FI20055661A - Process for producing saturated hydrocarbon component - Google Patents

Description

PROCESS FOR THE SATISFACTION OF A SATISFIED HYDROCARBON COMPONENT

PROCESS FÖR FRAMSTÄLLNING AV MÄTTADKOLVÄTE COMPONENT

ENGINEERING

The present invention relates to a process hydrocarbon component based on oligomerization and deoxygenation, and in particular to a hydrocarbon-based high quality saturated base oil or base oil component of biological origin. The feed used in the process may be derived from vegetable oils, animal and fish fats, natural waxes and similar synthetic materials, and combinations thereof.

BACKGROUND OF THE INVENTION

Base oils are commonly used in the manufacture of lubricants such as rolling stock lubricants, industrial lubricants and lubricating greases, process oils, white oils and metalworking fluids. Lubricants typically contain base oils and additives. In lubricant applications, in particular for the automotive industry, there has been an increasing demand for lubricants, and thus also base oils, for technical specifications, but the requirements for environmental and health effects have also become stricter. Conventional mineral oils are no longer capable of producing lubricants that meet the specifications of the most demanding car manufacturers. Mineral oils typically contain excessively high levels of aromatic, sulfur, and nitrogen compounds, and exhibit considerable volatility and a viscosity-temperature dependence of a mixed viscosity index. In addition, the response of mineral oils is e.g. Antioxidants are often weak.

Especially in automotive lubricants such as engine and gear oils, synthetic Jans. semisynthetic base oils have become increasingly important. A similar trend can be seen in industrial lubricants.

The lubricants are designed to last as long as possible, so that the user does not need to change the oil very often, maintenance intervals for commercial vehicles are maximized. The engine oil change interval for passenger cars has increased by up to five times over the last ten years to 50,000 km at its best. Heavy-duty vehicles now have an oil change interval of 100,000 km.

High quality lubricants use base oils according to API (American Petroleum Institute) Group III or IV classifications. The basic API classification is shown in Table 1.

Group HI oils are very high viscosity index VHVI base oils which are produced from crude oil by hydrocracking and then isomerization of waxy straight paraffins to branched paraffins. Group III oils also include base oils derived from mineral oil-based Slack Wax paraffin waxes (SW waxes) and Fischer-Tropsch synthesis, for example, from coal or natural gas waxes (GTL waxes). Group IV oils are synthetic polyalphaolefins.

ATIEL (Association of Technique De L'In-Dustrie Europeenne Des Lubrifiants or Technical Association of The European Lubricants Industry) has a similar rating, but ATIL has an additional rating of Group VI: Polyintem Lolefins (PIO). In addition to the official classification, the H + group, which includes saturated and sulfur-free base oils with a viscosity index greater than 110 but less than 120, is commonly used in the art. Saturated hydrocarbons include paraffinic and naphthenic compounds but not aromatics.

Lubricant production is generally influenced by the increasing life cycle and EHS (= Environment, Health and Safety) thinking that product life should be maximized and the damage caused by product manufacture, use and disposal minimized. Longer oil-change intervals reduce the consumption of non-renewable crude oil-based raw materials and the amount of waste oil that is classified as hazardous waste.

Lubricants should be as harmless to the user and the environment as possible during use and other handling. This means low concentrations of base oils, among others, for metals, aromatic compounds, volatile components, and nitrogen and sulfur compounds.

The use of renewable raw materials and recycled oils in the manufacture of lubricants is of increasing interest. The problems of recycled oils are their difficult refining and reprocessing into high quality liposomal oils and the cost of developing a functioning and comprehensive recycling system.

So far, bio-based lubricants, which refer to lubricants based on biological raw materials, use only esters, the use of which has been limited to a few specific applications such as cold compressor oils, biohydraulic fluids and metalworking fluids. In standard lubricants, such as automotive and industrial lubricants, they have been used mainly in the additive scale. The high price limits the use of esters. In addition, for example, in the automotive lubricant compositions, there are no exchange rules for esters, while for other base oils such exist. If the ester in the composition is to be replaced, all expensive engine tests must be repeated, even if the replacement ester is, in principle, chemically equivalent. Esters have encountered some technical problems because the lubricating oils produced from them have very different characteristics to other used petroleum oils. Ester bonds of ester base oils are prone to hydrolysis to produce corrosive acids in lubrication systems. If the esters are prepared from unsaturated carboxylic acids, the double bonds of the esters are extremely susceptible to oxidation, especially at higher temperatures. Esters are remarkably polar and more active. Elastomers for use as sealing materials and hoses are completely different from polar or less polar base oils. This has caused problems, especially in high-pressure hydraulics applications such as forest machines using biohydraulics. Another even more significant problem with esters is the loss of the effect of existing polar additives developed on less polar hydrocarbon base oils in polar ester-based base oils.

The use of hydrocarbon components of biological origin, i.e., bio-based raw materials in base oil compositions, is of growing interest, as renewable bio-based raw materials are available and generally desirable. Another aim is to improve the efficiency of the utilization of waste containing bio-based raw materials, such as animal carcasses.

Processes in which triglycerides are cross-linked in a controlled manner using a suitable metal salt or peroxide initiator which readily captures hydrogen from the C-H bond and a suitable amount of free oxygen are known in the art. Cross-linking caused the airborne Vian ^ n to remain silent without the need for any heat.

however, the reaction is slower. This cross-linking is based on oxygen-to-oxygen bonds formed on Mole villages. In the case of triglycerides crosslinking, the degree of crosslinking can be monitored by processing time and kinematic viscosity. Viscosity increases with crosslinking as time goes on and as the product decomposes.

It is also known to produce a batch process batch process oil (standoil) based on double bonds reaction from triglycerides in which carbon dioxide is introduced into the reactor to prevent oxidation. The cross-linking is then based on carbon-carbon bonds formed on the molecules. Products of thermal reaction decomposition by means of a stream of carbon dioxide gas evacuated or alternatively by vacuum. Cross-linking is an exothermic reaction, so maintaining the temperature at 280-300 ° C requires an efficient heating reaction as well as an effective cooling to prevent the product from overheating. Further, when the desired viscosity for the degree of crosslinking is achieved, the reaction vessel must be cooled rapidly.

Kirk-Othmer: Encyclopedia of Chemical Technology, 3rd Ed., Vol. 7, Dimer acids, p. 768 discloses a process for the preparation of dimeric acids from unsaturated carboxylic acids by radical reaction with a cationic catalyst at a reaction temperature of 230 ° C. In addition to the acyclic, branched, unsaturated dimeric acid end product, mono- and bicyclic dimers are formed.

Unsaturated alcohols can be oligomerized similarly to unsaturated carboxylic acids by heat and / or catalyst to alcohol dimers. The main product is an acyclic, unsaturated, branched diol dimer.

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

The above-mentioned triglyceride, carboxylic acid methyl ester, carboxylic acid podimer and fatty alcohol dimer products can be used in lubricant applications, but as having heteroatoms they have the same weaknesses as ester-based base oils.

Processes of oxygen deprotection of a carboxylic acid or ester are known in the art. Decarboxylation of carboxylic acids yields hydrocarbons having one carbon less than the parent molecule. The applicability of decarboxylation depends on the carboxylic acid used as starting material. The most active are ovazellic carboxylic acids having electron-withdrawing substituents on carbonyl carbon in alpha or beta carbon. Of these compounds, carbon dioxide is easily cleaved when the temperature is raised because of the weak bond of RC-COOH. With other types of carboxylic acids, the hydrocarbon chain causes an opposite increase in electron density in alpha carbon, making carbon dioxide cleavage difficult. Maier, W.F. et al., ChemischeBerichte (1982), 115 (2), 808-812 are prepared from carboxylic acids with hydrocarbon-containing heterogeneous Ni / AhO1 and Pd / SiO2 catalysts at 180 ° C under a hydrogen atmosphere. Combined decarboxylation and hydrodeoxygenation of oxo compounds is described in Laurent, E., Delmon, B., Applied Catalysis, A: General (1994), 109 (1), 77-96 and 97-115, in which hydrodeoxygenation of biomass-based pyrolysis was accomplished with CoMo / y -ALOa and NiMo / γ-AhCb catalysts at 260-300 ° C and 7 MPa hydrogen pressure. Reactions of the hydrodeoxygenation step are strongly exothermic and require high hydrogen.

FI 100248 discloses a two-step process for the preparation of a middle distillate from vegetable oil by hydrogenation of the carboxylic acids or triglycerides of vegetable oil to straight chain cinoneone paraffins and then isomerization of the n-paraffins to branched paraffins. For hydrogen treatment, a temperature of 330-450 ° C, a pressure of about 3MPa and a fluid flow rate of LHSV of 0.5-5 l / h were used. During the isomerization step, a temperature of 200-500 ° C, an excess pressure and a liquid flow rate of LHSV0.1 -10 1 / h were used.

