• 专利附录
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  • 权利要求
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    • 专利摘要:
    ln a method for preparing fuel components from crude tall oil, feedstockcontaining tall oil comprising unsaturated fatty acids is introduced to acatalytic HDO step (2) to convert unsaturated fatty acids, rosin acids andsterols to fuel components. Crude tall oil is purified in a purification step (1)by washing it with washing liquid and separating the purified crude tall oilfrom the washing liquid, whereafter the purified crude tall oil is introduceddirectly to the catalytic HDO step (2) as a purified crude tall oil feedstock.An additional feedstock, such as Fischer Tropsch (FT) wax or turpentine,may be supplied to the catalytic HDO step (2). Fig.1
    公开号:SE1150873A1
    申请号:SE1150873
    申请日:2010-02-26
    公开日:2011-11-28
    发明作者:Pekka Knuuttila；Petri Kukkonen；Ulf Hotanen
    申请人:Upm Kymmene Corp；
    IPC主号:
    专利说明:

    Document EP-1728844 A1 describes a process for producing hydrocarbon fractions useful as diesel fuel from biofuels, by pretreating the feedstock to remove contaminants, such as alkali metals, which can poison the catalyst downstream, and then subjecting the pretreated feedstock to catalytic hydration / catalytic hydration. hydrogen deoxidation step. Crude tall oil is mentioned as an example of bio-renewable raw material, alongside many triglyceride-based vegetable oils. The pretreatment step may include either ion exchange with an acidic ion exchange mass or washing with an acid. In the example presented later in this document, washing with soybean oil with 40% phosphoric acid solution was presented as an example of acid washing.
    Document WO-2008/058664 describes a process for the production of hydrocarbon fractions, which consists of successive hydrogen deoxidation (hydrodeoxygenation HDO) and hydroisomerization of a raw material of biological origin, where crude tall oil is an example of many possible raw materials. Prior to the HDO step, the raw material may be subjected to adsorption on a suitable material, ion exchanger, or weakly acidic wash by the use of sulfuric acid, nitric acid or hydrochloric acid, to remove alkaline metals and alkaline earth metals (Na, K, Ca). Gas phase separated after the HDO step and containing hydrogen, water, CO, CO 2 light hydrocarbons and possibly small quantities of H2S are subjected to purification by causative washing and treatment with amines, such as monoethanolamine or diethanolamine, to obtain reusable gas fractions consisting essentially of H and traces of CO.
    Document EP 1741768 A1 describes a process for the production of diesel hydrocarbons from bio-oil and fats consisting of water-treating the raw material in a water-treatment step and isomerizing it in an isomerization step. A pre-treatment system, degumming, is recommended for raw materials, such as crude vegetable oil or animal oil, to remove phosphorus components, such as phospholipids. Degumming is performed by washing the feed at 90-105 ° C, 300-500kPa (a), with H 3 PO 4, NaOH and soft water and separating the formed "gums". A large portion of the metal components which are harmful to the water treating catalyst are also removed from the raw material during the degumming step.
    Degumming as described above is a standard procedure for removing phospholipids and metals from vegetable oil of natural origin based on triglycerides and contains significant amounts of "gums". Iron and also other metals may be present in these oils in the form of metal-phosphatide complexes.
    Another process using biological raw materials is described in European Patent 1396531, where raw materials containing fatty acids and / or fatty acid esters, including tall oil, are converted to hydrocarbon components in a catalytic hydrogen deoxidation and isomerization step.
    Crude tall oil (CTO) is a promising candidate as a raw material for the manufacture of various fuel components. According to the prior art, expensive distillation steps are used to produce tall oil fatty acid fractions from crude tall oil. These fatty acid fractions are then processed e.g. by catalytic HDO (hydrogen deoxidation) and isomerization to desired fuel components while the fuel potential of other fractions omitted is lost. Conversion of crude tall oil into fuel components, especially diesel components, involves three fundamental problems, namely 1) quality of CTO. CTO consists of impurities, such as residual metals (ash) and phosphorus, which creates poisoning of the catalyst used in the process. Quality variations in CTOs also cause problems in the conversion of CTOs into fuel components. 2) quality of the produced diesel product. With known methods, it is difficult to produce fuel components from CTO that have low Cp (melting point) and high cetane number. It is also difficult to achieve good yields in these processes. 3) strongly exothermic reactions in the catalytic hydrogen deoxidation (HDO) stage, leading to the decomposition of the catalyst and shortening the life of the catalyst. This is often avoided by recycling the HDO product stream, which leads to more problems in the process. The product stream based on HDO contains the impurities that the CTO flow had when it was introduced into HDO. Thus, the impurities are enriched in the recycling HDO product stream and the recycling will increase the poisoning of the HDO catalyst.
