CN120818377A

CN120818377A - Preparation method of bright oil and bright oil

Info

Publication number: CN120818377A
Application number: CN202410449046.5A
Authority: CN
Inventors: 彭东岳; 李云鹏; 石利斌; 管翠诗; 王玉章; 丁洛
Original assignee: Sinopec Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Current assignee: Sinopec Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2024-04-15
Filing date: 2024-04-15
Publication date: 2025-10-21
Also published as: WO2025218650A1

Abstract

The invention relates to the technical field of petrochemical industry, and discloses a preparation method of bright stock and the bright stock. The preparation method of the bright stock comprises the steps of (1) reacting aromatic hydrocarbon oil with olefin oil in the presence of a catalyst, settling and separating an obtained reaction product to obtain an oil phase and a catalyst phase, (2) washing the oil phase, performing distillation and cutting on the washed oil phase, refining the obtained vacuum residue fraction to obtain the bright stock, and recycling the catalyst phase, wherein the distillation range of the aromatic hydrocarbon oil is 100-400 ℃, the aromatic hydrocarbon content in the aromatic hydrocarbon oil is more than or equal to 70wt%, the olefin carbon number distribution in the olefin oil is C8-C20, and the olefin content in the olefin oil is more than or equal to 50wt%. The method can continuously produce the bright stock, simplify the process flow, expand the raw material sources of the bright stock, and the obtained bright stock meets the requirements of high viscosity and high viscosity index.

Description

Preparation method of bright stock and bright stock

Technical Field

The invention relates to the technical field of petrochemical industry, in particular to a preparation method of bright stock and the bright stock.

Background

The bright stock is a lubricating oil base oil with high viscosity and high viscosity index, is used for adjusting the high-temperature viscosity of lubricating oil products, and is widely applied to the fields of industrial oil, heavy internal combustion engine oil and the like, such as heavy duty gears, hydraulic presses, heavy duty elevators, ship engines and the like.

At present, the raw material for producing bright stock is deasphalted oil obtained by deasphalting vacuum residuum with propane, and the production technology comprises the traditional process, the full hydrogen process and the hydrogenation and traditional combined process. The traditional process adopts a physical separation process route of solvent deasphalting, solvent refining and solvent dewaxing, has mature technical route and strong raw material applicability, but has the defects of low product yield, low product quality and the like. The full hydrogen route adopts the hydrofining-isodewaxing-hydrofining process to convert long side chain cycloalkanes in the raw materials into low pour point isomerous side chain alkanes, thereby realizing higher bright oil yield.

CN104449841a discloses a method for producing low pour point high viscosity bright stock by using perhydro process, which uses naphthenic base light deasphalted oil as raw material to produce high viscosity bright stock product, but naphthenic base crude oil resource is needed, and the viscosity index of the product is low. The combined process adopts a solvent deasphalting-solvent refining-hydrotreating-solvent dewaxing combined process to prepare the bright stock, and the process has strong applicability to raw materials, meets the product viscosity requirement, but has longer process flow.

CN101768470a discloses a preparation method of bright stock, which uses vacuum residuum as raw material, carries out solvent deasphalting to obtain refined oil containing wax, then carries out hydrotreating, solvent dewaxing, catalytic dewaxing, hydrofining and other treatments, and carries out gas stripping on the obtained product to obtain bright stock product, wherein the viscosity of the bright stock product is not lower than 30mm ²/s at 100 ℃ and the viscosity index is not lower than 100, but the comprehensive yield is lower.

With the development of industrial machinery, the application scene of bright oil is continuously amplified, and the performance index requirement is continuously improved. However, the bright stock product has complex composition structure, long process flow, and the quality of the product depends on the characteristics of crude oil, so that the proper crude oil resources are scarce. Although bright stock substitutes such as Polyisobutylene (PIB) and Polyalphaolefin (PAO) can meet the viscosity and viscosity index requirements, they are relatively expensive and have poor compatibility with additives, and are difficult to replace traditional bright stock on a large scale. On the molecular scale, the high viscosity, high viscosity index and good solubility of the bright stock are reflected by large molecular weight, long alkyl side chains and a certain aromatic ring structure. Such compounds can be synthesized directionally by alkylation of aromatic hydrocarbons with olefins.

CN109824467a discloses a method for preparing polyalkylnaphthalene by using ionic liquid as catalyst, using metal halide ionic liquid as catalyst, using naphthalene and alpha-olefin (C6 or C8) as raw material, making the naphthalene, olefin and catalyst undergo the process of polyalkylation reaction in high-purity argon atmosphere, and making reactant undergo the process of distillation treatment so as to obtain polyalkylnaphthalene compound, but the viscosity and viscosity index of said alkyl naphthalene base oil are low, and can not be used as bright stock product, and the ionic liquid catalyst is difficult to recover.

