons are preferably CÓ-10 aromatic hydrocarbons> more preferably C7.10 aromatic hydrocarbons. Carbon numbers denote the total number of carbon atoms contained in aromatic hydrocarbons, including carbon atoms contained in non-aromatic constituents (for example, alkyl substituent on an aromatic ring). Examples of aromatic hydrocarbons include ethylbenzene, xylenes, butyl benzene and ethyl butyl benzene.
    [0022] In one embodiment, the composition contains 2 to 15% by weight of aromatic hydrocarbons CÔ-IO- In another embodiment, the composition contains 2 to 15% by weight aromatic hydrocarbons Cy-io- In an additional embodiment, the composition contains 5 to 10% by weight of C & -io aromatic hydrocarbons. In yet another embodiment, the composition contains 5 to 10% by weight of Cy.io-
    [0023] The total amount of C4-12 alkanes in the composition is 40 to 80% by weight, preferably 40 to 70% by weight, more preferably 40 to 60% by weight and most preferably 45 to 55% by mass. "Alkanes" encompasses both straight and branched alkanes.
    [0024] The composition preferably comprises at least 80% by weight of the total C4.12 alkanes and C5-12 cycloalkanes, more preferably at least 85% by weight, most preferably at least 90% by weight. mass and most preferably 90 to 95% by mass in the total of C4.12 alkanes and C5.12 cycloalkanes.
    [0025] The composition contains € 4-12 alkanes, C5 cycloalkanes. 12 and Có-i2 aromatic hydrocarbons in a total amount of at least 95% by weight. Consequently, the composition contains a maximum of 5% by weight of other hydrocarbons. In particular, the composition contains a maximum of 1% by weight of alkenes. Such a low alkene content can be achieved using the hydroprocessing method of the invention. A low content of alkene is beneficial in terms of the oxidation stability of the composition.
    [0026] The composition contains a maximum of 0.5% by weight in the total of oxygen-containing compounds (oxygenates), thus complying with the EN 228 standard. This ensures that the composition is stable during storage and compatible with fuels petroleum products, particularly petroleum naphtha. The total amount of oxygen (eg esters) contained in the composition is preferably at most 0.2% by weight, more preferably at most 0.1% by weight. In elementary terms, it is preferred that the composition contains a maximum of 0.1% by weight of oxygen, more preferably, a maximum of 0.05% by weight of oxygen and most preferably, a maximum of 0.02% by weight of oxygen. oxygen.
    [0027] The density of the composition is typically 720 to 775 kg / m3, as measured at 15 ° C using the method of EN ISO 12185. This is comparable with the density of petroleum naphtha. exclusive. In one embodiment, the composition begins to distill at a temperature of about 30 ° C and the distillation is completed at a temperature of a maximum of 210 ° C, preferably a maximum of 200 ° C, as measured by the method of EN ISO 3405 It is preferred that at least 95% by volume of the composition is distilled at temperatures up to 180 ° C, more preferably, up to 170 ° C.
    [0028] The composition has unique distillation properties. In one embodiment, the composition begins to distill at a temperature of about 30 ° C and the distillation is completed at a temperature of a maximum of 210 ° C, preferably a maximum of 200 ° C, as measured by the EN method. ISO 3405. It is preferred that at least 95% by volume of the composition is distilled at temperatures up to 180 ° C, more preferably, up to 170 ° C.
    [0029] As an additional property, the average molecular weight of the composition can be from 100 g / mol. In one embodiment, the average molecular weight is 90 to 110 g / mol. In another embodiment, the average molecular weight is 98 to 108 g / mol.
    [0030] The method for producing the composition of the invention is explained in detail below.
    [0031] The method comprises the step of hydroprocessing a biological raw material with the use of one or more catalysts. Hydroprocessing chemically alters the compounds contained in the raw material. Typical reactions include hydrogenation of double bonds, deoxygenation (for example, by means of decarboxylation), desulfurization, denitrification, isomerization, ring opening, aromatization, de-aromatisation and cracking. For example, any terpenes contained in the raw material can be converted into non-terpenic cyclic and / or acyclic hydrocarbons (e.g., l-isopropyl-4-methylcyclohexane and 2,6-dimethyloctane) by hydrogenating olefinic bonds and opening the ring. Aromatic hydrocarbons (for example, 1,1,2,5-tetramethylbenzene, 1,1,2,3-tetramethylbenzene and 1-isopropyl-4-methylbenzene) can be produced by hydrogenating compounds containing cyclohexane derived from terpenes. Bound contaminants, such as sulfur, can be converted to gaseous compounds (for example, hydrogen sulfide), which can be removed in a subsequent step.
