BRPI0619628B1 - process for the production of a saturated hydrocarbon component - Google Patents

Abstract

process for the production of a saturated hydrocarbon component. The present invention relates to a process for producing high quality saturated base oil or a hydrocarbon based base oil component. The process of the invention comprises two main steps: oligomerization and deoxygenation. A biological starting material containing unsaturated carboxylic acids and / or carboxylic acid esters is preferably employed as the feedstock.

Description

Patent Descriptive Report for "PROCESS FOR THE PRODUCTION OF A SATURED HYDROCARBON COMPONENT".

Technical Field The present invention relates to a process based on oligomerization and deoxygenation for the production of a hydrocarbon component, and particularly for the production of high quality saturated base oil. In the process, the feedstock of biological origin is preferably used, optionally derived from vegetable and fish oils, animal fats, natural waxes, carbohydrates and corresponding synthetic materials and combinations thereof.

Background Art Base oils are generally employed for the production of lubricants such as automotive lubricating oils, industrial lubricants and lubricating greases. They are also employed as processing oils, white oils and metal beneficiation oils. Finished lubricants consist of two general components, base lubricating oil and additives. Lubricating base oil is the major component in these finished lubricants and contributes significantly to the properties of the finished lubricant. In general, some lubricating base oils are employed to produce a wide variety of finished lubricants by varying the mixtures of individual lubricating base oils and individual additives.

Base oils according to the American Petroleum Institute (API) classification of Group III or IV are used in high quality lubricants. The API base oil rating is shown in Table 1. Table 1. API base oil rating Group III oils are very high viscosity index (VHVI) base oils produced by modern methods from hydrocracking crude oil followed by isomerization of the waxy linear paraffins to produce branched paraffins. Group III oils also include base oils produced from Slack Wax paraffins of mineral oils, and from waxes obtained by Fischer-Tropsch synthesis (GTL waxes), for example from coal or natural gas employing corresponding isomerization techniques. Group IV are synthetic polyalphaolefins (PAO) A similar classification is also employed by the ATI EL (European Association of Lubricants Industry Technique), such classification also includes Group VI: Internal Polyolefins ( In addition to the official classification, Group 11+ is also commonly used in this field, this group comprises saturated and non-sulfur base oils which have viscosity indexes of more than 110 but below 120. In these classifications, saturated hydrocarbons include compounds. paraffinic and naphthenic, but not aromatic. for basic raw materials according to API 1509 as: "A basic raw material is a lubricant component that is produced by a single manufacturer to the same specifications (regardless of food source or manufacturer location); which receives the same specification from the manufacturer; and which is identified by a unique formula, product identification number, or both. Basic raw materials can be produced using a variety of different processes. "Base oil is the basic raw material or mixture of basic raw materials employed in API licensed oil. The known basic raw material types are 1) Mineral oil (paraffin, naphthenic, aromatic), 2) Synthetic (polyalphaolefins, alkyl aromatics, diesters, polyol esters, polyalkylene glycols, phosphate esters, silicones), and 3) vegetable oil. especially the automotive industry has required lubricants and therefore base oils with improved technical properties. Increasingly, specifications for finished lubricants require products with excellent low temperature properties, high oxidation stability and low volatility. Generally lubricating base oils are base oils. having a kinematic viscosity of about 3 cSt or greater at 100 ° C (KV100); (PP) of about -12 ° C or less, and viscosity index (VI) about 120 or greater. In addition to low spill points low temperature fluidity of multi-grade engine oils is required to ensure that in cold weather the engine starts easily. Low temperature flowability is demonstrated as visible viscosity in cold crankshaft simulator tests at -5 to -40 ° C. Lubricating base oils that have a KV100 of about 4 cSt typically should have a CCS viscosity at -30 ° C (CCS-30) less than 1800 and oils that have a KV100 of about 5 cSt should have a CCS-30 less than 2700. Lowest value is the best. In general, lubricating base oils should have a Noack volatility no higher than conventional Group I or Group II light neutral oils in circulation. Currently, only a small fraction of the base oils manufactured today can meet these required specifications. It is no longer possible to produce lubricants that meet the specifications of the most demanding car manufacturers from conventional mineral oils. Typically, mineral oils often contain very high concentrations of aromatic compounds, sulfur, and nitrogen, and in addition they also have high volatility and a modest viscosity index, that is, viscosity-temperature dependence. In addition, the response of mineral oils to antioxidant additives is often low. Synthetic base oils and so-called semi-synthetic oils play an increasingly important role especially in automotive lubricants such as engine and gear oils. A similar development can be observed with respect to industrial lubricants. The service life of lubricants is desirably as long as possible, thereby avoiding frequent oil changes by the user, and also allowing extended vehicle maintenance intervals for example in commercial transport. Over the past decade, passenger car engine oil change intervals have increased fivefold, at best 50,000 km. For heavy duty vehicles, engine oil change intervals are now at the 100,000 km level. Lubricant production is influenced by the increasingly common "Life Cycle Approach" (LCA) with regard to the environment, health and product safety factors. What is targeted by the LCA is an extended product life, and minimal damage to the environments associated with product production, use, handling and disposal. Longer oil change intervals of high quality base oils result in reduced consumption of raw materials based on nonrenewable mineral crude, and lower quantities of hazardous waste oil products.

In addition to demands on engine technology and base oil production, also stringent environmental requirements drive the industry to develop more sophisticated base oils. Sulfur-free fuels and base oils are required to take full effect of new and efficient anti-pollution technologies in modern vehicles and to cut emissions of nitrogen oxides, hydrocarbons and volatile particles, as well as to achieve direct reduction of sulfur dioxide in exhaust gases. -ment. The European Union has decided that these fuels will be available to the market from 2005 and they should be the only form for sale from 2009. Conventional mineral oil base oils contain sulfur, nitrogen, aromatic compounds, and typically also volatile compounds. They are less suitable for new engines and therefore also more environmentally harmful than newer basic oils without aromatics and sulfur.

Nowadays, the use of recycled oils and renewable raw materials in the production of lubricants is often an object of interest. The use of renewable raw materials of biological origin instead of non-renewable fossil raw materials to produce hydrocarbon components is desirable because fossil raw materials are exhaustible and their effect on the environment is detrimental. Problems associated with recycled oils include complicated purification and reprocessing steps to obtain high quality base oils. In addition, developing an extensive recycling and operating logistics system is costly.

For now, only esters are employed in renewable and biological lubricants. The use of esters is limited to some special applications such as refrigeration compressor lubricant oils, bio-hydraulic oils and metal beneficiation oils. In normal automotive and industrial lubricants, they are mainly employed on additive scale. The high price also limits the employment of esters. In addition, esters employed in motor oil formulations are not interchangeable with other esters without performing new engine tests, even in cases where the chemical composition of the substituent ester is in principle entirely similar. Instead, base oils consisting of pure hydrocarbon structure are partially interchangeable. There are also some technical problems associated with esters. As polar compounds, esters are more prone to seal-swell than pure hydrocarbons. This has created many problems concerning elastomers in hydraulic applications. In addition, base ester oils are hydrolysed, easier-to-produce acids, which in turn cause corrosion in lubrication systems. Furthermore, the even greater disadvantage of esters is that additives developed for nonpolar hydrocarbon base oils are not effective for ester base oils.

Processes in which triglycerides are cross-linked in a controlled manner employing a suitable metal salt or peroxide initiator, which easily capture hydrogen from the C-H bond, together with adequate amounts of oxygen are known in the art. Some cross-linking is also caused by unheated atmospheric oxygen, the reaction slowing down, however. This crosslinking is based on oxygen-oxygen bonds formed in the molecules. During triglyceride crosslinking, the degree of crosslinking can be controlled by processing time and kinematic viscosity. Viscosity increases with crosslinking as a function of time, and decreases as the product decomposes.

Also a batch thermal process based on double bond reactions for the production of refined triglyceride flaxseed oil is known, with carbon dioxide being introduced into the reactor to prevent oxidation. In this case, crosslinking is based on the carbon-carbon bonds formed in the molecules. Thermal decomposition products are removed by entrainment with the carbon dioxide gas stream, or alternatively by vacuum. Crosslinking is an exothermic reaction and therefore both efficient heating to provide the reaction and efficient cooling to prevent product overheating are required to maintain the temperature between 280 and 300 ° C. In addition, the reaction vessel should be cooled rapidly after reaching the desired viscosity, indicating the degree of crosslinking.

In Kirk-Othmer: Encyclopedia of Chemical Technology, 3rd Ed., Vol. 7, Dimer acids, p. 768 A method is presented for the production of dimeric acids of unsaturated carboxylic acids with a radical reaction employing a cationic catalyst, the reaction temperature being 230 ° C. In addition to unsaturated, branched acyclic dimeric acid as the main product, mono and bicyclic dimers are also formed. Unsaturated alcohols may be oligomerized in a similar manner as unsaturated carboxylic acids using heating and / or catalyst to produce alcohol dimers. A branched unsaturated acyclic diol dimer is the main product.

