Carrier, catalyst and method for producing lubricant base oil through hydroisomerization

Abstract

The invention discloses a carrier, a catalyst and a method for producing lubricant base oil through hydroisomerization. The carrier is a ZSM-22 / MCFs composite material, and the preparation method comprises the following steps: by taking water, an aluminum source, an alkali source, a template agent and a silicon source as raw materials, preparing a ZSM-22 molecular sieve precursor by adopting a hydrothermal crystallization method; the preparation method comprises the following steps: by taking a nonionic surfactant triblock copolymer P123, a hydrochloric acid solution, water, 1, 3, 5-trimethylbenzene and tetraethyl orthosilicate as raw materials, preparing an MCFs precursor by adopting a hydrothermal crystallization method; adding the ZSM-22 molecular sieve precursor into the MCFs precursor, so as to obtain a mixture; and sequentially crystallizing, heating, filtering, washing, drying and roasting the mixture to obtain the ZSM-22 / MCFs composite material. The carrier provided by the invention not only has proper acidity, but also retains the pore channel advantage of the mesoporous molecular sieve.

Description

Technical Field

[0001] The invention relates to the technical field of lubricating oil base oil production, and in particular to a carrier, a catalyst and a method for producing lubricating oil base oil by hydroisomerization. Background Art

[0002] The raw materials for producing lubricating oil base oils are becoming more diversified and inferior. High-wax raw materials such as FT synthetic oil, petroleum-based wax oil, propane deasphalted oil, and wax oil have become the raw materials for producing high-quality III and III + An important raw material for lubricant base oil.

[0003] Hydroisomerization dewaxing catalyst is a bifunctional catalyst. The active metal in the catalyst plays a role of dehydrogenation / hydrogenation, and the carrier provides suitable acid sites. The acidity of the catalyst is a key factor affecting the performance of the hydroisomerization catalyst, which affects the competition between isomerization and cracking. One-dimensional pore molecular sieves are widely used as carriers of hydroisomerization catalysts due to their unique pore characteristics and suitable acidity.

[0004] The one-dimensional pore molecular sieves commonly used for hydrogenation isomerization are microporous with small pore size, which makes it difficult for large molecules to enter the pores to undergo isomerization reactions, resulting in a decrease in the viscosity index of the lubricating oil base oil and a decrease in the yield. Mesopores are located between micropores and macropores, have a higher specific surface area, large adsorption capacity, and large pore size, which to a certain extent solve the problem of mass transfer and diffusion limitation. However, since the pore walls are in an amorphous state, the acidity is weak and the hydrothermal stability is poor, and industrial applications are limited. Therefore, the development of a molecular sieve catalyst with microporous-mesoporous channels is very important for improving the acidity of the catalyst, promoting the formation of multi-branched isomers, and improving the low-temperature fluidity of oil products.

[0005] Mesoporous foam material is an aerogel mesoporous material with ultra-large mesopores and three-dimensional continuous pore structure. Its morphology is similar to honeycomb or sponge. The unit cells are connected by uniform windows, and the pore size is adjustable. The open pore structure is more conducive to the diffusion and transmission of substances, reducing the mass transfer restriction when the product leaves, the active sites can be better evenly distributed, and it has good hydrothermal stability.

[0006] FT synthetic oil, petroleum-based wax oil, propane deasphalted oil, wax oil and other high-wax raw materials have high wax content, that is, high content of long-chain normal alkanes. The pore structure of microporous-mesoporous materials is adjustable, which is more conducive to the decondensation of long-chain normal alkanes.

[0007] CN112058303A discloses a composite molecular sieve for hydroisomerization dewaxing reaction. With microporous ZSM-22 as the core and mesoporous molecular sieve MCM-48 as the shell, a composite molecular sieve with a core-shell structure is formed by eutecticization. The prepared hydroisomerization dewaxing catalyst exhibits high activity and selectivity, and the condensation point and cloud point of the lubricating base oil produced are reduced, and the base oil yield is improved, but the cloud point is still relatively high, and the base oil yield is also low.

[0008] CN102874829A discloses a method for preparing a mesoporous-microporous zeolite molecular sieve. First, the microporous zeolite is mixed with an alkaline solution, subjected to ultrasonic treatment, then heat-treated in a closed system in the presence of an organic solvent, and then treated with an acid solution to prepare a mesoporous-microporous zeolite molecular sieve, thereby increasing the mesopore content in the material and improving the BET specific surface area of ​​the material.

