ES2800974T3 - Process for the production of a saturated hydrocarbon component - Google Patents

Abstract

Process for the production of a saturated hydrocarbon component, characterized in that a raw material comprising one or more components selected from the group consisting of carboxylic acids having numbers of carbon atoms from C4 to C38, esters of carboxylic acids from C4 to C38 and C1-C11 alcohols, C4-C38 carboxylic acid anhydrides, and C4-C38 alcohols, component (s) that are at least 50% unsaturated and / or polyunsaturated by weight, oligomerize in the presence of a catalyst of cationic clay and is deoxygenated to remove oxygen, where deoxygenation is carried out as a hydroxydesoxygenation, deoxygenation being carried out in the presence of hydrogen, at a temperature between 200 and 500 ° C, under a pressure of between 0 and 20 MPa, where the WHSV flow rate is between 0.1 and 10 1 / h, in the presence of a hydrodeoxygenation catalyst selected from a Pd, Pt, Ni, NiMo or CoMo catalyst having an alumina or silica gel support , before or after oligomerization.

Description

DESCRIPTION

Process for the production of a saturated hydrocarbon component

Technical field

The invention relates to a process based on oligomerization and deoxygenation to produce a hydrocarbon component, and particularly to produce high quality saturated base oil. Raw material of biological origin is preferably used in the process, possibly derived from vegetable and fish oils, animal fats, natural waxes, carbohydrates and corresponding synthetic materials and combinations thereof.

Previous technique

Base oils are commonly used for the production of lubricants, such as automotive lubricating oils, industrial lubricants, and lubricating greases. These are also used as process oils, white oils, and metal working oils. Finished lubricants consist of two general components, oil-based lubricant and additives. The oil-based lubricant is the main constituent of these finished lubricants and contributes significantly to the properties of the finished lubricant. In general, a few oil-based lubricants are used to make a wide variety of finished lubricants by varying the blends of individual oil-based lubricants and individual additives.

Group III or IV base oils, as classified by the American Petroleum Institute (API), are used in high-quality lubricants. Table 1 shows the API base oil classification.

Table 1. API Base Oil Classification

Group III oils are very high viscosity index (\ THVI) base oils produced by modern methods from crude oils by hydrocracking, followed by isomerization of the waxy linear paraffins to give branched paraffins. Group III oils also include base oils produced from Slack Wax paraffins derived from mineral oils, and from waxes obtained by Fischer-Tropsch synthesis (GTL waxes), for example, from coal or natural gas using the corresponding isomerization techniques. Group IV oils are synthetic polyalphaolefins (PAOs). The ATIEL (Association Technique de l'Industrie Européenne des Lubrifiants, or Technical Association of the European Lubricants Industry), also uses a similar classification, this classification also includes Group VI: Internal Polyolefins (PIO). In addition to the official classification, Group II + is also commonly used in this field, this group comprising saturated and non-sulfurous base oils that have viscosity indexes greater than 110, but less than 120. In these classifications, saturated hydrocarbons include paraffinic compounds. and naphthenic, but not aromatic. A definition of base raw material is also available according to API 1509 as: "A base raw material is a lubricant component that is produced by a single manufacturer with the same specifications (regardless of the raw material strength or location that meets the same manufacturer's specification and is identified by a single formula, product identification number, or both. Base raw materials can be manufactured using several different processes. Base oil is the base raw material or mixture of base raw materials used in an API homologated oil. Known types of base raw materials are 1) Mineral oil (paraffinic, naphthenic, aromatic), 2) Synthetic (polyalphaolefins, alkylated aromatics, diesters, polyol esters, polyalkylene glycols , phosphate esters, silicones, and 3) Vegetable oil For a long time the industry, especially the automotive industry, has required lubricant s 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, oil-based lubricants are base oils that have a kinematic viscosity of approximately 3 cSt or greater than 100 ° C (KV100); pour point (Pp) of about -12 ° C or less; and a viscosity index (VI) of about 120 or higher. In addition to low pour points, the low-temperature fluidity of multigrade motor oils is also needed to ensure that, in cold climates, the engine starts easily. Low temperature fluidity is demonstrated as apparent viscosity in cold start simulator tests from -5 to -40 ° C. Oil-based lubricants that have a KV100 value of approximately 4 cSt should normally have a CCS viscosity at -30 ° C (CCS-30) less than 1800 and Oils that have a KV100 value of approximately 5 cSt should have a CCS-30 less than 2700. The lower the value, the better. In general, oil-based lubricants should have a Noack volatility no greater than conventional Group I or Group II neutral light oils. Today, only a small fraction of the base oils manufactured today are capable of meeting these demanding specifications.

It is no longer possible to produce lubricants that meet the specifications of the most demanding automakers from conventional mineral oils. Normally, mineral oils often contain too high concentrations of aromatics, sulfur, and nitrogenous compounds and, furthermore, they also have high volatility and a modest viscosity index, that is, a dependence between temperature and viscosity. Furthermore, the response of mineral oils to antioxidant additives is often low. Synthetic base oils and so-called semisynthetics play an increasingly important role, especially in automotive lubricants such as motor and gearbox oils. A similar development can be observed in industrial lubricants. The useful life of the lubricants is desirably as long as possible, thus avoiding frequent oil changes by the user, and further allowing extended maintenance intervals of vehicles, for example, in commercial transport. In the last decade, motor oil change intervals for passenger cars have increased five times, being 50,000 km at best. For heavy duty vehicles, the engine oil change intervals are currently at the 100,000 km level.

Lubricant production is affected by the increasingly common "Life Cycle Strategy" (LCA) that includes environmental, health and safety factors of the product. What is claimed with the LCA is a long shelf life of the product, and minimal inconvenience to the environment associated with the production, use, handling and disposal of the product. Longer oil change intervals for high-quality base oils result in decreased consumption of raw materials based on non-renewable crude mineral oils, and lower amounts of hazardous waste oil products.

In addition to the production demands of engine and base oil technology, stringent environmental requirements also direct the industry to develop more sophisticated base oils. Sulfur-free fuels and base oils are required to achieve the full effect of new and effective anti-pollution technologies in modern vehicles and to cut emissions of nitrogen oxides, hydrocarbons and volatile particles, as well as to achieve a direct reduction of sulfur dioxide in gases exhaust. The European Union has decided that these fuels should be available on the market since 2005 and should only be the only form on sale since 2009. Conventional mineral oil base oils contain sulfur, nitrogen, aromatics, and usually also volatile compounds. They are less suitable for new engines and therefore more environmentally damaging than the newer aromatic and sulfur-free base oils.

Today, the use of recycled oils and renewable raw materials in the production of lubricants is often an object of interest. The use of bio-based renewable raw materials is desirable instead of non-renewable fossil raw materials to produce hydrocarbon components, since fossil raw materials are exhaustible and their effect on the environment is detrimental. The problems associated with recycled oils include complicated purification and reprocessing steps to obtain high quality base oils. Additionally, developing a long running and recycling logistics system is expensive.

At the moment, only esters are used in lubricants of renewable and biological origin. The use of esters is limited to a few special applications such as refrigeration compressor lubricant oils, biohydraulic oils, and metallurgical oils. In normal automotive and industrial lubricants, they are mainly used on an additive scale. The high price also limits the use of esters. Furthermore, the esters used in motor oil formulations are not interchangeable with other esters without carrying out new engine tests, even in cases where the chemical composition of the substituent ester is in principle totally similar. In contrast, base oils consisting of a pure hydrocarbon structure are partially interchangeable with each other. There are also some technical problems associated with esters. As polar compounds, esters suffer a greater tendency to seal swelling than pure hydrocarbons. This has created a number of problems related to elastomers in hydraulic applications. In addition, ester base oils hydrolyze more easily producing acids, which in turn cause corrosion in lubricating systems. Additionally, an even greater disadvantage of esters is that additives developed for nonpolar hydrocarbon base oils are not effective for ester base oils.

Processes where triglycerides are crosslinked in a controlled manner using a suitable metal salt or peroxide initiator, which readily capture hydrogen from the CH bond, along with suitable amounts of oxygen, are known in the art. Some crosslinking is also produced by atmospheric oxygen without heating the product, the reaction being, however, slower. This crosslinking is based on the oxygen-oxygen bonds formed in the molecules. During the crosslinking of triglycerides, the degree of crosslinking can be controlled by the processing time and kinematic viscosity. Viscosity increases with crosslinking as a function of time, and decreases as the product decomposes.

