A process and apparatus for producing bright stock, and the bright stock obtained

Abstract

The application discloses a method and device for producing bright stock, and the obtained bright stock, which comprises the following steps: (1) contacting heavy oil with a hydrogenation catalyst under the presence of hydrogen, and performing hydrogenation reaction under hydrogenation treatment conditions to obtain a hydrogenation product; (2) performing alkylation reaction of aromatics in the hydrogenation product and C10-C20 olefins in olefin oil under the presence of a strong acid catalyst and under alkylation reaction conditions to obtain an alkylation product; and (3) performing distillation separation on the alkylation product to separate and obtain a heavy fraction with a temperature greater than 500 DEG C as the bright stock product. The method provided by the application expands the raw material source of the bright stock, simplifies the process flow, and is convenient for industrial production; and the prepared bright stock product not only has high viscosity and viscosity index, but also has good low-temperature flow performance and high oxidation stability.

Description

Technical Field

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

[0002] Bright stock is a high-viscosity lubricating oil base oil used under high-temperature or heavy-load conditions. It adjusts the high-temperature viscosity of lubricating oil products and is widely used in industrial oils (such as gear oils, hydraulic oils, and greases) and heavy internal combustion engine oils (such as marine engine oils). As a heavy base oil, bright stock not only requires high viscosity but also a high viscosity index, good oxidation stability, and low-temperature fluidity. With the upgrading of global lubricating oil product quality, the demand structure of base oils has changed significantly. The proportion of Group I base oils has gradually decreased, but high-viscosity heavy Group I base oils still have a large market. According to incomplete statistics, the domestic demand for bright stock is approximately 400,000 tons per year, and the annual import of bright stock is approximately 200,000 tons, mainly high-viscosity 150BS products.

[0003] To meet the viscosity and viscosity index requirements of bright oil, its raw material is crude oil vacuum residue. The production processes mainly include conventional processes, all-hydrogen processes, and a combination of conventional and hydrotreating processes. The conventional process uses a solvent deasphalting-solvent refining-solvent dewaxing route, but the product yield is low and the heteroatom content is high. CN104449841A discloses a method for producing low-pour-point, high-viscosity bright oil using an all-hydrogen process. This method uses naphthenic light deasphalting oil as raw material and employs a hydrotreating pre-refining-isomer dewaxing-hydrotreating supplementary refining process to convert long-chain cycloalkanes in the raw material into low-pour-point isomeric alkanes, achieving a higher bright oil yield, but it requires naphthenic crude oil. CN101768470A discloses a method for preparing bright oil, using vacuum residue as raw material and employing a combined process of solvent deasphalting-solvent refining-hydrotreating-solvent dewaxing. This process has strong applicability to raw materials and produces products with kinematic viscosity meeting requirements and high viscosity index with low pour point. However, the process flow is relatively long, and the overall product yield is low. CN110607191A discloses a combined process of vacuum residue hydrotreating and bright oil production. This process first hydrotreats the vacuum residue, and then uses the tail oil from the hydrogenated vacuum residue as raw material to produce bright oil using traditional processes. This can significantly improve the product yield, but it requires a vacuum residue hydrotreating process.

[0004] With the decreasing availability of high-quality crude oil resources and the diversification of crude oil sources, the availability of high-quality resources for producing high viscosity index bright oils is dwindling. This leads to variations in the viscosity, viscosity index, and oxidation stability of bright oil products, causing fluctuations in product quality and making it difficult to produce high-quality bright oil products that combine both high viscosity and high viscosity index. Although bright oil substitutes such as polyisobutylene (PIB) and polyalphaolefin (PAO) can meet the viscosity and viscosity index requirements, their high price and poor compatibility with additives make it difficult to replace traditional bright oils on a large scale.

[0005] In the petroleum refining industry, crude oil undergoes catalytic cracking to produce a large amount of heavy distillate oil rich in aromatics. Catalytic cracking slurry, a low-value byproduct of refineries, is rich in polycyclic aromatic hydrocarbons and is often used as a raw material for carbon materials or, after hydrotreating, to produce specialty oil products such as rubber-filled oil. CN113122324A discloses a method for producing specialty oil products using catalytic cracking slurry as a raw material. The catalytic slurry is first refined by solvent, and the residual oil is contacted with hydrogen and a hydrotreating agent for a hydrotreating reaction. The diesel fraction obtained after hydrotreating is then dewaxing and hydrorefined to produce aviation kerosene and transformer oil base oil products, improving the economic efficiency of the catalytic slurry. CN104593067A discloses a method for producing white rubber oil by hydrotreating catalytic cracking slurry. The light fraction obtained from the fractionation of the catalytic slurry is hydrotreated, hydrorefined, and further hydrotreated to produce rubber-filled base oil. Hydrotreated catalytic cracking slurry is rich in cycloalkanes, and its structural characteristics are similar to those of cycloalkyl crude oil. However, the viscosity and viscosity index of hydrotreated catalytic cracking slurry are low, which cannot meet the requirements for bright oil properties. Summary of the Invention

[0006] One of the technical problems to be solved by the present invention is to provide a method for producing bright oil from heavy distillate oil, especially a method for producing high viscosity, high viscosity index bright oil from low value heavy distillate oil.

[0007] The second technical problem to be solved by the present invention is to provide a bright oil prepared from heavy distillate oil.

[0008] The third technical problem to be solved by the present invention is to provide an apparatus for preparing gloss oil using the above-mentioned method.

[0009] In a first aspect, the present invention provides a method for producing gloss varnish, comprising:

[0010] (1) In the presence of hydrogen, heavy distillate oil is contacted with a hydrogenation catalyst and hydrogenation reaction is carried out under hydrogenation treatment conditions to obtain hydrogenation products;

[0011] (2) In the presence of a strong acid catalyst, the aromatics in the hydrogenation product and the C10~C20 olefins in the olefin oil undergo an alkylation reaction under alkylation reaction conditions to obtain an alkylated product;

[0012] (3) The alkylation product is distilled to separate the heavy distillate at a temperature greater than 500°C to obtain a bright oil product.