Methods are also known for the preparation of diesel-grade saturated hydrocarbon components from organic oils by hydrogenation processes with NiMo and CoMo catalysts at 350-450 ° C.

The isomerization processes use precious metal catalysts which are expensive and very sensitive to catalyst poisons and water. Bio-based raw materials contain a lot of oxygen, which, when processed, produces hydrogen, carbon monoxide and carbon dioxide. In addition, bio-based raw materials often contain nitrogen, sulfur and phosphorus compounds which are known noble metal catalyst catalyst poisons and inhibitors. These lead to reduced catalyst life and often require repeated catalyst regenerations unless removed prior to the isomerization process.

Vegetable oils, animal fats and fish oils typically contain triesters of glycerol and fatty acids having the structure shown below:

wherein R 1, R 2 and R 1 are C 4 to C 30 hydrocarbon chains. Fatty acids are straight chain and long chain carboxylic acids. The main hydrocarbon chain length is 18 carbons (Cl8). C18 Fatty acids are typically bound to the middle hydroxyl group of glycerol. The fatty acids attached to the other two hydroxyl groups have a typical carbon number even and between C14-C22.

The fatty acid composition can vary considerably in fats and oils of different origins. Although fatty acids may have multiple double bonds, they are not conjugated, but have at least one -CH 2 unit in between. Configuration To the east, the double bonds of natural fatty acids are in the cis form, whereby the hydrogens are on the same side of the 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 chain and the amount of double doxes depend on the source of vegetable or animal fat or wax for the fatty acid. Animal fats typically contain more saturated fatty acids than double-bonded fatty acids. Fatty acids in fish oils are rich in double bonds and are on average longer in hydrocarbon chains than fatty acids in vegetable oils and animal fats. The fatty acid composition plays a major role in evaluating the oxidation resistance, heat resistance, cold properties, and what kind of oligomerization products are obtained of the feed to the oligomerization.

The waxes are mainly carboxylic acids esterified with long chain alcohols. In addition, waxes contain various amounts of paraffins (n-alkanes), ketones, jad ketones, primary and secondary alcohols, aldehydes, alkanoic (carboxylic) acids and terpenes. These carboxylic acid and alcohol chains typically have a carbon number of C12-C38.

Biological raw materials are generally pre-treated by appropriate known techniques, including thermal, mechanical, for example shear, chemical or acid or alkali treatment, or physical irradiation, distillation, cooling, or filtration prior to processing. The purpose of chemical and physical pre-treatment is to remove impurities that impede the processing or poison the catalysts and to reduce unwanted side reactions. Feed impurities are generally compounds containing heteroatoms which are catalyst poisons. Impurities can also be components of the product that are degraded during processing, such as aromatics,

In hydrolysis treatment, oils and fats react with water to obtain free carboxylic acids and glycerol. Three processes are known for the industrial production of fatty acids by hydrolysis: high pressure vaporization of triglycerides, basic hydrolysis and enzymatic hydrolysis. In a typical steam sputtering process, the hydrolysis of triglycerides by steam is achieved at a temperature of 250-260 ° C and a pressure of 4-5.5 MPa. Zinc oxide may be added to the catalyst to accelerate the reaction. High temperature and pressure make the fats dissolve in water.

Paraffinic synthetic base oil components prepared by oligomerization are known in the art, the most typical of which are PAO (polyalpha Olefins) and PIO (polyintemal Olefins) polyolefin. These are prepared using crude oil-based olefinic starting materials containing non-heteroatoms. The development of Polyalfaole-type base oils began in the 1930s in both the USA and Germany, where products with good cold performance, mainly for aircraft, were developed. The 1-alkene monomers used as starting material for PAO are typically prepared from ethylene. In commercial PAOs, C8-C12 alpha-olefins or C14-C18 alpha-olefins are used primarily as raw materials. In the preparation of PAO, the monomer is polymerized to a heavier product by thermal or Ziegler type or Friedel-Crafts type catalysts or by means of zeolite catalysts, distilled to the desired product fractions and hydrogenated to saturated paraffins. PAO products can be manufactured in many viscosity classes, with typical viscosities at 100 ° C (KV100) of 2, 4, 6 and 8 mm 2 / s. In addition, particularly thick base oils PAO40 and PAOIOO, having KV100 values of 40 and 100 mm2 / s, are commonly used for thick lubricants and viscosity index enhancers (VII). PAO products have a high viscosity index and, at the same time, excellent cold properties, with a melting point of up to -60 ° C. Product distillation-derived products have low volatility and high flash points. The antioxidant resistance is quite modest without antioxidant additives.

PIOs are prepared by oligomerizing internal olefins in which the double bond is not at the end of the olefinable olefin, such as alpha-olefins, but is statistically distributed over the entire hydrocarbon chain length. Internal olefins can be prepared by dehydrogenation of crude oil-based n-paraffins. Products made from internal C15-C16 linear oleyls have a different molecular structure from PAO. PIO has poorer properties compared to PAO; it has a lower viscosity index, a lower pour point and a higher volatility. PIOs are located qualitatively between PAO and VHVI. The production technology of PIO is similar to that of PAO, but the oligomerization of less reactive internal olefins requires a more aggressive catalyst system. The solubility of the additives in PAO and PIO is quite poor due to the lack of polarity. Esters are often used in formulations to improve solubility.

The use of a heteroatom-containing feedstock or intermediate, optionally thermally and / or chemically and / or physically and / or mechanically treated, in the process of making a high quality saturated base oil or base oil component has not yet been disclosed.

From the foregoing, it can be seen that there is an obvious need for a new alternative process for the manufacture of the hydrocarbon component, preferably from bio-based raw materials, which can bypass or at least substantially reduce the problems of prior art solutions. In addition, there is a need for a non-volatile saturated base oil that meets the quality requirements of a high quality base oil that is preferably bio-based and has a more beneficial effect on the environment and end users than conventional mineral base oils. There is also a need for a process based on saving non-renewable raw materials and utilizing renewable raw materials.

OBJECT OF THE INVENTION

It is an object of the invention to provide a process for the preparation of a saturated hydrocarbon component which preferably utilizes bio-based raw materials.

It is also an object of the invention to provide a process for preparing a base oil or base oil component.

It is also an object of the invention to provide a process for the preparation of a non-heteroatom-saturated base oil or base oil component from work-based raw materials.

It is also an object of the invention to provide a process for the preparation of a non-heteroatom-saturated diesel component and a gasoline component from bio-based raw materials.

It is also an object of the invention to provide a base oil or base oil component which meets the requirements of API Group III.

Characteristic features of the process according to the invention as well as the base oil and the base oil component are set forth in the claims.

GENERAL DESCRIPTION OF THE INVENTION

The process of the invention comprises an oligomerization step wherein the feedstock molecules react with each other to increase the carbon number of the resulting component, and a deoxygenation step. Deoxygenation can be accomplished either by a hydrodeoxygenation reaction or by a decarboxylation / decarbonylation reaction. The process of the invention may further comprise an optional isomerization step for isomerization of lighter products and / or a final step. Preferably, the primary feed is a bio-based feedstock.

By oligomerization herein is meant dimerization, trimerization and tetramerization reactions, as well as polymerization and crosslinking reactions.

The oligomerization step of the process of the invention is carried out to grow hydrocarbon chains of unsaturated carboxylic acids and / or derivatives thereof, such as esters, anhydrides and alcohols, from monomer units to dimers of two monomer units and larger oligomers. In this oligomerization reaction, the double bonds of the compounds react with one another under the influence of heat and / or magic catalyst.

Carboxylic acids and their derivatives also include derivatives of fatty acids and rabbits. Carboxylic acids and their derivatives have a carbon number of at least C4. Preferably, fatty acids of biological origin and / or derivatives thereof are used.

Deoxygenation herein refers to the removal of oxygen by either a hydrodeoxygenation reaction or a decarboxylation / decarbonylation reaction. After deoxygenation, the structure of the biological raw material has changed to either paraffinic or olefinic co-catalyst and reaction conditions.

Hydrodeoxygenation (HDO) here refers to the removal of oxygen by hydrogen. The reaction releases water. The structure containing the ester, alcohol, anhydride or carboxylic acid groups is then decomposed and any oxygen, nitrogen, phosphorus and sulfur compounds are removed as well as the light hydrocarbons as gases.

Decarboxylation herein refers to the removal of carboxylic acid as carbon dioxide, and decarboxylation refers to the removal of carboxylic acid as carbon monoxide.

Isomerization, as used herein, refers to the hydrogen isomerization of straight-chain paraffins, whereby branches are obtained in the structure.

In this context, saturated hydrocarbons include paraffinic and naphthenic compounds, but not aromatics. The paraffinic compounds may be either branched or unbranched. Naphthenic compounds are cyclic saturated hydrocarbons, or cycloparaffins. Such an annular hydrocarbon is typically a derivative of cyclopentane or cyclohexane. The naphthenic compound may have one or more ring structures.