A batch thermal process based on double bond reactions is also known to produce a support oil from triglycerides, introducing carbon dioxide into the reactor to prevent oxidation. In this case, crosslinking is based on the carbon-carbon bonds that are formed in the molecules. The decomposition products of the thermal reaction are removed by stripping with the carbon dioxide gas stream, or alternatively, using vacuum. Crosslinking is an exothermic reaction and therefore efficient heating is necessary to provide the reaction and effective cooling to prevent overheating of the product to maintain the temperature between 280 and 300 ° C. In addition, the reaction vessel should cool 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 to produce dimeric acids from unsaturated carboxylic acids with a radical reaction using a cationic catalyst, the reaction temperature being 230 ° C. In addition to the unsaturated branched, acyclic dimer acid as the main product, monodimers and bicyclic dimers are also formed.

Unsaturated alcohols can be oligomerized in a manner similar to unsaturated carboxylic acids using heat and / or a catalyst to provide dimers of alcohols. An acyclic unsaturated branched diol dimer is the main product.

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

Cross-linked triglyceride products, carboxylic acid methyl ester dimer, carboxylic acid dimer, and fatty alcohol dimers can be used in lubricating applications, but, as the products contain heteroatoms, they are endowed with corresponding weaknesses analogously to derived base oils. of esters.

Processes in which oxygen is removed from a carboxylic acid or ester are also known. Decarboxylation of fatty acids results in hydrocarbons with one less carbon atom than the original molecule. The feasibility of decarboxylation varies greatly with the type of carboxylic acid used as the starting material. Activated carboxylic acids contain electron-withdrawing substituents in the alpha or beta position relative to carbon dioxide. They lose the carboxylic group spontaneously at somewhat elevated temperatures. In this case, the RC-00011 bond is weakened by electronic displacement along the carbon chain.

With other types of carboxylic acids, the hydrocarbon chain causes an opposite increase in electron density at alpha carbon, and thus carbon dioxide cleavage is difficult. A suitable catalyst contributes to the reaction. In Maier, WF et al., Chemische Berichte (1982), 115 (2), 808-812, hydrocarbons are produced from carboxylic acids using the heterogeneous Ni / A ^ O ^a and Pd / SiO ² catalysts at 180 ° C in a hydrogen atmosphere.

The combined decarboxylation and hydrodeoxygenation of oxygen-containing compounds is disclosed in Laurent, E., Delmon, B .: Applied Catalysis, A: General (1994), 109 (1), 77-96, and 97-115, where Oils from biomass-derived pyrolysis were subjected to hydrodeoxygenation using the catalysts CoMo / yA ^ O ^s and NiMo / y-A120 ³ sulfurized at 260-300 ° C, at a hydrogen pressure of 7 MPa. The reactions of the hydrodeoxygenation stage are very exothermic, requiring high amounts of hydrogen.

Document FI 100248 presents a two-stage process in which intermediate distillate is produced from a vegetable oil by hydrogenating the carboxylic acids or triglycerides of the vegetable oil to result in linear normal paraffins, followed by the isomerization of said n- paraffins to give branched paraffins. The conditions for this hydrogen treatment include a temperature between 330 and 450 ° C, a pressure of 3 MPa, and a liquid space velocity per hour (LHSV) of 0.5 - 51 / h. In the isomerization stage, a temperature between 200 and 500 ° C was used at a pressure above atmospheric and an LHSV of 0.1-101 / h.

Document EP 0471 566 refers to a process for the polymerization of unsaturated fatty acids, wherein the fatty acid is heated to an elevated temperature in the presence of a polymerization catalyst, and the polymerized product is hydrogenated at a temperature of 180 ° C using a palladium catalyst having a carbon support.

In isomerization processes, noble metal catalysts are used which are very expensive and very sensitive to catalyst poisons. Starting materials from biological sources contain high amounts of water resulting in oxygen, carbon monoxide, and carbon dioxide as the starting material is processed. Furthermore, such biologically derived starting materials often contain nitrogen, sulfur and phosphorus compounds known as noble metal catalyst poisons and catalyst inhibitors. They lead to a decrease in the useful life of the catalyst, and require frequent regeneration of the catalysts unless they are removed before 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 that have the following structure:

where R1, R2 and R3 represent C4-C30 hydrocarbon chains. Fatty acids are carboxylic acids that have long unbranched hydrocarbon chains. The lengths of the hydrocarbon chains are mainly 18 carbon atoms (C18). C18 fatty acids are normally attached to the intermediate hydroxyl group of glycerol. The typical number of carbon atoms of the fatty acids attached to the other two hydroxyl groups are even, the numbers being between C14 and C22.

The fatty acid composition of the biologically sourced starting material can vary considerably between raw materials from different sources. Although several double bonds may be present in fatty acids, they are not conjugated, but at least one intermediate -C112- unit is between them. With respect to the configuration, the double bonds of natural fatty acids are in the cis form , therefore the hydrogen atoms are located on the same side of the rather rigid double bond. As the number of double bonds increases, they are generally located at the free end of the chain. The lengths of the hydrocarbon chains and the numbers of double bonds depend on the various vegetable or animal fats or waxes that serve as the source of the fatty acid. Animal fats normally contain more saturated fatty acids than unsaturated fatty acids. The fatty acids in fish oil contain high amounts of double bonds, and the average length of the hydrocarbon chains is greater compared to the fatty acids in vegetable oils and animal fats. The composition of the fatty acid plays an important role in the evaluation of the properties of oxidation resistance, thermal resistance, and low temperature of the raw material subjected to oligomerization, and also, the type of oligomerization products.

Waxes are primarily carboxylic acids esterified with alcohols that have long chains. Additionally, waxes contain varying amounts of paraffins (n-alkanes), ketones, and diketones, primary and secondary alcohols, aldehydes, acid alkanes (carboxylic acids), and terpenes. The number of carbon atoms of said carboxylic acid and alcohol chains is normally between C12 and C38.

Prior to processing, starting materials of biological origin are commonly pretreated by any suitable known method 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 goal of such chemical and physical pretreatments is to remove impurities that interfere with the process or poisoning of the catalysts, and to reduce unwanted side reactions.

In a hydrolysis treatment, oils and fats react with water resulting in free fatty acids and glycerol as a product. Three main processes are known for the industrial production of fatty acids: division of triglycerides with high pressure steam, basic hydrolysis, and enzymatic hydrolysis. In the steam splitting process, the hydrolysis of triglycerides using steam is carried out at temperatures between 100 and 300 ° C, at a pressure of 1 - 10 MPa, with the preferable conditions of 250 to 260 ° C and 4 to 5.5 MPa. Metal oxides such as zinc oxide can be added as a catalyst to accelerate the reaction. High temperature and pressure contribute to the dissolution of fats in water.

Paraffinic synthetic base oils produced by oligomerization are known in the art, the typical ones being PAO (polyalphaolefins) and PIO (internal polyolefins). In the production of the above, olefinic starting materials are used from crude oil, where said starting materials do not contain heteroatoms. The development of polyalphaolefin-type base oils began in the 30s of the 20th century in the United States. and in Germany where products with superior low temperature properties suitable for aircraft were mainly developed. The 1-alkene monomers to be used as starting materials for PAOs are normally produced from ethylene. For commercial PAOs, C8-C12 alpha olefins or C14-C18 alpha olefins are mainly used as starting materials. In the production of PAO, the monomer is polymerized thermally either using Ziegler or Friedel-Crafts type catalysts, or using zeolite catalysts to give heavier products, followed by distillation to obtain desired product fractions, and hydrogenation to give saturated paraffins. It is possible to produce PAO products belonging to various viscosity classes, having the typical representatives kinematic viscosities of 2, 4, 6 and 8 mm2 / s at 100 ° C (KV100). Furthermore, particularly thick PA040 and PA0100 base oils are produced having KV100 values of 40 and 100 mm2 / s, said base oils are generally used for the production of thick lubricants, and as viscosity index improvers (VII). PAO products have high viscosity indexes and, at the same time, excellent low-temperature properties, with pour points as low as -60 ° C. As the lighter monomeric compounds are removed by distillation, the volatilities of the products are low and the flash points are high. Resistance to oxidation is quite modest without antioxidant additives.

