HK1125399B - Process for producing a saturated hydrocarbon component - Google Patents

Description

Process for producing saturated hydrocarbon component

Technical Field

The present invention relates to a process for the production of hydrocarbon components, and in particular for the production of high quality saturated base oils, based on oligomerization and deoxygenation. In the process, preferably feedstocks of biological origin are used, which are ultimately derived from plant and fish oils, animal fats, natural waxes, carbohydrates and corresponding synthetic materials and combinations thereof.

Prior Art

Base oils are commonly used in the manufacture of lubricants, such as automotive lubricants, industrial lubricants, and lubricating greases. They are also used as process oils, white oils and metal working oils. Finished lubricants consist of two common components, a lubricating base oil and additives. Lubricating base oils are the major component in these final lubricants and contribute significantly to the properties of the final lubricant. Typically, some lubricating base oils are used to make a variety of final lubricants by varying the mixture of individual lubricating base oils and individual additives.

Base oils are used for high quality lubricants according to the classification of American Petroleum Institute (API) group III or IV. The API base oil classification is shown in table 1.

TABLE 1 API base oil classification

Group III oils are Very High Viscosity Index (VHVI) base oils produced by modern methods from crude oil by hydrocracking followed by isomerization of waxy linear paraffins to produce branched paraffins. Group III oils also include base oils derived from crude Wax (Slack Wax) paraffins from mineral oils, and base oils derived from waxes obtained by fischer-tropsch synthesis, for example from coal or natural gas (GTL waxes) using corresponding isomerization techniques. The oils of group IV are synthetic Polyalphaolefins (PAO). Similar classifications are also used by ATIEL (Association technology del's industrial europe yene des Lubrifiants, or Technical Association soft he europe lubrints Industry), which also include group VI: poly (internal olefin) (PIO). In addition to official classifications, group II + is also commonly used in the art, and this group includes saturated and non-sulfur containing base oils having viscosity indices greater than 110, but less than 120. In these classifications, saturated hydrocarbons include paraffinic and naphthenic compounds, but not aromatic compounds.

According to API 1509, the following definitions can also be used for the base stock: "base stock is a lubricant component produced by a single manufacturer to the same specifications (independent of the source of the raw materials or the location of the manufacturer); which meet the same manufacturing specifications; and is identified by a unique chemical formula, product identification number, or both. The base stock can be made using a variety of different methods ". The base oil is a base stock or base stock blend for the API-approved oil. Known types of base stocks are 1) mineral oils (paraffins, naphthenes, aromatics), 2) synthetic (polyalphaolefins, alkylated aromatics, diesters, polyol esters, polyalkylene glycols, phosphate esters, silicones), and 3) vegetable oils.

In particular, the automotive industry has long required lubricants and thus base oils to have improved processing properties. Increasingly, the specifications for finished lubricants require products with excellent low temperature properties, strong oxidation stability, and low volatility. Typically the lubricating base oil is one having a kinematic viscosity at 100 ℃ (KV100) of about 3cSt or greater; a Pour Point (PP) of about-12 ℃ or less; and a base oil having a Viscosity Index (VI) of about 120 or more. In addition to low pour points, it is also desirable that multi-grade engine oils have low temperature flow properties to ensure easy engine starting in cold climates. The low temperature fluidity is expressed as the apparent viscosity in a cold cranking simulation test (cold cranking templates) at a temperature of-5 to-40 ℃. Lubricating base oils with KV100 of about 4cSt should typically have a CCS viscosity at-30 deg.C of less than 1800 (CCS-30), and oils with KV100 of about 5cSt should have a CCS-30 of less than 2700. The lower the value, the better. Typically, the lubricating base oil should have a Noack volatility no greater than that of existing conventional group I or group II light neutral oils. Currently, only a small fraction of the base oils currently manufactured are able to meet these requirements specifications.

It is no longer possible to produce lubricants from conventional mineral oils which meet most of the specifications required by automotive manufacturers. In general, mineral oils often contain too high concentrations of aromatic hydrocarbons, sulfur and nitrogen compounds, and further, they also have high volatility and a moderate viscosity index, i.e., viscosity-temperature dependence. In addition, mineral oils often have a low response to antioxidant additives. Synthetic and so-called semi-synthetic base oils are increasingly playing an important role, especially in automotive lubricants, such as engine and gear oils. Similar developments can be seen for industrial lubricants. The service life of the lubricant is ideally as long as possible, thereby avoiding frequent oil changes by the user and further making it possible to extend the service intervals of the vehicle, for example in a commercial vehicle. In the last decade, the engine oil change interval of passenger cars has increased by five times, up to 50,000 km. For heavy vehicles, the engine oil change interval is currently already at the level of 100,000 km.

The manufacture of lubricants is increasingly influenced by the common "Life Cycle Approach" (LCA) concerning environmental, health and safety factors of the product. The goal of LCA is to extend the life of the product and minimize environmental disadvantages associated with the manufacture, use, handling and disposal of the product. Longer oil change intervals for high quality base oils result in reduced consumption of non-renewable mineral crude oil based feedstocks and a reduction in the amount of hazardous waste petroleum products.

In addition to the demands of engine technology and base oil manufacture, the stringent environmental requirements have also led the industry to develop more complex base oils. Sulfur-free fuels and base oils are needed in order to achieve the full effect of new and efficient anti-pollution technologies in modern vehicles, and to suppress the emission of nitrogen oxides, volatile hydrocarbons and particulates, as well as to achieve direct reduction of sulfur dioxide in exhaust gases. The european union has decided that these fuels should be available to the market from 2005 and that they must be the only form of sale from 2009. Conventional mineral oil base oils contain sulfur, nitrogen, aromatic compounds, and often also volatile compounds. They are less suitable for new engines and are therefore also more harmful in terms of the environment than new sulphur-free and aromatic base oils.

The use of reclaimed oils and renewable feedstocks in lubricant manufacture is now often a contemplated goal. The use of renewable feedstocks of biological origin rather than non-renewable fossil feedstocks for the production of hydrocarbon components is desirable because fossil feedstocks are depleted and their impact on the environment is detrimental. Problems associated with the recovered oil include the complexity of purification and reprocessing steps to obtain a base oil having high quality. Furthermore, the development of operational and large-scale recovery logistics systems is expensive.

Currently, only esters are used for lubricants of renewable and biological origin. The use of esters is limited to some specific applications, such as refrigeration compressor lubricant oils, bio-hydraulic oils, and metal working oils. In common automotive and industrial lubricants, they are used mainly on an additive scale. The high price also limits the use of esters. In addition, even in cases where the chemical composition of the replacement ester is substantially identical, the ester used in the engine oil formulation is not interchangeable with other esters without new engine testing. Alternatively, base oils composed of pure hydrocarbon structures may be partially interchanged with one another. There are also some technical problems associated with esters. As polar compounds, esters have a greater seal-swelling tendency than pure hydrocarbons. This has created a number of problems associated with elastomers in hydraulic applications. In addition, ester base oils are more susceptible to hydrolysis to produce acids, which in turn cause corrosion of the lubrication system. In addition, a greater disadvantage of esters is that the additives developed for non-polar hydrocarbon-based oils are not effective on ester base oils.

Methods for crosslinking triglycerides in a controlled manner using metal salts or peroxide initiators that readily abstract a hydrogen from a C-H bond, and appropriate amounts of oxygen, are known in the art. Some crosslinking is also caused by atmospheric oxygen without heating the product, but the reaction is slower. This crosslinking is based on oxygen-oxygen bonds formed in the molecule. During triglyceride crosslinking, the degree of crosslinking can be controlled by processing time and kinematic viscosity. The viscosity increases with crosslinking and decreases with product decomposition as a function of time.

Thermal batch processes for producing boiled oils (stand oils) from triglycerides based on double bond reactions are also known, which introduce carbon dioxide into the reactor for preventing oxidation. In this case, the crosslinking is based on carbon-carbon bonds formed in the molecule. The decomposition products of the thermal reaction are removed by entrainment with the carbon dioxide gas stream or by use of a vacuum. Crosslinking is an exothermic reaction and therefore requires efficient heating to provide the reaction and efficient cooling to prevent overheating to maintain the temperature between 280 and 300 ℃. In addition, the reaction vessel must be cooled rapidly after the desired viscosity, which indicates the degree of crosslinking, has been reached.

In Kirk-Othmer: encyclopedia of Chemical Technology, third edition, volume 7, dimer acid, page 768, proposes a process for producing dimer acid from unsaturated carboxylic acid by means of a free radical reaction using a cationic catalyst at a reaction temperature of 230 ℃. In addition to the acyclic branched unsaturated dimer acid as the major product, mono-and bicyclic dimers are formed.

The unsaturated alcohols can be oligomerized using heat and/or a catalyst in a similar manner to the unsaturated carboxylic acids to give alcohol dimers. The acyclic unsaturated branched diol dimer is the predominant product.

In Koster R.M. et al, Journal of Molecular Catalysis A: the oligomerization of carboxylic acids, methyl carboxylates and synthetic alcohols and olefins to give the corresponding dimers is described at page 159-169 of Chemical134 (1998).