[0009] CN114477226A discloses a composite molecular sieve and a hydrogenation reforming catalyst made of the composite molecular sieve as a carrier. The molecular sieve is a Y-MCFs composite molecular sieve, which has a three-dimensional topological microporous structure of a Y molecular sieve and a three-dimensional spherical mesoporous structure of a super-large mesoporous foam material MCFs, and the mesoporous channels are regular and orderly. The specific surface area of ​​the composite molecular sieve is 500-700m 2 / g, pore diameter is 10-15nm, pore volume is 1.5-2.0cm 3 / g. The hydrogenation reforming catalyst prepared by the composite molecular sieve is applied to the hydrogenation reforming reaction of FCC gasoline, the sulfur content is less than 10mg / kg, the olefin content is reduced and less than 10v%, and the octane number loss is less than 2.0 units.

[0010] CN103100399A discloses a method for preparing a mesoporous-microporous composite molecular sieve. The microporous molecular sieve after hydrothermal treatment is added to a mixed system of a silicon source, an acid solution and a surfactant, and the mesoporous-microporous composite molecular sieve is obtained through crystallization, filtration, washing, drying and calcination, which makes full use of the non-framework aluminum removed from the microporous molecular sieve, improves the hydrothermal and thermal stability of the composite molecular sieve, and is applied to the catalytic cracking reaction of producing intermediate distillate oil using heavy oil as raw material, thereby improving the conversion rate and selectivity of the reaction.

[0011] CN101186311A discloses a Y / MCM-48 composite molecular sieve and a preparation method thereof. The method synthesizes the Y / MCM-48 composite molecular sieve by a one-step method. However, the base oil product obtained by this method has a high pour point and cloud point, and a low base oil yield, which cannot meet the requirements. Summary of the invention

[0012] The present invention provides a carrier, a catalyst and a method for producing lubricating oil base oil by hydroisomerization.

[0013] In order to meet the problem of reducing the cloud point of different raw materials, especially heavy high-wax raw materials through hydrogenation isomerization, the present invention provides a ZSM-22 / MCFs composite material as a catalyst carrier, which has a dual pore structure of micropores of ZSM-22 molecular sieve and ultra-large mesopores of ultra-large mesoporous foam material MCFs, wherein MCFs has an ultra-large three-dimensional mesoporous structure and good thermal stability, a narrow pore size distribution, and spherical pores connected by windows, and has good pore connectivity and order; and the present invention modulates the acidity of the molecular sieve by using the primary structural units and secondary structural units of the ZSM-22 molecular sieve through the composite of meso-micropores, and at the same time fully utilizes the mass transfer performance of the mesoporous channels of the ultra-large mesoporous foam material MCFs, so that the carrier provided by the present invention has both suitable acidity and retains the pore advantages of the mesoporous molecular sieve.

[0014] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0015] The first aspect of the present invention provides a method for preparing a carrier for producing lubricating oil base oil by hydroisomerization, wherein the carrier is a ZSM-22 / MCFs composite material, and the preparation method comprises the following steps:

[0016] Using water, aluminum source, alkali source, template agent and silicon source as raw materials, a ZSM-22 molecular sieve precursor is prepared by a hydrothermal crystallization method;

[0017] The MCFs precursor was prepared by hydrothermal crystallization method using nonionic surfactant triblock copolymer P123, hydrochloric acid solution, water, 1,3,5-trimethylbenzene and tetraethyl orthosilicate as raw materials.

[0018] The ZSM-22 molecular sieve precursor is added to the MCFs precursor to obtain a mixture; the mixture is crystallized, heated, filtered, washed, dried and calcined in sequence to obtain the ZSM-22 / MCFs composite material.

[0019] According to the carrier preparation method of the present invention, preferably, the preparation steps of the ZSM-22 molecular sieve precursor include:

[0020] After mixing water, aluminum source and alkali source evenly, stir at room temperature; then add template agent dropwise, continue stirring at room temperature, and finally add silicon source and continue stirring; then hydrothermally crystallize the obtained mixture at 155-165° C. for 30h-50h to obtain ZSM-22 molecular sieve precursor.

[0021] In order to fully mix the various components, the stirring time after each addition is controlled to be 1 to 2 hours.

[0022] According to the carrier preparation method of the present invention, preferably, the molar ratio of the silicon source, aluminum source, alkali source, template and water is 1.0: (0.005-0.05): (0.002-0.1): (0.03-0.4): (7-15); wherein the molar ratio of the aluminum source, the silicon source and the alkali source is respectively Al 2 O 3 、SiO 2 , K 2 O plan.