[0013] Secondly, the present invention provides a gloss oil produced by the method for producing gloss oil provided in the first aspect.

[0014] Thirdly, the present invention provides an apparatus for preparing bright oil, used in the above-mentioned method for producing bright oil. The apparatus includes a hydrogenation reactor, an alkylation reactor, and a product distillation column connected in sequence. The hydrogenation reactor is filled with a hydrogenation catalyst and has a hydrogen inlet, a raw material inlet, and a hydrogenated product outlet. The alkylation reactor has a hydrogenated product inlet, an olefin oil inlet, an alkylation catalyst inlet, an alkylation product outlet, and an alkylation catalyst outlet. The product distillation column has an alkylation product inlet, a top product outlet, and a bottom product outlet.

[0015] Compared with the prior art, the beneficial effects of the method and apparatus for producing gloss varnish provided by the present invention, and the resulting gloss varnish, are as follows:

[0016] (1) The method provided by this invention uses heavy distillate oil containing aromatics as raw material, and obtains bright oil product through hydrogenation treatment, aromatic alkylation reaction and distillation separation. This method expands the source of raw materials for producing bright oil, simplifies the process flow, and facilitates industrial production;

[0017] (2) The bright oil products prepared by the method provided by the present invention not only have high viscosity and viscosity index, but also have good low temperature flow properties and high oxidation stability. Attached Figure Description

[0018] Figure 1 This is a schematic flowchart of one embodiment of the method for producing bright oil provided by the present invention.

[0019] Explanation of reference numerals in the attached figures

[0020] 1. Raw material distillation tower 2. Hydrogenation reactor 3. Alkylation reactor 4. Product distillation tower 5. Catalytic cracking slurry oil 6. Light fractions 7. Middle fraction 8. Heavy fraction 9. Hydrogen 10. Hydrogenation products 11. Olefin oil 12. Strong acid catalyst 13. Alkylation products 14. Alkylation waste catalyst 15. Light fraction of alkylation products 16. Heavy fraction of alkylation products Detailed Implementation

[0021] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0022] In a first aspect, the present invention provides a method for producing gloss varnish, comprising:

[0023] (1) In the presence of hydrogen, heavy distillate oil is contacted with a hydrogenation catalyst and hydrogenation reaction is carried out under hydrogenation treatment conditions to obtain hydrogenation products;

[0024] (2) In the presence of a strong acid catalyst, the aromatics in the hydrogenation product and the C10~C20 olefins in the olefin oil undergo an alkylation reaction under alkylation reaction conditions to obtain an alkylated product;

[0025] (3) The alkylation product is distilled to separate the heavy distillate at a temperature greater than 500°C to obtain a high-quality bright oil.

[0026] In the method provided by this invention, the heavy distillate oil contains aromatics selected from one or more of catalytic cracking slurry oil, catalytic cracking cycle oil, and coal tar middle fraction. Preferably, the heavy distillate oil has a boiling range of 300-540℃, more preferably 350-520℃, and more preferably 400-520℃, and its aromatic content is 60-90wt%, preferably 60-85wt%, and more preferably 70-85wt%.

[0027] Preferably, the process further includes a feedstock pretreatment step: (1-1) the middle fraction obtained by distillation separation of heavy distillate oil is used as the feedstock for heavy distillate oil in step (1); the heavy distillate oil is preferably the middle fraction from catalytic cracking slurry. When catalytic cracking slurry is used as feedstock, the process further includes a feedstock pretreatment step: (1-1) the middle fraction obtained by distillation separation after solidification treatment of catalytic cracking slurry from catalytic cracking process is used as the heavy distillate oil in step (1); preferably, the distillation range of the middle fraction is 400-520℃, and the aromatic content is 70-85wt%; preferably, the solid content in the catalytic cracking slurry after solidification treatment is ≤0.2wt%, more preferably 0.02-0.1wt%.

[0028] In the method provided by the present invention, the hydrogenation catalyst is a supported catalyst, comprising a support and an active component supported on the support, wherein the support is selected from alumina and / or silica, and the active component is selected from nickel and / or cobalt, and molybdenum and / or tungsten;

[0029] Preferably, the nickel and / or cobalt content is 0.5-8 wt%, more preferably 1-5 wt%, based on the total weight of the hydrogenation catalyst and calculated as metal oxides; the molybdenum and / or tungsten content is 5-35 wt%, more preferably 10-30 wt%.

[0030] In the method provided by this invention, the hydrogenation treatment conditions in step (1) include: a temperature of 290-380℃, preferably 320-360℃; a pressure of 8-18 MPa, preferably 10-16 MPa; and a volume hourly space velocity of 0.3-3 h⁻¹. -1 Preferably, the time is 0.5-1.5 h. -1 The hydrogen-to-oil volume ratio is 500-2000:1, preferably 1000-1500:1.

[0031] In this invention, unless otherwise specified, the pressure refers to gauge pressure.

[0032] In the method provided by the present invention, in order to obtain high-quality bright oil, it is preferable to control the conditions of the hydrogenation reaction to obtain a suitable hydrogenation product. Preferably, the aromatic content of the hydrogenation product is controlled to be 50-90 wt%, more preferably 60-80 wt%. Preferably, the refractive index of the hydrogenation product at 20°C is 1.50-1.52.

[0033] In the method provided by this invention, the strong acid catalyst is selected from strong acids with an acidity coefficient less than 0;

[0034] Preferably, the strong acid catalyst is selected from super-strong liquid acids with an acidity coefficient of less than -5;

[0035] Preferably, the strong acid catalyst is selected from at least one of concentrated sulfuric acid, trifluoromethanesulfonic acid, fluorosulfonic acid, perchloric acid and hydrobromic acid; more preferably concentrated sulfuric acid and / or trifluoromethanesulfonic acid.

