Method for producing lubricant base oil from heavy raw material and obtained lubricant base oil

Abstract

The invention provides a method for producing lubricating oil base oil from a heavy raw material and the obtained lubricating oil base oil, and the method comprises the following steps: cutting the heavy raw material to obtain a light component, a middle fraction and tower bottom wax; wherein the boiling point ranges of the light component, the middle fraction and the tower bottom wax are 170-300 DEG C, 300-500 DEG C and gt respectively; 500 DEG C; carrying out a first isomerization reaction on the tower bottom wax under the catalytic action of a first isomerization catalyst to obtain a first isomerization reaction product; performing a second isomerization reaction on the first isomerization reaction product and the middle fraction under the catalytic action of a second isomerization catalyst to obtain a second isomerization reaction product; and carrying out hydrofining on the second isomerization reaction product, and carrying out fractionation cutting on the obtained refined product to obtain the lubricant base oil. The lubricating oil base oil product produced by the method provided by the invention has the advantages of high yield, low condensation point, low pour point, low cloud point and high viscosity index, and is high-quality lubricating oil base oil.

Description

Technical Field

[0001] The invention relates to a method for producing lubricating oil base oil from heavy raw materials and the obtained lubricating oil base oil, belonging to the technical field of lubricating oil base oil production. Background Art

[0002] Lubricating oil base oil is one of the specialty products of oil refining and an important product for creating profits for refineries. With the increasingly stringent market requirements for high quality and long life of lubricating oil, the demand for Class II and Class III base oils produced by hydroisomerization technology is increasing year by year. The deep isomerization conversion catalyst of chain alkanes is the key to hydroisomerization technology. Among them, the active metal generally uses precious metals such as Pt, Rh, and Pd, which play a role in dehydrogenation and hydrogenation of alkanes or olefins; the carrier is mainly a molecular sieve such as SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-48 and IZM-2 with a one-dimensional straight pore structure, which provides acidity and plays a role in pore restriction and shape selectivity in the isomerization reaction process. Its pore confinement and acidic characteristics determine the conversion ability of different raw material molecules and the difference in product structure. Among them, the one-dimensional circular pore size of ZSM-48 molecular sieve is larger and has suitable acidity, which is more suitable for removing the single-branched / double-branched isomers formed by the isomerization of long-chain normal alkanes from the pores, and is suitable for the hydroisomerization of heavy raw materials such as Fischer-Tropsch synthesis oil, hydrocracking tail oil, and high-wax VGO to produce base oil. Therefore, the preparation of lubricating oil isomerization dewaxing catalyst with suitable silicon-aluminum ratio and grain size ZSM-48 molecular sieve as carrier has high application value.

[0003] The following will introduce some prior arts related to the present invention and briefly explain their defects or shortcomings relative to the present invention.

[0004] US 7704379B2 uses the hydrotreated SASOLTM PARAFLINTTMC80F-T synthetic wax obtained from Moore and Munger, Inc, (Shelton, Conn.) without other treatment as raw material, wherein C80 wax mainly contains straight-linked alkanes and a small amount of olefins and oxygenates, and SASOLTM contains three grades of FT synthetic wax: PARAFLINTTMH1, +371°C full-range FT synthetic wax, PARAFLINTTMC80 and C105, 371-593°C and +593°C fractions. This technology uses bifunctional catalytic hydrogenation isomerization FT synthetic wax and waxy raffinate, wherein the dual reaction beds are arranged in series, the first reaction bed is equipped with Pt / Beta catalyst, and the second reaction bed is equipped with Pt / ZSM-48 catalyst, which has high selectivity for wax isomerization, and the lubricating oil produces the least gas when hydrogenating and decondensing. The defects of this technology or the shortcomings of the present invention are: two dewaxing catalysts are required for heavier Fischer-Tropsch wax raw materials, which increases gas production and reduces lubricating oil yield.

[0005] US 6051129A first combines EU-1 molecular sieve with ZSM-48 or SSZ-32 to prepare a catalyst, and then uses the catalyst to catalyze bright oil / refined lubricating oil to react with hydrogen to dewax, so as to reduce the haze point of bright oil / refined lubricating oil. The defects of this technology or the shortcomings of the present invention include: two molecular sieves need to be used together to prepare the catalyst.

[0006] The prior art such as US 8263517B2 provides a process for producing naphtha, diesel and lubricating base oil under acidic medium, which reduces the processing cost under high S and high N conditions, increases the flexibility of raw material selection, and performs the dewaxing step without desulfurization and denitrogenation of the acidic raw material, or dewaxes under acidic conditions after separation under high pressure. Under acidic conditions, the raw material is preliminarily dewaxed and selectively hydrocracking and dewaxing, and the raw material is separated into diesel and bottom fractions, and the bottom fraction is further hydrocracking and dewaxed to form diesel and lubricating base oil. Fractional distillation and fractional separation improve the diesel yield. Various combinations of hydrotreatment, catalytic dewaxing, hydrocracking and hydrofining are used to produce fuel oil products and lubricating base oil products. Deionized water, 56% hexamethylammonium chloride, fumed silica, 45% sodium aluminate and 50% sodium hydroxide are used as raw materials, 0.15% ZSM-48 is used as a seed, and crystallization is carried out at 160°C for 48 hours at a rotation speed of 250r / min to prepare SiO 2 / Al 2 O 3 =70-110 ZSM-48 molecular sieve, and then load 0.6wt% Pt on the ZSM-48 molecular sieve to form a dewaxing catalyst. The defects of this technology or the shortcomings of the present invention are: the use of seed crystals in the preparation process of ZSM-48 molecular sieve has a high noble metal loading.

[0007] CN 115678602A provides a method for treating Fischer-Tropsch wax, which comprises the following steps: subjecting the Fischer-Tropsch wax to an isomerization cracking reaction to obtain product A; subjecting product A to a first separation to obtain fraction A1 with a distillation range of <150°C, fraction A2 with a distillation range of 150-350°C, fraction A3 with a distillation range of 350-580°C and fraction A4 with a distillation range of >580°C; subjecting fraction A3 to an isomerization dewaxing reaction to obtain product B; subjecting product B to a second separation to obtain fraction B1 with a distillation range of <150°C, fraction B2 with a distillation range of 150-350°C and base oil B3; subjecting fraction A4 to a deoiling treatment to obtain microcrystalline wax; and mixing fraction A2 and fraction B2 to obtain diesel. The adoption of this technical solution not only obtains high-grade API III+ base oil products, but also obtains high-performance microcrystalline wax and diesel, thereby realizing the efficient utilization of Fischer-Tropsch wax; the defects of this technology or the shortcomings relative to the present invention are: multiple distillations, high energy consumption and complex and difficult to control processes.

[0008] CN 115678610A provides a method for preparing lubricating oil base oil from Fischer-Tropsch wax, the method comprising: cutting Fischer-Tropsch wax to obtain a first fraction, a second fraction and a tower bottom wax; using a first activated isomerization catalyst and a second activated isomerization catalyst to perform isomerization reaction on the first fraction and the second fraction respectively to obtain a first isomerized oil and a second isomerized oil; using a first activated refining catalyst and a second activated refining catalyst to perform refining reaction on the first isomerized oil and the second isomerized oil respectively to obtain a first base oil product and a second base oil product; the preparation method of the first activated isomerization catalyst and the second activated isomerization catalyst comprises: performing a reduction reaction on the first isomerization catalyst and the second isomerization catalyst to obtain a reduced first isomerization catalyst and a reduced second isomerization catalyst; performing an initial activation stabilization reaction on the reduced first isomerization catalyst and the reduced second isomerization catalyst to obtain a first activated isomerization catalyst and a second activated isomerization catalyst. The defects of this technology or the shortcomings relative to the present invention are: two isomerization and two refining agents need to be used and the process is relatively complicated.

[0009] CN 111484873A discloses a method for preparing a lubricating oil base oil, comprising: (1) contacting Fischer-Tropsch wax with catalyst A, and fractionating material I obtained after the contact reaction to obtain a light component, a middle component and a heavy component, respectively, wherein the fractionation points of the light component and the middle component are 320-420° C., and the fractionation points of the middle component and the heavy component are 500-580° C.; (2) contacting the middle component with catalyst B to obtain material II; and contacting the heavy component with catalyst C to obtain material III; (3) contacting material II and material III with catalyst A, and fractionating material IV obtained after the contact reaction, wherein both catalyst B and catalyst C contain molecular sieves, and the pore size of the molecular sieve in catalyst C is larger than the pore size of the molecular sieve in catalyst B. Although this method obtains a high yield of lubricating base oil, the defects of this technology or the shortcomings relative to the present invention include that after the medium and heavy components are subjected to isomerization reactions on different isomerization catalysts, the products are mixed and then subjected to refining reactions, and then fractionated to obtain components such as lubricating base oil, which results in high energy consumption and reduced efficiency.