PIOs are produced by oligomerizing internal olefins, the double bonds of which are statistically distributed along the entire length of the hydrocarbon chain.

Internal olefins can be produced by dehydrogenating n-paraffins derived from crude oil. The molecular structures of the products produced from internal C15-C16 linear olefins differ from those of PAO. Compared to PAO, the properties of PIO are worse; the viscosity index is lower, the pour point is worse, and the volatility is higher. Considering quality, IOPs are between PAO and VHVI. The production technology of PIOs is similar to that of PAOs, with the exception of a more aggressive catalytic system for the oligomerization of the less reactive internal olefins. The solubility of the additives in PAO and PIO is quite low due to the absence of polarity. Esters are often used in formulations to improve solubility. The use of starting materials of biological origin containing heteroatoms has not been reported until now or the intermediates have been optionally thermally and / or chemically and / or physically and / or mechanically treated, in the production of high quality saturated base oils.

Based on the above teachings, it can be seen that there is an obvious need for a new alternative process to produce hydrocarbon components preferably from starting materials of biological origin, and to avoid the problems associated with the solutions of the prior art. or, at 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, such base oils preferably being of biological origin and having more preferable effects on the environment and for end users than mineral base oils. traditional. Furthermore, there is a need for a process based on the use of renewable raw materials, thus saving non-renewable raw materials.

Objectives of the invention

An object of the invention is a process for producing a saturated hydrocarbon component according to claim 1.

The characteristic features of the process of the invention are presented in the attached claims.

General description of the invention

The process of the invention comprises an oligomerization stage in which the molecules of the raw materials react with each other, thus increasing the number of carbon atoms of the component obtained and, in addition, a deoxygenation stage. Said deoxygenation is carried out as a hydrodeoxygenation reaction. Furthermore, the process of the invention may also comprise an optional isomerization step to isomerize the lighter products, and / or a finishing step. The raw material 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 carried out to extend the hydrocarbon chain of unsaturated cyclic acids and / or derivatives thereof, such as esters, anhydrides and alcohols from a monomeric unit to provide a dimer with two monomeric units, and to form higher oligomers. In this oligomerization reaction, the 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 at this point. The number of carbon atoms of carboxylic acids and derivatives thereof is at least C4. Fatty acids of biological origin and / or derivatives thereof are preferably used.

At this point, deoxygenation refers to the removal of oxygen by both the hydrodeoxygenation reaction and the decarboxylation / decarbonylation reaction. In deoxygenation, the structure of the biological starting material will be converted to both a paraffinic and an olefinic substance, according to the catalyst and reaction conditions used.

In this context, hydrodeoxygenation (1-1D0) refers to the removal of oxygen by hydrogen. Water is released in the reaction when the ester, alcohol, anhydride, or carboxylic acid groups break down. All oxygen, nitrogen, phosphorus and sulfur atoms are removed.

At this point, decarboxylation refers 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 hydroisomerization of linear hydrocarbons (paraffins) that results in a branched structure.

The term "saturated hydrocarbon" used in the specification refers to paraffinic and naphthenic compounds, but not aromatics. Paraffinic compounds can be both branched and linear. Naphthenic compounds are cyclic saturated hydrocarbons, that is, cycloparaffins. Said hydrocarbon with a cyclic structure is normally derived from cyclopentane or cyclohexane. A naphthenic compound can comprise a single ring structure (mononaphthene) or two isolated ring structures (isolated dinaphthene), or two fused ring structures (fused dynaphthene), or three or more fused ring structures (polycyclic naphthenes or polynaphthenes). .

Saturated base oils comprise, at this point, saturated hydrocarbons.

Carboxylic acids labeled, for example, C18: 1 denote a C18 chain with one double bond.

In this context, the pressures are gauge pressures relative to normal atmospheric pressure.

The classification of the periodic table of the elements is the IUPAC classification.

In this context, the width of the carbon atom range refers to the difference between the number of carbon atoms of the largest and smallest molecules, plus one, in the final product.

The invention is now illustrated with the attached figure 1 without intending to limit the scope of the invention to the embodiment of said figure.

Figure

Figure 1 shows a preferable embodiment of the process according to the invention. One or more raw materials selected from the group consisting of: triglyceride raw material stream 1, fatty acid raw material stream 2, fatty acid ester raw material stream 3 with alcohols having short chains, The fatty acid anhydride stream 4 and the fatty alcohol stream 6 are introduced into the oligomerization reactor 10 either as separate components or as mixtures. Part of the lighter product fraction to be recirculated (eg 52), or the hydrocarbon stream 201, can optionally be introduced into oligomerization reactor 10 as a diluent. Diluent stream 202 comprises recirculated stream 52 or hydrocarbon stream 201, or a mixture thereof. The product 11 containing raw material components whose double bonds have reacted, 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 product hydrogenated in the double bonds from the prehydrogenation reactor 20 are passed as stream 21, and the hydrogen is optionally passed as stream 7 to a deoxygenation reactor 30 which optionally also receives a diluent 202. When deoxygenation is carried out as a decarboxylation / decarbonylation reaction, a mixture of hydrogen 7 and an inert gas, eg nitrogen can be used as the gas stream (not shown in the figure). The product containing the saturated hydrocarbons from the deoxygenation reactor 30 is passed as stream 31 to a distillation and / or separation unit 40 to separate the various product fractions, gas 44, gasoline 43, diesel 42 and base oil 41 The lighter gasoline and diesel fractions, respectively 43 and 42, are optionally isomerized in a hydroisomerization unit 50 in the presence of hydrogen 7, thus resulting in gasoline and diesel streams, respectively 51 and 52, containing branched hydrocarbons . When the fatty acids 2 and / or the fatty acid esters 3 and / or the alcohols 6 are particularly oligomerized, the product stream 12 can be withdrawn from the oligomerization reactor 10 followed by removal of the non-oligomerized components, for example, by Distillation 60. Non-oligomerized light components are subsequently recycled to oligomerization reactor 10 as stream 61, and oligomerized components can be passed to prehydrogenation 20 as stream 62. In recirculation, stream 63 from distillation 69 can be passing to low temperature filtration 80 where the saturated components 81 are separated from the components 82 having double bonds that are to go to oligomerization 10. Alternatively, distillate 61 can be passed to post-oligomerization reactor 70 , in which 8 unsaturated carboxylic acids with smaller molecules, or olefins 5 can be introduced to branch ar the non-oligomerized unsaturated linear components. The components containing raw material product whose double bonds have reacted are passed from the post-oligomerization reactor 70 as stream 71 to an optional prehydrogenation reactor 20.

Detailed description of the invention

It has now been surprisingly discovered 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 from their derivatives, particularly from fatty acids, fatty acid esters, fatty alcohols, the corresponding anhydrides of fatty acids of biological origin, and / or mixtures thereof. The problems of the prior art processes and the products obtained from them can be avoided, or at least substantially reduced by the process of the invention.

In the process of the invention, especially the oligomerization reactions of the materials of biological origin can be used together with the deoxygenation reaction to produce saturated base oils in a novel way. For the oligomerization of unsaturated carboxylic acids and / or their derivatives, such as fatty acids, fatty acid esters, fatty alcohols, fatty acid anhydrides, and / or mixtures thereof, the monomers are converted into dimers with two monomers and in higher oligomers. When using starting materials of biological origin for the production of base oils, it is necessary to extend the length of the hydrocarbon chain to reach the range of the number of carbon atoms required in base oil applications, leaving only carbon-carbon bonds. in the main structure of the molecule. In accordance with the invention, this is carried out by allowing the compounds having double bonds to react with each other, thereby producing the desired carbon-carbon bonds and, furthermore, resulting in hydrocarbons with numbers of carbon atoms in the range of C18 to C550. In base oil applications, the carbon atom number range is usually C18 to C76, and particularly, the carbon atom number range of thick base oils can even be C150 to C550. In the oligomerization reaction, for example, the double bonds of triglyceride molecules react with each other, thus forming a polymeric network of triglycerides. With other raw materials, dimers, trimers, and tetramers are mainly formed. When the raw material contains chains of polyunsaturated hydrocarbons, after oligomerization and deoxygenation, higher amounts of trimers and hydrocarbons with a ring structure are obtained than with chains of monounsaturated hydrocarbons.

