Process for converting carboxylic acids and esters to base oil hydrocarbons
阅读说明：本技术 用于将羧酸和酯转化为基础油烃的方法 (Process for converting carboxylic acids and esters to base oil hydrocarbons ) 是由 尤卡·米吕奥亚 米卡·凯图宁 拉米·皮洛拉 于 2018-06-15 设计创作，主要内容包括：用于将羧酸和酯转化为基础油烃的方法。从包含脂肪酸的可再生油或包含脂肪酸的衍生物制备多种不同的具有星形构型(S)的支链烃化合物(式I)。支链烃化合物可以单独或以混合物分离,并且可以用作基础油,特别是可再生基础油(RBO)的一部分。用于制备式(I)的支链烃化合物的方法涉及有利于三聚反应的条件,然后是加氢处理条件。式(I)的化合物可以通过在方法中催化处理可再生材料来制备,并且该化合物具有与润滑、冷流动性有关的期望品质以及具有低的Noack挥发性。(A process for converting carboxylic acids and esters to base oil hydrocarbons. A variety of different branched hydrocarbon compounds (formula I) having a star configuration (S) are prepared from renewable oils comprising fatty acids or derivatives comprising fatty acids. The branched hydrocarbon compounds may be isolated individually or in mixtures and may be used as part of a base oil, particularly a Renewable Base Oil (RBO). The process for the preparation of branched hydrocarbon compounds of formula (I) involves conditions favoring the trimerization reaction followed by hydrotreating conditions. The compounds of formula (I) can be prepared by catalytically treating renewable materials in a process and have the desired qualities relating to lubrication, cold flow and low Noack volatility.)
1. A compound of formula I wherein n, m and p are, independently of each other, odd integer values from 9 to 41, and wherein the total carbon number of formula I is from 31 to 65, with the proviso that when n and m are both 9, then p is not 9 or 11, and with the proviso that n, m and p are not all 11
2. The compound of claim 1, wherein n is 13 or 15; and m and p are independently of each other 15 or 17.
3. The compound of claim 1 or 2, wherein n is 13; m and p are both 15.
4. Process for obtaining an isomerized star compound containing 1 to 5 methyl branches, characterized in that one or more compounds of formula I, in which n, m and p are, independently of one another, odd-numbered integer values from 9 to 41, and in which the total carbon number of formula I is from 31 to 65, with the proviso that when n and m are both 9, then p is not 9 or 11, and with the proviso that n, m and p are not all 11, are subjected to an isomerization step in the presence of hydrogen and an isomerization catalyst, such as a noble or non-noble metal isomerization catalyst, at a temperature in the range from 250 to 400 ℃, a pressure in the range from 10 to 60barg, and 0.1 to 5h-1WHSV and 100-800nl H in the range2H/l of feed2At a flow rate.
5. A compound of formula II wherein n is 13; m and p are both 15
6. A base oil mixture comprising one or more compounds of formula I, wherein n, m and p are, independently of each other, odd integer values from 9 to 41, and wherein the total carbon number of formula I is from 31 to 65
7. The base oil mixture according to claim 6 comprising one or more compounds of formula I wherein n is 13 or 15; m and p are independently of each other 15 or 17.
8. The base oil mixture according to claim 6 or 7 comprising a compound of formula I, wherein n is 13; m and p are both 15.
9. The base oil mixture of any one of claims 6-8, wherein the base oil mixture has a boiling point of 380 ℃ or more, such as 450 ℃ or more, such as 460 ℃ or more, such as 470 ℃ or more.
10. The base oil mixture according to any one of claims 6-9, wherein the base oil mixture comprises at least 2% or more, preferably 5% or more of the one or more compounds of formula I.
11. A process for base oil production comprising:
a) trimerizing a feed comprising at least one fatty acid to provide a trimerization product, wherein a mixture of fatty acid trimers is obtained; and
b) hydrotreating at least a portion of the trimerization product to provide a base oil product having a pour point of less than 5 ℃;
wherein the hydrotreated base oil product comprises one or more compounds of formula I wherein n, m and p are, independently of each other, integer values from 9 to 41, and wherein the total carbon number of formula I is from 31 to 65;
-wherein the carbon atoms of one or more compounds of formula I are derived solely from monocarboxylic fatty acids; and is
-wherein the trimerization is carried out at a conversion level of at least 99.5% of the at least one fatty acid of the feed.
12. The process for base oil production according to claim 11, wherein step a) comprises contacting at least one fatty acid with a trimerization catalyst in a trimerization zone under trimerization conditions to provide a mixture of fatty acid trimers; and step b) comprises contacting the mixture of fatty acid trimers with a hydrotreating catalyst in the presence of hydrogen in a hydrotreating zone under hydrotreating conditions to provide a base oil product.
13. A process for base oil production according to claim 12, wherein the trimerization conditions comprise a temperature in the range of from 300 to 400 ℃, a pressure in the range of from 5 to 100barg and 0.1-5h-1A WHSV in the range, and the trimerization catalyst comprises a metal oxide catalyst.
14. A process for base oil production according to any one of claims 11-13, wherein the trimerisation catalyst comprises one or more catalysts selected from the list consisting of: a metal oxide catalyst containing Ti, Mn, Mg, Ca; preferably, the trimerisation catalyst is a Ti-containing metal oxide catalyst.
15. A process for base oil production according to any one of claims 11-14, wherein the trimerisation catalyst comprises TiO2And one or more alkali metal oxides, preferably wherein the one or more alkali metal oxides are selected from one or more of the list consisting of: metallic oxygen containing Li, Na and KAnd (4) melting the mixture.
16. A process for base oil production according to any one of claims 11-15 wherein trimerisation comprises formation of a ketone from a reaction between two fatty acids followed by a condensation reaction between the ketone and another fatty acid to produce an a-substituted and a-unsaturated ketone.
17. A process for base oil production according to any one of claims 11-16, wherein the at least one fatty acid is selected from C9To C22A fatty acid.
18. A process for base oil production according to any one of claims 11-17, wherein the feed comprising at least one fatty acid is selected from one or more of the list consisting of: palm oil, canola oil, rapeseed oil, olive oil, sunflower oil, beef fat, lard, coconut oil, corn oil, soybean oil, jatropha oil, tall oil, crude tall oil, tall oil pitch, tall oil head, or tall oil fatty acids.
19. A process for base oil production according to any one of claims 11-18, wherein the feed comprising at least one fatty acid is diluted with a stream of hydrocarbons, or wherein the trimerization product is diluted with a stream of hydrocarbons.
20. A process for base oil production according to any one of claims 12-19, wherein the feed comprising at least one fatty acid is diluted with a stream of product withdrawn from the process, e.g. withdrawn from the trimerization zone or the hydrotreatment zone.
21. Process for base oil production according to any one of claims 11-20, wherein a gas feed is present in the trimerization zone, wherein the gas is selected from the list consisting of: nitrogen, carbon dioxide, water vapour, methane and/or hydrogen, preferably hydrogen.
22. A process for base oil production according to any one of claims 11-21, wherein the trimerization product is separated into fractions having a boiling point of more than 450 ℃.
23. The process for base oil production according to any one of claims 11-22, further comprising the steps of:
c) isomerizing the hydrotreated base oil product.