CN114507110a discloses a method for producing alkyl naphthalene, which uses trifluoromethane sulfonic acid and/or methane sulfonic acid as catalyst, naphthalene and olefin as raw materials, and mixes naphthalene and C5C25 alpha olefin with catalyst to react, and extracts the reactant to obtain alkyl naphthalene product, but the product has same low viscosity and viscosity index, and cannot be used as bright stock product. Unlike existing processes for preparing monoalkylbenzene or alkylnaphthalene, the synthesis of bright stock requires the synthesis of compounds having multiple long alkyl side chains.

Therefore, aiming at the bright stock product with high performance, the development of the continuous synthesis process is realized, and the method has important market application prospect.

Disclosure of Invention

The invention aims to solve the problems of long process flow, low viscosity and low viscosity index of the synthetic bright stock in the prior art, and provides a preparation method of the bright stock and the bright stock.

In order to achieve the above object, a first aspect of the present invention provides a method for preparing bright stock, wherein the method comprises:

(1) In the presence of a catalyst, carrying out reaction on aromatic hydrocarbon oil and olefin oil, and carrying out sedimentation separation on the obtained reaction product to obtain an oil phase and a catalyst phase;

(2) Washing the oil phase, distilling and cutting the washed oil phase, and refining the obtained vacuum residuum fraction to obtain bright stock;

Wherein the distillation range of the aromatic hydrocarbon oil is 100-400 ℃, and the aromatic hydrocarbon content in the aromatic hydrocarbon oil is more than or equal to 70wt%;

wherein the distribution of the carbon number of olefin in the olefin oil is C8-C20, and the content of olefin in the olefin oil is more than or equal to 50wt%.

Preferably, the mass ratio of the aromatic hydrocarbon oil to the olefin oil is 1:0.5-10.

In a second aspect, the present invention provides a bright stock prepared by the method of the first aspect.

Through the technical scheme, the invention has the following beneficial effects:

(1) According to the preparation method of the bright stock, the aromatic hydrocarbon oil with high aromatic hydrocarbon content and the olefin oil with high olefin content and carbon number distributed in C8-C20 are used as raw materials, the bright stock is continuously produced, the process flow is simplified, the raw material source of the bright stock is expanded, and the obtained bright stock meets the requirements of high viscosity and high viscosity index;

(2) The bright stock product obtained by the preparation method provided by the invention has excellent physicochemical properties, the telecontrol viscosity at 100 ℃ is not lower than 28mm ²/s, the viscosity is adjustable, the viscosity index is not lower than 95, the pour point is not higher than-9 ℃, and the bright stock product has good low-temperature flow property and high oxidation stability.

Drawings

The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention.

Fig. 1 is a flow chart of a preparation method of bright stock provided by the invention.

Description of the reference numerals

I. synthetic reaction kettle II, sedimentation separation kettle III and oil phase washing tower

IV, oil phase distillation column V, vacuum residuum refining device VI, catalyst recovery column

1. Aromatic hydrocarbon feed inlet 2, olefin feed inlet 3, catalyst inlet

4. Catalyst-containing synthetic oil outlet 5, oil phase outlet 6, and catalyst phase outlet

7. Washing liquid inlet 8, washing oil phase outlet 9, waste washing liquid outlet

10. Oil phase light fraction outlet 11, oil phase vacuum residue outlet 12, bright stock outlet

13. Recycle catalyst outlet 14, waste oil outlet

Detailed Description

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

The first aspect of the invention provides a preparation method of bright stock, wherein the method comprises the following steps:

(2) Washing the oil phase, distilling and cutting the washed oil phase, refining the obtained vacuum residue fraction to obtain bright stock, and recovering the catalyst phase.

In the method, the bright stock with high viscosity, high viscosity index and low pour point is obtained by taking the aromatic stock with high aromatic content and the olefin stock with high olefin content and carbon number distributed in C8-C20 as raw materials and adopting a continuous synthesis process route, and the yield of the obtained bright stock is higher.

In some embodiments of the present invention, the aromatic hydrocarbon oil preferably has a distillation range of 100-400 ℃, for example, may be 100 ℃, 150 ℃,200 ℃, 250 ℃, 300 ℃, 350 ℃,400 ℃ and any value in the range of any two values, more preferably 200-350 ℃, and the aromatic hydrocarbon oil preferably has an aromatic hydrocarbon content of 70wt%, for example, may be 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, and any value in the range of any two values, more preferably 80wt%. In the invention, the aromatic hydrocarbon oil has a wider distillation range and a higher aromatic hydrocarbon content.

In the present invention, the type of aromatic oil is not particularly limited, and various aromatic oils known in the art may be used as long as the above-mentioned distillation range and aromatic content are satisfied, and the aromatic oil is an aromatic-rich oil, preferably at least one selected from the group consisting of catalytic cracked diesel oil, catalytic cracked cycle oil, reformed heavy aromatic oil, ethylene tar and coal tar, and more preferably catalytic cracked diesel oil.