In Koster R.M. et al., Journal of Molecular Catalysis Chemical 134 (1998) 159-169, the oligomerization of carboxylic acids, carboxylic acid methyl esters, and synthetic alcohols and olefins is described, yielding corresponding dimers.

Fatty alcohol dimer, carboxylic acid dimer, carboxylic acid methyl ester dimer, and cross-linked triglyceride products may be employed in lubricant applications, but since the products contain heteroatoms, they are endowed with corresponding weaknesses. as base oils derived from esters.

Processes in which oxygen from an ester or carboxylic acid is removed are also known. Decarboxylation of fatty acids results in hydrocarbons having a lower carbon atom than the original molecule. The viability of decarboxylation varies greatly with the type of carboxylic acid employed as the starting material. Activated carboxylic acids containing electron attracting substituents at the alpha or beta position with respect to the carboxylic group spontaneously lose carbon dioxide at slightly elevated temperatures. In this case, the RC-COOH bond is weakened by the deviation of electrons along the carbon chain.

With other types of carboxylic acids, the hydrocarbon chain produces an opposite increase in electron density in alpha carbon, and so carbon dioxide breakdown is difficult. A suitable catalyst contributes to the reaction. In Maier, W.F. et al., Chemische Berichte (1982), 115 (2), 808-812, hydrocarbons are produced from carboxylic acids that employ heterogeneous Ni / Al 2 O 3 and Pd / Si 2 O catalysts at 180 ° C under a hydrogen atmosphere.

Combined decarboxylation and hydrodeoxygenation of oxygen-containing compounds are described in Laurent, E., Delmon, B .: Applied Ca-talysis, A: General (1994), 109 (1), 77-96, and 97-115, in which oils The biomass-derived pyrolysis plants were hydrodesoxygenated using sulfurized ΟοΜο / γ-Α1203 and ΝίΜο / γ-ΑΙ203 catalysts at 260 to 300 ° C under a hydrogen pressure of 7 MPa. Hydrodeoxygenation step reactions are highly exothermic, and require high amounts of hydrogen.

No. 100248 discloses a two step process wherein the intermediate distillate is produced from vegetable oil by hydrogenating the carboxylic acids or triglycerides of the vegetable oil. to produce linear normal paraffins, followed by isomerization of said n-paraffins to produce branched paraffins. Conditions of this hydrogen treatment include a temperature between 330 and 450 ° C, a pressure of 3 MPa, and a net hourly space velocity (LHSV) of 0.5 to 5 l / h. In the isomerization step a temperature between 200 and 500 ° C under higher than atmospheric pressure and LHSV of 0.1 to 10 l / h were employed.

In isomerization processes, very expensive noble metal catalysts and highly sensitive to catalyst poisons are employed. Starting materials from biological sources that contain high amounts of oxygen providing water, carbon monoxide, and carbon dioxide when the starting material is processed. Further, said biological source materials often contain nitrogen, sulfur and phosphorus compounds known as catalyst poisons and noble metal catalyst inhibitors. They produce decreased catalyst life, and cause frequent regeneration of required catalysts unless removed prior to the isomerization process. The typical basic structural unit of vegetable and fish oils and animal fats is a triglyceride. Triglyceride is a glycerol ester with three fatty acid molecules having the structure below: wherein R1, 1¾ and R3 represent C4-C30 hydrocarbon chains. Fatty acids are carboxylic acids having long unbranched hydrocarbon chains. Hydrocarbon chain sizes are mainly 18 carbons (C18). C18 fatty acids are typically attached to the intermediate glycerol hydroxyl group. Typical carbon numbers of fatty acids attached to the two other hydroxyl groups are identical, being between carbon numbers C14 and C22. The fatty acid composition of the biological source material may vary considerably between feedstocks from different sources. Although several double bonds may be present in fatty acids, they are unconjugated, but at least one intermediate -CH2 unit is in between. With respect to the configuration, the double bonds of natural fatty acids are cis-form, with hydrogen atoms thus located on the same side of the rather rigid double bond. As the number of double bonds increases, they are usually located at the free end of the chain. Hydrocarbon chain sizes and double bond numbers depend on the various vegetable or animal fats or waxes that serve as the source of fatty acid. Animal fats typically contain more saturated fatty acids than unsaturated fatty acids. Fish oil fatty acids contain high amounts of double bonds, and the average size of hydrocarbon chains is higher compared to fatty acids from vegetable oils and animal fats. Fatty acid composition plays an important role in the evaluation of oxidation resistance, thermal resistance, and low temperature properties of the feedstock subjected to oligomerization, as well as the type of oligomerization products.

Waxes are mainly esterified carboxylic acids with alcohols that have long chains. In addition, the waxes contain varying amounts of paraffins (n-alkanes), ketones, and diketones, primary and secondary alcohols, aldehydes, alkane acids (carboxylic acids), and terpenes. The carbon numbers of said carboxylic acid and alcohol chains are typically between C 12 and C 38.

Prior to processing, starting materials of biological origin are generally pretreated by any suitable known methods such as thermally, mechanically for example by shear forces, chemically for example with acids or bases, or physically with radiation, distillation, cooling, or filtration. The purpose of such chemical and physical pretreatments is to remove impurities by interfering with the process or poisoning the catalysts, and to reduce unwanted side reactions.

In a hydrolysis treatment, oils and fats react with water producing free fatty acids and glycerol as the product. Three major processes for the industrial production of fatty acids are known: high pressure triglyceride vapor division, basic hydrolysis, and enzymatic hydrolysis. In the vapor division process, the hydrolysis of triglycerides using steam is performed at temperatures between 100 and 300 ° C, under a pressure of 1 to 10 MPa, the preferred conditions being 250 to 260 ° C and 4 to 5.5 MPa. Metal oxides such as zinc oxide may be added as the catalyst to accelerate the reaction. High temperature and pressure contribute to the dissolution of fats in water. Paraffin synthetic synthetic oils produced by oligomerization are known in the art, the typical ones being PAO (polyalphaolefins) and PIO (internal polyolefins). In their production, crude oil olefinic starting materials are employed, said starting materials containing no heteroatoms. The development of polyalyolefin type base oils was started in the 1930s in both the U.S. and Germany where mainly products with superior low temperature properties suitable for aircraft were developed. 1-Alkene monomers to be employed as starting materials for PAO are typically produced from ethylene. With respect to commercial PAOs, C8-C12 alpha olefins or C14-C18 alpha olefins are mainly employed as starting materials. In PAO production, the monomer is thermally polymerized using either Ziegler or Friedel-Crafts type catalysts or using zeolite catalysts to produce heavier products followed by distillation to obtain desired product fractions, and hydrogenated to produce saturated paraffins. It is possible to produce PAO products belonging to various viscosity classes, the typical representatives having kinematic viscosities of 2, 4, 6 and 8 mm2 / s at 100 ° C (KV100). In addition, particularly thick base oils PAO40 and PAO10Q having KV100 values of 40 and 100 mm2 / s are produced, said base oils generally being employed for the production of thick lubricants, and as viscosity index (VII) enhancers. PAO products have high viscosity indexes, and at the same time, excellent low temperature properties, spill points being as low as -60 ° C. Because lighter monomeric compounds are distilled off, product volatilities are low and flash points are high. Oxidation resistance is quite modest without antioxidant additives. IOPs are produced by oligomerization of internal olefins, whose double bonds are statistically distributed over the entire length of the hydrocarbon chain. Internal olefins can be produced by dehydrogenation of crude oil derived n-paraffins. The molecular structures of the products produced from C15-C16 internal linear olefins differ from those of PAO. Compared to PAO, IOP properties are more unfavorable; and the viscosity index is lower, the pour point is more unfavorable, and the volatility is higher. Considering the quality, IOPs are between PAO and VHVI. The production technology for IOP is similar to that for PAO, with the exception of a more aggressive catalytic system for oligomerization of less reactive internal olefins. The solubility of additives in PAO and IOP is quite poor due to lack of polarity. Esters are often employed in formulations to improve solubility. The use of starting materials of biological origin containing heteroatoms has not been reported so far or optionally thermally and / or chemically and / or physically and / or mechanically treated intermediates in the production of high quality saturated base oils.

Based on the above instruction, it can be seen that there is an obvious need for a new alternative process for the production of hydrocarbon components preferably from biological source materials, and to avoid problems associated with prior art solutions or by least reduce them substantially. There is also a need for non-polar saturated base oils that meet the quality requirements for high quality base oils, said base oil being preferably of biological origin and having more preferable effects on the environment and end users. than traditional mineral base oils. In addition, there is a need for a process based on the use of renewable feedstocks, thereby saving nonrenewable feedstocks.