24. Base oil composition obtainable according to any of claims 11-23.
25. Use of the base oil composition according to claim 24 for improving the lubricating properties of a base oil.
26. Process for obtaining isomerized star compounds containing 1 to 5 methyl branches, characterized in that a feed containing at least 80 wt% of hydrocarbons and containing at least 2 wt%, preferably at least 5 wt%, of one or more compounds of formula I, in which n, m and p are, independently of one another, odd-numbered integer values from 9 to 41, and in which the total carbon number of formula I is from 31 to 65, with the proviso that when n and m are both 9, then p is not 9 or 11, and with the proviso that n, m and p are not all 11, is subjected to an isomerization step of isomerizing a noble metal in the presence of hydrogen and an isomerization catalyst, such as a noble metal or a non-isomerization catalyst, at a temperature in the range from 250 to 400 ℃, a pressure in the range from 10 to 60barg, and 1-5h-1WHSV and 100-800nl H in the range2H/l of feed2At a flow rate.
27. The process of claim 26, wherein the feed comprises at least 15 wt%, at least 20 wt%, at least 32 wt%, such as at least 50 wt% or at least 80 wt% of one or more compounds of formula I.
28. A method according to any one of claims 26-27, characterised in that the feed consists essentially of hydrocarbons.
29. The process of any one of claims 26 to 28, wherein the feed comprises at least 15 wt% of one or more compounds of formula I.
30. The process of claim 29, wherein the feed consists essentially of hydrocarbons and comprises at least 15 wt% of one or more compounds of formula I.
Technical Field
The present invention relates to the field of Renewable Base Oils (RBO), in particular to novel base oil compounds and intermediates thereof showing excellent lubricating properties, including base oil mixtures of excellent lubricating properties and a process for producing base oils from renewable feedstocks, base oil compositions obtained therefrom, and the use of the renewable base oil compositions of the present invention for improving the lubricating properties of base oils.
Background
Fluid film lubrication is important in order to reduce friction between adjacent surfaces and movement relative to each other. Without lubrication or insufficient lubrication, this friction can lead to increased heat and wear.
Base oils are used in the manufacture of products including lubricants, engine oils, and metal working fluids. One of the most important factors in base oils is the viscosity at various temperatures.
Synthetic oil feedstocks, such as polyalphaolefins, can be prepared by polymerizing an alpha olefin with 1-decene, as shown in figure 1.
Referring to fig. 1, depending on reaction conditions, poly-alpha-olefins may form straight chain hydrocarbons (L), highly branched Hydrocarbons (HB), or highly desirable star (S) configurations. Star orientation cannot be obtained from conventional isomerization reactions of straight chain hydrocarbons, which typically result in short methyl branches. It exhibits excellent lubricating properties, such as high viscosity index, compared to highly branched or straight chain molecules, and is therefore also an ideal base oil.
WO 2013/113976A 1 (to Neste Oil Oyj) discloses the use of a feed comprising fatty acids and derivatives thereof under hydrogen pressure with a dual catalyst system such as NiMo and K2O/TiO2The reaction involves a ketonization reaction that dimerizes the fatty acid, which is then hydrodeoxygenated to a linear hydrocarbon. This dimerization reaction produces a linear (L) base oil (see
WO 2014/099371 a2 (to ExxonMobil Research and Engineering Company) discloses a process for the preparation of saturated hydrocarbons from renewable feedstocks, wherein an acidic catalyst dimerizes two unsaturated fatty acids on the triglyceride backbone by double bond dimerization followed by hydrotreating. Dimerizing triglycerides using the double bond of fatty acids leads to Highly Branched (HB) hydrodimers, e.g. i-C34H70(see, e.g., FIG. 1 of WO 2014/099371A 2).
WO 2014/099373A 1 (to ExxonMobil Research and Engineering Company) discloses a process for preparing lubricant base oils from renewable feedstocks. Figure 3 of WO 2014/099373 a1 discloses the ketonization between triglycerides and citric acid followed by hydrotreatment. This results in a poly-alpha-olefin (PAO) -like structure with a star (S) orientation. Here, PAO-like structures are obtained by using a citric acid scaffold to direct the ketonization reaction between two carboxylic acids to obtain a star (S) configuration. Fig. 3 and 7 of WO 2014/099373 contain structural errors; no disclosure is made of what can accomplish those structures. In particular, star-shaped molecules according to the invention cannot and are not prepared in WO 2014/099373.
In view of the above cited prior art, there is a further need for a renewable base oil component having good lubricating properties and a process for preparing such a renewable base oil. In particular, there is also a need for renewable base oil components similar to Polyalphaolefins (PAO) types having a star orientation that exhibit excellent lubricating properties as well as other beneficial properties.
Disclosure of Invention
The present invention has been made in view of the above prior art, and an object of the present invention is to provide a novel base oil compound having a star orientation, particularly a method for obtaining a base oil mixture having good lubricity such as high viscosity index, including a base oil compound having a star orientation.
To solve this problem, the present invention provides compounds of formula I,
wherein n, m and p are, independently of one another, integer values from 9 to 41, for example odd integer values, and wherein the total carbon number of formula I is from 31 to 65. The selection of n, m and p of formula I may be subject to one or more conditions such that when n and m are both 9, then p is not 9 or 11, and the condition is that n, m and p are not all 11.
In particular, n, m and p may independently of each other be odd integer values of 9 to 41, wherein the total carbon number of formula I is 31 to 65, with the proviso that when n and m are both 9, then p is not 9 or 11, and with the proviso that n, m and p are not all 11.
The selection of n, m and p of formula I may be, wherein n is 13 or 15; m and p are independently of each other 15 or 17.
That is, the inventors of the present invention have found in a first aspect of the invention that these novel compounds having a star orientation and good lubricity, such as a high viscosity index, can be formed by one or more trimerization reactions, for example by a reaction scheme wherein two fatty acids are reacted under ketonizing conditions to produce a ketone and a condensation reaction wherein one of the alpha-carbon atoms of the ketone reacts with the fatty acid to form an intermediate compound of formula II,
wherein n, m and p are, independently of one another, integer values from 9 to 41, and wherein the total number of carbons in formula II is from 31 to 65.
The selection of n, m and p of formula II may be, wherein n is 13 or 15; m and p are independently of each other 15 or 17.
Formula II can be subjected to hydrogenation reactions such as double bond hydrogenation and hydrodeoxygenation to produce formula I.
The fatty acid used to prepare the compounds of formula I or II may be, for example, C16Fatty acid, C18Fatty acids or mixtures thereof. A compound of formula II wherein n is 13; m and p are both 15, and may consist of C only16Fatty acid preparation and compounds of formula I wherein n is 13; m and p are both 15, and may consist of C only16And (3) preparing fatty acid.
The compounds of formula I may be isomerized to produce isomerized star compounds, which may be obtained by subjecting one or more compounds of formula I to an isomerization step. The isomerized star compound obtained from the process of isomerizing a star compound may comprise one or more methyl branches, such as from 1 to 5 methyl branches. It would be advantageous to provide isomerization conditions that avoid or reduce cracking to the point where one of the three branches forming the star polymer is lost or reduced to a methyl, ethyl, or propyl branch.
The compounds of formula I may be present in a base oil mixture comprising one or more compounds of formula I, wherein n, m and p are, independently of each other, integer values, such as odd integer values of 9 to 41, and wherein the total carbon number of formula I is 31 to 65.
The base oil mixture may be prepared from a mixture comprising one or more compounds of formula I wherein n is 13 or 15; m and p are independently of each other 15 or 17.
The base oil mixture may comprise a compound of formula I wherein n is 13; m and p are both 15.