    [0032] The biological raw material can be selected from a range of raw materials. Particular examples are as follows: animal (including fish);
    [0033] i) fats, oils and waxes of plant (vegetable) and animal (including fish);
    [0034] ii) free fatty acids obtained by hydrolysis or pyrolysis of fats, oils and waxes from plants and animals;
    [0035] iii) fatty acid esters obtained by transesterification of fats, oils and waxes from plants and animals;
    [0036] iv) metal salts of fatty acids obtained by saponification of fats, oils and plant and animal waxes;
    [0037] v) fatty acid anhydrides obtained from plant and animal fats, oils and waxes;
    [0038] vi) esters obtained by esterification of free fatty acids of animal and vegetable origin with alcohols;
    [0039] vii) fatty alcohols or aldehydes obtained as fatty acid reduction products from plant and animal fats, oils and waxes;
    [0040] viii) recycled food-grade fats and oils;
    [0041] ix) fats, oils and waxes obtained by genetic engineering;
    [0042] x) dicarboxylic acids, polyols (including diols), hydroxy ketones, hydroxy aldehydes, hydroxy carboxylic acids and compounds containing corresponding nitrogen and sulfur and multifunctional;
    [0043] xi) compounds derived from algae; and
    [0044] xii) mixtures thereof.
    [0045] In one embodiment, the raw material comprises or consists of one or more among pine oil, pine oil components (for example, pine oil fatty acids) and pine oil derivatives (for example, acids pine oil resin and pine oil tar). Pine oil is obtained from the formation of wood kraft pulp, especially coniferous wood. In general, pine oil contains organic compounds containing saturated and unsaturated oxygen, such as resin acids (mainly abietic acid and its isomers), fatty acids (mainly linoleic acid, oleic acid and linolenic acid), non-saponifiable, fatty alcohols, sterols and other alkyl hydrocarbon derivatives, as well as minor amounts of inorganic impurities (for example, alkali metal compounds, sulfur compounds, silicon, phosphorus, calcium and iron). Pine oil usually does not contain a significant amount of triglycerides, as these compounds are decomposed during pulping processes. The “pine oil” includes soap oil, as well as crude pine oil.
    [0046] In a preferred embodiment, the raw material comprises at least 15% by weight, more appropriately at least 25% by weight, at least 35% by weight or at least 45% by weight, of C12-18 fatty acids ( for example, linoleic acid, oleic acid and linolenic acid); at least 5% by weight, more suitably at least 15% by weight, at least 20% by weight or at least 25% by weight, of resin acids (for example, abietic acid, pyramic acid and isomers thereof); and at least 10% by mass, more suitably at least 15% by mass or at least 20% by mass, of neutral products (for example, sterols) based on the mass of the raw material. This raw material is suitably pine oil.
    [0047] Hydroprocessing is performed with the use of one or more catalysts. Effective catalysts comprise one or more metals selected from Group VIA and Group VIII metals, of which particularly useful examples are Mo, W, Co, Ni, Pt and Pd. The catalyst (s) may also contain one or more support materials, examples of which are zeolite, alumina (AI2O3), zeolite-alumina, alumina-silica (SiO2), alumina-silica-zeolite and activated carbon.
    [0048] The method appropriately uses a hydrodeoxygenation catalyst (HDO), which is intended for the removal of oxygen, but also has the capacity to remove other heteroatoms, such as sulfur and nitrogen, from organic compounds, as well as catalyze the hydrogenation of unsaturated bonds. Effective HDO catalysts include those that contain a mixture of CoO and MoO3 (“C0M0”) and / or a mixture of NiO and MoO3 (“NiMo”), and one or more support materials selected from zeolite, alumina, zeolite -alumina, alumina-silica, alumina-silica-zeolite and activated carbon. A mixture of NiO and MoO3 in an alumina support is particularly effective.