The saturated base oil or base oil component herein comprises saturated hydrocarbons.

The pressures in this context are the pressures above normal atmospheric pressure.

The classification of a periodic system is the IUPAC classification.

The carbon number range herein refers to the difference between the highest and lowest molecular weight carbon numbers plus one.

The invention is illustrated by the following Figure 1, however, the embodiment of which is not intended to be limited.

PATTERN

Figure 1 shows a preferred embodiment of the process according to the invention. One or more feeds selected from the group consisting of: triglyceride feed stream 1, fatty acid feed stream 2, ester feed stream of fatty acids and short alcohols, fatty acid anhydride stream 4 and fatty alcohol stream 6, either as single components or as mixtures of O as a diluent, part of a lighter, recyclable product fraction (e.g., 52) or hydrocarbon stream 201. The diluent stream 202 comprises a cycle stream 52 or hydrocarbon stream 201 or a mixture thereof. From the oligomerization reactor 10, a product 11 containing feedstock reactants from its double bonds is derived and hydrogen is stream 7 into an optional prehydrogenation reactor 20, which optionally can be led to a diluent stream 202. The hydrogenated product from the prehydrogenation reactor 20 optionally, leads to a diluent 202. If deoxygenation is performed by a decarboxylation / decarbonylation reaction, a mixture of hydrogen 7 and an inert gas such as nitrogen (not shown) can be used as the gas stream. The product containing the saturated hydrocarbons obtained from the deoxygenation reactor 30 is fed as a stream 31 to a distillation and / or separation section 40, where the different product fractions gas, gasoline 43, diesel 42 and base oil 41 are separated. Optionally, the lighter fractions of gasoline 43 and diesel 42 are isomerized in the hydroisomerization unit 50 in the presence of hydrogen 7 to yield gasoline 51 and diesel 52 streams containing branched hydrocarbons.

Specifically, when fatty acids 2 and / or fatty acid esters 3 and / or fatty alcohols 6 are oligomerized, product stream 12 and non-oligomerized components can be taken from oligomerization reactor 10, for example by distillation 60. in connection with distillation 60, stream 63 can be led to cold filtration80 where the saturated components 81 are separated from the double bonded components 82 resulting from oligomerization 10. Alternatively, distillate 61 can be led to , From the Post-oligomerization Reactor 70, a product containing feeds reacted by their double bonds is fed as a stream 71 to the optional pre-hydrogenation reactor 20.

DETAILED DESCRIPTION OF THE INVENTION

Surprisingly, it has been found that in the process of the invention comprising the oligomerization step, the deoxygenation step and the optional isomerization step, the unsaturated carboxylic acids and their derivatives, especially the fatty acids, fatty acids, It can be used to make a saturated high quality base oil or base oil component. Problems with prior art processes and products made with them can be avoided or at least substantially reduced by the process according to the invention.

In particular, the process according to the invention can utilize oligomerization reactions of biological materials in combination with the deoxygenation reaction in a novel way for the production of a saturated base oil. Unsaturated carboxylic acids and / or derivatives thereof such as fatty acids, fatty acid esters, fatty alcohols, fatty acid anhydrides or mixtures thereof are oligomerized from monomer units to dimers containing two monomer units and larger. When using bio-based raw materials in the production of base oil, it is necessary to increase the length of their hydrocarbon chain to the carbon number range required by base oil applications so that non-carbon-carbon bonds remain in the molecular structure of the molecule. According to the invention, this is accomplished by reacting the double bonded compounds to form the desired carbon-carbon bonds in the molecules and causing the hydrocarbon stream carbon number to increase to the range CIS-C550. Typically, the carbon number range of base oil applications is Cl8 to C76 and the carbon number range of ultra-thick petroleum oils with power up to Cl50 to C550. In the oligomerization reaction, for example, the double bonds of the triglycerides react with each other to form a polymeric network of triglycerides. Other feedstocks provide dimers, trimers and tetramers formed mainly through double bonds. If the feed contains polyunsaturated hydrocarbon chains, oligomerization and deoxygenation will result in more trimeric ring hydrocarbons compared to monounsaturated hydrocarbon chains.

In the process of the invention, the feed of biological and / or synthetic origin is oligomerized and deoxygenated. Preferably, the oligomerization of the unsaturated feeds is first performed and then the product obtained is subjected to deoxygenation to remove heteroatoms to yield the saturated paraffins. Alternatively, the unsaturated feed is subjected to initial deoxygenation to remove heteroatoms and oligomerization of the olefinic product thus obtained, however, the deoxygenation is performed by a decarboxylation or decarbonylation reaction and is not suitable for the hydrodeoxygenation reaction.

The process may further comprise optional isomerization of lighter components after deoxygenation. As a by-product of the process, shorter-chain straight-chain paraffins of the non-base hydrocarbon class can be isomerized to form hydrocarbon side-branches which increase the fluidity of the product. These isomerized products can be used, for example, as gasoline art diesel precursor components, and the C18-C24 carbon number components can also be used as light base oil components.

Further, the process may comprise an optional prehydrogenation step prior to deoxygenation, an optional post-oligomerization step after the actual oligomerization step, optional intermediate purification steps, product recycling steps and a finishing step. Optionally, the feed may be subjected to one or more pre-treatment steps to purify and / or prepare the feed.

PASS

In the process according to the invention, the feed comprises one or more components selected from triglycerides, esters of C4-C38 carboxylic acids, C4-C38 carboxylic acids and C1-C11 alcohols, C4-C38 carboxylic acid anhydrides and C4-C38 alcohols. Preferably, the feed is selected from triglycerides, esters of C4-C24 fatty acids, C12-C24 fatty acids and C1-C3 alcohols, C12-C24 fatty anhydrides, C12-C24 fatty alcohols, and mixtures thereof. Preferably, the feed comprises bio-based raw material or mixtures thereof.

Suitable bio-based raw materials are selected from the group consisting of (a) vegetable fats, oils, waxes, animal fats, oils, waxes, and tallow oils, oils, waxes, and (b) vegetable fats, oils, waxes, animal fats , oils, waxes, fish fats, oils, waxes and their mixtures, by hydrolysis, by transesterification or by pyrolysis of carboxylic acids or liberated carboxylic acids; and (c) vegetable fats, oils, waxes, animal fats, oils, and (d) vegetable, animal and fish-based free carboxylic acids from esters obtained by alcohol esterification; (e) vegetable fats, oils, waxes, animal fats, oils, fatty alcohols derived from carboxylic acid reducing products of waxes and of fish fats, oils, waxes or their blends; and (f) recycled; edible fats and oils, fats, waxes and oils produced by genetic engineering; and (g) mixtures of the above.

In this context, plants include algae and animals include insects. The bio-derived raw material may contain free carboxylic acids and / or carboxylic acid esters or oligomerization products of the biological raw material without substantially impairing their processing. All feed types mentioned above which are either wholly or partially synthesized are also suitable as feed.

Since the purpose of the process is to oligomerize the double-bonded feed components with one another, it is preferred that the feed contains at least 50 wt% and preferably at least 80 wt% unsaturated and / or polyunsaturated compounds. Preferably, the unsaturated compound is mono-unsaturated; or a C18: 1 component having a concentration of more than 40% by weight in the feed mixture and preferably above 70% by weight.

Suitable biological raw materials are fish oils such as, for example, herring oil, lo oil, herring oil, tuna oil, anchovy oil, sardine oil and mackerel oil, vegetable oil tubes such as rapeseed oil, rapeseed oil, canola oil, tall oil, palm oil, sunflower oil, , peanut oil, castor oil and coconut oil, animal fats such as lard, tallow and trawl, as well as food recycling fats and oils. Other suitable biological raw materials are fats, waxes and oils produced by genetic manipulation and animal waxes such as beeswax, Chinese wax (insect wax), shellac wax and lanolin (wool wax) and herbal waxes such as Camauba palm wax, Ouricouri palm wax, Ouricouri palm wax, Japanese wax and rice bran oil. Also suitable are unsaturated alcohols naturally occurring, such as natural wax alcohols and natural branched alcohols.

The process can also be used to process mixtures of organic and synthetic feedstocks, whereupon, as appropriate, additional feeds may be used with other processes or synthetically produced feedstocks suitable for the particular stage of the process. Pure synthetic feeds are also suitable, provided the products are not based on renewable resources.

If desired, straight-chain and ring-shaped olefins, preferably C2-C14 olefins, can also be added to the feed, whereby the molecular weight of the product can be increased by lower carbon numbers than the C12-C24 range of typical carboxylic acids. Suitable additional olefinic components may be the components of the turpentine fraction of tall oil, such as alpha-pinene and / or double-bonded sugars and / or unsaturated compounds prepared from carboxylic acid metathesis and / or synthetic compounds such as ethene.

