SE1351563A1 - Biorefining of crude tall oil - Google Patents

Abstract

Summary The present invention provides an improved and efficient biorefining of crude tall oil (CTO) to valuable industries and fine chemicals. According to a first aspect of the present invention, there is provided an improved process for removing contaminants from a CTO. According to a second aspect of the invention, there is provided an efficient process for the production of refined tall diesel (RTD) or TOFA, especially the combined production of RTD or TOFA and RA (resin acid) Wan a CTO. According to yet another aspect of the present invention, there is provided a process for preparing an optimized RTD and also such an optimized RTD composition, said RTD composition comprising at least RA, FA (fatty acid) and also CST (Ira 'sulphate turpentine).

Description

Recovering valuable organic compounds present in the crude tall oil, thereby forming a refined tall oil flood, (b) removing the volatile fraction of the refined tall oil oil from step a), wherein after flow free of volatile material comprising organic components with cooking points, at atmospheric pressure, of 170 ° C or higher are formed; (c) separation in a vacuum fractionation tower of the oil stream from volatile substances from step b) two process stream or phases, a first process stream or phase substantially comprising components having boiling points, at atmospheric pressure, in the range 170-400 ° C and a second process stream or phase essentially comprising components having boiling points, at atmospheric pressure, below 400 ° C, and (d) collecting the oxygen content of the river comprising components having boiling points in the range 170-400 ° C from step c) by decarboxylation and / or decarbonylation .

An object of the present invention is to provide an improved method for refining CTO. Another specific object of the present invention is to provide an improved pretreatment of CTO. Yet another specific object of the present invention is to provide an improved process for the production of resin acids and refined tall diesel (RTD hereinafter) from CTO. There are other objects of the present invention, which are presented below.

Background of a First Aspect of the Invention Tall oil resin (or resin acids) produced by vacuum distillation of CTO find use as an important component in Um, rubber, printing ink, and emulsifiers, while tall oil fatty acids (TOFA) find use in the production of whey. and lubricants.

However, crude tall oil, which is after residual flow from kraft pulping operation, contains a wide range of impurities. Typical CTO impurities include residual mineral acid, alkali salts and / or whey, alkaline earth metal salts and / or whey, transition metals, cellulosic fibers and large organic lignin compounds with molecular weights of over 1000 units. The occurrence of impurities is most often caused by inefficient tall oil separation from saline solution during the CTO processing at the kraft pulp factory. The small amount of saline that% gives CTO contains most of the above mentioned impurities.

The contaminants cause problems during CTO processing and have a detrimental effect on the yield of the desired fractions, namely RTD, TOFA and tall oil resin acids (RA). Thus, different types of salt 3 and / or whey, cellulosic fibers and lignin deposition on different heating surfaces can cause river problems and / or limit heat transfer. Furthermore, the salts cause a stench in thin-film evaporator units (TFEs), which allows a chance for non-volatile components to be all entrained in the gas phase. The remaining mineral acid (usually sulfuric acid), various salts and transition metals act as catalysts during CTO storage and processing. H2SO4 is a very effective catalyst for esterification reactions between free fatty acids (FFA) and various components from the neutral fraction that have an (-OH) -functional group. The resulting esters are typically high molecular weight and thus end up in the smaller Onskvarda TOP fraction. These high molecular weight esters are typically formed during CTO storage. During CTO processing, sulfuric acid esters scratch double bonds within FFA, leading to high molecular weight polymerization products, which also end up in the TOP. Sulfuric acid is also an active catalyst for resin acid carboxylation which produces the corresponding hydrocarbons and thus significantly reduces the yield of tall oil resin acids. Depending on the storage equipment of the process, the obtained hydrocarbons are found either in RTDTTOFA oils in the resin acid fraction, in which case the quality of the respective fraction decreases. Various types of salts and especially transition metals are also very active catalysts for activating double bond functionality and resin acid carboxylation.

Under ken, efforts have been made for all the removed contaminants in the CTO for fractionation. The most successful approach to date seems to be so-called CTO depitching, where the incoming oil surface is passed through a TFE unit, where it is subjected to rapid heating and most of the FFA and resin acids are further processed and further processed to obtain the individual TOFA and tall oil resin acid fractions. With this approach, most pollutants follow the TOP flow that collects at the bottom of the TFE. Despite the short heat treatment, a substantial portion of the CTO components are subjected to undesirable reactions promoted by the contaminants described previously. In addition, some of the contaminants are included in the produced fumes.

CTO pretreatment described in a first embodiment of the present invention contributes to the removal of typical CTO contaminants.

The absence of CTO contaminants during the refining steps of the present invention leads to the preservation of the Onskvarda CTO components and thus higher yields for RTD / TOFA and RA products and also TOP of 4 better quality. In addition, the RA fraction will be of higher quality when it comes to color and isomer hardening because drying components are associated with harmful effects caused by the throrings, while RA isomerization is promoted by the CTO contaminants in combination with the elevated temperatures required for fractionation.

Technical solutions described in a second aspect of the present invention contribute to advantageous synergy for the production of RTD fraction and RA fraction of the highest quality. The solutions enable an energy-efficient process compared with previous prior art. The high energy consumption used for refining TOFA is avoided in the manufacture of RTD according to the present invention. In addition, the innovative fractionation sequence enables efficient separation of biofuels (RTDs) and fine chemicals (RA) compared to the strenuous and energy-intensive distillation steps commonly used in CTO fractionation processes.

A third aspect of the present invention relates to the use of crude sulphate turpentine (CST), which aims to further maximize the RTD yield and improve the RTD composition by (i) reducing the density of the resulting composition and (ii) improving the balance of the boiling point (BP) distribution. Thus, RTD without CST has a rather narrow BP distribution of 340-400 ° C (about 90% by weight of RTD has boiling points in defta range), while the RTD composition with CST has a more even BP distribution of 140,400 ° C (CST itself includes a series of components which in combination with the lighter TO fraction (TO heads) (sesqui- and diterpenes together with iatt FA C12-C16) fill the entire BP range for the final RTD product). In the following, we describe a process for improved tall oil refining and fractionation into valuable fractions obtained with higher yields and better quality compared with prior art.

Summary of a First Aspect of the Invention As mentioned above, in accordance with a first object of the present invention, an improved process for the removal of thrombi from a CTO is presented.

This object is achieved by a process for treating an Irish tall oil (CTO), said process comprising a first pretreatment step comprising a CTO wash and a separation of a first oil phase comprising refined CTO and an aqueous phase containing impurities, and after a second step comprising separating a second oil phase from the aqueous phase. It should be noted that the second stage comprises a separation of a second oil phase from the aqueous phase can be carried out in the same plant as the first stage, or in a unit or plant directly adjacent to the plant in which the first separation stage is carried out. , but the second step can also be performed in another plant, as after separation step, or in a subsequent step comprising finishing, in which separation is part of the purpose. Or according to a specific embodiment the second step comprising a separation of a second oil phase is performed from the aqueous phase in a subsequent step in a separate unit which is not directly adjacent to a unit in which the first pretreatment step is performed.

