Process for the preparation of bright stock and bright stock

Abstract

The present application relates to the technical field of petroleum chemical industry, and discloses a preparation method of bright stock and the bright stock.The preparation method of the bright stock comprises the following steps: (1) reacting aromatic oil and olefin oil in the presence of a catalyst, and performing settlement separation on the obtained reaction product to obtain an oil phase and a catalyst phase; (2) performing washing on the oil phase, performing distillation cutting on the oil phase after washing, performing refining on the obtained vacuum residue fraction, and obtaining the bright stock; and recycling the catalyst phase; the distillation range of the aromatic oil is 100-400 DEG C; the content of aromatic hydrocarbon in the aromatic oil is greater than or equal to 70 wt%; the carbon number distribution of olefins in the olefin oil is C8-C20; and the content of olefins in the olefin oil is greater than or equal to 50 wt%. The method can continuously produce the bright stock, simplifies the technological process, expands the raw material source of the bright stock, and the obtained bright stock meets the requirements of high viscosity and high viscosity index.

Description

Technical Field

[0001] This invention relates to the field of petrochemical technology, specifically to a method for preparing a bright oil and the bright oil itself. Background Technology

[0002] Bright oil is a lubricating oil base oil with both high viscosity and high viscosity index. It is used to adjust the high-temperature viscosity of lubricating oil products and is widely used in industrial oils and heavy internal combustion engine oils, such as heavy-duty gears, hydraulic presses, heavy-duty elevators, and marine engines.

[0003] Currently, the feedstock for bright oil production is deasphalted oil obtained from vacuum residue after propane deasphalting. Production technologies include traditional processes, all-hydrogen processes, and a combination of hydrogenation and traditional processes. Traditional processes employ a physical separation route of solvent deasphalting-solvent refining-solvent dewaxing, a mature technology with strong feedstock applicability; however, it suffers from low product yield and poor product quality. The all-hydrogen route uses a process of hydropre-refining-isomer dewaxing-supplementary hydrorefining, converting long-chain cycloalkanes in the feedstock into low-pour-point isomeric alkanes, achieving a higher bright oil yield.

[0004] CN104449841A discloses a method for producing low pour point, high viscosity bright oil using a fully hydrogenated process. This method uses naphthenic light deasphalting oil as raw material to produce high-viscosity bright oil products, but it requires naphthenic crude oil resources and the product viscosity index is relatively low. A combined process employing solvent deasphalting-solvent refining-hydrotreating-solvent dewaxing is also disclosed. This process has strong applicability to raw materials and produces products with the required viscosity, but the process flow is relatively long.

[0005] CN101768470A discloses a method for preparing bright oil, using vacuum residue as raw material, performing solvent deasphalting to obtain wax-containing refined oil, followed by hydrotreating, solvent dewaxing, catalytic dewaxing, and hydrorefining, and then stripping the resulting product to obtain a bright oil product with a viscosity of not less than 30 mmHg at 100℃. 2 The viscosity index is not less than 100, but the overall yield is low.

[0006] With the development of industrial machinery, the application scenarios of bright oils are constantly expanding, and the performance requirements are continuously improving. However, bright oil products have complex compositions and long processing flows, and their quality depends on the characteristics of crude oil, making suitable crude oil resources relatively scarce. Although bright oil alternatives such as polyisobutylene (PIB) and polyalphaolefin (PAO) can meet the viscosity and viscosity index requirements, their prices are high, and their compatibility with additives is poor, making it difficult to replace traditional bright oils on a large scale. At the molecular scale, the high viscosity, high viscosity index, and good solubility of bright oils are reflected in their large molecular weight, the presence of long alkyl side chains, and certain aromatic ring structures. Such compounds can be synthesized directionally through the alkylation reaction of aromatics and olefins.

[0007] CN109824467A discloses a method for preparing polyalkylnaphthalenes using ionic liquid catalysis. The method uses metal halide ionic liquids as catalysts and naphthalene and α-olefins (C6 or C8) as raw materials. Naphthalene, olefins and catalysts are subjected to polyalkylation reaction in a high-purity argon atmosphere. The reactants are distilled to obtain polyalkylnaphthalene compounds. However, the viscosity and viscosity index of the alkylnaphthalene base oil are low, making it unsuitable as a bright oil product. Furthermore, the method suffers from the drawback of difficulty in recovering the ionic liquid catalyst.

[0008] CN114507110A discloses a method for producing alkylnaphthalene, using trifluoromethanesulfonic acid and / or methanesulfonic acid as catalysts, and naphthalene and olefins as raw materials. Naphthalene and C5C25 α-olefins are mixed with the catalyst and reacted. The reactants are then extracted to obtain the alkylnaphthalene product. However, this product also has low viscosity and viscosity index, making it unsuitable as a bright oil. Unlike existing processes for preparing monoalkylbenzenes or alkylnaphthalenes, the synthesis of bright oils requires the synthesis of compounds with multiple long alkyl side chains.

[0009] Therefore, the development of continuous synthesis processes for high-performance bright oil products has significant market application prospects. Summary of the Invention

[0010] The purpose of this invention is to overcome the problems of long process flow, low viscosity and low viscosity index of existing synthetic bright oils, and to provide a method for preparing bright oil and a bright oil. This method adopts a continuous synthesis process route, and the synthesized bright oil has high performance with high kinematic viscosity, high viscosity index and low pour point.

