Hydrocarbon composition, and preparation method therefor and use thereof

Abstract

Disclosed in the present invention are a hydrocarbon composition, and a preparation method therefor and the use thereof. The hydrocarbon composition contains a bicyclic aromatic hydrocarbon and an aromatic hydrocarbon with three or more rings, wherein based on the total weight of the hydrocarbon composition, the total content of the aromatic hydrocarbons is greater than or equal to 90 wt%, the content of the bicyclic aromatic hydrocarbon is 60-100 wt%, and the content of the aromatic hydrocarbon with three or more rings is 0-40 wt%; the aromatic hydrocarbons have 35-80 carbon atoms; and the mass ratio NP / IP of n-alkane carbon to iso-alkane carbon is 4.0-6.8. The preparation method for the hydrocarbon composition comprises: (1) reacting an aromatic hydrocarbon oil with an olefin oil in the presence of a catalyst, and subjecting the resulting reaction product to sedimentation separation, so as to obtain an oil phase and a catalyst phase; and (2) washing the oil phase, distilling and cutting the washed oil phase, and refining the resulting vacuum residue fraction, so as to obtain the hydrocarbon composition The hydrocarbon composition of the present invention has a high viscosity, a high viscosity index, a low pour point and a good oxidation stability, and is suitable for being used as a high-quality high-viscosity special oil.

Description

Hydrocarbon composition, and preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of petroleum chemical industry, and particularly relates to a hydrocarbon composition, and a preparation method and application thereof. BACKGROUND

[0002] Base oils with high viscosity and high viscosity index are used to adjust the high temperature viscosity of lubricating oil products, and are widely used in the fields of industrial oils and heavy duty internal combustion engine oils, such as heavy load gears, hydraulic machines, heavy load elevators and ship engine, etc. The existing paraffin-based and naphthenic-based base oils have significant technical bottlenecks in realizing the synergistic optimization of high viscosity, high viscosity index and low pour point, and are limited by traditional refining processes and increasingly scarce suitable raw material resources.

[0003] Aromatic hydrocarbon-based high viscosity special oil exhibits excellent dissolving performance and heat conduction characteristics due to its unique molecular structure, and expands the source of raw oil, and is expected to replace traditional paraffin-based and naphthenic-based base oils for use in the field of special oil lubrication requiring high performance. However, the viscosity index of the aromatic hydrocarbon-based oil itself is relatively low, and based on the “seesaw” effect, the improvement of a single performance index often comes at the expense of other key performance, which makes it an unsolved problem in the industry to develop aromatic hydrocarbon-based high viscosity special oil with high viscosity (100℃ kinematic viscosity≥22mm 2 / s), high viscosity index (VI≥95) and low pour point (pour point≤-20℃). Other typical alternative synthetic base oils, such as PAO base oil, although have high viscosity index and low pour point, have low viscosity, and are mainly used in low viscosity lubricating oil application scenarios, such as engine oil, etc., and due to the lack of aromatic hydrocarbon structure, have low compatibility with additives.

[0004] In recent years, although the hydrogen treatment and hydroisomerization dewaxing technology has made breakthroughs in improving the performance of paraffin-based and naphthenic-based base oils, it has the defect of significant decrease in aromatic carbon retention when applied to aromatic hydrocarbon systems, which makes it lose the unique polarity and dissolving properties of aromatic oil. In addition, although deep hydrogen treatment can improve the viscosity index and oxidation stability, it will significantly reduce the kinematic viscosity (100℃ kinematic viscosity is usually lower than 22mm 2 / s), which is difficult to meet the demand of heavy load equipment for high viscosity lubrication.

[0005] With the increasing demand for ultra-low temperature lubricating materials in the fields of polar exploration, aerospace, etc., it is particularly urgent to develop high viscosity special oil that can have sufficient viscosity and dissolving performance at high temperature working conditions, and also maintain flowability at-20℃ or below extreme environment. The existing base oil system has been difficult to meet the comprehensive requirements of new generation lubricating technology for multi-dimensional performance, and it is urgent to realize technical breakthroughs through component structure design and process innovation. SUMMARY

[0006] One of the objects of the present application is to overcome the above-mentioned problems existing in the prior art, and to provide a hydrocarbon composition with high viscosity, high viscosity index, low pour point and good oxidation stability.

[0007] Another object of the present application is to provide a method for preparing the above-mentioned hydrocarbon composition by using a continuous synthesis process route.

[0008] Another object of the present application is to provide an apparatus for preparing the above-mentioned hydrocarbon composition.

[0009] Still another object of the present application is to provide the use of the above-mentioned hydrocarbon composition or the hydrocarbon composition prepared by the above-mentioned method.

[0010] Still another object of the present application is to provide a blended oil comprising the above-mentioned hydrocarbon composition or the hydrocarbon composition prepared by the above-mentioned method.

[0011] In order to achieve the above-mentioned objects, in a first aspect, the present application provides a hydrocarbon composition, characterized in that the hydrocarbon composition comprises bicyclic aromatic hydrocarbons and tricyclic and above aromatic hydrocarbons, wherein the total aromatic hydrocarbon content is ≥ 90 wt% based on the total weight of the hydrocarbon composition, the bicyclic aromatic hydrocarbon content is 60-100 wt%, and the tricyclic and above aromatic hydrocarbon content is 0-40 wt%, wherein the number of carbon atoms of the aromatic hydrocarbons is 35-80, and the mass ratio NP / IP of normal alkyl carbon to isomeric alkyl carbon is 4.0-6.8.

[0012] In a second aspect, the present application provides a method for preparing a hydrocarbon composition, preferably the hydrocarbon composition according to the first aspect, wherein the method comprises:

[0013] (1) reacting an aromatic hydrocarbon oil and an olefin oil in the presence of a catalyst, and subjecting the obtained reaction product to a settling separation to obtain an oil phase and a catalyst phase;

[0014] (2) subjecting the oil phase to a washing, and subjecting the washed oil phase to a distillation cut to obtain a vacuum residue fraction, and subjecting the vacuum residue fraction to a refining to obtain the hydrocarbon composition; and subjecting the catalyst phase to a recovery;

[0015] wherein the distillation range of the aromatic hydrocarbon oil is 100-400℃; and the aromatic hydrocarbon content in the aromatic hydrocarbon oil is ≥ 70 wt%;

[0016] wherein the carbon number distribution of the olefins in the olefin oil is C8-C18; and the olefin content in the olefin oil is ≥ 50 wt%.

[0017] In a third aspect, the present application provides an apparatus for preparing a hydrocarbon composition, preferably the hydrocarbon composition according to the first aspect, wherein the apparatus comprises: a synthesis reaction device, a settling separation device, an oil phase washing device, an oil phase distillation device, a vacuum residue refining device, and a catalyst recovery device.

[0018] In a fourth aspect, the present application provides the use of the hydrocarbon composition according to the first aspect or prepared by the method according to the second aspect as a high viscosity base oil, preferably a bright stock, and an additive for blending.

[0019] In a fifth aspect, the present application provides a blended oil composition comprising the hydrocarbon composition according to the first aspect or prepared by the method according to the second aspect as a high viscosity base oil.

[0020] By the above technical solution, the present application has the following beneficial effects:

[0021] (1) The hydrocarbon composition provided by the present application has excellent physicochemical properties, a 100℃ kinematic viscosity ≥ 22 mm 2 / s, and a viscosity that can be controlled, a viscosity index ≥ 95, a pour point ≤ -20℃, excellent low-temperature flow performance and high oxidation stability, and good compatibility with blended oil products and additives, and is suitable for use as high-quality high-viscosity special oil;

[0022] (2) The preparation method of the hydrocarbon composition provided by the present application uses high-aromatic-content aromatic oil and high-olefin-content olefin oil with a carbon number distribution of C8-C18 as raw materials to continuously produce high-viscosity special oil products, simplifying the process flow while expanding the raw material sources of high-viscosity special oil, and the obtained products have high viscosity, high viscosity index, low pour point, and good oxidation stability;

[0023] (3) The present application builds a multi-scale regulation model of process conditions-component structure-performance performance by systematically analyzing the correlation mechanism between process condition parameters and the reaction degree of raw oil. At the component structure level, the correlation between molecular carbon number and NP / IP and product properties is revealed, and the synergistic regulation of aromatic carbon retention and alkyl side chain length distribution is achieved. At the process flow level, by studying the influence law of raw material selection, process conditions and other factors on component structure, an optimized path of continuous alkylation-distillation cutting-refining of specific raw oil is built, which eliminates the step of hydrotreating and breaks through the bottleneck of mutual restriction between comprehensive yield and performance parameters in traditional processes. The research mode of integrating component structure characterization and process optimization is proposed, which provides quantifiable guidance for the preparation of aromatic high-viscosity special oil with high viscosity (100℃ kinematic viscosity ≥ 22 mm 2 / s), high viscosity index (VI ≥ 95), and low pour point (pour point ≤ -20℃), especially for the directional product development of ultra-low-temperature lubricating materials required in polar exploration, aerospace and other fields. BRIEF DESCRIPTION OF DRAWINGS

[0024] The accompanying drawings are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. Drawings wherein:

[0025] Figure 1 is a flow chart of a process for producing a hydrocarbon composition according to the present application.