In the present invention, if the distillation range of the aromatic hydrocarbon-rich oil does not satisfy the distillation range of the aromatic hydrocarbon oil, distillation and cutting treatment are performed to obtain the aromatic hydrocarbon oil rich in at least one of monocyclic aromatic hydrocarbon, bicyclic aromatic hydrocarbon and tricyclic aromatic hydrocarbon. The method and conditions for distillative cutting may be those well known in the art and will not be described here.

In the present invention, the type of 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 monocyclic, bicyclic and tricyclic 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 toluene, xylene, dodecylbenzene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, biphenyl, acenaphthylene, fluorenes and hexylbenzene, and still more preferably, methylnaphthalene and/or dimethylnaphthalene.

In some embodiments of the present invention, the olefin content in the olefin oil is preferably not less than 50wt%, for example, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, and any value in the range of any two values, more preferably not less than 70wt%, and the olefin carbon number distribution in the olefin oil is C8-C20, for example, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, and any value in the range of any two values, more preferably C10-C14. The structure of the olefin in the olefin oil of the present invention is not particularly limited as long as the carbon number distribution satisfies the above range, and preferably the olefin in the olefin oil is a linear alpha-olefin and/or an internal olefin. The olefin oil has a relatively high olefin content, and the olefin in the olefin oil has a suitable carbon chain length.

In the invention, the aromatic hydrocarbon oil with high aromatic hydrocarbon content and the olefin oil with high olefin content which meet the requirements are adopted as raw materials, thereby being beneficial to ensuring the synthetic reaction of aromatic hydrocarbon and olefin, and the obtained bright stock product meets the requirements of high viscosity and high viscosity index.

In the present invention, the amount of the aromatic oil and the olefin oil is selected within a wide range, preferably, the mass ratio of the aromatic oil to the olefin oil is 1:0.5-10, for example, may be any value in the range of 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 two values, preferably, 1:1-5. In the invention, the mass ratio of the aromatic oil to the olefin oil is controlled in the range, which is not only beneficial to synthesizing a product with a plurality of alkyl long side chains and meeting the requirements of high viscosity and high viscosity index of bright stock, but also beneficial to fully reacting the aromatic oil with the olefin oil, reducing the residual raw materials of the aromatic oil and the olefin oil and reducing side reactions such as olefin polymerization or aromatic polymerization.

In the present invention, the mass ratio of the aromatic oil to the catalyst has a wide Fan Ze range, preferably, the mass ratio of the aromatic oil to the catalyst is 1:0.01-1, for example, may be 1:0.01, 1:0.05, 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 in the range of any two values, preferably, 1:0.05-0.3. In the invention, the mass ratio of the aromatic oil to the catalyst is controlled in the range, which is favorable for fully catalyzing the reaction of the aromatic oil and the olefin, and simultaneously avoids excessive catalyst dosage and reduces side reactions.

In the present invention, the catalyst may be various catalysts conventionally used in the art for the reaction of aromatic hydrocarbon oil and olefin oil. Preferably, the catalyst is selected from liquid acids and/or organic acids containing metal halides.

In the present invention, the kind of the liquid acid is not particularly limited, and any liquid acid known in the art may be used in the present invention. Preferably, the liquid acid is selected from at least one of concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, perchloric acid, and hydrobromic acid, more preferably from at least one of concentrated sulfuric acid, trifluoromethanesulfonic acid, and methanesulfonic acid.

In the present invention, the kind of the metal halide is not particularly limited, and any metal halide known in the art may be used in the present invention. Preferably, the metal halide is selected from at least one of boron tribromide, boron trichloride, aluminum trichloride, boron trifluoride, iron trichloride and zinc trichloride, more preferably from boron tribromide and/or aluminum trichloride.

In the present invention, the type of the organic acid is not particularly limited, and various organic substances known in the art for providing acidity may be used. Preferably, the organic acid is selected from methane sulphonic acid and/or ethane sulphonic acid, more preferably methane sulphonic acid.

In the present invention, the concentration of the organic acid containing the metal halide has a wide selection range. Preferably, the metal halide is present in an amount of 1 to 30wt%, preferably 5 to 20wt%, based on the total amount of the metal halide-containing organic acid.

In the invention, in the step (1), aromatic hydrocarbon oil and olefin oil react in the presence of a catalyst to obtain an oil phase containing the catalyst as a reaction product, and the reaction product is subjected to sedimentation separation to obtain an upper-layer oil phase and a lower-layer catalyst phase. The aromatic hydrocarbon oil, the olefin oil and the catalyst are contacted in a synthesis reaction kettle for reaction. The reaction conditions are not particularly limited, and preferably the reaction pressure is normal pressure, the reaction temperature is 20 to 100 ℃, the reaction time is 5 to 300 minutes, more preferably the reaction temperature is 30 to 60 ℃, and the reaction time is 30 to 90 minutes. The reaction may be carried out in a synthesis reaction vessel. In the invention, the temperature and time of the reaction are controlled in the above range, which is more favorable for the full synthetic reaction of aromatic hydrocarbon and olefin, reduces side reaction, and simultaneously avoids unnecessary energy consumption and operation time.