Crosslinked triglyceride, methyl carboxylate dimer, carboxylic acid dimer, and fatty alcohol dimer products may be used in lubricant applications, but because the products contain heteroatoms, they have disadvantages corresponding to base oils derived from esters.

Methods in which the oxygen of the carboxylic acid or ester is removed are also known. Decarboxylation of fatty acids results in hydrocarbons with one carbon atom less than the original molecule. The feasibility of decarboxylation varies greatly with the type of carboxylic acid used as starting material. In the case of carboxyl groups, activated carboxylic acids containing an electron-withdrawing substituent in the alpha or beta position spontaneously lose carbon dioxide at slightly elevated temperatures. In this case, the RC-COOH bond is weakened by the displacement of electrons along the carbon chain.

For other types of carboxylic acids, the hydrocarbon chain causes a relative increase in the electron density at the alpha carbon, and thus carbon dioxide is difficult to dissociate. Suitable catalysts facilitate the reaction. In Maier, W.F. et Al, Chemische Berichte (1982), 115(2), 808-812, heterogeneous Ni/Al from carboxylic acids in a hydrogen atmosphere at 180 ℃ was used₂O₃And Pd/SiO₂A catalyst is produced.

Combined decarboxylation and hydrodeoxygenation (hydrodeoxygenation) of oxygenates is disclosed in Laurent, e., Delmon, b.: applied Catalysis, a: general (1994), pages 109(1), 77-96 and 97-115, in which sulphurized CoMo/gamma-Al is used at 260-300 ℃ under a hydrogen pressure of 7MPa₂O₃And NiMo/gamma-Al₂O₃A catalyst to hydrodeoxygenate a pyrolysis oil derived from biomass. The reaction of the hydrodeoxygenation step is highly exothermic and requires large amounts of hydrogen.

FI 100248 denotes a process with two steps, wherein middle distillates are produced from vegetable oils by hydrogenation of carboxylic acids or triglycerides of the vegetable oils, producing linear paraffins, followed by isomerization of said normal paraffins to branched paraffins. The conditions for this hydrotreatment include a temperature of 330 to 450 ℃, a pressure of 3MPa, and a Liquid Hourly Space Velocity (LHSV) of 0.5 to 5 l/h. In the isomerization step, a temperature of from 200 to 500 ℃ is used at a pressure above atmospheric pressure and an LHSV of from 0.1 to 10 l/h.

In the isomerization process, noble metal catalysts are used which are very expensive and highly sensitive to catalyst poisons. Raw materials from biological sources that contain significant amounts of oxygen produce water, carbon monoxide and carbon dioxide as the raw materials are processed. In addition, the raw materials of biological origin often contain nitrogen, sulfur and phosphorus compounds known as catalyst poisons and inhibitors of noble metal catalysts. Unless removed prior to the isomerization process, they cause a reduction in catalyst life and require frequent regeneration of the catalyst.

Typical basic building blocks of vegetable and fish oils and animal fats are triglycerides. Triglycerides are esters of glycerol with three fatty acid molecules, having the following structure:

wherein R is₁、R₂And R₃Represents a C4-C30 hydrocarbon chain. Fatty acids are carboxylic acids with long unbranched hydrocarbon chains. The length of the hydrocarbon chain is mostly 18 carbons (C18). The C18 fatty acid is typically bonded to the central hydroxyl group of glycerol. Typical carbon numbers of fatty acids bonded to two other hydroxyl groups average from carbon numbers C14 to C22.

The fatty acid composition of raw materials of biological origin may vary significantly among raw materials from different sources. Although some double bonds may be present in the fatty acids, they are not conjugated, but instead have at least one intermediate-CH between them₂-a unit. In terms of configuration, the double bond of a natural fatty acid is cis, and the hydrogen atom is therefore located on the same side of the stiffer double bond. As the number of double bonds increases, they are usually located at the mobile end of the chain. The length of the hydrocarbon chain and the number of double bonds depend on the respective vegetable or animal fat or wax used as the source of the fatty acid. Animal fats typically contain more saturated fatty acids than unsaturated fatty acids. Fatty acid content of fish oilA large number of double bonds and the average length of the hydrocarbon chain is longer than the fatty acids of vegetable oils and animal fats. The fatty acid composition plays an important role in the evaluation of the oxidation resistance, heat resistance and low temperature performance of the raw materials to be oligomerized and further of the oligomeric product type.

Waxes are mainly carboxylic acids esterified with alcohols having a long chain. In addition, waxes contain varying amounts of paraffins (n-alkanes), ketones and diketones, primary and secondary alcohols, aldehydes, alkane acids (carboxylic acids) and terpenes. The carbon number of the carboxylic acid and alcohol chain is typically C12 to C38.

Prior to processing, the raw material of biological origin is generally pretreated by any suitable known method, for example thermally, mechanically, for example by shear forces, chemically, for example acids or bases, or physically, for example by radiation, distillation, cooling or filtration. The purpose of the chemical and physical pretreatment is to remove impurities that interfere with the process or poison the catalyst, as well as to reduce undesirable side reactions.

In the hydrolysis process, oils and fats react with water to produce free fatty acids and glycerol as products. Three main processes for the industrial production of fatty acids are known: steam cracking, alkaline hydrolysis and enzymatic hydrolysis of triglycerides under high pressure. In the steam cracking process, triglycerides are hydrolyzed using steam at 100 to 300 ℃ and a pressure of 1-10MPa, preferably 250 to 260 ℃ and a pressure of 4 to 5.5 MPa. Metal oxides, such as zinc oxide, may be added as catalysts to accelerate the reaction. The high temperature and pressure aid in the dissolution of the fat in the water.

Paraffinic synthetic base oils produced by oligomerization are known in the art, typically PAO (polyalphaolefins) and PIO (poly internal olefins). In their production, olefinic raw materials from crude oil are used, which raw materials are free of heteroatoms. The development of base oils of the poly-alpha-olefin type started in 1930 us and germany, where products with excellent low temperature properties suitable for aircraft were mainly developed. The 1-olefin monomers used as starting materials for PAOs are typically produced from ethylene. For commercial PAOs, C8-C12 alpha-olefins or C14-C18 alpha-olefins are mainly used as starting materials. In thatIn the production of PAO, the monomers are polymerized thermally or using catalysts of the Ziegler or Friedel-Crafts type, or using zeolitic catalysts, to produce heavy products, which are subsequently distilled to obtain the desired product fractions and hydrogenated to obtain saturated paraffins. PAO products belonging to various viscosity classes, typically represented by 2, 4, 6 and 8mm at 100 ℃ can be produced²Kinematic viscosity in/s (KV 100). In addition, the production KV100 values are 40 and 100mm²Specific viscous base oils PAO40 and PAO100 in/s, which are commonly used in the production of viscous lubricants, and as Viscosity Index Improvers (VII). The PAO product has a high viscosity index and, at the same time, excellent low temperature properties with a pour point as low as-60 ℃. Since the lighter monomer compounds are removed by distillation, the product has a low volatility and a high flash point. On the basis of no antioxidant additive, the oxidation resistance is very moderate.

PIOs are produced by oligomerizing internal olefins, with double bonds distributed statistically along the entire length of the hydrocarbon chain. Internal olefins may be produced by dehydrogenating normal paraffins derived from crude oil. The molecular structure of the products produced from internal C15-C16 linear olefins is different from that of PAO. Compared with PAO, PIO has poorer performance; the viscosity index is low, the pour point is poor, and the volatility is high. In view of mass, PIOs are between PAO and VHVI. The production technology of PIO is similar to that of PAO, except that a more aggressive catalyst system is used to oligomerize the less aggressive internal olefins. Due to the lack of polarity, the solubility of the additive in PAO and PIO is rather poor. Esters are often used in formulations to improve solubility.

The use of starting materials of biological origin containing heteroatoms, or optionally thermally and/or chemically and/or physically and/or mechanically treated intermediates, in the production of high quality saturated base oils has not been reported so far.

In light of the above teachings, it is clear that there is a clear need for a new alternative process for producing hydrocarbon components preferably from raw materials of biological origin, and which avoids or at least substantially reduces the problems associated with prior art solutions. Furthermore, there is a need for non-polar saturated base oils meeting the quality requirements of high quality base oils, preferably of biological origin, and having a more preferable impact on the environment and the end user than traditional mineral base oils. In addition, there is a need for a process based on the use of renewable feedstocks, thereby saving non-renewable feedstocks.

Object of the Invention

The present invention is directed to a process for producing a saturated hydrocarbon component.

Another object of the invention is a process for producing a saturated hydrocarbon fraction, wherein raw materials of biological origin are used.

Another object of the invention is a process for producing a novel base oil.

Another object of the invention is a process for producing saturated base oils free of heteroatoms from raw materials of biological origin.

Furthermore, another object of the present invention is a process for the production of saturated diesel components and gasoline components free of heteroatoms from raw materials of biological origin.

Furthermore, the object of the present invention is a base oil meeting the API group III requirements.

The features of the process and base oil of the invention are given in the appended claims.

Summary of The Invention

The process of the present invention comprises an oligomerization step wherein the feedstock molecules react with each other, thereby increasing the carbon number of the resulting component, and further comprises a deoxygenation step. The deoxygenation may be carried out as a hydrodeoxygenation reaction or as a decarboxylation/decarbonylation reaction. In addition, the process of the present invention may also include an optional isomerization step for isomerizing the lighter product, and/or a finishing step. The starting material for the process is preferably from a biological source.