[0023] According to the carrier preparation method of the present invention, preferably, the aluminum source is selected from at least one of aluminum sulfate 18hydrate, sodium metaaluminate, and pseudo-boehmite, and more preferably aluminum sulfate 18hydrate.

[0024] According to the carrier preparation method of the present invention, preferably, the silicon source is selected from at least one of silica sol, white carbon black, fumed silica, ethyl orthosilicate, propyl orthosilicate, and silica gel, and more preferably is silica sol.

[0025] According to the carrier preparation method of the present invention, preferably, the alkali source is potassium hydroxide.

[0026] According to the carrier preparation method of the present invention, preferably, the template is 1,6-hexanediamine.

[0027] In the carrier preparation method of the present invention, in the MCFs precursor preparation step, the nonionic surfactant triblock copolymer P123 is a template agent, and 1,3,5-trimethylbenzene is a pore expanding agent. The pore structure of MCFs can be regulated by regulating the amount of P123 and 1,3,5-trimethylbenzene added to the raw materials.

[0028] According to the carrier preparation method of the present invention, preferably, the preparation steps of the MCFs precursor include:

[0029] At 38-42° C., the nonionic surfactant triblock copolymer P123 was dissolved in a hydrochloric acid solution, and then 1,3,5-trimethylbenzene was added and mixed evenly, and then tetraethyl orthosilicate was added to obtain an MCFs precursor through a hydrothermal crystallization method.

[0030] According to the carrier preparation method of the present invention, preferably, the molar ratio of the nonionic surfactant triblock copolymer P123, 1,3,5-trimethylbenzene, tetraethyl orthosilicate, HCl and water is (0.003-0.01): (0.3-0.5): 1.0: (3.0-7.0): (120-140).

[0031] According to the carrier preparation method of the present invention, preferably, in the step of mixing the ZSM-22 molecular sieve precursor and the MCFs precursor for treatment: the crystallization temperature is 100 to 120° C., and the time is 18 h to 45 h.

[0032] According to the carrier preparation method of the present invention, preferably, in the step of mixing the ZSM-22 molecular sieve precursor and the MCFs precursor for treatment: the heating temperature is 80 to 100° C. and the heating time is 48 h to 72 h.

[0033] According to the carrier preparation method of the present invention, preferably, in the step of mixing the ZSM-22 molecular sieve precursor and the MCFs precursor for treatment: the drying temperature is 80 to 120° C. and the drying time is 3 to 8 hours.

[0034] According to the carrier preparation method of the present invention, preferably, in the step of mixing the ZSM-22 molecular sieve precursor and the MCFs precursor for treatment: the calcination temperature is 450 to 650° C. and the calcination time is 4 to 8 hours.

[0035] In the carrier preparation method of the present invention, in the step of mixing the ZSM-22 molecular sieve precursor and the MCFs precursor for treatment, by controlling the mass ratio of tetraethyl orthosilicate in the preparation of the ZSM-22 molecular sieve precursor and the MCFs precursor, the quality of the ZSM-22 molecular sieve and the MCFs in the composite material can be regulated. Preferably, when the added mass of the ZSM-22 molecular sieve precursor is controlled to be 0.5 to 1.0 times the added mass of tetraethyl orthosilicate in the preparation of the MCFs precursor, the prepared ZSM-22 / MCFs composite material has a more suitable acid content and pore distribution.

[0036] The second aspect of the present invention provides a carrier for producing lubricating oil base oil by hydroisomerization, which is a ZSM-22 / MCFs composite material obtained by any of the preparation methods provided in the first aspect above.

[0037] The third aspect of the present invention provides a catalyst for producing lubricating oil base oil by hydroisomerization, wherein the catalyst comprises a carrier and an active component; the carrier is any one of the ZSM-22 / MCFs composite materials provided in the second aspect above, and the active component is platinum and / or palladium.

[0038] According to the catalyst of the present invention, preferably, the specific surface area of ​​the catalyst is 350m 2 / g~650m 2 / g, total pore volume is 0.5cm 3 / g~1.5cm 3 / g, the total acid content is 0.3mmol / g~0.5mmol / g.

[0039] According to the catalyst of the present invention, preferably, the content of the active component in the catalyst is 0.1wt% to 5wt%. More preferably, among the active components, the content of platinum in the catalyst is 0.3wt% to 2wt%.