[0036] In step (2), the weight ratio of the hydrogenation product to the olefin is 1:0.3-5, preferably 1:1-5; the weight ratio of the strong acid catalyst to the olefin is 0.01-0.5:1, preferably 0.3-0.5:1; the olefin oil contains 50-100 wt% olefins, preferably 70-100 wt%; the olefins are α-olefins, internal olefins, or dienes; C10-C20 olefins are preferably C12-C16 α-olefins, internal olefins, or dienes.

[0037] In step (2), the alkylation reaction conditions are: temperature of 0-60℃ and reaction time of 5-300 min; preferably, temperature of 20-55℃ and reaction time of 20-90 min.

[0038] In step (3), the heavy fraction obtained by distillation of the alkylation product is used as a bright oil product, with a cut point of 500°C or any temperature greater than 500°C, preferably 520°C.

[0039] The method provided by this invention uses heavy distillate oil rich in aromatics as raw material, and uses hydrogenation treatment to saturate polycyclic aromatics into oligocyclic aromatic components with cycloalkane rings, which have both aromatic ring structure and cycloalkane ring structure; the hydrogenation product increases the alkyl long side chain through alkylation reaction with olefins, thereby increasing the product viscosity and viscosity index, and thus the low-value heavy distillate oil is converted into a high-viscosity and high-viscosity index bright oil product.

[0040] In the method provided by this invention, the boiling range of the heavy distillate oil is 300-540℃, meaning that the boiling range of the heavy distillate oil falls within the range of 300-540℃. For example, the boiling range can be any two values ​​from 300℃, 350℃, 400℃, 420℃, 440℃, 460℃, 500℃, 520℃, and 540℃. When the boiling range of the heavy distillate oil is below 350℃, the viscosity of the feedstock is too low, and after hydrotreating and alkylation, it cannot meet the high viscosity requirements of bright oil. When the boiling range of the heavy distillate oil is above 540℃, the content of polycyclic aromatic hydrocarbons is too high, and after hydrotreating and alkylation, the viscosity index of the bright oil product is difficult to meet the requirements.

[0041] The source of the aromatic heavy distillate oil can be selected from one or a mixture of several of the following: catalytic cracking slurry oil, catalytic cracking cycle oil, and coal tar middle distillate, preferably the middle distillate section of catalytic cracking slurry oil.

[0042] In a preferred embodiment of the present invention, catalytic cracking slurry is used as feedstock, and a middle fraction with a distillation range of 350°C to 540°C, preferably 400°C to 520°C, is fractionated and used as feedstock for hydrotreating. Typically, the aromatic hydrocarbon content in the catalytic cracking slurry is 50-90 wt%, preferably 70-85 wt%; the kinematic viscosity of the catalytic cracking slurry at 100°C is ≤16 mm. 2 / s, preferably 10-15mm 2 / s. The aromatic content of the middle distillate is 60-90 wt%, preferably 70-85 wt%.

[0043] Unless otherwise specified, kinematic viscosity parameters are measured using GB / T 265 (Determination of kinematic viscosity and calculation of dynamic viscosity of petroleum products); aromatic content parameters are measured using SH / T 0659 (Determination of hydrocarbons in saturated hydrocarbon fractions of gas oil).

[0044] In this invention, to further ensure the long-term safe operation of the process unit, it is necessary to perform a solidification treatment on the catalytic cracking slurry. Solid powder in the catalytic cracking slurry can cause erosion and wear damage to the unit's pumps and control valves, necessitating control of the solid content. Preferably, the method further includes: performing a solidification treatment on the catalytic cracking slurry before the first distillation.

[0045] In some embodiments of the present invention, preferably, the solid content in the catalytic cracking slurry after the desolidification treatment is ≤0.2wt%, more preferably 0.02-0.1wt%. The solid content refers to the total amount of catalyst powder and other solid substances insoluble in xylene; the solid content parameter is measured using Q / SH 0742-2018.

[0046] In the method provided by this invention, the type of hydrogenation catalyst is not limited. The hydrogenation catalyst is a supported catalyst, comprising a support and an active component supported on the support. A wide range of types of support and active component are available, all being conventional supported catalyst supports and active components in the art. Preferably, the hydrogenation catalyst is selected from alumina and / or silica, and the active components are each independently selected from nickel and / or cobalt, and molybdenum and / or tungsten.

[0047] In some embodiments of the present invention, preferably, the hydrogenation catalyst contains, based on the total weight of the hydrogenation catalyst and calculated as metal oxides, 0.1-10 wt% nickel and / or cobalt, preferably 0.5-8 wt%, more preferably 1-5 wt%; and 5-35 wt% molybdenum and / or tungsten, preferably 10-30 wt%.

[0048] In this invention, the purpose of the hydrotreating is to hydrogenate and saturate the polycyclic aromatic hydrocarbons in the heavy distillate oil into oligocyclic aromatic hydrocarbons containing cycloalkane rings, while avoiding the ring-opening cracking of oligocyclic aromatic hydrocarbons after hydrogenation and saturation. This structure has aromatic active sites and can undergo subsequent alkylation reactions to produce high viscosity and high viscosity index bright oil products.

[0049] In this invention, the aromatic-containing heavy distillate oil is hydrogenated to saturate most of its polycyclic aromatic hydrocarbons (PAHs) into oligocyclic aromatic hydrocarbons containing cycloalkane rings. By adjusting the operating conditions of the hydrogenation reaction, the suitable aromatic hydrocarbon content of the hydrogenation product is 50-90 wt%, preferably 60-80 wt%, and the refractive index at 20°C is 1.50-1.52. When the refractive index at 20°C is less than 1.52, most of the PAHs in the hydrogenation product are converted into oligocyclic aromatic hydrocarbons. Simultaneously, to avoid further hydrogenation saturation and ring-opening of the oligocyclic aromatic hydrocarbons, the refractive index of the hydrogenation product cannot be too low; that is, the refractive index at 20°C is not less than 1.50.

[0050] Preferably, the refractive index of the hydrogenation product at 20°C is 1.50-1.52, for example, 1.5, 1.505, 1.51, 515, 1.52, or any value within the range of any two values, preferably 1.5-1.52, and the kinematic viscosity at 100°C is 6-10 mmHg. 2 / s, preferably 7-9mm 2 / s。 .