Here, oligomerization means dimerization, trimerization, and tetramerization reactions, as well as polymerization and crosslinking reactions.

The oligomerization step of the process of the present invention is carried out to extend the hydrocarbon chain of the unsaturated carboxylic acid and/or its derivatives such as esters, anhydrides and alcohols from the monomer units to obtain dimers having two monomer units, and to obtain higher oligomers. In this oligomerization reaction, the double bonds of the components react with one another under the influence of heat and/or catalyst.

Carboxylic acids and derivatives thereof also include fatty acids and derivatives thereof herein. The carbon number of the carboxylic acid and its derivatives is at least C4. It is preferred to use fatty acids of biological origin and/or derivatives thereof.

Deoxygenation here means deoxygenation by hydrodeoxygenation or decarboxylation/decarbonylation reactions. In deoxygenation, the structure of the biological raw material will be converted to paraffins or olefins, depending on the catalyst used and the reaction conditions.

Here, Hydrodeoxygenation (HDO) means deoxygenation by hydrogen. When the ester, alcohol, anhydride or carboxylic acid groups decompose, water is liberated in the reaction. All oxygen, nitrogen, phosphorus and sulfur atoms are removed.

Decarboxylation here means deoxygenation as carbon dioxide and decarbonylation means deoxygenation as carbon monoxide.

Here, isomerization means hydroisomerization of straight-chain hydrocarbons (paraffins) that produce a branched structure.

The term "saturated hydrocarbon" as used in the specification means paraffin and alicyclic hydrocarbon compounds, but not aromatic hydrocarbon compounds. The paraffin compounds may be branched or linear. The alicyclic hydrocarbon compound is a cyclic saturated hydrocarbon, i.e., cycloalkane. Such hydrocarbons having a cyclic structure are generally derived from cyclopentane or cyclohexane. The alicyclic hydrocarbon compound may include a single ring structure (monocycloparaffins) or two separate ring structures (separate dicycloalkanes), or two fused ring structures (fused dicycloalkanes), or three or more fused ring structures (polycyclic cycloalkanes or polycyclic alkanes).

Saturated base oils here include saturated hydrocarbons.

For example, a C18:1 labeled carboxylic acid represents a C18 chain with one double bond.

Here, the pressure is a gauge pressure relative to a standard atmospheric pressure.

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

Here, the wide range of carbon number means the difference between the maximum carbon number and the minimum carbon number of a molecule in a final product plus one.

The invention will now be illustrated with the attached figure 1 without wishing to limit the scope of the invention to the embodiments of said figure.

Drawings

Figure 1 shows a preferred embodiment of the process of the invention. One or more feedstocks, in the form of individual components or mixtures, selected from a triglyceride feed stream 1, a fatty acid feed stream 2, a feed stream 3 of esters of fatty acids with alcohols having short chains, a fatty acid anhydride stream 4 and a fatty alcohol stream 6, are introduced into the oligomerization reactor 10. A portion of the lighter product fraction (e.g., 52) to be recovered, or hydrocarbon stream 201, may be introduced into oligomerization reactor 10, optionally in the form of a diluent. The diluent stream 202 comprises the recycle stream 52, or the hydrocarbon stream 201, or a mixture thereof. Product 11, containing the feedstock components reacted at the double bonds, and hydrogen as stream 7, pass from the oligomerization reactor 10 to an optional pre-hydrogenation reactor 20, which pre-hydrogenation reactor 20 also optionally receives a diluent stream 202. The product hydrogenated at the double bond from the pre-hydrogenation reactor 20 is passed as stream 21 and hydrogen optionally as stream 7 to a deoxygenation reactor 30 which also optionally receives a diluent 202. In the case of deoxygenation in the decarboxylation/decarbonylation reaction form, a mixture of hydrogen 7 and an inert gas, such as nitrogen, may be used as the gas stream (not shown in the figure). The product containing saturated hydrocarbons from the deoxygenation reactor 30 is passed as stream 31 to a distillation and/or separation device 40 for separation of various product fractions, gas 44, gasoline 43, diesel 42 and base oil 41. The lighter gasoline and diesel fractions 43 and 42, respectively, are isomerized in a hydroisomerization unit 50, optionally in the presence of hydrogen 7, to produce gasoline and diesel streams 51 and 52, respectively, containing branched hydrocarbons.

In the case of the oligomerization of fatty acids 2 and/or fatty acid esters 3 and/or fatty alcohols 6 in particular, product stream 12 may leave oligomerization reactor 10, followed by separation of the non-oligomerized components, for example, by distillation vessel 60. The light, non-oligomerized components are recovered back to the oligomerization reactor 10 as stream 61 and the oligomerized components may pass to the pre-hydrogenation reactor 20 as stream 62. In recovery, stream 63 from distiller 69 may pass to a low temperature filter 80 where saturated components 81 are separated from components 82 having double bonds, which components 82 are to pass to oligomerization reactor 10. In addition, the distillate 61 may reach a post-oligomerization reactor 70, where unsaturated carboxylic acids 8 or olefins 5 having smaller molecules may be introduced for branching linear non-oligomerized unsaturated components. The product containing the feed components reacted at the double bonds passes from the post-oligomerization reactor 70 to the optional pre-hydrogenation reactor 20 as stream 71.

Detailed Description

It has now surprisingly been found that with the process according to the invention comprising an oligomerization and a deoxygenation step and optionally an isomerization step, high quality hydrocarbon components, in particular saturated base oils, can be produced from unsaturated carboxylic acids containing heteroatoms and derivatives thereof, in particular from fatty acids, fatty acid esters, fatty alcohols, individual fatty acid anhydrides and/or mixtures thereof of biological origin. The problems of the prior art processes and the products obtained therewith can be avoided, or at least substantially reduced, by the process of the present invention.

In the process of the invention, the oligomerization of materials of biological origin can be used in particular in combination with deoxygenation reactions to produce saturated base oils in a new manner. According to the oligomerization of unsaturated carboxylic acids and/or derivatives thereof, such as fatty acids, fatty acid esters, fatty alcohols, fatty anhydrides and/or mixtures thereof, the monomers are converted to dimers having two monomers, and to higher oligomers. In the case of raw materials of biological origin for the production of base oils, the hydrocarbon chain length must be extended to reach the carbon number range required for the base oil application, leaving only carbon-carbon bonds in the main structure of the molecule. According to the present invention, this is carried out by reacting compounds having a double bond with each other, thereby producing a desired carbon-carbon bond, and further producing a hydrocarbon having a carbon number of C18 to C550. In base oil applications, the carbon number is typically from C18 to C76, and especially viscous base oils may even have a carbon number from C150 to C550. In oligomerization reactions, for example, the double bonds of the triglyceride molecules react with each other, thereby forming a polymeric triglyceride network. For other feedstocks, dimers, trimers and tetramers are formed primarily. In the case of a polyunsaturated hydrocarbon chain, more trimer and hydrocarbons with a ring structure are obtained after oligomerization and deoxygenation than with a monounsaturated hydrocarbon chain.

In the process of the invention, the starting materials of biological and/or synthetic origin are oligomerized and deoxygenated. Preferably, the oligomerization of the unsaturated feedstock components is carried out first, followed by deoxygenation to obtain saturated paraffins free of heteroatoms. Alternatively, the unsaturated feedstock is first deoxygenated to remove heteroatoms and the resulting olefin product is subsequently oligomerized, but deoxygenation is therefore carried out by decarboxylation or decarbonylation reactions, since in this case hydrodeoxygenation reactions are not suitable.

After deoxygenation, the process may also include optional isomerization of light components. Linear paraffins with short chains, which do not belong to the base oil carbon family and are produced as a by-product of the process, can be isomerized to introduce branches into the hydrocarbon chains, improving the cold flow properties of the product. These isomerized products may be used, for example, as gasoline or diesel components, and further, components having carbon numbers of C18 to C24 may also be used as light base oil components.

The process may further comprise an optional pre-hydrogenation before deoxygenation, an optional post-oligomerization step after the actual oligomerization step, an optional purification step of intermediates, a recovery step of the product, and a finishing step. The feedstock may optionally be subjected to one or more pretreatment steps, such as purification.

Raw materials

In the process of the present invention, the feedstock comprises one or more components selected from triglycerides, carboxylic acids having a carbon number of from C4 to C38, esters of C4 to C38 carboxylic acids with C1 to C11 alcohols, C4 to C38 carboxylic anhydrides and C4 to C38 alcohols. The feedstock is preferably selected from triglycerides, fatty acids having a carbon number of from C4 to C24, esters of C12 to C24 fatty acids with C1-C3 alcohols, C12-C24 fatty acid anhydrides and C12-C24 fatty alcohols, and mixtures thereof. The feedstock is preferably derived from a raw material of biological origin or a mixture thereof.