    Summary of the Invention It is the object of the invention to provide a simple yet efficient process for converting tall oil catalytically to usable fuel components. This sewing is achieved by a method which is characterized by properties in the characterizing part of claim 1. The raw material in the process is crude tall oil containing fatty acids, resin acid, unsaponifiable matter, resin (natural compounds such as sterols), sulfur compounds and other impurities discussed above.
    The proportions of different components may vary depending on the origin of the tall oil. Crude tall oil (abbreviated CTO raw material) is purified in a purification step by washing it with washing liquid, and purified crude tall oil is separated from the washing liquid, after which the purified crude tall oil from the purification step is introduced as a purified tall oil raw material to the catalytic HDO step. The purified crude tall oil feedstock is introduced directly, without thermal intermediate purification step, into the catalytic HDO step. Ring opening of cyclic compounds of the crude tall oil is combined with the catalytic HDO step.
    The purification step can be batch or continuous. The crude tall oil can be washed with washing liquid in the batches, which are left in sufficient time to allow the washing liquid phase containing the impurities and the purified tall oil to sink based on specific gravity differences, and the purified tall oil phase is taken out as a purified raw material.
    If possible, the remaining water can be removed from the purified tall oil phase by centrifugation. A continuous purification step may possibly comprise a purification step where the purified tall oil material is continuously mixed with the washing liquid, after which the mixture is fed to a continuous separation step from which the washing liquid containing the impurities and the purified tall oil material is continuously drained. The continuous separation step may comprise a continuous operating centrifuge, for example a disk centrifuge.
    According to one embodiment, the washing liquid is pure water or water containing organic weak acid, complexing agent or adsorbent. Due to the fact that the phosphorus content in the crude tall oil is initially low, no treatment with phosphoric acid is needed, which would require neutralization with sodium hydroxide and thus the addition of harmful ions. The aqueous washing liquid and all solids can be easily separated by using differences in specific gravity, preferably by centrifugation.
    Because crude pine oil contains large amounts of metal in the form of sulfur salts, they are easy to remove with the aqueous washing liquid.
    According to a preferred embodiment, the HDO product stream discharged from the catalytic HDO is introduced into a separation step, where at least one hydrocarbon fraction is separated from the HDO product stream. According to a particularly preferred embodiment, different fuel components are separated into different product streams in a separation step and only the product stream corresponding to the diesel fraction is passed via an isomerization step.
    Continuing according to the preferred embodiment, the heavy fractions separated from the product stream by the catalytic HDO step in the separation step are circulated through a cracking step back to the inlet of the catalytic HDO step.
    Continuing according to the preferred embodiment, the temperature in the catalytic HDO step is controlled by introducing a first additional raw material separate from the main raw material (purified crude tall oil raw material), and its exothermic response is preferably lower than that of tall oil fatty acids. The first additional raw material is some thermally conductive liquid / reserve substance, which possibly also contributes to the production of a suitable fuel component. Preferably, Fisher-Tropsch (FT) wax from a biomass-to-liquid BTL process is used as the first additional raw material but also other components, for example n-hexadecane can be used.
    According to another embodiment, a second additional raw material is added to the process.
    The second additional raw material is preferably turpentine, which can be added either to the purification step or to the HDO step. The second additional raw material contributes to the production of suitable fuel components. The said first additional raw material and the said second additional raw material may be added as independent alternatives to the process, or they may be added simultaneously to the same process.
    The device according to the invention contains a purification section containing a washing section whose first inlet is connected to a source of CTO raw material and second inlets to a source of washing liquid, as well as a first outlet, which is connected to the catalytic HDO reactor to supply the crude tall oil to the catalytic HDO step directly. According to the preferred embodiment, the purification section also contains a separation section containing equipment for separating purified crude tall oil from the washing water, for example a Centrifuge.
    The catalytic HDO reactor contains a catalyst which has a ring-opening character. The catalyst used in the catalytic HDO reactor as an HDO catalyst may also have ring-opening properties, in which case it may function as a combined HDO and ring-opening catalyst.