As will be appreciated from the foregoing, this aspect of the present invention relates to the effective removal of typical contaminants from crude tall oil, such as residual mineral acid, alkali metal, alkaline earth metal salts, transition metals, fibers / foreign materials and the like. Embodiments of a process for pretreating a CTO according to the present invention are the fibers, salts, residual inorganic acid and / or lignin compounds. The remaining inorganic acid Jr acid is used in pulp mills to convert tall oil to tall oil, which is often sulfuric acid.

Mention may be made of other important aspects of the present invention, such as the separation of a volatile fraction from the refined tall oil and the fractionation of tall oil free of volatile substances into the river which comprises a) components boiling in the diesel range (RID); b) high quality resin acids (RA); and (c) high molecular weight fraction (tall oil pitch, TOP) of the highest quality, particularly suitable as energy cold in a wide range of industrial applications.

Specific Embodiments of a First Aspect of the Invention According to a first aspect of the present invention, the CTO stream is pretreated to remove contaminants prior to fractionation. In one embodiment of the CTO pretreatment process, the CTO is contacted with water in a CTO washing step, the amount of water used being less than about 5% by weight (based on incoming CTO). The wash water may contain additives. According to the present invention, the contact between CTO and tvaftvatska can be carried out with the aid of a dynamic stirrer. However, it will be mentioned which equipment which is capable of establishing an intimate contact between the CTO and the aqueous phase is suitable according to the present invention. The means for achieving efficient agitation is important due to the low amount of wash water. The wash water focuses on the removal of some GTOF impurities (inorganic salts and residual acid (H2604)), while water additives focus on the removal of other contaminants such as transition metals and various discharges. Furthermore, the additive modifies metal ions in order to increase their preference for the aqueous phase. Moderate stirring as such, such as a static stirrer, does not provide the necessary contact according to the present pretreatment procedure. Therefore, according to a specific embodiment, CTO waxing is performed by a stirring process which provides intimate contact between the CTO and the aqueous phase.

One parameter that facilitates intimate contact between wash water and CTO is temperature. Thus, according to a specific embodiment of the present invention, contact is made at temperatures above 90 ° C and preferably at about 95 ° C.

According to the invention, various additives can be added in the washing step and thereby facilitate the removal of CTO contaminants. One function of such additives may be to bind all metal ions within the CTO. The bond is usually formed by complex formation between ore metallurgy and the additive (but complex formation terminology is often referred to as ligand). Ligands can comprise alits from the ionic type to the molecular type and consequently varying scales for complex formation. According to the invention, the complex formed is thus water-soluble. There are several ligands that can be used as additives according to the invention. According to a specific embodiment, at least chelating agent is added in the first pretreatment step.

The term "chelating agent" herein specifies how a complex is formed. Oxalic acid depending on the dangerous chelating agent. Citric acid and ethylenediaminetetraacetic acid (EDTA) are also preferred chelating agents because they are also commonly used in other applications, and because they also cover a wide range of metal ions, i.e. are not specific for a particular ion, A possible example of how to use additives in the process of the present invention is described below. Color-heated CTO is combined with additional solution. The additive solution should be relatively concentrated, as e.g. 30% additive, as less water allows for increased efficiency of the distribution of the additive throughout the CTO and thus better contact with metal ions. The dose of additives often depends on about ten times the excess in relation to the total amount of metal impurities. CTO and additives are intimately stirred with the aid of, for example, a dynamic stirrer and the mixture thus obtained is transferred to a reactor (single tank without stirring) where the reactor size allows a minimum residence time of 15 minutes. The residence time is needed to ensure the completion of the reaction between additives and metal contaminants. After completion of the reaction, the mixture is combined with the remaining amount of water (up to 5% in total) which is passed through a stirrer (not necessarily of the dynamic type) and centrifuged. Thus, once additives and metal impurities have been contacted and reacted, the water-soluble metal impurities can be extracted with additional water.

As will be appreciated from the foregoing, the oil phase obtained according to the pre-treatment procedure is intended to be further processed. According to a specific embodiment of the present invention, the recovered second oil phase is introduced into the first oil phase comprising refined CTO. The total yield for further processing thus increases. Another option is to recycle the second oil phase back to the layer of (unrefined) CTO. The goal of recovering and / or recirculating the second oil phase in the first refined oil phase is to achieve a high CTO yield for the pretreatment step. The CTO yield for this pretreatment step (matt as unrefined CTO out) is higher than 96%, preferably more than 98% by weight.

The separation of the phases in said first and second pretreatment steps can be performed with different process equipment according to the present invention. According to a specific embodiment, the separation of phases is performed in the first pretreatment step in a separator unit where the separation is driven by centrifugal force. Other types of separation equipment can also be used alone or in combination, such as a combination of filtration and decantation. In the latter case, pre-filtration is advantageously decanting because lignin, fibers and other non-oily contaminants can prevent aqueous phase separation. A process unit where separation is driven by centrifugal force, on the other hand, is preferred process equipment because it effectively separates aqueous phase and solid contaminants from tall oil (TO) in a very short time in a single compact equipment. According to a further specific embodiment of the present invention, separation of phases in the second step is performed by decantation. For the flow intended in this step, the oil-water proportions are smoother and the flow rate for this flow is much lower, which opens up the possibility of using decanting efficiently. It is advantageous to maintain the high temperature used during the first washing step because the temperature assists the separation in the second separation step. After removal of hazardous impurities according to the principles described above, said refined CTO is further treated by removal of volatile substances from the refined CTO surface. According to a specific embodiment of the present invention, said refined CTO obtained from the dye treatment in a process system providing separation of volatile components with boiling points below 170 ° C may yield a "tall oil-depleted volatile matter". The process system used for removing volatile substances from the refined CTO surface may include unit combinations such as a flash vessel - TFE (thin film evaporator) or a stripper type tower (packed column thrsedd with star surface packing). A TFE is the most three-pronged process system for removing volatile substances from a flood of refined CTOs according to the invention.

It will be appreciated that there are a variety of volatile exercises which are completed in delta steps. Volatile formations include water, various gases in water (if water occurs), terpenes and various sulfur-containing compounds such as methyl sulfide and methyl mercaptan.

After removal of the volatiles from the refined CTO surface, refined CTO which is substantially free of volatile volatiles in RTD / TOFA and RA is fractionated by vacuum distillation systems comprising one or more vacuum fractionators. This further processing of refined CTO into individual valuable fractions is further described below. Background of a Second Aspect of the Invention Raw tall oil contains a wide range of organic compounds including turpentine, resin acids, sterols (5-10%), fatty acids (mainly palmitic acid, oleic acid and linoleic acid), fatty alcohols, and other derivatives of the alkyl carbonates. By fractional distillation of CTO, tall oil resin acids (RA) and tall oil fatty acids (TOFA) can be obtained. RA finds use as a component in adhesives, rubber and inks, and as an emulsifier. TOFA can be used as a raw material for the production of renewable diesel fuels, eg RTD (ratal diesel), fuel additives (cetane number enhancers) or used as a base material in the production of fine chemicals (cleaning agents, paints, etc.).