[0011] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a gloss oil, wherein the method includes:

[0012] (1) In the presence of a catalyst, aromatic oil and olefin oil are reacted, and the reaction products are separated by sedimentation to obtain an oil phase and a catalyst phase;

[0013] (2) The oil phase is washed, and the washed oil phase is distilled and cut. The vacuum residue fraction is refined to obtain bright oil; the catalyst phase is recovered.

[0014] The aromatic oil has a distillation range of 100-400℃ and an aromatic content of ≥70wt%.

[0015] The olefin oil has an olefin carbon number distribution of C8-C20 and an olefin content of ≥50wt%.

[0016] Preferably, the mass ratio of the aromatic oil to the olefin oil is 1:0.5-10.

[0017] A second aspect of the present invention provides a gloss oil prepared by the method described in the first aspect above.

[0018] Through the above technical solution, the present invention has the following beneficial effects:

[0019] (1) The method for preparing bright oil provided by the present invention uses aromatic oil with high aromatic content and olefin oil with high olefin content and carbon number distribution of C8-C20 as raw materials to continuously produce bright oil, which simplifies the process flow and expands the source of raw materials for bright oil. The obtained bright oil meets the requirements of high viscosity and high viscosity index.

[0020] (2) The method for preparing the bright oil provided by the present invention yields a bright oil product with excellent physicochemical properties, and a kinematic viscosity of not less than 28 mmHg at 100°C. 2 It has a viscosity that is adjustable, with a viscosity index of not less than 95 and a pour point of not more than -9℃, exhibiting good low-temperature flow properties and high oxidation stability. Attached Figure Description

[0021] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof.

[0022] Figure 1 This is a flowchart of the preparation method of the gloss oil provided by the present invention.

[0023] Explanation of reference numerals in the attached figures

[0024] I. Synthesis Reactor II. Sedimentation Separation Reactor III. Oil Phase Washing Tower

[0025] IV. Oil phase distillation tower; V. Vacuum residue refining unit; VI. Catalyst recovery tower

[0026] 1. Aromatic feedstock inlet; 2. Olefin feedstock inlet; 3. Catalyst inlet.

[0027] 4. Catalyst-containing synthetic oil outlet; 5. Oil phase outlet; 6. Catalyst phase outlet.

[0028] 7. Washing liquid inlet; 8. Washing oil phase outlet; 9. Waste washing liquid outlet.

[0029] 10. Oil phase light fraction outlet; 11. Oil phase vacuum residue outlet; 12. Bright oil outlet.

[0030] 13. Circulating catalyst outlet 14. Waste oil outlet Detailed Implementation

[0031] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0032] The first aspect of this invention provides a method for preparing a gloss oil, wherein the method includes:

[0033] (1) In the presence of a catalyst, aromatic oil and olefin oil are reacted, and the reaction products are separated by sedimentation to obtain an oil phase and a catalyst phase;

[0034] (2) The oil phase is washed, and the washed oil phase is distilled and cut. The vacuum residue fraction is refined to obtain bright oil; the catalyst phase is recovered.

[0035] The aromatic oil has a distillation range of 100-400℃ and an aromatic content of ≥70wt%.

[0036] The olefin oil has an olefin carbon number distribution of C8-C20 and an olefin content of ≥50wt%.

[0037] In this invention, the method uses aromatic oil with high aromatic content and olefin oil with high olefin content and carbon number distribution of C8-C20 as raw materials, and adopts a continuous synthesis process route to obtain a bright oil with high viscosity, high viscosity index and low pour point, and the yield of the bright oil is relatively high.

[0038] In some embodiments of the present invention, preferably, the aromatic oil has a distillation range of 100-400°C, for example, it can be 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, or any value within the range of any two values, more preferably 200-350°C; the aromatic oil has an aromatic content ≥70wt%, for example, it can be 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, or any value within the range of any two values, more preferably ≥80wt%. In the present invention, the aromatic oil has a wide distillation range and a high aromatic content.

[0039] In this invention, the type of aromatic oil is not particularly limited and can be any aromatic oil known in the art, as long as it meets the above-mentioned distillation range and aromatic content. The aromatic oil is an aromatic-rich oil, preferably selected from at least one of catalytic cracking diesel, catalytic cracking recycle oil, reformed heavy aromatic oil, ethylene tar and coal tar, and more preferably catalytic cracking diesel.

[0040] In this invention, if the distillation range of the aromatic oil does not meet the aforementioned distillation range range of aromatic oils, distillation cutting is required to obtain an aromatic oil rich in at least one of monocyclic aromatics, bicyclic aromatics, and tricyclic aromatics. The distillation cutting method and conditions can be those known in the art and will not be described in detail here.

[0041] In this invention, the type of aromatic hydrocarbon in the aromatic oil is not particularly limited. Preferably, the aromatic hydrocarbon in the aromatic oil is selected from at least one of monocyclic, bicyclic, and tricyclic aromatic compounds with a boiling point of 100-350℃; more preferably, the aromatic hydrocarbon in the aromatic oil is selected from at least one of toluene, xylene, dodecylbenzene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, biphenyl, acenaphthenes, fluorenes, and hexylbenzene, and even more preferably methylnaphthalene and / or dimethylnaphthalene.