[0051] In this invention, unless otherwise specified, the refractive index parameter is measured using SH / T 0724 (Method for determination of refractive index and refractive dispersion of liquid hydrocarbons).

[0052] In this invention, the olefin oil contains 50-100 wt% olefins, preferably 70%-100 wt%, and the olefins have C10-C20 carbon atoms, preferably C12-C16. The olefin type is at least one of α-olefins, internal olefins, or dienes. By using preferred conditions, it can be ensured that the hydrogenation product and the high-concentration olefin oil can undergo alkylation reaction, and that the alkyl side chain has a suitable number of carbon atoms, which can meet the requirements of bright oil for viscosity index and pour point.

[0053] In this invention, the weight ratio of the hydrogenation product to the olefin oil is 1:0.3-5, preferably 1:1-5. Using the preferred conditions, it can be ensured that the hydrogenation product undergoes a polyalkylation reaction with sufficient olefins, having 2-4 alkyl side chains, which gives the bright oil a high viscosity characteristic.

[0054] In this invention, a wide range of types of strong acid catalysts are available. The strong acid catalyst is selected from liquid strong acids with an acidity coefficient (pKa) less than 0, preferably from ultra-strong liquid acids with an acidity coefficient (pKa) less than -5, including at least one of concentrated sulfuric acid (98 wt%), trifluoromethanesulfonic acid, fluorosulfonic acid, perchloric acid, and hydrobromic acid; more preferably, the ultra-strong liquid acid is selected from concentrated sulfuric acid and / or trifluoromethanesulfonic acid. To achieve the polyalkylation reaction of the hydrogenation product with the olefin, the catalyst needs to meet the strong acidity requirement. Simultaneously, to ensure easy separation of the synthesis product from the catalyst, a liquid acid catalytic system that is immiscible with the reaction product is selected.

[0055] In this invention, the alkylation reaction can be carried out in a fully mixed-flow reactor. The alkylation reaction conditions are: temperature of 0-60℃, preferably 20-55℃, and reaction time of 5-300 min, preferably 20-90 min. Using these preferred conditions, polyalkylation reactions between aromatics and olefins can be achieved, resulting in high olefin conversion and high-viscosity bright oil synthesis, while avoiding olefin polymerization and improving olefin utilization. The sedimentation and separation time between the reaction product and the catalyst is 5-240 min, preferably 15-60 min. The upper liquid phase is the alkylation product, and the lower liquid phase is the catalyst phase.

[0056] The method provided by this invention uses heavy distillate oil rich in aromatics as raw material and employs hydrogenation treatment to saturate polycyclic aromatics into oligocyclic aromatic components with cycloalkane rings, possessing both aromatic ring and cycloalkane ring structures. The hydrogenation product increases the alkyl side chain by reacting with olefins in an aromatic alkylation reaction, thereby improving the product viscosity and viscosity index, and thus transforming low-value heavy distillate oil into high-viscosity and high-viscosity index bright oil products.

[0057] The second aspect of the present invention provides a gloss oil prepared by the method provided in the first aspect.

[0058] The bright oil product prepared using the method provided in this invention has high viscosity and a high viscosity index, as well as low pour point and high oxidation stability. Under preferred process conditions, the kinematic viscosity of the bright oil is ≥30 mm. 2 / s and viscosity index ≥90.

[0059] A third aspect of the present invention provides an apparatus for preparing bright oil, used in any of the methods described above for producing high viscosity and high viscosity index bright oil. The apparatus comprises a hydrogenation reactor, an alkylation reactor, and a product distillation column connected in sequence. The hydrogenation reactor is filled with a hydrogenation catalyst and has a hydrogen inlet, a raw material inlet, and a hydrogenated product outlet. The alkylation reactor has a hydrogenated product inlet, an olefin oil inlet, an alkylation catalyst inlet, an alkylation product outlet, and an alkylation catalyst outlet. The product distillation column has an alkylation product inlet, a top product outlet, and a bottom product outlet.

[0060] Preferably, it also includes a raw material pre-fractionation tower, which is provided with a raw material inlet, a top stream outlet, a side stream outlet, and a bottom stream outlet.

[0061] Preferably, the alkylation reactor is a fully mixed-flow batch reactor;

[0062] Preferably, both the raw material pre-fractionation tower and the product distillation tower are packed towers.

[0063] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention, but the drawings and embodiments do not constitute a limitation of the present invention.

[0064] Appendix Figure 1 This is a schematic flowchart of one embodiment of the method for producing gloss oil provided by the present invention. (See attached diagram) Figure 1 As shown, when using catalytic cracking slurry as feedstock, the catalytic cracking slurry 5 enters the feedstock distillation tower 1 for fractionation into light fraction 6, middle fraction 7, and heavy fraction 8. The middle fraction 7 and hydrogen 9 are introduced into the hydrogenation reactor 2, where they undergo a hydrogenation reaction in contact with the hydrogenation catalyst. The resulting hydrogenation product 10 enters the alkylation reactor 3. Simultaneously, olefin oil 11 and strongly acidic catalyst 12 also enter the alkylation reactor 3. Under alkylation reaction conditions, the aromatics in the hydrogenation product undergo alkylation with the olefins. The reactants are separated into layers, and the spent alkylation catalyst 14 is discharged from the reactor. The separated alkylation product 13 enters the product distillation tower for fractionation to obtain alkylation product light fraction 15 and alkylation product heavy fraction 16 (above 500°C). The alkylation product heavy fraction 16 is a bright oil product.

[0065] The present invention will be described in detail below through embodiments.

[0066] In the examples and comparative examples:

[0067] The catalytic cracking slurry and catalytic cracking circulating oil are taken from the catalytic cracking unit of Sinopec Jinan Branch.

[0068] The hydrogenation catalyst was purchased from Changling Catalyst, a commercially available product under the brand name RL-2, from Sinopec Catalyst Branch.