    [0049] Another effective hydroprocessing catalyst is a multifunctional catalyst. This type of catalyst has the capacity to catalyze the same reactions as HDO catalysts. In addition, multifunctional catalysts can effect isomerization (for example, conversion of linear alkanes to branched alkanes) and cracking, which shortens the hydrocarbon chain length. Both isomerization and cracking can improve cold flow properties.
    [0050] Useful multifunctional catalysts include those containing NiW and one or more support materials selected from zeolite, alumina, zeolite-alumina, alumina-silica, alumina-silica-zeolite and activated carbon. An alumina support with suitable acidic properties is preferred. The acidity can be adjusted by adding zeolites to the support. For example, the support comprises zeolite-alumina or alumina-silica-zeolite.
    [0051] An additional suitable hydroprocessing catalyst is a hydroisomerization catalyst (Hl). Hl catalysts are capable of causing isomerization reactions. The example catalysts contain a Group VIII metal (for example, Pt, Pd, Ni) and / or a molecular sieve. The preferred molecular sieves are zeolites (for example, ZSM-22 and ZSM-23) and silicoaluminophosphates (for example, SAPO-11 and SAPO-41). H1 catalysts can also contain one or more of the support materials described above. In one embodiment, the H1 catalyst comprises Pt, a molecular sieve of zeolite and / or silicoaluminophosphate, and alumina. The support may alternatively or additionally contain silica.
    [0052] According to a preferred modality, the hydroprocessing step is carried out using one or both of the following catalysts (i) and (ii), and, optionally, the following catalyst (iii):
    [0053] (i) a catalyst comprising MoO3, one or both of CoO and NiO, and one or more support materials;
    [0054] (ii) a catalyst comprising NiW and one or more support materials;
    [0055] (iii) a catalyst comprising a Group VIII metal and / or a molecular sieve;
    [0056] in which the support materials are selected from zeolite, alumina, zeolite-alumina, alumina-silica, alumina-silica-zeolite and activated carbon.
    [0057] Suitable catalyst combinations are (i) and (ii), (i) and (iii), (ii) and (iii), and (i), (ii) and (iii). It is also possible, however, that the hydroprocessing step is performed with the use of catalyst (i) alone or catalyst (ii) alone.
    [0058] It is preferable to remove sulfur compounds from the raw material before it is reacted with the catalyst (iii), in the case where the catalyst (iii) contains a Group VIII metal (for example, Pt) . This prevents poisoning of the catalyst (iii) by sulfur compounds. Preferably, the raw material is placed in contact with the catalyst (i) before the catalyst (iii).
    [0059] Hydroprocessing is carried out with the use of a reactor or with the use of two or more reactors (that is, separate pressure vessels). In the event that a plurality of hydroprocessing reactors are employed, the reactors can be connected in series so that the product from one reactor is fed to another reactor. Each reactor can contain a single "bed" comprising one or more catalysts and, optionally, other materials, such as an inert material (for example, for temperature control). Alternatively, any given reactor can contain a plurality of catalyst beds each containing one or more catalysts and, optionally, other materials, such as an inert material. Examples of inert material include alumina, silicon carbide and glass beads. Reactors containing more than one catalyst bed can comprise a cooling gas inlet and a distributor between any two catalyst beds.
    [0060] The catalyst beds can be monolayer (for example, contain a catalyst or a mixture of catalysts) or comprise a plurality of layers containing different proportions of two or more catalysts. The layers may vary in size.
    [0061] Layers containing inert material can be used to separate catalyst beds. In addition, an inert layer can be inserted before the first catalyst bed and / or after the final catalyst bed. Inert layers can be used to capture certain substances and provide an even distribution of the raw material / reaction mixture. An inert layer located upstream of the first catalyst bed can also be used to preheat the raw material.
    [0062] The inert layers may also contain active catalyst material that has the function of removing harmful components (for example, metals) from the raw material / feed mixture.
    [0063] Hydroprocessing can be performed using a reactor that contains a single catalyst, such as catalyst (i). This catalyst can be contained in a single bed or in multiple beds in the reactor.