Shorter-chain (<C12) unsaturated dicarboxylic acids, carboxylic acids, alcohols and alkyl esters can also be utilized as additional feeds in the oligomerization, whereby the molecular weight of the product can also be increased by lower carbon numbers than the typical C12-C24 carboxylic acids. Suitable unsaturated dicarboxylic acids include, for example, maleic acid, fumaric acid, citric acid, mesaconic acid, itaconic acid, 2-methylene glutaric acid, and muconic acid.

In the optional iced oligomerization reaction of the invention, the short hydrocarbon chain molecules mentioned in the example may be oligomerized to a double-bonded carboxylic acid or an alkyl ester of a carboxylic acid or other double-linked molecule. Because the double bonds of the carboxylic acid-based compounds are mainly in the middle of the hydrocarbon chain, smaller molecules are reacted to form a linear or ring-centered paraffinic molecule after the deoxygenation step.

Because of the short life span of the catalyst in the processing of carboxylic acids, the feed can be converted to esters less potent with respect to the catalyst or alcohols. Hereby the triglycerides can be interesterified with alcohol to alkyl esters, whereby the triglycerides are decomposed so that the carboxylic acid is esterified with the alcohol and the alcohol part of the triglyceride, i.e. glycerol, is released. Methanol is typically used as the alcohol, but other C 1 -C 11 alcohols may also be used. Typical transesterification conditions are as follows: temperature 60-70 ° C and pressure 0.1-2 MPa. The catalyst used is sodium and potassium hydroxides dissolved in methanol in excess. Inhibition of free carboxylic acids and alcohol requires higher temperature and pressure (e.g. 240 ° C and 9 MPa) or more acidic conditions.

Carboxylic acids can also be reduced in known ways to fatty alcohols, either directly by reduction of the acid groups to lithium aluminum hydride to alcohols leaving the double bonds in the alcohol, or by hydrogenation of the alkyl esters of the carboxylic acids to unsaturated fatty alcohols at -30 In the hydrogenation reaction, the alcohol moiety used for the esterification of the carboxylic acid is liberated and can be recycled for re-esterification and the unsaturated fatty alcohols are led to oligomerization.

Optionally, hydrocarbon, such as diesel-grade biocarbon, may be added to the feed and diluent at various process steps. The diesel-grade hydrocarbon boils in the range of 150 to 400 ° C, typically 180 to 360 ° C.

Preferably, the feedstock organic feedstock is pretreated and / or prepared by methods known in the art, e.g. to remove impurities. The hydrolysis reaction of triglycerides can be utilized to prepare carboxylic acids for use as oligomerization feed. Alternatively, the triglycerides can be hydrolyzed after oligomerization. Hydrolysis yields glycerol as a byproduct, and thus hydrogen is not consumed in the HDO step to hydrogenate glycerol to propane gas. For example, distillation can either feed or divide the product into fractions with a lower boiling range or carbon number, filtering through a suitable filter aid to remove impurities from the feed or end product.

PROCESS

According to a preferred embodiment of the process according to the invention, the feed comprising the double-linked triglyceride, carboxylic acid, acid anhydride or fatty alcohol components is oligomerized. The feed contains at least 50 wt.% Of unsaturated and / or polyunsaturated compounds. Preferably, one of the feed components for the oligomerization step is selected as the main feed and the oligomerization conditions are adjusted according to the main feed. Other inputs can be mixed with the main input to the extent that they do not interfere with processing or that they provide an advantage for processing.

The oligomerization reactions are catalyzed by heat and a suitable catalyst. Suitable catalysts are cationic clay catalysts, preferably zeolite catalysts, and particularly preferably montmorillonite. Additional reagents, such as water, can promote the course of the oligomerization reaction of carboxylic acids In the oligomerization of carboxylic acids, water is added to the feed at a maximum of 10 wt%, preferably 0.1 to 4 wt%, and very preferably 1-2 wt%. Excessive use of water is not recommended as this will result in the formation of by-products of esterides which are not dimerized with carbon-carbon bonds.

Suitable oligomerization reactors include, for example, a fixed bed reactor and a stirred-tank reactor. In the reaction, diluents may be used to adjust the oligomer distribution. A suitable diluent is, for example, a recyclable die cutter or other hydrocarbon obtained from the process. The pressure of the oligomerization step is typically 0 to 10 MPa and the temperature is 100 to 500 ° C, preferably 0 to 10 MPa and 200 to 400 ° C. If the reaction is carried out as a batch reaction, the amount of catalyst is 0.01 to 30 wt.% Of the total reaction mixture, preferably 0.5 to 10 wt.%, When using a solid bed reactor, the feed rate is in grams per hour per gram of catalyst 0.1-1001 / h.

In a stirred tank reactor, the reaction time is less than 16 hours, preferably less than 8, very preferably less than 4 hours. By using a short residence time, the lighter, non-oligomerized components can be separated from the heavier already oligomerized components, for example by distillation, and then the light components are recycled for oligomerization. During recycling, non-reactive saturated components can be separated from double bonded components, for example by cold filtration. The saturated components are subjected to deoxygenation and optional isomerisation to branch their hydrocarbon chains.

Hydrogenation catalysts lose their activity mainly due to the coke formed on the catalyst surface, so that the product obtained from the oligomerization step can optionally be subjected to prehydrogenation under mild conditions to hydrogenate the remaining double bonds in the reaction and reduce the formation of coke in the subsequent precipitation step. The prehydrogenation is carried out in the presence of a hydrogenation catalyst at a temperature of 50 to 400 ° C and a hydrogen pressure of 0.1 to 20 MPa and a flow rate of WHSV 0.1 to 10 1 / h, preferably 150 to 250 ° C, a hydrogen pressure of 1 to 10 MPa and 5 l / h. The prehydrogenation catalyst contains Group VIII and / or VIA metals of a periodic rigid system. Preferably, the prehydrogenation catalyst is a Pd, Pt, Ni, NiMo or Co-Mo catalyst on a support which is aluminum and / or silica.

Alternatively, deoxygenation can be performed either as a hydrodeoxygenation or as a decarboxylation / decarbonylation. The hydrodeoxygenation (HDO) deoxygenation step is suitable for all feedstocks. In the HDO step, the oxygen, as well as the oligomerized and optionally prehydrated stream, is fed to an HDO catalyst bed comprising one or more catalyst beds. In the HDO phase, the pressure is in the range of 0.1 to 20 MPa, preferably 1 to 15 MPa, very preferably 3 to 10 MPa and 100 to 500 ° C, preferably 200 to 400 ° C, very preferably 250 to 350 ° C and at a flow rate of WHSV 0. , 1 to 10 1 / h, preferably WHSV 1 to 5 1 / h, very preferably WHSV 1 to 3 1 / h. In the HDO step, special catalysts containing adult group VIII and / or VIA metal and / or aluminum and / or silica can be used. Preferably, the HDO catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst on a support , which is aluminum and / or silica.

If the feed contains carboxylic acids and / or carboxylic acid esters, the deoxygenation can be accomplished by a decarboxylation / decarbonylation reaction. In the decarboxylation / decarbonylation reaction, the feed and the optional diluent are conducted to the catalyst bed. The reaction takes place in the liquid phase and can be carried out under pressure. However, it is preferable to use a vapor pressure corresponding to the reaction temperature of the reaction mixture. Depending on the feed, the pressure in the decarboxylation / decarbonylation step is 0 to 20 MPa, preferably 0.1 to 5 MPa, and the temperature is 200 to 400 ° C, preferably 250 to 350 ° C and flow rate WHSV 0.1 to 10 1 / h, preferably WHSV 1 -5 l / h. In the decarboxylation / decarbonylation step, special catalysts containing an adult group VIII and / or VIA metal such as a Pd, Pt, Ni, NiMo or CoMo catalyst, such as aluminum and / or silica and / or activated carbon may be used. Preferably, the decarboxylation / decarbonylation catalyst is Pd on carbon when the process is hydrogen-free and sulfurized with NiMo aluminum when using a mixture of hydrogen and an inert gas such as nitrogen. The product from the decarboxylation / decarbonylation step has been depleted of functional groups so that it contains only carbon and hydrogen and its carbon number has been reduced by one carbon per deprotected functional group.

If deoxygenation is performed by decarboxylation / decarbonylation, the oligomerization may be carried out before the feed of the oligomerization step contains unsaturated carboxylic acids and / or carboxylic acid esters. If the oligomerization is carried out after the decarboxylation / decarbonylation step, the feed of the oligomerization step contains decarboxylated / decarbonylated unsaturated compounds having a one-carbon deprotected carbon number per functional group.

In the deoxygenation step of the invention, the above-described HDO and decarboxylation / decarbonylation reactions may also occur simultaneously, with part of the functional groups being treated being cleaved by carbon dioxide or carbon monoxide and some of the groups being treated being hydrogenated.

Optionally, after the deoxygenation step, the light fractions can be led to a separate isomerization step in which the hydrogen gas and hydrogenated component are introduced into an isomerization unit. In the isomerization step, the pressure is between 0.1 and 20 MPa, preferably between 5 and 10 MPa. The temperature is in the range 100-500 ° C, preferably 200-400 ° C. In the isomerization step, special catalysts containing a molecular sieve and a group VIII metal element, for example Pt and Pd, may be used. Aluminum and / or silica may be used as the carrier.