Suitable starting materials of biological origin are selected from:

a) vegetable fats, vegetable oils, vegetable waxes; animal fats, animal oils, animal waxes; fish fat, fish oil, fish wax and mixtures thereof, and

b) free fatty acids or fatty acids obtained by hydrolysis, transesterification or 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 of vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes, fish fats, fish oils, fish waxes and mixtures thereof, and

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

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

f) waste and recovered food grade fats and oils, as well as genetically engineered fats, oils and waxes, and mixtures thereof, and

g) a mixture of said raw materials.

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

Since the purpose of the process is to oligomerize the components having double bonds, the feedstock is preferably at least 50 wt.%, and more preferably at least 80 wt.% of unsaturated and/or polyunsaturated compounds. The unsaturated compounds are preferably monounsaturated components, in particular the C16:1 and/or C18:1 components present in the feed preferably in a concentration of more than 40 wt.%, preferably more than 70 wt.%.

Examples of suitable biological raw materials include fish oils such as baltic herring oil, salmon oil, herring oil, tuna oil, anchovy oil, sardine oil, and mackerel oil; vegetable oils, such as rapeseed oil, canola oil, tall oil, sunflower seed oil, soybean oil, corn oil, hemp seed oil, olive oil, cottonseed oil, mustard oil, palm oil, peanut oil, castor oil, jatropha seed oil, palm nut oil, and coconut oil; and, in addition, also suitable are animal fats, such as lard, tallow, as well as waste and recycled food-grade fats and oils, and fats, waxes and oils produced by genetic engineering. In addition to fats and oils, suitable raw materials of biological origin include animal waxes, such as beeswax, chinese wax (insect wax), shellac wax (shellac wax) and lanolin (wool wax), and vegetable waxes, such as carnauba wax (carnauba palmwax), ouricouri wax, jojoba seed oil (jojoba seed oil), candelilla wax (candelilla wax), esparto wax (esparto wax), japan wax and rice bran oil (rice bran oil).

The process can also be used for processing mixtures of biologically derived and synthetic raw materials using other processes or, if appropriate, other raw materials for the production of synthetic raw materials suitable for the process steps. Pure synthetic raw materials are furthermore suitable, but in this case the product is not based on renewable natural resources.

If desired, linear olefins and olefins having a ring structure, preferably C2-C14 olefins, may also be added to the feedstock, thereby increasing the molecular weight at lower carbon numbers compared to typical C12-C24 carboxylic acids. Components of the turpentine fraction of tall oil, such as, for example, limonene, and/or compounds derived from sugars having double bonds, and/or unsaturated compounds produced from carboxylic acids via metathesis, and/or synthon compounds, such as, for example, ethylene or propylene, may be used as suitable other olefin components.

Unsaturated dicarboxylic acids, carboxylic acids, alcohols and alkyl esters with short chains (< C12) can also be used as further starting materials in the oligomerization, which can increase the molecular weight of the lower carbons compared to typical C12-C24 carboxylic acids, or derivatives of carboxylic acids. Suitable unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 2-methyleneglutaric acid, and muconic acid.

In the optional post-oligomerization reaction of the present invention, molecules with short chains such as the above may be oligomerized with carboxylic acids or alkyl esters of carboxylic acids or triglycerides or other molecules with double bonds. The double bond of the compound derived from a carboxylic acid is usually located in the middle of the hydrocarbon chain. Smaller molecules react with the double bond, creating a linear or cyclic structure located in the middle of the hydrocarbon chain.

Because the cycle time of the catalyst is short in the carboxylic acid process, the feedstock can be converted first to an ester or alcohol, which is less aggressive to the catalyst. Triglycerides can be transesterified with alcohols to produce alkyl esters. The triglycerides decompose to form esters with the alcohols and glycerol. Methanol is typically used as the alcohol, but other C1-C11 alcohols can also be used. Typical conditions for transesterification are as follows: the temperature is 60 to 70 ℃ and the pressure is 0.1 to 2 MPa. Excess sodium hydroxide and potassium hydroxide dissolved in methanol were used as catalysts. Esterification of the free carboxylic acid and alcohol requires higher temperatures and pressures (e.g., 240 ℃ and 9MPa) or acidic conditions.

The carboxylic acids can also be reduced in a known manner to fatty alcohols by direct reduction of the acid groups to alcohols with lithium aluminium hydride, whereby the double bonds remain in the alcohol, or the alkyl esters of carboxylic acids can be hydrogenated to unsaturated fatty alcohols using copper-zinc catalysts at temperatures of 200 to 230 ℃ and hydrogen pressures of 20 to 30 MPa. In the hydrogenation reaction, the alcohol used for the esterification of the carboxylic acid is released and can be recycled back to the esterifier, while the unsaturated fatty alcohol reaches the oligomerizer.

In each process step, a hydrocarbon may be used as a diluent in the feedstock. The hydrocarbons may, for example, come from biological sources and boil in diesel from 150 to 400 ℃, typically 180 to 360 ℃.

The biological raw material from which the feedstock is derived is preferably pretreated to remove impurities using known methods. The hydrolysis reaction of triglycerides can be used to produce carboxylic acids to be used as starting material for the oligomerization step. Alternatively, the triglycerides may be hydrolyzed after oligomerization. In the hydrolysis, glycerol is obtained as a by-product, and thus no hydrogen is consumed in the HDO step for hydrogenating glycerol to produce propane gas. For example, the feedstock or product may be fractionated by distillation into fractions having a narrow boiling range or carbon number, and further, impurities of the feedstock or final product may be removed by filtration through a suitable filter aid.

Method of producing a composite material

Step of oligomerization

According to a preferred embodiment of the process according to the invention, the starting material comprising at least one component having a double bond is selected from triglycerides, carboxylic acids, anhydrides and/or fatty alcohols and oligomerization takes place. The feedstock contains at least 50 wt% of unsaturated and/or polyunsaturated compounds. One of the components of the feedstock is preferably selected as the main starting material for the oligomerization step, and the oligomerization conditions are adjusted according to this main starting material. Other raw materials may be mixed with the main raw materials as long as they do not interfere with or contribute to the process.

The oligomerization reaction is catalyzed by heat and a suitable catalyst. Suitable catalysts include cationic clay catalysts, preferably zeolite catalysts, particularly preferably montmorillonite. The oligomerization of carboxylic acids may be enhanced by additional reactants, such as water. In the oligomerization of carboxylic acids, up to 10% by weight, preferably from 0.1 to 4% by weight, and particularly preferably from 1 to 2% by weight of water is added to the starting material. The use of an excess amount of water is not preferred because the anhydride (estolide) which does not dimerize with carbon-carbon bonds is subsequently produced as a by-product.

Suitable oligomerization reactors include fixed bed reactors and mixed tank reactors. A diluent to adjust oligomerization can be used in the reaction. The diesel fraction or another hydrocarbon obtained from the process is a suitable diluent that can be recovered. The pressure of the oligomerization step is 0 to 10MPa, the temperature is 100 to 500 ℃, the pressure is preferably 0 to 5MPa, and the temperature is preferably 200 to 400 ℃. In the case where the reaction is carried out as a batch reaction, the amount of the catalyst is 0.01 to 30% by weight of the whole reaction mixture, preferably 0.5 to 10% by weight of the whole reaction mixture. In the case of a fixed-bed reactor, the amount of starting material, expressed in grams per hour per gram of catalyst, is from 0.1 to 100 l/h.

In the mixed-tank reactor, the reaction time is less than 16 hours, preferably less than 8 hours, particularly preferably less than 4 hours. In case a short residence time is used, the lighter non-oligomerized components may be separated from the already oligomerized heavier components, e.g. by distillation, followed by recovery of the lighter components for oligomerization. During the recovery, the inert saturated components can be separated from the components having double bonds, for example by low-temperature filtration. The saturated components reach the deoxygenator and, optionally, isomerize, branching the hydrocarbon chains.

A step of pre-hydrogenation

The activity of the hydrogenation catalyst is substantially lost due to the formation of coke on the catalyst surface, and thus the product from the oligomerization step can optionally be pre-hydrogenated under mild conditions, hydrogenating the double bonds and further reducing the coke formation in the next deoxygenation step. The prehydrogenation is carried out in the presence of a prehydrogenation catalyst at a temperature of from 50 to 400 ℃, a hydrogen pressure of from 0.1 to 20MPa, a flow rate WHSV of from 0.1 to 10l/h and preferably at a temperature of from 150 to 250 ℃, a hydrogen pressure of from 1 to 10MPa, a flow rate of from 1 to 5 l/h. The prehydrogenation catalyst contains a metal of group VIII and/or VIA of the periodic table of the elements. The pre-hydrogenation catalyst is preferably a supported Pd, Pt, Ni, NiMo or CoMo catalyst, and the carrier is alumina and/or silica.

A deoxidation step

Deoxygenation may alternatively be carried out as hydrodeoxygenation or decarboxylation/decarbonylation. Deoxygenation in the form of Hydrodeoxygenation (HDO) is suitable for all feedstocks. In the HDO step, the oxygen and the oligomerized and optionally pre-hydrogenated stream reach a HDO catalyst bed comprising one or more catalyst beds. In the HDO step, the pressure is from 0 to 20MPa, preferably from 1 to 15MPa, particularly preferably from 3 to 10MPa, the temperature is from 100 to 500 ℃, preferably from 200 to 400 ℃, particularly preferably from 250 to 350 ℃, and the flow rate WHSV is from 1 to 5l/h, particularly preferably from 1 to 3 l/h. In the HDO step, special hydrodeoxygenation catalysts containing metals of group VIII and/or VIA of the periodic table of the elements can be used. The HDO catalyst is preferably a supported Pd, Pt, Ni, NiMo or CoMo catalyst with alumina and/or silica as the support.