Sources of the Invention An object of the invention is a process for producing a saturated hydrocarbon component.

A further object of the invention is a process for producing a saturated hydrocarbon component in which starting materials of biological origin are employed.

Another object of the invention is a process for producing a new type of base oils.

Still another object of the invention is a process for the production of saturated base oils that do not contain heteroatoms of starting materials of biological origin.

In addition, another object of the invention is a process for producing saturated diesel components and gasoline components that do not contain heteroatoms of biological source starting materials.

An object of the invention is furthermore a base oil that meets the requirements of APf Group III.

Characteristic aspects of the process and base oils of the invention are set forth in the appended claims.

General Description of the Invention The process of the invention comprises an oligomerization step wherein the feedstock molecules react with each other thereby increasing the number of carbons of the obtained component and also a deoxygenating step. Said deoxygenation may either be performed either as a hydrodeoxygenation reaction or de-carboxylation / decarbonylation reactions. In addition, the process of the invention may also comprise an optional isomerization step for isomerization of lighter products, and / or a finishing step. The feedstock for the process is preferably of biological origin.

In this context, oligomerization refers to dimerization, trimerization and tetramerization reactions, as well as polymerization and cross-linking reactions. The oligomerization step of the process of the invention is performed to extend the hydrocarbon chain of unsaturated carboxylic acids and / or derivatives thereof, such as esters, anhydrides and alcohols of one monomeric unit to produce a two-monomeric dimer, and to higher oligomers. In this oligomerization reaction, double bonds of the components react with each other under the influence of heat and / or a catalyst. Carboxylic acids and derivatives thereof also include fatty acids and derivatives thereof. The number of carbons of carboxylic acids and derivatives thereof is at least C4. Fatty acids of biological origin and / or derivatives thereof are preferably employed. Deoxygenation refers here to the removal of oxygen either by hydrodeoxygenation or by decarboxylation / decarbonylation reaction. On deoxygenation, the structure of the biological starting material will be converted to either paraffinic or olefinic according to the catalyst and reaction conditions employed.

In this context, hydrodeoxygenation (HDO) refers to the removal of oxygen through hydrogen. Water is released in the reaction when esters, alcohols, anhydrides or carboxylic acid groups are decomposed. All atoms of oxygen, nitrogen, phosphorus and sulfur are removed.

Decarboxylation refers here to the removal of oxygen as carbon dioxide, and decarbonylation refers to the removal of oxygen as carbon monoxide.

In this context, isomerization refers to the linear hydrocarbon hydroisomerization (paraffins) resulting in a branched structure. The term "saturated hydrocarbon" as used in the descriptive report refers to paraffinic and naphthenic compounds, but not to aromatics. Paraffin compounds can either be branched or linear. Naphthenic compounds are cyclic saturated hydrocarbons, ie cycloparaffins. Such a hydrocarbon with a cyclic structure is typically derived from cyclopentane or cyclohexane. A naphthenic compound may comprise a single ring structure (mononaphthene) or two isolated ring structures (isolated dynaphene), or two fused ring structures (fused disaphthene) or three or more fused ring structures (polycyclic naphthenes or polyphenols). Saturated basic oils herein comprise saturated hydrocarbons. Carboxylic acids designated for example C18: 1 mean C18 chain with a double bond.

In this context, pressures are gauge pressures relative to normal atmospheric pressure. The classification of the periodic table of elements is the deiUPAC classification.

In this context, the range of the carbon number range refers to the difference in carbon numbers of the largest and smallest molecules plus one in the final product. The invention is now illustrated with attached figure 1 without wishing to limit the scope of the invention to the embodiment of said figure.

Figure 1 shows a preferred embodiment of the process according to the invention. One or more feedstock (s) selected from the group consisting of: triglyceride feed stream 1, fatty acid feed stream 2, feed esters feed stream 3 fatty acids with alcohols having short chains 3, fatty acid anhydride stream 4, and fatty alcohol stream 6 are introduced into oligomerization reactor 10 either as separate components or as mixtures. Part of the lighter product fraction to be recycled (e.g. 52), or hydrocarbon stream 201 may optionally be introduced into oligomerization reactor 10 as a diluent. Diluent stream 202 comprises recycled stream 52, or hydrocarbon stream 201, or a mixture thereof. The product 11 containing reactive feedstock components in the double bonds, and hydrogen as stream 7 are passed from the oligomerization reactor 10 to an optional prehydrogenation reactor 20 optionally also receiving a diluent stream 202. The hydrogenated product in the double bonds of prehydrogenation reactor 20 is passed as stream 21, and hydrogen is optionally passed as stream 7 to a deoxygenation reactor 30 optionally also receiving a diluent 202. In the case where deoxygenation is performed as decarboxylation / decarbonylation reaction , a mixture of hydrogen 7 and an inert gas for example nitrogen may be employed as the gas stream (not shown in the figure). The saturated hydrocarbon-containing product of deoxygenation reactor 30 is passed as stream 31 to a distillation and / or separation unit 40 for the separation of various product fractions, gas 44, gasoline 43, diesel 42, and base oil 41. Lighter gasoline and diesel, respectively 43 and 42, are optionally isomerized in hydroisomerization unit 50 in the presence of hydrogen 7, thereby producing gasoline and diesel streams, respectively 51 and 52, containing branched hydrocarbons.

Particularly in the case where fatty acids 2 and / or fatty acid esters 3 and / or fatty alcohols 6 are oligomerized, product stream 12 may be removed from oligomerization reactor 10 followed by separation of non-oligomerized components for example by distillation. Light non-oligomerized components are recycled back to oligomerization reactor 10 as stream 61, and oligomerized components can be passed to prehydrogenation 20 as stream 62. In recycling, distillation stream 63 can be recycled. low temperature filtration 80 wherein saturated components 81 are separated from components 82 having double bonds to be passed for oligomerization 10. Alternatively, distillate 61 may be passed to post oligomerization reactor 70, in which carboxylic acids are not 8 with smaller molecules, or olefins 5 may be introduced for branching unsaturated components the linear non-oligomerized ones. The product containing components of the reactive feedstock in the double bonds is passed from post-Jigomerization reactor 70 as stream 71 to an optional prehydrogenation reactor 20.

Detailed Description of the Invention It has now surprisingly been found that with the process of the invention comprising oligomerization and deoxygenation steps and an optional isomerization step, high quality hydrocarbon components and particularly saturated base oils can be produced from unsaturated carboxylic acids containing heteroatoms, and derivatives thereof, particularly fatty acids, fatty acid esters, fatty alcohols, respective fatty acid anhydrides of biological origin, and / or mixtures thereof. The problems of prior art processes and products obtained therefrom can be avoided, or at least substantially reduced by the process of the invention.

In the process of the invention, especially oligomerization reactions of materials of biological origin may be used in combination with deoxygenation reaction to produce saturated base oils in a new way. For the oligomerization of unsaturated carboxylic acids and / or derivatives thereof, such as fatty acids, fatty acid esters, fatty alcohols, fatty acid anhydrides, and / or mixtures thereof, monomers are converted to two-monomer dimers and into oligomers. higher numbers. Where biological source starting materials are employed for the production of base oils, it is necessary to extend the size of the hydrocarbon chain to reach the carbon number range required in base oil applications, leaving only carbon-carbon bonds. in the main structure of the molecule. According to the invention, this is accomplished by allowing compounds having double bonds to react with one another, thereby producing desired carbon-carbon bonds, and also producing hydrocarbons having carbon numbers in the range of C18 to C550. In base oil applications, the carbon number range is typically from C18 to C76, and particularly the carbon number range of thick base oils may even be from C150 to C550. In the oligomerization reaction, for example double bonds of triglyceride molecules react with each other, thereby forming a polymeric triglyceride network. With other feedstocks, mainly dimers, trimers, and tetramers are formed. In case the feedstock contains polyunsaturated hydrocarbon chains, after oligomerization and deoxygenation, larger amounts of ring-structure trimers and hydrocarbons are obtained than with monounsaturated hydrocarbon chains.

In the process of the invention the feedstock of biological and / or synthetic origin is oligomerized and deoxygenated. Oligomerization of unsaturated feedstock components is preferably performed first, followed by deoxygenation to obtain saturated paraffins without heteroatoms. Alternatively, the unsaturated feedstock is first subjected to deoxygenation to remove heteroatoms, followed by oligomerization of the olefin product obtained, but deoxygenation is then performed by decarboxylation or decarbonylation reaction, since the hydrogenation reaction -drodeoxygenation is in this case inadequate.

Following deoxygenation, the process may also comprise an optional isomerization of the lighter components. Linear normal paraffins that have shorter chains, not belonging to the basic oil carbon class, and produced as process by-products, can be isomerized to introduce branching in the hydrocarbon chain improving the cold flow properties of the product. These isomerized products may be employed for example as gasoline or diesel components, and also, components having carbon numbers from C18 to C24 may also be employed as light base oil components. The process may also comprise an optional prehydrogenation step prior to deoxygenation, an optional postoligomerization step following the current oligomerization step, optional intermediate purification steps, product recycling steps, and a finishing step . Feed materials may optionally undergo one or more pretreatment steps (s), for example purification.