[0010] Therefore, providing a new method for producing lubricating oil base oil from heavy raw materials and the obtained lubricating oil base oil has become a technical problem that needs to be solved urgently in the field. Summary of the invention

[0011] In order to solve the problems of low yield, high freezing point, high cloud point, etc. in the prior art when producing lubricating oil base oil, an object of the present invention is to provide a method for producing lubricating oil base oil from heavy raw materials.

[0012] Another object of the present invention is to provide a lubricating oil base oil, which is produced by the above-mentioned method for producing lubricating oil base oil from heavy raw materials.

[0013] In order to achieve the above objectives, on the one hand, the present invention provides a method for producing lubricating oil base oil from heavy raw materials, wherein the method comprises:

[0014] Step 1: Cut the heavy raw material to obtain light components, middle fractions and bottom wax; wherein the boiling point ranges of the light components, middle fractions and bottom wax are 170-300°C, 300-500°C and >500°C respectively;

[0015] Step 2: subjecting the tower bottom wax to a first isomerization reaction under the catalytic action of a first isomerization catalyst to obtain a first isomerization reaction product;

[0016] Step 3: subjecting the first isomerization reaction product and the intermediate fraction to a second isomerization reaction under the catalytic action of a second isomerization catalyst to obtain a second isomerization reaction product;

[0017] Step 4: subjecting the second isomerization reaction product to hydrofining, and then fractionating and cutting the obtained refined product to obtain lubricating oil base oil.

[0018] As a specific embodiment of the method described above in the present invention, the heavy feedstock includes one or a combination of several of Fischer-Tropsch synthetic oil, hydrocracking tail oil, high-wax VGO and Fischer-Tropsch wax.

[0019] In the present invention, the cutting points for cutting the heavy raw material are 300°C and 500°C respectively, the fraction with a boiling point range of 170-300°C belongs to the light component, the fraction with a boiling point range of greater than 300°C and less than or equal to 500°C belongs to the middle fraction, and the fraction with a boiling point range of greater than 500°C belongs to the bottom wax. If the bottom wax and the middle fraction in the heavy raw material are not cut, but are subjected to isomerization reaction together, when the reaction temperature is low, the isomerization reaction of the bottom wax (heavy component) is not sufficient, and the pour point reduction effect is poor. When the reaction temperature is high, the isomerization reaction of the bottom wax is sufficient, but the middle fraction will overreact due to side reactions, such as cracking reactions, thereby reducing the base oil yield and failing to achieve the desired effect. Therefore, the method for producing lubricating oil base oil from heavy raw materials provided by the present invention first performs a first isomerization reaction on the bottom wax, and then mixes the first isomerization reaction product with the middle fraction to perform a second isomerization reaction together, so that the bottom wax reaches the desired isomerization reaction degree, and the middle fraction will not overreact.

[0020] In the present invention, when the heavy raw material is Fischer-Tropsch synthetic oil, Fischer-Tropsch wax or high-wax VGO, it is necessary to hydrotreat these heavy raw materials before cutting them. However, the present invention does not make specific requirements on the operating steps of hydrotreating and the process parameters used, as long as it can ensure that the heavy raw materials can be subjected to olefin saturation and deoxygenation reactions, thereby removing olefins and oxygen-containing compounds therein and avoiding the generation of water in the subsequent isomerization reaction.

[0021] As a specific embodiment of the above method of the present invention, the volume ratio of the first isomerization catalyst to the second isomerization catalyst is 1-2:1.

[0022] As a specific embodiment of the method described above, the volume space velocity of the first isomerization reaction is 0.2-1.0h -1 , the hydrogen-oil ratio is 300:1-1000:1, the reaction temperature is 300-400°C, and the pressure is 3-16MPa.

[0023] As a specific embodiment of the method described above, the volume space velocity of the first isomerization reaction is 0.5-1.0h -1 , the hydrogen-oil ratio is 500:1-800:1, and the reaction temperature is 310-350°C.

[0024] As a specific embodiment of the method described above, the volume space velocity of the second isomerization reaction is 1.0-2.0h -1 , the hydrogen-oil ratio is 300:1-1000:1, the reaction temperature is 300-400°C, and the pressure is 3-16MPa.

[0025] As a specific embodiment of the method described above, the volume space velocity of the second isomerization reaction is 1.5-1.8h -1 , the hydrogen-oil ratio is 500:1-800:1, and the reaction temperature is 310-350°C.

[0026] As a specific embodiment of the above method of the present invention, the first isomerization reaction and the second isomerization reaction are both carried out in an isomerization reactor, and the hydrotreating is carried out in a hydrotreating reactor, and both the isomerization reactor and the hydrotreating reactor are conventional equipment.

[0027] As a specific embodiment of the method described above, the first isomerization catalyst and the second isomerization catalyst are the same or different. When the first isomerization catalyst and the second isomerization catalyst are different, they can be the silicon-aluminum ratio of the ZSM-48 molecular sieve in the ZSM-48 molecular sieve carrier, that is, SiO 2 and Al 2 O 3The invention relates to isomerized catalysts having different molar ratios of the active components and / or different loading amounts of the active components.

[0028] As a specific embodiment of the above method of the present invention, the carrier of the first isomerization catalyst and the second isomerization catalyst is a ZSM-48 molecular sieve carrier, the active component is a noble metal, and the total weight of the carrier is 100%, and the loading amount of the active component is 0.1-1.0wt%, preferably 0.1-0.5wt%;

[0029] The ZSM-48 molecular sieve carrier comprises ZSM-48 molecular sieve, SiO 2 and Al 2 O 3 The molar ratio is 50-400, preferably 100-200, the crystal length of ZSM-48 molecular sieve is 0.1-0.5 μm, the crystal diameter is 50-100 nm, and the axis-to-diameter ratio is less than 20, preferably 2-10. In the present invention, the axis-to-diameter ratio is the ratio of the molecular sieve crystal length to the cross-sectional width.

[0030] As a specific embodiment of the above method of the present invention, the precious metal includes platinum and / or palladium.

[0031] As a specific embodiment of the above method of the present invention, the preparation method of the first isomerization catalyst and the second isomerization catalyst comprises:

[0032] Step (1): dissolving a noble metal salt in a mixed solution of water, alcohol and ligand and mixing them evenly to obtain a noble metal precursor solution;

[0033] Step (2): impregnating particles of the ZSM-48 molecular sieve carrier into a precious metal precursor solution, and then drying and calcining the impregnated product to obtain the first isomerization catalyst and the second isomerization catalyst.

[0034] As a specific embodiment of the above method of the present invention, the noble metal salt includes one or a combination of chloroplatinic acid hexahydrate, palladium chloride, platinum dichloride, ammonium hexachloroplatinate, etc.

[0035] As a specific embodiment of the above method of the present invention, the ligand includes one or a combination of sorbic acid, salicylic acid, niacinamide, lactic acid, citric acid, hyaluronic acid, etc., and the molar ratio of the ligand to the noble metal atom is 6-18: 1. In the process of preparing the isomerized catalyst, the ligand is complexed with the noble metal atom and loaded on the carrier, which is conducive to the dispersion of the noble metal atoms. The presence of the ligand can also hinder the aggregation of the noble metal to form large particles to a certain extent.

[0036] As a specific embodiment of the above method of the present invention, the alcohol includes one or a combination of ethanol, propanol, isopropanol, glycerol, etc., preferably glycerol, and the mass ratio of water to alcohol is 50-1:1, preferably 20-10:1.

[0037] As a specific embodiment of the above method of the present invention, in step (1), the uniform mixing is performed at 30-60° C. for 2-6 hours.

[0038] As a specific embodiment of the above method of the present invention, in step (2), the calcination is carried out in an air atmosphere at 400-600° C. for 4-14 hours, preferably at 400-500° C. for 6-14 hours.

[0039] In the preparation method of the isomerized catalyst provided by the present invention, extrusion, drying, and baking are all conventional operations, and the operating steps of extrusion, drying, and baking and the process parameters involved can be reasonably adjusted according to the actual operation needs on site.

[0040] As a specific embodiment of the above method of the present invention, the preparation method of the ZSM-48 molecular sieve carrier includes:

[0041] Mix ZSM-48 molecular sieve, alumina, titanium dioxide, acid solution, binder and deionized water evenly;

[0042] The obtained mixture is then extruded, dried and calcined to obtain a ZSM-48 molecular sieve carrier;

[0043] Among them, the mass ratio of ZSM-48 molecular sieve, alumina, titanium dioxide, acid solution, adhesive and deionized water is 1:0.3-9:0.01-0.5:0.01-0.6:0.3-1:0.2-1, preferably 1:0.5-2:0.02-0.05:0.02-0.5:0.5-0.8:0.5-0.8.