[0026] Figure 2 is a mass spectrum of a hydrocarbon composition produced according to Example 1 of the present application.

[0027] Figure 3 is a mass spectrum of a hydrocarbon composition produced according to Example 5 of the present application.

[0028] BRIEF DESCRIPTION OF DRAWINGS I, synthesis reactor II, settling separator III, oil phase washing column IV, oil phase distillation column V, vacuum residue refining unit VI, catalyst recovery column 1, aromatic feed inlet 2, olefin feed inlet 3, catalyst inlet 4, catalyst-containing product outlet 5, oil phase outlet 6, catalyst phase outlet 7, washing liquid inlet 8, washed oil phase outlet 9, waste washing liquid outlet 10, oil phase light ends outlet 11, oil phase vacuum residue outlet 12, hydrocarbon composition outlet 13, recycled catalyst outlet 14, waste oil outlet DETAILED DESCRIPTION

[0029] The specific embodiments of the application will now be described in detail with reference to the accompanying drawings. It should be appreciated that the detailed description of the specific embodiments is merely intended to teach one skilled in the art how to make and use the best mode of the application and not to limit the scope of the application. Therefore, the drawings and detailed description provided herein should not be interpreted as imposing limitations on the application.

[0030] Any specific numerical values (including numerical ranges) disclosed herein are not intended to be limiting, but rather to provide examples of values that can be used. Unless otherwise stated, the numerical values are approximations. Accordingly, the numerical values disclosed herein are not to be construed as being limited to the precise values. Moreover, all ranges disclosed herein are to be understood to encompass the end points of the ranges and all the individual numerical values within the ranges. Unless otherwise stated, all ranges include any and all end points of the ranges and any and all intermediate points. It is intended, for example, that all ranges discussed herein include the end points of the ranges and all the individual numerical values between the end points. Any numerical value, however, can only be approximate — to the extent reasonably possible, exact numerical values are to be avoided. Additionally, the terms "first," "second," and the like, as used herein do not denote any

[0031] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. If any definitions are provided herein, those definitions are intended to apply uniformly in the descriptions of the application, unless otherwise stated.

[0032] In the present application, except for the explicitly stated content, any matter or item not mentioned is directly applicable to those known in the art without any change. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are all considered as part of the original disclosure or original description of the present application, and should not be considered as new content not disclosed or anticipated herein, unless the combination is considered to be obviously unreasonable by those skilled in the art.

[0033] All patents and non-patent literatures mentioned herein, including but not limited to textbooks and journal articles, etc., are incorporated herein by reference in their entirety.

[0034] In a first aspect, the present application provides a hydrocarbon composition, characterized in that the hydrocarbon composition comprises bicyclic aromatic hydrocarbons and tricyclic and above aromatic hydrocarbons, wherein the total aromatic hydrocarbon content is ≥ 90 wt%, the bicyclic aromatic hydrocarbon content is 60-100 wt%, and the tricyclic and above aromatic hydrocarbon content is 0-40 wt%, based on the total weight of the hydrocarbon composition, wherein the number of carbon atoms of the aromatic hydrocarbons is 35-80, and the mass ratio of n-alkanes to iso-alkanes NP / IP is 4.0-6.8.

[0035] In some embodiments of the present application, preferably, the total aromatic hydrocarbon content of the hydrocarbon composition is ≥ 90 wt%, for example, can be 90 wt%, 92 wt%, 95 wt%, 98 wt%, 100 wt%, and any value in the range consisting of any two of the numerical values, more preferably ≥ 95 wt%, and still more preferably ≥ 98 wt%.

[0036] In some embodiments of the present application, preferably, the bicyclic aromatic hydrocarbon content of the hydrocarbon composition is 60-100 wt%, for example, can be 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, and any value in the range consisting of any two of the numerical values, more preferably 80-95 wt%.

[0037] In some embodiments of the present application, preferably, the tricyclic and above aromatic hydrocarbon content of the hydrocarbon composition is 0-40 wt%, for example, can be 0 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, and any value in the range consisting of any two of the numerical values, more preferably 3-20 wt%.

[0038] The inventors have found that it is particularly advantageous for obtaining a hydrocarbon composition having the desired properties when the content of bicyclic aromatic hydrocarbons and the content of tricyclic and higher aromatic hydrocarbons of the hydrocarbon composition are within the defined ranges, in particular within the preferred ranges.

[0039] In some embodiments of the present application, preferably, the hydrocarbon composition comprises aromatic hydrocarbons having a number of carbon atoms in the range of 35 to 80, for example, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, and any value in the range between any two of these values, and more preferably in the range of 45 to 75.

[0040] In some embodiments of the present application, preferably, the hydrocarbon composition comprises aromatic hydrocarbons having a relative molecular mass in the range of 450 to 1200, for example, 450, 480, 500, 520, 550, 580, 600, 620, 650, 680, 700, 720, 750, 780, 800, 820, 850, 880, 900, 920, 950, 980, 1000, 1100, 1200, and any value in the range between any two of these values.

[0041] In some embodiments of the present application, preferably, the hydrocarbon composition comprises aromatic hydrocarbons having a mass ratio of n-alkanes to iso-alkanes NP / IP in the range of 4.0 to 6.8, for example, 6.8, 6.7, 6.6, 6.5, 6.4, 6.3, 6.2, 6.1, 6.0, 5.9, 5.8, 5.7, 5.6, 5.5, 5.4, 5.3, 5.2, 5.1, 5.0, 4.9, 4.8, 4.7, 4.6, 4.5, 4.4, 4.3, 4.2, 4.1, 4.0, and any value in the range between any two of these values, and more preferably in the range of 5.5 to 6.5. In the present application, the mass ratio of n-alkanes to iso-alkanes NP / IP is determined by 13 C-NMR analysis to determine the content of n-alkanes NP and iso-alkanes IP.

[0042] The inventors have found that when the number of carbon atoms of the aromatic hydrocarbons and the mass ratio NP / IP of the n-alkanes carbon to iso-alkanes carbon of the hydrocarbon composition are within the defined range, especially the preferred range, it is particularly advantageous for obtaining a hydrocarbon composition with the desired properties, especially a hydrocarbon composition with high viscosity, high viscosity index and low pour point. When the number of carbon atoms is too low, the hydrocarbon composition exhibits insufficient viscosity, when NP / IP is too low, the hydrocarbon composition exhibits insufficient viscosity index; when the number of carbon atoms is too high and / or NP / IP is too high, the hydrocarbon composition exhibits an undesirable increase in pour point.

[0043] In some embodiments of the present application, preferably, the aromatic hydrocarbons contained in the hydrocarbon composition have 2-8 alkyl side chains, more preferably 3-7 alkyl side chains.

[0044] In some embodiments of the present application, preferably, the aromatic hydrocarbons contained in the hydrocarbon composition have 2-8 alkyl side chains, more preferably 3-7 alkyl side chains.

[0045] In some embodiments of the present application, preferably, the aromatic hydrocarbons contained in the hydrocarbon composition have 6%-45%, preferably 12%-25% of the aromatic carbon rate; 55%-94%, preferably 75%-88% of the paraffin carbon rate. In the present application, the aromatic carbon rate and the paraffin carbon rate are measured according to SH / T 0725.

[0046] In some embodiments of the present application, preferably, the bicyclic aromatic hydrocarbons in the hydrocarbon composition comprise naphthalene derivatives of the following formula (I):

[0047] wherein m≥0, n≥0, and 5≤m+n≤15, preferably 7≤m+n≤13;

[0048] 0≤i≤4, preferably 0≤i≤1;

[0049] 3≤a≤5, 0≤b≤3, preferably 4≤a≤5, 1≤b≤2.

[0050] In some embodiments of the present application, preferably, the content of the naphthalene derivatives is 40-98 wt%, for example, it can be 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, and any value in the range between any two of the values, more preferably 60-80 wt%, based on the total weight of the hydrocarbon composition.