Feedstock In the process of the invention, the feedstock comprises one or more component (s) selected from the group consisting of triglycerides, carboxylic acids having carbon numbers from C4 to C38, esters of C4 to C38 carboxylic acids and . C1-C11 alcohols, C4-C38 carboxylic acid anhydrides, and C4-C38 alcohols. The feedstock is preferably selected from the group consisting of triglycerides, fatty acids having carbon numbers of C4 to C24, esters of C12 to C24 fatty acids and C1-C3 alcohols, C12-C24 anhydrides, fatty acid, and C 12 -C 24 fatty alcohols, and mixtures thereof. Preferably the feedstock is from bio-based starting materials or mixtures thereof.

Suitable starting materials of biological origin are selected from the group consisting of: a) vegetable fats, vegetable oils, vegetable waxes; animal fats, animal oils, animal waxes; fish fats, fish oils, fish waxes and mixtures thereof, and (b) free fatty acids or fatty acids obtained by hydrolysis, acid transesterification or pyrolysis reactions of vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and mixtures thereof, and (c) esters obtained by transesterification of vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, vegetable oils fish, fish waxes and mixtures thereof, and d) esters obtained by esterifying free fatty acids of plant, animal and piscine origin with alcohols, and mixtures thereof, and e) fatty alcohols obtained as fatty acid reduction products from vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and mixtures thereof, and f) fats and oils waste and recycled food classification, and genetically engineered fats, oils and waxes, and mixtures thereof, and (g) mixtures of said starting materials.

In this context, plants and animals also include algae and insects respectively. The starting material of biological origin may also contain free carboxylic acids and / or carboxylic acid esters, or oligomerization products of biological starting materials, without substantially interfering with the process. Suitable feed materials are also all types of compound mentioned which are synthetically produced wholly or partially.

Since the purpose of the process is the oligomerization of double bonded components, the feedstock preferably contains at least 50%, and more preferably at least 80% by weight, of unsaturated and / or polyunsaturated compounds. . The unsaturated compound is preferably a monounsaturated component, particularly preferably a C16: 1 and / or C18: 1 component present in the feedstock in concentrations above 40%, and preferably above 70% by weight. .

Examples of suitable biological starting materials include fish oils such as Baltic herring oil, salmon oil, herring oil, tuna oil, anchovy oil, sardine oil, and horse oil; Vegetable oils such as rapeseed oil, rapeseed oil, canola oil, high oil, sunflower seed oil, soybean oil, corn oil, hemp oil, olive oil, cottonseed oil, mustard oil, palm oil, peanut oil, castor oil, jatropha seed oil, palm seed oil, and coconut oil; In addition, suitable are also animal fats such as lard, tallow, as well as residual and recycled food grade fats and oils, as well as genetically engineered fats, waxes and oils. In addition to fats and oils, suitable starting materials of biological origin include animal waxes such as beeswax, Chinese wax (insect wax), varnish wax, and lanolin (wool wax), as well as vegetable waxes such as beeswax. carnauba palm, ouricuri palm wax, jojoba seed oil, candelilla wax, esparto wax, japan wax, and rice bran oil. The process may also be employed for processing mixtures of bio-feed materials and synthetic feed materials by employing additional feed materials produced from other processes or synthetic feed materials, appropriate, for the process step in question. Also pure synthetic feed materials are suitable, but in this case the products are not based on renewable natural resources.

If desired, also linear olefins and ring-bearing olefins, preferably C2-C14 olefins, may also be added to the feedstock, thereby allowing molecular weight increase with lower carbon numbers than C12-14. C24 typical carboxylic acids. High oil turpentine fraction components olefins such as pinene alpha, and / or compounds having sugar-derived double bonds, and / or unsaturated compounds produced by carboxylic acids by metathesis, and / or synthetic compounds such as ethylene or propylene may be employed as suitable additional olefinic components.

In oligomerization, also unsaturated dicarboxylic acids that have shorter chains (<C12), carboxylic acids, alcohols, and alkyl esters may be employed as additional raw materials, allowing lower molecular weight to increase carbon than C12-C24. typical carboxylic acids, or derivatives of carboxylic acids. Suitable unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 2-methylene glutaric acid, and muconic acid.

In the optional postoligomerization reaction of the invention, for example the above molecules having short chains may be oligomerized to carboxylic acids or alkyl esters of a carboxylic acid or triglycerides or other double bonded molecules. Double bonds of compounds derived from carboxylic acids are generally located in the middle of the hydrocarbon chain. Smaller molecules are reacted with double bonds to produce linear or ring structures located in the hydrocarbon chain medium.

Since the catalyst cycle length is short in carboxylic acid processes, the feedstock may first be converted into esters or alcohols that are less aggressive to the catalyst. Triglycerides may be transesterified with an alcohol to obtain alkyl esters. Triglycerides break down to form an ester with alcohol and glycerol. Typically methanol is employed as alcohol, but also other C1-C11 alcohols may be employed. Typical conditions for transesterification are as follows: temperature between 60 and 70 ° C, pressure between 0.1 and 2 MPa. Excessive amounts of sodium and potassium hydroxides dissolved in methanol are employed as catalysts. Esterification of carboxylic acids and alcohol requires high temperature and pressure (e.g. 240 ° C and 9 MPa), or acidic conditions. Carboxylic acids may also be reduced in known manner to fatty alcohols, or by direct reduction of acidic groups to alcohols with lithium aluminum hydride, thus remaining double bonds in alcohols, or by hydrogenation of the alkyl esters of carboxylic acids to produce alcohols. unsaturated fatty acids employing a copper-zinc catalyst at a temperature between 200 and 230 ° C and under a hydrogen pressure between 20 and 30 MPa. In the hydrogenation reaction, the alcohol employed for carboxylic acid esterification is released and can be recycled again for esterification, while unsaturated fatty alcohols are passed on to oligomerization.

At various stages of the process, hydrocarbons may be employed as diluents in the feedstock. The hydrocarbon may for example be of biological origin and die-sel fuel boiling in the range 150 to 400 ° C, typically 180 to 360 ° C. The biological starting material producing the feedstock is preferably pretreated by known methods for example to remove impurities. The triglyceride hydrolysis reaction can be used to produce carboxylic acids for use as a food for oligomerization step. Alternatively, triglycerides may be hydrolyzed following oligomerization. In hydrolysis, glycerol is obtained as the byproduct, and thus no hydrogen is consumed in the HDO step during glycerol hydrogenation to produce propane gas. For example, either the feedstock or product may be fractionated by distillation to narrower fractions with respect to boiling ranges or carbon numbers, and furthermore impurities from the feedstock or final product may be removed by filtration through suitable filter aid. The Process Oligomerization Step According to a preferred embodiment of the process of the invention, the feedstock comprising at least one double bonded component is selected from the group of triglycerides, carboxylic acids, acid anhydrides, and / or fatty alcohols and oligomerized. The feedstock contains at least 50% by weight of unsaturated and / or polyunsaturated compounds. One of the feedstock components is preferably selected as the main starting material for the oligomerization step and the oligomerization conditions are adjusted according to this main starting material. Other feed materials may be mixed with said main starting materials as long as they do not interfere with the process, or are advantageous for processing.

Oligomerization reactions are heat catalyzed and a suitable catalyst. Suitable catalysts include cationic clay catalysts, preferably zeolite catalysts, particularly preferably montmorillonite. Oligomerization reactions of carboxylic acids may be enhanced by additional reagents such as water. In the oligomerization of carboxylic acids, up to 10%, preferably from 0.1 to 4%, and particularly preferably from 1 to 2% by weight of water is added to the feedstock. It is not preferable to employ excessive amounts of water because non-dimerized carbon-carbon "stolides" are then produced as by-products.

Suitable oligomerization reactors include fixed bed reactors and mixing tank reactors. Diluents to adjust oligomerization may be employed in the reaction. The diesel or other hydrocarbon fraction obtained from the process is a suitable diluent that can be recycled. The pressure of the oligomerization step is between 0 and 10 MPa, the temperature between 100 and 500 ° C, preferably 0 to 5 MPa, and 200 to 400 ° C, respectively. In this case the reaction is carried out as a batch reaction, the catalyst amount is 0.01 to 30 wt% of the total reaction mixture, preferably 0.5 to 10 wt%. In this case a fixed bed reactor is employed, the amount of feedstock, expressed as grams per hour per gram of catalyst, ranges from 0.1 to 100 l / h.