In the process of the invention, the raw material of biological and / or synthetic origin is oligomerized and deoxygenated. The oligomerization of the unsaturated raw material components is preferably carried out first, followed by deoxygenation to obtain saturated paraffins without heteroatoms. Alternatively, the unsaturated raw material is first subjected to deoxygenation to remove heteroatoms, followed by oligomerization of the olefinic product obtained, the deoxygenation being, however, subsequently carried out by a decarboxylation or decarbonylation reaction, since the The hydrodeoxygenation reaction is inadequate in this case.

Following deoxygenation, the process may also comprise optional isomerization of the lighter components. The normal linear paraffins that have shorter chains, which do not belong to the base oil carbon class, and which are produced as by-products of the process, can isomerize to introduce branching in the hydrocarbon chain that improve the cold flow properties of the product. These isomerized products can be used, for example, as gasoline or diesel components, and furthermore, components having carbon atom numbers from C18 to C24 can also be used as light base oil components. The process may further comprise an optional prehydrogenation step before deoxygenation, an optional post oligomerization step after the actual oligomerization step, optional purification steps of intermediates, product recirculation steps, and a finishing step. The raw materials can optionally undergo one or more pretreatment steps, eg purification.

Raw material

In the process of the invention, the food comprises one or more components selected from the group consisting of triglycerides, carboxylic acids having numbers of carbon atoms from C4 to C38, esters of carboxylic acids from C4 to C38 and C1 - C11 alcohols. , C4-C38 carboxylic acid anhydrides, and C4-C38 alcohols. The raw material is preferably selected from the group consisting of triglycerides, fatty acids having carbon atom numbers from C4 to C24, esters of C12 to C24 fatty acids and C1-C3 alcohols, C12-C24 fatty acid anhydrides, and C12-C24 fatty alcohols, and mixtures thereof. The raw material preferably originates from starting materials of biological origin, 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 reactions of pyrolysis 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 from vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and their mixtures, and

d) esters obtained by esterification of free fatty acids of vegetable, animal and fish origin with alcohols, and their mixtures, and

e) fatty alcohols obtained as products of reduction of fatty acids from vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and their mixtures, Y

f) residual fats and food grade recirculated fats and oils, 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 can also contain free carboxylic acids and / or esters of carboxylic acids, or oligomerization products of biological starting materials, without substantially interfering with the process. Suitable raw materials are also all the types of compounds mentioned which are produced wholly or partially synthetically.

Since the objective of the process is the oligomerization of the components having double bonds, the raw material 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 Cl6: 1 and / or C18: 1 component present in the raw material in concentrations above 40% and preferably above 70%, by weight.

Examples of suitable biological starting materials include fish oils such as Baltic herring oils, salmon oil, herring oil, tuna oil, anchovy oil, sardine oil, and mackerel oil; vegetable oils such as rapeseed oil, rapeseed oil, canola oil, tallow oil, sunflower seed oil, soybean oil, corn oil, hemp oil, olive oil, cottonseed oil, mustard, palm oil, peanut oil, castor oil, jatropha seed oil, palm kernel oil, and coconut oil; and furthermore, Animal fats such as lard, tallow, and also residual fats and recirculated food grade fats and oils, as well as fats, waxes and oils produced by genetic engineering are also suitable. In addition to fats and oils, suitable bio-based starting materials include animal waxes such as beeswax, Chinese wax (insect wax), shellac, and lanolin (wool wax), as well as vegetable waxes such as wax. carnauba palm, ouricouri palm wax, jojoba seed oil, candelilla wax, esparto wax, Japan wax, and rice bran oil.

The process can also be used to process mixtures of bio-based raw materials and synthetic raw materials, using additional raw materials produced with other processes, or synthetic raw materials, if necessary, in a way suitable for the process step in question. Pure synthetic raw materials are also suitable, but in this case the products are not based on renewable natural sources.

If desired, linear olefins and olefins having ring structures, preferably C2-C14 olefins, can also be added to the feedstock, thus allowing the increase in molecular mass with lower numbers of carbon atoms than C12-carboxylic acids. Typical C24. Components of the tall oil turpentine fraction such as alpha pinene, and / or compounds having double bonds derived from sugars, and / or unsaturated compounds produced from carboxylic acids by metathesis, and / or synthetic compounds can be used. such as ethylene or propylene as additional olefinic components.

In oligomerization, unsaturated dicarboxylic acids having shorter chains (<C12) of carboxylic acids, alcohols, and alkyl esters can also be used as additional raw materials, allowing for increased molecular mass with less carbon than C12-carboxylic acids. Typical C24, or derived from 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 post-oligomerization reaction of the invention, for example, the above molecules having short chains can be oligomerized to carboxylic acids or alkyl esters of a carboxylic acid or triglycerides or other molecules with double bonds. The double bonds of compounds derived from carboxylic acids are usually located in the middle of the hydrocarbon chain. Smaller molecules are reacted with double bonds to provide linear or ring structures located in the middle of the hydrocarbon chain.

Since the cycle length of the catalyst is short in carboxylic acid processes, the raw material can be converted first to esters or alcohols, which are less aggressive to the catalyst. The Triglycerides can be transesterified with an alcohol to obtain alkyl esters. Triglycerides break down to form an ester with alcohol and glycerol. Methanol is normally used as the alcohol, but other C1-C11 alcohols can also be used. Typical conditions for transesterification are as follows: temperature between 60 and 70 ° C, pressure between 0.1 and 2 MPa. Excess amounts of sodium and potassium hydroxides dissolved in methanol are used as catalysts. The esterification of the free carboxylic acids and alcohol requires higher temperature and pressure (eg 240 ° C and 9 MPa), or acidic conditions.

Carboxylic acids can also be reduced to fatty alcohols in a known way, either by direct reduction of the acid groups to alcohols with lithium aluminum hydride, therefore, the double bonds remain in the alcohols, or by hydrogenation of the alkyl esters of carboxylic acids. to give unsaturated fatty alcohols using a copper-zinc catalyst at a temperature between 200 and 230 ° C, and at a hydrogen pressure between 20 and 30 MPa. In the hydrogenation reaction, the alcohol used for the esterification of the carboxylic acid is released and can be recycled to the esterification again, while the unsaturated fatty alcohols are passed to the oligomerization.

In various process stages, hydrocarbons can be used as diluents for the feedstock. The hydrocarbon can be, for example, of biological origin and boiling in diesel fuel in a range between 150 and 400 ° C, usually between 180 and 360 ° C.

The biological starting material that provides the raw material is preferably pretreated by known methods for example to remove impurities. The hydrolysis reaction of triglycerides can be used to produce carboxylic acids to be used as food in the oligomerization step. Alternatively, the triglycerides can be hydrolyzed after oligomerization. In hydrolysis, glycerol is obtained as a by-product and therefore no hydrogen is consumed in the HDO stage of hydrogenation of glycerol to give propane gas. For example, both the raw material and the product can be fractionated by distillation to narrower fractions with respect to the boiling ranges or the numbers of carbon atoms and, furthermore, impurities can be removed from the raw material or the final product by filtering through suitable filter aids.

The process

Oligomerization stage

According to a preferred embodiment of the process of the invention, the raw material comprising at least one component with double bonds is selected from the group of triglycerides, carboxylic acids, acid anhydrides and / or fatty alcohols, and is oligomerized. The raw material contains at least 50% by weight of unsaturated and / or polyunsaturated compounds. One of the raw material components is preferably selected as the main starting material of the oligomerization step, and the oligomerization conditions are adjusted in accordance with the main starting material. Other raw material materials can be mixed with such main starting materials as long as they do not interfere with the process or are advantageous for processing. The oligomerization reactions are catalyzed by heat and a suitable catalyst. Suitable catalysts include cationic clay catalysts, preferably zeolite catalysts, particularly preferably montmorillonite. The oligomerization reactions of the carboxylic acids can be enhanced by additional reagents such as water. In the oligomerization of carboxylic acids, up to 10%, preferably 0.1 to 4%, and particularly preferably 1 to 2%, by weight, of water is added to the raw material. It is not preferable to use excessive amounts of water, since in this case non-dimerized stolides with carbon-carbon bonds are formed as by-products.