    [0064] In a more preferred modality, hydroprocessing is carried out using one or more reactors that each contain catalyst (i) and one or both of the catalysts (ii) and (iii). In this case, catalyst (i) and catalyst (ii) and / or (iii) can be contained in the same bed (for example, in a reactor that has a single catalyst bed), separate beds or a mixture of them in any given reactor. Preferably, at least one reactor contains catalyst (i) as well as catalyst (ii) and / or catalyst (iii), and the total amount of catalyst (ii) and / or catalyst (iii) in relation to the total amount of catalysts (i), (ii) and (iii) continuously increase in the direction of flow of biological raw material in the reactor. This can occur over a single catalyst bed that contains all catalysts (in mixed or layered form) or over a plurality of catalyst beds (e.g., two beds) that each contain one or all of the catalysts. The exact proportions of the catalysts can be varied according to the nature of the raw material. The increased amounts of catalysts (ii) and (iii) can be used to increase cracking and isomerization levels.
    [0065] In a particular example, a hydroprocessing reactor contains two or three catalyst beds and the proportion of catalyst (ii) and / or (iii) increases in the movement between the catalyst beds in the flow direction. The first bed contains only catalyst (i) or a mixture of catalysts (i) and (ii) in a particular mass ratio (for example, 70 to 99: 1 to 30), the second bed contains a mixture of catalyst (i ) and one or both of the catalysts (ii) and (iii) at a lower mass ratio (for example, 30 to 70: 30 to 70 (total of (ii) and (iii)), and the third bed (when present) contains a mixture of catalyst (i) and one or both of the catalysts (ii) and (iii) in an even lower mass ratio (eg 2 to 15: 85.98) or contains only catalyst (ii) and / or catalyst (iii).
    [0066] In another embodiment, a reactor contains two catalyst beds only, the first bed (closest to the raw material inlet) containing the catalyst (i) and no catalyst (ii) or catalyst (iii), and the second bed containing catalyst (ii) and / or catalyst (iii), but not catalyst (i).
    [0067] In an alternative preferred embodiment, the relative quantities of the catalysts vary across two or more interconnected reactors. For example, a first reactor contains a catalyst bed that comprises only catalyst (i) or a mixture of catalysts (i) and (ii) in a particular mass ratio (for example, 70 to 95: 5 to 30), and a second reactor connected downstream of the first reactor contains a catalyst bed comprising a mixture of catalyst (i) and one or both of the catalysts (ii) and (iii) at a lower mass ratio (for example, 1 to 15: 85. <) 9 (total of (ii) and (iii)) or comprising only catalyst (ii) and / or catalyst (iii).
    [0068] It is preferable that the hydroprocessing reactors are connected in such a way that no component of the reaction mixture leaving a first reactor (for example, a reactor containing the catalyst (i)) is removed before passing the mixture to the next reactor (for example, a reactor containing catalyst (ii)). Thus, there is a single closed hydroprocessing system (in addition to the reactor outputs and inputs) divided by more than one reactor. Similarly, it is preferable that the product that has passed through one or more protection beds (see below) passes to the hydroprocessing bed (s) without removing by-products or other components. In general, all catalyst beds are preferably connected in this way.
    [0069] Figure 1 illustrates a hydroprocessing reactor suitable for use in the manufacturing method of the present invention. The hydroprocessing reactor 1 contains three catalyst beds (beds 2, 2 'and 2 ”), which are optionally separated by cooling gas distributors. The bed of catalyst 2 is located closest to the inlet of biological raw material and the bed of catalyst 2 ”is located closest to the outlet, which is connected to line 5. At least 0 bed 2 contains the catalyst (i) described above (for example, NÍMO / AI2O3), at least 0 bed 2 ”contains the catalyst (ii) described above (for example, NiW / zeolite / AFOs) and at least one bed contains 0 catalyst (i) in combination with 0 catalyst (ii). For example, beds 2 and 2 'contain catalysts (i) and (ii), with the proportion of catalyst (ii) in bed 2' being greater than that in bed 2. The content ratios are 70 to 99 (catalyst (i)): 1 to 30% by mass (catalyst (ii)) and 30 to 70: 30 to 70% by mass for beds 2 and 2 ', respectively. The proportion of catalyst (ii) in bed 2 ”is even greater (for example, 85 to 100% by mass), preferably 100% by mass.
    [0070] Line 3 supplies the raw material for 0 reactor 1, while line 4 supplies pure hydrogen or a hydrogen-containing gas for reactor 1. Hydrogen line 4 connects to supply line 3 just before the feed enters reactor 1, thus allowing the pre-mixing of raw material and hydrogen. In an alternative mode, lines 3 and 4 are connected separately to reactor 1.