In a mixed tank reactor, the reaction time is less than 16 hours, preferably less than 8 hours, particularly preferably less than 4 hours. In the case where short residence time is employed, the lighter non-oligomerized components may be separated from the heavier components already oligomerized for example by distillation, followed by recycling of the lighter oligomerization components. During recycling, non-reactive saturated components may be separated from components that have double bonds eg by low temperature filtration. Saturated components are passed to deoxygenation, and optional isomerization for branching hydrocarbon chains.

Prehydrogenation Step The activity of hydrogenation catalysts is primarily lost due to the coke formed on the catalyst surface, and therefore the product of the oligomerization step may optionally be subjected to prehydrogenation under mild conditions to hydrogenate the double bonds, and further reduce coke formation in the next step of deoxygenation. Prehydrogenation is performed in the presence of prehydrogenation catalyst at a temperature between 50 and 400 ° C under a hydrogen pressure ranging from 0.1 to 20 MPa, the WHSV flow rate being between 0.1 and 10 l / h, preferably at a temperature between 150 and 250 ° C, under a hydrogen pressure ranging from 1 to 10 MPa, the flow rate being from 1 to 5 l / h. The prehydrogenation catalyst contains Group VIII and / or VIA metals from the periodic table of elements. The prehydrogenation catalyst is preferably a supported Pd, Pt, Ni, NiMo or CoMo catalyst, the support being any alumina and / or silica.

Deoxygenation Step Deoxygenation may alternatively be performed either as hydrodeoxygenation or decarboxylation / decarbonylation. Deoxygenation performed as hydrodeoxygenation (HDO) is suitable for all feed materials. In the HDO step, the oligomerized and optionally prehydrogenated oxygen stream is passed to the HDO catalyst bed comprising one or more catalyst bed (s). In the HDO step, the pressure is between 0 and 20 MPa, preferably between 1 and 15 MPa, particularly preferably from 3 to 10 MPa, the temperature being from 100 to 500 ° C, preferably from 200 to 400 ° C, particularly preferably from 250 to 350 ° C, the WHSV flow rate is from 1 to 5 l / h, particularly preferably WHSV from 1 to 3 l / h. In the HDO stage, special hydrodesoxygenation catalysts containing a Group VIII metal and / or VIA from the periodic table of elements, and a support can be employed. The HDO catalyst is preferably a supported Pd, Pt, Ni, NiMo or CoMo catalyst, the support being any alumina and / or silica.

Where the feedstock contains carboxylic acids and / or carboxylic acid esters, deoxygenation may be performed using a decarboxylation / decarbonylation reaction. In the decarboxylation / decarbonylation reaction, the feedstock and an optional diluent are introduced into the catalyst bed. The reaction takes place in the liquid phase and can be performed at atmospheric pressure. However, it is preferable to employ vapor pressure according to the reaction temperature of the reaction mixture. Depending on the feedstock, the pressure in the decarboxylation / decarbonylation step is between 0 and 20 MPa, preferably between 0.1 and 20 MPa, the temperature is from 200 to 400 ° C, preferably from 250 to 350 ° C. The flow rate WHSV is from 0.1 to 10 l / h, preferably WHSV from 1 to 5 l / h. In the decarboxylation / decarbonylation step, special catalysts are employed. The catalyst contains a Group VIII and / or VIA metal from the periodic table of elements, such as a supported Pd, Pt, Ni, NiMo or CoMo catalyst, the support being any alumina and / or silica and / or activated carbon. . The decarboxylation / decarbonylation catalyst is preferably carbon-supported Pd if no hydrogen is employed in the process, and alumina-supported sulfurized NiMo where a mixture of hydrogen and an inert gas such as nitrogen is employed in the process. process. Functional groups no longer exist in the decarboxylation / decarbonylation step product and the products contain only carbon and hydrogen. The number of carbons has been reduced by one carbon per functional group removed. In the case where deoxygenation is performed as decaroxylation / decarbonylation, oligomerization may be performed prior to deoxygenation, and therefore the feedstock of the oligomerization step contains unsaturated carboxylic acids and / or carboxylic acid esters. In the case where oligomerization is performed after the decarboxylation / decarbonylation step, the feed from the oligomerization step contains unsaturated decarboxylation / decarbonylation compounds which have the carbon numbers reduced by one carbon per removed functional group compared to matter. raw food.

In the deoxygenation step, HDO and decarboxylation / decarbonylation reactions described above can be performed simultaneously to produce carbon dioxide or carbon monoxide from part of the functional groups and part of the functional groups is hydrodeoxygenated.

Following the deoxygenation step, light fractions may be passed with hydrogen to a separate isomerization step. The pressure of the isomerization step is from 0.1 to 20 MPa, preferably from 5 to 10 MPa. The temperature is between 100 and 500 ° C, preferably 200 to 400 ° C. In the isomerization step, special isomerization catalysts containing a Group VIII molecular sieve and metal from the periodic table of elements such as Pd and Pt may be employed. Alumina and / or silica may be employed as the support.

Following the oligomerization and deoxygenation steps, the product stream may optionally be finished to remove aromatic double bonds. In the case where the finishing step is performed using hydrogen in the presence of a catalyst, the step is called hydro-finishing. In the hydro-finishing step, the pressure is from 1 to 20 MPa, preferably from 5 to 15 MPa. The temperature is between 50 and 500 ° C, preferably 100 to 400 ° C. In the hydro-finishing step, special catalysts containing a Group VIII metal as well as alumina and / or silica may be employed. The hydro-finishing catalyst is preferably a supported Pd, Pt, or Ni catalyst, the support being any alumina and / or silica. Finishing can also be performed without hydrogen by removing the polar components using adsorption materials, for example clay or molecular sieve.

Following oligomerization, deoxygenation and optional isomerization and finishing steps, the product is fractionated, for example by distillation. Typical carbon number ranges of the product components are as follows: C1-C4 gas, C5-C10 gasoline, C11-C26 diesel, C18-C76 base oil.

If desired, the hydrocarbon component obtained as the product or other suitable hydrocarbon stream may be recycled to various process steps such as oligomerization and deoxygenation steps to improve conversion and / or selectivity, or to control the exothermic nature of the reactions. .

In one embodiment of the invention, the already oligomerized product may be oligomerized again by introducing an additional monomer (mixing tank reactor) into the process, or by repeatedly recycling the already oligomerized product during monomer addition (continuous reactor). Accordingly, especially thick base oils having carbon numbers as high as C150-C550 may be provided, said thick base oils being useful in the production of thick lubricants and as viscosity index enhancers.

It was surprisingly found that the high quality saturated non-polar hydrocarbon component preferably of biological origin, having excellent viscosity and low temperature properties, especially suitable as base oil was obtained with the process of the invention. The product is branched by carbon-carbon bonds.

A preferably hydrocarbon component of biological origin suitable as a solvent, gasoline or diesel fuel or diesel fuel component is also obtained. The diesel component or C18-C24 base oil component can be isomerized to improve low temperature properties. The gasoline component can be isomerized to increase the octane index. There is no need for isomerization in the case where short chain olefins or unsaturated short chain carboxylic acids are employed in the postoligomerization process to branch off the remaining double bonds. The carbon number and the carbon number range of the base oil both depend on the biological starting material of the feedstock and the production process. The conventional carbon number range of prior art base oil applications is from C18 to C76, while the particularly thick carbon number range of base oils can be as high as from C150 to C550. Where the KV100 kinematic viscosity range of 4 to 7 mm2 / s is desired, single-carbon branched and / or cyclic paraffins are typically obtained from feed materials containing carboxylic acids of identical chain sizes. employing the process of the invention following the oligomerization and HDO steps. The carbon number range of the base oil or base oil component produced by the combined oligomerization and HDO-decarboxylation / decarbonylation process of the invention is extremely small, the carbon number range of the product being from C30 to C32 for raw materials. feed containing typically C16 components, and from C34 to C36 for feed raw materials containing C18 components, in which case the viscosity range KV100 between 4 and 7 mm2 / s is desired. In the case where the feedstock is a mixture of C16 and C18 components, the range of the carbon number range of the product is typically seven carbons. The carbon number range of the base oil of the invention may also be at a very high level, even as high as from C150 to C550 in the case of particularly heavy base oils suitable as viscosity enhancers and viscosity index enhancers. desired.

In Table 2 below, typical carbon numbers and structures of biological base oils according to the invention (1 and 2), and prior art synthetic base oils having a KV100 of 4 to 6 mm2 / s (3 to 5 ) are presented. Most typical carbon numbers are in bold. With respect to molecular structures, the base oil or base oil component of the invention differs from prior art products as shown in the table.

In Table 2, naphthene structures are typical examples of a compound group. In structural examples, the carbon number ranges of the C18-produced oligomeric dimers No. 1 and 2 are between C34 and C36, and between C51 and C54, respectively, while the carbon number ranges of known synthetic hydrocarbon base oils The same viscosity class, such as PAO, are between C32 and C48, and C30 and C48 for PIO.