Suitable oligomerization reactors include fixed bed reactors and mixing tank reactors. Diluents can be used in the reaction to adjust oligomerization. The diesel or other hydrocarbon fraction obtained from the process is a suitable diluent that can be recirculated. The pressure of the oligomerization step is between 0 and 10 MPa, the temperature being between 100 and 500 ° C, preferably between 0 and 5 MPa, and between 200 and 400 ° C, respectively. When the reaction is carried out as a batch reaction, the amount of catalyst is 0.01 to 30% by weight of the total reaction mixture, preferably 0.5 to 10% by weight. When a fixed-bed reactor is used, the amount of raw material, expressed as grams per hour per gram of the catalyst, is between 0.1 and 1001 / h.

In a mixed tank reactor, the reaction time is less than 16 hours, preferably less than 8, particularly preferably less than 4 hours. When a short residence time is used, the lighter non-oligomerized components can be separated from the already oligomerized heavier components for example, by distillation, followed by recirculation of the lighter components to oligomerization. During recirculation, the unreactive saturated components can be separated from the components having double bonds, for example, by low temperature filtration. The saturated components are passed to deoxygenation and optional isomerization to branch the hydrocarbon chains.

Prehydrogenation stage

The activity of the catalysts is lost mainly due mainly to the coke formed on the surface of the catalyst, and therefore, the product of the oligomerization step can optionally be subjected to prehydrogenation under mild conditions to hydrogenate the double bonds and furthermore to reduce the formation of coke in the next stage of deoxygenation. The prehydrogenation is carried out in the presence of a prehydrogenation catalyst, at a temperature between 50 and 400 ° C, under a hydrogen pressure that varies from 0.1 to 20 MPa, the WHSV flow rate being between 0.1 and 101 / h, preferably at a temperature between 150 and 250 ° C, at a hydrogen pressure of 1 to 10 MPa, the flow rate being 1 to 51 / h. The prehydrogenation catalyst contains metals from Group VIII and / or VIA of the periodic table of elements. The prehydrogenation catalyst is preferably a supported Pd, Pt, Ni, NiMo or CoMo catalyst, the support being both alumina and silica. Deoxygenation stage

Deoxygenation can alternatively be carried out either as hydrodeoxygenation or as decarboxylation / decarbonylation which is not according to the invention. Deoxygenation carried out as hydrodeoxygenation (IIDO) is suitable for all raw materials. In the MO step, oxygen and the oligomerized and optionally prehydrogenated stream are passed to the MO catalyst bed comprising one or more catalyst beds. In the MO stage, the pressure is between 0 and 20 MPa, preferably between 1 and 15 MPa, particularly preferably between 3 and 10 MPa, the temperature being 200 to 500 ° C, preferably 200 to 400 ° C, particularly preferably 250 to 350 ° C, the WHSV flow rate is 1 to 5 1 / h, particularly preferably of WHSV 1 to 3 1 / h. In the MO stage, special hydrodeoxygenation catalysts containing a metal from Group VIII and / or VIA of the periodic table of elements, and a support can be used. The MO catalyst is a supported PD, Pt, Ni, NiMo or CoMo catalyst, the support being both alumina and silica.

When the raw material contains carboxylic acids and / or carboxylic acid esters, deoxygenation can be carried out using a decarboxylation / decarbonylation reaction, which is not according to the invention. In the decarboxylation / decarbonylation reaction, the raw material and an optional diluent are introduced into the catalyst bed. The reaction takes place in the liquid phase, and can be carried out at atmospheric pressure. However, it is preferable to use vapor pressure according to the reaction temperature of the reaction mixture. Depending on the raw material, the pressure in the decarboxylation / decarbonylation step is between 0 and 20 MPa, preferably between 0.1 and 20 MPa, the temperature is between 200 and 400 ° C, preferably between 250 and 350 ° C, and the flow rate WHSV is 0.1 to 10 1 / h, preferably WHSV 1 to 5 1 / h. In the decarboxylation / decarbonylation step a special catalyst is used. The catalyst contains a metal from Group VIII and / or VIA of the periodic table of elements, such as a supported Pd, Pt, Ni, NiMo or CoMo catalyst, the support being both alumina and silica and / or activated carbon. The decarboxylation / decarbonylation catalyst is preferably Pd supported on carbon when hydrogen is not used in the process, and sulfurized NiMo supported on alumina when a mixture of hydrogen and an inert gas such as nitrogen is used in the process. There are no more functional groups left in the product from the decarboxylation / decarbonylation step and the products only contain carbon and hydrogen. The number of carbon atoms has been reduced by one carbon per functional group removed.

When deoxygenation is carried out as decarboxylation / decarbonylation, oligomerization can be carried out before deoxygenation, and therefore the raw material of the oligomerization step contains unsaturated carboxylic acids and / or carboxylic acid esters. When the oligomerization is carried out after the decarboxylation / decarbonylation step, the raw material of the oligomerization step contains unsaturated compounds from the decarboxylation / decarbonylation that have the number of carbon atoms reduced by one carbon atom per functional group removed. , compared to the raw material. In the deoxygenation step, IIDO and the decarboxylation / decarbonylation reactions described above can be carried out simultaneously to result in carbon dioxide or carbon monoxide from a part of the functional groups and a part of the functional groups are hydrodeoxygenated. After the deoxygenation step, the light fractions can be passed with hydrogen to a separate isomerization step. The pressure of the isomerization step is 0.1 to 20 MPa, preferably 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 molecular sieve and a metal from Group VIII of the periodic table of the elements such as Pd and Pt can be used. Alumina and / or silica can be used as a support.

Following the oligomerization and deoxygenation steps, the product stream can optionally be terminated to remove double bonds and aromatics. When the finishing step is carried out using hydrogen in the presence of a catalyst, the step is called hydrofinishing. In the hydrofinishing step, the pressure is 1 to 20 MPa, preferably 5 to 15 MPa. The temperature is between 50 and 500 ° C, preferably 100 to 400 ° C. In the hydrofinishing step, special catalysts containing a Group VIII metal as well as alumina and / or silica can be used. the hydrofinishing catalyst is preferably supported Pd, Pt, or Ni catalyst, the support being both alumina and silica. Hydrogen-free finishing can also be carried out, removing polar components using adsorption materials, eg, clay or a molecular sieve.

Following oligomerization, deoxygenation and optional isomerization and finishing steps, the product is fractionated, for example, by distillation. The typical number of carbon atoms varies between product components 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 can be recirculated to various process stages such as the 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 can be further oligomerized by introducing an additional monomer (mixing tank reactor) into the process, or by repeated recirculation of the already oligomerized product while adding the monomer (continuous reactor). In this way, especially thick base oils having carbon atom numbers as high as C150-C550 can be provided, such thick base oils being useful in the production of thick lubricants and as viscosity index improvers.

Product

It has surprisingly been 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 oils, was obtained with the process of the invention. The product is branched through carbon-carbon bonds.

A hydrocarbon component preferably of biological origin, suitable as a solvent, gasoline or diesel, or a component of diesel fuel was also obtained. The diesel component of the C18-C24 base oil component can be isomerized to improve low temperature properties. The gasoline component can be isomerized to increase the octane number. There is no need for isomerization in the case of using short chain olefins or short chain unsaturated carboxylic acids in the post-oligomerization process to branch the remaining double bonds.

The number of carbon atoms and the range of the number of carbon atoms of the base oil both depend on the biological starting material of the raw material and the production process. The conventional carbon atom number range of prior art base oil applications is C18 to C76, while the carbon atom number range of particularly thick base oils can be as high as C150 to C550. . When the KV100 kinematic viscosity is desired to be between 4 and 7 mm2 / s, branched and / or cyclic paraffins with a single number of carbon atoms are normally obtained from raw materials containing carboxylic acids with identical chain lengths using the process of the invention, followed by oligomerization and IMO steps.

The range of the number of carbon atoms of the base oil or component of the base oil produced by the oligomerization and the combined HDO-decarboxylation / decarbonylation process is extremely narrow, with the range of the number of carbon atoms of the product being from C30 to C32 for the raw materials normally containing C16 components and from C34 to C36 for the raw materials containing C18 components, when the viscosity range KV100 is desired to be between 4 and 7 mm2 / s. When the raw material is desired to be a mixture of C16 and C18 components, the width of the carbon atom number range of the product is normally seven carbons. The carbon atom number range of the base oil of the invention can also be at a very high level, even as high as C150 to C550 when particularly heavy base oils are desired as viscosity improvers and index improvement is desired. viscosity.