CTO contains more or less sulfur compounds in ranges from about 500 ppm up to several thousand ppm. The sulfur compounds that often have a strong odor include a wide range of organic and inorganic sulfur purifications including sulfate, sulfite, polysulfide, elemental sulfur, mercaptans, organic sulfides, and organic sulfones and sulfonates. The sulfur compounds are primarily linked to low molecular weight components, which are present in 9 in crude tall oil (terpene fin), but may be present in both the crude and diter pendulum parts of crude oil.

Pulp mills often use specialty chemicals to further enhance their pulp yield. A typical chemical used in power processes is anthraquinone (AQ). Thus, CTOs taken from flan pulp mills using AQ contain a certain amount of AQ up to 2000 ppm.

CTO contains a significant proportion of fatty acids, which are also abbreviated FA (fatty acids). FA includes components on the order of C12 up to C26, where the C18 fatty acid isomers are major components. FA has two functional group types, carboxyl group and double bonds. The FA components stack from matte to components with varying degrees of unmatched up to three double bonds (isolated or conjugated).

The crude tall oil also contains a significant proportion of valuable C20 diterpenic acids (also abbreviated RA) including abietic acid, the aromatic dehydroabietic acid and sulfonic acid derivatives of diterpenic acids formed by arena substitution. Diterpenic acids have two functional group types, carboxyl group and double bonds. Almost all diterpenic acids have the same basic skeleton: eft 3-ring condensed system with the empirical formula C19H29C00H. Diterpenic acids occur in pines in a number of isomeric forms having the molecular formula C19H29COOH and in certain related structures. The most common diterpenic acids Abietin-type acids Abietic acid abieta-7,13-diene-18-oinoic acid 13-isopropylpodocarpa-7,13-diene-15-oinoic acid neoabietic acid dehydroabietic acid palustrinic acid typically tall oil. structurally shown as (CH3) 4C15H17COOH molecular weight 302 Acids of pimar type pimaric acid pimara-8 (14), 15-dien-18-oinic acid levopimaric acid isopimaric acid tri-clad form! C20H3502 or C19H34COOH structurally shown as (CH3) 3 (CH2) C15H23C00H molecular weight 307 The manufacture of tramass grade chemical cellulose using chemical kraft pulp manufacturing processes releases these diterpenic acids in the liquor.

RA Crude sulphate turpentine (often CST, ie crude sulphate turpentine) is an organic liquid obtained as a residual product in the production of kraft pulp. The strong-smelling raw pulp turpentine is often handled in closed systems and collected at the pulp mill site and burned as fuel or exported, ie removed, for upgrading. Turpentine can also be obtained by fractionation of crude pine oil or by distillation of resin obtained from it, mainly pine. Turpentine fractions include a wide range of organic compounds often called terpenes. Terpenes are classified in terms of the number of isoprene units C5H8 that need to build up each component and thus hemi- (C5H8), mono (C10H16). sesqui- (C15H24), diterpenes (C20H32) and sA further. Turpentine fractions frail CTO typically boil in the range of 120 to 180 ° C at atmospheric pressure, where monoterpenes, such as alpha- and beta-pinene, are the main components. Turpentine has a density of 0.7 - 0.87 kg / l. Summary of a Second Aspect of the Invention The present invention also relates to the conversion of CTO (crude tall oil) optionally including turpentine, fatty acid and resin acid (RA) fractions to a renewable diesel fuel (refined tall diesel (RTD)) or TOFA and purified resin acids ( RA)). According to this aspect of the present invention there is provided a process for the combined production of RTDTTOFA and RA from crude tall oil (CTO), said process relating to refining CTO, the process comprising fractionation under vacuum of a refined CTO in at least one stream of refined tall diesel (RTD). ) or TOFA, wherein said RTD or TOFA comprises 2-40% by volume of resin acids and 20-90% by volume of fatty acids, and At least one surface of resin acid (RA) comprising 11 less than 5% by volume of fatty acids, wherein the flow of RTD or TOFA optionally in a subsequent step are deoxidized, forming carbonate compounds. It may further be mentioned that RTD or TOFA may also comprise, for example, 2-8% by volume of neutral components, such as sequi- and diterpenes and / or their partially oxidized counterparts such as alcohols, ketones, aldehydes, etc. Such components may further have boiling points near FA and RA, which can Ora them svka aft separate.

The remaining TOP fraction (after extraction of RTD / TOFA and RA) constitutes less than 30% by weight of CTO, which is introduced into the fractionation steps.

For fractionation, CTO is advantageously pretreated and converted to refined CTO according to the first aspect of the present invention discussed above. In a first pretreatment step, the CTO is treated to remove contaminants by centrifugation and / or filtration, followed by a step of removing water and volatile furnaces to thereby form a stream of refined CTO. In a second step, the high boiling point (high molecular weight) components are separated as liquid flood (tall oil pitch, TOP) under vacuum from the gaseous river which mainly comprises fatty and resin acids.

Gaseous fatty and resin acids are drawn into the fractionation tower operating under vacuum, whereby an RTD / TOFA fraction rich in fatty acids is deposited from the upper part of the tower and an RA-rich fraction is deposited from the bottom of the tower. The gaseous fatty acid-rich RTD / TOFA river is condensed into liquid refined pine diesel "RTD", which RID can be exported for further upgrading, such as premium biofuel components.

Alternatively, the RTD / TOFA river is exported, with or without further refining, to reduce the RA content, before being used in the manufacture of fine chemicals (soap, lubricants, adhesives and varnishes).

In another specific embodiment of the invention, ie imported compounds are imported, such as grains from pulp processing and boiling in the range 120 - 180 ° C (including eg turpentine), and added to RTD. Organic compounds (including turpentine) can also be recovered from the volatile fraction deposited as described above and, advantageously, added to RTD. Turpentine compounds (with the main components alpha- and betapine) have a fairly low density and such addition to RTD reduces the overall density of RTD. This addition of turpentine and / or other organic chemicals originating in the processing of trabe processing 12 and boiling in the range of 120-170 ° C is further described below, and relates to a third aspect of the present invention.

In an optional fourth step, RTD, with or without turpentine chemicals as an additive, is treated under catalytic conditions in at least one reaction zone of a reactor operating at a temperature above 150 ° C, whereby the fatty acids and resin acids in RTD are decarboxylated and / or decarbonylated, thereby forming renewable industry components in the diesel area.

The use of strategically placed TFE and CTO pre-treatment, where CTO contaminants are eliminated, works together for the preservation of the unwanted RTD / TOFA and RA components, which in turn increases the RTD / TOFA and RA exchanges in comparison with prior art. . In addition, the use of fractionation towers operating at low vacuum levels and can be characterized by profiles with minimal pressure drop slows down I6ga operating temperatures during fractionation, which provides an energy efficient process for CTO fractionation compared to prior art.