In the case where the feedstock contains a carboxylic acid and/or ester, the deoxygenation may be carried out using a decarboxylation/decarbonylation reaction. In the decarboxylation/decarbonylation reaction, the feedstock and optionally a diluent are introduced into a catalyst bed. The reaction takes place in the liquid phase and it can be carried out at atmospheric pressure. However, depending on the reaction temperature of the reaction mixture, it is preferred to use vapor pressure. Depending on the feedstock, the pressure in the decarboxylation/decarbonylation step is from 0 to 20MPa, preferably from 0.1 to 20MPa, the temperature is from 200 to 400 ℃, preferably from 250 to 350 ℃, and the flow rate WHSV is from 0.1 to 10l/h, preferably from 1 to 5 l/h. In the decarboxylation/decarbonylation step, a special catalyst is used. The catalyst contains a metal of group VIII and/or VIA of the periodic table of the elements, for example as a supported Pd, Pt, Ni, NiMo or CoMo catalyst, the support being alumina and/or silica and/or activated carbon. The decarboxylation/decarbonylation catalyst is preferably Pd supported on carbon in case no hydrogen is used in the process, and sulfided NiMo supported on alumina in case a mixture of hydrogen and an inert gas such as nitrogen is used in the process. Functional groups are no longer present in the product of the decarboxylation/decarbonylation step and the product contains only carbon and hydrogen. The carbon number has been reduced by one carbon per removal of one functional group.

In the case where deoxygenation is carried out in decarboxylated/decarbonylated form, the oligomerization may be carried out prior to deoxygenation, and thus the feedstock to the oligomerization step contains unsaturated carboxylic acids and/or esters of carboxylic acids. In the case where the decarboxylation/decarbonylation step is followed by oligomerization, the starting material for the oligomerization step contains unsaturated compounds from decarboxylation/decarbonylation, the number of carbons being reduced by one carbon per functional group removed as compared to the starting material.

In the deoxidation step, the above-mentioned HDO and decarboxylation/decarbonylation reactions may be simultaneously carried out, carbon dioxide or carbon monoxide being produced from a part of the functional groups, and a part of the functional groups being hydrodeoxygenated. After the deoxygenation step, the hydrogen fraction may be passed with hydrogen to a separate isomerization step. The pressure of the isomerization step is from 0.1 to 20MPa, preferably from 5 to 10 MPa. The temperature is from 100 to 500 deg.C, preferably from 200 to 400 deg.C. In the isomerization step, a special isomerization catalyst containing a molecular sieve and a metal of group VIII of the periodic table of elements, such as Pd and Pt, may be used. Alumina and/or silica may be used as the support. After the oligomerization and deoxygenation steps, the product stream may optionally be finished to remove double bonds and aromatics. In the case where the finishing step is carried out using hydrogen in the presence of a catalyst, this step is called hydrofinishing. In the finishing step, the pressure is from 1 to 20MPa, preferably from 5 to 15 MPa. The temperature is 50 to 500 deg.C, preferably 100 to 400 deg.C. In the finishing step, special catalysts containing metals of group VIII and alumina and/or silica can be used. The hydrofinishing catalyst is preferably a supported Pd, Pt or Ni catalyst, the support being alumina and/or silica. Finishing can also be carried out in the absence of hydrogen by removing polar components using adsorbent materials such as clays or molecular sieves. After oligomerization, deoxygenation and optional isomerization and work-up steps, the product is fractionated, for example by distillation. Typical carbon numbers for the product components are as follows: gas C1-C4, gasoline C5-C10, diesel oil C11-C26 and base oil C18-C76. If desired, the hydrocarbon component obtained as product or another suitable hydrocarbon stream can be recycled to the various process steps in order to be able to carry out oligomerization and deoxygenation steps for improving the conversion and/or selectivity, or to control the exothermic nature of the reaction.

In one embodiment of the invention, the already oligomerized product can be further oligomerized by introducing further monomers into the process (mixing tank reactor) or by repeatedly recovering the already oligomerized product while adding monomers (continuous reactor). In this way, it is possible in particular to provide viscous base oils having a carbon number up to C150-C550 which can be used for the production of viscous lubricants and as modifiers of the viscosity index.

Product(s)

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

Likewise, hydrocarbon components of preferably biological origin are obtained which are suitable as solvents, gasoline or diesel, or diesel components. The diesel component or the C18-C24 base oil component can be isomerized to improve low temperature performance. Gasoline components can be isomerized to increase octane number. In the case of the post-oligomerization process using olefins having short chains or unsaturated carboxylic acids having short chains for branching residual double bonds, no isomerization is necessary.

The carbon number and carbon number range of the base oil are based on the biological raw materials and production process of the feedstock. The conventional carbon number range for base oils applications of the prior art is C18 to C76, whereas the carbon number range for extra viscous base oils can be as high as C150 to C550. KV100 is 4-7mm in the required kinematic viscosity range²In the case of/s, branched and/or cyclic paraffins having a single carbon number are generally obtained from a feedstock containing carboxylic acids of the same chain length using the process of the present invention after the oligomerization and HDO steps.

KV100 is 4 to 7mm in the required viscosity range²In the case of/s, the base oil or base oil component produced by the combined HDO-decarboxylation/decarbonylation process of the invention by oligomerization is in a very narrow carbon number range, with the carbon number range of the product being C30 to C32 for feedstocks typically containing the C16 component and C34 to C36 for feedstocks containing the C18 component. The raw material is a mixture of C16 and C18 componentsIn the case of (2), the width of the carbon number range of the product is usually seven carbons. The carbon number range of the base oils of the present invention may also be at a very high level, even up to C150 to C550, in case special heavy base oils are required which are suitable as tackifiers and viscosity index improvers.

In Table 2 below, the bio-derived base oils (1 and 2) of the present invention are given, and KV100 is 4 to 6mm²Carbon number and typical structure of the prior art synthetic base oils (3-5) per second. The most typical carbon numbers are in bold. The base oil or base oil component of the present invention differs from the prior art products in terms of molecular structure, as shown in the table.

In table 2, the structure of cycloalkane is a typical example of the compound group. In structural examples, oligomeric dimers 1 and 2 produced from C18 have carbon numbers ranging from C34 to C36 and C51 to C54, respectively, while known synthetic hydrocarbon base oils of the same viscosity class, such as PAOs, have carbon numbers ranging from C32 to C48 and PIOs have carbon numbers ranging from C30 to C48.

TABLE 2

Carbon number and typical Structure of base oil

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

1C (n) H (2n +2) alkanes

2C (n) H (2n) monocycloparaffins

3C (n) H (2n-2) bicycloalkane

4C (n) H (2n-4) tricycloalkane

5C (n) H (2n-6) tetracycloalkanes

6C (n) H (2n-8) pentacycloalkane

In table 2, the percentages (%, by FIMS) represent the groups of the compounds determined according to the method.

The base oil components of table 2 were produced as follows:

1. according to the invention oligomeric and hydrogenated C18 fatty acid dimers produced from tall oil

2. According to the invention, oligomeric and hydrogenated C18 fatty acid trimer is produced from tall oil

3. PAO C16 produced by oligomerization of 1-hexadecene using heterogeneous catalyst

4. PAO C10 produced from oligomerization of 1-decene using homogeneous catalysts

5. PIO produced by dimerization of internal C15-C16 olefins.

The oligomeric dimers and trimers of the present invention (structures 1 and 2 of table 2) are branched at the double bond within the C18 hydrocarbon chain, thereby having a pair of tertiary carbons on adjacent carbon atoms in the molecular structure. PIO is typically a dimer produced from shorter C15-C16 hydrocarbons, whereas the products of the present invention are C16 and/or C18 dimers. In addition, the products of the invention exhibit a high amount, even more than 50%, of monocycloparaffins, calculated as FIMS.