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

In Table 2, the structures of naphthalenes are typical examples of a group of compounds. In the structural examples, the number of carbon atoms varies from the number 1 and 2 oligomeric dimers produced from C18 is between C34 and C36 and between C51 and C54, respectively, while the number of carbon atoms of base oils of Known synthetic hydrocarbons of the same viscosity class, such as PAO, vary between C32 and C48, and C30 and C48 for PIO.

Table 2.

Saturated hydrocarbons are classified according to carbon and hydrogen atoms by field ionization mass spectrometry (using the FIMS)

1 C (n) .H (2n + 2) paraffins

2 C (n) .H (2n) mononaphthenes

3 C (n) .H (2n-2) dynaphthenes

4 C (n) .H (2n-4) trinaphthenes

5 C (n) .H (2n-6) tetranaphthenes

6 C (n) .H (2n-8) pentanaphthenes

In Table 2, the percentages (%, by FIMS) refer to the groups of compounds determined according to said method.

The base oil components in Table 2 are produced as follows:

1. Hydrogenated oligomerized C18 fatty acid dimer produced according to the invention, produced from tall oil

2. Hydrogenated oligomerized C18 fatty acid trimer produced according to the invention, produced from tall oil

3. C16 PAO produced by oligomerization from 1-hexadecene using a heterogeneous catalyst 4. C10 PAO produced by oligomerization from 1-decene using a homogeneous catalyst 5. PIO produced by dimerization of the internal C15-C16 olefin.

The dimers and trimers of the invention (structures 1 and 2 of Table 2) branch in the double bonds of a C18 hydrocarbon chain, thus having pairs of tertiary carbon atoms on 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. Furthermore, a significant amount, even more than 50%, by FIMS, of mononaphthenes is present in the product of the invention. In the prior art method of producing polyalphaolefins, the reaction usually takes place with boron trifluoride catalysts in double bonds at the end of the C10 chain, thus leaving a methylene group (- ^CH 2-) between tertiary carbon atoms. (Structure 4 of Table 2). When oligomerization is carried out using a heterogeneous catalyst, the double bonds are displaced from the alpha position, while simultaneously, skeletal isomerization occurs, thus leaving 1 to 10 methylene groups between tertiary carbon atoms in the typical structure of the base oil obtained (structure 3 from Table 2, for example, 4 methylene groups). When oligomerization is carried out using a homogeneous catalyst, skeletal isomerization takes place respectively in the hydrogenation step after oligomerization, and thus C1-C3 side branches are formed next to the double bonds in the structure 4 molecules. which are shown in Table 2. There are mainly alkyl branches in the PAO and PIO base oils of the prior art, while the naphthenic components branched by ring structures 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 best less than -40 ° C and therefore the base oil is well suited for the demanding low temperature conditions. The viscosity index of the product can be as high as 125, thus making it suitable for Group III base oil applications.

The molecular mass of the product can be adjusted according to the ranges of the numbers of carbon atoms necessary for different applications by adding unsaturated carboxylic acids or olefins suitable for the raw material. Carboxylic acids having small molecules, or olefins crosslinking or oligomerizing with the fatty acids of the triglycerides form short branches on the main hydrocarbon chain of the fatty acid. When other natural cyclic compounds such as alpha pinene are used as additional components of the raw material, molecules are obtained having ring structures on the secondary chain within the molecular chain. One or two additional components are preferably oligomerized in the product. According to the invention, corresponding products tailored with respect to hydrocarbon chain lengths can also be produced from other carboxylic acids and from other short-chain biocomponents. The lighter branched components of the IMO treatment are well suited as components of biodiesel.

The biologically derived base oil produced according to the invention comprises a branched saturated hydrocarbon product. Said product is produced from a biological starting material, said product containing at least 90%, preferably at least 95%, particularly preferably at least 97% and in the best case at least 99% in weight, of saturated hydrocarbons. Furthermore, the product prepared according to the invention contains more than 20%, but not more than 90%; preferably more than 20%, but not more than 80%; and particularly preferably more than 20%, but not more than 60% mononaphthenes, 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 prepared according to the invention contains up to 20%, preferably up to 10%, and particularly preferably up to 5%, and in the best case up to 1% by weight of linear paraffins (GC) .

For base oils prepared according to 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 D2270.

The product prepared according to the invention is branched with carbon-carbon bonds, this structure endowing the product with a very low pour point not higher than 0 ° C, preferably, not higher than -10 ° C, and particularly preferably not higher than -35 ° C (ASTM D 5950).

For base oils, having a KV100 viscosity of 4-7 mtn2 / s, the width of the range of the number of carbon atoms is not more than 9 carbons, preferably not more than 7 carbons, and particularly preferably not more than 3 carbons (determined by field ionization mass spectrometry, FIMS). More than about 50%, preferably more than 75%, and particularly preferably more than 90% by weight of the base oil contains the hydrocarbons belonging to this narrow carbon atom number distribution.

The sulfur content of said base oil prepared according to 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 prepared according to 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 prepared according to the invention contain the carbon 14C isotope, which can be considered as an indication of the use of renewable raw materials. The typical 14C isotope content of the product of completely biological origin is at least 100%, determined as the radioactive carbon content based on the content of radioactive carbon in the atmosphere in 1950 for a product based entirely on biological materials (ASTM D 6866). The 14C isotope content of the base oil is lower when other biological components are used in the processing of the product, said content being, however, more than 50%, preferably more than 90%, particularly preferably more than 99%. In this way, even low amounts of biologically based base oil can be detected in other types of hydrocarbon base oil.

The volatility of the base oil component with a narrow boiling range, obtained according to the invention, is extremely low compared to similar products of the prior art. For the base oil of the invention, the volatility of the product, which has a KV100 value of 3 cSt to 8 cSt, is not higher than 2271.2 * (KV100) -15373% by weight as determined with the DIN 51581 method- 2 (Noack mathematical method based on ASTM D2887 for GC distillation).

The cetane number of the product obtained with the process of the invention, suitable as a diesel component, is more than 40, preferably more than 55, and particularly preferably more 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 aromatic compounds, 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 less than 0 ° C, preferably less than -15 ° C and particularly less than -30 ° C. Normally, the diesel product obtained is entirely of biological origin. In the product of the invention, there are branches formed by carbon-carbon bonds, this structure resulting in a very low cloud point. Due to their biological origin, these products of biological origin also contain the 14C isotope, which indicates the use of renewable raw materials. The 14C content of a product of totally biological origin is at least 100%.

The selection of the biological raw material has a strong influence on the composition and the boiling range of the product. Furthermore, the raw material can be fractionated by distillation into fractions having narrow carbon atom numbers that can be tailor-made for different applications. For raw materials having hydrocarbon chain lengths of C16, C18, C20, and C22, typical carbon numbers of dimeric products are respectively C32, C36, C40, and C44 after hydrodeoxygenation, said numbers of carbon atoms being reduced. carbon in two for C30, C34, C38, and C42 after decarboxylation / decarbonylation. Since the distillation range of the product depends mainly on the length of the hydrocarbon chain, narrow product fractions were obtained.

Advantages of the invention

The process of the invention and the product obtained have several advantages, including, for example, the use of renewable raw materials instead of non-renewable raw materials to reduce carbon dioxide emissions that contribute to the greenhouse effect. A biological starting material containing heteroatoms serves according to the invention as a completely new source of raw material for high quality saturated base oils.

The starting materials of the process of the invention are available worldwide, and furthermore, the use of the process is not limited by significant initial investments, unlike for example with GTL technology. The products of the inventive process are carbon dioxide neutral with respect to its use and disposal, that is, they will not increase the carbon dioxide load 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 in humid conditions, unlike esters and other base oils that contain heteroatoms, such as fatty alcohol dimers. Furthermore, the oxidation resistance of saturated hydrocarbons is better than that of corresponding base oils containing unsaturated groups based on dimers of fatty acids or fatty alcohols, or base oils of esters. A saturated hydrocarbon component does not decompose as easily as esters that form corrosive acids. A non-polar and saturated hydrocarbon component is obtained using the process of the invention by removing oxygen from alcohols, esters, or carboxylic acids in the deoxygenation step, as well as the heteroatoms of any raw material impurities. Oligomerizing the carboxylic acid derivatives results in a structure having branches formed by carbon-carbon bonds upon deoxygenation. In the oligomerization of C12: 1-C20: 1, the lengths of the branches obtained are usually C3 to C11. These hydrocarbons have very low pour points favorable for base oil applications and, therefore, the product is liquid at very low temperatures, and also has a higher viscosity index. The saturated hydrocarbon product produced is a suitable component of base oils without any mixing limitation and is also compatible with lubricant additives.