[0042] In some embodiments of the present invention, preferably, the olefin content in the olefin oil is ≥50wt%, for example, it can be 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, or any value within any range of any two values, more preferably ≥70wt%; the carbon number distribution of the olefins in the olefin oil is C8-C20, for example, it can be C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, or any value within any range of any two values, more preferably C10-C14. The structure of the olefins in the olefin oil of the present invention is not particularly limited, as long as the carbon number distribution meets the above range. Preferably, the olefins in the olefin oil are straight-chain α-olefins and / or internal olefins. The olefin oil has a high olefin content, and the olefins in the olefin oil have suitable carbon chain lengths.

[0043] In this invention, using aromatic oils with high aromatic content and olefin oils with high olefin content that meet the above requirements as raw materials is beneficial to ensuring that aromatics and olefins undergo a synthesis reaction and that the resulting compound has a suitable carbon chain length. The resulting bright oil product meets the requirements of high viscosity and high viscosity index.

[0044] In this invention, the amount of aromatic oil and olefin oil used has a wide range of selection. Preferably, the mass ratio of aromatic oil to 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, or any value within any range of any two values, preferably 1:1-5. In this invention, controlling the mass ratio of aromatic oil to olefin oil within the above range is not only beneficial for synthesizing products with multiple long alkyl side chains, meeting the requirements of high viscosity and high viscosity index of bright oil, but also beneficial for the full reaction of aromatic oil and olefin oil, reducing the residue of aromatic oil and olefin oil raw materials, and reducing side reactions such as olefin polymerization or aromatic polymerization.

[0045] In this invention, the mass ratio of aromatic oil to catalyst has a wide range. Preferably, the mass ratio of aromatic oil to catalyst is 1:0.01-1, for example, it can 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, or any value within any range of two such values, preferably 1:0.05-0.3. In this invention, controlling the mass ratio of aromatic oil to catalyst within the above range is beneficial for fully catalyzing the reaction between aromatic oil and olefins, while avoiding excessive catalyst usage and reducing side reactions.

[0046] In this invention, the catalyst can be any catalyst conventionally used in the art for the reaction of aromatic oils and olefin oils. Preferably, the catalyst is selected from liquid acids and / or organic acids containing metal halides.

[0047] In this invention, the type of liquid acid is not particularly limited, and any liquid acid known in the art can be used in this 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, and more preferably from at least one of concentrated sulfuric acid, trifluoromethanesulfonic acid, and methanesulfonic acid.

[0048] In this invention, the type of metal halide is not particularly limited, and any metal halide known in the art can be used in this invention. Preferably, the metal halide is selected from at least one of boron tribromide, boron trichloride, aluminum trichloride, boron trifluoride, ferric trichloride, and zinc trichloride, more preferably from boron tribromide and / or aluminum trichloride.

[0049] In this invention, the type of organic acid is not particularly limited and can be any organic compound known in the art for providing acidity. Preferably, the organic acid is selected from methanesulfonic acid and / or ethanesulfonic acid, and more preferably methanesulfonic acid.

[0050] In this invention, the concentration of the organic acid containing metal halides has a wide range of selection. Preferably, based on the total amount of the organic acid containing metal halides, the content of metal halides is 1-30 wt%, more preferably 5-20 wt%.

[0051] In this invention, in step (1), aromatic oil and olefin oil are reacted in the presence of a catalyst to obtain an oil phase containing the catalyst as the reaction product. The reaction product is then separated by sedimentation to obtain an upper oil phase and a lower catalyst phase. The aromatic oil, olefin oil, and catalyst described in this invention react in contact in a synthesis reactor. The reaction conditions are not particularly limited; preferably, the reaction pressure is atmospheric pressure, the reaction temperature is 20-100°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 this invention, controlling the reaction temperature and time within the above ranges is more conducive to the full synthesis reaction of aromatics and olefins, reducing side reactions, and avoiding unnecessary energy consumption and operating time.

[0052] In this invention, the catalyst-containing oil phase reaction product obtained from the reaction is introduced into a sedimentation separation device for sedimentation separation. The sedimentation separation device can be a conventional sedimentation separation device used in the art. Preferably, the sedimentation separation device has multiple sedimentation separation vessels, which facilitates the use of gravity to cause the catalyst phase to settle in the catalyst-containing oil phase, thereby separating the upper oil phase and the lower catalyst phase. The number of sedimentation separation vessels is not particularly limited, as long as all the catalyst-containing oil phase reaction product obtained from the reaction can be introduced into the sedimentation separation vessels for sedimentation.

[0053] In some embodiments of the present invention, preferably, the sedimentation includes distributing the obtained reaction products in multiple sedimentation separation vessels for sedimentation. In the present invention, the aromatic oil and olefin oil react relatively quickly, and the obtained reaction products need to be introduced into different sedimentation separation vessels in the order of synthesis for sedimentation separation. Specifically, when the reaction products in the sedimentation separation vessel reach 2 / 3 of the vessel's volume, feeding is stopped, and the remaining reaction products are introduced into the next sedimentation separation vessel for sedimentation. The method of using multiple sedimentation separation vessels for sedimentation in the present invention is beneficial to improving the efficiency of sedimentation separation.