    [0071] The hydrogen supply line 4 optionally splits to form one or more branch lines that are connected to reactor 1 downstream of the raw material inlet. In Figure 1, the optional cooling gas lines are connected between the catalyst beds to allow control of the hydrogen content of the catalyst beds and control of the reactor temperature.
    [0072] HDO and multifunctional catalysts (catalysts (i) and (ii)) can benefit from the addition of sulfur before the raw material is introduced into the reactor. A suitable sulphidating agent is dimethyl disulfide. On the other hand, the performance of an Hl catalyst (catalyst (iii)) can be optimized by preventing sulfur from coming into contact with the catalyst. Consequently, as mentioned above, if a hydroprocessing reactor contains an H1 catalyst, means are preferably provided to prevent sulfur from coming into contact with the H1 catalyst catalyst. Sulfur can be removed from the reactor downstream from an HDO / multifunctional catalyst, but upstream from an HL catalyst
    [0073] A suitable reactor temperature during hydroprocessing is 280 to 450 ° C, preferably 350 to 420 ° C and most preferably 350 to 390 ° C. A suitable reactor pressure is 10 to 250 bar, preferably 30 to 130 bar and most preferably 80 to 110 bar.
    [0074] Hydroprocessing products are influenced by the feed rate of the raw material. The hourly space velocity in weight (WHSV) of the raw material can be from 0.1 to 5.0 h'1, preferably 0.2 to 0.8 h'1 and most preferably 0.3 to 0.7 h'1. WHSV is defined as follows: WHSV = V / m
    [0075] where “V” is the feed rate of the raw material (g / h) and “m” is the mass of the catalyst (g).
    [0076] The ratio between the amount of hydrogen supplied to the hydroprocessing reactor (s) and the amount of raw material supplied to the reactor (s) also has an influence on the reaction. It is preferable that this ratio is 600 to 4,000 Nl / 1 (NI = normal liter), more preferably, 1,300 to 2,200 Nl / 1
    [0077] The amount of monoaromatic hydrocarbons can be controlled by the appropriate selection of hydroprocessing conditions. For example, the amount of monoaromatics can be increased by increasing the temperature of the hydro-processing reactor. Reducing the reactor pressure also causes an increase in the monoaromatics content.
    [0078] The process of the invention can include additional steps before and / or after the hydroprocessing step. Such optional steps include the purification of the raw material and the purification of the hydroprocessing product before fractionation.
    [0079] The raw material can be purified by means of evaporation. This can be done in one or more stages. In the case where two or more evaporators are employed, the temperature is typically increased successively from the first to the second and subsequent evaporators. In one embodiment, the raw material is heated to 110 to 230 ° C at a pressure of 40 to 80 mbar, in order to remove light compounds, such as water and short-chain hydrocarbons. In another embodiment, two evaporators are employed, the first evaporator (for example, a thin film evaporator) operating at 150 to 230 ° C and 40 to 80 mbar, and the second evaporator operating at 300 to 390 ° C and 0 , 01 to 15 mbar. In an additional modality, three evaporators are employed, the first evaporator that operates at 150 to 230 ° C and 40 to 80 mbar, the second evaporator that operates at 200 to 280 ° C and approximately 2 to 3 mbar, and the third evaporator that operates at 250 to 360 ° C and approximately 0.3 mbar. These modalities are particularly suitable for purifying crude pine oil. The residue from the first evaporator is fed to the second evaporator, and the distillate from the second evaporator is fed to the third evaporator. The use of an initial evaporation step allows the boiling in the subsequent step to be carried out in a controlled manner, since the low boiling compounds are removed in the first step.
    [0080] Before hydroprocessing, the raw material can be passed through one or more protection units together with hydrogen, in order to remove toxic substances, such as metal residues, thus protecting the hydroprocessing catalysts against poisoning and inlay. For this, the protection units can comprise an HDO and / or multifunctional catalyst arranged in one or more beds. These catalysts are as described above for the hydroprocessing step, the difference being that the catalysts used in the protection unit (s) typically have less activity; for example, a NiMo catalyst used in a protection unit has relatively low hydrogenation activity.
    [0081] Protection units are typically separate from the hydroprocessing reactor (s). However, it is possible to include one or more protection beds upstream of the hydroprocessing catalyst bed (s) in the same unit (pressure vessel).