In the prior art production processes for polyalphaolefins, the reaction typically takes place at the double bond at the end of the C10 chain using a boron trifluoride catalyst, thus leaving a methylene (-CH) group between the tertiary carbons₂- (Structure 4 in Table 2). In the case of oligomerization using a heterogeneous catalyst, double bonds are transferred from the α -position while skeletal isomerization occurs, thus leaving 1 to 10 methylene groups (structure 3 in table 2, for example, 4 methylene groups) between the tertiary carbons in the typical structure of the resulting base oil. In the case of oligomerisation using a homogeneous catalyst, skeletal isomerisation occurs in the hydrogenation step, and subsequent oligomerisation, respectively, so that C1-C3 side branches are formed next to the double bonds in the molecule of structure 4 shown in table 2. In the prior art, PAO and PIO groupsWhile alkyl branches are predominantly present in the base oil, in the product of the invention there is an alicyclic hydrocarbon component branched by a ring structure in addition to the alkyl branches. The high quality base oils obtained by the process of the invention have a pour point of at most below-40 c and are therefore very suitable for the desired low temperature conditions. The viscosity index of the product can be as high as 125, so the product is suitable for group III base oil applications. By adding the appropriate unsaturated carboxylic acid or olefin to the feedstock, the molecular weight of the product can be adjusted according to the carbon number range required for different applications. Carboxylic acids with small molecules, or olefins crosslinked or oligomerized with fatty acids of triglycerides, form short branches on the main hydrocarbon chain of the fatty acid. In the case where other natural cyclic compounds, such as, for example, an alga alkene, are used as an additional component of the raw material, a molecule having a ring structure in a side chain within the molecular chain is obtained. One or both of the additional components are preferably oligomerized in the product. Suitable corresponding products can also be produced according to the invention, in terms of hydrocarbon chain length, from other carboxylic acids and from other biological components having short chains. The lighter branched components from the HDO treatment are very suitable as biodiesel components. According to the invention, the base oil of biological origin comprises a branched saturated hydrocarbon product. The product is produced from biological raw materials and contains at least 90 wt.%, preferably at least 95 wt.%, particularly preferably at least 97 wt.%, and at most 99 wt.% saturated hydrocarbons. Furthermore, the product of 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%, of monocycloparaffins, based on the FIMS process, and less than 3.0%, preferably less than 1.0%, and particularly preferably less than 0.1%, of multicycloparaffins, based on FIMS. In addition, the products of the invention contain up to 20% by weight, preferably up to 10% by weight, and particularly preferably up to 5% by weight, and up to 1% by weight, of linear alkanes (GC). For the base oils of the present 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 products of the invention are branched by means of carbon-carbon bonds, this structure imparting to the product not more than 0 ℃, preferably not more than-10 ℃, and particularly preferably not more than-35 ℃ (ASTM D)5950) Very low pour point. For the base oils of the invention, the viscosity KV100 is from 4 to 7mm²A carbon number in the width range of at most 9 carbons, preferably at most 7 carbons, and particularly preferably at most 3 carbons (determined by field ionization mass spectrometry FIMS). More than about 50 wt.%, preferably more than 75 wt.% and particularly preferably more than 90 wt.% of the base oil contains hydrocarbons belonging to this narrow carbon number distribution. The sulphur content of the base oils of the present invention is below 300ppm, preferably below 50ppm, and particularly preferably below 1ppm (ASTM D3120). The nitrogen content of the base oils of the present invention is below 100ppm, preferably below 10ppm, and particularly preferably below 1ppm (ASTM D4629). The base oil of the present invention contains carbon¹⁴C isotope, which can be considered as an indication of the use of renewable raw materials. Typical of products of purely biological origin¹⁴C isotope content of at least 100%, said¹⁴C isotope content was determined as radioactive carbon content for a product based entirely on biomaterial according to radioactive carbon content in atmosphere in 1950 (ASTM D6866). Of base oils in the case of non-biological components for the processing of products¹⁴The C isotope content is low, but the content is more than 50%, preferably more than 90%, particularly preferably more than 99%. In this way even small amounts of base oils of biological origin can be detected in other hydrocarbon-based oil types. The narrow boiling base oil component obtained according to the present invention has a very low volatility compared to similar products of the prior art. For the base oils of the invention, the volatility of the products having a KV100 of from 3cSt to 8cSt is at most 2271.2 (KV100)^-3.5373wt%, as determined by DIN 51581-2 method (Matmatic Noack method based on ASTM D2887 GC distillation). The cetane number of the products obtained by the process of the invention which are suitable as diesel fuel components is greater than 40, preferably greater than 55, and particularly preferably greater than 70. It contains more than 60% by volume, preferably more than 99% by volume, of paraffins and less than 30% by volume, preferably less than 1% by volume, of aromatics, based on the IP-391 process. The diesel product comprises less than 40 wt%, preferably less than 10 wt% linear normal paraffins. The cloud point of the diesel component is below 0 ℃, preferably below-15 ℃ and especially below-30 ℃. Typically, the resulting diesel product is entirely of biological origin. In the products of the invention, there are compounds consisting ofCarbon-carbon bond forming branches, this structure produces a very low cloud point. Due to the biological origin, the product of biological origin also contains carbon indicating the use of renewable raw materials¹⁴Isotope of C. Of products of purely biological origin¹⁴The C content is at least 100%. The choice of biological raw material has a strong influence on the composition and boiling range of the product. Furthermore, the feedstock may be fractionated by distillation into fractions having a narrow carbon number, which may be suitable for different applications. For feedstocks with C16, C18, C20 and C22 hydrocarbon chain lengths, typical carbon numbers of the dimer product after hydrodeoxygenation are C32, C36, C40 and C44, respectively, which after decarboxylation/decarbonylation are reduced by two to C30, C34, C38 and C42. Since the distillation range of the product depends to a large extent on the length of the hydrocarbon chains, a narrow product cut is obtained.

THE ADVANTAGES OF THE PRESENT INVENTION

The process of the present invention and the resulting product have several advantages, including, for example, the use of renewable feedstocks instead of non-renewable feedstocks reduces carbon dioxide emissions that accelerate the greenhouse effect. According to the present invention, the biological raw material containing the heteroatom can be used as a completely new raw material source for high-quality saturated base oil. The raw materials of the process of the invention are available worldwide and, in addition, the use of the process is not limited by significant initial investments, in contrast to, for example, GTL technology. The products of the process of the invention are carbon dioxide neutrals in terms of use and waste, i.e. they do not increase the carbon dioxide load of the atmosphere compared to products derived from fossil raw materials. Unlike esters and other base oils containing heteroatoms, such as dimer fatty alcohols, the base oils prepared according to the present invention are more hydrolytically stable and have a structure that does not decompose under humid conditions. In addition, the oxidation resistance of saturated hydrocarbons is better than that of corresponding base oils containing unsaturated groups based on fatty acids or fatty alcohol dimers, or ester base oils. The saturated hydrocarbon components do not decompose as readily as the esters which form corrosive acids. The non-polar and saturated hydrocarbon components are obtained using the process of the present invention by removing the oxygen of the alcohol, ester or carboxylic acid, as well as any impurity heteroatoms of the feedstock, in a deoxygenation step. Oligomeric carboxylic acid derivatives inThe deoxygenation is followed by a carbon-carbon bond to create a structure with branching. In the C12:1-C20:1 oligomerization, the resulting branches are typically C3 to C11 in length. Such hydrocarbons have a very low pour point, which is advantageous for base oil applications, and therefore the product is liquid at very low temperatures, and further, it has a good viscosity index. The saturated hydrocarbon product produced is a suitable base oil component without any mixing restrictions and further, is compatible with the lubricant additives. With conventional hydrocarbon oils of the corresponding viscosity class, especially where KV100 is from 4 to 7mm²Compared with the situation of/s, the base oil has excellent processing performance. A narrow boiling range means that the product does not contain any initial light ends and that the average molecules are significantly lighter than the indicated average as the volatility of the product decreases and the emissions in practical use decrease. The base oil product is free of heavy ends "tails," meaning that the molecules are significantly heavier than average, resulting in superior low temperature performance of the product.

For the base oils of the present invention, the carbon number and boiling range depend on the feedstock composition. For the prior art base oils, the boiling range is adjusted by distilling the product to obtain a fraction with the desired kinematic viscosity. It is preferred for the lubricant that the base oil has a narrow carbon number and thus a narrow boiling range, and therefore, the composition contains molecules of similar size that behave in a similar manner under different conditions.

For a base oil or base oil component, the high viscosity index of the product means that the amount of viscosity index improver typically used in lubricating compositions can be reduced. In engine oils, for example, it is generally known that the VII component is a major cause of engine contamination. In addition, the reduced amount of VII results in significant savings in cost. In contrast to conventional base oils derived from crude oil, no sulfur or nitrogen is present in the product. The process of purifying raw materials based on natural fatty acids allows the product to be safely used in such applications where the user is exposed to the oil or oil vapors. Furthermore, the products of the invention respond well to antioxidants and pour point reducing agents, thus allowing longer use of lubricants made from the base oils, as well as allowing their use in cold weather conditions. With ester phasesThe base oils of the present invention are more compatible than conventional base oil components derived from crude oil and other hydrocarbon-based oils, as well as lubricating additives. Furthermore, there are no such problems encountered with esters for elastomers such as sealing materials. Advantages of the base oil of the present invention include that it meets the requirements for base oils according to group II, preferably group III, of the API, and that it can be used in engine oil compositions as other base oils classified according to group II or group III of the API, according to the same oil change rules. E.g. from the product¹⁴As is clear from the C isotope content, the base oils of the present invention are derived from renewable natural resources. Of products¹⁴A product of biological origin having a C isotope content of at least 100%, and 0% of a product derived from crude oil. The proportions of the components of the base oil of biological origin may also be according to that of the base oil¹⁴C isotope content with an accuracy of at least 1%. The low temperature properties and cetane number of the middle distillate produced by the process of the present invention, which is suitable as diesel oil, are also excellent, and the middle distillate is therefore suitable for the desired low temperature applications. For the optional prehydrogenation step, side reactions of the double bonds, such as polymerization, cyclic structures and aromatization, which are detrimental to the viscosity properties of the product and cause the formation of coke on the HDO catalyst, can be reduced. By optionally recovering unreacted starting components, more double bond reactions can be achieved to improve product yield. Instead of or in addition to biological raw materials, synthetic compounds having corresponding chemical structures may also be used as starting materials for the present invention. The hydrocarbon components produced according to the present invention and described in the following examples are excellent in properties, and further, the carbon number range and distillation range are very narrow. The method of the present invention provides a molecular structure with excellent viscosity properties and excellent low temperature properties. The product is well suited as a base oil without blending restrictions and further, the product is also compatible with lubricant additives. The invention will now be illustrated by the following examples. However, the intention is not to limit the scope of the invention to the particular embodiments described or combinations thereof. The invention may be carried out in different ways without departing from the specific description of the appended claims.