[0044] As a specific embodiment of the above method of the present invention, the binder includes sesbania powder and / or methyl cellulose, etc., preferably sesbania powder; the acid solution includes nitric acid or phosphoric acid solution with a concentration of 5-15wt%, etc., preferably nitric acid. The alumina is common alumina such as pseudo-boehmite.

[0045] As a specific embodiment of the above method of the present invention, the obtained mixture is extruded, dried and calcined at 400-500° C. for 6-14 hours to obtain a ZSM-48 molecular sieve carrier.

[0046] As a specific embodiment of the above method of the present invention, the preparation method of the ZSM-48 molecular sieve comprises:

[0047] First, an aluminum source, a silicon source, an alkali source, a crystallization inducing agent, a template agent, deionized water, a pore-forming agent and a charge balancing agent are uniformly mixed to obtain a gel solution, and then the gel solution is pre-crystallized at 70-90° C. for 2-6 hours, crystallized at 120-140° C. for 2-6 hours, and crystallized at 140-170° C. for 10-48 hours, and then the crystallized product is washed, dried and calcined to obtain a molecular sieve precursor, and then the molecular sieve precursor is mixed with an ammonium salt at 70-80° C. for 4-6 hours, and then washed, dried and calcined to obtain;

[0048] Among them, Al 2 O 3 Aluminum source, OH - The alkali source, template, H 2 O and SiO 2 The molar ratio of the silicon source is 0.0025-0.02:0.006-0.38:0.11-1.5:10-50:1, preferably 0.005-0.01:0.015-0.25:0.2-1:20-40:1;

[0049] Pore-forming agent and SiO 2 The molar ratio of the silicon source is 0.01-0.2:1, preferably 0.01-0.1:1;

[0050] M 2 O-based crystallization inducing agent and SiO 2 The molar ratio of the silicon source is 0.002-0.2:1, preferably 0.005-0.03:1, wherein M is one or more of alkali metals;

[0051] Charge balancer and H 2 The molar ratio of O is 0.1-1:1, preferably 0.2-0.5:1.

[0052] As a specific embodiment of the above method of the present invention, in the preparation method of ZSM-48 molecular sieve, the amount of the pore former is within 5wt% of the total weight of the gel solution.

[0053] As a specific embodiment of the method described above, in the preparation method of ZSM-48 molecular sieve, M 2 The amount of the crystallization inducing agent is within 5 wt % of the total weight of the gel solution.

[0054] As a specific embodiment of the above method of the present invention, the aluminum source includes one or a combination of aluminum sulfate, sodium aluminate, aluminum nitrate, etc., preferably aluminum sulfate;

[0055] The silicon source includes one or a combination of silica sol, white carbon black, ethyl orthosilicate, etc., preferably silica sol;

[0056] The alkali source includes NaOH and / or KOH and the like.

[0057] As a specific embodiment of the above method of the present invention, wherein the template comprises a first template and a second template, and the molar ratio of the first template to the second template is 1-400:1;

[0058] The first template agent includes one or a combination of cyclohexylamine, dodecylamine, 1,6-hexanediamine, 1,8-octanediamine and benzylamine, and is preferably 1,6-hexanediamine. The second template agent includes one or a combination of hexamethylammonium chloride, hexamethylammonium bromide, ammonium oxalate, ammonium acetate and benzyltriethylammonium bromide, and is preferably hexamethylammonium chloride.

[0059] As a specific embodiment of the above method of the present invention, the ammonium salt includes one or a combination of ammonium chloride, ammonium nitrate and ammonium sulfate, preferably ammonium chloride.

[0060] As a specific embodiment of the above method of the present invention, the crystallization inducing agent includes one or a combination of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, etc., preferably potassium chloride;

[0061] The pore-forming agent includes one or a combination of P123, Triton-100, polyhexamethylene biguanide, ammonium chloride, polyvinyl alcohol, etc., preferably P123;

[0062] The charge balancing agent includes one or a combination of glycerol, ethylene glycol, isopropyl alcohol, propanol, 2-butanol, etc., preferably isopropyl alcohol.

[0063] As a specific embodiment of the above method of the present invention, the relative molecular weight of P123 is 4000-8000.

[0064] As a specific embodiment of the above method of the present invention, aluminum source, silicon source, alkali source, crystallization inducing agent, template agent, deionized water, pore-forming agent and charge balancing agent are first mixed uniformly at 40-60° C. to obtain a gel solution.

[0065] As a specific embodiment of the above method of the present invention, the crystallized product is washed, dried and calcined at 500-600° C. for 6-30 hours to obtain a molecular sieve precursor.

[0066] As a specific embodiment of the above method of the present invention, the molecular sieve precursor is mixed with ammonium salt at 70-80°C for 4-6 hours, washed, dried and calcined at 500-600°C for 6-40 hours, preferably 6-30 hours, to obtain the ZSM-48 molecular sieve.

[0067] In the preparation method of the ZSM-48 molecular sieve provided by the present invention, washing, drying, etc. are all conventional operations, and the washing and drying operation steps and the process parameters involved can be reasonably adjusted according to the actual on-site operation needs.

[0068] As a specific embodiment of the method described above, in step 4, the temperature of the hydrofining is 200-300°C, and the volume space velocity is 0.5-2.0h -1 , pressure is 3-16MPa, hydrogen-oil volume ratio is 300-1000:1.

[0069] The present invention does not make specific requirements on the cutting point of the fractionation cutting in step 4, and the cutting point can be reasonably adjusted according to the properties of the heavy raw material and the properties of the target lubricating oil base oil.

[0070] On the other hand, the present invention also provides a lubricating oil base oil, wherein the lubricating oil base oil is produced by the above-mentioned method for producing lubricating oil base oil from heavy raw materials.

[0071] As a specific embodiment of the lubricating oil base oil described above in the present invention, the lubricating oil base oil has a solidification point ≯ -16°C, a pour point ≯ -10°C, a cloud point ≯ -1°C, and a viscosity index greater than 130.

[0072] Compared with the prior art, the beneficial technical effects that can be achieved by the present invention include:

[0073] 1) The present invention uses a crystallization inducer when preparing the ZSM-48 molecular sieve, which can induce more crystal nuclei to form quickly, greatly shorten the crystallization time, and reduce the grain size, that is, to form more small-grain molecular sieves, so that the grain length is only 0.1-0.5 μm. When the isomerization catalyst (whose carrier contains the above-mentioned ZSM-48 molecular sieve) is used to catalyze the production of lubricating oil base oil from heavy raw materials, it is beneficial for the product to diffuse out of the pores, thereby reducing the occurrence of cracking reactions;

[0074] 2) The present invention uses alcohols as charge balance agents when preparing ZSM-48 molecular sieves. Alcohols are soluble in water, and their molecular size is between that of water molecules and structure-directing agents (i.e., template agents, including first template agents and second template agents). Alcohols can enter the pores. In the process of molecular sieve synthesis, they can replace part of the water molecules to support / fill the pores. The hydroxyl groups contained in the alcohols form hydrogen bonds with the inorganic anion skeleton of the molecular sieve to maintain the charge balance in the pores, so that more water molecules in the crystallization system can act as solvents in the system (equivalent to an increase in the water phase), enhance fluidity, and evenly disperse the crystals in the solvent, making it easier to form small-crystal molecular sieves, that is, facilitating the formation of small crystals. In addition, alcohols as charge balance agents will not change the pH value of the system, thereby avoiding the formation of impurities, and the added charge balance agent is also beneficial to the uniform distribution of the acid sites of the molecular sieve. When the isomerized catalyst (whose carrier contains the above-mentioned ZSM-48 molecular sieve) is used to catalyze the production of lubricating oil base oil from heavy raw materials, the reaction efficiency can be improved.

[0075] 3) The present invention uses a pore-forming agent when preparing the ZSM-48 molecular sieve, and mesopores and micropores can be directly formed during the synthesis of the molecular sieve. When the isomerization catalyst (whose carrier contains the above-mentioned ZSM-48 molecular sieve) is used to catalyze the production of lubricating oil base oil from heavy raw materials, it is beneficial for the reactants and products to diffuse in the pores, thereby improving the diffusion efficiency of the reactants and products, improving the reaction efficiency and isomerization conversion rate, reducing the cracking rate, and reducing the amount of molecular sieve in the catalyst;

[0076] 4) When preparing the ZSM-48 molecular sieve of the present invention, the gel solution is pre-crystallized at 70-90° C. for 2-6 hours, crystallized at 120-140° C. for 2-6 hours, and crystallized at 140-170° C. for 10-48 hours, wherein the first stage of crystallization forms a primary structure, and the second stage of crystallization forms a large number of crystal nuclei, which is conducive to rapid growth into small crystals under the temperature conditions of the third stage of crystallization. The molecular sieve of small crystals has a short pore length, which is conducive to the rapid diffusion of reaction products from the pores, thereby reducing secondary cracking reactions;

[0077] 5) The preparation method of the present invention can directly synthesize short-axis ZSM-molecular sieves, shorten the pore length, and significantly improve the reaction efficiency when the isomerization catalyst (whose carrier contains the above-mentioned ZSM-48 molecular sieve) is used to catalyze heavy raw materials to produce lubricating oil base oil;

[0078] In summary, the pore size and acidity of the isomerization catalyst used in the present invention are suitable, which is conducive to the isomerization reaction of long-chain alkanes to produce more double-branched or multi-branched isomers. Small crystals and small axis-diameter ratios are conducive to the rapid diffusion of double-branched or multi-branched isomer products from the pores, thereby reducing the occurrence of cracking reactions.