    [0082] The hydro-processed composition can be cooled and light gaseous compounds, such as water, hydrogen, hydrogen sulfide, carbon monoxide and carbon dioxide, removed from the composition. The removed gases can be passed through an amine purifier in order to separate hydrogen sulfide and carbon dioxide from the remaining gases. The hydrogen can be separated and reused as a cooling gas in the hydro-processing reactor.
    [0083] The composition of the invention is isolated by fractionation of the hydroprocessed composition, preferably after removal of gases, as described above. Fractionation separates the composition of the invention from relatively heavy hydrocarbons, such as those in the diesel fuel range. The fractionation step typically makes use of the distillation properties discussed above. The composition can be distilled over the temperature range of 30 to 210 ° C, preferably 40 to 200 ° C.
    [0084] The composition of the invention can be used as a pure biofuel or as a renewable component of a fuel. The composition is most notably suitable for use as a substitute for petroleum naphtha. The composition can be mixed with a petroleum derived fuel, such as petroleum naphtha or petroleum gasoline, in order to reduce the proportion of non-renewable components. The composition can be additionally or alternatively mixed with ethanol, which can be bioethanol (that is, produced from a renewable source). Other compounds that may be included in a fuel mixture together with the composition of the invention include compounds containing oxygen, such as higher alcohols (C3. E) (for example, isobutanol) and ethers (for example, ethyl tert-butyl ether) . A fuel mixture can also contain additional hydrocarbons, such as butane.
    [0085] A fuel blend may contain the composition of the invention in varying amounts depending on the desired properties of the blend and the identity of the other components of the blend. For example, a fuel blend can contain the composition in an amount of 2 to 85% by volume, preferably 3 to 25% by volume. Ethanol can be contained in the fuel mixture in an amount of up to 85% by volume, preferably 60 to 85% by volume, more preferably 70 to 85% by volume and most preferably 75 to 85% by volume . The fuel mix can also contain up to 2% by volume of higher alcohols (C3-8).
    [0086] In one embodiment, a mixture of fuel comprises 2 to 25% by volume of the composition of the invention, 75 to 85% by volume of ethanol, 1 to 5% by volume of ether compounds comprising five or more carbon atoms (for example, ethyl tert-butyl ether) and up to 2% by volume of higher alcohols (C3-C8) (for example, isobutanol), with the total amount of butane contained in the fuel mixture being 2 to 10% in volume. The blend may additionally contain 0.5 to 2% by volume of methanol, and the blend may contain petroleum gasoline and / or petroleum naphtha, preferably in a smaller amount.
    [0087] In another embodiment, a mixture of fuel comprises 2 to 25% by volume of the composition of the invention, and 75 to 86% by volume in the total of ethanol and higher alcohols (C3.8), the amount of alcohols being up to 2% by volume, and the total amount of butane contained in the mixture is 2 to 10% by volume. The blend may additionally contain one or more of petroleum gasoline, petroleum naphtha, 0.5 to 2% by volume of methanol, and ether compounds that comprise five or more carbon atoms, preferably in smaller amounts. The additional butane may not be necessary if the composition of the invention contains a sufficient amount of butane. EXAMPLES EXAMPLE 1
    [0088] A hydrocarbon composition was produced by subjecting the crude pine oil to a hydroprocessing treatment. Crude pine oil originated from the pine oil soap obtained from the chemical digestion of a mixture of northern softwood (pine and spruce) and birch. Crude pine oil contained 51% by weight of fatty acids, 26% by weight of resin acids and 23% by weight of neutral compounds.
    [0089] The crude pine oil was purified by a three step evaporation process to remove 4% of the oil as a light fraction and 6% of the oil as a heavy tar fraction. The purified oil was fed to the pilot reactor system in conjunction with hydrogen. The pilot reactor system contained a protection unit that has two layers of catalyst arranged in series. Each of the catalyst layers contained Ni, Mo and W as active metals and SiO2 and AI2O3 as support materials and metal scavengers.
    [0090] From the protection unit, the composition was passed to a hydroprocessing reactor together with hydrogen. The hydro-processing reactor comprised four monolayer catalyst beds through which the reaction mixture was passed in a series manner. The compositions of the catalyst beds are detailed in Table 1 below. Hydrogen was also introduced between the catalyst layers.