Following the oligomerization and deoxygenation steps of the components, the product stream may optionally be finalized to remove any double bonds and aromatics. If finishing is done with hydrogen in the presence of a catalyst, this is called hydrogen finishing. In the hydrogen finishing step, the pressure is 1-20 MPa, preferably 5-15 MPa. The temperature is 50-500 ° C, preferably 200-400 ° C. In the hydrofinishing step, special catalysts containing the Group VIII metal and aluminum and / or silica may be used. Preferably, the hydrofinishing catalyst is a Pd, Pt or Ni catalyst on a support which is aluminum and / or silica. The finishing can also be carried out in the absence of hydrogen by removing the polar components by adsorption with a material such as clay or molecular sieve.

After the oligomerization, deoxygenation and optional isomerization and finalization steps, the product fraction is separated and separated into various types of fractions by example distillation. Typical carbon number ranges for product components are as follows: gas C1-C4, gasoline C5-C10, diesel C1-C26, base oil C18-C76.

The resulting hydrocarbon component or other suitable hydrocarbon can be recycled, if desired, to various process steps such as an oligomerization or deoxygenation step to increase conversion and / or selectivity or to control reaction exotherm.

In one embodiment of the invention, the already oligomerized product can be allowed to go beyond oligomerization by adding more monomer (stirring tank reactor) to the process or by recirculating the already oligomerized product with additional monomer (continuous reactor). In this way it is possible to obtain particularly thick petroleum oils with carbon numbers up to C150-C550, which can be used to make thick lubricants and to improve the viscosity index.

PRODUCT

Surprisingly, it has been found that the process of the invention provides a high quality saturated polar hydrocarbon component, preferably of biological origin suitable for use as a base oil or base oil component with excellent viscosity and cold properties. The product is branched with carbon-carbon bonds.

As a by-product, a hydrocarbon component suitable for use as a solvent, gasoline or diesel fuel, or a diesel fuel component, is obtained, preferably of biological origin. The diesel component or the C18-C24 base oil component may be isomerized to improve cold performance. The gasoline component may be isomerized to increase the octane number. If the process utilizes short chain olefins or short chain unsaturated carboxylic acid residues in the post-oligomerization, there is no need for isomerization.

The carbon number and carbon number range of the base oil or base oil component according to the invention also depend on the biological raw material used and the manufacturing process used. For conventional base oil applications, the conventional carbon number range is from Cl8 to C76, and for particularly thick base oils, the range may be up to Cl50 to C550. By targeting the base oil to a viscosity range of KV100 of 4-7 mm 2 / s, the process according to the invention typically produces one carbon number of branched and / or cyclic paraffins after oligomerization and HDO step feeds with one carboxylic acid chain length.

Also, the carbon number range of the base oil or base oil component produced by the oligomerization and combined HDO and decarboxylation / decarbonylation process of the invention is very narrow, typically with C16 components, the product has a C30 range with C30 containing C11 feeds. -C36 for the target viscosity rangeKV100 4-7 mm2 / s. When the feed is a mixture of C16 and C18 components, the product's carbon number range is typically seven carbons wide. The base oil according to the invention may also have a very high carbon number, even in the range of C150 to C550, if desired, for heavy viscosity and viscosity index enhancer suitable pem oils.

The following Table 2 shows the carbon numbers and typical structures of the bio-based base oils (1 and 2) of the invention and the synthetic KV100 4-6 mm2 / s synthetic base oils (3-5) of the prior art. The most typical carbon number is shown in bold. The base oil or base oil component of the invention differs from the prior art products in molecular structure as shown in the table.

In Table 2, the naphthenic structures are typical examples of the group of compounds. In the Structure Examples, the C10-C40-C C48.

Table 2. Carbon numbers and typical structures of base oils

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

The percentages in Table 2 (% FIMS) refer to the compound groups determined by this method.

The base oil components of Table 2 are prepared as follows: 1. C18 fatty acid dimer of tall oil, oligomerized and hydrogenated according to the invention 2. C18 fatty acid dimer of tall oil, oligomerized and hydrogenated according to the invention 3. PAO prepared by 1 H-hexadecene heterogeneous catalyst

PAO CIO5 prepared by oligomerization of 4.1-decene with homogeneous catalyst, PIO prepared by dimerization of internal C15-C16 olefin

The oligomerized dimer and trimer components of the invention (structures 1 and 2 of Table 2) are branched by double bonds at the center of the C18 hydrocarbon chain, with tertiary carbons in pairs of adjacent carbon atoms in the molecule structure. PIO is typically a dimer made from the shorter C15-C16 hydrocarbons when the product of the invention is a Cl6 and / or C18 dimer. In addition, the product of the invention contains a significant amount of mononaphylenes, up to more than 50% FIMS.

In the process for preparing the prior art polyalphaolefins, the boron trifluoride catalysts typically react with double bonds at the ends of the C10 chain leaving one tertiary carbon (-CH2 -) in the tertiary carbons (structure 2 in Table 2). When the oligomerization is carried out with a heterogeneous catalyst, the double bonds are displaced from the alpha position while skeletal isomerization occurs, resulting in the typical structure of the resulting base oil component leaving 1-10 methylene groups between the tertiary carbons (structure 3 in Table 2). Similarly, when the oligomerization is carried out with a homogeneous catalyst, skeletal isomerization is carried out in the post-oligomerization hydrogenation step, whereby the molecules of structure 4 of Table 2 are born in addition to the double bonds near the C1-C3 side branches. Prior art PAO and PIO base oil components have predominantly alkyl moieties, but the product according to the invention contains, in addition to the alkyl moieties, ring-structured naphthenic components.

The high quality base oil obtained by the process according to the invention has a pour point at best below -40 ° C and is therefore well suited for use in demanding cold conditions. The viscosity index of the product is at best over 125, making it suitable for use in Group 111 base oil applications.

By adding various short-chain unsaturated carboxylic acids or olefins to the biological feed, the molecular weight of the product can be adjusted to the carbon number ranges required by different applications. When cross-linked or oligomerized with fatty acids of triglycerides, small molecule carboxylic acids or olefins form short branches in the main hydrocarbon chain of the fatty acid. Using other naturally occurring unsaturated cyclic compounds, such as alpha-pinene, as feed additives, results in molecules having a ring structure in the side chain in the middle of the molecular chain. Most preferably, one or two additional components are oligomerized in the product. According to the invention, similar hydrocarbon chain tailored products can also be prepared from memory carboxylic acids and other short chain biocomponents. The lighter, branched and HDO-treated components are well suited as bio-diesel components.

The organic base oil or base oil component of the invention comprises a product made from a bio-based raw material which, according to gas chromatography, contains at least 90 wt%, preferably at least 95 wt%, and most preferably at least 97 wt% of saturated hydrocarbons. In addition, the product according to the invention contains more than 20% FIMS, preferably more than 30% FIMS and very preferably more than 40% FIMS, and mono-naphthenees less than 3.0% FIMS, preferably less than 1.0% FIMS, according to the FIMS assay. very preferably, 0.1% FIMS. Further, the product according to the invention contains up to 20 wt%, preferably not more than 10 wt%, particularly preferably not more than 5 wt% and most preferably not more than 1 wt% of straight chain paraffins.

In the base oil or base oil component of the invention, the proportion of paraffinic carbon atoms of all carbon atoms is> 60%, preferably> 70% and particularly preferably> 75%, and the base oil or base oil component contains less than 10%, preferably less than 5% aromatic carbon. % as determined by DIN 51378.

The base oil or base oil component of the invention has a viscosity index of at least 100, preferably at least 110 and particularly preferably at least 128 (ASTM D 2270).

The product according to the invention is branched by carbon-carbon bonds, which structure provides an excellent low solid point, not more than 0 ° C, preferably not more than -10 ° C and particularly preferably not more than -35 ° C.

The base oil or base oil component of the invention having a viscosity KV100 of 4-7 mm 2 / s has a carbon number range of up to 9 carbons, preferably up to 7 carbons and very preferably up to 3 carbons (as determined by field ionization mass spectrometry, FIMS).

The base oil or base oil component of the invention has a sulfur content of less than 300 ppm, preferably less than 50 ppm and particularly preferably less than 1 ppm (ASTM D3120).

The base oil or base oil component of the invention has a nitrogen content of less than 100 ppm, preferably less than 10 ppm and particularly preferably less than 1 ppm (ASTM D4629).

The base oil or base oil component of the invention has a volatility of less than 20 wt.%, Preferably less than 15 wt.%, And particularly preferably less than 10 wt.%, For products having a KV100 of at least 4 mm 2 / s (DIN 51581-2).