The boiling point of the base oil mixture may be 380 ℃ or higher, or for example 450 ℃ or higher.
The base oil mixture may comprise at least 2%, such as at least 5%, such as at least 10% or more of one or more compounds of formula I.
The base oil may be produced by a process for base oil production comprising: a) trimerizing a feed comprising at least one fatty acid to provide a trimerization product, wherein a mixture of fatty acid trimers is obtained; and b) hydrotreating at least a portion of the trimerization product to provide a base oil product; wherein the hydrotreated base oil product comprises one or more compounds of formula I wherein n, m and p are, independently of each other, integer values from 9 to 41, and wherein the total carbon number of formula I is from 31 to 65;
the process may be characterized by the pour point of the hydrotreated base oil product being below 5 ℃.
The process may be characterized in that the carbon atoms of one or more compounds of formula I are derived solely from monocarboxylic fatty acids.
The process may also be characterized by conducting the trimerization until 99.5% of the at least one fatty acid has been converted.
The process may also be characterized in that the trimerization is carried out with a conversion of at least 99.5% of the at least one fatty acid in the feed.
The process may also be characterized by conducting the trimerization until at least 5% of the trimerization product is formed.
The process may also be characterized wherein the base oil comprises at least in part a trimerization product of formula I.
The process may also be characterized in that it comprises or does not comprise a step of isomerizing the trimerization product.
The process may further comprise contacting at least one fatty acid with a trimerisation catalyst in a trimerisation zone under trimerisation conditions to provide a mixture of fatty acid trimers under step a); and step b) comprises contacting the mixture of fatty acid trimers with a hydrotreating catalyst in the presence of hydrogen in a hydrotreating zone under hydrotreating conditions to provide a base oil product.
The trimerization conditions may comprise a temperature in the range of from 300 to 400 ℃, a pressure in the range of from 5 to 100barg and 0.1-5h-1A WHSV in the range, and the trimerization catalyst comprises a metal oxide catalyst.
The trimerisation catalyst may comprise a catalyst selected from one or more of the list consisting of: a metal oxide catalyst containing Ti, Mn, Mg, Ca; preferably, the trimerisation catalyst is a Ti-containing metal oxide catalyst. For example, the trimerisation catalyst may comprise TiO2And one or more alkali metal oxides, preferably wherein the one or more alkali metal oxides are selected from one or more of the list consisting of: metal oxide containing Li, Na and K.
Trimerization under step a) of the process may comprise formation of a ketone from a reaction between two fatty acids, followed by a condensation reaction between the ketone and another fatty acid to produce alpha-substituted and alpha-unsaturated ketones.
In this process, the at least one fatty acid may be chosen from C9To C22A fatty acid.
In the process, the feed comprising at least one fatty acid may be selected from one or more of the list consisting of: palm oil, canola oil, olive oil, sunflower oil, beef fat, lard, coconut oil, corn oil, soybean oil, jatropha oil, tall oil, crude tall oil, tall oil pitch, tall oil fatty acids, tall oil head (tall oil head).
In the process, the feed comprising at least one fatty acid may be diluted with a stream of hydrocarbons, or wherein the trimerization product is diluted with a stream of hydrocarbons. The stream of hydrocarbons may be a recycled product of the process, for example a ratio of feed comprising at least one fatty acid to recycled product of the process of from 1:9 to 9: 1. The feed comprising at least one fatty acid may also be diluted with a product stream withdrawn from the process, for example from the trimerization zone or the hydrotreatment zone.
There may be a gas feed in the trimerization zone wherein the gas may be selected from the list consisting of: nitrogen, carbon dioxide, water vapor, methane, and/or hydrogen; such as nitrogen, carbon dioxide or hydrogen, preferably hydrogen.
In this process, the trimerization product can be separated into fractions having boiling points greater than 380 ℃ (e.g., greater than 450 ℃). The process may further comprise a step c) of isomerizing the hydrotreated base oil product. A base oil composition may be obtained according to the described method.
The base oil compositions described herein may be used to improve the lubricity of a base oil.
Drawings
FIG. 1 shows a schematic view of aExamples of poly-alpha-olefins of 1-decene are shown.
FIG. 2An exemplary reaction scheme for producing terpolymers is shown.
FIG. 3Shows trimerized palmitic acid, C, with palmitic acid saturated16A fatty acid.
FIG. 4A trimerized Palm Fatty Acid Distillate (PFAD) comprising saturated C is shown16And C18A mixture of fatty acids.
FIG. 5Trimer as a function of fatty acid conversion is shown. It can be seen that the higher the conversion of the palmitic acid feed (C16FA), the more the trimer content increases.
FIG. 6Is an enlarged view of fig. 5, where it can be seen that the trimer content of the product increases with increasing fatty acid conversion for each individual reaction condition, and that greater than 5 wt% trimer can be formed when a fatty acid conversion of 99.5% or higher is ensured.
FIG. 7The fraction of tripalmitic acid boiling above 450 ℃ is shown, where it can be seen that the main product is C47A paraffinic product identified by analysis as a compound of formula I.
FIG. 8The tripalmitate fraction boiling at 380 to 450 ℃ is shown, where it can be seen that the main product is C31Paraffinic products, analytically determined to be produced by dimerization of fatty acids by ketonizationThe product of (1).
FIG. 9The effect of the amount of trimerization product (x-axis) in% on the improvement of the viscosity index (y-axis) is shown.
Detailed Description
In describing embodiments of the present invention, specific terminology will be resorted to for the sake of clarity. However, the invention is not intended to be limited to the specific terms so selected, and it is to be understood that each specific term includes all technical equivalents that operate in a similar manner to accomplish a similar purpose.
For simplicity of discussion, while the benefits of the present invention have been described in some cases with reference to engine oils, the benefits of the present invention are not limited to engine oils.
The base oil for passenger car engines may include, for example, 85-90% base oil and 10-15% performance enhancing additive package. Since base oil is generally the largest component in passenger car engines, it has a significant impact on fluid performance. Base oils affect many parameters such as viscosity, oxidative stability, volatility, viscosity index, and low temperature flow properties such as pour point and/or cloud point.
The performance enhancing additive package may include various additives such as friction modifiers, viscosity modifiers, and pour point depressants.
The American Petroleum Institute (API) divides base oils into five major groups. Groups I-III are petroleum base oils of varying qualities.
TABLE 1 API basic feedstock classes
The API defines the difference between group II and group III only in terms of Viscosity Index (VI), and group III base oils are also known as very high viscosity base oils (VHVI). However, low temperature flow properties as well as Noack volatility values are also important characteristics of the base oil.
Oil volatility is typically measured using a Noack volatility test (e.g., ASTM D5800 or CECL-40-93-B). The flash point of the lubricant was used to estimate the oil volatility prior to the Noack test. In the Noack test, an oil sample is weighed and heated to 250 ℃ for one hour (250 ℃ to simulate the maximum engine temperature). Dry air is passed through the sample, carrying the vaporized oil vapor and depositing it in the beaker. The original sample was removed and reweighed. Any reduction in weight is reported as a percentage of the original weight loss. The Noack volatility limit in% weight loss (g/100g) as measured using ASTM D5800 must meet standards. For example, the API SN performance classification requires no more than 15% weight loss due to volatility for all viscosity grades of engine oil. The lower the Noack number, the better, since it is a measure of the evaporation of light weight molecules in the equilibrium oil, which evaporates more readily when exposed to high temperatures, which reduces the oil level. When used as an engine oil, a low Noack number oil with better volatility resistance can reduce oil consumption, thereby maximizing engine performance. Most conventional passenger car engine oils in 2016 typically have Noack values > 13%, while synthetic passenger car engine oils can be about 9-11%. The Noack value of the fully synthesized heavy-duty engine oil can be as low as 8-9%.