    [0091] The hydroprocessing conditions are detailed in Table 2 below. TABLE 2

    [0092] The hydro-processed composition was passed to a separator for the removal of water and light gases. The composition was then passed to a fractionator, in which a fraction distilled in the temperature range of 80 to 190 ° C was collected. Table 3 below details the quantities of the different components of the distillate, as determined by gas chromatography. (ASTM D6729, high performance gas chromatography with 100 meter capillary).

    [0093] The density of the composition was 740 kg / m when measured at 15 ° C using the method of EN ISO 3675.
    [0094] The initial boiling point of the composition was 84.6 ° C, 10% by volume of the composition was distilled at temperatures up to 98.4 ° C, 50% by volume of the composition was distilled at temperatures up to 115.9 ° C, 90% by volume of the composition were distilled at temperatures up to 146.2 ° C, and the cut-off temperature (final boiling point) was 185.7 ° C.
    权利要求:
    Claims (29)
    [0001]
    1. Composition CHARACTERIZED because it is produced from a renewable biological raw material, in which the composition comprises from 8 to 30% by weight of C4-12 linear alkanes, from 20 to 50% by weight of C4-12 branched alkanes, from 25 to 60% by weight of C5-12 cycloalkanes, from 1 to 25% by weight of C6-12 aromatic hydrocarbons, at most 1% by weight of alkenes, and at most 0.5% by weight in the total of compounds containing oxygen; wherein the total amount of C4-12 alkanes is 40 to 70% by weight, and the total amount of C4-12 alkanes, C5-12 cycloalkanes and C6-12 aromatic hydrocarbons is at least 95% by weight; and where the amounts are based on the mass of the composition.
    [0002]
    2. Composition according to claim 1, CHARACTERIZED by the amount of linear alkanes C4-12 being 10 to 20% by weight.
    [0003]
    Composition according to either of Claims 1 and 2, characterized in that the amount of branched alkanes C4-12 is 20 to 40% by weight.
    [0004]
    Composition according to any one of the preceding claims, characterized in that the amount of C5-12 cycloalkanes is 30 to 50% by weight.
    [0005]
    5. Composition according to any one of the preceding claims, CHARACTERIZED by the amount of aromatic hydrocarbons C6-12 being from 2 to 15% by weight.
    [0006]
    6. Composition according to any one of the preceding claims, CHARACTERIZED that the linear alkanes are C5-10 linear alkanes.
    [0007]
    Composition according to any one of the preceding claims, CHARACTERIZED that the branched alkanes are C5-11 branched alkanes.
    [0008]
    8. Composition according to any one of the preceding claims, CHARACTERIZED by the cycloalkanes being CIO-IO cycloalkanes.
    [0009]
    9. Composition, according to any one of the preceding claims, CHARACTERIZED by the aromatic hydrocarbons being CÓ-IO aromatic hydrocarbons.
    [0010]
    10. Method for the production of a composition, as defined in any of the preceding claims, CHARACTERIZED by comprising the steps of: (i) hydroprocessing a biological raw material with the use of one or more catalysts; and (ii) fractionate the product from step (i).
    [0011]
    11. Method according to claim 10, CHARACTERIZED by the biological raw material comprising a vegetable oil and / or an animal fat.
    [0012]
    12. Method according to claim 10, CHARACTERIZED by the biological raw material comprising at least 15% by weight of C12-18 fatty acids, at least 15% by weight of resin acids and at least 10% by weight of neutral compounds based on the mass of the raw material.
    [0013]
    13. Method according to any one of claims 10 to 12, CHARACTERIZED by the hydroprocessing step being carried out with the use of one or more catalysts, which each comprise one or more metals selected from metals of the VIA Group and Group VIII and one or more support materials selected from zeolite, alumina, zeolite-alumina, alumina-silica, alumina-silica-zeolite and activated carbon.
    [0014]
    14. Method, according to claim 13, CHARACTERIZED by the fact that each metal is selected from Mo, W, Co, Ni, Pt and Pd.
    [0015]
    15. Method, according to claim 13 or 14, CHARACTERIZED by the hydroprocessing step to be carried out using one or both of the following catalysts (i) and (ii), and, optionally, the following catalyst (iii): (i) a catalyst comprising MoOs, one or both of CoO and NiO, and one or more support materials; (ii) a catalyst comprising NiW and one or more support materials; (iii) a catalyst comprising a Group VIII metal and / or a molecular sieve; where support materials are selected from zeolite, alumina, zeolite-alumina, alumina-silica, alumina-silica-zeolite and activated carbon.