Bio-based products also contain carbon 14 isotopes due to their biological origin, which can be used as an indicator of the use of renewable raw materials. The typical 14C content of a bio based product is , the base oil or base oil component has a lower 14C isotope content, however, more than 50%, preferably more than 90%, very preferably more than 99%. In this way, even a small amount of bio-based base oil can be identified from other types of hydrocarbon base oil.

The product suitable for use as a diesel component in the process of the invention has a Cetane number of more than 40, preferably greater than 55 and very preferably greater than 70. It contains more than 60% by volume of paraffins, % by volume according to method IP-391. The product contains less than 40 wt%, preferably less than 10 wt% of straight chain n-paraffins. The diesel component has a cloud point of 0 ° C, preferably below -15 ° C and particularly preferably below -30 ° C. The resulting diesel product is typically completely bio-based. The product according to the invention has carbon-carbon-bonded side branches, which results in an extremely low cloud point. In addition, because of its organic origin, organic products contain 14C isotopes, which can be used as evidence of the use of renewable raw materials. The fully organic product has a 14C content of at least 100%.

The choice of organic feed has a profound effect on the composition of the product and the steaming range. In addition, the feed can be divided by distillation into narrow carbon numbers, which can be tailored to different applications. Typical carbon numbers for dimeric products at feeds having C16, C18, C20 and C22 hydrocarbon chain lengths after hydrodeoxygenation are C32, C36, C40 and C44, respectively, and after C2, C34, C38 and C42 2 carbons lower. Since the product distillation region is mainly dependent on the length of the feed hydrocarbon chain, narrow product fractions are obtained. The base oil component of the narrow boiling range obtained according to the invention has a very low volatility compared to similar products of the prior art.

ADVANTAGES OF THE INVENTION

The process according to the invention and the product made with it have several advantages, among which can be mentioned e.g. the use of renewable raw materials to reduce greenhouse gas emissions instead of non-renewable raw materials. According to the invention, high-quality saturated base oils provide a completely new source of raw material from a heteroatom-containing feedstock, in addition to conventional crude oil.

The raw materials for the process of the invention are available worldwide and the utilization of the process is not limited by significant upfront investments, such as in the case of GTL technology.

The products of the process according to the invention are carbon dioxide neutral in their use and disposal, i.e. they do not increase the carbon dioxide content of the air, such as those derived from fossil raw materials.

Oligomerisation under non-acidic conditions and subsequent deoxygenation yields a hydrolytically more stable base oil which does not decompose under humid conditions compared to esters or other heteroatom-containing base oils such as fatty alcohol dimer base oils. In addition, the oxidation resistance of saturated hydrocarbons is better than that of the corresponding unsaturated fatty or fatty alcohol based dimer or ester base oils. The saturated hydrocarbon component does not readily decompose as the esters which form corrosive acids. By deprotecting the alcohols, esters or carboxylic acids in the deoxygenation step, as well as the heteroatoms of any feedstock impurities, the process of the invention provides a non-polar and saturated hydrocarbon component. When oligomerized, the long-chain carboxylic acid derivatives form a structure which, after deoxygenation, has carbon-carbon-linked side branches. In C12: 1 to C20: 1 oligomerization, the side branches are typically C3 to C11. Such a hydrocarbon has an extremely low melting point for base oil applications, which is liquid at very low temperatures, and has a good viscosity index. The prepared saturated hydrocarbon is suitable as a base oil component without any blending restrictions and is also compatible with lubricant additives.

The base oils or base oil component according to the invention have very good technical properties compared to conventional hydrocarbon type lenses of the corresponding viscosity class, especially when the KV100 is 4-7 mm 2 / s. A narrow boiling range means that the product lacks a light starter, that is, molecules that are significantly lighter than average, which is reflected in the lower volatility of the product, which in practice leads to reduced emissions.

The product also lacks molecules made up of heavier components that are significantly heavier than the average, which results in the product having excellent cold properties, the carbon number and the boiling range of the base oil or base oil component of the invention depending on the feed composition. The aim of the prior art base oils is to adjust the distillation product to a fraction of the desired kinematic viscosity. It is advantageous for the lubricants that the carbon number range of the base oil, and thus the boiling range, is narrow when the composition contains molecules of the same size that behave in the same way under different conditions.

With the base oil or base oil component of the invention, the high viscosity index of the product means that the amount of viscosity index enhancer typically used in lubricant compositions can be reduced. It is generally known that in motor oils, for example, it is VII that has the most cause of engine hardening. In addition, reducing the amount of VII will result in significant cost savings.

Due to the natural fatty acid-based, refined feedstock process, the base oil or base oil component does not contain sulfur, nitrogen or aromatic compounds such as conventional crude oil based products, making it safer to use in applications where users are exposed to oil or oil mist. Further, the product of the invention has an excellent response to antioxidants and pour point depressants. lubricants made from base oil can be extended and can be used in colder conditions.

The base oil or base oil component of the invention is more ester compatible with conventional crude base oil base components, Fischer-Tropsch process base base oil components and hydrocarbon demix oils as well as lubricant additives. In addition, it does not have the same problems as esters with elastomers such as sealing materials.

It is also an advantage of the base oil or base oil component of the invention that it settles API Group II, preferably Group III, base oil requirements and can be used in motor oil compositions as other API Group Π or IH base oils within the same exchange rules.

The base oil or base oil component of the invention is based on renewable natural resources, which is clearly evident from the I4C isotope content of the product. The 14C isotope content is 100% for organic products and 0% for crude oil based products. The proportion of the organic base oil component can also be determined with an accuracy of at least 1% of the I4C isotope content of the base oil.

The cold distillate and the Cetane number of the middle distillate suitable for use as a diesel component in the process according to the invention are also excellent and are therefore well suited for use in demanding cold conditions.

The optional pre-hydrogenation step can reduce the side reactions of the double bonds, such as polymerization, ring formation and aromatization, which degrade the viscosity properties of the products and cause HDO catalyst oxidation.

An optional recycling step for the unreacted feeder components can be used to increase double bond reactions to increase product yield.

In the invention, synthetic compounds of similar chemical structure may be used as a feed instead of or in addition to organic raw materials.

The invention is illustrated by the following examples. However, it is to be understood that the invention is not intended to be limited to the embodiments described herein, or combinations thereof, and that the invention may be practiced in ways other than those specifically described above.

EXAMPLES

The hydrocarbon components of the invention described in the following examples have excellent properties and very narrow carbon numbers and distillation ranges. The process according to the invention has provided a molecular structure with good viscosity and excellent cold properties. The products are well suited as base oil components without any mixture restrictions and also compatible with lubricant additives.

Example 1

Manufacture of hydrocarbon component from vegetable oil

A feed mixture containing 200 ml of soybean oil, 6 g of montmorillonite catalyst and 5 ml of distilled water was loaded into a Parr high pressure reactor. The temperature was raised to 270 ° C and the oil was allowed to oligomerize with slow stirring for 7 hours.

Then, in the HDO step, the above oligomerized mixture was hydrogenated in a Parr high pressure reactor with dried and activated NiMo / AhOO catalyst to i-paraffin. 200 ml of the oligomerized soybean oil mixture was hydrogenated at 325 ° C and 5 MPa hydrogen pressure until no acid groups were detected in the sample FTIR spectrum. The reaction mixture was stirred at 300 rpm. The final product was distilled and the product predominantly branched and cyclic C36 paraffin.

The properties of the hydrocarbon component obtained after the oligomerization and HDO step are shown in Table 3. Similarly, hydrocarbon components can be prepared from other double-bonded vegetable and fish oils and animal fats.

Example 2

Preparation of hydrocarbon component from soybean oil based carboxylic acid methyl esters

The soybean oil was pretreated by basic esterification with methanol under basic conditions at 70 ° C and 0.1 MPa in the presence of sodium methoxide catalyst in two steps to form the methyl esters of the carboxylic acids. The reaction mixture was purified by acid and water washing and the carboxylic acid methyl ester dried. The carboxylic acid composition of the soybean oil-based methyl ester was as follows: C16: O11%, C18: O20%, C18: 18%, C18: 254% and C18: 366%.

The carboxylic acid methyl ester obtained above was oligomerized in a Parr high pressure reactor. 200 ml of feed and 6 g of bentonite catalyst were charged to the reactor, deoxygenated twice to displace oxygen, then the temperature was raised to 350 ° C and the carboxylic acid methyl ester allowed to oligomerize with slow agitation for 7.5 hours. From the reaction mixture, monomer dimer and trimeric methyl esters were separated on a silica column.

Then, in the HDO step, the dimeric methyl ester and trimeric methyl ester obtained above were hydrogenated separately as in Example 1 and the final product was distilled to give 26 wt.% Of branched and cyclic C36 paraffin and 15 wt.% Of cyclic C54 paraffin.

The properties of the hydrocarbon component obtained after the pre-treatment step (interesterification) and the oligomerization and HDO steps are shown in Table 3. The product has excellent properties and very narrow molecular distribution. Similarly, hydrocarbon components can also be prepared from other double, double-bonded plant, animal and fish-based carboxylic acid methyl esters. By recycling the unreacted monomers, the process yield is increased.