For base oils, it is generally observed that the higher the boiling range temperature, the higher the viscosity, and the lower the oil volatility. Conversely, lower viscosity is also generally observed to correlate with higher oil volatility.
The higher the oil volatility, the more the engine oil evaporates, making the oil heavier. Heavier, more viscous oils are poorly circulated, which affects fuel economy, oil consumption, and emissions.
The cold start is measured by a cold start simulator (CCS) at low temperature (e.g., -30 ℃) and the value is given in centipoise (cP), which is the same as millipascal-seconds (mPa · s). This test simulates the effect of a starter motor on the engine. This test is important because it is related to the resistance encountered by the battery and starter motor when producing sufficient starting speed at low temperatures, such as when starting the engine in winter.
The SAE low temperature viscosity requirements relating to start-up dictate that for a 0W SAE viscosity grade, the maximum allowable start-up is 3250cP (lower values are better) at-30 ℃.
A variety of different branched hydrocarbon compounds (formula I) having a star configuration (S) are prepared from renewable oils comprising fatty acids or derivatives comprising fatty acids. The branched hydrocarbon compounds may be isolated individually or in mixtures and may be used as part of a base oil, particularly a Renewable Base Oil (RBO). The process for preparing the branched hydrocarbon compounds of formula I involves conditions favoring the trimerization reaction followed by hydrotreating conditions. The compounds of formula I can be prepared by catalytically processing a renewable material containing some form of fatty acid (e.g., free fatty acid or a derivative containing fatty acid, such as a triglyceride or other ester) in a process, and which has desirable qualities associated with lubrication, low temperature flow, and low Noack volatility.
Base oil compounds
New base oil compounds of the poly-alpha-olefin type (PAO) have been produced with a star configuration (S). The compounds of formula I may be isolated individually or as mixtures. The new base oil compounds may be prepared from renewable feedstocks containing fatty acids, and thus the new base oil compounds may be considered renewable base oil compounds. The base oil compounds of the poly alpha olefin type (PAO) having a star configuration (S) produced according to the process of the present invention give one or more properties selected from good lubricity (e.g. high viscosity index), good low temperature flow properties (e.g. low cloud point and/or pour point) and low Noack volatility.
The base oil compound has the structure of the compound of formula I
The compounds of markush formula I are hydrocarbons and in formula I n, m and p may independently of each other be integer values of 7 or higher, such as 7 to 41. For example, the integer values of n, m, and p may be 9 to 41 to emphasize that the branching is in a star configuration (S) as compared to, for example, Highly Branched (HB) or linear (L) compounds (see fig. 1), as well as isomerized linear compounds, which produce predominantly methyl branches. The compounds of the present invention may be obtained from the trimerization of fatty acid containing materials, and the integer values of n, m and p may be 25 or less, independently of each other, to concentrate more on the length of fatty acids often encountered in renewable oils. For example, the integer values of n, m and p may be 7 to 41, such as 7 to 25, such as 9 to 41, such as 9 to 25.
The total carbon number of formula I is 26 or more. In mineral oil refining, it is common to use fractions of compounds having 26 to 40 carbon atoms for the production of lubricating oils. The heaviest and largest hydrocarbons with carbon numbers in excess of 40 are employed and are commonly used in bituminous products. The compound of formula I may have at least 40 carbon atoms, for example more than 40 carbon atoms, such as 45 carbon atoms or more, such as 47 carbon atoms or more. For example, each can be separately selected from C using the methods described herein16-、C18-or C22Fatty acids starting from the preparation of compounds of formula I having 47, 53 or even 65 carbon atoms. The upper limit of the number of carbon atoms of formula I is not precisely defined. The upper limit of the carbon number may be 65, which corresponds to erucic acid (C)22Fatty acids) which can be found in many renewable oils, such as rapeseed oil, particularly in high erucic acid rapeseed oil.
The total carbon number of formula I may be 31 or more, which corresponds to that of lauric, capric and caprylic (C) acids such as may be found in many renewable oils such as coconut oil12、C10And C8Fatty acids) which generally contain a significant amount of lauric acid.
For example, the total carbon number of formula I may be, for example, 31 to 65.
Compounds of formula I markush can be advantageously obtained from renewable oils containing fatty acids, esters or triglycerides thereof. Renewable oils are considered oils collected from resources that are naturally replenished in the human time frame, as opposed to fossil oils. Most fatty acids of plant or animal origin are straight chain compounds, most often comprising an even number of carbon atoms, and usually comprise no or only trace amounts of odd fatty acids. With regard to the compounds of formula I, if they are prepared from fatty acids obtained from renewable oils of fatty acids having an even number of carbon atoms, the integer values of n, m and p are odd integers. E.g., 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41; e.g., 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41; such as 9, 11, 13, 15, 17, 19, 21, 23, 25.
The selection of n, m, and p of formula I may be subject to one or more conditions, such as one or more of the conditions described below, in conjunction with the integer values of n, m, and p being odd integer values as described above.
The one or more conditions may be selected from 1, 2 or 3 of the following conditions.
With the proviso that when n and m are both 7, then p is not 9;
with the proviso that when n and m are both 9, then p is not 9 or 11;
with the proviso that n, m and p are not all 11.
Other conditions may be selected to more clearly focus on the compounds of formula I prepared according to the process of the present invention and using the renewable oils described herein.
For example, n, m and p may independently of each other be odd integer values from 7 to 41, wherein the total carbon number of formula I is from 26 to 65, with the proviso that when both n and m are 7 then p is not 9; provided that when n and m are both 9, then p is not 9 or 11, and provided that n, m and p are not all 11.
For example, n, m, and p may independently be odd integer values from 9 to 41, wherein the total carbon number of formula I is from 31 to 65, with the proviso that when n and m are both 9, then p is not 9 or 11, and with the proviso that n, m, and p are not all 11.
For example, n, m and p may independently of each other be odd integer values from 7 to 25, wherein the total carbon number of formula I is from 31 to 65, with the proviso that when both n and m are 7 then p is not 9; provided that when n and m are both 9, then p is not 9 or 11, and provided that n, m and p are not all 11.
The selection of n, m and p of formula I may be, wherein n is 13 or 15; m and p are independently of each other 15 or 17. These compounds of formula I can for example comprise C by trimerization using the process of the invention16And C18A mixture of fatty acids, see compounds 1-6 of table 2 below.
The compound of formula I may also be, wherein n is 13; m and p are both 15. The combination ofThe substance may consist of C only16Fatty acid preparation (see compound 1 of table 2 below).
In the same way, the compounds of formula I may also be, wherein n is 15; m and p are both 17. The compound may consist of C alone18Fatty acid preparation (see
The following specific compounds in table 2 may be prepared, for example, according to the present invention. Referring also to FIG. 4, shown is a graph containing C47-C53Peak of trimerization product of carbon product.
TABLE 2 Compounds of formula I
The novel compounds having star orientation described above have good lubricating properties, including high viscosity index. In addition, it was found that novel intermediate compounds of formula II can be prepared.
The intermediate compounds of formula II as well as the compounds of formula I may be formed by one or more trimerization reactions (see figure 2).