The base oil prepared according to the invention is endowed with superior technical properties compared to conventional hydrocarbon oils of the corresponding viscosity class, particularly when the KV100 value is 4 to 7 mm2 / s. The narrow boiling range indicates that the product does not contain any initial light fraction, which means that considerably lighter than average molecules show decreased product volatility and result in reduced emissions in practical applications. The base oil product does not contain heavy distillation "tails" which means that the molecules are considerably heavier than average, resulting in excellent low temperature product properties.

For the base oil prepared according to the invention, the number of carbon atoms and the boiling ranges are controlled by the composition of the raw material. For prior art base oils, the boiling range was adjusted by distilling the product to obtain a fraction having the desired kinematic viscosity. It is preferable that the lubricants have base oils with narrow carbon atom numbers and thus narrow boiling ranges, and consequently the compositions contain molecules of similar sizes that behave in different conditions in a similar manner.

For the base oil or the base oil component, the high viscosity index of the product indicates that the amount of the viscosity index improver used in the lubricating compositions can be reduced. It is generally known that, for example, in motor oils, Component VII is the main cause of engine fouling. Furthermore, reducing the amounts of VII results in significant cost savings.

Compared to conventional base oils derived from crude oil, sulfur or nitrogen are not present in such products. Processes based on purified starting materials derived from natural fatty acids allow the safe use of products in such applications where users are exposed to such oil or oil vapor. In addition, the response of the product prepared according to the invention to antioxidant agents and agents that lower the pour point is excellent, thus allowing a longer use of lubricants prepared from said base oil, as well as the use of the same in cold weather conditions.

Compared to esters, the base oil prepared according to the invention is more compatible with conventional base oil components derived from crude oil and with other hydrocarbon base oils, as well as with lubricating additives. Furthermore, there are no problems with elastomers such as those with ester sealing materials.

The advantages of the base oil prepared according to the invention include the fact that it meets the requirements of base oils according to API Group II classification, preferably Group II, and can be used in motor oil compositions analogously to other oils. base of API Group II or III classification, according to the same oil change rules.

The base oil prepared according to the invention is derived from renewable natural sources as is clearly seen by the content of the 14C isotope 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 bio-based base oil component can also be determined on the basis of the 14C isotope content of the base oil with an accuracy of at least 1%.

The low temperature properties and the cetane number of the middle distillate produced by the process of the invention, suitable as diesel fuel, are also excellent, thus being the middle distillate suitable in demanding low temperature applications.

With the optional prehydrogenation step, side reactions of double bonds such as polymerization, ring formation and aromatization can be decreased, said side reactions being detrimental to the viscosity properties of the products and causing the formation of coke on the IMO catalyst. By optional recirculation of unreacted raw material components, more double bond reactions can be achieved to improve product yield.

Instead of or in addition to the biological starting materials, the synthetic compounds having a corresponding chemical structure can also be used in the invention as the raw material.

The properties of the hydrocarbon components produced according to the invention, and described in the following examples are excellent, and furthermore, the ranges of the number of carbon atoms and the distillation ranges are very narrow. The process of the invention provides a molecular structure that has superior viscosity properties and excellent low temperature properties. The products are very suitable as base oils without mixing limitations and, furthermore, the products are also compatible with lubricant additives.

The invention is illustrated below by the following examples. The objective is, however, not to limit their scope to the described embodiments or to combinations thereof. The invention may also be carried out in a manner other than that described without departing from the appended claims.

Examples

Example 1

Preparation of a hydrocarbon component derived from vegetable oil

Raw material containing 200 ml of soybean oil, 6 g of montmorillonite catalyst and 5 ml of distilled water, was introduced into a high pressure Parr reactor. The temperature was increased to 270 ° C and the oil was allowed to oligomerize with slow mixing for 7 hours.

Subsequently, in the IMO step, the previously oligomerized mixture was hydrogenated in the high pressure Parr reactor using the dried and activated NiMo / A ^ Oa catalyst to result in 200 ml of i-paraffin from the oligomerized soybean oil mixture that it was hydrogenated at 325 ° C, at a hydrogen pressure of 5 MPa, until no acid groups were detected in the FTIR spectrum of the sample. The reaction mixture was mixed at 300 rpm. The final product was distilled and mainly branched and cyclic C36 paraffin was obtained as the product.

Table 3 shows the properties of the hydrocarbon component obtained. The hydrocarbon components can also be produced in a similar way from other vegetable and fish oils and animal fats that comprise double bonds.

Example 2

Preparation of a hydrocarbon component from carboxylic acid methyl esters derived from soybean oil

Soybean oil was pretreated by transesterification with methanol under basic conditions, at a temperature of 70 ° C at a pressure of 0.1 MPa in the presence of a two-stage sodium methoxide catalyst. The carboxylic acid methyl esters were purified by washing with an acid and water, and then dried. The carboxylic acid composition of the methyl ester derived from soybean oil was as follows: C16: 0.11%; C18: 2.10%; Cl8: 1.8%; C18: 2.54%; and C18: 3.6%. The carboxylic acid methyl ester mixture obtained above was oligomerized in a Parr reactor under high pressure. 200 ml of the raw material and 6 g of bentonite catalyst were introduced into the reactor, the reactor was pressurized with nitrogen twice to displace the oxygen, then the temperature was increased to 350 ° C, and the mixture of the methyl ester of the carboxylic acid was allowed to oligomerize while mixing slowly for 7.2 hours. The monomeric, dimeric and trimeric methyl esters were separated from the reaction mixture using a column of silica gel.

Next, the dimeric and trimeric methyl esters obtained above were hydrogenated respectively as described in example 1 and the final product was distilled, thus giving a yield of 26%, by weight, of branched and cyclic C36 paraffin, and 15 %, by weight, of branched and cyclic C54 paraffin.

The properties of the hydrocarbon component obtained are presented in Table 3. The properties of the product are excellent, the molecular distribution being very narrow. The hydrocarbon components can also be produced in a manner similar to that of the other carboxylic acid methyl esters of plant, fish or animal origin comprising several double bonds. Process performance can be improved by recirculating unreacted monomers.

Example 3

Preparation of a hydrocarbon component from tall oil derived carboxylic acids

In the pretreatment step, tall oil carboxylic acids were distilled. Subsequently, the carboxylic acids were oligomerized in a high pressure Parr reactor. 200 g of the raw material (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 with slow mixing for 3 hours. The mixture was cooled and the catalyst was removed by filtration. The monomers were separated from the dimers and trimers (acids) of the reaction mixture using a column of silica gel. The yield of the carboxylic acid dimer was 45%, by weight.

In the IMO step, the dimers containing the fraction were hydrogenated as in Example 1 until the peak of the carboxylic acid was not present in the FTIR spectrum. Both branched and cyclic paraffins were obtained as the product.

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

Example 4

Preparation of a hydrocarbon component from tall oil derived carboxylic acids, using prehydrogenation

In the pretreatment step, tall oil carboxylic acids were distilled. The raw material then comprised 30% C18: 1 carboxylic acids, 42% C18: 2, and 9% C18: 3, by weight. Furthermore, the raw material contained 2% resin acids. The tall oil carboxylic acids were oligomerized in a high pressure Parr reactor. 200 g of the raw material mixture, 16 g of montmorillonite catalyst and 10 g of water were charged to the reactor. For oxygen displacement, 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. The temperature was then increased to 225 ° C and the carboxylic acids were allowed to oligomerize with slow mixing for 2 hours. The product was cooled and the catalyst was removed by filtration. Monomers, dimers and trimers (acids) were separated from the reaction mixture using a silica gel column. The yield of the carboxylic acid dimer was 45%, by weight.