[0051] In some embodiments of the present application, preferably, the saturated hydrocarbon content in the hydrocarbon composition is not higher than 5wt%, for example, can be 5wt%, 4wt%, 3wt%, 2wt%, 1.5wt%, 1wt%, 0.8wt%, 0.5wt%, 0.2wt%, 0wt%, and any value in the range between any two of the values, more preferably not higher than 2wt%, based on the total weight of the hydrocarbon composition.

[0052] In some embodiments of the present application, preferably, the monocyclic aromatic hydrocarbon content in the hydrocarbon composition is not higher than 5wt%, for example, can be 5wt%, 4wt%, 3wt%, 2wt%, 1.5wt%, 1wt%, 0.8wt%, 0.5wt%, 0.2wt%, 0wt%, and any value in the range between any two of the values, more preferably not higher than 2wt%, based on the total weight of the hydrocarbon composition.

[0053] In some embodiments of the present application, preferably, the bicyclic aromatic hydrocarbon in the hydrocarbon composition further comprises at least one of indene derivative, acenaphthene derivative, fluorene derivative; preferably, the total content of the indene derivative, acenaphthene derivative, fluorene derivative is 0-30wt%, for example, can be 0wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, and any value in the range between any two of the values, more preferably 15-25wt%, based on the total weight of the hydrocarbon composition.

[0054] In some embodiments of the present application, preferably, the tricyclic aromatic hydrocarbon in the hydrocarbon composition comprises at least one of anthracene derivative and phenanthrene derivative; preferably, the total content of the anthracene derivative and phenanthrene derivative is 0-40wt%, for example, can be 0wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 8wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, and any value in the range between any two of the values, more preferably 3-20wt%, based on the total weight of the hydrocarbon composition.

[0055] In some embodiments of the present application, preferably, the hydrocarbon composition has a kinematic viscosity at 100°C ≥22mm 2 / s, more preferably 28-44mm 2 / s, and the viscosity is controllable. In the present application, the kinematic viscosity is measured according to the standard method of GB / T 265.

[0056] In some embodiments of the present application, preferably, the viscosity index of the hydrocarbon composition is ≥ 95, for example, can be 95, 100, 105, 110, 115, and any value in the range between any two numerical values, more preferably 95-115. In the present application, the viscosity index is measured according to the GB / T 1995 standard method.

[0057] In some embodiments of the present application, preferably, the pour point of the hydrocarbon composition is ≤ -20℃, for example, can be -20℃, -21℃, -22℃, -23℃, -24℃, -25℃, -26℃, -27℃, -28℃, -29℃, -30℃, -31℃, -32℃, and any value in the range between any two numerical values, more preferably -20 to -32℃. In the present application, the pour point is measured according to the GB / T 3535-2008 standard method.

[0058] In some embodiments of the present application, preferably, the oxidation stability of the hydrocarbon composition is ≥ 190 min, more preferably ≥ 250 min. In the present application, the oxidation stability is measured according to the SH / T0193 standard method.

[0059] In some embodiments of the present application, preferably, the distillation range of the hydrocarbon composition is 500-800℃, for example, 520-800℃.

[0060] The present application discloses the correlation between the molecular carbon number and NP / IP of aromatic hydrocarbon and the product properties, realizes the synergistic regulation of aromatic carbon retention and alkyl side chain length distribution, thereby providing a hydrocarbon composition with excellent physical and chemical properties, including 100℃ kinematic viscosity ≥ 22 mm 2 / s, and viscosity-controllable, viscosity index ≥ 95, pour point ≤ -20℃, oxidation stability ≥ 190 min. At the same time, due to the appropriate aromatic carbon retention, the hydrocarbon composition also has good compatibility with blending oil and additives, and is suitable as high-quality high-viscosity special oil.

[0061] In a second aspect, the present application provides a method for preparing a hydrocarbon composition, preferably the hydrocarbon composition according to the first aspect, wherein the method comprises:

[0062] (1) reacting an aromatic hydrocarbon oil and an olefin oil in the presence of a catalyst, and subjecting the obtained reaction product to settling separation to obtain an oil phase and a catalyst phase;

[0063] (2) washing the oil phase, and subjecting the washed oil phase to distillation cutting to obtain a vacuum residue fraction, and subjecting the vacuum residue fraction to refining to obtain the hydrocarbon composition; and recovering the catalyst phase;

[0064] The aromatic hydrocarbon oil has a distillation range of 100-400 ℃, and an aromatic hydrocarbon content of ≥70 wt%.

[0065] The olefin oil has a carbon number distribution of C8-C18, and an olefin content of ≥50 wt%.

[0066] In the present application, the method uses aromatic hydrocarbon oil with high aromatic hydrocarbon content and olefin oil with high olefin content and a carbon number distribution of C8-C18 as raw materials, adopts a continuous synthesis process route, and obtains a hydrocarbon composition with high viscosity, high viscosity index, low pour point and good oxidation stability, and the yield of the obtained hydrocarbon composition is high.

[0067] In some embodiments of the present application, preferably, the distillation range of the aromatic hydrocarbon oil is 100-400 ℃, for example, it can be 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, and any value in the range composed of any two numerical values, and more preferably 200-350 ℃; the aromatic hydrocarbon content in the aromatic hydrocarbon oil is ≥70 wt%, for example, it can be 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, and any value in the range composed of any two numerical values, and more preferably ≥80 wt%. In the present application, the aromatic hydrocarbon oil has a specific distillation range and a high aromatic hydrocarbon content.

[0068] In the present application, the type of the aromatic hydrocarbon oil is not particularly limited, and it can be various aromatic hydrocarbon oils known in the art, as long as the above-mentioned distillation range and aromatic hydrocarbon content are met, preferably, the aromatic hydrocarbon oil is aromatic-rich oil, preferably selected from at least one of catalytic cracking diesel, catalytic cracking heavy oil, reforming heavy aromatic oil, ethylene tar and coal tar, and more preferably catalytic cracking diesel.

[0069] In the present application, if the distillation range of the aromatic-rich oil does not meet the above-mentioned distillation range of the aromatic hydrocarbon oil, it needs to be subjected to distillation cutting treatment to obtain aromatic hydrocarbon oil rich in at least one of double-ring aromatic hydrocarbons and triple-ring aromatic hydrocarbons, in particular, aromatic hydrocarbon oil rich in double-ring aromatic hydrocarbons. The method and conditions of the distillation cutting can be the method and conditions of the distillation cutting known in the art, which are not described herein.

[0070] In the present application, the type of the aromatic hydrocarbon in the aromatic hydrocarbon oil is not particularly limited, preferably, the aromatic hydrocarbon in the aromatic hydrocarbon oil is selected from at least one of double-ring and triple-ring aromatic hydrocarbon compounds with a boiling point of 100-350 ℃; more preferably, the aromatic hydrocarbon in the aromatic hydrocarbon oil is selected from at least one of methyl naphthalene, dimethyl naphthalene, ethyl naphthalene, biphenyl, acenaphthene and fluorene, and further preferably methyl naphthalene and / or dimethyl naphthalene.

[0071] In some embodiments of the present application, preferably, the olefin content of the olefin oil is ≥ 50 wt%, for example, it can be 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, and any value within the range between any two of the numerical values, more preferably ≥ 70 wt%; the carbon number distribution of the olefin in the olefin oil is C8-C18, for example, it can be C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, and any value within the range between any two of the numerical values, more preferably C10-C14. The structure of the olefin in the olefin oil of the present application is not particularly limited as long as the carbon number distribution meets the above range, preferably, the olefin in the olefin oil is linear alpha-olefin and / or internal olefin. The olefin oil has a high olefin content, and the olefin in the olefin oil has a suitable carbon chain length.

[0072] In the present application, the mass ratio of the aromatic oil and the olefin oil has a wide selection range, preferably, the mass ratio of the aromatic oil and the olefin oil is 1:0.5-10, for example, it can be 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, and any value within the range between any two of the numerical values, preferably 1:1-5. In the present application, the mass ratio of the aromatic oil and the olefin oil is controlled within the above range, which not only facilitates the synthesis of the product with multiple alkyl long side chains to meet the requirements of high viscosity and high viscosity index of the product, but also facilitates the full reaction of the aromatic oil and the olefin oil to reduce the remaining of the aromatic oil and the olefin oil raw materials.

[0073] In the present application, the mass ratio of the aromatic oil and the catalyst has a wide selection range, preferably, the mass ratio of the aromatic oil and the catalyst is 1:0.01-1, for example, it can be 1:0.01, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, and any value within the range between any two of the numerical values, preferably 1:0.05-0.3. In the present application, the mass ratio of the aromatic oil and the catalyst is controlled within the above range, which facilitates the full catalysis of the reaction of the aromatic oil and the olefin, while avoiding excessive use of the catalyst to reduce side reactions.