Table 2. Carbon Numbers and Typical Base Oil Structures Saturated hydrocarbons are classified according to carbon and hydrogen atoms by field ionization mass spectrometry (using FIMS) 1 C (n) .H (2n +2) paraffins 2 C (n) .H (2n) mononaphenes 3 C (n) .H (2n-2) dinaphenes 4 C (n) .H (2n-4) ■ 5 C (n) .H trinaphenes 2n-6) tetranaphthenes 6 C (n) .H (2n-8) pentanaphenes In Table 2, the percentages (% by FIMS) refer to the groups of compounds determined according to said method.

The base oil components of Table 2 are produced as follows: 1. Hydrogenated oligomerized fatty acid C18 dimer according to the invention produced from high oil 2. Hydrogenated oligomerized fatty acid C18 dimer according to the invention produced high oil content 3. C16 PAO produced by 1-hexadecene oligomerization using a heterogeneous catalyst 4. C10 PAO produced by 1-decene oligomerization using a homogeneous catalyst 5. PIO produced by internal C15-C16 olefin dimerization. Oligomerized dimers and trimers of the invention (structures 1 and 2 of Table 2) are branched at the double bonds within the C18 hydrocarbon chain, thereby having tertiary carbon pairs at adjacent carbon atoms in the molecular structure. PIO is typically a dimer produced from shorter C15-C16 hydrocarbons, while the product of the invention is a C16 and / or C18 dimer. In addition, a significant amount, even more than 50%, by FIMS of mononaphenes is present in the product of the invention.

In the prior art polyalphaolefin production method, the reaction typically occurs with double bond boron trifluoride catalysts at the terminus of the C10 chain, thereby leaving a methylene group (-CH2-) between tertiary carbons (structure 4 in Table 2 ). Where oligomerization is performed using a heterogeneous catalyst, double bonds are displaced from the alpha position, while simultaneously skeletal isomerization occurs, thereby leaving 1 to 10 methylene groups between tertiary carbons in the typical structure of the. base oil obtained (structure 3 in Table 2, for example 4 methyl groups). In the case where oligomerization is performed using a homogeneous catalyst, skeletal isomerization occurs respectively in the hydrogenation step following oligomerization, and therefore C1-C3 side branches are formed near double bonds in the molecules of structure 4 shown. Table 2. There are mainly alkyl branches in prior art PAO and IOP base oils, while ring-structure branched naphthenic components are present in the product of the invention in addition to the alkyl branches. The pour point of the high quality base oil obtained with the process of the invention is at least less than -40 ° C, and therefore the base oil is very suitable for the required low temperature conditions. The product viscosity index can be as high as 125 and is thus suitable for Group III base oil applications. The molecular weight of the product may be adjusted to the carbon number ranges required for different applications by addition of unsaturated carboxylic acids or olefins suitable for the feedstock. Carboxylic acids having small molecules, or olefins cross-linking or oligomerizing with triglyceride fatty acids form short branches in the main hydrocarbon chain of the fatty acid. In the event that other natural cyclic compounds such as pinene alpha are employed as additional components of the feedstock, molecules having side chain ring structures within the molecular chain are obtained. One or two additional components are preferably oligomerized in the product. According to the invention, corresponding products adapted with respect to hydrocarbon sizes may also be produced from other carboxylic acids and other short chain bio-components. Lighter branched components of HDO treatment are very suitable as biodiesel components. The base oil of biological origin according to the invention comprises a branched saturated hydrocarbon product. Said product is produced from biological starting material, said product containing at least 90%, preferably at least 95%, particularly preferably at least 97%, and at best 99% by weight of saturated hydrocarbons. . Furthermore, the product of the invention contains more than 20% but not more than 90%; preferably more than 20% but no more than 80%; and particularly preferably more than 20%, but not more than 60% of mononaphenes, based on the FIMS method, and less than 3.0%, preferably less than 1.0%, and particularly preferably less than 0, 1% polycyclic naphthenes by FIMS. Furthermore, the product of the invention contains up to 20%, preferably up to 10%, and particularly preferably up to 5%, and at best up to 1% by weight of linear paraffins (GC).

For base oils of the invention, the viscosity index is at least 100 and preferably at least 110, and particularly preferably at least 128, as determined by the method of ASTM D 2270. The product of the invention is branched with carbon-carbon bonds. , this structure providing the product with a very low pour point no higher than 0 ° C, preferably no higher than -10 ° C, and particularly preferably no higher than -35 ° C (ASTM D 5950).

For base oils of the invention, having a KV100 viscosity of 4 to 7 mm2 / s, the range of the carbon number range is no greater than 9 carbons, preferably no greater than 7 carbons, and particularly preferably no greater than 3 carbons. (determined by field ionization mass spectrometry, FIMS). Over approximately 50%, preferably over 75% and particularly preferably over 90% by weight of the base oil contains hydrocarbons belonging to this reduced carbon number distribution. The sulfur content of said base oil of the invention is less than 300 ppm, preferably less than 50 ppm, and particularly preferably less than 1 ppm (ASTM D 3120). The nitrogen content of said base oil of the invention is less than 100 ppm, preferably less than 10 ppm, and particularly preferably less than 1 ppm (ASTM D 4629).

The base oils of the invention contain carbon 14C isotope which can be considered as an indication of the use of renewable raw materials. The typical 14C isotope content of the fully biological product is at least 100%, determined as the radioactive carbon content based on the radioactive carbon content in the atmosphere in 1950 for a completely biological material based product (ASTM D 6866). The 14C isotope content of the base oil is lower when different biological components are employed in the processing of the product, however, said content being more than 50%, preferably more than 90%, particularly preferably more than 99%. %. In this way, even low quantities of base oil of biological origin can be detected in other types of hydrocarbon base oils. The volatility of the low boiling range base oil component obtained according to the invention is extremely low compared to similar prior art products. For base oil of the invention the volatility of the product having a KV100 of 3 cSt to 8 cSt is no more than 2271.2 * (KV100) 3.5373 wt% as determined by DIN 51581-2 (Noack Mathematical Method based on GC distillation of ASTM D 2887). The ketanic number of the product obtained with the process of the invention, suitable as a diesel component, is greater than 40, preferably greater than 55, and particularly preferably greater than 70. It contains more than 60%, preferably more than 99%. by volume of paraffins and less than 30%, preferably less than 1% by volume of aromatics based on the IP-391 method. The diesel product comprises less than 40%, preferably less than 10% by weight, of linear n-paraffins. The cloud point of the diesel component is below 0 ° C, preferably below -15 ° C, and particularly below -30 ° C. Typically, the diesel product obtained is wholly of biological origin. In the product of the invention, there are branches formed by carbon-carbon bonds, resulting in a very low cloud point structure. Due to their biological origin, said products of biological origin also contain the carbon 14C isotope indicating which renewable raw materials are employed. The 14C content of a fully biological product is at least 100%. Selection of organic feedstock has a strong influence on product composition and boiling range. In addition, the feed can be fractional distilled to fractions having reduced carbon numbers that can be adjusted for different applications. For feedstock having C16, C18, C20, and C22 hydrocarbon chain sizes, typical carbon numbers of the dimer products are respectively C32, C36, C40, and C44 following hydrodeoxygenation, with said carbon numbers are reduced by two for C30, C34, C38, and C42 following decarboxylation / decarbonylation. Since the distillation range of the product depends mainly on the hydrocarbon chain size, reduced product fractions are obtained.

Advantages of the Invention The process of the invention, and the product obtained, have a number of advantages, including for example the use of renewable raw materials instead of non-renewable feedstocks to reduce carbon dioxide emissions by contributing to greenhouse effect. A heteroatom-containing biological starting material according to the invention serves as a totally new source of raw material for high quality saturated base oils.

The process starting materials of the invention are available worldwide, and furthermore, the use of the process is not limited by significant initial investments, in contrast to for example GTL technology.

The products of the inventive process are carbon dioxide neutral with respect to their use and disposition, that is, they do not increase the carbon dioxide charge of the atmosphere, in contrast to products derived from fossil starting materials. The base oil prepared according to the present invention is hydrolytically more stable and has a structure that does not decompose under wet conditions, unlike esters and other heteroatom-containing base oils, such as fatty alcohol dimers. In addition, the oxidation resistance of saturated hydrocarbons is better than that of corresponding base oils containing unsaturated groups based on fatty acid or fatty alcohol dimers, or ester base oils. A saturated hydrocarbon component is not as easily decomposed as corrosive acid-forming esters. A non-polar saturated hydrocarbon component is obtained by employing the process of the invention by removing oxygen from alcohols, esters, or carboxylic acids in the deoxygenation step as well as heteroatoms from any feedstock impurities. Oligomerization of carboxylic acid derivatives produces a structure that has branches formed by carbon-carbon bonds following deoxygenation. In C12: 1 - C20: 1 oligomerization, the branch sizes obtained are typically from C3 to C11. Such hydrocarbons have very low pour points favorable for base oil applications, and therefore the product is liquid at very low temperatures, and moreover, has a higher viscosity index. The saturated hydrocarbon product produced is a suitable component of base oils without any mixing limitations, and furthermore is compatible with lubricant additives. The base oil of the invention is endowed with superior technical properties as compared to conventional hydrocarbon oils of the corresponding viscosity class, particularly in cases where KV100 is 4 to 7 mm2 / s. The reduced boiling range indicates that the product contains no initial light fraction, meaning considerably lighter than average molecules shown as decreased product volatility and resulting in reduced emissions in practical applications. The base oil product does not contain heavy distillation "tail" meaning t the molecules are considerably heavier than average, resulting in excellent low temperature properties of the product.