[0054] In this invention, the sedimentation separation time is not particularly limited, as long as the oil phase and catalyst phase in the reaction products in the sedimentation vessel are sufficiently separated into oil and catalyst phases. Preferably, for a 20L sedimentation vessel, the sedimentation time of the reactants in each sedimentation vessel is 5-120 min, preferably 30-60 min.

[0055] In this invention, in step (2), the oil phase obtained from the sedimentation separation process is contacted with a detergent for washing to remove acid from the oil phase. This washing can be carried out in an oil phase washing tower. In this invention, the amounts of the oil phase and the washing liquid have a wide range of selection. Preferably, the mass ratio of the oil phase to the washing liquid is 1:0.5-5, more preferably 1:1-2.

[0056] In some embodiments of the present invention, preferably, the acid value of the washed oil phase is ≤0.05 mg KOH / g. In the present invention, the acid value of the oil phase is measured according to the standard method of GB / T 7304.

[0057] In this invention, the type of washing liquid is not particularly limited, and various washing liquids conventionally used in the art for oil-phase washing can be employed. Preferably, the washing liquid is selected from water and / or metal alkaline solutions, and more preferably water.

[0058] In this invention, the washed oil phase is subjected to distillation and separation, utilizing the differences in volatility of each component to separate the lighter components, thus obtaining vacuum residue fraction. The distillation range of the vacuum residue fraction described in this invention is not particularly limited. Preferably, the distillation and separation temperature is ≥500℃, more preferably ≥520℃. The distillation and separation process described in this invention can be carried out in a distillation and separation tower.

[0059] In this invention, the vacuum residue fraction obtained from distillation is refined. The refining method is not particularly limited and can be any refining method known in the art. Preferably, the refining process is selected from at least one of clay refining, hydrorefining, and molecular sieve adsorption refining, more preferably clay refining.

[0060] In this invention, preferably, the specific method for refining the clay includes: contacting the vacuum residue oil fraction with a clay adsorbent to refine the clay, and separating the bright oil and the waste adsorbent.

[0061] In this invention, the contact between the vacuum residue oil and the clay adsorbent can be carried out in a vacuum residue oil refining unit. Refining is carried out under clay refining conditions to remove some by-products and avoid by-product residues affecting product properties. After the oil and adsorbent are separated, a bright oil is obtained.

[0062] In this invention, the clay adsorbent is preferably high-quality bentonite with a montmorillonite content of more than 85% by weight, and more preferably activated clay.

[0063] In this invention, the amount of bleaching clay used has a wide range of selection. Preferably, based on the total mass of the vacuum residue fraction, the amount of bleaching clay added is 1-10 wt%, more preferably 2-5 wt%.

[0064] In some embodiments of the present invention, preferably, the conditions for refining the clay include: a refining temperature of 50-200℃, more preferably 80-150℃; and a refining time of 5-120 min, more preferably 20-60 min.

[0065] In this invention, the contact between the clay adsorbent and the vacuum residue fraction can be achieved through mixing. The mixing method can be either a spiral conveyor for circulating stirring or a stirring paddle. Solid-liquid mixing is a conventional technique and will not be elaborated further here.

[0066] In this invention, the method of separating the adsorbent from the vacuum residue fraction after contact with the adsorbent to obtain bright oil is typically solid-liquid separation. This solid-liquid separation can employ conventional methods in the art, such as natural sedimentation and filtration. The solid-liquid separation method can be carried out using existing technology, and will not be elaborated further here.

[0067] In this invention, the method for recovering the catalyst can employ conventional catalyst recovery methods in the art. Preferably, the method for recovering the catalyst is selected from at least one of atmospheric distillation, vacuum distillation, and vacuum rectification, and more preferably vacuum rectification.

[0068] In this invention, vacuum distillation is used to lower the recovery temperature and improve the recovery efficiency. The conditions for vacuum distillation are not particularly limited and can be conventional vacuum distillation conditions in the art, such as a vacuum distillation temperature of 50-300°C and a vacuum distillation pressure of 100-100000 Pa.

[0069] In this invention, the recovery conditions for the catalyst by vacuum distillation are related to the type of catalyst. Preferably, when trifluoromethanesulfonic acid is used as the catalyst phase, the vacuum distillation temperature is 180-200℃ and the pressure is 30000-50000 Pa; when concentrated sulfuric acid is used as the catalyst phase, the vacuum distillation temperature is 280-300℃ and the pressure is 5000-20000 Pa; when methanesulfonic acid is used as the catalyst phase, the vacuum distillation temperature is 200-240℃ and the pressure is 5000-20000 Pa. In this invention, controlling the vacuum distillation conditions within the above ranges when using the above catalysts is beneficial to improving the catalyst recovery rate.

[0070] In this invention, unless otherwise specified, the pressure of vacuum distillation refers to absolute pressure.

[0071] The second aspect of the present invention provides a gloss oil prepared by the method described in the first aspect above.