Before the IMO step, the double bonds of the dimers obtained above were hydrogenated using a presulfurized NiMo / A ^ Oa catalyst in a 450 ml Parr reactor at high temperature. Prehydrogenation was carried out using a dry activated catalyst at 230 ° C, at a hydrogen pressure of 5 MPa with mixing at 300 rpm. Hydrogenation of the dimers was continued until no double bonds were observed in the FTIR spectrum. The dimers were hydrogenated in the IMO step as in Example 1, until the carboxylic acid peak disappeared from the FTIR spectrum, followed by filtration of the paraffinic kieselguhr product. Branched and cyclic C34, C35, C36 paraffins were obtained as the final products.

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

Example 5

Preparation of a hydrocarbon component from carboxylic acid methyl esters derived from soybean oil and alpha pinene

Soybean oil was transesterified with methanol as in Example 2, resulting in methyl carboxylic acid esters. The reaction mixture was purified by washing with acid and water. Finally, the carboxylic acid methyl ester was dried. The carboxylic acid composition of the methyl ester was as follows: C16: 0.11%; C18: 0.20%; C18: 1.8%; C18: 2.54%; and C18: 3.6%.

The soybean methyl ester obtained above was oligomerized with alpha pinene, the molecular ratio being 2: 1 respectively, in a high pressure Parr reactor using 8% of a bentonite catalyst and 4% of water.

200 ml of the raw material mixture was introduced into the reactor. Oxygen displacement was performed as in Example 4. The temperature and pressure were increased respectively to 310 ° C, and 2 MPa, and the soybean oil methyl ester was allowed to oligomerize with alpha pinene with slow 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, thus yielding a pinene-branched C28 isoparaffin, and a mixture of paraffinic dimers and trimers derived from carboxylic acid methyl ester. The properties of the hydrocarbon component obtained as the product are presented in Table 3. Branched hydrocarbon components can also be produced in a similar way from other carboxylic acids of origin. vegetable, animal or fish, or of fats, said acids comprising several double bonds, or methyl esters of carboxylic acids and suitable compounds with small molecular sizes, preferably of biological origin.

Example 6

Preparation of a heavy hydrocarbon component from tall oil carboxylic acids. The tall oil was oligomerized as in Example 3, except that the reaction was carried out with slow mixing for 7 hours. The trimers were separated from the dimers and monomers in the reaction mixture using a column of silica gel.

The trimers obtained above were hydrogenated in an IMO step as in Example 1 until the peak of the carboxylic acid was not present in the FTIR spectrum. Both branched and cyclic paraffin were obtained as the product. Table 3 shows the properties of the product. Hydrocarbon components can also be produced in a similar way to free carboxylic acids derived from oils other than tall oil, or from hydrolyzed carboxylic acids from vegetable or fish oil or animal fats, said acids comprising double bonds .

Table 3

Table 4. Properties of prior art base oils

continuation

Example 7

Demonstration of the biological origin of the hydrocarbon component

The biologically derived hydrocarbon component from Example 6 was weighed into a Group III mineral oil derived base oil and mixed thoroughly. For the first sample, 0.5014 g of the bio-based hydrocarbon component was weighed, and the Group II base oil component was added in sufficient quantity to obtain a total weight of 10.0 g; For the second sample, 1.0137 g of the bio-based hydrocarbon component was weighed, and the Group II base oil component was added in sufficient quantity to obtain a total weight of 10.0232 g. then. The results were expressed as "percentage of modern carbon", based on the content of radioactive carbon in the 1950 atmosphere. Currently, the percentage of modern carbon in the atmosphere is approximately 107%. 313 C which is the quotient of stable 13c / 12c carbon isotopes. Using this value, you can correct for isotope fractionation that occurs during the sample treatment process. The current results are presented in the last column. The method is ASTM D6866.

Table 5

Example 8

Distribution of the number of carbon atoms

The carbon atom number distribution of base oils according to the invention is described as narrower than that of conventional base oils. The base oils of the invention contain higher amounts of higher boiling C34-C36 fractions compared to conventional products of the same viscosity range (KV100 about 4 cSt), as shown in Figure 2. The distribution of the number of carbon atoms is determined by FIMS. The FIMS test sample is that of Example 4 with C18 tall oil fatty acid feedstock. In addition to hydrodeoxygenation to produce C36 compounds, also decarboxylation / decarbonylation produces C35 / C34 paraffinic compounds (combined HDO-decarboxylation / decarbonylation).

Claims (15)

1. Process for the production of a saturated hydrocarbon component, characterized in that a raw material comprising one or more components selected from the group consisting of carboxylic acids having numbers of carbon atoms from C4 to C38, carboxylic acid esters of C4 to C38 and C1-C11 alcohols, C4-C38 carboxylic acid anhydrides, and C4-C38 alcohols, component (s) that are at least 50% unsaturated and / or polyunsaturated by weight, oligomerizes in the presence of a cationic clay catalyst and is deoxygenated to remove oxygen, where deoxygenation is carried out as a hydroxydesoxygenation, deoxygenation being carried out in the presence of hydrogen, at a temperature between 200 and 500 ° C, under a pressure between 0 and 20 MPa, the WHSV flow rate being between 0.1 and 101 / h, in the presence of a hydrodeoxygenation catalyst selected from a Pd, Pt, Ni, NiMo or CoMo catalyst that has an alumina or silica gel support. e, before or after oligomerization. 2. The process according to claim 1, characterized in that the cationic clay catalyst is a zeolite catalyst. 3. The process according to claims 1 or 2, characterized in that the raw material comprises one or more components selected from the group consisting of carboxylic acids having carbon atom numbers from C4 to C24, carboxylic acid esters C12 to C24 and C1-C3 alcohols, C12-C24 carboxylic acid anhydrides and C12-C24 alcohols. 4. The process according to any of claims 1-3, characterized in that the raw material comprises at least one starting material of biological origin, selected from the group consisting of triglycerides, fatty acids, esters of fatty acids and alcohols, anhydrides of fatty acid and fatty alcohols. 5. The 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 fats, fish oils, fish waxes, and their mixtures, and c) esters obtained by transesterification from vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and mixtures of the same, and d) esters obtained by esterification of free fatty acids of vegetable, animal and fish origin with alcohols, and their mixtures, and e) fatty alcohols obtained as products of reduction of fatty acids from vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes, and their mixtures, Y f) residual fats and food grade recirculated fats and oils, and genetically engineered fats, oils and waxes, and mixtures thereof, and g) mixtures of said starting materials. 6. The process according to any of claims 1-5, characterized in that the components contain at least 80% by weight of unsaturated and / or polyunsaturated compounds. The process according to any one of claims 1-6, characterized in that the oligomerization is carried out at a pressure of 0 to 10 MPa and a temperature of 100 to 500 ° C. 8. The process according to any of claims 1-7, characterized in that up to 10%, preferably 0.1 to 4% by weight of water is added to the raw material containing the carboxylic acids in the oligomerization step. 9. The process according to any of claims 1-8, characterized in that before hydrodeoxygenation, the product of the oligomerization stage is subjected to prehydrogenation in the presence of a catalyst, at a temperature of between 50 and 400 ° C, under a hydrogen pressure between 0.1 and 20 MPa, the WHSV flow rate being between 0.1 and 101 / h. 10. The process according to claim 9, characterized in that the catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst having an alumina and / or silica gel support. The process according to any of claims 1-8, characterized in that the raw material of the process, or the product of the oligomerization step, is subjected to decarboxylation / decarbonylation in the presence of a decarboxylation / decarbonylation catalyst, at a temperature between 200 and 400 ° C, a pressure between 0 and 20 MPa, the WHSV flow being between 0.1 and 101 / h. 12. The process according to claim 11, characterized in that the decarboxylation / decarbonylation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst having an alumina and / or silica gel support or a activated carbon. 13. The process according to any of claims 1-12, characterized in that after the oligomerization and deoxygenation stages, the product is subjected to isomerization in the presence of hydrogen gas at a pressure of between 0.1 and 20 MPa, at a temperature between 100 and 500 ° C, in the presence of an isomerization catalyst. 14. The process according to claim 13, characterized in that the isomerization catalyst is a supported catalyst containing a molecular sieve and a metal from Group VIII of the periodic table of elements. 15. Use of the process according to any one of claims 1-14 to produce fractions of base oil, gasoline, solvent and / or diesel.