For the base oil of the invention, the number of carbons and boiling ranges are regulated by the feedstock composition. For prior art base oils, the boiling range is adjusted by distillation of the product to obtain a fraction having the desired kinematic viscosity. It is preferable for the lubricants to have basic oils with reduced carbon numbers and therefore reduced boiling ranges, and therefore the compositions contain molecules of similar size that behave under different conditions in a similar manner.

For the base oil or base oil component, the high viscosity index indicates that the amount of viscosity index improver typically employed in lubricating compositions may be reduced. It is generally known that for example in engine oils, component VII is the main cause for engine dirt. In addition, reducing the quantities of VII results in significant cost savings.

Compared to conventional base oils derived from crude oil, no sulfur or nitrogen is present in these products. The process based on purified starting materials derived from natural fatty acids allows the safe use of products in similar applications where users are exposed to said oil or oil vapor. Moreover, the response of the product of the invention to antioxidant agents and pour point lowering agents is excellent, thereby allowing longer use of the prepared lubricants of said base oil as well as their use under cold weather conditions.

Compared to esters, the base oil of the invention is more compatible with conventional base oil components derived from crude oil and other hydrocarbon base oils, also with lubricant additives. In addition, there is no similar problem with elastomers such as sealing materials as found for esters.

Advantages of the base oil of the invention include the fact that it meets the requirements for API Group II base oils, preferably Group III, and may be employed in engine oil compositions as other classification base oils. API Group II or III according to the same oil change rules. The base oil of the invention is derived from renewable natural resources as clearly observed from the 14C isotope content of the product. The 14C isotope content of the product is at least 100% for products of biological origin, and 0% for products derived from crude oil. The proportion of the base oil component of biological origin may also be determined based on the isotope content 14C of the base oil to an accuracy of at least 1%.

The low temperature properties and the ketone number of the intermediate distillate produced by the process of the invention suitable as a diesel fuel are also excellent, and the intermediate distillate is therefore suitable in required low temperature applications.

With the optional prehydrogenation step, double bond side reactions such as polymerization, ring formation, and aromatization can be reduced, said side reactions being detrimental to the viscosity properties of the products and causing coke formation in the catalyst. from HDO.

By optional recycling of unreacted feedstock components, further double bond reactions can be obtained to improve product production.

Instead of or in addition to biological starting materials, synthetic compounds having a corresponding chemical structure may also be employed in the invention as food.

The properties of the hydrocarbon components produced according to the invention and described in the following examples are excellent, and furthermore, the carbon number ranges and distillation ranges are very small. The process of the invention provides a molecular structure that has superior viscosity properties and excellent low temperature properties. The products are well-suited as base oils without mixing limitations, and in addition, the products are also compatible with lubricant additives. The invention is now illustrated by the following examples. The purpose is not, however, to limit its scope to the described embodiments or combinations thereof. The invention may also be carried out otherwise than as specifically described without departing from the appended claims.

Examples Example 1 Preparation of a vegetable oil hydrocarbon component Feedstock containing 200 ml of soybean oil, 6 g of montmorillonite catalyst, and 5 ml of distilled water was charged to a high pressure Parr reactor. The temperature was increased to 270 ° C and the oil was allowed to oligomerize thereby slowly mixing for 7 hours.

Thereafter, in the HDO step, the above oligomerized mixture was hydrogenated in the high pressure Parr reactor using activated dry NIM / Al2 O3 catalyst to produce i-paraffin. 200 ml oligomerized soybean oil mixture was hydrogenated at 325 ° C under a hydrogen pressure of 5 MPa until no acidic group was detected in the FTIR spectrum of the sample. The reaction mixture was mixed at 300 rpm. The final product was distilled, and mainly cyclic branched C36 paraffin was obtained as the product.

The properties of the obtained hydrocarbon component are shown in Table 3. Hydrocarbon components can also be produced in a similar manner from other vegetable oils and fish oils comprising double bonds.

Example 2 Preparation of a hydrocarbon component of soya oil derived carboxylic acid methyl esters Soybean oil was pretreated by transesterification with methanol under basic conditions at a temperature of 70 ° C under a pressure of 0.1 MPa in the presence of a two-step sodium methoxide catalyst. Carboxylic acid methyl esters were purified by washing with an acid and water, and then they were dried. The carboxylic acid composition of the soybean-derived methyl ester was as follows: C16: 0.11%; C18: 2.20%; C18: 1.8%; C18: 2.54%; and C18: 3.6%. The carboxylic acid methyl ester mixture obtained above was oligomerized in a high pressure Parr reactor. 200 ml of feedstock and 6 g of bentonite catalyst were introduced into the reactor, the reactor was pressurized twice with nitrogen to remove oxygen, then the temperature was raised to 350 ° C, and the methyl ester mixture of carboxylic acid was allowed to oligomerize while slowly mixing for 7.2 hours. Monomeric, dimeric and trimeric methyl esters were separated from the reaction mixture using a silica column.

Then the dimeric and trimeric methyl esters obtained above were respectively hydrogenated as described in example 1, and the final product was distilled, thereby yielding 26 wt% cyclic branched paraffin C36 and 15 wt%. C54 cyclic branched paraffin wax.

The properties of the obtained hydrocarbon component are presented in Table 3. The properties of the product are excellent, with a very small molecular distribution. Hydrocarbon components may also be made in a similar manner to other methyl esters of carboxylic acids of plant, piscine or animal origin comprising various double bonds. Process yield can be improved by recycling unreacted monomers.

Example 3 Preparation of a hydrocarbon component of high oil derived carboxylic acids In the pretreatment step, high oil free carboxylic acids were distilled. Thereafter, the carboxylic acids were oligomerized in a high pressure Parr reactor. 200 g of feedstock (carboxylic acids), 16 g of montmorillonite catalyst, and 10 g of water were introduced into the reactor. The temperature was increased to 255 ° C, and the carboxylic acids were allowed to oligomerize while mixing. slowly for 3 hours. The mixture was cooled, and the catalyst was filtered. The monomers were separated from the dimers and trimers (acids) of the reaction mixture using a silica column. The yield of the carboxylic acid dimer was 45% by weight.

In the HDO step, the dimer-containing fraction was hydrogenated as in Example 1 until no carboxylic acid peaks were present in the FTIR spectrum. Both branched and cyclic paraffin were obtained as the product.

The properties of the obtained hydrocarbon component are presented in Table 3. Hydrocarbon components can also be produced in a similar manner to free carboxylic acids derived from oils other than high oil, or hydrolyzed vegetable oil or fish or animal fats, said acids comprising double bonds.

Example 4 Preparation of a hydrocarbon component of high oil derived carboxylic acids using prehydroenation In the pretreatment step, high oil free carboxylic acids were distilled. Then, the feedstock comprised 30% C18: 1, 42% C18: 2, and 9% C18: 3 carboxylic acids by weight. In addition, the feedstock contained 2% resin acids. High oil carboxylic acids were oligomerized in a high pressure Parr reactor. 200 g of the feed mixture, 16 g of a montmorillonite catalyst, and 10 g of water were charged to a reactor. For oxygen removal, the nitrogen pressure was increased to 0.5 MPa, and the mixture was stirred at 600 rpm for a moment. The pressure was released, and the pressurization with nitrogen was repeated. Then the temperature was increased to 225 ° C, and the carboxylic acids were allowed to oligomerize while slowly mixing for two hours. The product was cooled, and the catalyst was filtered. The monomers, dimers, and trimers (acids) were separated from the reaction mixture using a silica column. The yield of the carboxylic acid dimer was 45% by weight.

Prior to the HDO step, the double bonds of the dimers obtained above were hydrogenated by employing a pressulfurized NIM0 / Al2O3 catalyst in a 450 ml high pressure Parr reactor. Prehydrogenation was performed using a dry, activated catalyst at 230 ° C under a hydrogen pressure of 5 MPa during mixing at 300 rpm. Hydrogenation of the dimers continued until no double bond was observed in the FTIR spectrum.