[0074] In some embodiments of the present application, preferably, the feeding mode of the aromatic oil, the olefin oil, and the catalyst is continuous feeding according to the mass ratio.

[0075] In the present application, the catalyst can be various catalysts commonly used in the art for the reaction of the aromatic oil and the olefin oil, preferably, the catalyst is selected from liquid acids and / or organic acids containing metal halides.

[0076] In the present application, the kind of the liquid acid is not particularly limited, and any liquid acid known in the art can be used in the present application. Preferably, the liquid acid is at least one selected from the group consisting of concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, perchloric acid and hydrobromic acid, more preferably at least one selected from the group consisting of concentrated sulfuric acid, trifluoromethanesulfonic acid and methanesulfonic acid.

[0077] In the present application, the kind of the metal halide is not particularly limited, and any metal halide known in the art can be used in the present application. The metal halide is at least one selected from the group consisting of boron tribromide, boron trichloride, aluminum trichloride, boron trifluoride, iron trichloride and zinc trichloride, preferably boron tribromide and / or aluminum trichloride.

[0078] In the present application, the kind of the organic acid is not particularly limited, and can be any organic acid known in the art for providing acidity. Preferably, the organic acid is at least one selected from the group consisting of methanesulfonic acid and / or ethanesulfonic acid, more preferably methanesulfonic acid.

[0079] In the present application, the concentration of the metal halide-containing organic acid has a wide selection range. Preferably, the content of the metal halide is 1-30 wt%, preferably 5-20 wt%, based on the total weight of the metal halide-containing organic acid.

[0080] In the present application, in step (1), the aromatic hydrocarbon oil, the olefin oil and the catalyst are continuously fed according to the mass ratio, so that the aromatic hydrocarbon oil and the olefin oil are reacted in the presence of the catalyst to obtain a reaction product in the form of an oil phase containing the catalyst. The reaction product is subjected to settling separation to obtain an upper oil phase and a lower catalyst phase. The aromatic hydrocarbon oil, the olefin oil and the catalyst in the present application are contacted and reacted in a synthesis reactor. The reaction is carried out at normal pressure, and the reaction temperature is 20-80°C, and the reaction time is 5-300 min, more preferably the reaction temperature is 30-60°C, and the reaction time is 30-90 min. The reaction can be carried out in a synthesis reactor. In the present application, the reaction temperature and time are controlled in the above range, which is more conducive to the full occurrence of the target reaction between the aromatic hydrocarbon and the olefin, reduces the side reaction, and at the same time avoids unnecessary energy consumption and operation time.

[0081] The inventors have found that the degree of alkylation reaction needs to be controlled by optimizing the reaction conditions, so as to obtain a hydrocarbon composition with a desired component structure. For example, if the reaction conditions result in too fast alkylation reaction rate, the product NP / IP will increase, the isomerization degree of the alkyl side chain will decrease, and the pour point of the obtained hydrocarbon composition will rise, which cannot meet the use requirements under extremely low temperature conditions.

[0082] In the present application, the reaction product containing catalyst obtained from the reaction is introduced into a settling separation device for settling separation. The settling separation device can be a conventional settling separation device used in the art, and preferably, the settling separation device is provided with a plurality of settling separation tanks, which are advantageous for separating the upper oil phase and the lower catalyst phase by using the gravity to make the catalyst phase settle from the reaction product containing catalyst.

[0083] In some embodiments of the present application, preferably, the settling includes distributing the obtained reaction product into a plurality of settling separation tanks for settling. In the present application, the aromatic oil and the olefin oil have a relatively fast reaction speed, and the obtained reaction product needs to be introduced into different settling separation tanks in the order of synthesis for settling separation. Specifically, when the reaction product in the settling separation tank reaches 2 / 3 of the volume of the settling separation tank, the feeding is stopped, and the subsequent reaction product is introduced into the next settling separation tank for settling according to this method. The way of settling of the plurality of settling separation tanks in the present application is advantageous for improving the efficiency of the settling separation.

[0084] In the present application, the time of the settling separation is not particularly limited, as long as the oil phase and the catalyst phase in the reaction product in the settling tank can be fully layered, and the oil phase and the catalyst phase can be obtained after the separation. Preferably, the time of the reaction product in each settling separation tank is 5-120 min, and more preferably 30-60 min, relative to a 20 L settling separation tank.

[0085] In the present application, in step (2), the oil phase obtained from the settling separation treatment is contacted with a washing agent for washing treatment to remove the acid in the oil phase. The washing can be carried out in an oil phase washing tower. In the present application, the mass ratio of the oil phase to the washing agent has a relatively wide selection range, and preferably, the mass ratio of the oil phase to the washing agent is 1:0.5-5, and more preferably 1:1-2.

[0086] In some embodiments of the present application, preferably, the acid value of the oil phase after the washing is ≤0.05 mgKOH / g. In the present application, the acid value of the oil phase is measured according to the standard method of GB / T 7304.

[0087] In the present application, the type of the washing agent is not particularly limited, and various washing agents for oil phase washing conventionally used in the art can be used. Preferably, the washing agent is selected from water and / or a metal alkali solution, and preferably is water.

[0088] In the present application, the oil phase after washing is subjected to distillation cutting treatment, and light components are separated by using the difference in volatility of each component to obtain a vacuum residue fraction. The distillation range of the vacuum residue fraction in the present application is not particularly limited, and preferably, the cutting temperature of the distillation cutting is ≥ 500°C, preferably ≥ 520°C. The distillation cutting treatment in the present application can be carried out in a distillation cutting tower.

[0089] In the present application, the vacuum residue fraction obtained by distillation cutting is subjected to refining, and the method of refining is not particularly limited and can be a method of refining known in the art. Preferably, the refining is at least one selected from the group consisting of clay refining, hydrorefining, and molecular sieve adsorption refining, and more preferably clay refining.

[0090] In the present application, preferably, the specific method of clay refining includes contacting the vacuum residue fraction with a clay adsorbent to perform clay refining, and separating to obtain a hydrocarbon composition and a waste adsorbent.

[0091] In the present application, the contacting of the vacuum residue with the clay adsorbent can be carried out in a vacuum residue refining device, and the refining is carried out under clay refining conditions to remove part of the by-products, so as to avoid the influence of the residual by-products on the product properties. After the oil and the adsorbent are separated, a hydrocarbon composition is obtained.

[0092] In the present application, the clay adsorbent is preferably high-quality bentonite with a montmorillonite content of greater than 85% by weight, and more preferably activated clay.

[0093] In the present application, the amount of clay added has a relatively wide selection range, and preferably, the amount of clay added is 1-10% by weight, preferably 2-5% by weight, based on the total weight of the vacuum residue fraction.

[0094] In some embodiments of the present application, preferably, the conditions of clay refining include a refining temperature of 50-200°C, preferably 80-150°C, and a refining time of 5-120 min, preferably 20-60 min.

[0095] In the present application, the mixing method of contacting the clay adsorbent with the vacuum residue fraction can be mixing by a screw conveyor circulating stirring mixer or a stirring paddle stirring mixer. The solid-liquid mixing is a conventional technology, and will not be described here.

[0096] In the present application, the separation of the adsorbent after the vacuum residue fraction is contacted with the adsorbent to obtain the hydrocarbon composition is usually solid-liquid separation, and the solid-liquid separation can use a conventional solid-liquid separation method in the art, such as natural sedimentation and filtration separation. The method of solid-liquid separation can use the prior art, and will not be described here.

[0097] In the present application, the method for recovering the catalyst can adopt a method for recovering the catalyst in the art, preferably, the method for recovering the catalyst is selected from at least one of atmospheric distillation, vacuum distillation and vacuum rectification, more preferably, vacuum rectification.

[0098] In the present application, vacuum rectification is adopted to reduce the recovery temperature and improve the recovery efficiency, and the conditions for vacuum rectification are not particularly limited and can be the conditions for vacuum rectification in the art, for example, the temperature for vacuum rectification is 50-300℃, and the pressure for vacuum rectification is 100-100000 Pa.

[0099] In the present application, the recovery conditions for vacuum rectification of the catalyst are related to the type of catalyst. Preferably, when triflic acid is used as the catalyst phase, the temperature for vacuum rectification is 180-200℃, and the pressure for vacuum rectification is 30000-50000 Pa; when concentrated sulfuric acid is used as the catalyst phase, the temperature for vacuum rectification is 280-300℃, and the pressure for vacuum rectification is 5000-20000 Pa; when methanesulfonic acid is used as the catalyst phase, the temperature for vacuum rectification is 200-240℃, and the pressure for vacuum rectification is 5000-20000 Pa. In the present application, when the above catalysts are used, the conditions for vacuum rectification are controlled within the above ranges, which is beneficial to improving the recovery rate of the catalyst.