[0079] 6) In the method for producing lubricating base oil from heavy raw materials provided by the present invention, the bottom wax is subjected to a first isomerization reaction under the catalytic action of a first isomerization catalyst to obtain a first isomerization reaction product; and the first isomerization reaction product and the intermediate fraction are subjected to a second isomerization reaction under the catalytic action of a second isomerization catalyst to obtain a second isomerization reaction product; wherein, the first isomerization reaction and the second isomerization reaction both use an isomerization catalyst whose carrier is a ZSM-48 molecular sieve carrier (i.e., a ZSM-48 molecular sieve catalyst having the same topological structure), and follow the same reaction law, which can reduce gas generation, and the lubricating base oil product has a high yield, a low freezing point, a low pour point, a low cloud point and a high viscosity index; and the bottom wax with a heavier fraction undergoes two isomerization reactions, which can deepen the degree of isomerization reaction and reduce the cloud point of the obtained lubricating base oil; in addition, the present invention can flexibly adjust the reaction conditions according to different raw materials and target products to control the reaction depth. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0081] Figure 1 A flow chart of a method for producing lubricating oil base oil from Fischer-Tropsch wax provided in an embodiment of the present invention.

[0082] Figure 2 This is the XRD diagram of the ZSM-48 molecular sieve provided in Example 1 of the present invention.

[0083] Figure 3 This is a SEM image of the ZSM-48 molecular sieve provided in Example 1 of the present invention.

[0084] Figure 4 The XRD pattern of the ZSM-48 molecular sieve provided for Comparative Example 2.

[0085] Figure 5 This is the SEM image of the ZSM-48 molecular sieve provided for Comparative Example 2.

[0086] Figure 6 The XRD pattern of the ZSM-48 molecular sieve provided for Comparative Example 3.

[0087] Figure 7 This is a SEM image of the ZSM-48 molecular sieve provided for Comparative Example 3.

[0088] Figure 8 The XRD pattern of the ZSM-48 molecular sieve provided for Comparative Example 5.

[0089] Fig. 9 The XRD pattern of the ZSM-48 molecular sieve provided for Comparative Example 6.

[0090] Description of main figures:

[0091] 1. The first fractionation tower;

[0092] 2. The first isomerization reactor;

[0093] 3. Second isomerization reactor;

[0094] 4. The first hydrotreating reactor;

[0095] 5. Second fractionation tower;

[0096] 6. The second hydrotreating reactor. DETAILED DESCRIPTION

[0097] It should be noted that the term "comprises" and any variations thereof in the specification and claims of the present invention and the above-mentioned drawings are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0098] "Scope" disclosed in the present invention is given in the form of lower limit and upper limit. It can be one or more lower limits, and one or more upper limits respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower limit and upper limit define the boundaries of a particular range. All ranges defined in this way are combinable, i.e. any lower limit can be combined with any upper limit to form a range. For example, for a specific parameter, a range of 60-120 and 80-110 is listed, and it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​listed are 1 and 2, and the maximum range values ​​listed are 3, 4 and 5, then the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.

[0099] In the present invention, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in the present invention, and "0-5" is just an abbreviation of these numerical combinations.

[0100] In the present invention, unless otherwise specified, all embodiments and preferred embodiments mentioned in the present invention can be combined with each other to form a new technical solution.

[0101] In the present invention, unless otherwise specified, all technical features and preferred features mentioned in the present invention can be combined with each other to form a new technical solution.

[0102] In the present invention, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0103] In the present invention, unless otherwise specified, "first" and "second" do not indicate a sequence or limit the materials or steps, but are only used to distinguish that they are not the same steps or materials. For example, "first" and "second" in "first isomerization reaction" and "second isomerization reaction" are only used to indicate that they are not the same isomerization reaction.

[0104] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the attached table, drawings and examples. The following described embodiments are some embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. If the specific conditions are not specified in the embodiments, they are carried out according to the normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0105] Isomerization Catalyst Examples and Comparative Examples

[0106] Example 1

[0107] This embodiment provides an isomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0108] Preparation of ZSM-48 molecular sieve:

[0109] Step 1): 0.32 g aluminum nitrate, 18 g ethyl orthosilicate, 1 g KOH, 2.58 g KCl, 0.2 g ammonium oxalate, 16 g 1,6-hexanediamine, 62.3 g deionized water, 5.1 g Triton X-100, and 100 g isopropanol are mixed uniformly at a temperature of 45° C. to obtain a gel solution;

[0110] Among them, Al 2 O 3 Aluminum source, OH - The alkali source, template, H 2 O and SiO 2 The molar ratio of the silicon source is 0.01:0.2:1.5:40:1;

[0111] Pore-forming agent and SiO 2 The molar ratio of the silicon source is 0.2:1;

[0112] K 2 O-based crystallization inducing agent and SiO 2 The molar ratio of the silicon source is 0.2:1;

[0113] Charge balancer and H 2 The molar ratio of O is 0.48:1;

[0114] The molar ratio of the first template to the second template is 85:1;

[0115] Step 2): pre-crystallizing the gel solution at 80° C. for 4 h, crystallizing at 130° C. for 4 h, and crystallizing at 160° C. for 20 h to obtain a crystallized product;

[0116] Step 3): washing, drying and calcining the crystallized product at 550° C. for 20 hours to obtain a molecular sieve precursor;

[0117] Step 4): the molecular sieve precursor is mixed with ammonium chloride at 75° C. for 4 hours, washed, dried and calcined at 530° C. for 24 hours to obtain a ZSM-48 molecular sieve;

[0118] Preparation of ZSM-48 molecular sieve carrier:

[0119] 10 g of the above-prepared ZSM-48 molecular sieve, 50 g of pseudo-boehmite, 2 g of titanium dioxide, 3 g of nitric acid solution (5 wt%), 5 g of sesbania powder, and 8 g of deionized water were uniformly mixed, wherein the mass ratio of each component was: ZSM-48 molecular sieve: alumina: titanium dioxide: acid solution: binder: deionized water = 1:5:0.2:0.3:0.5:0.8, and then the obtained mixture was extruded, dried, and calcined at 450° C. for 8 hours to obtain a ZSM-48 molecular sieve carrier;

[0120] Preparation of isomerization catalyst:

[0121] 0.27 g of platinum dichloride was dissolved in a mixture of 90 g of water, 10 g of isopropanol and 1.64 g of lactic acid, and mixed at 30° C. for 2 hours to obtain a noble metal precursor solution;

[0122] 100 g of ZSM-48 molecular sieve carrier particles were immersed in a precious metal precursor solution for 2 hours, then dried at 100°C for 2 hours, and finally calcined at 450°C in an air atmosphere for 4 hours to obtain an isomerized catalyst with a Pt loading of 0.20 wt%, recorded as catalyst A1.

[0123] Example 2

[0124] This embodiment provides an isomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0125] Preparation of ZSM-48 molecular sieve:

[0126] Step 1): 0.12 g aluminum nitrate, 18 g silica sol (40 wt% solid content), 1.86 g NaOH, 0.43 g potassium sulfate, 0.1 g benzyltriethylammonium bromide, 10 g benzylamine, 100 g deionized water, 7.2 g P123, and 46 g 2-butanol were mixed at 50° C. to obtain a gel solution;

[0127] Among them, Al 2 O 3 Aluminum source, OH - The alkali source, template, H 2 O and SiO 2 The molar ratio of the silicon source is 0.0026:0.38:0.76:50:1;

[0128] Pore-forming agent and SiO 2 The molar ratio of the silicon source is 0.01:1;

[0129] K 2 O-based crystallization inducing agent and SiO 2 The molar ratio of the silicon source is 0.02:1;

[0130] Charge balancer and H 2 The molar ratio of O is 0.1:1;

[0131] The molar ratio of the first template to the second template is 254:1;

[0132] Step 2): pre-crystallizing the gel solution at 85° C. for 5 h, crystallizing at 135° C. for 5 h, and crystallizing at 160° C. for 30 h to obtain a crystallized product;

[0133] Step 3): washing, drying and calcining the crystallized product at 530° C. for 12 hours to obtain a molecular sieve precursor;