In the invention, the oil phase reaction product containing the catalyst obtained by the reaction is introduced into a sedimentation separation device for sedimentation separation. The sedimentation separation device may be a sedimentation separation device conventionally used in the art, and preferably, the sedimentation separation device is provided with a plurality of sedimentation separation kettles, which is favorable for sedimentation of the catalyst phase in the oil phase containing the catalyst by gravity, thereby separating an upper layer oil phase and a lower layer catalyst phase. The number of the sedimentation separation tanks is not particularly limited as long as the oil phase reaction product containing the catalyst in total obtained by the reaction can be introduced into the sedimentation separation tanks for sedimentation.

In some embodiments of the invention, preferably, the settling comprises distributing the resulting reaction product in a plurality of settling separation tanks for settling. In the invention, the reaction speed of the aromatic hydrocarbon oil and the olefin oil is higher, the obtained reaction products are required to be introduced into different sedimentation separation kettles according to the sequence of synthesis for sedimentation separation, specifically, when the reaction products in the sedimentation separation kettles reach 2/3 of the volume of the sedimentation separation kettles, the feeding is stopped, and the rest reaction products are introduced into the next sedimentation separation kettles, so that sedimentation is carried out according to the method. The sedimentation mode of the plurality of sedimentation separation kettles is beneficial to improving the sedimentation separation efficiency.

In the present invention, the time for the sedimentation separation is not particularly limited as long as the oil phase and the catalyst phase in the reaction product in the sedimentation tank can be sufficiently layered, and the oil phase and the catalyst phase are obtained after separation. Preferably, the time for the reactants to settle in each of the settling separation tanks is from 5 to 120 minutes, preferably from 30 to 60 minutes, relative to a 20L settling separation tank.

In the present invention, in the step (2), the oil phase obtained by the sedimentation separation treatment is contacted with a detergent to conduct a washing treatment for removing the acid in the oil phase, and the washing may be conducted in an oil phase washing column. In the present invention, the amounts of the oil phase and the washing liquid used have a wide selection range. Preferably, the mass ratio of the oil phase to the washing liquid is 1:0.5-5, more preferably 1:1-2.

In some embodiments of the invention, preferably, the acid value of the oil phase after washing is less than or equal to 0.05mgKOH/g. In the present invention, the acid value of the oil phase is measured according to GB/T7304 standard method.

In the present invention, the kind of the washing liquid is not particularly limited, and various washing liquids conventionally used in the art for washing an oil phase can be used. Preferably, the washing liquid is selected from water and/or a metal lye, more preferably water.

In the invention, the washed oil phase is subjected to distillation cutting treatment, and light components are separated by utilizing the difference of the volatilities of the components to obtain vacuum residuum fraction. The distillation range of the vacuum residuum fraction of the present invention is not particularly limited. Preferably, the cutting temperature of the distillative cutting is equal to or higher than 500 ℃, more preferably equal to or higher than 520 ℃. The distillative cutting treatment according to the present invention may be carried out in a distillative cutting tower.

In the present invention, the vacuum residuum fraction obtained by the distillation and cleavage is purified, and the method of purification is not particularly limited and may be any known method of purification in the art. Preferably, the purification is at least one selected from clay purification, hydrofinishing, and molecular sieve adsorption purification, more preferably clay purification.

In the present invention, preferably, the clay refining method comprises contacting the vacuum residue fraction with clay adsorbent to perform clay refining, and separating to obtain bright stock and waste adsorbent.

In the invention, the contact of the vacuum residue and the clay adsorbent can be performed in a vacuum residue refining device, and refining is performed under clay refining conditions to remove part of byproducts, prevent the byproduct residues from influencing the product properties, and obtain the bright stock after the oil is separated from the adsorbent.

In the present invention, the clay adsorbent is preferably a high-quality bentonite having a montmorillonite content of more than 85% by weight, and more preferably an activated clay.

In the present invention, the amount of clay used has a wide range of options. Preferably, clay is added in an amount of 1 to 10wt%, more preferably 2 to 5wt%, based on the total mass of the vacuum residuum fraction.

In some embodiments of the present invention, the clay refining conditions preferably include a refining temperature of 50-200 ℃, more preferably 80-150 ℃, and a refining time of 5-120min, more preferably 20-60min.

In the invention, the contact mode of the clay adsorbent and the vacuum residue fraction can be mixing, the mixing mode can adopt a screw conveyor for circularly stirring and mixing, or can adopt a stirring paddle for stirring and mixing, and the solid-liquid mixing belongs to the conventional technology and is not repeated here.

In the present invention, the manner of separating the adsorbent after the vacuum residuum fraction is contacted with the adsorbent to obtain bright stock is usually solid-liquid separation, and the solid-liquid separation can be performed by a conventional solid-liquid separation manner in the art, for example, natural sedimentation, filtration separation and the like. The solid-liquid separation method can be performed by adopting the prior art, and is not described herein.