Specific Embodiments of a Second Aspect of the Invention Hereinafter, particular embodiments are set forth which relate to the process for the combined preparation of RIDTTOFA and RA from CTO of the present invention.

The inventors have discovered that CTO can be transformed in a series of innovative 6gards into a flood of refined pine diesel (RID) or TOFA and a resin-acid-rich flood (RA). RTD mainly comprises fatty acids, fatty alcohols and resin acids. RTD can be further characterized by the boiling points of the organic compounds in RTD. RTD components boil in the range of 120-420 ° C, more preferably in the range of 160-400 ° C at atmospheric pressure and the typical RTD mixture has a density of 0.88 to 0.95 kg / l. The fatty acid-rich flocculation can alternatively be exported and used as TOFA in the manufacture of fine chemicals.

As described, there may be one or more CTO pretreatment steps performed before the actual fractionation under vacuum of a refined CTO and subsequent recovery of the RTD / TOFA and RA rich river.

CTO is optionally pretreated by the procedures described, followed by at least one separation treatment which removes the tall oil fraction including components having boiling points below about 200 ° C, more preferably below about 170 ° C at atmospheric pressure (hereinafter referred to as volatile tall oil). The volatile fraction present in the CTO is typically in the range of a few tenths% by weight up to 2% by weight, in addition to 0.5 to 3% by weight of water carried by the CIO. The former fraction comprises a number of components with varying molecular weight, primarily C8 to C16 carbon compounds (turpentine, hydrocarbons, hydrocarbons with varying content of heterogeneous elements such as sulfur, oxygen, nitrogen, etc.) Volatile organic materials which boil at atmospheric pressure below about 200 ° C but above about 120 ° C is removed from the flow of crude tall oil. The volatile substances (including turpentine) can be deposited in one or more thin film evaporators or strippers and combinations thereof, which operate at a temperature in the range of 100-220 ° C and a set pressure in the range 30-60 kPa, in a following process steps, CTO components with high boiling point or tall oil pitch, TOP (residual ash, organic fraction with average boiling points for the individual components selection Over 440 ° C) are separated from RTD / TOFA components and resin acids present in GTO. In addition to ash, tall oil pitch typically consists of (i) components comprising the non-digestible fraction (> C28); (ii) high molecular weight esters (500-600 g mol-1) of sterile and / or wax type and (iii) products of intermolecular Diels-Alder type dimerization reaction. Typical compounds with a high boiling point in non-digestible CTO substances are campesterol (C28), stigmasterol and sitosterol (C29), squalene, betulinol, lupeol (C30), methylbetulinol (C31), etc.

In one embodiment of the present invention, TOP is separated from fatty and resin acids by using one or more thin film evaporators (TFE) operating in parallel or in series at 250 ° C to 320 ° C and applying pressures of 0.711.5 kPa. Heat is supplied to TFE by steam or hot oil. The temperature of the degassed tall oil (fatty acids and resin acids) leaving TFE should be in the range of 200 to 330 ° C, preferably 200-250 ° C, before being fed into a fractionation tower equipped with one or more structured gaskets.

The main fractionation tower used for the separation of RTD / TOFA and RA operates under vacuum conditions (1-25 mbar, preferably 1-10 mbar) and at a temperature in the range 150-280 ° C. The main fractionation tower and its feed section deformation are optimized according to the following template: (i) maximum yield of RIDTTOFA fraction with components boiling in the temperature range 170-420 ° C (at atmospheric conditions), (ii) clear fractionation section at about 370-420 ° C (at atmospheric conditions) ), (iii) minimum undesirable reactions for the purpose of extracting high quality resin acids and yields in the lower part of the tower and (iv) lowest pressure and temperature in the lower part of the fractionation tower, which minimizes degradation of undesirable product components.

As can be seen from the above, according to a specific embodiment, fractionation under vacuum is carried out in at least ten steps (TFE for removing TOP from refined CTO, a fractionation tower separates RTD / TOFA and RA and after fractionation tower for refining RA).

According to the specific embodiment described above, CTO (purified by the methods described in a first fractionation step for separating tall oil pitch (TOP) from CTO is introduced following a second fractionation step (after a vacuum fractionation tower), a river rich in RTD components having a boiling point atmospheric pressure within the range of 170-420 ° C, a flood of RA components with a boiling point above about 420 ° C is separated from the atmospheric pressure, and in a third fractionation step, RA is further refined to RA with a low content of fatty acid.

Through the use of TFE units for aft tailbeck from CTO, levels of less than 5% of resin acids remaining in tall oil basin can be achieved. The gaseous fatty acid and resin acid rich liquid leaving TFE is discharged into the main fractionator designed to separate RTD components and resin acids. In an alternative and preferred configuration, refined CTO is fed into a first TFE, which outputs preferred TOFA and RA into the main fractionator and outputs RA-rich and TOFA-poor CTO into a second TFE, which outputs FA and RA into the main fractionator and an RA. -flow still rich in RA, which flow is fed into a third TFE, which outputs RA into an RA purification stage (RA polishing tower) and output of TOP for export from the plant.

As can be seen from the above, the% Met from the first TFE unit can be combined with the similar flow from a second TFE unit into the fractionation tower where the RTD and RA flows are produced. Another possible route according to the present invention is to drive the gas stream from the first TFE unit separately and then further process this gas stream to TOFA or treat this stream by one or more of deoxidation, decarbonylation and decarboxylation to produce a paraffin-rich feedstock or petroleum refining refinery. to steam cracking plants for the production of fine chemicals such as ethylene, propylene, etc.

According to a specific embodiment, the RA-rich river recovered from the lower part of the fractionation tower is discharged in the RA purification stage (polishing tower) and further processed in a thin film evaporator for separating entrained TOP components from RA, said RA being further refined by processing under vacuum in the RA purification step (a fractionation tower which is an RA polishing tower) to produce high quality RA which contains less than about 4% by weight of fatty acids.

It should be understood that the RA-rich river extracted from the fractionation tower can be further processed in a TFE unit only to produce RA fraction of sufficient quality (RA content, color, FA content, melting point, etc.) in the stable kV aft process delta flow in eft other RA fractionation tom.

A packed fractionation atom typically comprises one or more baths of structured packing, an athercooker arrangement in the lower part of the column and preferably a backflow device at the upper part of the column.

Modern structured packing usually includes thin corrugated metal plates or wafers arranged appropriately, where the overarching purpose of custom design is to force water shoes pumped into the column to follow these predetermined paths and thereby provide a large surface area which in turn allows maximum contact between water shoes and angor. Although they are superior in relation to funnel-type distillation columns, columns with packed baths also show some pressure drop. Utilization of specially designed structured packing ensures that the pressure drop achieved in the column top to the bottom is less than 15 mbar, preferably 10 mbar and most preferably 5 mbar.

According to preferred embodiments of the present invention, structured gaskets are used which are characterized by minimal pressure drop.