[0040] The fourth aspect of the present invention provides a method for preparing a catalyst for producing lubricating oil base oil by hydroisomerization, wherein the preparation method comprises the following steps:

[0041] Any carrier provided in the second aspect above is impregnated in a salt impregnation solution corresponding to the active component, and then dried and calcined to obtain the catalyst.

[0042] This step is the process of loading the active metal component onto the carrier, and the loading can be completed by the equal volume impregnation method conventionally used in the art.

[0043] According to the preparation method of the fourth aspect of the present invention, preferably, the salt corresponding to the active component is selected from at least one of chloroplatinic acid, platinum nitrate, tetraamineplatinum acetate, tetraamineplatinum nitrite, tetraamineplatinum sulfate, and tetraamineplatinum chloride; more preferably, chloroplatinic acid or tetraamineplatinum nitrate.

[0044] According to the preparation method of the fourth aspect of the present invention, preferably, the drying temperature is 80-120° C.; the calcination temperature is 450-650° C., and the calcination time is 4h-8h.

[0045] A fifth aspect of the present invention provides a method for producing a lubricating oil base oil by hydroisomerization, wherein the method comprises the following steps:

[0046] The high wax content crude oil is subjected to isomerization dewaxing reaction under the action of the catalyst to obtain a lubricating oil base oil product;

[0047] The high wax content feedstock oil is selected from at least one of petroleum-based wax oil, FT synthetic oil, propane deasphalted oil, and wax-derived oil.

[0048] The isomeric dewaxing reaction conditions include: hydrogen partial pressure of 12-15 MPa, reaction temperature of 350-380°C, volume liquid hourly space velocity of 0.7-1.5 h -1 , hydrogen to oil volume ratio (500~800):1.

[0049] The catalyst of the present invention can significantly reduce the pour point of high-wax content crude oil, and obtain a base oil product with good low-temperature fluidity.

[0050] The catalyst prepared by the present invention has a microporous-mesoporous composite structure, and the pore structure is between micropores and mesopores, which is more conducive to the raw materials with higher wax content (alkanes with longer carbon chains) entering the molecular sieve pores, and isomerization reaction occurs. The isomerization reaction deepens, which is conducive to the conversion of high-freezing point components and generates more low-freezing point components. In addition, the carrier and catalyst preparation process of the present invention are short, the process is simple, the pore size adjustment range is wide, and the base oil produced by using the same has low pour point and cloud point. DETAILED DESCRIPTION

[0051] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the following specific description is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0052] All numerical specifications herein (e.g., temperature, time, concentration, and weight, etc., including ranges for each thereof) are generally approximate values ​​that may be appropriately varied (+) or (-) in increments of 0.1 or 1.0. All numerical specifications may be understood as being preceded by the term "about."

[0053] Example 1

[0054] This embodiment prepares a ZSM-22 / MCFs composite material and a catalyst prepared using the composite material as a carrier, comprising the following steps:

[0055] 1) Preparation of ZSM-22 molecular sieve precursor

[0056] According to the molar ratio of silicon source, aluminum source, alkali source, template agent and water of 1.0:0.005:0.0023:0.044:7, 126g water, 3.33g Al 2 (SO 4 ) 3 18H 2 O and 0.13g KOH were mixed and stirred at room temperature for 1h to obtain a mixed solution; then 5.11g hexamethylenediamine was slowly added dropwise to the mixed solution, and after continuing to stir at room temperature for 1h, 200g silica sol (SiO 2 The mixture was placed in a stainless steel autoclave and subjected to hydrothermal crystallization at 160° C. for 35 h to obtain a ZSM-22 molecular sieve precursor.

[0057] 2) Preparation of MCFs Precursors

[0058] 709.24 g of deionized water and 161.08 g of concentrated HCl (HCl mass fraction 37%, 12 mol / L) solution were prepared into a hydrochloric acid solution. The molar ratio of P123, 1,3,5-trimethylbenzene, tetraethyl orthosilicate, HCl, and water was 0.004:0.35:1.0:4.9:137. 7.73 g of template P123 was added to the above-prepared hydrochloric acid solution at 40°C, and the mixture was stirred and dissolved until the obtained solution was clear and transparent. 14 g of 1,3,5-trimethylbenzene was added thereto and stirring was continued for 1 h. Then, 88.0 g of TEOS (tetraethyl orthosilicate) was added and stirring was continued for 4 h to obtain the precursor of foam mesoporous MCFs.