[0100] In the present application, the pressure for vacuum rectification refers to the absolute pressure unless otherwise specified.

[0101] In a preferred embodiment of the present application, the method for preparing the hydrocarbon composition comprises:

[0102] (1) continuously feeding aromatic oil, olefin oil and a catalyst at a mass ratio of aromatic oil to olefin oil of 1:0.5-10 and a mass ratio of aromatic oil to catalyst of 1:0.01-1, allowing the aromatic oil and the olefin oil to react in the presence of the catalyst, and subjecting the obtained reaction product to settling separation to obtain an oil phase and a catalyst phase, wherein the catalyst is a liquid acid and / or an organic acid catalyst containing a metal halide;

[0103] (2) washing the oil phase, distillation cutting of the washed oil phase, refining of the vacuum residue fraction obtained by distillation cutting to obtain the hydrocarbon composition, and recovering the catalyst phase; wherein the acid value of the oil phase after washing is ≤0.05 mgKOH / g;

[0104] wherein the distillation range of the aromatic oil is 100-400℃, and the content of aromatic hydrocarbons in the aromatic oil is ≥70 wt%;

[0105] wherein the carbon number distribution of olefins in the olefin oil is C8-C18, and the content of olefins in the olefin oil is ≥50 wt%.

[0106] In the present application, aromatic hydrocarbon oil with required high aromatic hydrocarbon content and olefin oil with high olefin content are used as raw materials, and through the optimized path of continuous alkylation-washing-distillation cutting-refining, controllable reaction of aromatic hydrocarbon and olefin is ensured, compounds with suitable aromatic carbon retention and alkyl side chain length distribution are generated, and the obtained hydrocarbon composition has high viscosity (100℃ kinematic viscosity≥22mm 2 / s), high viscosity index (VI≥95), low pour point (pour point≤-20℃) and good oxidation stability (time≥190min).

[0107] The preparation method of the hydrocarbon composition provided by the present application is further described in detail through FIG. 1.

[0108] As shown in FIG. 1, the aromatic hydrocarbon oil, the olefin oil and the catalyst are continuously fed into the synthesis reactor I through the aromatic hydrocarbon raw material inlet 1, the olefin raw material inlet 2 and the catalyst inlet 3 respectively for reaction, and the obtained reaction product enters the settling separation tank II through the catalyst product outlet 4 for settling separation, and the upper oil phase and the lower catalyst phase are obtained through the settling separation, the oil phase enters the oil phase washing tower III through the oil phase outlet 5 for washing, the washing liquid is introduced into the oil phase washing tower III through the washing liquid inlet 7, the oil phase treated by washing enters the oil phase distillation tower IV through the washing oil phase outlet 8 for distillation cutting, the waste washing liquid treated by washing is discharged through the waste washing liquid outlet 9 as liquid waste treatment; the light fraction treated by distillation cutting is discharged through the oil phase light fraction outlet 10, the vacuum residue fraction collected by distillation cutting enters the vacuum residue refining device V through the oil phase vacuum residue outlet 11 for refining, and the hydrocarbon composition is discharged through the hydrocarbon composition outlet 12 after the vacuum residue is refined, and the hydrocarbon composition product is obtained; the lower catalyst phase obtained by settling separation enters the catalyst recovery tower VI through the catalyst phase outlet 6 for distillation, and the catalyst treated by distillation obtains the circulating catalyst which is discharged through the circulating catalyst outlet 13, and the waste oil is discharged through the waste oil outlet 14 as solid / liquid waste treatment.

[0109] In a third aspect, the present application provides a device for preparing a hydrocarbon composition, preferably the hydrocarbon composition according to the first aspect, wherein the device comprises: a synthesis reaction device, a settling separation device, an oil phase washing device, an oil phase distillation device, a vacuum residue refining device and a catalyst recovery device.

[0110] In some embodiments of the present application, the synthesis reactor is provided with an aromatic feedstock inlet, an olefin feedstock inlet, a catalyst inlet, and a catalyst-containing product outlet, the settling separation device is provided with a feedstock inlet, an oil phase outlet, and a catalyst phase outlet, the oil phase washing device is provided with a feedstock inlet, a washing liquid inlet, a washed oil phase outlet, and a waste washing liquid outlet, the oil phase distillation device is provided with a feedstock inlet, an oil phase light fraction outlet, and an oil phase vacuum residue outlet, the vacuum residue refining device is provided with a feedstock inlet, a hydrocarbon composition outlet, and the catalyst recovery device is provided with a feedstock inlet, a recycled catalyst outlet, and a waste oil outlet.

[0111] In some embodiments of the present application, the catalyst-containing product outlet of the synthesis reactor is in fluid communication with the feedstock inlet of the settling separation device, the oil phase outlet of the settling separation device is in fluid communication with the feedstock inlet of the oil phase washing device, the catalyst phase outlet is in fluid communication with the feedstock inlet of the catalyst recovery device, the washed oil phase outlet of the oil phase washing device is in fluid communication with the feedstock inlet of the oil phase distillation device, and the oil phase vacuum residue outlet of the oil phase distillation device is in fluid communication with the feedstock inlet of the vacuum residue refining device.

[0112] In some embodiments of the present application, the settling separation device is provided with at least one settling separation vessel, preferably 2-3 settling separation vessels.

[0113] In some embodiments of the present application, the feedstock inlet of the oil phase washing device is provided in the lower part of the oil phase washing device, and the washing liquid inlet of the oil phase washing device is provided in the upper part of the oil phase washing device.

[0114] In a fourth aspect, the present application provides the use of the hydrocarbon composition according to the first aspect or prepared by the method according to the second aspect as a high viscosity base oil, preferably a bright stock, and as an additive for blending.

[0115] In a fifth aspect, the present application provides a blended oil composition comprising the hydrocarbon composition according to the first aspect or prepared by the method according to the second aspect as a high viscosity base oil.

[0116] In some embodiments of the present application, preferably, the blended oil composition further comprises at least one low viscosity base oil having a kinematic viscosity at 100°C of 6-12 mm 2 / s, a viscosity index of > 95, a saturated hydrocarbon content of > 92%, and a pour point of < -12°C.

[0117] In some embodiments of the present application, preferably, the low viscosity base oil is selected from the group consisting of a hydrogenated mineral oil, a PAO base oil, and combinations thereof.

[0118] In some embodiments of the present application, preferably, the content of the high viscosity base oil is 5-50wt%, for example, can be 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, and any value in the range consisting of any two numerical values; the content of the low viscosity base oil is 50-95wt%, for example, can be 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, and any value in the range consisting of any two numerical values, relative to the total weight of the blended oil composition.

[0119] In some embodiments of the present application, preferably, the kinematic viscosity at 100℃ of the blended oil composition is 7-22mm 2 / s, the pour point is ≤-15℃.

[0120] The hydrocarbon composition of the present application has good compatibility with blending oil and additives, and as a high viscosity base oil, it is blended with other blending oil and / or additives to obtain a blended oil composition with excellent performance.

[0121] The present application also discloses the following embodiments:

[0122] Scheme 1, a method for preparing a bright stock oil, characterized in that the method comprises:

[0123] (1) reacting an aromatic oil and an olefin oil in the presence of a catalyst to obtain a reaction product, and performing settling separation on the reaction product to obtain an oil phase and a catalyst phase;

[0124] (2) washing the oil phase, distillation cutting the washed oil phase, refining the vacuum residue fraction obtained by distillation cutting to obtain a bright stock oil, and recovering the catalyst phase;

[0125] wherein the distillation range of the aromatic oil is 100-400℃; the content of aromatic hydrocarbons in the aromatic oil is ≥70wt%;

[0126] wherein the carbon number distribution of olefins in the olefin oil is C8-C20; the content of olefins in the olefin oil is ≥50wt%.

[0127] Scheme 2, the method according to scheme 1, wherein the distillation range of the aromatic oil is 200-350℃; the content of aromatic hydrocarbons in the aromatic oil is ≥80wt%;

[0128] Preferably, the aromatic oil is selected from at least one of catalytic cracking diesel oil, catalytic cracking heavy oil, reforming heavy aromatic oil, ethylene tar and coal tar, preferably catalytic cracking diesel oil;

[0129] and / or, the aromatics in the aromatic oil are selected from at least one of mono-, bi- and tri-cyclic aromatic hydrocarbon compounds having a boiling point of 100-350℃, preferably at least one of toluene, xylene, dodecylbenzene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, biphenyl, acenaphthene, fluorene and hexylbenzene, more preferably methylnaphthalene and / or dimethylnaphthalene.