Examples

Example 1

Preparation of hydrocarbon component from vegetable oil A feedstock containing 200ml soybean oil, 6g montmorillonite catalyst and 5ml distilled water was charged to a high pressure Parr reactor. The temperature was raised to 270 ℃ and the oil was oligomerized while mixing slowly for 7 hours. Thereafter, in the HDO step, dried and activated NiMo/Al was used₂O₃The catalyst, hydrogenated the above oligomerized mixture in a high pressure Parr reactor, to produce i-paraffins. 200ml of the oligomeric soybean oil mixture was hydrogenated at 325 ℃ under 5MPa of hydrogen pressure until no acid groups were detected in the FTIR spectra of the samples. The reaction mixture was mixed at 300 rpm. The final product is distilled and mainly branched to give cyclic C36 paraffins as product. The properties of the resulting hydrocarbon component are shown in table 3. The hydrocarbon component can also be produced in a similar manner from other plant and fish oils and animal fats which include double bonds.

Example 2

Preparation of hydrocarbon components from methyl esters of carboxylic acids derived from soybean oil

Soybean oil was pretreated by transesterification with methanol in the presence of sodium methoxide catalyst at a pressure of 0.1MPa, 70 ℃ and under alkaline conditions in two steps. The methyl esters of the carboxylic acids are purified by washing with acid and water, and then they are dried.

The composition of methyl carboxylate derived from soybean oil is as follows: 0, 11 percent of C16; 2, 20 percent of C18; 1, 8 percent of C18; 2, 54 percent of C18; and C18:3, 6%. The methyl carboxylate mixture obtained above was oligomerized in a high pressure Parr reactor. 200ml of the feedstock and 6g of the bentonite catalyst were introduced into a reactor, which was pressurized twice with nitrogen to displace the oxygen and then the temperature was raised to 350 ℃ to oligomerize the methyl carboxylate mixture while slowly mixing for 7.2 hours. The monomeric, dimeric and trimeric methyl esters were separated from the reaction mixture using a silica column. The dimerized and trimerized methyl esters obtained above were then hydrogenated separately as described in example 1 and the final product was distilled, thereby producing 26 wt% of branched and cyclic C36 paraffins and 15 wt% of branched and cyclic C54 paraffins. The properties of the resulting hydrocarbon component are given in table 3. The product performance is excellent, and the molecular distribution is extremely narrow. The hydrocarbon component can also be produced in a similar manner from methyl carboxylates of other plant, fish or animal origin which comprise some double bonds. The productivity of the process can be increased by recovering unreacted monomer.

Example 3

Preparation of hydrocarbon components from carboxylic acids derived from tall oil in a pre-treatment step, the free carboxylic acids of tall oil are distilled. Thereafter, the carboxylic acid was oligomerized in a high pressure Parr reactor. 200g of the starting material (carboxylic acid), 16g of montmorillonite catalyst and 10g of water were introduced into the reactor. The temperature was raised to 255 ℃ and the carboxylic acid was oligomerized while mixing slowly for 3 hours. The mixture was cooled and the catalyst was filtered off. The monomers were separated from the dimers and trimers (acids) of the reaction mixture using a silica column. The productivity of the carboxylic acid dimer was 45% by weight. In the HDO step, the dimer containing fraction was hydrogenated as in example 1 until no carboxylic acid peak was present in the FTIR spectrum. Branched and cyclic paraffins are obtained as products. The properties of the resulting hydrocarbon component are given in table 3. The hydrocarbon component can also be produced in a similar manner from free carboxylic acids derived from other oils than tall oil, or from hydrolysed carboxylic acids derived from plant or fish oils or animal fats, said acids comprising double bonds.

Example 4

Production of hydrocarbon components from carboxylic acids derived from tall oil by means of pre-hydrogenation in a pre-treatment step, the free carboxylic acids of tall oil are distilled. The feed then comprised 30 wt% C18:1, 42 wt% C18:2 and 9 wt% C18:3 carboxylic acid. In addition, the feed contained 2 wt% resin acids. Tall oil carboxylic acid oligomerized in a high pressure Parr reactor. 200g of the raw mixture, 16g of montmorillonite catalyst and 10g of water were fed into the reactor. To displace the oxygen, the nitrogen pressure was increased to 0.5MPa and the mixture was stirred for a while at 600 rmp. The pressure was released and pressurized again with nitrogen. The temperature was then raised to 225 ℃ and the carboxylic acid was allowed to relaxOligomerization was carried out for 2 hours while slowly mixing. The product was cooled and the catalyst was filtered off. The monomer, dimer and trimer (acid) were separated from the reaction mixture using a silica column. The productivity of the carboxylic acid dimer was 45% by weight. Prior to the HDO step, pre-sulfided NiMo/Al was used in a 450ml high pressure Parr reactor₂O₃The catalyst hydrogenates the double bonds of the dimer obtained above. The prehydrogenation was carried out using the dried and activated catalyst while mixing at 300rpm under a hydrogen pressure of 5MPa at 230 ℃. Hydrogenation of the dimer was continued until no double bonds were observed in the FTIR spectra. The dimer was hydrogenated in the HDO step as in example 1 until the carboxylic acid peak disappeared from the FTIR spectrum, followed by filtration of the paraffin product through celite. Branched and cyclic C34, C35, C36 paraffins are obtained as the final product. The properties of the resulting hydrocarbon component are given in table 3. The hydrocarbon component has excellent performance and extremely narrow molecular distribution. The hydrocarbon component can also be produced in a similar manner from free carboxylic acids derived from other oils than tall oil, or from hydrolysed carboxylic acids derived from plant or fish oils or animal fats, said acids comprising double bonds.

Example 5

Preparation of hydrocarbon components from methyl ester of carboxylic acid derived from soybean oil and limonene as in example 2, soybean oil was transesterified with methanol, thereby producing methyl ester of carboxylic acid. The reaction mixture was purified by washing with acid and water. Finally, the methyl carboxylate is dried. The composition of the methyl carboxylate is as follows: 0, 11 percent of C16; 0, 20 percent of C18; 1, 8 percent of C18; 2, 54 percent of C18; and C18:3, 6%. The soybean oil methyl ester and the algae alkene obtained above were oligomerized in a high pressure Parr reactor using 8% of a bentonite catalyst and 4% of water, the molecular ratio was 2:1, respectively. 200ml of the starting mixture were fed into the reactor. Replacement of oxygen was performed as in example 4. The temperature and pressure were raised to 310 ℃ and 2MPa, respectively, and the soy oil methyl esters were oligomerized with the limonene for 6 hours while slowly mixing. The oligomerization product was hydrodeoxygenated as described in example 1. The monomers were separated from the final product by distillation, thereby producing a mixture of "pinene-branched" C28 isoparaffins, and paraffin dimers and trimers from the methyl carboxylate. The properties of the hydrocarbon component obtained as a product are given in table 3. Branched hydrocarbon components can also be produced in a similar manner from other plant, animal or fish-derived or aliphatic carboxylic acids or methyl esters of carboxylic acids, and preferably suitable compounds of biological origin having a small molecular size, the acids comprising some double bonds.

Example 6 production of heavy Hydrocarbon Components from carboxylic acids of tall oil

Tall oil was oligomerized as in example 3, except that the reaction was carried out for 7 hours while mixing slowly. The trimer is separated from the dimer and monomer of the reaction mixture using a silica column. In the HDO step, the trimer obtained above was hydrogenated as in example 1 until no carboxylic acid peak was present in the FTIR spectrum. Branched and cyclic paraffins are obtained as products. The properties of the product are shown in table 3. The hydrocarbon component can also be produced in a similar manner from free carboxylic acids derived from other oils than tall oil, or from hydrolysed carboxylic acids derived from plant or fish oils or animal fats, said acids comprising double bonds.