    By washing the raw material before it is introduced into the HDO step, CTO impurities that would interfere with the subsequent catalytic steps are reduced. The purification step involves contacting the crude tall oil with the wash liquor and removing the wash liquor and impurities from the tall oil in a physical separation step. Examples of impurities that are removed are inorganic impurities, such as alkaline (Na, K) metal compounds, sulfur, silicone, phosphorus, calcium and ionic compounds. These compounds cause poisoning of the catalyst and they can also be called ash. Heavy polymeric macromolecular compounds that could interfere with the porous structure of the catalyst can also be removed. The separation step, if used directly after the washing step, is a physical separation step and preferably contains centrifugation. In the physical separation step, water, substances dissolved or diluted therein from crude tall oil, possible precipitated and possible solid absorbents are removed with the aqueous phase.
    The defrosting operation and subsequent distillation, as well as degumming followed by drying, which involves the use of extensive equipment can be omitted altogether. The washing step used does not contain any inorganic acids to avoid inorganic anions such as sulfates or phosphatases. The pH of the washing liquid can be acidic, within 4-6. For example, the ion exchange water may have an acidic pH due to dissolved carbon dioxide.
    Crude pine oil contains small amounts of phospholipids which, on contact with water, form micelles that can retain parts of water, phosphorus and metal ions in the pine oil phase.
    Organic acids in the washing liquid, such as acetic acid or oxalic acid, break down and hydrolyze the metal complexes formed via phospholipids. Thus, the metals can be removed with water. Oxalic acid is also an effective calcium ion binder.
    Through a simple pretreatment process by washing and separation, organic carbon compounds such as fatty acids, resin acid and sterols are retained in the purified tall oil raw material as fully as possible and they can be further processed into useful fuel components.
    The key step in the process, the catalytic HDO step, is extremely exothermic. This heat release can be reduced by feeding, in addition to the tall oil raw material, a first additional raw material that is less exothermic per carbon atom in the catalytic HDO reaction than the tall oil fatty acids. A suitable first additional raw material of this type may be a wax containing saturated hydrocarbons. By supplying such a first raw material to the HDO reactor, the increase in the heat of reaction in the catalyst bed is controlled and the life of the catalyst is improved.
    Turpentine, also a by-product of alkaline Kraft wood pulp production, can also be used as an additional raw material, as a second additional raw material. Turpentine contains C10 hydrocarbons which can be converted into valuable fuel components in the same process as tall oil. It therefore increases the amount of hydrocarbon components produced.
    Brief Description of the Figures The invention will be described in the following with reference to the accompanying drawings, in which Fig. 1 schematically shows a device carrying out the process according to the invention, and Fig. 2 shows another embodiment of the device.
    Detailed Description of Preferred Embodiments In the stated specifications and claims, the following terms have meanings defined below.
    The term "catalytic HDO" or "catalytic hydrodeoxidation" refers to a catalytic treatment of raw materials with hydrogen under catalytic conditions, in which the following reactions take place: deoxidation by removal of carboxylic acid as water by means of hydrogen during catalyst injection and hydrogenation by saturation of carbon-carbon double bonds with the aid of hydrogen under the action of catalyst. According to a preferred embodiment, the catalytic HDO step also has a ring-opening character. The preferred HDO of the invention also removes unwanted impurities such as sulfur such as hydrogen sulfides and nitrogen such as ammonia.
    The terms "decarboxylation" and "decarbonylation" refer to the removal of carboxylic acid such as CO 2 (decarboxylation) and as CO (decarbonylation) with or without the action of hydrogen.
    The term “isomerization” refers to the catalytic and hydrogen-assisted introduction of short chain (typically methyl) branches into n-paraffinic hydrocarbons.
    The term "cracking" refers to the catalytic decomposition of organic hydrocarbon materials through the use of hydrogen.
    The term “n-pairs” refers to normal alkanes or linear alkanes that do not contain side chains.
    The term "isoparanes" means alkanes having one or more C1-C9, usually C1-C2 alkyl side chains, usually mono-, di-, tri- or tetramethylalkanes The term "FT" or "Fischer Tropsch" refers to a synthesis which contains catalyzed chemical reactions in which hydrogen and carbon monoxide are converted into a substantial Gaussian distribution of hydrocarbon chains of varying length (designated (Cl to Cmog). Typically used catalysts are based on iron or cobalt. The term "Fisher Tropsch wax" refers to a heavy fraction separated after FT reaction containing mostly C21 to C100, hydrocarbons.