[0130] Scheme 3, the method according to Scheme 1 or 2, wherein the olefin carbon number distribution in the olefin oil is C10-C14; the olefin content in the olefin oil is ≥70wt%; the olefins in the olefin oil are linear alpha-olefins and / or internal olefins.

[0131] Scheme 4, the method according to any one of Schemes 1-3, wherein the mass ratio of the aromatic oil and the olefin oil is 1:0.5-10, preferably 1:1-5;

[0132] Preferably, the mass ratio of the aromatic oil and the catalyst is 1:0.01-1, preferably 1:0.05-0.3.

[0133] Scheme 5, the method according to any one of Schemes 1-4, wherein the catalyst is selected from liquid acids and / or metal halide-containing organic acids;

[0134] Preferably, the liquid acid is selected from at least one of concentrated sulfuric acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, perchloric acid and hydrobromic acid, preferably at least one of concentrated sulfuric acid, trifluoromethanesulfonic acid and fluorosulfonic acid;

[0135] Preferably, the metal halide is selected from at least one of boron tribromide, boron trichloride, aluminum trichloride, boron trifluoride, iron trichloride and zinc trichloride, preferably boron tribromide and / or aluminum trichloride;

[0136] Preferably, the organic acid is selected from methanesulfonic acid and / or ethanesulfonic acid;

[0137] Preferably, the content of the metal halide is 1-30wt%, preferably 5-20wt%, based on the total amount of the metal halide-containing organic acid.

[0138] Scheme 6, the method according to any one of Schemes 1-5, wherein in step (1), the reaction temperature is 20-100℃, preferably 30-60℃; the reaction time is 5-300min, preferably 30-90min;

[0139] Preferably, the settling comprises: distributing the obtained reaction product in a plurality of settling separation tanks for settling;

[0140] Preferably, the settling time of the reactants in each settling separation kettle is 5-120 min, preferably 30-60 min, relative to a 20 L settling separation kettle.

[0141] Preferably, in step (2), the mass ratio of the oil phase to the washing liquid is 1:0.5-5, preferably 1:1-2.

[0142] Preferably, the acid value of the washed oil phase is ≤0.05 mgKOH / g.

[0143] Preferably, the washing liquid is selected from water and / or a metal alkali liquid, preferably water.

[0144] Scheme 7, the method according to any one of schemes 1-6, wherein the cutting temperature of the distillation cutting is ≥500℃, preferably ≥520℃.

[0145] Preferably, the refining in step (2) is selected from at least one of clay refining, hydrorefining and molecular sieve adsorption refining, preferably clay refining.

[0146] Preferably, the conditions of the clay refining include: the clay addition amount is 1-10 wt% of the vacuum residue fraction, preferably 2-5 wt%; the refining temperature is 50-200℃, preferably 80-150℃; and the refining time is 5-120 min, preferably 20-60 min.

[0147] Scheme 8, the method according to any one of schemes 1-7, wherein in step (2), the method for recovering the catalyst is selected from at least one of atmospheric distillation, vacuum distillation and vacuum rectification, preferably vacuum rectification.

[0148] Scheme 9, a bright stock oil prepared by the method according to any one of schemes 1-8.

[0149] Scheme 10, the bright stock oil according to scheme 9, wherein the kinematic viscosity of the bright stock oil at 100℃ is ≥28 mm 2 / s, preferably 28-44 mm 2 / s; the viscosity index is ≥95, preferably 95-115; and the pour point is ≤-9℃, preferably -12 to -32℃.

[0150] The above describes preferred embodiments of the present application, but the present application is not limited to the specific details of the above embodiments, and within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, and these simple modifications all belong to the protection scope of the present application.

[0151] Examples

[0152] The present application will be described in detail below through examples.

[0153] Main analysis method of the present application:

[0154] Density: measured according to GB / T 13377 standard method;

[0155] Kinematic viscosity: measured according to GB / T 265 standard method;

[0156] Hydrocarbon composition: measured according to SH / T 0659 standard method;

[0157] Acid value: measured according to GB / T 7304 standard method;

[0158] Pour point: measured according to GB / T 3535-2008 standard method;

[0159] Viscosity index: calculated according to GB / T 1995 standard method;

[0160] Oxidation stability (rotating bomb method): measured according to SH / T 0193 standard method;

[0161] Saturated hydrocarbon content: calculated according to SH / T 0753 standard method;

[0162] Normal alkane NP and isoparaffin IP content were determined by nuclear magnetic resonance spectrometer (Agilent 700 MHz) for C-NMR analysis. 13 C-NMR analysis.

[0163] Main raw materials and sources of the present application:

[0164] The properties and compositions of the aromatic oil I, aromatic oil II and aromatic oil IV used in the following examples and comparative examples are shown in Table 1.

[0165] Aromatic oil I: catalytically cracked heavy diesel oil, taken from the catalytic cracking unit of a refinery, the diesel fraction being 200-350℃;

[0166] Aromatic oil II: catalytically cracked recycle oil, taken from the catalytic cracking unit of a refinery, the recycle oil fraction being 250-450℃, the recycle oil fraction of 250-350℃ being obtained by distillation cutting, the recycle oil after distillation cutting being aromatic oil II;

[0167] Aromatic oil III: methyl naphthalene, the aromatic content being 98wt%, purchased from Shanghai Aldrin Biochemical Science and Technology Co., Ltd.;

[0168] Aromatic oil IV: catalytically cracked gasoline, taken from the catalytic cracking unit of a refinery, the gasoline fraction of 80-100℃ being obtained by distillation cutting, the gasoline after distillation cutting being aromatic oil IV;

[0169] Olefin oil I: dodecene, olefin content 99.5wt%, purchased from Shanghai Aldrin Biochemical Technology Co., Ltd.;

[0170] Olefin oil II: tetradecene, olefin content 99.5wt%, purchased from Shanghai Aldrin Biochemical Technology Co., Ltd.;

[0171] Liquid acid catalyst: triflic acid, concentrated sulfuric acid, both purchased from Shanghai Aldrin Biochemical Technology Co., Ltd.;

[0172] Metal halide catalyst: boron tribromide, purchased from Shanghai Aldrin Biochemical Technology Co., Ltd.;

[0173] Acid clay: purchased from Huangshan Baiyue Active Clay Co., Ltd.

[0174] Example 1

[0175] (1) According to the aromatic oil I feed amount of 100 g / min, dodecene feed amount of 300 g / min, triflic acid feed amount of 15 g / min, continuously add aromatic oil I, dodecene and triflic acid into the synthesis reactor for stirring and mixing, and react at a temperature of 50°C for 60 min;

[0176] (2) The reaction product obtained in step (1) is continuously introduced into two 20L volume settling separation tanks, until the liquid level of the settling separation tank reaches 2 / 3 of the tank height, the feeding is stopped, and after 30 min of settling, the upper oil phase and the lower catalyst phase are obtained;

[0177] (3) The upper oil phase is introduced into the lower part of the washing tower, and the washing water is introduced from the upper part of the washing tower, the mass ratio of oil phase to water is 1:2, and the acid value of the oil phase after washing is 0.04 mgKOH / g;

[0178] (4) The oil phase after washing is introduced into the distillation cutting tower for distillation cutting, and a vacuum residue fraction ≥520°C is obtained;

[0179] (5) The vacuum residue fraction is introduced into the clay refining device for refining, the clay addition amount is 3wt% of the vacuum residue fraction, and the refining is carried out at a temperature of 120°C for 60 min, and a hydrocarbon composition is obtained.

[0180] (6) The lower catalyst phase in step (2) is introduced into the catalyst recovery tower, and the recovery temperature is 180°C, and the triflic acid catalyst is recovered by distillation, and the recovery rate is 72.3%.

[0181] The mass spectrum of the hydrocarbon composition obtained in Example 1 is shown in Figure 2, and the product properties and hydrocarbon composition are listed in Table 2. By 13 The NP / IP mass ratio measured by C-NMR is 6.1.