[0059] 3) Preparation of ZSM-22 / MCFs composites

[0060] 37.9 g of ZSM-22 molecular sieve precursor was added to the MCFs precursor and crystallized at 120°C for 26 h. The crystallized solution system was then heated at 100°C for 55 h. The product was then filtered and the solid product was washed with water, dried at 100°C, and calcined at 570°C for 8 h in an air atmosphere to obtain a ZSM-22 / MCFs composite material.

[0061] 4) Loading of active components

[0062] The water absorption rate of the carrier was determined to be 65%, 0.79g of chloroplatinic acid was weighed and dissolved in 65g of deionized water to prepare an aqueous solution of chloroplatinic acid; 100g of ZSM-22 / MCFs composite material was immersed in the aqueous solution of chloroplatinic acid prepared above to form a catalyst wet strip, the catalyst wet strip was dried at 100°C, and calcined at 450°C in an air atmosphere for 8h to obtain a hydroisomerization catalyst. Among them, the mass content of the active metal component Pt in the hydroisomerization catalyst is 0.3wt%, and the pore structure and acid content data of the catalyst are shown in Table 1.

[0063] Example 2

[0064] This embodiment prepares a ZSM-22 / MCFs composite material and a catalyst prepared using the composite material as a carrier, comprising the following steps:

[0065] 1) Preparation of ZSM-22 molecular sieve precursor

[0066] According to the molar ratio of silicon source, aluminum source, alkali source, template agent and water of 1.0:0.0056:0.006:0.14:8.6, 154.8g water, 3.73g Al 2 (SO 4 ) 3 18H 2O and 0.34g KOH were mixed and stirred at room temperature for 1h to obtain a mixed solution; then 16.27g hexamethylenediamine was slowly added dropwise to the mixed solution, and after continuing to stir at room temperature for 1h, 200g silica sol (SiO 2 The mixture was placed in a stainless steel autoclave and subjected to hydrothermal crystallization at 155° C. for 40 h to obtain a ZSM-22 molecular sieve precursor.

[0067] 2) Preparation of MCFs Precursors

[0068] Take 668.1g of deionized water and 151.35g of concentrated HCl (HCl mass fraction 37%, 12mol / L) solution to prepare a hydrochloric acid solution, according to the molar ratio of P123, 1,3,5-trimethylbenzene, tetraethyl orthosilicate, HCl, and water being 0.006:0.32:1.0:4.6:129, add 11.6g of template P123 to the above-prepared hydrochloric acid solution at 38°C, stir and dissolve until the resulting solution is clear and transparent, add 12.8g of 1,3,5-trimethylbenzene thereto and continue stirring for 1h, then add 88g of TEOS, and continue stirring for 4h to obtain the precursor of foam mesoporous MCFs.

[0069] 3) Preparation of ZSM-22 / MCFs composites

[0070] 93.8 g of ZSM-22 molecular sieve precursor was added to the MCFs precursor and crystallized at 110°C for 35 hours. The crystallized solution system was then heated at 100°C for 60 hours. After heating, it was filtered, and the solid product obtained by filtration was washed, dried at 110°C, and calcined at 550°C for 5 hours in an air atmosphere to obtain a ZSM-22 / MCFs composite carrier.

[0071] 4) Loading of active components

[0072] The water absorption rate of the carrier was determined to be 66%. 2.63 g of chloroplatinic acid was weighed and dissolved in 66 g of deionized water to prepare an aqueous solution of chloroplatinic acid. 100 g of ZSM-22 / MCFs was immersed in the aqueous solution of chloroplatinic acid to form a catalyst wet strip. The catalyst wet strip was dried at 120° C. and calcined at 500° C. for 4 h in an air atmosphere to obtain a hydroisomerization catalyst. The mass content of the active metal component Pt in the hydroisomerization catalyst was 1 wt%. In addition, the pore structure and acid content data of the catalyst are shown in Table 1.

[0073] Example 3

[0074] This embodiment prepares a ZSM-22 / MCFs composite material and a catalyst prepared using the composite material as a carrier, comprising the following steps:

[0075] 1) Preparation of ZSM-22 molecular sieve precursor

[0076] According to the molar ratio of silicon source, aluminum source, alkali source, template agent and water of 1.0:0.01:0.02:0.32:10.1, 181.8g water, 6.66g Al 2 (SO 4 ) 3 18H 2 O and 1.12g KOH were mixed and stirred at room temperature for 1h to obtain a mixed solution, and then 37.18g hexamethylenediamine was slowly added dropwise to the mixed solution. After stirring at room temperature for 1h, 200g silica sol (SiO 2 The mixture was placed in a stainless steel autoclave and subjected to hydrothermal crystallization at 165° C. for 50 h to obtain a ZSM-22 molecular sieve precursor.