    [0016]
    16. Method, according to claim 15, CHARACTERIZED by the hydroprocessing step to be carried out with the use of one or more reactors that each comprise the catalysts (i) and (ii).
    [0017]
    17. Method according to claim 16, CHARACTERIZED by the amount of catalyst (ii) in relation to the total amount of catalysts (i) and (ii) continuously increasing in the direction of flow of the biological raw material in the reactor (s) ( es).
    [0018]
    18. Method, according to claim 15, CHARACTERIZED by the hydroprocessing step to be carried out using two or more reactors, at least one reactor comprising catalyst (i) and at least one other reactor comprising catalyst (ii ) and / or the catalyst (iii).
    [0019]
    19. Use of a composition, as defined in any one of claims 1 to 9, CHARACTERIZED as a fuel or a fuel component.
    [0020]
    20. Fuel mixture CHARACTERIZED for comprising a composition, as defined in any one of claims 1 to 9.
    [0021]
    21. Fuel mixture according to claim 20, CHARACTERIZED by the amount of the composition being 2 to 85% by volume based on the volume of the fuel mixture.
    [0022]
    22. Fuel mixture according to claim 21, CHARACTERIZED by the amount of the composition being 5 to 25% by volume.
    [0023]
    23. Mixture of fuel according to either of claims 21 or 22, CHARACTERIZED by additionally comprising a fuel derived from petroleum.
    [0024]
    24. Fuel mixture, according to claim 23, CHARACTERIZED by the oil derivative being petroleum naphtha and / or petroleum gasoline.
    [0025]
    25. Fuel mixture according to any one of claims 20 to 24, characterized in that it additionally comprises ethanol.
    [0026]
    26. Fuel mixture, according to claim 25, CHARACTERIZED by the amount of ethanol being up to 85% by volume based on the volume of the fuel mixture.
    [0027]
    27. Fuel mixture, according to claim 26, CHARACTERIZED by the amount of ethanol being 75 to 85% by volume.
    [0028]
    28. Fuel mixture according to any one of claims 20 to 27, characterized in that it additionally comprises at least one of butane, isobutanol and ethyl tert-butyl ether.
    [0029]
    29. Fuel mixture according to any one of claims 20 to 24 and 28, CHARACTERIZED by comprising from 2 to 25% by volume of the composition, from 75 to 85% by volume of ethanol, from 1 to 5% by volume of ether compounds containing five or more carbon atoms, and up to 2% by volume of alcohols higher than C3-8, with the amount of butane contained in the fuel mixture being 2 to 10% by volume.
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    同族专利:
    公开号 | 公开日
    CA2903354A1|2014-10-09|
    DE202014011065U1|2017-08-09|
    EP2981595B1|2017-05-03|
    EP2981595A1|2016-02-10|
    BR112015024645A2|2018-02-06|
    US20160032204A1|2016-02-04|
    CN105102588A|2015-11-25|
    US20180044601A1|2018-02-15|
    FI20135310A|2014-10-03|
    RU2645350C2|2018-02-21|
    SG11201508153RA|2015-10-29|
    FI11677U1|2017-05-30|
    PT2981595T|2017-06-12|
    CA2903354C|2020-12-15|
    CN105102588B|2017-11-07|
    US10450521B2|2019-10-22|
    RU2015146775A|2017-05-16|
    PL2981595T3|2017-08-31|
    DK2981595T3|2017-06-19|
    UY35519A|2014-10-31|
    ES2633846T3|2017-09-25|
    WO2014161736A1|2014-10-09|
    FI126331B|2016-10-14|
    US9885000B2|2018-02-06|
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    法律状态:
    2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-16| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-06-09| B09A| Decision: intention to grant|
    2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FI20135310|2013-04-02|
    FI20135310A|FI126331B|2013-04-02|2013-04-02|Renewable hydrocarbon composition|
    PCT/EP2014/055828|WO2014161736A1|2013-04-02|2014-03-24|Renewable hydrocarbon composition|
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