For example, formula II can be prepared by one such trimerization reaction scheme, wherein two fatty acids are reacted in at least two steps to form the compound of formula II. One such sequence of two steps may involve reacting two fatty acids under ketonizing conditions, resulting in a ketone and condensation reaction in which one of the alpha-carbon atoms of the ketone reacts with the fatty acid to form an intermediate compound of formula II,
wherein n, m and p are independently of each other integer values of 7 or higher, such as 7 to 41, such as 9 to 41 or 9 to 25, and wherein the total number of carbons of formula II is 26 or more, such as 31 to 65.
For example, the intermediate compound of formula II may be wherein n, m and p are, independently of each other, integer values from 9 to 41, and wherein the total number of carbons of formula I is from 31 to 65.
In addition to the values of n, m and p specifically mentioned for formula II, n, m and p for formula II may also be selected as described for formula I.
The selection of n, m and p of formula II may be, wherein n is 13 or 15; m and p are independently of each other 15 or 17.
TABLE 3 Compounds of formula II
The intermediate compound of formula II may be subjected to hydrotreating in the form of hydrogenation reactions, such as double bond hydrogenation and hydrodeoxygenation, to produce the compound of formula I.
The fatty acid used to prepare the compounds of formula I or II may be, for example, C16Fatty acid, C18Fatty acids or mixtures thereof or containing C16Fatty acid, C18Fatty acids or mixtures of both. The compound of formula II (wherein n is 13; m and p are both 15) may consist of C only16Fatty acids and the compounds of formula I (where n is 13; m and p are both 15) may be prepared from C alone16Fatty acid preparation (see compound 7 of table 3).
In the same way, the compound of formula II may also be wherein n is 15; m and p are both 17. The compound may consist of C alone18Fatty acid preparation (see
The compounds of formula I may be isomerized to produce isomerized star compounds, which may be obtained by subjecting one or more compounds of formula I to an isomerization step. In order to avoid or reduce the amount of cracking, which may include cracking of the branches that cause the compound of formula I to assume a star configuration (S), in obtaining an isomerized star compound comprising 1 to 5 methyl branches, less severe conditions during the isomerization step may be employed, such as lower temperatures and/or less acidic catalyst materials during the isomerization step. Referring to example 3 and table 6, exemplary isomerization catalysts and exemplary isomerization conditions are shown.
As shown in fig. 5 and 6, at least 2 wt% of trimer is formed when the conversion of fatty acid is ensured to be 99.5% or more, and as described in fig. 6, more than 5 wt% of trimer may be formed when the conversion of fatty acid is ensured to be 99.5% or more. Thus, the feed to the isomerization step may comprise at least 2 wt%, preferably at least 5 wt% of one or more compounds of formula I.
The feed to the isomerization step may comprise at least 80 wt% hydrocarbons, for example it may consist essentially of hydrocarbons.
The compound of formula I may be separated from the other components, for example by fractional distillation, to provide a higher concentration of the compound of formula I to the isomerization step. For example, the feed may consist of at least 80 wt% hydrocarbons and comprise at least 15 wt%, at least 20 wt%, at least 32 wt%, such as at least 50 wt% or even at least 80 wt% of compounds of formula I, such as one or more compounds of formula I, wherein n, m and p are, independently of each other, odd integers from 9 to 41, and wherein the total carbon number of formula I is from 31 to 65, with the proviso that when n and m are both 9, then p is not 9 or 11, and with the proviso that n, m and p are not all 11.
The isomerized star compound may comprise at least one methyl branch, such as at least two or at least three methyl branches, for example 1 to 5 methyl branches. It would be advantageous to provide isomerization conditions that avoid or reduce cracking as described above. Ethyl groups or higher branches may also be present. The following is a graphical representation of how the isomerized star compound looks when the compound of formula I is isomerized to produce four methyl branches. The branches are typically located immediately adjacent to the ends of the carbon chain of the star compound.
Base oil mixture
One or more compounds of formula I and/or isomerized star compounds of formula I as described above may be present in the base oil mixture.
The values of n, m and p may be, independently of each other, an integer from 7 to 41, and the total number of carbons of formula I may be from 31 to 65, or from 40 to 65, such as from 45 to 65, such as from 47 to 65. The number of carbons and the values and ranges of n, m and p may be selected as described above for formula I.
For example, the base oil mixture may comprise one or more compounds of formula I, wherein n, m and p are as described above for formula I. For example, independently of each other, an integer value, such as an odd integer value of 9 to 41, and wherein the total carbon number of formula I is 31 to 65, or an isomerized star polymer of formula I as described above.
The base oil mixture may comprise more than two compounds of formula I and/or their isomerized star compounds, for example more than four or more than six compounds. Such base oil mixtures may comprise one or more of compounds 1-6 of table 2.
For example, the base oil mixture may comprise one or more compounds of formula I wherein n is 13 or 15; m and p are independently 15 or 17, which are compounds 1-6 of Table 2 above. The base oil mixture may comprise a compound of formula I wherein n is 13; m and p are both 15, which is compound 1 of table 2 above, or the base oil mixture may comprise a compound of formula I, wherein n is 15; and m and p are both 17, which is
As shown in Table 1, the base oil blend has a mass of one of groups I-V according to the API base stock category. The base oil mixture may have 90% or more saturates and a viscosity index of 80 or more, for example 120 or more. The base oil mixture may have a sulfur content of 0.03 wt% or less. The oxygenate content of the base oil mixture may be 5 wt% or less, for example 1 wt% or less than 0.1 wt%. The additive which is then added to the base oil mixture prepared according to the invention may comprise an oxygenate.
The base oil mixture may be a base oil stock and it may be used, for example, blended with other base oil stocks to provide a base oil stock having the desired properties. The base oil mixture may also be a finished base oil that may be used directly (e.g., as an engine oil). When the base oil blend is a finished base oil, an additive package is typically added to the base oil stock to modify the base oil stock and impart the desired properties to the finished base oil.
The boiling point of the base oil mixture may be 350 ℃ or greater, such as 380 ℃ or greater, such as 400 ℃ or greater, such as 450 ℃ or greater, such as 460 ℃ or greater, such as 470 ℃ or greater. The boiling point may be up to 730 ℃, such as up to 650 ℃, such as up to 620 ℃, such as up to 600 ℃, such as up to 550 ℃. For example, it was found in table 8 of example 4 that the boiling point range of 380 ℃ to 730 ℃ includes base oil mixtures comprising compounds of formula I, e.g. boiling point ranges above 380 ℃, e.g. 380 ℃ to 730 ℃, and 380 ℃ to 620 ℃ or to 550 ℃, in particular boiling point ranges above 450 ℃, e.g. 470 ℃ to 730 ℃, and 460 ℃ to 620 ℃ or to 550 ℃.
The initial boiling point (IBP/SP) and the final boiling point (FBP/EP) can be determined by distillation or simulated distillation (Sim Dist) based on ASTM D6352 or D2887. The boiling point range can be calculated between the initial boiling point (IBP/SP) and the final boiling point (FBP/EP) or between the initial boiling point (IBP/Sp) and the 95% boil off point.
The base oil mixture may comprise at least 2%, such as at least 5%, such as at least 10% or more of one or more compounds of formula I, as measured using GC as an area%.