[0069] The strong acid catalysts trifluoromethanesulfonic acid and concentrated sulfuric acid were purchased from Aladdin Reagent Company; dodecene, tetradecene, and dodecane were also purchased from Aladdin Reagent Company. The analytical methods involved are as follows:

[0070] The kinematic viscosity parameters were measured according to GB / T 265;

[0071] The refractive index parameter was measured according to SH / T 0724;

[0072] The hydrocarbon composition was determined using SH / T 0659.

[0073] Pour point parameters were measured according to GB / T 3535-2008;

[0074] Viscosity index was calculated according to GB / T 1995;

[0075] Oxidation stability (rotational oxygen and nitrogen) was measured using SH / T 0193.

[0076] Example 1

[0077] (1) After the catalytic cracking slurry is desolidified, the solid content of the desolidified catalytic cracking slurry is 0.05wt%. The slurry is then distilled to obtain the middle fraction with a distillation range of 400-520℃, which is used as heavy distillate oil I. The properties and hydrocarbon composition are listed in Table 1.

[0078] (2) In the presence of hydrogen, heavy distillate oil I is introduced into the hydrogenation reactor and contacted with hydrogenation catalyst RL-2 to carry out hydrogenation treatment reaction to obtain hydrogenation products. The reaction operating conditions and the properties of hydrogenation products are listed in Table 2.

[0079] (3) In the presence of trifluoromethanesulfonic acid catalyst, the above hydrogenation product is subjected to alkylation reaction with dodecene (temperature is 50℃, time is 60min) to obtain alkylated product; wherein, the weight ratio of hydrogenation product to olefin is 1:2, and the weight ratio of trifluoromethanesulfonic acid catalyst to dodecene is 0.2:1.

[0080] (4) The above alkylation products were distilled to obtain a bright oil product with a distillation range of >520℃. The main physical properties are listed in Table 2.

[0081] Example 2

[0082] (1) In the presence of hydrogen, heavy distillate oil I was hydrogenated with hydrogenation catalyst RL-2 to obtain hydrogenated products. The reaction operating conditions and physical properties of the hydrogenated products are listed in Table 2.

[0083] (2) In the presence of concentrated sulfuric acid catalyst, the above hydrogenation product was subjected to alkylation reaction with dodecene (temperature 40℃, time 30min) to obtain alkylated product; wherein the weight ratio of hydrogenation product to olefin was 1:2, and the weight ratio of concentrated sulfuric acid catalyst to dodecene was 0.2:1.

[0084] (3) The above alkylation products were fractionated to obtain a bright oil product with a distillation range of >520℃. The main physical properties are listed in Table 2.

[0085] Example 3

[0086] (1) In the presence of hydrogen, heavy fraction I was hydrogenated with hydrogenation catalyst RL-2 to obtain hydrogenation product, and the physical properties are listed in Table 2.

[0087] (2) In the presence of a trifluoromethanesulfonic acid catalyst, the above hydrogenation product was subjected to an alkylation reaction with dodecene (at a temperature of 50°C for 60 min) to obtain an alkylated product; wherein the weight ratio of the hydrogenation product to the olefin was 1:1 and the weight ratio of the trifluoromethanesulfonic acid catalyst to the dodecene was 0.2.

[0088] (3) The above alkylation product is subjected to a second distillation to obtain a bright oil from the heavy distillate with a distillation range of >520℃. The main physical properties of the bright oil product are listed in Table 2.

[0089] Example 4

[0090] (1) After the catalytic cracking slurry is desolidified, the desolidified catalytic cracking slurry with a solid content of 0.05wt% is distilled to obtain an intermediate fraction with a distillation range of 400-500℃, which is used as heavy oil fraction II containing aromatics (the properties and hydrocarbon composition are listed in Table 1).

[0091] (2) In the presence of hydrogen, the heavy oil fraction II containing aromatics was contacted with the hydrogenation catalyst RL-2 for hydrogenation treatment to obtain the hydrogenation product. The physical properties are listed in Table 2.

[0092] (3) In the presence of a trifluoromethanesulfonic acid catalyst, the above hydrogenation product was subjected to an alkylation reaction with olefin oil (temperature 30°C, time 90 min) to obtain an alkylated product; wherein the olefin oil consisted of 70 wt% dodecene and 30 wt% dodecane. The weight ratio of dodecene in the hydrogenation product and the olefin oil was 1:3, and the weight ratio of trifluoromethanesulfonic acid catalyst to dodecene was 0.3;

[0093] (4) The above alkylation product was subjected to a second distillation to obtain a bright oil product with a distillation range of >500℃. The main physical properties are listed in Table 2.

[0094] Example 5

[0095] (1) The catalytic cracking cycle oil is distilled to obtain an intermediate fraction with a distillation range of 350-500℃ as heavy oil fraction III containing aromatics (the properties and hydrocarbon composition are listed in Table 1).

[0096] (2) In the presence of hydrogen, the heavy oil fraction III containing aromatics was contacted with the hydrogenation catalyst RL-2 for hydrogenation treatment to obtain the hydrogenation product. The physical properties are listed in Table 3.

[0097] (3) In the presence of trifluoromethanesulfonic acid catalyst, the above hydrogenation product is subjected to alkylation reaction with tetradecene (temperature is 50℃, time is 60min) to obtain alkylated product; wherein, the weight ratio of hydrogenation product to olefin is 1:2, and the weight ratio of trifluoromethanesulfonic acid catalyst to tetradecene is 0.2.

[0098] (4) The above alkylation products were fractionated to obtain a bright oil product with a distillation range of >500℃. The main physical properties are listed in Table 3.

[0099] Example 6

[0100] (1) In the presence of hydrogen, heavy distillate oil I was contacted with hydrogenation catalyst RL-2 for hydrogenation treatment to obtain hydrogenation products. The physical properties are listed in Table 3.