The dimers were hydrogenated in the HDO step as in Example 1 until the carboxylic acid peak disappeared from the FTIR spectrum, followed by filtration of the diatomite paraffinic product. Also C34, C35, C36 branched and cyclic paraffins were obtained as the end products.

The properties of the hydrocarbon components obtained are presented in Table 3. The properties of the hydrocarbon component are excellent with the molecular distribution being very low. The hydrocarbon components may also be produced in a similar manner from carboxylic acids derived from oils other than high oil, or from hydrolyzed vegetable or fish oil carboxylic acids, or animal fats, said acids comprising double bonds. Example 5 Preparation of a hydrocarbon component of soya oil-derived carboxylic acid methyl esters. and Pinene alfa Soybean oil was transesterified with methanol as in Example 2, thereby producing methyl esters of carboxylic acids. The reaction mixture was purified by washing with an acid and water. Finally, the carboxylic acid methyl ester was dried. The methyl ester carboxylic acid composition was as follows: C16: 0.11%; C18: 0.20%; C18: 1.8%; C18: 2.54%; and C18: 3.6%. The soybean oil methyl ester obtained above was oligomerized with pinene alfa, the molecular ration being 2: 1 respectively, in a high pressure Parr reactor employing 8% bentonite catalyst, and 4% water. 200 ml of the feedstock mixture was loaded into the reactor. Oxygen removal was done as in Example 4. Temperature and pressure were respectively increased to 310 ° C, and 2MPa, and soybean methyl ester was allowed to oligomerize with pinene alpha while slowly mixing. for 6 hours. The oligomerized product was subjected to hydrodeoxygenation as described in Example 1. The monomers were separated from the final product by distillation, thereby producing "pinene-branched" isoparaffin C28, and a mixture of carboxylic acid methyl ester paraffinic dimers and trimers. The properties of the hydrocarbon component obtained as the product are presented in Table 3. Branched hydrocarbon components may also be produced in a similar manner to other carboxylic acids of vegetable, animal or piscine origin, or fats, said acids comprising various double bonds, or methyl esters of carboxylic acids and suitable compounds of small molecular size, preferably of biological origin Example 6 Preparation of a heavy hydrocarbon component of high oil carboxylic acids High oil was oligomerized as in Example 3 , except that the reaction was performed during slow mixing for 7 hours. The trimers were separated from the dimers and monomers of the reaction mixture using a silica column.

The trimers obtained above were hydrogenated in an HDO step as in Example 1 until no carboxylic acid peaks were present in the FTIR spectrum. Both branched and cyclic paraffin were obtained as the product. The properties of the product are shown in Table 3. Hydrocarbon components may also be produced in a similar manner to free carboxylic acids derived from oils other than high oil, or hydrolyzed carboxylic acids from vegetable or fish oil, or animal fats. said acids comprising double bonds.

Table 3 Properties of processed hydrocarbon components_____________ Table 4. Properties of prior art base oils HC-CDW = hydrocracked, wax isomerized base oil Example 7 Demonstration of the biological origin of the hydrocarbon component The biological origin hydrocarbon component of Example 6 was weighed into a Group III mineral oil base oil, and mixed thoroughly. For the first sample, 0.5014 g of the hydrocarbon component of biological origin was weighed, and Group II base oil component was added in an amount to obtain a total weight of 10.0 g; For the second sample, 1.0137 g of the hydroxy carbide component of biological origin was weighed, and base oil component of Group II was added in an amount to obtain a total weight of 10.0232 g. The measured results are in Table 5, below. Results are expressed as "percent modern carbon" based on the radioactive carbon content of the atmosphere in 1950. At present, the percentage of modern carbon in the atmosphere is approximately 107%. & 13 C values show the stable carbon isotope ratio 13C / 12C. By this value, isotope fractionation occurs in the treatment process sample and can be corrected. Current results are presented in the last column. The method is ASTM D6866.

Table 5 Radioactive carbon results Example 8 Carbon number distribution ■ The carbon number distribution of the base oils of a-cordo with the invention is described lower than that of conventional base oils. The base oils of the invention contain high amount of high boiling C34 - C36 fractions compared to conventional products of the same viscosity range (approximately 4 cSt KV100) as shown in Figure 2. The carbon number distribution is determined by FIMS. The FIMS analysis sample is that of example 4 with high oil C18 fatty acid feed. In addition to hydrodeoxygenation to produce C36 compounds, decarboxylation / decarbonylation also leads to paraffinic C35 / C34 compounds (combined HDO-decarboxylation / decarbonylation).

Claims (18)

Process for the production of a saturated hydrocarbon component, characterized in that the feedstock comprising at least 50% by weight of unsaturated and / or polyunsaturated compounds and one or more selected component (s) (s) from the group consisting of carboxylic acids having carbon numbers from C4 to C38, esters of carboxylic acid C4 to C38 and C1-C11 alcohols, anhydrides of carboxylic acid C4-C38, and C4-C38 alcohols are oligomerized in presence of a deoxygenated cationic clay catalyst in the presence of a Group VIII metal and / or VIA metal - containing catalyst from the periodic table of the elements. Process according to Claim 1, characterized in that the cationic clay catalyst is a zeolite catalyst. Process according to Claim 1 or 2, characterized in that the feedstock comprises one or more component (s) selected from the group consisting of carboxylic acids having carbon numbers from C4 to C24. , esters of carboxylic acid C12 to C24 and C1-C3 alcohols, anhydrides of carboxylic acid C12-C24 and C12-C24 alcohols. Process according to any one of Claims 1 to 3, characterized in that the feedstock comprises at least one starting material of biological origin selected from the group consisting of triglycerides, fatty acids, acid esters. fatty acids and alcohols, fatty acid anhydrides, and fatty alcohols. Process according to Claim 4, characterized in that the starting material is selected from the group consisting of: a) vegetable fats, vegetable oils, vegetable waxes; animal fats, animal oils, animal waxes; fish fats, fish oils, fish waxes and mixtures thereof, and (b) free fatty acids or fatty acids obtained by hydrolysis, acid transesterification or pyrolysis reactions of vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fat, fish oils, fish waxes, and mixtures thereof, and (c) esters obtained by transesterification of vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes and mixtures thereof, and d) esters obtained by esterifying free fatty acids of vegetable, animal and piscine origin with alcohols, and mixtures thereof, and e) fatty alcohols obtained as fatty acid reduction products vegetable oils, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and mixtures thereof, and f) fats and oils waste and recycled food classification, and genetically engineered fats, oils and waxes, and mixtures thereof, and (g) mixtures of said starting materials. Process according to any one of Claims 1 to 5, characterized in that the feedstock contains at least 80% by weight of unsaturated and / or polyunsaturated compounds. Process according to any one of Claims 1 to 6, characterized in that the oligomerization is carried out under a pressure of 0 to 10 MPa and at a temperature of 100 to 500Ό. Process according to any one of claims 1 to 7, characterized in that up to 10%, preferably 0.1 to 4% by weight of water is added to the feedstock containing carboxylic acids in the step of oligomerization. Process according to any one of claims 1 to 8, characterized in that the deoxygenation is carried out as hydro-deoxygenation or as decarbonylation / decarboxylation, the deoxygenation being performed before or after oligomerization. Process according to Claim 9, characterized in that the hydrodeoxygenation is performed in the presence of hydrogen at a temperature between 100 and 500Ό, under a pressure between 0 and 20 MPa, the WHSV current rate being between 0, 1 and 10 l / h in the presence of a hydrodeoxygenation catalyst. Process according to Claim 9 or 10, characterized in that the hydrodeoxygenation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst having an alumina and / or silica support. Process according to any one of claims 9 to 11, characterized in that prior to hydrodeoxygenation, the product of the oligomerization step is subjected to prehydrogenation in the presence of a catalyst at a temperature between 50 and 400 ° C under hydrogen pressure between 0.1 and 20 MPa, the current rate WHSV being between 0.1 and 10 l / h. Process according to Claim 12, characterized in that the catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst having an alumina and / or silica support. Process according to Claim 9, characterized in that the process feedstock or oligomerization step product is subjected to decarboxylation / decarbonylation in the presence of a decarboxylation / decarbonylation catalyst at a temperature between 200 and 40010, pressure between 0 and 20 MPa, the current rate WHSH being between 0.1 and 10 l / h. Process according to Claim 14, characterized in that the decarboxylation / decarbonylation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst having an alumina and / or silica support or an activated carbon support. Process according to any one of Claims 1 to 15, characterized in that following the oligomerization and deoxygenation steps, the product is isomerized in the presence of hydrogen gas at a pressure between 0.1 and 20 MPa. at a temperature between 100 and 500 ° C in the presence of an isomerization catalyst. Process according to Claim 16, characterized in that the isomerization catalyst is a supported catalyst containing a molecular sieve and a Group VIII metal from the periodic table of the elements. Use of the process as defined in any one of claims 1 to 17 for the production of gasoline, solvent, and / or die-sel fractions.