Process for base oil production
The base oil may be produced by a process for base oil production, the process comprising: a) trimerizing a feed comprising at least one fatty acid to provide a trimerization product, wherein a mixture of fatty acid trimers is obtained; and b) hydrotreating at least a portion of the trimerization product to provide a base oil product; wherein the hydrotreated base oil product comprises one or more compounds of formula I wherein n, m and p are, independently of each other, integer values from 5 to 41, and wherein the total carbon number of formula I is from 19 to 65;
the process for base oil production involves one or more trimerization reactions followed by a hydrotreating step. The process produces a base oil, such as the base oil mixture described herein, for example, under the heading "base oil mixture". The base oil produced according to the process of the present invention may have very little oxygenates and saturated hydrocarbons due to the hydroprocessing step. The amounts of oxygenates and saturated hydrocarbons are described herein, for example under the heading "base oil blend". The process for base oil production may comprise the steps of: providing a distillate boiling in the base oil boiling range, e.g., providing a distillate boiling at 380 ℃ or above, e.g., as described under the "base oil mixture" heading above.
The method includes the step of trimerizing a feed comprising at least one fatty acid. Fig. 2 shows an exemplary scheme for producing a terpolymer by trimerizing a feed comprising at least one fatty acid, wherein the fatty acid is palmitic acid (C16: 0). Without wishing to be bound by any theory, the inventors found that trimerization of the feed can occur by several possible reactions, one example of which is given in fig. 2. It has been found that starting from palmitic acid as a model feed, a ketone product can be obtained by a ketonization reaction. It was further found that under trimerization, aldehydes were present in the feed to the process. Aldehydes and dimeric ketones may react to form aldol condensation products of formula II-trimerization products. Other mechanisms for obtaining the intermediate of formula II are also possible, such as a hydroxy alcohol condensation reaction followed by a ketonization reaction. The trimerization product may comprise one or more compounds of formula II, wherein n, m and p are independently of each other an integer from 5 to 41, and wherein the total number of carbons of formula II is from 25 to 65, or wherein n, m and p and the total number of carbons are as selected above under the heading "base oil compound" or "base oil mixture".
The process uses a feed comprising at least one fatty acid. The at least one fatty acid may be selected from C6Or higher fatty acids, e.g. C7Or higher, e.g. C8Or higher, e.g. C9Or higher. For example, it may be C30Or lower fatty acids, e.g. C26Or lower fatty acids or C22Or lower fatty acids, e.g. one or more of the fatty acids may have C7To C22Fatty acids of fatty acids. The at least one fatty acid includes a mixture of fatty acids having different carbon numbers, and also includes a fatty acid which is a fatty acid derivative having a carboxylic acid moiety, such as a fatty acid ester or a glycerate ester of a fatty acid. The at least one fatty acid need not be linear and may be branched or include a ring structure. Preferably, at least one fatty acid comprises a portion of a straight chain/non-branched fatty acid, as such a structure will react more readily to provide a compound for use in formula I. Most of the fatty acids contained in renewable oils include straight/non-branched fatty acids, usually as free fatty acids or as glycerates of fatty acids, and also as free fatty acids. In contrast to fossil oils, renewable oils are oils that can be replenished in the human time frame. As noted above, the feed may comprise at least one fatty acid. The renewable oil may be an oil or fat of vegetable origin, an animal oil or fat, a fish oil or fat or a waste oil or fat. For example, the feed may be selected from one or more of the list consisting of: palm oil, canola oil, rapeseed oil, olive oil, sunflower oil, beef fat, lard, coconut oil, corn oil, soybean oil, jatropha oil, tall oil, crude tall oil, tall oil pitch, tall oil head, tall oil fatty acids or different fractions thereof, such as palm oil fatty acid distillate (PFAD) or waste oils, such as used cooking oils. The feed may comprise any fatty acids comprising a tall oil fraction, and the term fatty acids also includes resin acids, such as tall oil, which may have branched and cyclic structures. When the process involves a reaction between two free fatty acids, a feed containing free fatty acids is particularly suitable.
In the case of a feed comprising unsaturated fatty acids, a pre-hydrogenation step may be used prior to the trimerisation step to saturate any unsaturation, for example unsaturated fatty acids. As shown in FIG. 1, conducting the trimerization reaction with a saturated feed can avoid or at least significantly reduce double bond isomerization reactions that will form Highly Branched (HB) products.
The trimerization product obtained from the trimerization step may comprise an intermediate product having the formula II described above under the heading "base oil compound". It may be present in a mixture of fatty acid trimers together with other fatty acid trimers.
The trimerization product may be isolated or it may undergo other reactions than trimerization.
The process involves hydrotreating at least a portion of the trimerization product to obtain a base oil product. Hydrotreating is a catalytic hydrogenation reaction in which the trimerization product is contacted with a hydrotreating catalyst and hydrogen. This results in a variety of hydrogenation reactions, including double bond hydrogenation and hydrodeoxygenation reactions to produce a hydrotreated hydrocarbon base oil product.
The hydrotreated base oil product comprises one or more compounds of formula I wherein n, m and p are independently of each other integers from 5 to 41, and wherein the total carbon number of formula I is from 25 to 65, or wherein n, m and p and the total carbon number are as selected above under the heading "base oil compound" or "base oil mixture".
The process may be characterized by a pour point of the hydrotreated base oil product of less than 5 ℃. The process may also be characterized in that the base oil comprises at least in part the trimerization product of formula I. That is, when the trimerization reaction is performed followed by the hydroprocessing reaction, a base oil mixture comprising the star compound of formula I will be prepared which improves the pour point of the hydrocarbon mixture, such as the obtained base oil mixture. For example, the pour point is improved by referring to the straight chain hydrocarbon (L) obtainable only by the ketonization reaction.
The process may further comprise a step involving isomerization of the hydrotreated base oil product. The pour point obtained before subjecting the base oil mixture to an optional isomerization step, which may or may not be present in the process, is 5 ℃ or lower, such as 0 ℃ or lower, such as-5 ℃ or lower. Depending on the severity of the isomerization step, the isomerization step further increases the pour point of the hydrotreated base oil product to-10 ℃ or less, for example-20 ℃ or less, for example-30 ℃ or less.
The isomerized star compound may also be obtained using a suitable catalyst and suitable conditions in combination with the steps of hydrotreating and isomerization, for example using a NiW catalyst, e.g. NiW on a support such as alumina, or NiW/zeolite on a support such as alumina. That is, the process may include a trimerization step followed by a combined hydrotreating and isomerization step, where both hydrotreating and isomerization reactions occur.
The process may be characterized in that the carbon atoms of one or more compounds of formula I are derived solely from monocarboxylic fatty acids. The monocarboxylic fatty acids may be in the form of free fatty acids or fatty acid derivatives containing the carboxylic acid moiety, for example fatty acid esters such as triglycerides.
The process may also be characterized by conducting the trimerization until 99.5% of the at least one fatty acid has been converted. For example, the process may be further characterized in that the trimerization is performed at a level of conversion of at least 99.5% of the at least one fatty acid of the feed, i.e. the conversion is kept at a high level, e.g. 99.6%, even 99.8% or 99.9% of the at least one fatty acid has been converted as measured in area% using GC. In prior art ketonization processes, wherein fatty acids are dimerized and hydrodeoxygenated to linear hydrocarbon base oils (L), such a ketonization step is typically conducted at a conversion of about 97% or less, as this is considered more efficient. Complete conversion of the fatty acids to ketonized products is not required because the remaining fatty acids will be hydrotreated into normal paraffins and can be fractionated and used as, for example, diesel products. In addition, modifications to the given feed ketonization parameters are required to achieve higher conversions.