[0101] (2) In the presence of a trifluoromethanesulfonic acid catalyst, the above hydrogenation product was subjected to an alkylation reaction with dodecene (at a temperature of 50°C for 60 min) to obtain an alkylated product; wherein the weight ratio of the hydrogenation product to the olefin was 1:2, and the weight ratio of the trifluoromethanesulfonic acid catalyst to the dodecene was 0.2:1.

[0102] (4) The above alkylation product was subjected to a second distillation to obtain a bright oil product with a distillation range of >520℃. The main physical properties are listed in Table 3.

[0103] Example 7

[0104] (1) In the presence of hydrogen, heavy distillate oil II was contacted with hydrogenation catalyst RL-2 for hydrogenation treatment to obtain hydrogenation products. The physical properties are listed in Table 3.

[0105] (2) In the presence of a trifluoromethanesulfonic acid catalyst, the above hydrogenation product was subjected to an alkylation reaction with dodecene (at a temperature of 50°C for 60 min) to obtain an alkylated product; wherein the weight ratio of the hydrogenation product to the olefin was 1:2, and the weight ratio of the trifluoromethanesulfonic acid catalyst to the dodecene was 0.2:1.

[0106] (3) The above alkylation product is subjected to a second distillation to obtain a bright oil from the heavy distillate with a distillation range of >520℃. The main physical properties of the bright oil product are listed in Table 3.

[0107] Example 8

[0108] (1) In the presence of hydrogen, heavy distillate oil II was contacted with hydrogenation catalyst RL-2 for hydrogenation treatment to obtain hydrogenation product. The physical properties are listed in Table 3.

[0109] (2) In the presence of a trifluoromethanesulfonic acid catalyst, the above hydrogenation product was subjected to an alkylation reaction with dodecene (at a temperature of 70°C for 60 min) to obtain an alkylated product; wherein the weight ratio of the hydrogenation product to the olefin was 1:5, and the weight ratio of the trifluoromethanesulfonic acid catalyst to the dodecene was 0.5:1.

[0110] (3) The above alkylation products were distilled and separated to obtain a bright oil product with a distillation range of >520℃. The main physical properties are listed in Table 3.

[0111] Example 9

[0112] (1) Heavy oil fraction with a distillation range of 350-500℃ taken from the vacuum distillation tower of Sinopec Jinan Branch was used as raw material as heavy oil fraction IV. Its properties and hydrocarbon composition are listed in Table 1.

[0113] (2) In the presence of hydrogen, heavy distillate IV is introduced into the hydrogenation reactor and contacted with hydrogenation catalyst RL-2 to carry out hydrogenation treatment reaction to obtain hydrogenation products. The reaction operating conditions and properties of hydrogenation products are listed in Table 3.

[0114] (3) In the presence of trifluoromethanesulfonic acid catalyst, the above hydrogenation product is subjected to alkylation reaction with dodecene (temperature is 50℃, time is 60min) to obtain alkylated product; wherein, the weight ratio of hydrogenation product to olefin is 1:2, and the weight ratio of trifluoromethanesulfonic acid catalyst to dodecene is 0.2:1.

[0115] (4) The above alkylation products were separated by distillation to obtain a bright oil product with a distillation range of >520℃. The main physical properties are listed in Table 3.

[0116] Comparative Example 1

[0117] (1) In the presence of trifluoromethanesulfonic acid catalyst, the catalytic cracking slurry in Table 1 was alkylated with dodecene (temperature 50℃, time 60min) to obtain alkylated products; wherein the weight ratio of hydrogenation product to olefin was 1:2, and the weight ratio of trifluoromethanesulfonic acid catalyst to dodecene was 0.2:1.

[0118] (2) The above alkylation product was subjected to a second distillation to obtain a bright oil product with a distillation range of >520℃. The main physical properties are listed in Table 4.

[0119] Comparative Example 2

[0120] (1) After the catalytic cracking slurry is desolidified, the solid content of the desolidified catalytic cracking slurry is 0.05wt%. The slurry is then distilled to obtain the middle fraction with a distillation range of 400-520℃, which is used as heavy distillate oil I. The properties and hydrocarbon composition are listed in Table 1.

[0121] (2) In the presence of hydrogen, heavy distillate oil I is introduced into the hydrogenation reactor and contacted with hydrogenation catalyst RL-2 to carry out hydrogenation treatment reaction to obtain hydrogenation products. The reaction operating conditions and properties of hydrogenation products are listed in Table 4.

[0122] (3) In the presence of aluminum trichloride catalyst, the above hydrogenation product was subjected to alkylation reaction with dodecene (temperature 90℃, time 30min) to obtain alkylated product; wherein the weight ratio of hydrogenation product to olefin was 1:2, and the weight ratio of aluminum trichloride catalyst to dodecene was 0.1:1.

[0123] (4) The above alkylation products were distilled to obtain a bright oil product with a distillation range of >520℃. The main physical properties are listed in Table 2.

[0124] Table 1

[0125] project Heavy distillate oil I Heavy distillate oil II Heavy distillate oil III Heavy distillate IV crude oil FCC oil slurry FCC oil slurry FCC circulating oil Vacuum distillate oil Distillation range, °C 400~520 400~500 350~500 350~500 <![CDATA[Density (20 °C) / kg / m 3 > 1090 1043 1053 910.7 <![CDATA[Kinematic viscosity (100 °C) / mm 2 / s]]> 13.21 11.23 10.58 7.485 Refractive index (70℃) 1.6023 1.5911 1.6156 1.4820 Hydrocarbon composition, wt% Alkanes 1.7 1.6 5.2 23.5 Total cycloalkanes 14.4 15.1 11.9 33.5 Total aromatics 83.9 83.3 82.9 43.0 Total mono- and dicyclic aromatic hydrocarbons 13.0 24.1 19.2 27.8 Total tricyclic aromatic hydrocarbons 70.9 59.2 63.7 15.2