[0134] Step 4): the molecular sieve precursor is mixed with ammonium chloride at 70° C. for 4 hours, washed, dried and calcined at 560° C. for 28 hours to obtain a ZSM-48 molecular sieve;

[0135] Preparation of ZSM-48 molecular sieve carrier:

[0136] 100 g of the above-prepared ZSM-48 molecular sieve, 50 g of pseudo-boehmite, 5 g of titanium dioxide, 8 g of nitric acid solution (5 wt%), 40 g of sesbania powder, and 30 g of deionized water were uniformly mixed, wherein the mass ratio of each component was: ZSM-48 molecular sieve: alumina: titanium dioxide: acid solution: binder: deionized water = 1:0.5:0.05:0.08:0.4:0.3, and then the obtained mixture was extruded, dried, and calcined at 480° C. for 10 hours to obtain a ZSM-48 molecular sieve carrier;

[0137] Preparation of isomerization catalyst:

[0138] 0.69 g of ammonium hexachloroplatinate was dissolved in a mixture of 95 g of water, 5 g of glycerol and 2.2 g of salicylic acid, and the mixture was mixed at 30° C. for 2 hours to obtain a noble metal precursor solution;

[0139] 100 g of ZSM-48 molecular sieve carrier particles were immersed in a precious metal precursor solution for 2 hours, then dried at 100°C for 2 hours, and finally calcined at 450°C in an air atmosphere for 4 hours to obtain an isomerized catalyst with a Pt loading of 0.30 wt%, recorded as catalyst A2.

[0140] Comparative Example 1

[0141] This comparative example provides an isomerization catalyst, which is denoted as catalyst A11, and the only difference between the catalyst and Example 1 is that Triton X-100 and isopropanol are not used in the preparation of ZSM-48 molecular sieve.

[0142] Comparative Example 2

[0143] This comparative example provides an isomerization catalyst, which is denoted as catalyst A12, and the only difference between the catalyst and Example 1 is that KCl is not used in the preparation of ZSM-48 molecular sieve.

[0144] Comparative Example 3

[0145] This comparative example provides an isomerization catalyst, which is denoted as catalyst A13, and the only difference between the catalyst and Example 1 is that isopropanol is not used in the preparation of ZSM-48 molecular sieve.

[0146] Comparative Example 4

[0147] This comparative example provides an isomerization catalyst, which is denoted as catalyst A14. The only difference between the catalyst and Example 1 is that in step 2), the gel solution is crystallized at 160° C. for 28 h.

[0148] Comparative Example 5

[0149] This comparative example provides an isomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0150] Preparation of ZSM-48 molecular sieve:

[0151] Step 1): 0.32 g aluminum nitrate, 18 g tetraethyl orthosilicate, 1 g KOH, 2.58 g KCl, 0.2 g ammonium oxalate, 16 g 1,6-hexanediamine, 62.3 g deionized water, 5.1 g Triton X-100, and 314.2 g bis(cyclopentadienyl)cobalt were mixed at 45° C. to obtain a gel solution;

[0152] Among them, Al 2 O 3 Aluminum source, OH - The alkali source, template, H 2 O and SiO 2 The molar ratio of the silicon source is 0.01:0.2:1.5:40:1;

[0153] Pore-forming agent and SiO 2 The molar ratio of the silicon source is 0.2:1;

[0154] K 2 O-based crystallization inducing agent and SiO 2 The molar ratio of the silicon source is 0.2:1;

[0155] Charge balancer and H 2 The molar ratio of O is 0.48:1;

[0156] The molar ratio of the first template to the second template is 85:1;

[0157] Step 2): pre-crystallizing the gel solution at 80° C. for 4 h, crystallizing at 130° C. for 4 h, and crystallizing at 160° C. for 20 h to obtain a crystallized product;

[0158] Step 3): washing, drying and calcining the crystallized product at 550° C. for 20 hours to obtain a molecular sieve precursor;

[0159] Step 4): the molecular sieve precursor is mixed with ammonium chloride at 75° C. for 4 hours, washed, dried and calcined at 530° C. for 24 hours to obtain a ZSM-48 molecular sieve, which also contains ZSM-5 impurities and amorphous silicon-aluminum;

[0160] Preparation of ZSM-48 molecular sieve carrier:

[0161] 10 g of the above-prepared ZSM-48 molecular sieve, 50 g of pseudo-boehmite, 2 g of titanium dioxide, 3 g of nitric acid solution (5 wt%), 5 g of sesbania powder, and 8 g of deionized water were uniformly mixed, wherein the mass ratio of each component was: ZSM-48 molecular sieve: alumina: titanium dioxide: acid solution: binder: deionized water = 1:5:0.2:0.3:0.5:0.8, and then the obtained mixture was extruded, dried, and calcined at 450° C. for 8 hours to obtain a ZSM-48 molecular sieve carrier;

[0162] Preparation of isomerization catalyst:

[0163] 0.27 g of platinum dichloride was dissolved in a mixture of 90 g of water, 10 g of isopropanol and 1.64 g of lactic acid, and mixed at 30° C. for 2 hours to obtain a noble metal precursor solution;

[0164] 100 g of ZSM-48 molecular sieve carrier particles were immersed in a precious metal precursor solution for 2 hours, then dried at 100°C for 2 hours, and finally calcined at 450°C in an air atmosphere for 4 hours to obtain an isomerized catalyst with a Pt loading of 0.20 wt%, recorded as catalyst A15.

[0165] Comparative Example 6

[0166] This comparative example provides an isomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0167] Preparation of ZSM-48 molecular sieve:

[0168] Step 1): 0.32 g aluminum nitrate, 18 g tetraethyl orthosilicate, 1 g KOH, 2.58 g KCl, 0.2 g ammonium oxalate, 16 g 1,6-hexanediamine, 62.3 g deionized water, 5.1 g Triton X-100, and 193.1 g 1,6-hexanediamine were mixed uniformly at a temperature of 45° C. to obtain a gel solution;

[0169] Among them, Al 2 O 3 Aluminum source, OH - The alkali source, template, H 2 O and SiO 2 The molar ratio of the silicon source is 0.01:0.2:1.5:40:1;

[0170] Pore-forming agent and SiO 2 The molar ratio of the silicon source is 0.2:1;

[0171] K 2 O-based crystallization inducing agent and SiO2 The molar ratio of the silicon source is 0.2:1;

[0172] Charge balancer and H 2 The molar ratio of O is 0.48:1;

[0173] The molar ratio of the first template to the second template is 85:1;

[0174] Step 2): pre-crystallizing the gel solution at 80° C. for 4 h, crystallizing at 130° C. for 4 h, and crystallizing at 160° C. for 20 h to obtain a crystallized product;

[0175] Step 3): washing, drying and calcining the crystallized product at 550° C. for 20 hours to obtain a molecular sieve precursor;

[0176] Step 4): the molecular sieve precursor is mixed with ammonium chloride at 75° C. for 4 hours, washed, dried and calcined at 530° C. for 24 hours to obtain a ZSM-48 molecular sieve, which also contains ZSM-5 impurities and amorphous silicon-aluminum;

[0177] Preparation of ZSM-48 molecular sieve carrier:

[0178] 10 g of the above-prepared ZSM-48 molecular sieve, 50 g of pseudo-boehmite, 2 g of titanium dioxide, 3 g of nitric acid solution (5 wt%), 5 g of sesbania powder, and 8 g of deionized water were uniformly mixed, wherein the mass ratio of each component was: ZSM-48 molecular sieve: alumina: titanium dioxide: acid solution: binder: deionized water = 1:5:0.2:0.3:0.5:0.8, and then the obtained mixture was extruded, dried, and calcined at 450° C. for 8 hours to obtain a ZSM-48 molecular sieve carrier;

[0179] Preparation of isomerization catalyst:

[0180] 0.27 g of platinum dichloride was dissolved in a mixture of 90 g of water, 10 g of isopropanol and 1.64 g of lactic acid, and mixed at 30° C. for 2 hours to obtain a noble metal precursor solution;

[0181] 100 g of ZSM-48 molecular sieve carrier particles were immersed in a precious metal precursor solution for 2 hours, then dried at 100°C for 2 hours, and finally calcined at 450°C in an air atmosphere for 4 hours to obtain an isomerized catalyst with a Pt loading of 0.20 wt%, recorded as catalyst A16.

[0182] The total BET specific surface area, micropore specific surface area and mesopore specific surface area data of the ZSM-48 molecular sieves provided by Examples 1 to 2 of the present invention and Comparative Examples 1 to 6 are shown in Table 1 below, respectively.

[0183] Table 1

[0184]

[0185] It can be seen from Table 1 above that the ZSM-48 molecular sieves provided in Examples 1 to 2 of the present invention and Comparative Examples 1 to 4 all have micropores and mesopores, but the total BET specific surface area and mesopore specific surface area of ​​the ZSM-48 molecular sieves prepared in the comparative examples are significantly lower than those of the ZSM-48 molecular sieves provided in the examples of the present invention.