EXAMPLE 3

Manufacture of hydrocarbon component from tall oil based carboxylic acids

During the pretreatment step, tall carboxylic acids of tall oil were distilled. The carboxylic acids were then oligomerized in a Parr high pressure reactor. 200 g of feed mixture (carboxylic acids), 16 g of montmorillonite catalyst and 10 g of water were loaded into the reactor. The temperature was raised to 255 ° C and the carboxylic acids were allowed to oligomerize with slow stirring for 3 hours. The mixture was cooled and the catalyst was filtered off. The monomer fraction from the reaction mixture was separated from the dimeric and trimeric acids on a silica column. The carboxylic acid dimer was obtained in 45 wt%.

In the HDO step, the dimeric fraction obtained above was hydrogenated as in Example 1 until the carboxylic acid peak had disappeared from the FTIR spectrum. The product obtained was branched as well as cyclic paraffin,

The properties of the hydrocarbon component obtained after the oligomerization and HDO step are shown in Table 3. Similarly, hydrocarbon components can be prepared from non-tall oil based free carboxylic acid or hydrolyzed double bonded vegetable oil and fish oil oils.

Example 4

Preparation of a Hydrocarbon Component Using Tall Oil-Based Carboxylic Acids Pre-Hydrogenation

In the pretreatment step, tall carboxylic acids of tall oil were distilled. The feed mixture contained mainly C18: 1 30% by weight, C18: 242% by weight and C18: 399% by weight carboxylic acids. In addition, the fraction contained 2% resin acids. The tall oil carboxylic acids thus obtained were oligomerized in a Parr high pressure reactor. 200 g of feed mixture, 16 g of montmorillonite catalyst and 10 g of water were charged to the reactor. To displace the oxygen, the nitrogen pressure was raised to 0.5 MPa and stirred for 600 rpm. The pressure was released and the nitrogen was repeated. The temperature was then raised to 255 ° C and the carboxylic acids were allowed to oligomerize with slow stirring for 2 hours. The mixture was cooled and the catalyst filtered off. From the reaction mixture, monomeric, dimeric and trimeric acids were separated on a silica column. The carboxylic acid dimer was obtained at 45% by weight.

Before the HDO step, the double bonds of the dimeric fraction obtained above were hydrogenated in 450 mL of a Parr high pressure reactor with NiMo / ALO 2 pre-sulfurized catalyst. Pre-hydrogenation was performed on dried and activated catalyst at 230 ° C and 5MPa hydrogen / min. The dimeric acid was hydrogenated until no double bonds were detected in the sample FTIR spectrum.

In the HDO step, the prehydrogenated dimeric acid obtained above was hydrogenated as in Example 1 until the carboxylic acid peak had disappeared from the FTIR spectrum, after which the paraffinic product was filtered through diatomaceous earth. The end product was a branched and cyclic C36 paraffin.

The hydrocarbon component properties obtained after the oligomerization, prehydrogenation, and HDO step are shown in Table 3. The hydrocarbon component has ovarian characteristics and very narrow molecular distribution. Similarly, hydrocarbon components may be prepared from non-tall oil-based free carboxylic acids or from hydrolysis-free double-bonded vegetable and fish oils or animal fat-based carboxylic acids.

Example 5

Preparation of hydrocarbon component from soybean oil-based carboxylic acid methyl esters and alpha-pinene

The soybean oil was transesterified as in Example 2 with methanol to form methyl esters of carboxylic acids. 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: 011%, C18: 020%, C18: 18%, C18: 254% and C18: 366%.

The above soybean oil methyl ester was oligomerized in a Parr high pressure reactor with alpha-pinene in a 2: 1 molar ratio using 8% bentonite catalyst and 4% water. 200 ml of the feed mixture was charged to the reactor. To displace oxygen in the feed mixture, the nitrogen pressure was raised to 0.5 MPa and the mixture was stirred for 600 rpm for a moment. The pressure was released and the nitrogen was repeated. The temperature was then raised to 310 ° C, pressure 2 MPa and soybean oil methyl ester allowed to oligomerize with alpha-pinene with slow stirring for 6 hours.

The oligomerized product was subjected to hydrodeoxygenation as in Example 1. The final product was distilled off monomers to give C28 "pin-branched" isoparaffin and a carboxylic acid methyl ester-derived paraffin dimer and trimer as a mixture. The properties of the resulting hydrocarbon component are shown in Table 3. Similarly, branched hydrocarbon components can also be prepared from other double-bonded plant, animal and fish-based carboxylic acids, or from carboxylic acid methyl esters and suitable small molecule, preferably biocompound.

Example 6

Preparation of the Heavy Hydrocarbon Compound from Tall Oil Carboxylic Acids Tall oil was oligomerized otherwise as in Example 3 but the reaction was carried out with slow stirring for 7 hours. From the reaction mixture, the trimer fraction was separated from the dimer and monomer fractions on a silica column.

The trimer fraction obtained above was hydrogenated in the HDO step as in Example 1 until the carboxylic acid peak had disappeared from the FTIR spectrum. The product obtained was branched as well as cyclic paraffin. The product characteristics are given in Table 3.

Similarly, hydrocarbon components can be prepared from free carboxylic acids other than tall oil or from vegetable and fish oil or animal fat based carboxylic acids with hydrolysis.

Table 3. Properties of Processed Hydrocarbon Component

Table 4. Properties of base oils according to the prior art

HC-IDW = hydrocracked, wax-isomerized base oil

Example 7

Demonstration of the hydrocarbon component's bio-origin

The biobased hydrocarbon component of Example 6 was weighed into a mineral oil based Group III base oil and mixed thoroughly. In the first sample, 0.5014 g of the bio-based hydrocarbon component was weighed and the Group II base oil component was added until the total mass was 10.0 g; another sample was weighed 1.0137 g of the bio-based hydrocarbon component and the dumb base II component was added until the total mass was 10.0232 g. Table 5 below shows the probed measurement results. Radiocarbon content is reported in "percent modem carbon", which is based on atmospheric radioactive carbon content in 1950. Atmospheric carbon carbon content is currently approximately 107%. The value of reference D indicates the background level of the method. A value of 6 ° C describes the ratio of stable 13C / 12C carbon isotopes. This value can be used to account for isotope fractionation in the sample processing process. The last column indicates the actual result.

Table 5. Radiocarbon results.

Base oil, characterized in that the base oil is a branched hydrocarbon component containing at least 90% by weight of saturated hydrocarbons, at least 40% by weight FIMS% of mononaphthenes, up to 20% by weight of straight chain paraffins, less than 10% by weight, aromatic carbon and 9 carbons, KV100 equal to or greater than 4 mm2 / s, volatility less than 20% by weight, and a solid point not exceeding 0 ° C.

Base oil according to Claim 1, characterized in that the base oil contains at least 95% by weight of saturated hydrocarbons, at least 50% by weight FIMS% of mononaphthenes, up to 10% by weight of straight chain paraffins, aromatic carbon less than 5% by weight, carbon up to 7 carbons, volatility less than 15% by weight and a pour point not exceeding -10 ° C.

Base oil according to claim 1 or 2, characterized in that the base oil contains at least 97% by weight of saturated hydrocarbons, at least 60FIMS% of mononaphthenes, up to 5% by weight of straight chain paraffins, aromatic carbon of less than 1% by weight, carbon up to 3 carbon , volatility less than 10% by weight, and solidification point not exceeding -35 ° C.

Base oil according to any one of Claims 1 to 3, characterized in that the base oil has a 14C isotope content of more than 50%, preferably more than 90% of the 1950C 14C isotope.

Base oil according to one of Claims 1 to 4, characterized in that the base oil has a 14C isotope content of at least 100% of the total carbon content.

A process for the preparation of a base oil, base oil or base oil component according to any one of claims 1 to 5, characterized in that the process comprises the steps of feeding one or more components selected from esters of C4-C38 carboxylic acids, C4-C38 carboxylic acids and C1-C11 alcohols, Of C4-C38 carboxylic acid anhydrides and C4-C38 alcohols, and containing at least 50% by weight of unsaturated and / or polyunsaturated compounds, is oligomerized in the presence of a cationic clay catalyst at a pressure of from 10 to 100 ° C and 100 to 500 ° C at a temperature of 0.1 to 20 MPa in the presence of a hydrodeoxygenation catalyst as an art carbonylation / decarboxylation in the presence of a decarbonylation / decarboxylation catalyst at 200 to 400 ° C and at a pressure of 0 to 20 MPa.

Process according to Claim 6, characterized in that it comprises one or more components selected from the group consisting of C4-C24 carboxylic acids, C12-C24 carboxylic acids and C1-C3 alcohol esters, C12-C24 carboxylic acid anhydrides and C12-C24 alcohols.