    The term “BLT” refers to the biomass-to-liquid process, which is a multi-step process for producing liquid biofuels from biomass. The main process used for BLT is the Fisher Tropsch process.
    The term "CTO" or "crude tall oil" refers to a by-product of the Kraft process of wood pulp production. Crude tall oil generally contains both saturated and unsaturated oxygen-containing organic compounds such as resins, unsaponifiables, sterols, resin acids (mainly sapinic acid and its isomers), fatty acids (mainly linoleic acid, oleic acid and linolenic acid), fatty alcohols, sterols and other alkyl hydrocarbon derivatives, as well as inorganic impurities discussed above (alkali metal (Na, K) compounds, sulfur, silicon, phosphorus, calcium and iron components).
    The term "turpentine" refers to a liquid obtained via the distillation of resin obtained from trees, mainly conifers. It contains terpenes, mainly monoterpenema alpha-pinene and beta-pipene. It is also a by-product of alkaline Kraft wood pulp production.
    The device contains a catalytic HDO reactor 2, a raw material inlet 2a connected to the upper part of the reactor 2, a hydrogen inlet 2b connected to the upper part of reactor 2, and an HDO product stream outlet 2c connected to the lower part of the reactor. Hydrogen conductor 12 for supplying hydrogen needed for the catalytic HDO reaction is connected to the hydrogen inlet 2b. The product stream outlet 2c is connected via a conductor 3 to an fl ash separator 4 where one or fl your hydrocarbon fractions containing useful components are separated based on differences in boiling point. The remaining fraction containing heavier components (C21 to C100) is taken from the lower part of the reactor 4 and circulated through a circulation conductor 5 to a catalytic cracking reactor 6 where the heavier components are cracked into lighter components. The outlet from the cracking reactor 6 is connected to the raw material inlet 2a of the catalytic HDO reactor, for example the second raw material conductor F2 led to the reactor 2.
    The raw material for catalytic HDO reactor is purified crude tall oil which is recovered from a purification step (described later). The purified crude tall oil generally contains both saturated and unsaturated oxygen-containing organic compounds, such as various acids and alcohols suitable for conversion to fuel components, as described above.
    To convert the unsaturated fatty acids in the tall oil feedstock to useful aliphatic fuel components, the catalyst in the catalytic HDO reactor section 2 is a suitable catalyst. In the case of fatty acids, the HDO step involves deoxidation where, under the effect of hydrogen, oxygen atoms are removed from carboxyl groups such as water and replaced with hydrogen, this conversion is called hydrodeoxidation (HDO). This can possibly be combined with simultaneous decarboxylation and decarbonylation where the carbon atom in the carboxyl group is also removed. The catalyst is preferably a sulphate resistant, since the pure crude tall oil fed to the catalytic HDO reactor 2 may contain residual organic sulfur components which are not removed in the washing step. Known commercial desulphurisation catalysts, for example based on nickel and / or molybdenum, can be used as catalyst. The catalyst can be a supported NiMo or CoMo catalyst, for example on aluminum and / or silicone support. These catalysts are well known and are not described in more detail. ll In the HDO step, hydrogen is fed in abundance by the theoretical hydrogen consumption. The pressure can be between 50 and 100 bar and the temperature between 280 ° C and 340 ° C.
    The catalyst used in the catalytic HDO reactor preferably also has ring-opening properties, in which case it can then function as both HDO and ring-opening catalyst. When the above-mentioned NiMo or CoMo catalyst is used in the HDO step, no ring components initially present in resin acid of the purified tall oil raw material or corresponding hydrogenated ring components are detected in the product stream. Thus, the catalytic HDO reactor 2 is a combined HDO / ring-opening reactor. The original resin acid has an undesirable pour point and cloud point increasing effect in diesel fuel, and they have a very poor centane number.
    Upstream of the reactor 2, the device contains a purification part 1 for purifying crude tall oil. The purification section consists of a washing section W for contacting the crude tall oil with the washing liquid, and optimally a separation section S (denoted by dashed lines) for separating the purified crude tall oil. The washing section W contains a washer, which may be any suitable equipment for washing the CTO.
    The washer may contain mixing equipment for shaking the CTO / washing liquid mixture. Crude tall oil material is fed through a first raw material conductor F1 and an inlet 1a to the washing section W of the cleaning section 1 where it is washed with washing liquid introduced through the washing liquid conductor L to the cleaning stage 1 via inlet 1b. An optional additive, such as organic weak acid, complexing agent or adsorbent discussed below, may be introduced at point A to the washing liquid conductor L to increase the cleaning effect of the washing liquid.