[0072] In some embodiments of the present invention, preferably, the kinematic viscosity of the bright oil at 100°C is ≥28 mm. 2 / s, more preferably 28-44mm 2 / s; viscosity index ≥95, more preferably 95-115; pour point ≤-9℃, more preferably -12 to -32℃. The bright oil obtained by the method for preparing bright oil provided by the present invention has a dynamic viscosity that meets the requirements, a high viscosity index, a low pour point, good low-temperature flow properties and high oxidation stability, and a high yield of bright oil.

[0073] In this invention, the kinematic viscosity is measured according to the GB / T 265 standard method; the pour point parameter is measured according to the GB / T3535-2008 standard method; and the viscosity index is calculated according to the GB / T 1995 standard method.

[0074] In a preferred embodiment of the present invention, the method for preparing the gloss oil includes:

[0075] (1) In the presence of liquid acid and / or organic acid catalyst containing metal halide, aromatic oil and olefin oil are reacted at a mass ratio of 1:0.5-10. The reaction products are separated by sedimentation to obtain an oil phase and a catalyst phase, wherein the mass ratio of aromatic oil to catalyst is 1:0.01-1.

[0076] (2) The oil phase is washed, and the washed oil phase is distilled and cut. The vacuum residue fraction is refined to obtain bright oil; the catalyst phase is recovered; wherein, the acid value of the washed oil phase is ≤0.05mgKOH / g;

[0077] The aromatic oil has a distillation range of 100-400℃ and an aromatic content of ≥70wt%.

[0078] The olefin oil has an olefin carbon number distribution of C8-C20 and an olefin content of ≥50wt%.

[0079] pass Figure 1 The preparation method of the gloss oil provided by the present invention will be described in further detail.

[0080] like Figure 1As shown, aromatic oil, olefin oil, and catalyst are fed into synthesis reactor I via aromatic feedstock inlet 1, olefin feedstock inlet 2, and catalyst inlet 3, respectively, for reaction. The resulting reaction products are fed into sedimentation separation reactor II via catalyst-containing synthesis oil outlet 4 for sedimentation separation. After sedimentation separation, an upper oil phase and a lower catalyst phase are obtained. The oil phase is fed into oil phase washing tower III via oil phase outlet 5 for washing. The washing liquid is introduced into oil phase washing tower III via washing liquid inlet 7. The washed oil phase is fed into oil phase distillation tower IV via washed oil phase outlet 8 for distillation and separation. The waste washing liquid is discharged from waste washing liquid outlet. 9. The light fraction after distillation and cutting is discharged through the oil phase light fraction outlet 10. The oil phase vacuum residue fraction collected after distillation and cutting enters the vacuum residue refining unit V for refining through the oil phase vacuum residue outlet 11. After refining, the vacuum residue is discharged through the bright oil outlet 12 to obtain the bright oil product. The lower catalyst phase obtained by sedimentation separation enters the catalyst recovery tower VI for distillation through the catalyst phase outlet 6. After distillation, the catalyst is used to obtain the recycled catalyst product, which is discharged through the recycled catalyst outlet 13. The waste oil obtained is discharged through the waste oil outlet 14 and treated as solid waste.

[0081] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0082] The present invention will be described in detail below through embodiments.

[0083] The main analytical method of this invention:

[0084] Density parameter: Measured according to the standard method of GB / T 13377;

[0085] Kinematic viscosity parameters: measured according to the standard method of GB / T 265;

[0086] Hydrocarbon composition: determined according to the standard method of H / T 0659;

[0087] Acid value parameter: measured according to the standard method of GB / T 7304;

[0088] Pour point parameters: measured according to the standard method of GB / T 3535-2008;

[0089] Viscosity index: Calculated according to the standard method of GB / T 1995;

[0090] Oxidation stability (rotating oxygen and nitrogen): measured according to the standard method of SH / T 0193.

[0091] The main raw materials and their sources in this invention are as follows:

[0092] The properties and composition of aromatic oil I, aromatic oil II and aromatic oil IV used in the following examples and comparative examples are shown in Table 1;

[0093] Aromatic Oil I: Catalytic cracking heavy diesel oil, taken from the refinery's catalytic cracking unit, with a diesel fraction of 200-350℃;

[0094] Aromatic Oil II: Catalytic cracking recycled oil, taken from the refinery's catalytic cracking unit, with a recycled oil fraction of 250-450℃. After distillation and cutting, a recycled oil fraction of 250-350℃ is obtained. This recycled oil after distillation and cutting is Aromatic Oil II.

[0095] Aromatic Oil III: Methylnaphthalene, with an aromatic content of 98 wt%, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0096] Aromatic Oil IV: Catalytic cracking gasoline, taken from the catalytic cracking unit of the refinery, is obtained by distillation and cutting to obtain gasoline with a fraction of 80-100℃. This gasoline after distillation and cutting is aromatic oil IV.

[0097] Olefin oil I: dodecene, with an olefin content of 99.5 wt%, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0098] Olefin oil II: tetradecene, olefin content 99.5 wt%, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0099] Liquid acid catalysts: trifluoromethanesulfonic acid and concentrated sulfuric acid, both purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0100] Metal halide catalyst: boron tribromide, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0101] Acidic clay: purchased from Huangshan Baiyue Activated Clay Co., Ltd.