In the present invention, the method of recovering a catalyst may employ a method of recovering a catalyst which is conventional in the art. Preferably, the method for recovering the catalyst is selected from at least one of atmospheric distillation, vacuum distillation and vacuum distillation, more preferably vacuum distillation.

In the present invention, the reduced pressure distillation is employed for reducing the recovery temperature and improving the recovery efficiency, and the conditions of the reduced pressure distillation are not particularly limited, and may be conditions of reduced pressure distillation conventional in the art, for example, the temperature of reduced pressure distillation is 50 to 300 ℃, and the pressure of reduced pressure distillation is 100 to 100000Pa.

In the present invention, the recovery conditions of the recovery catalyst by vacuum distillation are related to the kind of the catalyst. Preferably, when trifluoro methane sulfonic acid is used as a catalyst phase, the temperature of the decompression rectification is 180-200 ℃ and the pressure is 30000-50000Pa, when concentrated sulfuric acid is used as the catalyst phase, the temperature of the decompression rectification is 280-300 ℃ and the pressure is 5000-20000Pa, and when methane sulfonic acid is used as the catalyst phase, the temperature of the decompression rectification is 200-240 ℃ and the pressure is 5000-20000Pa. In the present invention, when the catalyst is used, the conditions for vacuum distillation are controlled within the above-mentioned ranges, which is advantageous for improving the recovery rate of the catalyst.

In the present invention, the pressure of the reduced pressure rectification refers to absolute pressure, unless otherwise specified.

In a second aspect, the present invention provides bright stock prepared by the method of the first aspect.

In some embodiments of the invention, it is preferred that the bright stock has an kinematic viscosity at 100 ℃ of greater than or equal to 28mm ²/s, more preferably 28-44mm ²/s, a viscosity index of greater than or equal to 95, more preferably 95-115, and a pour point of less than or equal to-9 ℃, more preferably from-12 to-32 ℃. The bright stock obtained by the method for preparing the bright stock provided by the invention has the advantages of high viscosity index, low pour point, good low-temperature fluidity, high oxidation stability and higher yield of the bright stock, and the telecontrol viscosity meets the requirements.

In the invention, the kinematic viscosity is measured according to a GB/T265 standard method, the pour point parameter is measured according to a GB/T3535-2008 standard method, and the viscosity index is measured according to a GB/T1995 standard method.

In a preferred embodiment of the present invention, the preparation method of the bright stock includes:

(1) In the presence of liquid acid and/or an organic acid catalyst containing metal halide, carrying out reaction on aromatic oil and olefin oil according to the mass ratio of 1:0.5-10, and carrying out sedimentation separation on the obtained reaction product to obtain an oil phase and a catalyst phase, wherein the mass ratio of the aromatic oil to the catalyst is 1:0.01-1;

(2) Washing the oil phase, distilling and cutting the washed oil phase, and refining the obtained vacuum residue fraction to obtain bright stock, and recovering the catalyst phase, wherein the acid value of the washed oil phase is less than or equal to 0.05mgKOH/g;

The preparation method of the bright stock provided by the invention is further described in detail by means of fig. 1.

As shown in figure 1, aromatic oil, olefin oil and catalyst respectively enter a synthesis reaction kettle I through an aromatic raw material inlet 1, an olefin raw material inlet 2 and a catalyst inlet 3 for reaction, the obtained reaction product enters a sedimentation separation kettle II through a catalyst-containing synthetic oil outlet 4 for sedimentation separation, an upper-layer oil phase and a lower-layer catalyst phase are obtained through sedimentation separation, the oil phase enters an oil phase washing tower III through an oil phase outlet 5 for washing, washing liquid is introduced into the oil phase washing tower III through a washing liquid inlet 7, the washed oil phase enters an oil phase distillation tower IV through a washing oil phase outlet 8 for distillation cutting, the washed waste washing liquid is discharged through a waste washing liquid outlet 9 for liquid waste treatment, the light fraction after distillation cutting treatment is discharged through an oil phase light fraction outlet 10, the oil phase vacuum residue fraction collected through distillation cutting treatment enters a vacuum residue outlet 11 for refining through a vacuum residue refining device V for refining, the lower-layer catalyst phase obtained through sedimentation separation enters a catalyst phase outlet 6 for distillation recovery tower VI for distillation, the catalyst is discharged through a catalyst phase outlet 13 for circulation, and the catalyst is discharged through a waste oil phase outlet for recycling 13 for waste liquid waste treatment.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.

The present invention will be described in detail by examples.

The main analysis method of the invention comprises the following steps:

Density parameters are measured according to the GB/T13377 standard method;

kinematic viscosity parameters are measured according to a GB/T265 standard method;

hydrocarbon composition as measured according to H/T0659 standard method;

The acid value parameter is measured according to the GB/T7304 standard method;

pour point parameters were measured according to GB/T3535-2008 standard methods;

viscosity index is measured and calculated according to GB/T1995 standard method;

Oxidation stability (rotaxane) was measured according to SH/T0193 standard method.