[0077] 2) Preparation of MCFs Precursors

[0078] 668.1 g of deionized water and 151.35 g of concentrated HCl (HCl mass fraction 37%, 12 mol / L) solution were prepared into a hydrochloric acid solution, and the molar ratio of P123, 1,3,5-trimethylbenzene, tetraethyl orthosilicate, HCl, and water was 0.008:0.48:1.0:4.9:137. 15.47 g of the template P123 was added to the above-prepared hydrochloric acid solution at 42 ° C, and stirred to dissolve until the obtained solution was clear and transparent, 19.2 g of 1,3,5-trimethylbenzene was added thereto and continued to stir for 1 h, and then 88 g of TEOS was added, and continued to stir for 4 h to obtain a precursor of foam mesoporous MCFs;

[0079] 3) Preparation of ZSM-22 / MCFs composites

[0080] 117.2 g of ZSM-22 molecular sieve precursor was added to the precursor solution of MCFs, crystallized at 110°C for 18 hours, and then the crystallized solution system was heated at 100°C for 72 hours; after the heating was completed, it was filtered, and the solid product obtained by filtration was washed, dried at 120°C, and calcined at 650°C in an air atmosphere for 4 hours to obtain a ZSM-22 / MCFs composite carrier.

[0081] 4) Loading of active components

[0082] The water absorption rate of the carrier was determined to be 64%. 5.26 g of chloroplatinic acid was weighed and dissolved in 64 g of deionized water to prepare an aqueous solution of chloroplatinic acid. 100 g of ZSM-22 / MCFs was immersed in the chloroplatinic acid solution to form a catalyst wet strip. The catalyst wet strip was dried at 120° C. and calcined at 650° C. for 4 h in an air atmosphere to obtain a hydroisomerization catalyst, wherein the mass content of the active metal component Pt in the hydroisomerization catalyst is 2 wt%. In addition, the pore structure and acid content data of the catalyst are shown in Table 1.

[0083] Comparative Example 1

[0084] Compared with Example 1, this comparative example uses only ZSM-22 molecular sieve as a carrier, and includes the following steps:

[0085] 1) Preparation of ZSM-22 molecular sieve

[0086] According to the molar ratio of silicon source, aluminum source, alkali source, template agent and water of 1.0:0.005:0.0023:0.044:7, 126g water, 3.33g Al 2 (SO 4 ) 3 , 0.13g KOH, and stirred at room temperature for 1h to obtain a mixed solution, then 5.11g hexamethylenediamine was slowly added dropwise to the mixed solution, and after stirring at room temperature for 1h, 200g silica sol (SiO 2 mass concentration of 30%) and continued stirring for 2 hours, placing the obtained mixture in a stainless steel high-pressure reactor, and hydrothermally crystallizing it at 160° C. for 35 hours to obtain a ZSM-22 molecular sieve precursor solution; after filtering the ZSM-22 molecular sieve precursor solution, the filtered solid product was washed with deionized water, dried at 100° C., and calcined at 570° C. in an air atmosphere for 8 hours to obtain a ZSM-22 molecular sieve.

[0087] 2) Loading of active components

[0088] The water absorption rate of the carrier was determined to be 65%. 0.79 g of chloroplatinic acid was weighed and dissolved in 65 g of deionized water to prepare an aqueous solution of chloroplatinic acid. 100 g of the ZSM-22 molecular sieve carrier obtained in step 1) was immersed in the chloroplatinic acid solution to form a catalyst wet strip. The catalyst wet strip was dried at 100° C. and calcined at 450° C. for 8 h in an air atmosphere to obtain a hydroisomerization catalyst, wherein the mass content of the active metal component Pt in the hydroisomerization catalyst was 0.3 wt%. In addition, the pore structure and acid content data of the catalyst are shown in Table 1.