The flow of the structured bath is closely related to the desired degree of fractionation, ie the number of theoretical steps required to achieve a certain degree of fractionation. As can be seen from the above, the fractionation tower comprises one or more structured baths. Thus, the height of the primary structured gasket / bath used for the invention is tailor-made to achieve a high yield of RTD / TOFA. RTDTTOFA materials recovered in the upper part of the bath may comprise as much as 20% by weight of resin acids, arida up to 30% by weight, but the preferred content of resin acid of RTDTTOFA is between 1-10% by weight, more preferably the range 1-5 weight% of RTD / TOFA associations. RTD / TOFA can be further refined by distillation, filtration, cooling, etc. before use as a raw material for the production of fine chemicals, for use as a fuel, as an input material for partial or complete decarboxylation in a catalytic bath 16 for the production of oxygen-poor renewable diesel fuel components, or for export treatment to renewable industry components in the diesel field in a petroleum refinery. It can be mentioned by the term "renewable industry components in diesel areas have been understood to be the hydrocarbons boiling in the range 170-400 ° C. Nevertheless, the primary function of this gasket is to separate the main part RTD / TOFA as the top flow and produce RA-rich boften flede.

According to a preferred embodiment of the present invention, separation of RTD / TOFA and diterpene acids (resin acids) from a gas flow leaving a TFE in a vacuum fractionation tower with packed baths connected to TFE is achieved.

Within the TFE unit, which unit is connected to the fractionation tower in all embodiments according to the present invention, the input material is dried in the form of a thin film. The residence time in a TFE is therefore very short and is responsible for the preservation of the desired RTD / TOFA and RA components and thus higher RTD / TOFA and RA yields.

A typical approach for further defining RTD / TOFA fractionation cut is to install a return device on the column top operating in the temperature range of 150-220 ° C. For the recirculation, a large portion of the product is usually returned to the column in a position near the upper end of the column. In general, after higher runoff, a sharper distillation cut results. With fordol, another structural gasket is mounted just below the incoming reflux. The gasket can then (i) evenly redistribute the relatively cold backflow and (ii) ensure the availability of large surface area, which in turn maximizes the backflow effect.

Accordingly, according to a specific embodiment of the present invention, the fractionation tower is equipped with a reflux configuration at the upper end of the column. According to another specific embodiment of the present invention, the upper part of the river comprising components with boiling points of 370-420 ° C is made clearer by selecting suitable reflux treatment. In addition, according to yet another specific embodiment of the present invention, the homogeneity of the backflow into the column is achieved by further structured packing in the column.

In order to achieve efficient separation, however, a homogeneous fluid flow throughout the column should also be ensured. When homogeneous fluid flow is realized, the components which are in liquid form under the present conditions are preferably present as fine droplets on the packing surface, while components 17 which boil move as angles. Homogeneous flow in the column is achieved by suitable distributors and / or structured packing.

Typically, heat and corresponding steam are supplied to the fractionation tower with a packed bath via an ather boiler device installed at the bottom of the tower.

As can be seen from the above, one goal in optimizing the fractionation tower is to minimize unintentional reactions that can be induced by extensive heating. Thus, the necessary heat and vapors are preferably provided only by TEE directly connected to the fractionation tower. The volume of water in the tower is kept to a minimum. For example, a heat exchanger that supports TFE can also be arranged in the system.

The main rivers obtained after fractionation in the main tower using packed addition fractions towers are RTD and RA rich rivers which are further refined into high purity RA products according to the process described by the present invention.

The further treatment of RA is carried out in a second fractionation tower (RA polishing tower) according to the present invention. In the second fractionation tower, an RTENTOFA flow is obtained which is rich in fatty acid components with boiling points in the range of 170-420 ° C and after the flow of high quality RA and possibly a TOP flow comprising color components and other undesirable components with high boiling point. The design of the second fractionation tower is optimized according to the following may: (i) maximum yield of RA fraction (ii) RA fraction with lowest content FFA and (iii) RA fraction of high (light) color.

According to the invention, the RA polishing tower is after a fractionation tower with packed baths, comprising one or more structured baths. The tower operates on a separate vacuum line, which gives a pressure of 0.1-1.0 mbar. The low vacuum levels are facilitated by the absence of the RTD / TOFA bulk fraction. In addition, the low vacuum levels allow the utilization of essentially the same operating temperatures (150-280 ° C) that are to be used for RA fractionation and thus significantly reduce the risk of degradation reactions typical of RA when exposed to high temperatures.

RA fractionation in the RA polishing tower is achieved within the primary packing (intermediate in relation to other packing baths installed tower) of the fractionation tower installed in the middle part of the tower.

The packing deformation enables an efficient separation of the remaining FFA from the RA fraction. The separation can also be influenced by the choice of suitable backflow ratio through the backflow device installed at the top part of the tower 18 together with the structured gasket which ensures the homogeneity of the backflow.

The recovered stream comprising RTD / TOFA components is discharged from a draw tray installed below the upper gasket, while the RA stream is discharged from a draw tray installed below the intermediate gasket.

Necessary heat and steam are supplied through the flood of RA-rich material discharged to the Wan main tower and one or more TFE units that precede the RA polishing tower. The vapors from a TFE are discharged into the polishing tower under a layer packed bath which is optimized to separate all heavy and / or colored components which in turn are discharged as TOP-flocle to the TFE frail bottom of the tower. This TFE unit can, for example, be supplemented with a falling film evaporator (FFE).

Salunda describes the present invention according to a method in which purified CTO flux from volatile substances is separated into three separate streams or phases, a surface or phase, RTD / TOFA, comprising components with boiling points of about 170400 ° C, a flOcle or phase, Tall oil pitch (TOP), includes components with boiling points above 440 ° C and a third flood, including diterpene or resin acids boiling at approximately 390 to 440 ° C, all at atmospheric pressure.

A fourth stream of deodorized and at least partially desulfurized turpentine (including alpha-pinene) may optionally be satiated to an RTD floc after recovery of RTD from the first fractionation tower, said turpentine boiling in the range of 120-200 ° C at atmospheric pressure. Turpentine and other low-boiling materials have been added to the RTD product to reduce the density of RTD and increase the proportion of components that boil below about 200 ° C in RTD. Thus, turpentine and other low boiling organic components may be added to increase the proportion of C8-C12 carbon molecules in RTD by as much as 15% by weight. Preferably, RTD comprises about 2-15% by weight of C8-C12 turpentine components, more preferably 2-8% by weight of such components.

According to a specific embodiment of the present invention, the total yield of RTD / TOFA is based on the influence of refined CTO Over 50% by weight, for example Over 55% by weight, and the total yield of RA is Over 15% by weight. According to a specific embodiment, the total yield of RTD / TOFA is based on CTO influence in the range of 55 - 70% by weight, eg about 60% by weight, and the total yield of RA is in the range of 10 - 25% by weight, e.g. 15% by weight. The first RTD / TOFA phase obtained from the fractionation tower may comprise about 60% by weight of 19 refined CTO influences, and the second RTD phase from the RA polishing tower about 3% by weight of refined CTO influences to the first fractionation tower. The first fractionation tower can be checked and adjusted to achieve the desired RA content of RTD / TOFA normally within the range of 2 - 30%. The total yield of RTD can, as described, be further reduced by the addition of turpentines.