The main raw materials and sources of the invention are as follows:

the properties and compositions of aromatic oil I, aromatic oil II, and aromatic oil IV used in the following examples and comparative examples are shown in table 1;

the aromatic hydrocarbon oil I is catalytic cracking heavy diesel oil, which is taken from a catalytic cracking device of a refinery, and the diesel oil fraction is 200-350 ℃;

The aromatic oil II is catalytic cracking cycle oil, which is obtained from a catalytic cracking device of a refinery, the cycle oil fraction is 250-450 ℃, the cycle oil with the fraction of 250-350 ℃ is obtained through distillation and cutting, and the cycle oil after distillation and cutting is the aromatic oil II;

aromatic oil III, methylnaphthalene, aromatic content 98wt%, available from Shanghai Ala Biochemical technology Co., ltd;

the aromatic oil IV is catalytic cracking gasoline, which is obtained from a catalytic cracking device of a refinery and is distilled and cut to obtain gasoline with the fraction of 80-100 ℃, and the distilled and cut gasoline is the aromatic oil IV;

Olefin oil I, dodecene with an olefin content of 99.5wt%, available from Shanghai Ala Biochemical technologies Co., ltd;

tetradecene, with an olefin content of 99.5wt%, is available from Shanghai Ala Latin Biochemical technologies Co., ltd;

The liquid acid catalyst, namely trifluoro methane sulfonic acid and concentrated sulfuric acid, is purchased from Shanghai Ala Biochemical technology Co., ltd;

metal halide catalyst, boron tribromide, available from Shanghai Ala Biochemical technologies Co., ltd;

acid clay available from Huang Shanbai Yue Huoxing clay limited.

Example 1

(1) Continuously adding aromatic oil I, dodecene and trifluoromethanesulfonic acid into a synthesis reaction kettle according to the feed amount of the aromatic oil I being 100g/min, the feed amount of dodecene being 300g/min and the feed amount of trifluoromethanesulfonic acid being 15g/min, stirring and mixing, and reacting for 60min at the temperature of 50 ℃;

(2) Continuously introducing the reaction product obtained in the step (1) into 2 sedimentation separation kettles with the volume of 20L, stopping feeding until the liquid level of the sedimentation separation kettles reaches 2/3 of the height of the kettles, and settling for 30min to obtain an upper oil phase and a lower catalyst phase;

(3) Introducing the upper oil phase into the lower part of a washing tower, introducing detergent water from the upper part of the washing tower, wherein the mass ratio of the oil phase to the water is 1:2, and the acid value of the washed oil phase is 0.04mgKOH/g;

(4) Introducing the washed oil phase into a distillation cutting tower for distillation cutting to obtain vacuum residuum fraction with the temperature of more than or equal to 520 ℃;

(5) The vacuum residue fraction was refined in a clay refining apparatus with clay addition of 3wt% of the vacuum residue fraction, and refined at 120 ℃ for 60min to obtain a bright stock product, the properties of which are shown in table 2.

(6) Introducing the lower catalyst phase in the step (2) into a catalyst recovery tower, wherein the recovery temperature is 180 ℃, and the recovery rate of the triflic acid catalyst is 72.3 percent.

Example 2

(1) Continuously adding aromatic oil I, dodecene and trifluoromethanesulfonic acid into a synthesis reaction kettle according to the feed amount of the aromatic oil I being 100g/min, the feed amount of dodecene being 500g/min and the feed amount of trifluoromethanesulfonic acid being 15g/min, stirring and mixing, and reacting for 90min at the temperature of 60 ℃;

(2) Continuously introducing the reaction product obtained in the step (1) into 3 sedimentation separation kettles with the volume of 20L, stopping feeding until the liquid level of the sedimentation separation kettles reaches 2/3 of the kettle height, and settling for 60min to obtain an upper oil phase and a lower catalyst phase;

(3) Introducing the upper oil phase into the lower part of a washing tower, introducing detergent water from the upper part of the washing tower, wherein the mass ratio of the oil phase to the detergent is 1:2, and the acid value of the washed oil phase is 0.05mgKOH/g;

(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 vacuum residue fraction is refined for 60min at 150 ℃ to obtain a bright stock product, and the product properties are shown in table 2.

(6) Introducing the lower catalyst phase in the step (2) into a catalyst recovery tower, wherein the recovery temperature is 180 ℃, and the recovery rate of the triflic acid catalyst is 74.3% by distillation.