TABLE 3

Properties of the resulting hydrocarbon component

Analysis of	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Method of producing a composite material
								KV100(mm2/s)	5,2	6,0	5,6	6,6	5,4	25,1	ASTM D445
KV40(mm2/s)	28,9	35,8	32,0	38,0	31,8	248,4	ASTM D445
								VI(-)	113	111	113	129	104	129	ASTM D2270
Pour point (. degree. C.)	-9	-12	-57	-39	0	-9	ASTM D5950
								GC distillation (. degree.C.)							ASTM D2887
5％			394	398	380	335
								50％			458	469	427	478
95％			482	626	495	647
								GC-Noack，wt％			6,7	5,7			DIN51581-2
Molecular distribution, wt.%
								Aromatic hydrocarbons				0,0			ASTM D2549
n-alkanes				＜1			GC
								Alkane hydrocarbons				28			FIMS
Monocyclic cycloalkane				57			FIMS
								Bicyclic alkanes				15			FIMS
Other cycloalkanes				0			FIMS
								Sulfur, ppm				＜1			ASTM D3120/D 4294
Nitrogen, ppm				1,5			ASTM D4629
								14C,% modern carbon				100

TABLE 4 Properties of the base oils of the prior art

HC-CDW ═ hydrocracked, wax isomerized base oils

Example 7

Description of the biological origin of the Hydrocarbon Components

The biologically derived hydrocarbon component from example 6 was weighed into a base oil derived from group III mineral oil and mixed thoroughly. For the first sample, 0.5014g of the biogenic hydrocarbon component were weighed out and group II base oil component was added in an amount to give 10.0g total weight; for the second sample, 1.0137g of the biogenic hydrocarbon component were weighed out and group II base oil components were added in an amount of 10.0232g total weight. The results of the measurements are in table 5 below. The results are expressed as "percent modern carbon", based onRadioactive carbon content in the atmosphere in 1950. Currently, the% modern carbon in the atmosphere is about 107%. Delta¹³C value represents a stable carbon isotope¹³C/¹²The ratio of C. By means of this value, isotope fractionation performed in the sample processing method can be corrected. The actual results are given in the last column. The method is ASTM D6866.

TABLE 5

Result from radioactive carbon

Test specimen	14C content%	δ13C	Modern carbon percentage%
				Mineral oil	0,1±0,07	-29,4	0
Biological oil	106,7±0,4	-28,9	100
				Mineral oil + biologics, 5 wt.%	5,0±0,3	-29,3	4,60±0,28
Mineral oil + biologics, 10 wt.%	10,8±0,3	-29,6	10,04±0,29

Example 8

Carbon number distribution

According to the present invention, the carbon number distribution of the base oil is narrower than that of the conventional base oil. The base oils of the present invention contain a larger amount of high boiling C34-C36 fraction than conventional products of the same viscosity range (KV100 of about 4cSt), as shown in FIG. 2. The carbon number distribution was determined by FIMS. The sample for FIMS analysis was the C18 tall oil fatty acid feedstock of example 4. Decarboxylation/decarbonylation also produces paraffinic C35/C34 compounds (combined HDO-decarboxylation/decarbonylation) in addition to hydrodeoxygenation to produce C36 compounds.

Claims (25)

1.A process for producing a saturated hydrocarbon component, characterized by oligomerizing and deoxygenating a feedstock comprising one or more components selected from the group consisting of carboxylic acids having a carbon number of C4 to C38, esters of C4 to C38 carboxylic acids with C1-C11 alcohols, C4-C38 carboxylic anhydrides, and C4-C38 alcohols, the oligomerization is carried out in the presence of a cationic clay catalyst at a pressure of 0 to 10MPa and a temperature of 100 to 500 ℃, said feedstock containing at least 50 wt% of unsaturated and/or polyunsaturated compounds, said deoxygenation being carried out in the presence of hydrogen, at a temperature of from 100 to 500 ℃, a pressure of from 0 to 20MPa, a flow rate WHSV of from 0.1 to 10l/h, in the form of hydrodeoxygenation in the presence of a hydrodeoxygenation catalyst, or in the presence of a decarboxylation/decarbonylation catalyst, in decarbonylation/decarboxylation at a temperature of from 200 to 400 ℃, a pressure of from 0 to 20MPa, a flow rate WHSV of from 0.1 to 10 l/h.

2. The process according to claim 1, characterized in that the feedstock comprises one or more components selected from the group consisting of carboxylic acids having a carbon number of from C4 to C24, esters of C12 to C24 carboxylic acids with C1-C3 alcohols, C12-C24 carboxylic anhydrides and C12-C24 alcohols.

3. The process according to claim 1, characterized in that the feedstock comprises at least one raw material of biological origin selected from the group consisting of fatty acids, esters of fatty acids and alcohols, fatty acid anhydrides and fatty alcohols.

4. The method according to claim 1, characterized in that the raw material comprises at least one raw material of biological origin, which is a triglyceride.

5. A process according to claim 3, characterized in that the starting material is selected from:

a) vegetable fats, vegetable oils, vegetable waxes; animal fats, animal oils, animal waxes; and mixtures thereof, and

b) free fatty acids or fatty acids obtained from vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes and mixtures thereof by hydrolysis, transesterification or pyrolysis reactions, and

c) esters obtained by transesterification from vegetable fats, vegetable oils, vegetable waxes, animal fats, animal oils, animal waxes and mixtures thereof, and

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

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

f) waste and recovered food grade fats and oils, as well as genetically engineered fats, oils and waxes, and mixtures thereof, and

g) a mixture of said raw materials.

6. The method according to claim 5, characterized in that the starting material is selected from the group consisting of:

a) fish fat, fish oil, fish wax and mixtures thereof, and

b) free fatty acids or fatty acids obtained from fish fat, fish oil, fish wax and mixtures thereof by hydrolysis, transesterification or pyrolysis, and

c) esters obtained by transesterification from fish fat, fish oil, fish wax and mixtures thereof, and

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

e) fatty alcohols obtained as reduction products of fatty acids from fish fat, fish oil, fish wax and mixtures thereof, and

g) a mixture of said raw materials.

7. The process according to claim 1, characterized in that the feedstock contains at least 80% by weight of unsaturated and/or polyunsaturated compounds.

8. A process according to claim 1, characterized in that the oligomerization is carried out in the presence of a zeolite catalyst.

9. A process according to claim 1, characterized in that up to 10% by weight of water is added to the carboxylic acid containing feedstock in the oligomerization step.

10. A process according to claim 1, characterized in that 0.1 to 4 wt% of water is added to the carboxylic acid containing feedstock in the oligomerization step.

11. A process according to claim 1, characterized in that deoxygenation is carried out before or after oligomerization.

12. The process according to claim 1, characterized in that the hydrodeoxygenation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst with an alumina and/or silica support.

13. The process according to claim 1, characterized in that prior to hydrodeoxygenation, the product from the oligomerization step is prehydrogenated in the presence of a prehydrogenation catalyst at a temperature of from 50 to 400 ℃, a hydrogen pressure of from 0.1 to 20MPa, and a flow rate WHSV of from 0.1 to 10 l/h.

14. The process according to claim 13, characterized in that the prehydrogenation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst with an alumina and/or silica support.

15. The process according to claim 1, characterized in that the decarboxylation/decarbonylation catalyst is a Pd, Pt, Ni, NiMo or CoMo catalyst with an alumina and/or silica support or an activated carbon support.

16. The process according to claim 1, characterized in that after the oligomerization and deoxygenation steps, the product is isomerized in the presence of hydrogen at a pressure of 0.1 to 20MPa at a temperature of 100 to 500 ℃ in the presence of an isomerization catalyst.

17. The process according to claim 16, characterized in that the isomerization catalyst is a supported catalyst comprising a molecular sieve and a metal of group VIII of the periodic table of the elements.

18. Use of the process according to any one of claims 1 to 17 for the production of gasoline, solvent and/or diesel fractions.

19. A saturated hydrocarbon component characterized by the saturationThe hydrocarbon component contains at least 90 wt% of saturated hydrocarbons, 20-90% of monocycloparaffins, less than 3.0% of polycyclic cycloalkanes, up to 20 wt% of linear alkanes, and at least 50 wt% of the saturated hydrocarbons have a carbon number range breadth of up to 9 carbons, and the saturated hydrocarbon component is of biological origin and has a kinematic viscosity at 100 ℃ of from 3cSt to 8cSt, and the volatility of the saturated hydrocarbon component is not greater than 2271.2 ANGSTROM (KV100)^-3.5373% and pour point of 0 ℃ or less.

20. Saturated hydrocarbon component according to claim 19, characterized in that the saturated hydrocarbon component contains at least 95 wt% of saturated hydrocarbons, 20-80% of monocycloparaffins, up to 10 wt% of linear paraffins, and at least 75 wt% of the saturated hydrocarbons have a carbon number range width of up to 9 carbons.

21. The saturated hydrocarbon component according to claim 19, characterized in that the saturated hydrocarbon component contains at least 97 wt% of saturated hydrocarbons, 20-60% of monocycloparaffins, at most 5 wt% of linear paraffins, and at least 90 wt% of the saturated hydrocarbons have a carbon number range width of at most 9 carbons.

22. Saturated hydrocarbon component according to claim 20, characterized in that the saturated hydrocarbon component contains at least 97 wt% saturated hydrocarbons, 20-60% monocycloparaffins, at most 5 wt% linear paraffins, and at least 90 wt% of the saturated hydrocarbons have a carbon number range width of at most 9 carbons.

23. The saturated hydrocarbon component according to claim 19, characterized in that the carbon number range width is at most 7 carbons.

24. The saturated hydrocarbon component according to claim 19, characterized in that the carbon number range width is at most 3 carbons.

25. The saturated hydrocarbon component according to claim 19, characterized in that the saturated hydrocarbon component has a 14C isotope content of at least 100%.