In all embodiments of RTD / TOFA and RA recovery from CTO described herein, a final high boiling residual product TOP is produced which represents between 10 and 30% by weight, or perhaps up to 35% by weight, of CTO fed for CTO fractionation. Furthermore, the process of the present invention may be characterized by law-specific energy consumption in comparison with traditional and prior art CTO fractionation procedures. The total energy consumption (hot oil and / or steam) for fractionation of CTO in RTD / TOFA and RA is lower than about 600 kWh / ton of refined CTO influence, four times lower than about 500 kWh / ton of refined CTO influence. Current CTO fractionation procedures use choices Over 1000 kWh / ton specific energy for CTO fractionation.

According to one embodiment of the second aspect of the present invention, there is provided a process for the combined production of RID and RA frail CTO, wherein refined CTO has been obtained from CTO which has been processed in a pretreatment step comprising CTO washing and separation of hazardous impurities, from which pretreatment step according to the first refined CTO flow is obtained, said first refined CTO fluid then being further processed by flashing, stripping and / or treating in a thin film evaporator to remove volatile components from the CTO and then forming other refined CTO fluid substantially free of the volatile matter. surface is further processed in a thin film evaporator, to separate and remove TOP from a third stream rich in fatty acids and resin acids, which is then invested in the first fractionation tower for the extraction of RTD / TOFA and RA in rapid yield.

RTD fraction can be combined with lower boiling organic material (boiling point 120-200 ° C at atmospheric pressure) comprising turpentine removed from a tall oil fractionation plant or imported turpentine from a pulp mill. Partial organic matter with a low density (density 0,7 - 0,87 kg / l) of preferably desulfurized and deodorized turpentine and / or tall oil fractions (C8-C16 carbon compounds) extracted in a rata * fractionation plant or imported turpentine.

RTD produced according to the present invention can be used as an oxygenated refined diesel fuel as such, but RTD can be advantageously upgraded to premium type diesel fuels by decarboxylation and / or optional petrochemical deoxidation / hydrogenation processes. RTD recovered from a fractionation column (with or without addition of turpentine) can be advantageously charged, directly or indirectly, to an additional processing step connected to the tall oil fractionation plant or at a remote location, where at least a portion of the oxygen content in RTD is reduced via decarboxylation and / or decarbonylation reaction. in the presence of a catalyst.

Decarboxylation and / or decarbonylation reactions are carried out at a temperature in the range of 150 - 350 ° C in solid bath directorates with one or more catalytic baths. The decarboxylation and decarbonylation reactions are promoted by suitable catalysts. Typical decarboxylation / decarbonylation catalysts include activated carbon, carbon noble and transition metals, activated (acidic) alumina, zirconia, etc., fuller soils, carbonate based catalysts and transition metal catalysts. Among transition metal catalysts, common sulfur tolerant catalysts such as NiMO / Al 2 O 3 can be used.

Decarboxylation reactions are endothermic and fate may be injected during decarboxylation to give off hot Iran exothermic hydrogenation reactions.

Thus, the second aspect of the present invention describes a process for recovering resin acids and a ratal diesel RTD or TOFA from crude tall oil. Ratal diesel RTD is further treated under catalytic conditions to deposit oxygen, thereby forming carbonaceous renewable diesel compounds.

Summary of a Third Aspect of the Invention and Specific Embodiments Thereof The present invention also relates to an optimized RTD composition and a process for preparing such a composition. The optimized RTD composition of the present invention comprises 1-30% by weight of resin acid (RA) and 70 to 95% by weight of fatty acid (FA) and further comprises from 1 to 10% by weight of sulphate turpentine (CST) and 0-1% by weight of anthraquinone. As mentioned above, the RTD composition may further comprise, for example, 2-8 vol / neutral components.

The benefits obtained with the RTD composition of the present invention include co-produced crude sulphate turpentine (CST) and, optionally, the content of anthraquinone used as valuable components, that is to say, to increase the overall yield of RTD in the process. In addition, CST reduces the density of the RTD mixture and increases the yield of RTD from forest-based raw materials. CST produced by the CTO biorefining described in saval as imported CST can be added to the RTD composition prepared according to the present invention.

According to an embodiment of the present invention, there is still provided for the preparation of an optimized RTD composition. This process focuses on the preparation of a refined tall diesel (RTD) composition, in which crude sulfafterpentine (CST) is added to the refined tall diesel (RTD) composition.

CST to be mixed into the RTD composition is boron. renas. This purification is directed to the removal of Si, which Si is derived from antifoaming agents used by pulp and paper mills, and this purification can be achieved, for example, by adsorption on media such as bauxite, activated carbon.

According to a specific embodiment, the CST produced during the separation of volatile components (which have boiling points in the range 120-250 ° C) from CTO or a refined CTO. As mentioned above, CST can also be imported from a kraft pulp mill and added to an RTD composition according to the present invention.

According to a specific embodiment of this process aspect of the present invention, the volatile components have boiling points below 200 ° C. The removal of volatile components can, for example, be carried out in a process system which comprises anxiety strips and / or a thin film evaporator.

This process can also be advantageously integrated into the other aspects of this invention, i.e. said process is supplemented with a first pretreatment step which comprises a CTO washing and separation of Throrenings for the production of a refined CTO, followed by separation of volatile components having boiling points in range of 120 - 200 ° C 1 refined CTO for the production of effluent oil flow depleted on volatile material. The tall oil surface depleted of volatile material is then treated in a thin film evaporator (TFE) to remove tall oil pitch (TOP).

The processing in TFE is carried out under vacuum at a temperature of about 300 ° C (residence time at this temperature about 2 minutes.) The removal of TOP from the refined tallow flow in TFE gives TOP in the range of 10 - 30% by weight and flow of gaseous fatty acids and resin acids. which corresponds to about 70-22 80% by weight of refined tall oil flood is fed into TFE. It should be noted that with reference to the first and third aspects of the present invention, the term "TFE" may naturally refer to a single TFE but also several TFEs, also several TFEs which are treated in the second aspect of the present invention.

According to a further specific embodiment of the present invention, the further refined tall oil surface is introduced substantially free of TOP into a fractionation body, where a stream of refined tall diesel (RID) rich in components with boiling points in a range is fractionated! of 170 - 420 ° C and a surface of resin acid with a boiling point in the range 410 - 440 ° C is obtained. CST added with fart part to RTD after RTD has been discharged to the fractionation tower, may further improve the yield of RTD and decrease the density of RTD.

According to a further embodiment, the total yield of RTD is over 5% by weight, for example Mien Over 65% by weight, and the total yield of RA is Over 15% by weight based on CTO fed to the fractionation plant. As an example, the first RTD phase obtained from the fractionation tower is about 60% by weight.