[0102] Example 1

[0103] (1) Aromatic oil I, dodecene and trifluoromethanesulfonic acid were continuously added to the synthesis reactor at a feed rate of 100 g / min, a feed rate of 300 g / min, and a feed rate of 15 g / min. The mixture was stirred and mixed, and the reaction was carried out at 50°C for 60 min.

[0104] (2) The reaction product obtained in step (1) is continuously introduced into two sedimentation separation vessels, each with a volume of 20L, until the liquid level in the sedimentation separation vessel reaches 2 / 3 of the vessel height. Then the feeding is stopped. After sedimentation for 30 minutes, the upper oil phase and the lower catalyst phase are obtained.

[0105] (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 oil phase to water is 1:2, and the acid value of the oil phase after washing is 0.04 mg KOH / g.

[0106] (4) The washed oil phase is introduced into a distillation cutting tower for distillation cutting to obtain vacuum residue fraction at ≥520℃;

[0107] (5) The vacuum residue fraction is introduced into the clay refining unit for refining. The amount of clay added is 3 wt% of the vacuum residue fraction. The refining is carried out at 120°C for 60 min to obtain a bright oil product. The properties of the product are shown in Table 2.

[0108] (6) The lower catalyst phase described in step (2) is introduced into the catalyst recovery tower at a recovery temperature of 180°C. The trifluoromethanesulfonic acid catalyst is recovered by distillation, with a recovery rate of 72.3%.

[0109] Example 2

[0110] (1) Aromatic oil I, dodecene and trifluoromethanesulfonic acid were continuously added to the synthesis reactor at a feed rate of 100 g / min, a feed rate of 500 g / min, and a feed rate of 15 g / min. The mixture was stirred and mixed, and the reaction was carried out at 60°C for 90 min.

[0111] (2) The reaction product obtained in step (1) is continuously introduced into three sedimentation separation vessels, each with a volume of 20L, until the liquid level in the sedimentation separation vessel reaches 2 / 3 of the vessel height. The feeding is stopped, and after sedimentation for 60 minutes, the upper oil phase and the lower catalyst phase are obtained.

[0112] (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 oil phase to detergent is 1:2, and the acid value of the oil phase after washing is 0.05mgKOH / g.

[0113] (4) The washed oil phase is introduced into a distillation cutting tower for distillation cutting to obtain vacuum residue fraction at ≥520℃;

[0114] (5) The vacuum residue fraction is introduced into the clay refining unit for refining. The amount of clay added is 5 wt% of the vacuum residue fraction. The refining is carried out at 150°C for 60 min to obtain a bright oil product. The properties of the product are shown in Table 2.

[0115] (6) The lower catalyst phase described in step (2) is introduced into the catalyst recovery tower at a recovery temperature of 180°C. The trifluoromethanesulfonic acid catalyst is recovered by distillation, with a recovery rate of 74.3%.

[0116] Example 3

[0117] (1) Aromatic oil I, dodecene and concentrated sulfuric acid were continuously added to the synthesis reactor at a feed rate of 100 g / min, a feed rate of 200 g / min, and a feed rate of 30 g / min. The mixture was stirred and mixed, and the reaction was carried out at 30°C for 30 min.

[0118] (2) The reaction product obtained in step (1) is continuously introduced into two sedimentation separation vessels, each with a volume of 20L, until the liquid level in the sedimentation separation vessel reaches 2 / 3 of the vessel height. Then the feeding is stopped. After sedimentation for 30 minutes, the upper oil phase and the lower catalyst phase are obtained.

[0119] (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 oil phase to detergent is 1:2, and the acid value of the oil phase after washing is 0.05mgKOH / g.

[0120] (4) The washed oil phase is introduced into a distillation cutting tower for distillation cutting to obtain vacuum residue fraction at ≥520℃;

[0121] (5) The vacuum residue fraction is introduced into the clay refining unit for refining. The amount of clay added is 3 wt% of the vacuum residue fraction. The refining is carried out at 120°C for 30 min to obtain a bright oil product. The properties of the product are shown in Table 2.

[0122] (6) The lower catalyst phase described in step (2) is introduced into the catalyst recovery tower at a recovery temperature of 300°C. The concentrated sulfuric acid catalyst is recovered by distillation, with a recovery rate of 53.1%.

[0123] Example 4

[0124] (1) Aromatic oil I, tetradecene and methanesulfonic acid were continuously added to the synthesis reactor at a feed rate of 100 g / min, a feed rate of 200 g / min, a feed rate of 25 g / min, and a feed rate of 5 g / min. The mixture was stirred and mixed, and the reaction was carried out at 50°C for 30 min.

[0125] (2) The reaction product obtained in step (1) is continuously introduced into two sedimentation tanks with a volume of 20L each. Feeding is stopped when the liquid level in the separation tank reaches 2 / 3 of the tank height. After sedimentation for 60 minutes, the upper oil phase and the lower catalyst phase are obtained.

[0126] (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 oil phase to detergent is 1:2, and the acid value of the oil phase after washing is 0.04 mg KOH / g.