[0126] Table 2

[0127] project Example 1 Example 2 Example 3 Example 4 Hydrogenation operation conditions: Temperature / °C 350 350 360 320 Hydrogen partial pressure / MPa 14 14 10 16 <![CDATA[Space velocity per hour -1 > 1 1 0.5 1.5 Hydrogen-to-oil volume ratio 1200 1200 1000 1500 Properties of hydrogenation products: <![CDATA[Kinematic viscosity (100 °C) / (mm 2 / s)]]> 8.239 8.239 9.124 8.765 Refractive index (20℃) 1.5021 1.5021 1.5123 1.5089 Aromatics / wt% 64.7 64.7 78.5 75.4 Alkylation operating conditions Reaction temperature / ℃ 50 40 50 30 Reaction time / min 60 30 60 90 feedstock / olefin weight ratio 1:2 1:2 1:1 1:3 catalyst / olefin weight ratio 0.2:1 0.2:1 0.2:1 0.3:1 Properties of alkylated heavy fraction: Heavy distillation range / ℃ >520 >520 >520 >500 <![CDATA[Kinematic viscosity (100 °C) / (mm 2 / s)]]> 39.24 33.69 44.72 41.51 Viscosity Index 99 96 92 94 Pour point / ℃ -18 -18 -12 -12 Total acid value (mgKOH / g) <0.02 <0.02 <0.02 <0.02 Oxidation stability time / min 385 235 189 201

[0128] Table 3

[0129] project Example 5 Example 6 Example 7 Example 8 Example 9 Hydrogenation operation conditions: Temperature / °C 350 380 310 350 350 Hydrogen partial pressure / MPa 12 17 9 14 14 <![CDATA[Space velocity per hour -1 > 1 1.5 0.5 1 1 Hydrogen-to-oil volume ratio 1200 1200 1200 1200 1200 Properties of hydrogenation products: <![CDATA[Kinematic viscosity (100 °C) / (mm 2 / s)]]> 9.012 7.104 10.52 8.239 5.984 Refractive index (20℃) 1.5123 1.487 1.532 1.5021 1.452 Aromatics / wt% 71.2 35.2 84.2 67.3 37.1 Alkylation operating conditions Reaction temperature / ℃ 50 50 50 70 50 Reaction time / min 60 60 60 60 60 feedstock / olefin weight ratio 1:2 1:2 1:2 1:5 1:2 catalyst / olefin weight ratio 0.2:1 0.2:1 0.2:1 0.5:1 0.2:1 Properties of alkylated heavy fraction: Heavy distillation range / ℃ >500 >520 >520 >520 >520 <![CDATA[Kinematic viscosity (100 °C) / (mm 2 / s)]]> 32.34 24.15 46.72 23.2 14.32 Viscosity Index 97 98 82 104 75 Pour point / ℃ -18 -27 -6 -18 9 Total acid value (mgKOH / g) <0.02 <0.02 <0.02 <0.02 <0.02 Oxidation stability time / min 267 313 174 289 156

[0130] Table 4

[0131] project Comparative Example 1 Comparative Example 2 crude oil Heavy distillate oil I Heavy distillate oil I Hydrogenation operation conditions: No hydrogen added Hydrogenation Temperature / °C / 350 Hydrogen partial pressure / MPa / 14 <![CDATA[Space velocity per hour -1 > / 1 Hydrogen-to-oil volume ratio / 1200 Properties of hydrogenation products: / <![CDATA[Kinematic viscosity (100 °C) / (mm 2 / s)]]> / 8.239 Refractive index (20℃) / 1.5021 Aromatics / wt% / 64.7 Alkylation operating conditions / catalyst Trifluoromethanesulfonic acid Aluminum trichloride Reaction temperature / ℃ 50 90 Reaction time / min 60 30 feedstock / olefin weight ratio 1:2 1:2 catalyst / olefin weight ratio 0.2:1 0.1:1 Properties of alkylated heavy fraction: Heavy distillation range / ℃ >520 >520 <![CDATA[Kinematic viscosity (100 °C) / (mm 2 / s)]]> 51.2 33.15 Viscosity Index 51 97 Pour point / ℃ 3 -18 Total acid value (mgKOH / g) <0.02 0.15 Oxidation stability time / min 142 297

[0132] As shown in Table 2, the method provided by this invention, especially with the hydrotreating conditions specified, is within the preferred protection range; combined with alkylation treatment, especially with the alkylation treatment conditions specified within the preferred protection range, using catalytic cracking slurry as feedstock, a kinematic viscosity > 30 mm is obtained. 2 Bright oil products with a viscosity index ≥90 and a viscosity index of ≥90.

[0133] Compared to Example 1, the hydrogenation treatment conditions specified in Example 6 are all higher than the protection range specified in this invention. The refractive index of the hydrogenated product is lower than 1.50, and the viscosity index of the product is higher, but the viscosity is lower, but it still meets the viscosity index requirements of bright oil products.

[0134] Compared to Example 1, the hydrogenation treatment conditions specified in Example 7 are all lower than the protection range specified in this invention. The refractive index of the hydrogenated product is higher than 1.52, and the viscosity of the resulting bright oil product is higher, but the viscosity index is lower. However, it still meets the viscosity index requirements for bright oil products.

[0135] Compared to Example 1, the alkylation reaction conditions specified in Example 8 are not within the preferred protection range defined by this invention. The resulting bright oil product has a higher viscosity index but a lower viscosity, but still meets the viscosity requirements for bright oil products.

[0136] Compared to Example 1, the catalytic cracking slurry in Comparative Example 1 was not hydrogenated and was reacted with olefins through alkylation to obtain heavy component products. The product had a higher viscosity, but a lower viscosity index, which did not meet the viscosity index requirements for bright oil products.

[0137] Compared to Example 1, Comparative Example 2 uses aluminum trichloride, which reacts with olefins via alkylation to obtain a heavy component product. The viscosity and viscosity index of the heavy component product are comparable to those of the product when trifluoromethanesulfonic acid is used, but the acid value of the product is too high, which cannot meet the requirement of bright oil for an acid value ((mgKOH / g)) of less than 0.05%.

[0138] Therefore, the method and apparatus provided by this invention can produce bright oil products with both high viscosity and high viscosity index, which not only expands the source of raw materials, but also the products have good low-temperature fluidity and oxidation stability.