In the final RA polishing fractionation tower, RTD is extracted in the upper part and high quality RA is extracted in the lower part. RID recovered in the polishing tower essentially comprises fatty acids representing about 1-5 ° / c., Of the total RTD yield. High quality RA with an acid number of 160-180 mg KOH per gram of sample is extracted from the lower section of the RA polishing tower and exported from the plant. Depending on the market for RA and / or RTD, the RA content of the RTD river extracted from the fractionation tower can be regulated between 2-40%, as in the range from 2-30%. As irises are combined with both the first and second RTD surfaces and exported from the plant with or without the addition of CST produced in the plant or imported into the plant.

According to a further embodiment of the present invention, referred to above, the fraction rich in RA obtained from the fractionation tower is further refined in the RA polishing tower, whereby RA is refined to the desired purity (RA content 90% by weight or less, FFA less 4% by weight, softening point higher than 70 ° C and thrg between 6-7 on the Gardner scale).

Detailed Description of the Drawings Figure 1 shows various steps during the processing of CTO according to the first aspect of the present invention. In the first step, referred to as "CTO washing", the crude oil is treated in a series of stirring, reaction and separation steps, where the level of impurities in the resulting surface (referred to as "Refined CTO") is substantially reduced or significantly reduced. taken down to the limit for analysis methods used for quantification. In order to obtain precipitation of compounds, the CTO is brought into contact with a relatively small amount of water (up to 5% by weight on a CTO base) which contains at least one additive component by intensive stirring at elevated temperatures (just below the boiling point of the water). The mixture thus obtained is then passed into a separation unit capable of separating the river into oil (refined CTO) and aqueous phase. The use of water is governed by the marked laxity that CTO contaminants have in water, such as residual mineral acid and various inorganic salts and salts that are dangerous. It should be emphasized that the water used should meet certain quality requirements (pH 6.5 to 7.2; hardness <5 ° dH, Ca + Mg Na <1 mg / kg), where a typical example is steam condensate. The additive component is typically a chelating agent having a high affinity for metal cations and especially transition metal cations. Such additives form very stable and water-soluble complexes with these metal cations. Additives with affinity for a wide range of metal cations are preferred to keep the whole process simple where typical examples are, but are not limited to, oxalic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), etc. The separation unit facilitates the phase separation. Particularly hazardous units are those which use centrifugal force for phase separation. Typical such separation units combine, together with the liquid phase separation, separation and discharge of any solids (such as fibers, non-oily components and lignin). In view of the limited amount of water added, clarifier type separators are of particular interest in the present invention. Thus, the use of a combination of agitation, reaction and separation owes the entire diversity of CTO hazard contaminants and securities to their significant reduction or practical removal.

The aqueous phase is subjected to a partition after the second separation step where the second oil phase is separated from the aqueous phase and other solid compounds. The second oil phase thus obtained can be combined with the refined CTO surface (possibility shown by the dashed arrow in Figure 1).

Another alternative is to assess the quality of the second oil phase thus recovered and then satisfactorily return it to the CTO for a second pass through the pretreatment sequence (possibility shown by the dashed arrow in Figure 1).

Figure 2 shows different steps during the processing of CTO according to the second aspect of the present invention. The solid lines indicate basic design 5 for the main river, while dashed lines show the optional river.

According to the second aspect of the present invention, CTO or, preferably, refined raditated CTO is fed into a process system which provides a unit for the separation of volatile components present in the CTO. Volatile components are components with boiling points below about 170 ° C at atmospheric pressure. Typical examples are the components which comprise turpentine fraction such as some carboxylic acids eg C12-C14. Other volatile substances include water, sulfur-containing and other gases, etc. The removal of volatile substances is a necessary requirement with respect to subsequent vacuum fractionation steps. The removal of volatile substances is most advantageously carried out in a TFE unit operating at a relatively low vacuum (approx. 50 mbar), which combines efficient evaporation of the light components controlled by the short diffusion wave and the short residence time of said refined CTO at elevated temperatures. . On the other hand, reasonable deposition of volatile substances can also be affected by countercurrent contact of refined CTO with stripping media in a column with packed bath at low vacuum and elevated temperatures.

With the help of one or more TFE units (TFE resin), the tall oil liquid is depleted depleted on volatile substances into a liquid heavy bottom fraction, poor in TOFA but fortifying rich in RA and a gas phase fraction comprising TOFA and resin acids. Angfloclet is controlled into the main fractionation tower. Careful selection of operating conditions may depend on the boiling point range can be tailored to the lightest fraction (designated RTD product), which consists mainly of FFA and a certain amount of resin acids. The desired boiling point range for this fraction is from 170 and up to about 400 ° C at atmospheric pressure. The RTD fraction thus obtained is further used for the preparation of high-quality industry compositions in the diesel area or is further refined to TOFA for use in fine chemical production. A resin-acid-rich fraction of relatively high quality can be obtained as a bottom product from the main fractionation tower. The quality of the resin acid fraction can be further improved in a separate fractionation tower referred to as "RA polishing", which operates at a very deep vacuum, enables the use of relatively mild temperatures and thus essentially preserves the resin acids. The RA polishing tower is fed with a surface rich in resin acids discharged from the lower part of the main fractionation device and gaseous fraction produced in a TFE unit connected to the RA polishing tower. TFE is fed with resin-rich feed stream flan TFE or one or more TFEs connected to the main fractionation column. TOP is discharged from the system from the lower section of this TFE unit. A small portion of the high boiling point components is discharged from the RA fractionation tower as a bottom fraction and discharged into the TFE connected to the polishing column. The lighter fraction recovered from the upper section of the RA polishing tower comprising FFA and some amount of RA is combined with the RTD fraction recovered from the main fractionation tower. If any, part of the RA flock extracted from the RA polishing tower is discharged to RTD storage or recycled back to the TFE unit as the pre * RA polishing tower. Figure 3 shows different steps during the processing of CTO according to the third aspect of the present invention. In the third aspect of the present invention, the CTO is treated in a manner similar to that described for the second aspect of the invention. The additional steps have bertir (i) processing of RTD composition with the addition of a turpentine fraction recovered from CTO during the volatilization step removal step and / or (ii) imported CST fraction. Both turpentine (recovered frail CTO) and imported CST (dashed arrows Figure 3) were added to the combined RTD fraction, thus constituting an improved RTD composition.