Process according to claim 6 or 7, characterized in that the feed comprises at least one raw material of biological origin selected from the group consisting of antiglycerides, esters of fatty acids, fatty acids and alcohols, fatty anhydrides and fatty alcohols.

Process according to claim 8, characterized in that the raw material of biological origin is selected from the group consisting of a) vegetable fats, oils, waxes, animal fats, oils, waxes and tallow fats, oils, waxes; (b) carboxylic acids of vegetable fats, oils, waxes, animal fats, oils, waxes, fish fats, oils, waxes or mixtures thereof by hydrolysis, transesterification or pyrolytic carboxylic acids; (c) vegetable fats, oils, waxes, animal fats, oils, waxes, fish fats, oils, waxes and mixtures thereof of esters obtained by transesterification; (d) esters obtained by esterification of free carboxylic acids with vegetable, animal or fish acids; (e) fatty alcohols obtained as carboxylic acid reducing products obtained from vegetable fats, oils, waxes, animal fats, oils, waxes, fish fats, oils, waxes or mixtures thereof; (f) recycled edible fats and oils, fats, waxes and oils produced by genetic engineering; and (g) mixtures of the above.

Process according to one of Claims 6 to 9, characterized in that the feed contains at least 80% by weight of unsaturated and / or polyunsaturated compounds.

Process according to one of Claims 6 to 10, characterized in that the oligomerization is carried out at a temperature of 200-400 ° C.

Process according to one of Claims 6 to 11, characterized in that the oligomerization is carried out in the presence of a zeolite catalyst.

Process according to one of Claims 6 to 12, characterized in that when the feed contains carboxylic acids, during the oligomerization step, water is added in an amount of up to 10% by weight, preferably 0.1 to 4% by weight.

Process according to one of Claims 6 to 13, characterized in that the deoxygenation is carried out before the oligomer ion or after the oligomerization.

Process according to one of Claims 6 to 14, characterized in that the hydrodeoxygenation is carried out at a temperature of 200-400 ° C and a pressure of 1-15 M at a flow rate of WHSV 0.1 to 101 / h.

Process according to one of Claims 6 to 15, characterized in that the hydrodeoxygenation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst on an aluminum and / or silica support.

Process according to one of Claims 6 to 16, characterized in that, prior to hydrodeoxygenation, the product of the oligomerization step is subjected to hydrogenation in the presence of a hydrogenation catalyst at a temperature of from 50 to 400 ° C at a pressure of 0.1 to 20 MPa.

Process according to claim 17, characterized in that the hydrogenation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst on an aluminum and / or silica support.

Process according to one of Claims 6 to 18, characterized in that the process feed or the polymerization product is subjected to decarbonation / decarboxylation at a temperature of 250-350 ° C and a pressure of 0.1 to 5 M at a flow rate of WHSV 0.1 to 101 / h.

Process according to one of Claims 6 to 19, characterized in that the decarbonylation / decarboxylation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst on an aluminum and / or silica support and / or a activated carbon support.

Process according to one of Claims 6 to 20, characterized in that, after the oligomerization and deoxygenation step, the product is subjected to isomerization in the presence of hydrogen gas at a pressure of 0.1 to 20 MPa at a temperature of 100 to 500 ° C in the presence of an isomerization catalyst.

Process according to Claim 21, characterized in that the isomerization catalyst contains a molecular sieve and a metal group VIII element on a support.

Process according to one of Claims 6 to 22, characterized in that petrol, solvent and diesel fractions are produced as a by-product.

Claims (23)

A process for producing a saturated hydrocarbon component, characterized in that an input comprising one or more components is selected from among the carbon numbers of C4 - C38 carboxylic acids, esters of C4 - C3S carboxylic acids and C1 - C1 alcohols, C4 - C38 carboxylic anhydrides and C4-C38 alcohols, oligomerized and deoxygenated, and the feed comprises at least 50% by weight of unsaturated and / or polyunsaturated compounds. " Process according to claim 1, characterized in that the feed comprises one or more components selected from the carbon number of C4-C24 carboxylic acids, esters of C12-C24 carboxylic acids and C1-C3 alcohols, C12-C24 carboxylic anhydrides and C12-C24 alcohols. . Process according to claim 1 or 2, characterized in that the feed comprises at least one raw material of bio-origin selected from triglycerides, fatty acids, esters of fatty acids and alcohols, fatty acid anhydrides and fatty alcohols. 4. A process according to claim 3, characterized in that the raw material is selected from a group consisting of a) plant fats, oils, waxes, animal fats, oils, waxes and fish fats, oils, waxes; b) carboxylic acids obtained by hydrolyzing, transesterifying or pyrolytically of plant fats, oils, waxes, animal fats, oils, waxes, fish fats, oils, waxes, and mixtures thereof, or free fatty acids; c) esters obtained by transesterification of plant fats, oils, waxes, animal fats, oils, waxes, fish fats, oils, waxes, and mixtures thereof; d) esters obtained by esterification of plant, animal and fish based free carboxylic acids with alcohols; e) fatty alcohols obtained as reducing products of carboxylic acids of plant fats, oils, waxes, animal fats, oils, waxes, fish fats, oils, waxes, and mixtures thereof; (f) recycled food fats and oils, by genetically engineered fats, waxes and oils; and (g) mixtures of the above. Process according to any one of claims 1-4, characterized in that the feed contains at least 80% by weight of unsaturated and / or polyunsaturated compounds. Process according to any one of claims 1 to 5, characterized in that the oligomerization is carried out at a pressure of 0 - 10 MPa and at a temperature of 100 - 500 ° C. Process according to any one of claims 1-6, characterized in that the oligomerization is carried out in the presence of a cationic clay catalyst, preferably a zeolite catalyst. Process according to any one of claims 1 to 7, characterized in that when the feed contains carboxylic acids, the feed in the oligomerization step water is added at most 10% by weight, preferably 0.1-4% by weight. Process according to any one of claims 1-8, characterized in that the deoxygenation is carried out as hydrodeoxygenation or decarbonylation / decarboxylation and the deoxygenation is carried out before the oligomerization or after the oligomerization. Process according to Claim 9, characterized in that the hydrodeoxygenation is carried out in the presence of hydrogen at a temperature of 100 - 500 ° C at a pressure of 0.1 - 20 MPa with a flow rate WHSV of 0.1 - 101 / 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 with an aluminum and / or silica support. Process according to any one of claims 9 to 11, characterized in that enforhydration is carried out prior to the hydrodeoxygenation on the product of the oligomerization step in the presence of a hydrogenation catalyst at a temperature of 50 - 400 ° C at a hydrogen pressure of 0.1-20. MPa with a WHSV flow rate of 0.1 - 101 / h. Process according to claim 12, characterized in that the hydrogenation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst with an aluminum and / or silica support. Process according to claim 9, characterized in that the decarbonylation / decarboxylation is carried out on the process feed or oligomerization product in the presence of a decarbonylation / decarboxylation catalyst at a temperature of 200 - 400 ° C at 0-20 MPa with a single flow rate WHSV of 0.1 - 101 / h. Process according to Claim 14, characterized in that the decarbonylation / decarboxylation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst with an aluminum and / or silica support and / or an active carbon carrier. Process according to any one of claims 1-15, characterized in that isomerization is carried out on the product after the oligomerization and deoxygenation step in the presence of hydrogen gas at a pressure of 0.1-20 MPa, at a temperature of 100-500 ° C in the presence of an isomerization catalyst. 17. A process according to claim 16, characterized in that the isomerization catalyst contains a molecular sieve and a metal from element group VIII with a support. Use of a process according to any one of claims 1 to 17 for the production of gasoline, solvent and diesel fractions. 19. Base oil or base oil component, characterized in that the base oil or base oil component contains at least 90% by weight saturated hydrocarbons, at least 40 FIMS% monon nights, not more than 20% by weight straight chain paraffins, below 10% by weight aromatic carbon and the base oil or base oil component is the carbon content of the base oil. 9 carbon, KV100 is at least 4 mm2 / s and volatility is less than 20% by weight. 20. Base oil or base oil component according to claim 19, characterized in that the base oil or base oil component contains at least 95 wt% saturated hydrocarbons, at least 50 FIMS% monon nights, maximum 10 wt% straight chain paraffins, below 5 wt. % aromatic carbon, its carbon number gap is at most 7 carbon and the volatility below 15% by weight. 21. Base oil or base oil component according to claim 19 or 20, characterized in that the base oil or base oil component contains at least 97% by weight saturated hydrocarbons, at least 60 FIMS% monon nights, at most 5% by weight straight chain paraffins, below 1% by weight aromatic carbon , its carbon number average is no more than 3 carbon and volatility below 10% by weight. Base oil or base oil component according to any one of claims 19-21, characterized in that the base oil or base oil component 14C isotope content is at least 100%. Base oil or base oil component according to any one of claims 19-22, characterized in that the base oil or base oil component has been prepared by a process according to any one of claims 1-18.