[0127] (4) The washed oil phase is introduced into a distillation cutting tower for distillation cutting to obtain vacuum residue fraction at ≥520℃;

[0128] (5) The vacuum residue fraction is introduced into the clay refining unit for refining. The amount of clay added is 5 wt% of the vacuum residue fraction. The refining is carried out at 80°C for 60 min to obtain a bright oil product. The properties of the product are shown in Table 2.

[0129] (6) The lower catalyst phase described in step (2) is introduced into the catalyst recovery tower at a recovery temperature of 200°C. The mixture of methanesulfonic acid and boron tribromide catalyst is recovered by distillation, with a recovery rate of 83.5%.

[0130] Example 5

[0131] (1) Aromatic oil I, tetradecene and trifluoromethanesulfonic acid were continuously added to the synthesis reactor at a feed rate of 100 g / min for aromatic oil III, 100 g / min for tetradecene, and 5 g / min for trifluoromethanesulfonic acid. The mixture was stirred and mixed, and the reaction was carried out at 50°C for 60 min.

[0132] (2) The reaction product obtained in step (1) is continuously introduced into a sedimentation separation vessel with a volume of 20L until the liquid level in the sedimentation separation vessel reaches 2 / 3 of the vessel height. The feeding is stopped and the upper oil phase and the lower catalyst phase are obtained after sedimentation for 30 minutes.

[0133] (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 oil phase to detergent is 1:1, and the acid value of the oil phase after washing is 0.04 mg KOH / g.

[0134] (4) The washed oil phase is introduced into a distillation cutting tower for distillation cutting to obtain vacuum residue fraction at ≥520℃;

[0135] (5) The vacuum residue fraction is introduced into the clay refining unit for refining. The amount of clay added is 2wt% of the vacuum residue fraction. The refining is carried out at 120℃ for 20 minutes to obtain a bright oil product. The properties of the product are shown in Table 2.

[0136] (6) The lower catalyst phase described in step (2) is introduced into the catalyst recovery tower at a recovery temperature of 180°C. The trifluoromethanesulfonic acid catalyst is recovered by distillation, with a recovery rate of 67.2%.

[0137] Example 6

[0138] The method of Example 1 was followed, except that in step (1), dodecene was replaced with octaene in equal amounts; a bright oil product was obtained, the properties of which are shown in Table 2; the catalyst recovery rate was 74.8%.

[0139] Example 7

[0140] The method of Example 1 was followed, except that in step (1), dodecene was replaced with an equal amount of eicosene; a bright oil product was obtained, the properties of which are shown in Table 2; the catalyst recovery rate was 76.8%.

[0141] Example 8

[0142] The method of Example 1 was followed, except that in step (1), the feed rate of trifluoromethanesulfonic acid was changed from 15 g / min to 1 g / min; a bright oil product was obtained, and the properties of the product are shown in Table 2; the catalyst recovery rate was 32.1%.

[0143] Comparative Example 1

[0144] The method of Example 1 was followed, except that in step (1), dodecene was replaced with hexaene in equal amounts; a bright oil product was obtained, the properties of which are shown in Table 2; the catalyst recovery rate was 71.2%.

[0145] Comparative Example 2

[0146] The method of Example 1 was followed, except that in step (1), dodecene was replaced with an equal amount of pentadecene; a bright oil product was obtained, the properties of which are shown in Table 2; the catalyst recovery rate was 77.3%.

[0147] Comparative Example 3

[0148] The method of Example 1 was followed, except that in step (1), aromatic oil I was replaced with an equal amount of aromatic oil IV; a bright oil product was obtained, the properties of which are shown in Table 2; the catalyst recovery rate was 72.3%.

[0149] Table 1 Properties and Composition of Aromatic Oils

[0150]

[0151] Table 2 Product Properties

[0152]

[0153]

[0154] As can be seen from the results in Table 1, the bright oil product prepared by the method described in this invention has excellent physicochemical properties, with a kinematic viscosity of not less than 28 mmHg at 100°C. 2 It has a viscosity that is adjustable, with a viscosity index of not less than 95 and a pour point of not more than -9℃, exhibiting good low-temperature flow properties and high oxidation stability.

[0155] Based on Examples 1, 6-8, and Table 1, it can be seen that, compared with Example 1, the olefins in the olefin oils used in Examples 6 and 7 are not within the preferred range provided by the present invention, and the performance of the obtained bright oil products meets the requirements. However, the viscosity index and oxidation stability index of the bright oil product in Example 6 are relatively low, and the viscosity of the bright oil product in Example 7 is relatively low, and the pour point is relatively high. In Example 8, the mass ratio of aromatic oil to catalyst is not within the preferred range provided by the present invention, and the viscosity of the obtained bright oil product is relatively low, and the catalyst recovery rate is relatively low.

[0156] Based on Example 1, Comparative Examples 1-3, and Table 1, it can be seen that, compared with Example 1, Comparative Example 1 did not use the olefin oil provided by the present invention, resulting in a bright oil product with low oxidation stability and viscosity index, which could not meet the requirements for high-quality bright oil; Comparative Example 2 did not use the olefin oil provided by the present invention, resulting in a bright oil product with a high pour point, which also could not meet the requirements for bright oil; Comparative Example 3 did not use the aromatic oil provided by the present invention, resulting in a bright oil product with low viscosity, which could not meet the requirements for high-viscosity bright oil.