Claims (37)

26 Patent claims A process for treating a crude tall oil (CTO) for removing faith impurities, the method comprising a first pretreatment step comprising a CTO wash and a separation of a first oil phase comprising refined CTO and an aqueous phase containing faith impurities, and then others steps comprising separating a second oil phase from the aqueous phase. The method of claim 1 according to claim 1, wherein said CTO is contacted with water in an amount of less than 5% by weight of the CTO water, A method according to claim 1 or 2, wherein at least one additive is added in the first pretreatment step to bind metal ions in the CTO to produce water-soluble metal complexes. A process according to any one of the preceding claims, wherein at least a chelating agent is added in the first pretreatment step. The method of claim 4, wherein the chelating agent is oxalic acid. A method according to any one of claims 1-5, wherein the recovered second oil phase is fed into the first oil phase comprising refined CTO. A method according to any one of claims 1-5, wherein the recovered second oil phase is fed into said CTO. A method according to any one of claims 1 to 6, wherein the separation of the first wood treatment step is performed in a separator unit where the separation is driven by centrifugal force. A method according to any one of claims 1-8, wherein the separation of the second step is performed by decantation. A process according to any one of claims 1-9, wherein fiber, salts, residual inorganic acid, transition metals and or lignin constitute the impurities, A method according to any one of claims 1-10, wherein said refined CTO is incorporated into a process system providing separation of volatile components with boiling points below 170 ° C present in the CTO to provide after tall oil flood depleted on volatile substances. A process according to claim 11, wherein the tall oil liquid depleted on volatile substances is fed into a vacuum distillation system to obtain individual valuable fractions of fatty and resin acids. A method according to any one of the preceding claims, wherein the second step comprises a separation of a second oil phase from the aqueous phase is carried out in subsequent steps in a separate unit which is not directly adjacent to a unit in which the first pretreatment step is carried out. A process according to any one of claims 1-13, wherein said refined CTO is further treated in a process comprising vacuum fractionation of a refined CTO into at least one stream of refined tall diesel (RTD) or tall oil fatty acids (TOFA), said RTD or TOFA comprising 2-30% by volume of resin acids and 20-90% by volume of fatty acids, and at least after flow of resin acid (RA) comprising less than 5% by volume of fatty acids, whereby the flow of RTD or TOFA is deoxidized, forming hydrocarbon pellets in a subsequent step. The method according to claim 14, wherein the specific energy consumption for producing RTD and / or TOFA and RA from CTO is lower than about 600 kWh / ton of refined CTO inflOcle. A process according to claim 14 or 13, wherein the RTD or TOFA river comprises less than 10% by volume of resin acids, preferably less than 5% by volume of resin acids and wherein the content of resin acids of RTD or TOFA is further reduced by subsequent refining to a level of resin acids which is lower than about 3%. Process according to any one of claims 14-16, wherein TOFA with a low content of resin acid, lower than 5% by volume, is exported, possibly after further refining, for use in the manufacture of fine chemicals such as whips, detergents, liner and varnish. 28 A process according to any one of claims 14-17, wherein deoxidation by Mrs in the presence of hydrogen. A method according to any one of claims 14-18, wherein the fractionation of CTO 5 is performed under vacuum in at least three units. A method according to any one of claims 14-19, wherein refined CTO is fed in after the first fractionation step for separation of a tall oil fatty acid (TOFA) and resin acid (RA) river (s), said separation being optionally performed in one or more TFEs arranged in parallel or in series Mgt of after second fractionation step, wherein a flow rich in RTD or TOFA components with a boiling point at atmospheric pressure within a range of 170-420 ° C is separated from an RA-rich flow and further followed by a third resin acid purification step performed during deep vacuum. The method of claim 20, wherein said RA-rich stream discharged from the first separation step is further processed in a thin film evaporator (TFE) to separate Transferred TOP components, said RA being further processed under vacuum in a fractionation tower after RA. aft produce RA of high quality. A method according to any one of claims 14-20, wherein an RA-rich river is discharged from a lower part of the main fractionation tower in the second fractionation step and fed into another thin film evaporator (TEE) or a fractionation tower which is an RA polishing tower. A method according to claim 21 or 22, wherein further processing of RA in a third separation step is carried out in a fractionation tower which is after RA polishing tower, in which after flow rich in fatty acid components with boiling points in a range of 170-420 ° C and a flow which is rich in RA erhalls. A method according to any one of claims 14-23, wherein refined CTO is fed in after the first fractionation step performed in a first thin film evaporator (TFE) and wherein after TOFA-rich gaseous effluent from the first thin film evaporator (TFE) is evaporated off and then further processed. assisted by at least one of deoxidation, decarboxylation and decarbonylation Mr 29 removal of oxygen atoms from the TOFA-rich gas stream and thereby producing a paraffin-rich oil. A process according to claim 24, wherein a paraffin-rich oil is fed into a hydroprocessing unit for the production of biofuel or fed into a steam cracking plant for the production of ethylene or propylene. The method of any one of claims 14 to 25, wherein the total yield of RTD based on the CTO influx is over 55% by weight and the total yield of RA is over 15% by weight. A method according to any one of the preceding claims, wherein, from said pre-treatment of a Ca tall oil (CTO) to remove contaminants, a first refined CTO flood is obtained, wherein said first refined CTO river is then further treated in an anxiety stripper or a thin film evaporator for removed volatile components and give a second refined CTO flood substantially free of volatile substances, which is further processed in a thin film evaporator to separate and remove after tall oil pitch fluid and give a third refined CTO fluid which is fed into the fractionation tower operating under 25 mbar, preferably 1-10 mbar). A process according to any one of claims 14-27, wherein said refined CTO is further processed in a process comprising vacuum fractionation of refined CTO to at least after reflux of refined tall diesel (RTD) and wherein crude sulfate turpentine (CST) is added to the refined tall diesel (RTD). ) - the composition, for the production of a refined low density diesel (RTD) composition. The method of claim 28, wherein said CST has been prepared in prior processing steps during separation of volatile components with boiling points in the range of 120-250 ° C in a crude tall oil (CTO) or a refined CTO. The method of claim 29, wherein the volatile components have boiling points below 200 ° C. A method according to claim 29 or 30, wherein the deposition of volatile components is sacrificed in an anxiety stripper and / or a thin film evaporator. A method according to any one of claims 28-31, wherein said crude sulphate turpentine (CST) added is purified comprising at least Si removal. A process according to any one of claims 28-32, wherein purification of said crude sulphate turpentine (CST) is effected by adsorption. A process according to any one of claims 27-33, wherein said process also comprises the first pretreatment step comprising a CTO wash and separation of contaminants to produce a refined CTO, then separating volatile components with boiling points in the range of 120200 ° C in said refined process. CTO for producing a tall oil floc depleted on volatile substances, then further processing the tall oil floc depleted on volatile substances in a thin film evaporator to produce an additional refined tall oil stream and remove the tall oil basin (TOP) from said refined tall oil stream. The method of claim 34, wherein the further refined tall oil stream is fed into a vacuum fractionation tower operating in which a stream of refined tall diesel (RTD) rich in components having boiling points in a range of 170-410 ° C and another pocket rich in resin acids (RA) is obtained, and wherein CST added to RTD after RTD has been discharged from the fractionation tower. The method of claim 35, wherein the total yield of RTD is Over 55% and the total yield of RA is over ea 15%. The method of claim 35 or 36, wherein the RA-rich stream is further processed in a further thin film evaporator to produce an additional refined RA-rich stream and deposited TOP and then feed the refined RA-rich stream into a fractionation tower which is an RA polishing tower operating under deep vacuum (0.1-1.0 mbar) to separate after flow of fatty acid-rich materials and a flow of RA of high purity with a fatty acid content of less than about 4% by volume. Water & Additives