[0182] Example 2

[0183] (1) The aromatic oil I, dodecene and triflic acid were continuously added to the synthesis reactor according to the aromatic oil I feed rate of 100 g / min, dodecene feed rate of 500 g / min and triflic acid feed rate of 15 g / min, and stirred and mixed, and reacted at a temperature of 60°C for 90 min;

[0184] (2) The reaction product obtained in step (1) was continuously introduced into 3 settling separation tanks, each with a volume of 20 L, until the liquid level of the settling separation tank reached 2 / 3 of the tank height, and the feeding was stopped. After settling for 60 min, the upper oil phase and the lower catalyst phase were obtained;

[0185] (3) The upper oil phase was introduced into the lower part of the washing tower, and the washing agent water was introduced from the upper part of the washing tower. The mass ratio of the oil phase to the washing agent was 1:2, and the acid value of the oil phase after washing was 0.05 mgKOH / g;

[0186] (4) The oil phase after washing was introduced into the distillation cutting tower for distillation cutting, and a vacuum residue fraction ≥520°C was obtained;

[0187] (5) The vacuum residue fraction was introduced into the clay refining device for refining, and the clay addition amount was 5wt% of the vacuum residue fraction. The refining was carried out at a temperature of 150°C for 60 min, and a hydrocarbon composition was obtained.

[0188] (6) The lower catalyst phase in step (2) was introduced into the catalyst recovery tower, and the recovery temperature was 180°C. The triflic acid catalyst was recovered by distillation, and the recovery rate was 74.3%.

[0189] The product properties and hydrocarbon composition of the hydrocarbon composition obtained in Example 2 are listed in Table 2. The NP / IP mass ratio was calculated by C-NMR to be 6.4. 13 C-NMR measured NP / IP mass ratio was 6.4.

[0190] Example 3

[0191] (1) The aromatic oil I, dodecene and concentrated sulfuric acid were continuously added to the synthesis reactor according to the aromatic oil I feed rate of 100 g / min, dodecene feed rate of 200 g / min and concentrated sulfuric acid feed rate of 30 g / min, and stirred and mixed, and reacted at a temperature of 30°C for 30 min;

[0192] (2) The reaction product obtained in step (1) was continuously introduced into 2 settling separation tanks, each with a volume of 20 L, until the liquid level of the settling separation tank reached 2 / 3 of the tank height, and the feeding was stopped. After settling for 30 min, the upper oil phase and the lower catalyst phase were obtained;

[0193] (3) The upper oil phase is introduced into the lower part of the washing tower, and the detergent water is introduced from the upper part of the washing tower, the mass ratio of the oil phase and the detergent is 1:2, and the acid value of the oil phase after washing is 0.05 mgKOH / g;

[0194] (4) The oil phase after washing is introduced into a distillation cutting tower for distillation cutting to obtain a vacuum residue fraction ≥520°C;

[0195] (5) The vacuum residue fraction is introduced into a clay refining device for refining, the clay addition amount is 3wt% of the vacuum residue fraction, and the refining is carried out at a temperature of 120°C for 30 min to obtain a hydrocarbon composition.

[0196] (6) The lower catalyst phase in step (2) is introduced into a catalyst recovery tower, and the recovery temperature is 300°C, and the concentrated sulfuric acid catalyst is recovered by distillation.

[0197] The product properties and hydrocarbon composition of the hydrocarbon composition obtained in Example 3 are listed in Table 2.

[0198] Example 4

[0199] (1) Aromatic oil II, tetradecene and methanesulfonic acid are continuously added to the synthetic reaction kettle at an aromatic oil II feed rate of 100 g / min, a tetradecene feed rate of 200 g / min, a methanesulfonic acid feed rate of 25 g / min, and a boron tribromide feed rate of 5 g / min for stirring and mixing, and the reaction is carried out at a temperature of 50°C for 30 min;

[0200] (2) The reaction product obtained in step (1) is continuously introduced into two 20L volume settling separation tanks, and the feeding is stopped when the liquid level of the tank reaches 2 / 3 of the tank height, and after settling for 60 min, an upper oil phase and a lower catalyst phase are obtained;

[0201] (3) The upper oil phase is introduced into the lower part of the washing tower, and the detergent water is introduced from the upper part of the washing tower, the mass ratio of the oil phase and the detergent is 1:2, and the acid value of the oil phase after washing is 0.04 mgKOH / g;

[0202] (4) The oil phase after washing is introduced into a distillation cutting tower for distillation cutting to obtain a vacuum residue fraction ≥520°C;

[0203] (5) The vacuum residue fraction is introduced into a clay refining device for refining, the clay addition amount is 5wt% of the vacuum residue fraction, and the refining is carried out at a temperature of 80°C for 60 min to obtain a hydrocarbon composition;

[0204] (6) The lower catalyst phase in step (2) is introduced into a catalyst recovery tower, and the recovery temperature is 200°C, and the mixture catalyst of methanesulfonic acid and boron tribromide is recovered by distillation.

[0205] The product properties and hydrocarbon composition of the hydrocarbon composition obtained in Example 4 are listed in Table 2.

[0206] Example 5

[0207] (1) Aromatic hydrocarbon oil I, tetradecene and triflic acid were continuously added into a synthesis reactor at a rate of 100 g / min, 100 g / min and 5 g / min respectively, and stirred and mixed, and reacted at a temperature of 50 °C for 60 min;

[0208] (2) The reaction product obtained in step (1) was continuously introduced into a 20 L volume settling separation kettle, and the feeding was stopped until the liquid level of the settling separation kettle reached 2 / 3 of the kettle height, and after settling for 30 min, an upper oil phase and a lower catalyst phase were obtained;

[0209] (3) The upper oil phase was introduced into the lower part of a washing tower, and washing agent water was introduced from the upper part of the washing tower, and the mass ratio of the oil phase to the washing agent was 1:1, and the acid value of the oil phase after washing was 0.04 mgKOH / g;

[0210] (4) The oil phase after washing was introduced into a distillation cutting tower for distillation cutting, and a vacuum residue fraction ≥520 °C was obtained;

[0211] (5) The vacuum residue fraction was introduced into a clay refining device for refining, and the clay addition amount was 2 wt% of the vacuum residue fraction, and the refining was carried out at a temperature of 120 °C for 20 min, and a hydrocarbon composition was obtained.

[0212] (6) The lower catalyst phase in step (2) was introduced into a catalyst recovery tower, and the recovery temperature was 180 °C, and the triflic acid catalyst was recovered by distillation.

[0213] The mass spectrum of the hydrocarbon composition obtained in Example 5 is shown in Figure 3, and the product properties and hydrocarbon composition are listed in Table 2.

[0214] Example 6

[0215] The method of Example 1 was followed, except that in step (1), the dodecene was replaced with octene in equal amounts, and a hydrocarbon composition was obtained, and the product properties and hydrocarbon composition are listed in Table 2.

[0216] Example 7

[0217] The method of Example 1 was followed, except that in step (1), the triflic acid feed rate was replaced with 1 g / min instead of 15 g / min, and a hydrocarbon composition was obtained, and the product properties and hydrocarbon composition are listed in Table 2.

[0218] Comparative Example 1

[0219] The procedure of Example 1 was followed except that in Step (1), dodecene was replaced by equal amount of hexene to obtain a hydrocarbon composition, the product properties and hydrocarbon composition of which are listed in Table 2. The viscosity of the hydrocarbon composition was adjusted by adding 0.5 wt% of a viscosity index improver to obtain a hydrocarbon composition with a kinematic viscosity at 100°C of 28 mm 13 The NP / IP mass ratio measured by C-NMR was 3.7.

[0220] Comparative Example 2

[0221] The procedure of Example 1 was followed except that in Step (1), dodecene was replaced by equal amount of eicosene to obtain a hydrocarbon composition, the product properties and hydrocarbon composition of which are listed in Table 2. The viscosity of the hydrocarbon composition was adjusted by adding 0.5 wt% of a viscosity index improver to obtain a hydrocarbon composition with a kinematic viscosity at 100°C of 28 mm 13 The NP / IP mass ratio measured by C-NMR was 7.1.

[0222] Comparative Example 3

[0223] The procedure of Example 1 was followed except that in Step (1), aromatic oil I was replaced by equal amount of aromatic oil IV to obtain a hydrocarbon composition, the product properties and hydrocarbon composition of which are listed in Table 2.

[0224] Table 1. Properties and composition of aromatic oils

[0225] As can be seen from the results in Table 2, the hydrocarbon composition according to the present application has excellent physical and chemical properties, a kinematic viscosity at 100°C of no less than 28 mm 2 / s, and the viscosity can be adjusted, a viscosity index of no less than 95, a pour point of no higher than -20°C, and excellent low-temperature flow performance and high oxidation stability.

[0226] As can be seen from the results in Table 2, the hydrocarbon composition according to the present application has excellent physical and chemical properties, a kinematic viscosity at 100°C of no less than 28 mm

[0227] Example 8

[0228] The hydrocarbon composition of Example 1 was blended with a hydroprocessed mineral oil to obtain a blended oil 1, the properties of the hydroprocessed mineral oil are shown in Table 3, the mass ratio of the high viscosity base oil to the hydroprocessed mineral oil was 15:85, the properties of the blended oil 1 are shown in Table 4.