[0089] Comparative Example 2

[0090] Compared with Example 2, this comparative example uses ZSM-23 molecular sieve instead of ZSM-22 molecular sieve, and comprises the following steps:

[0091] 1) According to the molar ratio of silicon source, aluminum source, alkali source, template agent and water of 1.0:0.0056:0.006:0.14:8.6, 154.8g water, 3.73g Al 2 (SO 4 ) 3 18H 2 O and 0.24g NaOH were mixed and stirred at room temperature for 1h to obtain a mixed solution, and then 8.27g isopropylamine was slowly added dropwise to the mixed solution. After stirring at room temperature for 1h, 200g silica sol (SiO 2 The mixture was placed in a stainless steel autoclave for hydrothermal crystallization at 155° C. for 40 h to obtain a ZSM-23 molecular sieve precursor solution; the ZSM-23 molecular sieve precursor solution was filtered, and the filtered solid product was washed, dried at 110° C., and calcined at 550° C. for 5 h in an air atmosphere to obtain a ZSM-23 molecular sieve carrier;

[0092] 2) Preparation of MCFs Precursors

[0093] Take 668.1g of deionized water and 151.35g of concentrated HCl (HCl mass fraction 37%, 12mol / L) solution to prepare a hydrochloric acid solution, according to the molar ratio of P123, 1,3,5-trimethylbenzene, tetraethyl orthosilicate, HCl, and water being 0.006:0.32:1.0:4.6:129, add 11.6g of template P123 to the above-prepared hydrochloric acid solution at 38°C, stir and dissolve until the resulting solution is clear and transparent, add 12.8g of 1,3,5-trimethylbenzene thereto and continue stirring for 1h, then add 88g of TEOS, and continue stirring for 4h to obtain the precursor of foam mesoporous MCFs.

[0094] 3) Preparation of ZSM-23 / MCFs composites

[0095] 93.8 g of ZSM-23 molecular sieve precursor was added to the MCFs precursor and crystallized at 110°C for 35 hours. The crystallized solution system was then heated at 100°C for 60 hours. After heating, it was filtered, and the solid product obtained by filtration was washed, dried at 110°C, and calcined at 550°C for 5 hours in an air atmosphere to obtain a ZSM-23 / MCFs composite carrier.

[0096] 4) Loading of active components

[0097] The water absorption rate of the carrier was determined to be 66%. 2.63 g of chloroplatinic acid was weighed and dissolved in 66 g of deionized water to prepare an aqueous solution of chloroplatinic acid. 100 g of ZSM-22 / MCFs was immersed in the aqueous solution of chloroplatinic acid to form a catalyst wet strip. The catalyst wet strip was dried at 120° C. and calcined at 500° C. for 4 h in an air atmosphere to obtain a hydroisomerization catalyst. The mass content of the active metal component Pt in the hydroisomerization catalyst was 1 wt%. In addition, the pore structure and acid content data of the catalyst are shown in Table 1.

[0098] Comparative Example 3

[0099] Compared with Example 3, this comparative example uses ZSM-48 molecular sieve instead of ZSM-22, and comprises the following steps:

[0100] 1) According to the molar ratio of silicon source, aluminum source, alkali source, template agent and water of 1.0:0.01:0.02:0.32:10.1, 181.8g water, 6.66g Al 2 (SO 4 ) 3 18H 2 O and 0.8g NaOH were mixed and stirred at room temperature for 1h to obtain a mixed solution, and then 115.84g hexamethylammonium bromide was slowly added dropwise to the mixed solution. After stirring at room temperature for 1h, 200g silica sol (SiO 2 The mixture was placed in a stainless steel autoclave for hydrothermal crystallization at 165° C. for 50 h to obtain a ZSM-48 molecular sieve precursor solution; the ZSM-48 molecular sieve precursor solution was filtered, and the filtered solid product was washed, dried at 120° C., and calcined at 650° C. for 4 h in an air atmosphere to obtain a ZSM-48 molecular sieve carrier;

[0101] 2) Preparation of MCFs Precursors

[0102] 668.1 g of deionized water and 151.35 g of concentrated HCl (HCl mass fraction 37%, 12 mol / L) solution were prepared into a hydrochloric acid solution, and the molar ratio of P123, 1,3,5-trimethylbenzene, tetraethyl orthosilicate, HCl, and water was 0.008:0.48:1.0:4.9:137. 15.47 g of the template P123 was added to the above-prepared hydrochloric acid solution at 42 ° C, and stirred to dissolve until the obtained solution was clear and transparent, 19.2 g of 1,3,5-trimethylbenzene was added thereto and continued to stir for 1 h, and then 88 g of TEOS was added, and continued to stir for 4 h to obtain a precursor of foam mesoporous MCFs;

[0103] 3) Preparation of ZSM-48 / MCFs composites

[0104] 117.2 g of ZSM-48 molecular sieve precursor was added to the precursor solution of MCFs, crystallized at 110°C for 18 hours, and then the crystallized solution system was heated at 100°C for 72 hours; after heating, it was filtered, and the solid product obtained by filtration was washed, dried at 120°C, and calcined at 650°C in an air atmosphere for 4 hours to obtain a ZSM-48 / MCFs composite carrier.