[0186] The XRD pattern and SEM pattern of the ZSM-48 molecular sieve provided in Example 1 of the present invention are as follows: Figure 2 and Figure 3 As shown, the XRD pattern and SEM pattern of the ZSM-48 molecular sieve provided in Comparative Example 2 are respectively as shown in Figure 4 and Figure 5 As shown, the XRD pattern and SEM pattern of the ZSM-48 molecular sieve provided in Comparative Example 3 are respectively as shown in Figure 6 and Figure 7 As shown, the XRD pattern of the ZSM-48 molecular sieve provided in Comparative Example 5 is as follows Figure 8 As shown, the XRD pattern of the ZSM-48 molecular sieve provided in Comparative Example 6 is as follows Fig. 9 shown.

[0187] from Figure 2 It can be seen that the ZSM-48 molecular sieve prepared in Example 1 of the present invention is a pure phase ZSM-48 molecular sieve without impurity crystal formation; Figure 3 As can be seen from Table 1, the ZSM-48 molecular sieve prepared in Example 1 of the present invention has a grain length of 100-500 nm, a grain diameter of 50-100 nm, and an axis-to-diameter ratio of about 2-10, indicating that it is a short-axis ZSM-molecular sieve. Figure 3 , Figure 5 and Figure 7 As can be seen from the experimental data in Table 1, compared with the ZSM-48 molecular sieve provided in Example 1 of the present invention, the grain size of the ZSM-48 molecular sieve provided in the comparative example is larger.

[0188] contrast Figure 2 , Figure 8 and Fig. 9It can be seen that the ZSM-48 molecular sieve prepared in Example 1 of the present invention is a pure phase ZSM-48 molecular sieve without impurity crystal formation, while Comparative Examples 5 and 6 respectively add organic metal complexes (bis (cyclopentadiene) cobalt) and organic amines (1,6-hexanediamine) and other non-alcohol charge balance agents to prepare ZSM-48 molecular sieves. These non-alcohol charge balance agents will affect the pH value or structural orientation of the system, and are prone to produce impurity crystals or amorphous. At the same time, as shown in Table 1 above, compared with the ZSM-48 molecular sieve provided in Example 1, the ZSM-48 molecular sieves provided in Comparative Examples 5-Comparative Examples 6 have larger grain sizes and axial diameter ratios.

[0189] In summary, by comparing the ZSM-48 molecular sieves provided in Example 1 and Examples 5-6, it can be seen that compared with the bis(cyclopentadienyl)cobalt and 1,6-hexanediamine charge balancers used in Examples 5 and 6, Example 1 of the present invention uses isopropanol as an alcohol charge balancer to obtain a pure phase molecular sieve, and the molecular sieve has smaller parameters such as grain size and axial diameter ratio.

[0190] The acidity data of the isomerization catalysts provided by Examples 1 to 2 of the present invention and Comparative Examples 1 to 6 are shown in Table 2 below.

[0191] Table 2

[0192]

[0193]

[0194] As can be seen from Table 2, the contents of weak B acid (200°C) and medium-strong B acid (350°C) of the isomerized catalyst provided in the embodiment of the present invention are significantly higher than those of the isomerized catalyst provided in the comparative example. When the isomerized catalysts are used to produce lubricating oil base oil from heavy raw materials, the reaction efficiency can be significantly improved. For the isomerized catalysts provided in Comparative Examples 5 and 6, since the ZSM-48 molecular sieve used therein contains ZSM-5 miscellaneous crystals and amorphous silicon aluminum, the contents of weak B acid (200°C) and medium-strong B acid (350°C) of the isomerized catalysts are lower than those of the isomerized catalyst provided in Example 1.

[0195] Method Examples and Comparative Examples

[0196] Example 1-1

[0197] This embodiment provides a method for producing lubricating oil base oil with Fischer-Tropsch wax, and its flow chart is as follows: Figure 1 Said, from Figure 1 It can be seen that the method comprises the following specific steps:

[0198] Step 1: Hydrofining the Fischer-Tropsch wax in the first hydrofining reactor 4 to carry out olefin saturation and deoxygenation reactions to remove olefins and oxygen-containing compounds in the Fischer-Tropsch wax to avoid the generation of water in the subsequent isomerization reaction, and then cutting the hydrofined Fischer-Tropsch wax in the first fractionation tower 1 to obtain light components, middle fractions and bottom wax; wherein the boiling point ranges of the light components, middle fractions and bottom wax are 170-300°C, 300-500°C and >500°C, respectively;

[0199] Among them, the property parameters of the Fischer-Tropsch wax raw material are shown in Table 3 below.

[0200] Table 3

[0201]

[0202]

[0203] Step 2: allowing the tower bottom wax to enter the first isomerization reactor 2 filled with the catalyst A1, and subjecting the tower bottom wax to a first isomerization reaction under the catalytic action of the catalyst A1 to obtain a first isomerization reaction product;

[0204] Step 3: The first isomerization reaction product and the intermediate fraction are fed into a second isomerization reactor 3 filled with catalyst A1 to perform a second isomerization reaction to obtain a second isomerization reaction product;

[0205] The volume ratio of the catalyst A1 loaded in the second isomerization reactor 3 to the catalyst A1 loaded in the first isomerization reactor 2 is 1:1;

[0206] The volumetric space velocity of the first isomerization reaction is 0.2h -1 , hydrogen-oil ratio is 300:1, reaction temperature is 380°C, and pressure is 5MPa;

[0207] The volume space velocity of the second isomerization reaction is 2.0h -1 , hydrogen-oil ratio is 1000:1, reaction temperature is 300°C, pressure is 5MPa;

[0208] Step 4: the second isomerization reaction product is fed into the second hydrofining reactor 6 for hydrofining, and the obtained refined product is fractionated and cut in the second fractionation tower 5 to obtain lubricating oil base oil;

[0209] The hydrofining temperature is 200°C and the volume space velocity is 1.0h -1 , pressure is 5MPa, and the volume ratio of hydrogen to oil is 1000:1.

[0210] In this embodiment, the yield of the lubricating oil base oil is 62%, the solidification point is not greater than -17°C, the pour point ≯ -12°C, the cloud point ≯ -2°C, and the viscosity index is 136.

[0211] Example 2-1

[0212] This embodiment provides a method for producing lubricating oil base oil from Fischer-Tropsch wax, wherein the method comprises the following specific steps:

[0213] Step 1: Hydrofining the Fischer-Tropsch wax in the first hydrofining reactor to perform olefin saturation and deoxygenation reactions to remove olefins and oxygen-containing compounds in the Fischer-Tropsch wax to avoid the generation of water in the subsequent isomerization reaction, and then cutting the hydrofined Fischer-Tropsch wax (property parameters are shown in Table 3) in the first fractionation tower to obtain light components, middle fractions and bottom wax; wherein the boiling point ranges of the light components, middle fractions and bottom wax are 170-300°C, 300-500°C and >500°C, respectively;

[0214] Step 2: allowing the tower bottom wax to enter a first isomerization reactor filled with catalyst A2, and subjecting the tower bottom wax to a first isomerization reaction under the catalytic action of catalyst A2 to obtain a first isomerization reaction product;

[0215] Step 3: The first isomerization reaction product and the intermediate fraction are fed into a second isomerization reactor filled with catalyst A2 to perform a second isomerization reaction to obtain a second isomerization reaction product;

[0216] Wherein, the volume ratio of the catalyst A2 loaded in the second isomerization reactor to the catalyst A2 loaded in the first isomerization reactor is 1:2;

[0217] The volume space velocity of the first isomerization reaction is 1.0h -1 , hydrogen-oil ratio is 1000:1, reaction temperature is 300°C, and pressure is 8MPa;

[0218] The volumetric space velocity of the second isomerization reaction is 1.0h -1 , hydrogen-to-oil ratio is 300:1, reaction temperature is 370°C, and pressure is 8MPa;

[0219] Step 4: the second isomerization reaction product is introduced into a second hydrofining reactor for hydrofining, and then the obtained refined product is fractionated and cut in a second fractionation tower to obtain a lubricating oil base oil;

[0220] The hydrofining temperature is 300°C and the volume space velocity is 2.0h -1 , pressure is 8MPa, and the hydrogen-oil volume ratio is 800:1.

[0221] In this embodiment, the yield of the lubricating oil base oil is 56%, the solidification point is not greater than -19°C, the pour point ≯ -12°C, the cloud point ≯ -2°C, and the viscosity index is 142.