For example, by specifically controlling the temperature and feed flow rate (WHSV), and to some extent the pressure, the conversion can be controlled to a level of 99.5% or more in a continuous fixed bed reactor. Generally, the reaction temperature increases the reaction rate. Lower feed rates increase residence time, which generally results in higher conversion. The effect of pressure depends on the reaction chemistry. For example, if gaseous products or products lighter than the feed are formed during the reaction, a lower pressure may be advantageous in some cases so that these light products can be desorbed from the catalyst active sites into the gas phase.
No individual parameter (temperature, pressure, WHSV, type of gas or amount of gas) significantly promotes the formation of the trimerization product, but the formation of the trimerization product is a result of a suitable combination of reaction condition parameters. It is desirable to maintain high palmitic acid conversion and this can be achieved by the reaction condition parameters described herein. As shown in example 2, the formation of trimerization products unexpectedly increased only when the conversion remained above 99.5%.
In particular, conversions above 97% may require modification of the ketonization parameters, such as hydrogen amount, WHSV, temperature and pressure.
The inventors found that providing ketonization conditions that ensure a conversion of at least one fatty acid of 99.5% or more results in an amount of trimerization product of 2 wt% or more, as shown in figures 5 and 6.
The process may also be characterized by conducting the trimerization until at least 2 wt% trimer product has been formed, for example at least 5 wt% trimer product. Adjusting parameters such as hydrogen amount, WHSV, temperature and pressure allows production of 2 wt% to 20 wt% of the trimerization product.
As described in the examples, the conversion of at least one fatty acid and the formation of 2 wt% or greater trimerization products can be monitored using GC.
The process may further comprise in the trimerization step a): contacting at least one fatty acid with a trimerization catalyst in a trimerization zone under trimerization conditions to provide a mixture of fatty acid trimers; and step b) comprises contacting the mixture of fatty acid trimers with a hydrotreating catalyst in the presence of hydrogen in a hydrotreating zone under hydrotreating conditions to provide a base oil product.
Trimerization under step a) of the process may comprise formation of a ketone from a reaction between two fatty acids followed by a condensation reaction between the ketone and another fatty acid to produce alpha-substituted and alpha-unsaturated ketones.
The trimerisation catalyst may comprise a catalyst selected from one or more of the list consisting of: a metal oxide catalyst containing Ti, Mn, Mg, Ca; preferably, the trimerisation catalyst is a Ti-containing metal oxide catalyst. The metal oxide of Ti, Mn, Mg and Ca may be titanium oxide, manganese oxide, magnesium oxide or calcium oxide. The primary metal oxide may be combined with other metal oxides, for example metal oxides of alkali metals such as Na, Li, K. When it is desired to produce the trimerization product, the catalyst titanium dioxide is preferred together with a metal oxide of an alkali metal, for example TiO2And K2And O. It is advantageous to prepare the metal oxide as a catalyst metal oxide. This may include a specific BET surface area, a specific average pore size, and crystallinity. For example, the BET surface area may be higher than 40m2G, e.g. 40 to 200m2G, e.g. 45 to 100m2(ii) in terms of/g. The average pore diameter may be from 100 to
The trimerization zone can be one or more catalyst beds in a reactor or fixed bed reactor, which can contain a trimerization catalyst.
If the feed comprises triglycerides or other esters of fatty acids, it has been found that the combination of a trimerisation catalyst with a certain amount of a hydrotreating catalyst can contribute to the cleavage of ester bonds, but at the same time cannot completely convert the fatty acids into n-paraffins before they can undergo trimerisation. The trimerisation catalyst may be mixed with art-recognized hydrotreating catalysts, such as molybdenum or tungsten catalysts, usually on a support such as Al2O3May or may not be facilitated. Typical promoters are Ni and/or Co. The promoted hydrotreating catalyst may be, for example, NiMo, CoMo, NiW, CoW, NiCoMo. The hydrotreating catalyst may be present in an amount up to the total amount of catalystUp to 50 wt%, for example 25 wt% or less. As can be seen from table 8, a feed comprising 80% titania catalyst and 20% NiMo effectively converted 30% of Palm Fatty Acid Distillate (PFAD) and 70% of a feed of purified palm oil, which comprises triglycerides.
The trimerization conditions may include a temperature in the range of from 300 to 400 ℃, a pressure in the range of from 5 to 100barg and 0.1 to 5 hours-1A WHSV in the range, and wherein the trimerization catalyst comprises a metal oxide catalyst. Adjusting these parameters within these ranges allows production of 2 wt% to 20 wt% of the trimerization product.
For example, the temperature range may be 340 ℃ or higher. For example, it may be between 300 ℃ and 370 ℃, such as between 340 ℃ and 365 ℃, between 345 ℃ and 365 ℃ or between 345 ℃ and 355 ℃.
For example, the pressure may range from 5 to 100barg, for example from 5 to 30 barg. WHSV can be in the range of 0.1-5h-1In the range of, for example, 0.5 to 2.5h-1E.g. 0.5-1.5h-1。
There may be a gas feed in the trimerization zone wherein the gas may be selected from the list consisting of: nitrogen, carbon dioxide, water vapor, methane or hydrogen, preferably hydrogen. It was found that the nitrogen addition increased the conversion of the fatty acid containing feed compared to no gas. It was also found that the use of nitrogen as hydrogen further increased the conversion of the fatty acid containing feed while also increasing trimer formation, see example 2.
For example, by selecting an amount of hydrogen from 4 to 6l/h as gaseous feed, at a reaction temperature of 340 to 360 ℃, a reaction pressure of 8 to 15barg and a WHSV of 0.5 to 1.2h-1At the same time, will contain C16The feed of fatty acid (e.g. palmitic acid) to the reactor can maintain a conversion level in the continuously operated fixed catalyst bed reactor of above 99.5, for example about 99.7%. The amount of trimer product obtained is above 2 wt%, preferably above 4 wt%.
The mixture of fatty acid trimers is contacted with a hydrotreating catalyst. The hydrotreating catalyst may be a hydrotreating catalyst typical in the art, for example, it may be contained in a carrierA hydrogenation metal on the body, such as a catalyst selected from the group consisting of Pd, Pt, Ni, Co, Mo, Ru, Rh, W, or any combination of these. The hydrotreating step is conducted under hydrotreating conditions to provide a base oil product. The hydrotreating step may be carried out, for example, at a temperature of 100 ℃ and 500 ℃ and a pressure of 0 to 150 barg. Examples of hydrotreating conditions can be found in example 3 and table 6. The hydrotreating step may be carried out, for example, at a temperature of 250-350 ℃ at a pressure of 30 to 80barg for 0.5-2h-1WHSV of (1) and 500-1500nl/l of H2At a ratio of oil to oil. Furthermore, in the process, the feed comprising at least one fatty acid may be diluted with a stream of hydrocarbons. Dilution may also be performed once the trimerization product is produced, prior to the hydrotreating step. The dilution may be 30 wt% hydrocarbon and 70 wt% trimerization product, for example 30 to 85 wt% hydrocarbon and 15 to 70 wt% trimerization product. The stream of hydrocarbons used for dilution may be partially or totally recycled for product.