Example 3

(1) Continuously adding aromatic oil I, dodecene and concentrated sulfuric acid into a synthesis reaction kettle according to the feed amount of the aromatic oil I of 100g/min, the feed amount of dodecene of 200g/min and the feed amount of concentrated sulfuric acid of 30g/min, stirring and mixing, and reacting for 30min at the temperature of 30 ℃;

(5) The vacuum residue fraction was refined in a clay refining apparatus with clay addition of 3wt% of the vacuum residue fraction, and refined at 120 ℃ for 30min to obtain a bright stock product, the properties of which are shown in table 2.

(6) Introducing the lower catalyst phase in the step (2) into a catalyst recovery tower, wherein the recovery temperature is 300 ℃, and distilling to recover concentrated sulfuric acid catalyst, and the recovery rate is 53.1%.

Example 4

(1) Continuously adding aromatic oil I, tetradecene and methanesulfonic acid into a synthesis reaction kettle according to the feed amount of the aromatic oil II of 100g/min, the feed amount of tetradecene of 200g/min, the feed amount of methanesulfonic acid of 25g/min and the feed amount of boron tribromide of 5g/min, stirring and mixing, and reacting for 30min at 50 ℃;

(2) Continuously introducing the reaction product obtained in the step (1) into 2 sedimentation separation tanks with the volume of 20L, stopping feeding until the liquid level of the separation tanks reaches 2/3 of the tank height, and settling for 60min to obtain an upper oil phase and a lower catalyst phase;

(3) Introducing the upper oil phase into the lower part of a washing tower, introducing detergent water from the upper part of the washing tower, wherein the mass ratio of the oil phase to the detergent is 1:2, and the acid value of the washed oil phase is 0.04mgKOH/g;

(5) Introducing the vacuum residue fraction into a clay refining device for refining, wherein the clay addition amount is 5wt% of the vacuum residue fraction, and refining for 60min at 80 ℃ to obtain a bright stock product, and the product properties are shown in table 2;

(6) Introducing the lower catalyst phase in the step (2) into a catalyst recovery tower, wherein the recovery temperature is 200 ℃, and distilling to recover the mixture catalyst of the methanesulfonic acid and the boron tribromide, and the recovery rate is 83.5%.

Example 5

(1) Continuously adding aromatic oil I, tetradecene and trifluoromethanesulfonic acid into a synthesis reaction kettle according to the feed amount of the aromatic oil III of 100g/min, the feed amount of tetradecene of 100g/min and the feed amount of trifluoromethanesulfonic acid of 5g/min, stirring and mixing, and reacting for 60min at the temperature of 50 ℃;

(2) Continuously introducing the reaction product obtained in the step (1) into 1 sedimentation separation kettle with the volume of 20L, stopping feeding until the liquid level of the sedimentation separation kettle reaches 2/3 of the kettle height, and settling for 30min to obtain an upper oil phase and a lower catalyst phase;

(3) Introducing the upper oil phase into the lower part of a washing tower, introducing detergent water from the upper part of the washing tower, wherein the mass ratio of the oil phase to the detergent is 1:1, and the acid value of the washed oil phase is 0.04mgKOH/g;

(5) The vacuum residue fraction was refined in a clay refining apparatus with clay addition of 2wt% of the vacuum residue fraction, and refined at 120 ℃ for 20min to obtain a bright stock product, the properties of which are shown in table 2.

(6) Introducing the lower catalyst phase in the step (2) into a catalyst recovery tower, wherein the recovery temperature is 180 ℃, and the recovery rate of the triflic acid catalyst is 67.2% by distillation.

Example 6

The procedure of example 1 was followed except that in step (1), dodecene was replaced with octaene in equal amounts to give a bright stock product, the properties of which are shown in Table 2, and the recovery of the catalyst was 74.8%.

Example 7

The procedure of example 1 was followed, except that in step (1), dodecene was replaced with eicosane in equal amounts, to give a bright stock product, the properties of which are shown in Table 2, and the recovery of the catalyst was 76.8%.

Example 8

The procedure of example 1 was followed except that in step (1), the fed amount of trifluoromethanesulfonic acid was changed from 15g/min to 1g/min, to give a bright stock product, the properties of which are shown in Table 2, and the recovery rate of the catalyst was 32.1%.

Comparative example 1

The procedure of example 1 was followed, except that in step (1), dodecene was replaced with hexaene in equal amounts, to give a bright stock product, the properties of which are shown in Table 2, and the recovery of the catalyst was 71.2%.

Comparative example 2

The procedure of example 1 was followed, except that in step (1), equal amounts of dodecene were replaced with eicosapentaene, to give a bright stock product, the properties of which are shown in Table 2, and the recovery of the catalyst was 77.3%.

Comparative example 3

The procedure of example 1 was followed, except that in step (1), aromatic oil I was replaced with aromatic oil IV in equal amounts to give a bright stock product, the properties of which are shown in Table 2, and the recovery of the catalyst was 72.3%.

TABLE 1 Properties and compositions of aromatic oils

TABLE 2 Properties of the product

As can be seen from the results in Table 1, the bright stock product prepared by the preparation method of the bright stock has excellent physicochemical properties, the tele-movement viscosity at 100 ℃ is not lower than 28mm ²/s, the viscosity is adjustable, the viscosity index is not lower than 95, the pour point is not higher than-9 ℃, and the bright stock product has good low-temperature flow property and high oxidation stability.