    The washing liquid used is pure water or pure water mixed with an additive such as a weak organic acid, complexing agent or adsorbent. The water can be ion exchange water or some other sufficiently clean water. The weak organic acid may be acetic acid or oxalic acid. Weak organic acids do not bring inorganic anions to the process and they break up the phospholipid micelles mentioned herein earlier. 12 Oxalic acid is also a known calcium binder. The additive can also be a complexing agent for metal ions, for example calcium ions, such as EDTA. An alternative to the additive is an adsorbent diluted in water. As a solid adsorbent, an active aluminum, a very porous alumina can be used.
    The separation of the purified crude tall oil from the washing liquid can be performed in the washing section W, by allowing the aqueous phase to separate from the purified tall oil. This can be done either in the scrubber itself or by assisting with a separate sedimentation tank in the separation section S. Alternatively, or in addition to a sedimentation tank, the separation section may also contain a centrifuge to separate the purified crude tall oil from the aqueous phase. Thus, the separation section S may contain a sedimentation tank or a centrifuge or both.
    If the separation of the purified crude tall oil is done in the scrubber or in a separate sedimentation tank, the purified water can be removed by centrifugation in the separation section S, if necessary. It is also possible to supply the mixture of the washing liquid and the crude tall oil from the washer to the centrifuge where the separation is carried out. Thus, depending on the purification method, it is possible to supply the purified and separated crude tall oil directly from the purification section W or via a separation part S to the catalytic HDO reactor 2.
    The purification step can be batch or continuous. In batch operation, the batches of crude tall oil are washed with appropriate amounts of washing liquid in the scrubber, and the batches obtained are treated according to the alternatives mentioned above. It is also possible to carry out continuous purification by continuously supplying crude tall oil material and washing liquid to the scrubber in the washing section W and performing a continuous separation in the separation section S, for example by adding a mixture of washing liquid and crude tall oil to a continuously operating centrifuge separating the water and the impurities of an aqueous phase containing the impurities and the purified crude tall oil to a continuous stream of purified tall oil raw materials. The centrifuge may be of a known type, for example a disk centrifuge. The purified tall oil raw material leaves the purification section 1 via an outlet 1c, which is connected directly to the catalytic HDO reactor 2 via a second raw material conductor F2.
    The aqueous phase containing impurities separated from the crude pine oil is discharged via outlet ld. Figure 1 shows a case where the outlets 1c and 1d are in the washing section W, but they may be in the separating section S if the purified tall oil raw material and the washing liquid are separated there. There may be an intermediate tank (not shown) between outlet 1c and the catalytic HDO reactor 2 to smooth out the actuations in the outlet of the purifying section 1 to contribute to a constant continuous supply of raw materials to the catalytic HDO reactor 2. especially if the purifying step is driven batchwise.
    A catalyst that produces the degree of deoxidation that is as complete as possible, preferably around 100% is preferably used in HDP reactor 2. Therefore, to control the temperature of the reactor caused by the heat evolution of the catalytic reaction, a first additional feedstock is fed to reactor 2. through a conductor 7, which is connected to reactor 2 via inlet 2e. This first additional raw material is not converted by the HDO section of the catalyst in a heat generation reaction, but is capable of absorbing additional heat in the reactor 2 and may participate in other reactions of the device, for example an isomerization reaction.
    The first additional raw material is preferably FT (Fischer Tropsch) wax from a BTL (biomass to liquid) process. The FT wax does not interfere with the HDO reactions but acts only as a solvent and enhances the function of the catalyst and at the same time the local temperature differences that may arise due to the HDO reactions. The FT wax is also capable of generating fuel components as it passes through the device, and the heavier fractions of the wax end up in the cracking reactor 6 from the separator 4 together with components derived from CTO.
    The first additional raw material may also be n-hexadecane, which does not participate in the catalytic reaction of the HDO step but acts as a heat sink and therefore has a cooling effect similar to the F T wax. N-14 hexadecane is also a known cetane number enhancer in diesel fuel and will eventually end up in the diesel fraction. Both n-hexadecane and F T-wax can be added as the first additional raw material.
    Alternatively, the conductor 7 from the first additional feedstock may be connected to a second additional feedstock conductor F2 upstream of the inlet 2a and the additional feedstock will enter the catalytic HDO reactor together with the purified CTO feedstock. This alternative fate is marked in Figure 1 with a dashed line.