[0157] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a gloss varnish, characterized in that, The method includes: (1) In the presence of a catalyst, aromatic oil and olefin oil are reacted, and the reaction products are separated by sedimentation to obtain the oil phase and the catalyst phase; (2) The oil phase is washed, and the washed oil phase is distilled and cut. The vacuum residue fraction is refined to obtain bright oil; the catalyst phase is recovered. The aromatic oil has a distillation range of 200-350℃ and an aromatic content of ≥80 wt%. The olefin oil has an olefin carbon number distribution of C10-C14 and an olefin content of ≥50 wt%. The catalyst is selected from liquid acids and / or organic acids containing metal halides; the mass ratio of the aromatic oil to the catalyst is 1:0.05-0.

3. The mass ratio of the aromatic oil to the olefin oil is 1:0.5-10; In step (1), the reaction temperature is 20-100℃; the reaction time is 5-300 min; 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; The organic acid is selected from methanesulfonic acid and / or ethanesulfonic acid.

2. The method according to claim 1, wherein, The aromatic oil is selected from at least one of catalytic cracking diesel, catalytic cracking recycle oil, reformed heavy aromatic oil, ethylene tar, and coal tar. And / or, the aromatics in the aromatic oil are selected from at least one of monocyclic, bicyclic and tricyclic aromatic compounds with a boiling point of 100-350°C.

3. The method according to claim 2, wherein, The aromatic hydrocarbons in the aromatic oil are selected from at least one of toluene, xylene, dodecylbenzene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, biphenyl, acenaphthenes, fluorenes, and hexylbenzene.

4. The method according to claim 3, wherein, The aromatics in the aromatic oil are selected from methylnaphthalene and / or dimethylnaphthalene.

5. The method according to claim 1, wherein, The olefin oil contains ≥70wt% olefins; the olefins in the olefin oil are straight-chain α-olefins and / or internal olefins.

6. The method according to claim 1, wherein, The mass ratio of aromatic oil to olefin oil is 1:1-5.

7. The method according to claim 1, wherein, The metal halide is selected from at least one of boron tribromide, boron trichloride, aluminum trichloride, boron trifluoride, ferric chloride, and zinc trichloride; And / or, based on the total amount of the organic acids containing metal halides, the content of metal halides is 1-30 wt%.

8. The method according to claim 7, wherein, The liquid acid is selected from at least one of concentrated sulfuric acid, trifluoromethanesulfonic acid, and fluorosulfonic acid; And / or, the metal halide is selected from boron tribromide and / or aluminum trichloride; And / or, based on the total amount of the organic acids containing metal halides, the content of metal halides is 5-20 wt%.

9. The method according to claim 1, wherein, The sedimentation includes: distributing the obtained reaction products in multiple sedimentation separation vessels for sedimentation; And / or, relative to a 20L settling separator, the settling time of the reactants in each settling separator is 5-120 min; And / or, in step (2), the mass ratio of the oil phase to the washing liquid is 1:0.5-5; And / or, the acid value of the oil phase after washing is ≤0.05mgKOH / g; And / or, the washing solution is selected from water and / or metal alkaline solution.

10. The method according to claim 9, wherein, In step (1), the reaction temperature is 30-60℃; the reaction time is 30-90 min; And / or, relative to a 20L settling separator, the settling time of the reactants in each settling separator is 30-60 min; And / or, in step (2), the mass ratio of the oil phase to the washing liquid is 1:1-2; And / or, the washing solution is selected from water.

11. The method according to claim 1, wherein, The cutting temperature of the distillation cutting is ≥500℃; And / or, the refining process in step (2) is selected from at least one of clay refining, hydrogenation refining and molecular sieve adsorption refining; And / or, the conditions for refining the clay include: the amount of clay added is 1-10 wt% of the vacuum residue fraction; the refining temperature is 50-200℃; and the refining time is 5-120 min.

12. The method according to claim 11, wherein, The cutting temperature of the distillation cutting is ≥520℃; And / or, the refining process described in step (2) is clay refining; And / or, the conditions for refining the clay include: the amount of clay added is 2-5 wt% of the vacuum residue fraction; the refining temperature is 80-150℃; and the refining time is 20-60 min.

13. The method according to claim 1, wherein, In step (2), the method for catalyst recovery is selected from at least one of atmospheric distillation and vacuum distillation.

14. The method according to claim 1, wherein, In step (2), the method for catalyst recovery is vacuum distillation.

15. A gloss varnish prepared by the method of any one of claims 1-14.

16. The gloss varnish according to claim 15, wherein, The kinematic viscosity of the brightening oil at 100℃ is ≥28 mm. 2 / s; viscosity index ≥95; pour point ≤-9℃.

17. The gloss varnish according to claim 16, wherein, The kinematic viscosity of the brightening oil at 100°C is 28-44 mm. 2 / s; And / or, viscosity index of 95-115; And / or, with a pour point of -12 to -32°C.

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