As can be seen from the combination of examples 1, examples 6 to 8 and Table 1, the olefin in the olefin oil used in examples 6 and 7 is not in the preferred range provided by the present invention, and the obtained bright stock product has satisfactory properties, but the bright stock product of example 6 has a lower viscosity index and oxidation stability index, the bright stock product of example 7 has a lower viscosity and a higher pour point, and the mass ratio of the aromatic hydrocarbon oil to the catalyst in example 8 is not in the preferred range provided by the present invention, and the obtained bright stock product has a lower viscosity and a lower catalyst recovery rate, as compared with example 1.

As can be seen from the combination of example 1, comparative examples 1-3 and Table 1, the comparative example 1 does not use the olefin oil provided by the present invention, and the bright stock product has low oxidation stability and viscosity index, and cannot meet the use requirements of high-quality bright stock, the comparative example 2 does not use the olefin oil provided by the present invention, and the bright stock product has high pour point, and cannot meet the use requirements of bright stock, and the comparative example 3 does not use the aromatic oil provided by the present invention, and the obtained bright stock product has low viscosity, and cannot meet the use requirements of high-viscosity bright stock product.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims

1. A method for preparing bright stock, characterized in that the method comprises:

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

(2) washing the oil phase, distilling and cutting the washed oil phase, refining the obtained vacuum residue fraction to obtain bright oil; and recovering the catalyst phase;

Wherein, the distillation range of the aromatic oil is 100-400°C; the aromatic content in the aromatic oil is ≥70wt%;

The carbon number distribution of olefins in the olefin oil is C8-C20; and the olefin content in the olefin oil is ≥50wt%.

2. The method according to claim 1, wherein the distillation range of the aromatic oil is 200-350°C; the aromatic content in the aromatic oil is ≥80wt%;

Preferably, the aromatic oil is selected from at least one of catalytic cracking diesel, catalytic cracking recycled oil, reformed heavy aromatic oil, ethylene tar and coal tar, preferably catalytic cracking diesel;

And/or, the aromatic hydrocarbon in the aromatic oil is selected from at least one of monocyclic, bicyclic and tricyclic aromatic hydrocarbon compounds with a boiling point of 100-350°C, preferably selected from at least one of toluene, xylene, dodecylbenzene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, biphenyl, acenaphthenes, fluorenes and hexylbenzene, more preferably methylnaphthalene and/or dimethylnaphthalene.

3. The method according to claim 1 or 2, wherein the carbon number distribution of the olefins in the olefin oil is C10-C14; the olefin content in the olefin oil is ≥70wt%; and the olefins in the olefin oil are linear α-olefins and/or internal olefins.

4. The method according to any one of claims 1 to 3, wherein the mass ratio of the aromatic oil to the olefin oil is 1:0.5-10, preferably 1:1-5;

Preferably, the mass ratio of the aromatic oil to the catalyst is 1:0.01-1, preferably 1:0.05-0.3.

5. The method according to any one of claims 1 to 4, wherein the catalyst is selected from liquid acid and/or organic acid containing metal halide;

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 selected from at least one of 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, ferric chloride and zinc trichloride, preferably selected from boron tribromide and/or aluminum trichloride;

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

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

6. The method according to any one of claims 1 to 5, wherein in step (1), the reaction temperature is 20-100°C, preferably 30-60°C; the reaction time is 5-300 min, preferably 30-90 min;

Preferably, the settling comprises: distributing the obtained reaction products in a plurality of settling separation tanks for settling;

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

Preferably, 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 ≤0.05 mgKOH/g;

Preferably, the washing liquid is selected from water and/or metal alkali solution, preferably water.

7. The method according to any one of claims 1 to 6, wherein the cutting temperature of the distillation cutting is ≥500°C, preferably ≥520°C;

Preferably, the refining in step (2) is selected from at least one of clay refining, hydrogenation refining and molecular sieve adsorption refining, preferably clay refining;

Preferably, the conditions for refining the clay include: the amount of clay added is 1-10wt%, preferably 2-5wt% of the vacuum residue fraction; the refining temperature is 50-200°C, preferably 80-150°C; and the refining time is 5-120min, preferably 20-60min.

8. The method according to any one of claims 1 to 7, wherein in step (2), the catalyst recovery method is selected from at least one of atmospheric distillation, vacuum distillation and vacuum rectification, preferably vacuum rectification.

9. A bright stock prepared by the method according to any one of claims 1 to 8.

The bright stock according to claim 9, wherein the bright stock has a kinematic viscosity at 100°C of ≥28 mm ² /s, preferably 28-44 mm ² /s; a viscosity index of ≥95, preferably 95-115; and a pour point of ≤-9°C, preferably -12 to -32°C.