    Also other materials which can be converted to useful hydrocarbon fractions and which do not participate in heat dissipation reactions catalyzed by the HDO catalyst can be used as a first additional raw material to control the temperature of reactor 2.
    The ratio of the first additional raw material to the purified crude tall oil may vary, and it may vary within a range, for example 1/10 and 3/1, preferably 1 / 10-1 / 1, based on weight.
    As an alternative to the first additional raw material or simultaneously with it, large amounts of excess hydrogen can be used for the temperature control in the catalytic HDO reactor. The hydrogen used may in any case be partly circulated hydrogen. The excess hydrogen can act as a heat sink and its cooling effect can be increased by cooling the hydrogen before it is introduced into the catalyst.
    The HDO product stream is fed to separator 4, where various fuel components having a boiling point lower than 370 ° C are separated into various product streams based on their common boiling point differences, and some of these may be subjected to further catalytic isomerization reaction. The separator is connected via a conductor 10 to an isomerization reactor 9 to introduce a fraction of a certain boiling point range into a further isomerization step. In the embodiment 15 presented in Figure 1, gasoline, naphtha and diesel fractions removed from the separator 4 are shown as examples of such product streams containing different surface hydrocarbon fractions. Of these obtained fractions, only the diesel fraction, that is, the fraction which can be used as diesel fuel, is introduced via the conductor 10 to the isomerization reactor 9, which contains non-crackling catalyst capable of converting straight carbon chains of n-para (linear alkanes) to branched chains of isoparanes (branched alkanes). The N-pairs are moderately isomerized so that the cold fl fate properties of diesel fuel will be improved but the cetane number will not be reduced too much. The isomerization also depends on whether the diesel fuel is for winter use or summer use. By separating the different fractions and isomerizing only those fractions (diesel fractions) that need isomerization by introducing it via the isomerization reactor 9, large savings in equipment costs can be achieved. The heavier fractions with a boiling point above 370 ° C, such as sterol components and polymers, usually hydrocarbons with more than 21 carbon atoms, are circulated from the separator 4 via the circulation conductor 5 to a catalytic cracking reactor 6 and back to the catalytic HDO reactor 2.
    Isomerization catalyst in the isomerization reactor 9 may contain Pt or Pd and SAPO or ZSM. Examples are Pt / SAPO-11 or Pt / ZSM-23. Hydrogen is introduced to the lower part of the reactor 9 via a conductor 13 which branches off from the hydrogen conductor 12, and is led countercurrent to the diesel fractions through the catalyst bed in the reactor. In the isomerization reactor 9, the pressure can be 30-100 bar and the temperature can be 280-400 ° C.
    The catalyst in the cracking reactor 6 has more acid support than the catalyst in the isomerization reactor 9, for example ZSM-5. The metal in the catalyst is Pt. Hydrogen is also introduced into the catalytic cracking reactor 6 (not shown). High temperature is normally used in the cracking reactor 6 to effect thermal cracking in addition to acid-catalyzed cracking supplied by the catalyst. The product stream from the isomerization reactor 9 can be used as diesel fuel or as diesel fuel components which increase the centane number and lower the cloud point of the fuel.
    The device also contains a membrane separator 8 for separating hydrogen from other gas components contained in the gas discharge from the upper part of the flash separator 4.
    The hydrogen is circulated back to the hydrogen inlet 2b in the reactor 2. Another alternative for separating hydrogen from gas components is to first wash the gas discharged from the membrane separator 8 with amine, such as MEA (monoethanolamine) or DEA (diethanolamine), to initially remove hydrogen disul fi d, and then separate the hydrogen from the gas carbon components through a hydrogen permeable membrane. This option is shown in Figure 2.
    Figure 2 shows another alternative where similar process steps are denoted by the same reference numbers as in Figure 1. The purification section 1 is the same as that in the embodiment in Figure 1 and it may have the same alternative as in Figure 1.
    The components from the tall oil raw material are converted to petrol, naphtha and diesel fractions in general in the same way as in Figure 1. In this embodiment, turpentine, another important by-product of alkaline pulping of wood in addition to tall oil, is used as an additional raw material.