[0229] Comparative Example 4

[0230] A conventional high viscosity base oil was blended with a hydroprocessed mineral oil to obtain a blended oil 2, the properties of the conventional high viscosity base oil are shown in Table 3, the mass ratio of the conventional high viscosity base oil to the hydroprocessed mineral oil was 15:85, the properties of the blended oil 2 are shown in Table 4.

[0231] Table 3. Properties of hydrogenated mineral oil and conventional high viscosity base oil

[0232] Table 4. Properties of blended oil

[0233] From the combination of Example 8 and Comparative Example 4, compared with Example 8, Comparative Example 4 uses conventional high viscosity base oil and hydrogenated mineral oil for blending, the viscosity index of the obtained blended oil product is less than that of the hydrogenated mineral oil, and the pour point is high, which cannot meet the use requirements under extreme low temperature conditions.

[0234] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application, and all fall within the protection scope of the present application.

Claims

1. A hydrocarbon composition, characterized in that, The hydrocarbon composition comprises bicyclic aromatic hydrocarbons and tricyclic and higher aromatic hydrocarbons, wherein the total aromatic hydrocarbon content is ≥ 90 wt%, the bicyclic aromatic hydrocarbon content is 60-100 wt%, preferably 80-95 wt%, and the tricyclic and higher aromatic hydrocarbon content is 0-40 wt%, preferably 3-20 wt%, based on the total weight of the hydrocarbon composition, wherein the aromatic hydrocarbons have a carbon number of 35-80, preferably 45-75, and the mass ratio of normal paraffin carbon to isoparaffin carbon NP / IP is 4.0-6.8, preferably 5.5-6.

5.

2. The hydrocarbon composition of claim 1, wherein, The aromatic hydrocarbons have 2-8 alkyl side chains, wherein the number of alkyl side chains having a carbon number of 8-18, preferably 10-16, is 3-5, preferably 4-5.

3. The hydrocarbon composition according to claim 1 or 2, characterized in that, The aromatic hydrocarbons have an aromatic carbon content of 6%-45%, preferably 12%-25%, and a paraffin carbon content of 55%-94%, preferably 75%-88%.

4. The hydrocarbon composition according to any one of the preceding claims, characterized in that, The bicyclic aromatic hydrocarbon comprises a naphthalene derivative of the following formula (I), wherein m≥0, n≥0, and 5≤m+n≤15, preferably 7≤m+n≤13; 0≤i≤4, preferably 0≤i≤1; 3≤a≤5, 0≤b≤3, preferably 4≤a≤5, 1≤b≤2; Preferably, the content of the naphthalene derivative is 40-98 wt%, preferably 60-80 wt%, based on the total weight of the hydrocarbon composition.

5. The hydrocarbon composition according to any one of the preceding claims, characterized in that, The hydrocarbon composition has the following properties: 100°C kinematic viscosity ≥ 22 mm 2 / s, preferably 28-44 mm 2 / s; a viscosity index ≥ 95, preferably 95-115; a pour point ≤ -20°C, preferably -20 to -32°C; an oxidation stability ≥ 190 min, preferably ≥ 250 min; a distillation range of 500-800°C.

6. The method of producing a hydrocarbon composition according to any one of claims 1 to 5, characterized in that, The method comprises: (1) reacting an aromatic hydrocarbon oil and an olefin oil in the presence of a catalyst, and subjecting the obtained reaction product to settling separation to obtain an oil phase and a catalyst phase; (2) washing the oil phase, and subjecting the washed oil phase to distillation cutting to obtain a vacuum residue fraction, and subjecting the vacuum residue fraction to refining to obtain the hydrocarbon composition; and recovering the catalyst phase; wherein the aromatic hydrocarbon oil has a distillation range of 100-400°C, preferably 200-350°C, and the aromatic hydrocarbon content in the aromatic hydrocarbon oil is ≥ 70 wt%, preferably ≥ 80 wt%; wherein the olefin oil has a carbon number distribution of C8-C18, preferably C10-C14, and the olefin content in the olefin oil is ≥ 50 wt%, preferably ≥ 70 wt%.

7. The method of claim 6, wherein, The aromatic hydrocarbon oil is selected from at least one of catalytically cracked diesel oil, catalytically cracked heavy oil, reforming heavy aromatic oil, ethylene tar and coal tar, preferably catalytically cracked diesel oil; and / or, The aromatic hydrocarbons in the aromatic hydrocarbon oil are selected from at least one of bicyclic and tricyclic aromatic hydrocarbon compounds having a boiling point of 100-350°C, preferably at least one of methyl naphthalene, dimethyl naphthalene, ethyl naphthalene, biphenyl, acenaphthene and fluorene, more preferably methyl naphthalene and / or dimethyl naphthalene; and / or, The olefins in the olefin oil are linear α-olefins and / or internal olefins.

8. The method of claim 6 or 7, wherein, The mass ratio of the aromatic hydrocarbon oil to the olefin oil is 1:0.5-10, preferably 1:1-5; and / or, The mass ratio of the aromatic hydrocarbon oil to the catalyst is 1:0.01-1, preferably 1:0.05-0.

3.

9. The method of any one of claims 6-8, wherein, The catalyst is selected from liquid acids and / or organic acids containing metal halides. Preferably, the liquid acid is selected from at least one of concentrated sulfuric acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, perchloric acid and hydrobromic acid, preferably at least one selected from concentrated sulfuric acid, trifluoromethanesulfonic acid and fluorosulfonic acid; Preferably, the metal halide is selected from at least one of boron tribromide, boron trichloride, aluminum trichloride, boron trifluoride, iron trichloride and zinc trichloride, preferably boron tribromide and / or aluminum trichloride; Preferably, the organic acid is selected from methanesulfonic acid and / or ethanesulfonic acid; Preferably, the content of metal halide is 1-30wt%, preferably 5-20wt%, based on the total weight of the metal halide-containing organic acid.

10. The method according to any one of claims 6-9, wherein, In step (1), The temperature of the reaction is 20-80℃, preferably 30-60℃; the time of the reaction is 5-300min, preferably 30-90min; Preferably, the settling comprises: distributing the obtained reaction product in multiple settling separation tanks for settling; Preferably, the settling time of the reaction product in each settling separation tank is 5-120min, preferably 30-60min, relative to a 20L settling separation tank.

11. The method of any one of claims 6-10, wherein, In step (2), The mass ratio of the oil phase to the washing liquid is 1:0.5-5, preferably 1:1-2; preferably, the acid value of the oil phase after washing is ≤0.05mgKOH / g; preferably, the washing liquid is selected from water and / or metal alkali liquid, preferably water; Preferably, the cutting temperature of the distillation cutting is ≥500℃, preferably ≥520℃; Preferably, the refining is selected from at least one of clay refining, hydrorefining and molecular sieve adsorption refining, preferably clay refining; preferably, the conditions of the clay refining comprise: the clay addition amount is 1-10wt%, preferably 2-5wt%, of the vacuum residue fraction; the refining temperature is 50-200℃, preferably 80-150℃; the refining time is 5-120min, preferably 20-60min; Preferably, the method of catalyst recovery is selected from at least one of atmospheric distillation, vacuum distillation and vacuum rectification, preferably vacuum rectification.

12. Use of a hydrocarbon composition according to any one of claims 1-5 or produced by the method according to any one of claims 6-11 as a high viscosity base oil, preferably a bright stock, or as a blending additive.

13. A blended oil composition comprising a hydrocarbon composition according to any one of claims 1-5 or produced by the method according to any one of claims 6-11 as a high viscosity base oil.

14. The blended oil composition according to claim 13, further comprising at least one low viscosity base oil having a kinematic viscosity at 100°C of 6-12 mm2 / s, a viscosity index > 95, a saturated hydrocarbon content > 92%, a pour point < -12°C. 2 / s, a viscosity index > 95, a saturated hydrocarbon content > 92%, a pour point < -12°C. Preferably, the low viscosity base oil is selected from hydrogenated mineral oil, PAO base oil and combinations thereof; Preferably, the content of the high viscosity base oil is 5-50wt%, and the content of the low viscosity base oil is 50-95wt%, relative to the total weight of the blended oil composition.

15. The blended oil composition according to claim 13 or 14 having a kinematic viscosity at 100°C of 7 to 22 mm2 / s and a pour point of < -15°C. 2 / s, a pour point of < -15°C.

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