The stream of hydrocarbons may be a recycle product of the process, for example the ratio of feed comprising at least one fatty acid to recycle product of the process may be from 1:9 to 9: 1. The product recycle may be fractionated prior to recycle, for example it may be a recycled fraction boiling above 380 ℃, or any other fraction of the base oil mixture described herein. The amount of formula I in the base oil mixture obtained by the process of the invention can be increased when product recycle is used as a stream for diluting the (fresh) feed of hydrocarbons. For example, product recycle may increase the amount of compounds of formula I in the base oil mixture to 5 wt% or greater, such as 15 wt% or greater, for example up to 32 wt% or greater. When the trimerization zone comprises more than one catalyst bed, the product recycle can be recycled to any one of the catalyst beds, for example, the product recycle can be recycled to the first catalyst bed of the trimerization zone, the last bed of the trimerization zone, or an intermediate bed of the trimerization zone.
Any product withdrawn from the process may be recycled in the manner described above, for example, the withdrawn product may be recycled to the first catalyst bed of the trimerization zone, the last bed of the trimerization zone or the intermediate bed of the trimerization zone. For example, the ratio of feed comprising at least one fatty acid to any product removed from the process can be from 1:9 to 9: 1. For example, the product may be removed from the trimerization zone or the hydrotreating zone. When the zones contain catalyst beds, the products can be withdrawn after the first catalyst bed, after the last bed or after an intermediate bed in the zones.
The hydrotreating catalyst may be, for example, usually on a support such as Al2O3Molybdenum or tungsten catalyst on. The catalyst may or may not be promoted. Typical promoters are Ni and/or Co. The promoted hydrotreating catalyst may be, for example, NiMo, CoMo, NiW, CoW, NiCoMo. When a tungsten based catalyst, such as a NiW catalyst, is used, it is a further advantage that it can also catalyze the isomerization reaction. The hydrotreating is carried out in the presence of hydrogen in a hydrotreating zone, which may be a catalyst bed in a fixed bed reactor.
The process may also be characterized in that it comprises or does not comprise a step of isomerizing the trimerization product.
The product of the hydrotreating step may be subjected to an isomerization step in the presence of hydrogen and an isomerization catalyst. The hydrotreating step and the isomerization step may be carried out in the same reactor, even in the same reactor bed.
The hydroisomerization reaction may be carried out in the presence of an isomerization catalyst, such as a catalyst comprising a group VIII metal, preferably Pt, and optionally a supported molecular sieve. The support may, for example, be selected from silica, alumina, clay, titania, boria, zirconia, which may be used alone or as a mixture, preferably silica and/or alumina. The molecular sieve may, for example, be a zeolite, such as ZSM or an aluminum phosphate molecular sieve, such as SAPO, e.g. SAPO-11, MeAPO, MeAPSO, wherein Me is, e.g., Fe, Mg, Mn, Co or Zn or other element (El) molecular sieve ElAPO or ElAPSO, e.g. silica-alumina, Y zeolite, SAPO-11, SAPO-41, ZSM-22, ferrierite, ZSM-23, ZSM-48, ZBM-30, IZM-1, COK-7. Suitable molecular sieves and the properties of molecular sieves suitable for use in hydroisomerization applications are known to the skilled artisan and have been described in the literature,for example, Handbook of heterologous catalysis, VCHVerlagsgesellschaft mbH, eds Ertl,
The isomerization catalyst can be a bifunctional catalyst comprising a noble metal (e.g., Pt or Pd) or alternatively a non-noble metal or combination of metals (e.g., NiW) and a molecular sieve. The molecular sieve may be a zeolite having a medium pore (10 rings) or large pore (12 rings) size, such as SAPO molecular sieve, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, zeolite Y, zeolite beta. The isomerization catalyst may be a noble metal bifunctional catalyst, such as a commercially available catalyst containing Pt, e.g., Pt and molecular sieves or zeolites of medium and/or large pore size; pd and molecular sieves or zeolites of medium and/or large pore size. For example, a Pt-SAPO or Pt-ZSM-catalyst or for example a non-noble catalyst, for example NiW alone or together with a molecular sieve as described above, and optionally on a support. For example, NiW/Al2O3Or NiW/zeolite/Al2O3. The hydrotreating and isomerization steps may be carried out on the same catalyst bed, for example using a NiW catalyst in both the hydrotreating and isomerization steps. The isomerization step may be carried out, for example, at a temperature of 200 ℃ to 400 ℃ and a pressure of 20 to 150 bar. As explained elsewhere in this specification, it is desirable to reduce the severity of the isomerization reaction to avoid or reduce the amount of cracking of star compounds, particularly cracking of star compounds, which may completely remove the side branches that make up a portion of the star. Cracking side reactions are well known in hydroisomerization reactions. The conditions to reduce cracking will depend on the structure of the star compound. Those skilled in the art know how to alter the severity of the isomerization reaction by adjusting one or more of the reaction conditions (e.g., temperature, pressure, residence time, and hydrogen to oil ratio) to achieve isomerization and reduce and/or avoid undesirable cracking. For example, the isomerization step may be carried out in the presence of hydrogen and an isomerization catalyst, such as a noble or non-noble metal isomerization catalyst, at a temperature in the range of from 250 to 400 ℃, in the range of from 10 to 60bargInternal pressure, and 0.1-5h-1WHSV and 100-800nl H in the range2H/l of feed2The flow-down was conducted. Examples of isomerization conditions can be found in example 3 and table 6. The isomerization step may be carried out, for example, at a temperature of 280-330 ℃ and a pressure of 30 to 80barg for 0.5-2h-1WHSV of (1) and 600-1200nl/l H2At a ratio of oil to oil. The isomerization catalyst may be supported or supported on a carrier such as Al2O3、TiO2、SiO2Or a combination thereof.
The process may further comprise isolation of the trimerization product. For example, the trimerization product may be separated from the dimerization product and separated into a fraction comprising very little dimerization product, for example wherein the dimerization product is less than 5 wt%, for example less than 1 wt%. By using various techniques in the art, such as field ionization mass spectrometry, see example 3 and fig. 7 and 8, it is possible to analyze whether any particular fraction contains dimeric or trimeric products. For example, the trimerization product may be separated into fractions having boiling points greater than 380 ℃, such as greater than 450 ℃, such as greater than 460 ℃ or greater, such as 470 ℃ or greater, such as 480 ℃ or greater, or such as 500 ℃ or greater, such as the ranges described above under the heading "base oil mixture".
According to the method described herein, a base oil composition is obtained.
The base oil compositions described herein may be used to improve the lubricity of a base oil, for example to improve the viscosity index. According to this process, the fractions boiling above 450 ℃ coming from the trimerization and hydrotreatment reactions comprise the trimerization product obtained from the trimerization of palmitic acid. It has a high viscosity index of 164 compared to a base oil fraction having a viscosity index of 155 at 380-450 ℃. As shown in FIG. 9, only 10% of the trimerization product was mixed into the base oil fraction at 380-450 ℃ and the viscosity index increased to 160. This indicates that the effect of the trimer containing fraction on the viscosity index is not linear.
Further specific examples showing the effect of different reaction conditions on the feed and the conversion of the resulting star compound of the formula I can be seen in the examples.
When describing embodiments of the present invention, not all possible combinations and permutations of the embodiments are explicitly described. The mere fact that certain measures are recited in mutually different dependent claims or described in different embodiments does not indicate that a combination of these measures cannot be used to advantage. The invention contemplates all possible combinations and permutations of the described embodiments.
The inventors intend herein that the terms "comprising", "including" and "comprising" in each case optionally can be replaced by the terms "consisting of", "consisting of" and "consisting of", respectively.
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