    Turpentine is introduced via a conductor 7 to the tall oil purification step l to the washing step W. In the washing step W, turpentine is mixed with tall oil and finally ends up with the purified crude tall oil raw material to HDO reactor 2. Turpentine itself contains essentially pinenes and vessels, which after ring opening and hydration the catalytic HDO step produces useful fuel components which are separated in the separator 4 to gasoline fraction. Figure 2 shows how, like Figure 1, only the diesel fraction separated in the separator 4 is led via the isomerization reactor 9, while other fuel components (petrol and naphtha) bypass the isomerization step. 17 The product for the isomerization reactor 9 in both Figure 1 and Figure 2 is preferably EN 590 quality diesel.
    The gas components discharged from separator 4 are first washed in a 1 l washer with amine, such as MEA (monoethanolamine) or DEA (diethanolamine), to initially remove hydrogen sulfide, and then the hydrogen is separated from gas carbon compounds through a hydrogen permeable membrane 8 in the membrane separator 8. The hydrogen can be reused for the catalytic HDO step. As in the embodiment of Figure 1, in the embodiment of Figure 2, a conductor 13 is branched by the hydrogen conductor 12 to the hydrogen feed to the isomerization reactor 9 to maintain sufficient level of hydrogen required by the kinetics of the isomerization reaction.
    Turpentine can also be introduced directly to the HDO stage or to the second raw material conductor F2 upstream of the inlet 2a in Figure 2 in the same way as FT wax in embodiment in Figure 1, which is denoted by broken lines 7. It is also possible to use two additional raw materials at the same time. Both turpentine and FT wax can be fed to the HDO reactor by feeding them directly to reactor 2 or to the other feedstock conductor F2, or one of them directly to HDO reactor 2 and the other to the other feedstock conductor F2, and turpentine to the washing section. W as in Figures 1 and 2, respectively.
    The invention is not limited to the above embodiments, but can be modified within the scope of the present claims. The cracking step (reactor 6) is optional, and the heavy fractions from separator 4 can be circulated through conductor 5 back to the process without cracking, or they can be taken out of the process as a product or a product waste stream on its own, or as a raw material stream for a another process. In this case, the circulation conductor 5 can be removed.
    权利要求:
    Claims (22)
    [1] 1. A method for preparing fuel components from crude tall oil, where crudetall oil is purified in a purification step (1) by washing it with washing liquidand the purified crude tall oil is separated from the washing liquid,whereafter the purified crude tall oil is introduced as a purified crude tall oilfeedstock directly to a catalytic HDO step (2), which also includes ring-opening of components of the purified tall oil feedstock, to convertunsaturated fatty acids, rosin acids and sterols to fuel components,characterized in that a HDO product stream is supplied from the catalyticHDO step (2) to a separation step (4), where various usable fuel componentsare separated to various liguid hydrocarbon fractions issuing from theseparation step (4) as various product streams separatelv from qasesdischarqed from the separation step (4), and only the product streamcorresponding to the diesel fraction is led through an isomerizing step (9) forproducing a hydrocarbon fraction usable as a diesel fuel or a diesel fuelcomponent.
    [2] 2. The method as claimed in claim 1, characterized in that the washing liquidis pure water or water containing at least one of the following: organic weakacid, complexing agent or adsorbent.
    [3] 3. The method as claimed in claim 1 or 2, characterized in that the purifiedcrude tall oil is separated from the washing liquid by settling or centrifugation.
    [4] 4. The method as claimed in any of the claims 1 to 3, characterized in thatin the purification step (1), inorganic impurities and heavy macromolecularpolymeric compounds are removed from the crude tall oil with the washingliquid.
    [5] 5. The method as claimed in any of claims 1 to 4, characterized in that crudetall oil is purified continuously or batchwise in the purification step (1), fromwhere the purified crude tall oil feedstock is supplied continuously to thecatalytic HDO step (2).
    [6] 6. The method as claimed in any of the claims 1 to 5 , characterized in thatin the catalytic HDO step (2) a sulphur resistant catalyst is used. 18
    [7] 7. The method as claimed in any of claims 1 to 6, characterized in thatheavier fractions separated in the separation step (4) are circulated through acracking step (6) to the in|et (2a) of the catalytic HDO step (2).
    [8] 8. The method as claimed in any of claims 1 to 7, characterized in that thetemperature of the catalytic HDO step (2) is controlled by supplying a firstadditional feedstock different from the purified CTO feedstock to the catalyticHDO step (2).
    [9] 9. The method as claimed in claim 8, characterized in that the firstadditional feedstock is Fischer Tropsch (FT) wax from a biomass-to-Iiquid(BTL) process and/or n-hexadecane.