[0222] Example 3-1

[0223] This embodiment provides a method for producing lubricating oil base oil from Fischer-Tropsch wax, wherein the method comprises the following specific steps:

[0224] Step 1: Hydrofining the Fischer-Tropsch wax in the first hydrofining reactor to perform olefin saturation and deoxygenation reactions to remove olefins and oxygen-containing compounds in the Fischer-Tropsch wax to avoid the generation of water in the subsequent isomerization reaction, and then cutting the hydrofined Fischer-Tropsch wax (property parameters are shown in Table 3) in the first fractionation tower to obtain light components, middle fractions and bottom wax; wherein the boiling point ranges of the light components, middle fractions and bottom wax are 170-300°C, 300-500°C and >500°C, respectively;

[0225] Step 2: allowing the tower bottom wax to enter a first isomerization reactor filled with catalyst A1, and subjecting the tower bottom wax to a first isomerization reaction under the catalytic action of catalyst A1 to obtain a first isomerization reaction product;

[0226] Step 3: The first isomerization reaction product and the intermediate fraction are fed into a second isomerization reactor filled with catalyst A2 to perform a second isomerization reaction to obtain a second isomerization reaction product;

[0227] The volume ratio of the catalyst A2 loaded in the second isomerization reactor to the catalyst A1 loaded in the first isomerization reactor is 1:2;

[0228] The volumetric space velocity of the first isomerization reaction is 0.6h -1 , hydrogen-to-oil ratio is 600:1, reaction temperature is 320°C, and pressure is 7MPa;

[0229] The volumetric space velocity of the second isomerization reaction is 1.6h -1 , hydrogen-to-oil ratio is 700:1, reaction temperature is 350°C, and pressure is 10MPa;

[0230] Step 4: the second isomerization reaction product is introduced into a second hydrofining reactor for hydrofining, and then the obtained refined product is fractionated and cut in a second fractionation tower to obtain a lubricating oil base oil;

[0231] The hydrofining temperature is 250°C and the volume space velocity is 1.0h -1 , pressure is 10MPa, hydrogen-oil volume ratio is 800:1.

[0232] In this embodiment, the yield of the lubricating oil base oil is 60%, the solidification point is not greater than -19°C, the pour point ≯ -12°C, the cloud point ≯ -2°C, and the viscosity index is 138.

[0233] Comparative Example 1-1

[0234] This comparative example provides a method for producing lubricating oil base oil from Fischer-Tropsch wax, which differs from Example 1-1 only in that:

[0235] The first isomerization reactor and the second isomerization reactor are both filled with catalyst A11.

[0236] In this comparative example, the yield of the lubricating base oil is 45%, the solidification point is not greater than -15°C, the pour point ≯ -8°C, the cloud point ≯ 0°C, and the viscosity index is 113.

[0237] Comparative Example 1-2

[0238] This comparative example provides a method for producing lubricating oil base oil from Fischer-Tropsch wax, which differs from Example 1-1 only in that:

[0239] The first isomerization reactor and the second isomerization reactor are both filled with catalyst A12.

[0240] In this comparative example, the yield of the lubricating oil base oil is 42%, the solidification point is not greater than -15°C, the pour point ≯ -8°C, the cloud point ≯ 0°C, and the viscosity index is 115.

[0241] Comparative Examples 1-3

[0242] This comparative example provides a method for producing lubricating oil base oil from Fischer-Tropsch wax, which differs from Example 1-1 only in that:

[0243] The first isomerization reactor and the second isomerization reactor are both filled with catalyst A13.

[0244] In this comparative example, the yield of the lubricating oil base oil is 46%, the solidification point is not greater than -15°C, the pour point ≯ -8°C, the cloud point ≯ 0°C, and the viscosity index is 115.

[0245] Comparative Examples 1-4

[0246] This comparative example provides a method for producing lubricating oil base oil from Fischer-Tropsch wax, which differs from Example 1-1 only in that:

[0247] The first isomerization reactor and the second isomerization reactor are both filled with catalyst A14.

[0248] In this comparative example, the yield of the lubricating oil base oil is 42%, the solidification point is not greater than -15°C, the pour point ≯ -8°C, the cloud point ≯ 0°C, and the viscosity index is 117.

[0249] Comparative Examples 1-5

[0250] This comparative example provides a method for producing lubricating oil base oil from Fischer-Tropsch wax, wherein the method comprises the following specific steps:

[0251] The Fischer-Tropsch wax is hydrotreated in the first hydrotreating reactor to perform olefin saturation and deoxygenation reactions to remove olefins and oxygen-containing compounds in the Fischer-Tropsch wax to avoid the generation of water in the subsequent isomerization reaction, and then the hydrotreated Fischer-Tropsch wax (property parameters are shown in Table 3) is cut in the first fractionating tower to obtain an intermediate fraction (450-500° C.) and a bottom wax (520-570° C.);

[0252] The middle distillate and the bottom wax are intermittently fed into the isomerization reactor filled with catalyst A1 for isomerization reaction, wherein the volume space velocity of the isomerization reaction is 1.0h -1 , hydrogen-to-oil ratio is 1000:1, reaction temperature is 300°C;

[0253] The reaction product of the isomerization reactor enters the second hydrofining reactor, and after hydrofining, is fractionated and cut in the second fractionation tower to obtain a lubricating oil base oil fraction;

[0254] The temperature of the hydrofining is 200-300°C, and the volume space velocity is 0.5-2.0h -1 , pressure is 3-16MPa, hydrogen-oil volume ratio is 300-1000:1.

[0255] In this comparative example, the yield of the lubricating oil base oil is 51%, the solidification point is not greater than -15°C, the pour point ≯ -8°C, the cloud point ≯ 0°C, and the viscosity index is 118.

[0256] Comparative Examples 1-6

[0257] This comparative example provides a method for producing lubricating oil base oil from Fischer-Tropsch wax, which differs from Example 1-1 only in that:

[0258] The first isomerization reactor and the second isomerization reactor are both filled with catalyst A15.

[0259] In this comparative example, the yield of the lubricating oil base oil is 40%, the solidification point is not greater than -13°C, the pour point ≯ -5°C, the cloud point ≯ 1°C, and the viscosity index is 112.

[0260] Comparative Examples 1-7

[0261] This comparative example provides a method for producing lubricating oil base oil from Fischer-Tropsch wax, which differs from Example 1-1 only in that:

[0262] The first isomerization reactor and the second isomerization reactor are both filled with catalyst A16.

[0263] In this comparative example, the yield of the lubricating oil base oil is 39%, the solidification point is not greater than -13°C, the pour point ≯ -6°C, the cloud point ≯ 2°C, and the viscosity index is 113.

[0264] In order to more intuitively compare the parameters of the lubricating base oils obtained in Examples 1-1 to 3-1 of the present invention and Comparative Examples 1-1 to 1-7, the parameters of these lubricating base oils are now listed in the following Table 4.

[0265] Table 4

[0266] Yield / % Condensation point / ℃ Pour point / ℃ Cloud point / ℃ Viscosity Index Example 1-1 62 ≯-17 ≯-12 ≯-2 136 Example 2-1 56 ≯-19 ≯-12 ≯-2 142 Example 3-1 60 ≯-19 ≯-12 ≯-2 138 Comparative Example 1-1 45 ≯-15 ≯-8 ≯0 113 Comparative Example 1-2 42 ≯-15 ≯-8 ≯0 115 Comparative Examples 1-3 46 ≯-15 ≯-8 ≯0 115 Comparative Examples 1-4 42 ≯-15 ≯-8 ≯0 117 Comparative Examples 1-5 51 ≯-15 ≯-8 ≯0 118 Comparative Examples 1-6 40 ≯-13 ≯-5 ≯1 112 Comparative Examples 1-7 39 ≯-13 ≯-6 ≯2 113

[0267] From the data of lubricating base oil provided by Example 1-1, Example 2-1 and Example 3-1 as shown in Table 4 above, it can be seen that in the embodiments of the present invention, the tower bottom wax is subjected to a first isomerization reaction under the catalytic action of the first isomerization catalyst to obtain a first isomerization reaction product; and the first isomerization reaction product and the intermediate fraction are subjected to a second isomerization reaction under the catalytic action of the second isomerization catalyst to obtain a second isomerization reaction product; wherein, the first isomerization reaction and the second isomerization reaction both use an isomerization catalyst whose carrier is a ZSM-48 molecular sieve carrier (i.e., a ZSM-48 molecular sieve catalyst having the same topological structure), follow the same reaction law, can reduce gas generation, and the lubricating base oil product has a high yield, a low freezing point, a low pour point, a low cloud point and a high viscosity index; and the tower bottom wax with a heavier fraction undergoes two isomerization reactions, which can deepen the degree of isomerization reaction and reduce the cloud point of the obtained lubricating base oil;

[0268] By comparing the data of the lubricating base oils obtained in Example 1-1, Example 2-1 and Example 3-1 and Comparative Examples 1-1 to Comparative Examples 1-5, it can be seen that, under the premise of the same method, the use of a specific isomerization catalyst in the embodiment of the present invention can obtain a higher yield of lubricating base oil products, and the obtained lubricating base oil products have a low solidification point, a low pour point, a low cloud point and a high viscosity index; under the premise of the same isomerization catalyst, compared with the existing method for producing lubricating base oil from Fischer-Tropsch wax, the method provided by the embodiment of the present invention has a high yield of lubricating base oil products, and the obtained lubricating base oil products have a low solidification point, a low pour point, a low cloud point and a high viscosity index, that is, compared with the comparative example, the embodiment of the present invention can obtain a higher quality lubricating base oil.