[0139] 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 producing gloss varnish, characterized in that, The method includes: (1) In the presence of hydrogen, heavy distillate oil is contacted with a hydrogenation catalyst and hydrogenation reaction is carried out under hydrogenation treatment conditions to obtain hydrogenation products; the heavy distillate oil contains aromatics, selected from one or more of catalytic cracking slurry oil, catalytic cracking cycle oil and coal tar middle fraction; the boiling range of the heavy distillate oil is 300-540℃, and its aromatic content is 60-90wt%; the aromatic content of the hydrogenation products is controlled to be 60-80wt%, and the refractive index at 20℃ is 1.50-1.52; (2) In the presence of a strong acid catalyst, the aromatics in the hydrogenation product and the C10~C20 olefins in the olefin oil undergo an alkylation reaction under alkylation reaction conditions to obtain an alkylated product; (3) The alkylation product is distilled to separate the heavy distillate at a temperature greater than 500°C to obtain a bright oil product.

2. The method for producing gloss varnish according to claim 1, characterized in that, The distillation range of the heavy distillate oil is 350-520℃, and its aromatic content is 60-85wt%.

3. The method for producing gloss varnish according to claim 2, characterized in that, The heavy distillate oil has a boiling range of 400-520℃ and an aromatic content of 70-85wt%.

4. The method for producing gloss varnish according to claim 1, characterized in that, The method also includes a raw material pretreatment step: (1-1) After the catalytic cracking slurry is desolidified, the intermediate fraction obtained by distillation is used as the heavy distillate in step (1); the distillation range of the intermediate fraction is 400-520℃, and the aromatic content is 70-85wt%; the solid content in the catalytic cracking slurry after desolidification is ≤0.2wt%.

5. The method for producing gloss varnish according to claim 4, characterized in that, The solid content in the catalytic cracking slurry after solidification treatment is ≤0.1wt%.

6. The method for producing gloss varnish according to any one of claims 1-5, characterized in that, The hydrogenation catalyst is a supported catalyst, comprising a support and an active component supported on the support. The support is selected from alumina and / or silica, and the active component is selected from nickel and / or cobalt, as well as molybdenum and / or tungsten.

7. The method for producing gloss varnish according to claim 6, characterized in that, In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst and calculated as metal oxides, the content of nickel and / or cobalt is 0.5-8 wt%; and the content of molybdenum and / or tungsten is 5-35 wt%.

8. The method for producing gloss varnish according to claim 7, characterized in that, In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst and calculated as metal oxides, the content of nickel and / or cobalt is 1-5 wt%, and the content of molybdenum and / or tungsten is 10-30 wt%.

9. The method for producing gloss varnish according to any one of claims 1-5, characterized in that, In step (1), the hydrogenation conditions are: temperature 290-380℃, pressure 8-18 MPa, and volume hourly space velocity 0.3-3 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500-2000:

1.

10. The method for producing gloss varnish according to claim 9, characterized in that, In step (1), the hydrogenation conditions are: temperature 320-360℃, pressure 10-16 MPa, and volume hourly space velocity (VHSV) 0.5-1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 1000-1500:

1.

11. The method for producing gloss varnish according to any one of claims 1-5, characterized in that, In step (2), the strong acid catalyst is selected from liquid acids with an acidity coefficient of less than 0.

12. The method for producing gloss varnish according to claim 11, characterized in that, The strong acid catalyst is selected from super-strong liquid acids with an acidity coefficient of less than -5.

13. The method for producing gloss varnish according to claim 12, characterized in that, The strong acid catalyst is selected from at least one of concentrated sulfuric acid, trifluoromethanesulfonic acid, fluorosulfonic acid, perchloric acid, and hydrobromic acid.

14. The method for producing gloss varnish according to claim 13, characterized in that, The strong acid catalyst is selected from concentrated sulfuric acid and / or trifluoromethanesulfonic acid.

15. The method for producing gloss varnish according to any one of claims 1-5, characterized in that, In step (2), the weight ratio of the hydrogenation product to the olefin is 1:0.3-5, the weight ratio of the strong acid catalyst to the olefin is 0.01-0.5:1, the olefin oil contains 50-100 wt% olefins, and the olefins are α-olefins, internal olefins, or dienes.

16. The method for producing gloss varnish according to claim 15, characterized in that, The hydrogenation product is subjected to an alkylation reaction with C12-C16 olefins in the olefin oil, wherein the olefin content in the olefin oil is 70wt%~100wt%.

17. The method for producing gloss varnish according to claim 15, characterized in that, The weight ratio of the hydrogenation product to the olefin is 1:1-5, and the weight ratio of the strong acid catalyst to the olefin is 0.2-0.5:

1.

18. The method for producing gloss varnish according to any one of claims 1-5, characterized in that, In step (2), the alkylation reaction conditions are: temperature 0-60℃ and time 5-300 min.

19. The method for producing gloss varnish according to claim 18, characterized in that, The temperature is 20-55℃, and the time is 20-90 min.

20. An apparatus for producing bright varnish, characterized in that, A method for producing bright oil according to any one of claims 4-19, the apparatus comprising a feed pre-fractionation tower, a hydrogenation reactor, an alkylation reactor, and a product distillation tower connected in sequence, wherein the feed pre-fractionation tower has a feed inlet, a top stream outlet, a side stream outlet, and a bottom stream outlet; the side stream outlet is connected to the hydrogenation reactor, the hydrogenation reactor is packed with a hydrogenation catalyst, and has a hydrogen inlet, a feed inlet, and a hydrogenated product outlet; the alkylation reactor has a hydrogenated product inlet, an olefin oil inlet, an alkylation catalyst inlet, an alkylation product outlet, and an alkylation catalyst outlet, and the alkylation reactor is a mixed-flow reactor; the product distillation tower has an alkylation product inlet, a top product outlet, and a bottom product outlet; both the feed pre-fractionation tower and the product distillation tower are packed towers.

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