    [10] 10. The method as claimed in claim 8 or 9, characterized in that the firstadditional feedstock is supplied to the catalytic HDO step (2) separately fromthe purified CTO feedstock, or to the purified CTO feedstock upstream of thecatalytic HDO step (2).
    [11] 11. The method as claimed in any of claims 1 to 10, characterized in that asecond additional feedstock is supplied to the purification step (1), fromwhere it is introduced together with the purified CTO feedstock to thecatalytic HDO step (2), or a second additional feedstock is supplied straightto the catalytic HDO step (2) through conduit (7) or to the purified CTOfeedstock upstream of the catalytic HDO step (2).
    [12] 12. The method as claimed in claim 11, characterized in that the secondadditional feedstock is turpentine.
    [13] 13. An apparatus for preparing fuel components from crude tall oil,comprising- a catalytic HDO reactor (2), 19- a feedstock inlet (2a) to the catalytic HDO reactor (2) for introducingcrude tall oil to the catalytic HDO reactor (2),- a hydrogen inlet (2b) to the catalytic HDO reactor (2),- an outlet (2c) for taking out a HDO product stream from the catalyticHDO reactor (2), characterized in that the apparatus further comprises a purification section(1) comprising a washing section (W) whose first inlet (1a) is connectedthrough a first feedstock conduit (F1) to source of crude tall oil feedstock andwhose second inlet (1b) is connected to source of washing liquid, thepurification section (1) further comprising an outlet (1c) that is connected tothe catalytic HDO reactor (2) for supplying the purified crude tall oil directly tothe catalytic HDO step (2), which contains a catalyst having ring-openingproperties; and that the outlet (2c) of the catalytic HDO reactor (2) isconnected to a separator (4), which is arranged to separate various ligghydrocarbon fractions from the HDO product stream of the catalytic HDOreactor (2) and to discharqe qases, the separator (4) being connectedthrough a conduit (10) to a catalytic isomerization reactor (9), and dieselfraction separated in the separator (4) is arranged to be supplied to acatalytic isomerization reactor (9) through the conduit (10), whereas conduitsfor other ligfihydrocarbon fractions separated in the separator (4) bypassthe catalytic isomerization reactor (9).
    [14] 14. The apparatus as claimed in claim 13, characterized in that thepurification section (1) comprises a separation section (S) for separatingpurified tall oil from the washing liquid.
    [15] 15. The apparatus as claimed in claim 14, characterized in that theseparation section (S) comprises a settling tank or a centrifuge.
    [16] 16. The apparatus as claimed in claim 13, 14 or 15, characterized in that theoutlet (1c) of the purification section (1) is directly connected to the catalyticHDO reactor (2) through a second feedstock conduit (F2).
    [17] 17. The apparatus as claimed in any of claims 13 to 16, characterized in thatthe catalyst in the catalytic HDO reactor (2) is sulphur resistant.
    [18] 18. The apparatus as claimed in any of claims 13 to 17, characterized inthat the separator (4) is connected through a circulation conduit (5) and acracking reactor (6) to the inlet (2a) of the catalytic HDO reactor (2) forcirculating heavier fractions separated in the separator (4) back to thecatalytic HDO reactor (2).
    [19] 19. The apparatus as claimed in any of claims 13 to 18, characterized inthat the apparatus comprises a conduit (7) connecting the catalytic HDOreactor (2) to source of additional feedstock for introducing the additionalfeedstock to the catalytic HDO reactor (2).
    [20] 20. The apparatus as claimed in claim 19, characterized in that the conduit(7) for introducing additional feedstock is connected directly to the catalyticHDO reactor (2) or to the second feedstock conduit (F2) upstream of thecatalytic HDO reactor (2).
    [21] 21. The apparatus as claimed in claim 19 or 20, characterized in that thesource of additional feedstock is a source of Fischer Tropsch (FT) wax, n-hexadecane or turpentine.
    [22] 22. The apparatus as claimed in claim 21, characterized in that the conduit(7) for introducing additional feedstock is connected to a source of turpentineand it is connected to the purification section (1).
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    同族专利:
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    WO2010097519A2|2010-09-02|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FI20095198A|FI124508B|2009-02-27|2009-02-27|Method and apparatus for making fuel components from crude tall oil|
    PCT/FI2010/050156|WO2010097519A2|2009-02-27|2010-02-26|Method and apparatus for preparing fuel components from crude tall oil|
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