[0269] From the data of the lubricating base oils obtained in Comparative Example 1-1 and Comparative Example 1-6 and Comparative Example 1-7, it can be seen that Comparative Example 5 and Comparative Example 6 use di(cyclopentadienyl)cobalt and 1,6-hexanediamine as charge balancing agents to prepare ZSM-48 molecular sieves, respectively, while Example 1 of the present invention uses isopropanol, an alcohol charge balancing agent, to prepare ZSM-48 molecular sieves. Compared with the ZSM-48 molecular sieves prepared in Comparative Examples 5 and 6, the ZSM-48 molecular sieve prepared in Example 1 is a pure phase molecular sieve, and the parameters such as the grain size and axial diameter ratio of the molecular sieve are smaller, and the isomerized catalyst prepared from the ZSM-48 molecular sieve has a higher content of weak B acid (200°C) and medium-strong B acid (350°C), so that when the isomerized catalyst is used to produce lubricating base oil, a higher yield of lubricating base oil product can be obtained, and the obtained lubricating base oil product has a low pour point and a high viscosity index.

[0270] The above is only a specific embodiment of the present invention, and cannot be used to limit the scope of the invention. Therefore, the replacement of equivalent components, or equivalent changes and modifications made according to the protection scope of the patent of the present invention, should still fall within the scope of this patent. In addition, the technical features of the present invention can be freely combined with each other, with each other and with each other, and with each other.

Claims

1. A method for producing lubricating oil base oil from heavy raw materials, characterized in that: The method comprises: Step 1: Cut the heavy raw material to obtain light components, middle fractions and bottom wax; wherein the boiling point ranges of the light components, middle fractions and bottom wax are 170-300°C, 300-500°C and >500°C respectively; Step 2: subjecting the tower bottom wax to a first isomerization reaction under the catalytic action of a first isomerization catalyst to obtain a first isomerization reaction product; Step 3: subjecting the first isomerization reaction product and the intermediate fraction to a second isomerization reaction under the catalytic action of a second isomerization catalyst to obtain a second isomerization reaction product; Step 4: subjecting the second isomerization reaction product to hydrofining, and then fractionating and cutting the obtained refined product to obtain lubricating oil base oil.

2. The method according to claim 1, characterized in that The heavy raw material includes one or a combination of Fischer-Tropsch synthetic oil, hydrocracking tail oil, high-wax VGO and Fischer-Tropsch wax.

3. The method according to claim 1, characterized in that The volume ratio of the first isomerization catalyst to the second isomerization catalyst is 1-2:

1.

4. The method according to claim 1 or 3, characterized in that: The volume space velocity of the first isomerization reaction is 0.2-1.0h -1 , the hydrogen-oil ratio is 300:1-1000:1, the reaction temperature is 300-400°C, and the pressure is 3-16MPa.

5. The method according to claim 1 or 3, characterized in that: The volume space velocity of the second isomerization reaction is 1.0-2.0h -1 , the hydrogen-oil ratio is 300:1-1000:1, the reaction temperature is 300-400°C, and the pressure is 3-16MPa.

6. The method according to claim 1 or 3, characterized in that: The first isomerization catalyst and the second isomerization catalyst are the same or different.

7. The method according to claim 6, characterized in that The carrier of the first isomerization catalyst and the second isomerization catalyst is a ZSM-48 molecular sieve carrier, the active component is a noble metal, and the loading amount of the active component is 0.1-1.0wt% based on the total weight of the carrier as 100%; The ZSM-48 molecular sieve carrier contains ZSM-48 molecular sieve, the molar ratio of SiO2 to Al2O3 in the ZSM-48 molecular sieve is 50-400, the grain length of the ZSM-48 molecular sieve is 0.1-0.5 μm, the grain diameter is 50-100 nm, and the axis-to-diameter ratio is less than 20.

8. The method according to claim 7, characterized in that The preparation method of the first isomerization catalyst and the second isomerization catalyst comprises: Step (1): dissolving a noble metal salt in a mixed solution of water, alcohol and ligand and mixing them evenly to obtain a noble metal precursor solution; Step (2): impregnating particles of the ZSM-48 molecular sieve carrier into a precious metal precursor solution, and then drying and calcining the impregnated product to obtain the first isomerization catalyst and the second isomerization catalyst.

9. The method according to claim 8, characterized in that The noble metal salt includes one or a combination of chloroplatinic acid hexahydrate, palladium chloride, platinum dichloride, and ammonium hexachloroplatinate.

10. The method according to claim 8 or 9, characterized in that: The ligand includes one or a combination of sorbic acid, salicylic acid, niacinamide, lactic acid, citric acid, and hyaluronic acid, and the molar ratio of the ligand to the noble metal atom is 6-18:

1.

11. The method according to claim 8 or 9, characterized in that: The alcohol includes one or a combination of ethanol, propanol, isopropanol, and glycerol, and the mass ratio of water to alcohol is 50-1:

1.

12. The method according to claim 8 or 9, characterized in that: In step (2), the calcination is carried out in an air atmosphere at 400-600° C. for 4-14 hours.

13. The method according to claim 7, characterized in that The preparation method of the ZSM-48 molecular sieve carrier comprises: Mix ZSM-48 molecular sieve, alumina, titanium dioxide, acid solution, binder and deionized water evenly; The obtained mixture is then extruded, dried and calcined to obtain a ZSM-48 molecular sieve carrier; Among them, the mass ratio of ZSM-48 molecular sieve, alumina, titanium dioxide, acid solution, adhesive and deionized water is 1:0.3-9:0.01-0.5:0.01-0.6:0.3-1:0.2-1.

14. The method according to claim 13, characterized in that The adhesive comprises sesbania powder and / or methyl cellulose; the acid solution comprises a nitric acid or phosphoric acid solution with a concentration of 5-15wt%.

15. The method according to any one of claims 7-8, 13-14, characterized in that: The preparation method of the ZSM-48 molecular sieve comprises: First, an aluminum source, a silicon source, an alkali source, a crystallization inducing agent, a template agent, deionized water, a pore-forming agent and a charge balancing agent are uniformly mixed to obtain a gel solution, and then the gel solution is pre-crystallized at 70-90° C. for 2-6 hours, crystallized at 120-140° C. for 2-6 hours, and crystallized at 140-170° C. for 10-48 hours, and then the crystallized product is washed, dried and calcined to obtain a molecular sieve precursor, and then the molecular sieve precursor is mixed with an ammonium salt at 70-80° C. for 4-6 hours, and then washed, dried and calcined to obtain; Among them, the aluminum source in terms of Al2O3 and the - The molar ratio of the alkali source, the template, H2O and the silicon source as SiO2 is 0.0025-0.02:0.006-0.38:0.11-1.5:10-50:1; The molar ratio of the pore former to the silicon source calculated as SiO2 is 0.01-0.2:1; The molar ratio of the crystallization inducing agent calculated as M2O to the silicon source calculated as SiO2 is 0.002-0.2:1, wherein M is one or more of alkali metals; The molar ratio of the charge balance agent to H2O is 0.1-1:

1.

16. The method according to claim 15, characterized in that The aluminum source includes one or a combination of aluminum sulfate, sodium aluminate, and aluminum nitrate; The silicon source includes one or a combination of silica sol, white carbon black, and tetraethyl orthosilicate; The alkali source includes NaOH and / or KOH.

17. The method according to claim 15, characterized in that The template comprises a first template and a second template, and the molar ratio of the first template to the second template is 1-400:1; The first template agent includes one or a combination of cyclohexylamine, dodecylamine, 1,6-hexanediamine, 1,8-octanediamine and benzylamine, and the second template agent includes one or a combination of hexamethylammonium chloride, hexamethylammonium bromide, ammonium oxalate, ammonium acetate and benzyltriethylammonium bromide.

18. The method according to claim 15, characterized in that The crystallization inducing agent includes one or a combination of sodium chloride, potassium chloride, sodium sulfate, and potassium sulfate; The pore-forming agent includes one or a combination of P123, Triton-100, polyhexamethylene biguanide, ammonium chloride, and polyvinyl alcohol; The charge balancing agent includes one or a combination of glycerol, ethylene glycol, isopropyl alcohol, propanol, and 2-butanol.

19. A lubricating oil base oil, characterized in that: The lubricating oil base oil is produced by the method for producing lubricating oil base oil from heavy raw materials according to any one of claims 1-18.

Images