[0105] 4) Loading of active components

[0106] The water absorption rate of the carrier was determined to be 70%. 5.26 g of chloroplatinic acid was weighed and dissolved in 70 g of deionized water to prepare an aqueous solution of chloroplatinic acid. 100 g of ZSM-48 / MCFs was immersed in the chloroplatinic acid solution to form a catalyst wet strip. The catalyst wet strip was dried at 120° C. and calcined at 650° C. for 4 h in an air atmosphere to obtain a hydroisomerization catalyst. The mass content of the active metal component Pt in the hydroisomerization catalyst was 2 wt%. In addition, the pore structure and acid content data of the catalyst are shown in Table 1.

[0107] Comparative Example 4

[0108] This comparative example adopts another method to prepare the ZSM-22 / MCFs composite material and the catalyst thereof, comprising the following steps:

[0109] 1) Preparation of ZSM-22 molecular sieve precursor

[0110] According to the molar ratio of silicon source, aluminum source, alkali source, template agent and water of 1.0:0.005:0.0023:0.044:7, 126g water, 3.33g Al 2 (SO 4 ) 3 18H 2 O and 0.13g KOH were mixed and stirred at room temperature for 1h to obtain a mixed solution; then 5.11g hexamethylenediamine was slowly added dropwise to the mixed solution, and after continuing to stir at room temperature for 1h, 200g silica sol (SiO 2 The mixture was placed in a stainless steel autoclave for hydrothermal crystallization at 160°C for 35 hours, the product was washed and filtered until the filtrate was neutral, and the filter cake was dried at 120°C for 6 hours to obtain ZSM-22 molecular sieve raw powder.

[0111] 2) Preparation of ZSM-22 / MCFs composites

[0112] 709.24g of deionized water and 161.08g of concentrated HCl (HCl mass fraction 37%, 12mol / L) solution were prepared into a hydrochloric acid solution. According to the molar ratio of P123, 1,3,5-trimethylbenzene, tetraethyl orthosilicate, HCl, and water of 0.004:0.35:1.0:4.9:137, 7.73g of template P123 was added to the above-prepared hydrochloric acid solution at 40°C, and stirred to dissolve until the resulting solution was clear and transparent. 37.9g ​​of ZSM-22 molecular sieve raw powder and 14g of 1,3,5-trimethylbenzene were added thereto. Stirring was continued for 1h, and then 88g of TEOS (tetraethyl orthosilicate), after continuing stirring for 4 hours, crystallize at 120°C for 26 hours, and then heat the crystallized solution system at 100°C for 55 hours; then filter, wash the solid product with water, dry it at 100°C, and calcine it at 570°C in air atmosphere for 8 hours to obtain ZSM-22 / MCFs composite material.

[0113] 3) Loading of active components

[0114] The water absorption rate of the carrier was determined to be 61%. 0.79 g of chloroplatinic acid was weighed and dissolved in 61 g of deionized water to prepare an aqueous solution of chloroplatinic acid. 100 g of the ZSM-22 / MCFs carrier was immersed in the aqueous solution of chloroplatinic acid to form a catalyst wet strip. The catalyst wet strip was dried at 100° C. and calcined at 450° C. for 8 h in an air atmosphere to obtain a hydroisomerization catalyst. The mass content of the active metal component Pt in the hydroisomerization catalyst was 0.3 wt%. In addition, the pore structure and acid content data of the catalyst are shown in Table 1.

[0115] The pore structure and acid content data of the catalysts prepared in the examples and comparative examples are shown in Table 1.

[0116] Table 1

[0117]

[0118] In the data in Table 1, it can be seen from the comparison between Example 1 and Comparative Example 1 that, compared with the conventional catalyst using ZSM-22 molecular sieve as a carrier, the specific surface area of ​​the catalyst prepared by the present invention is significantly increased, and the total pore volume is also significantly increased.

[0119] Comparison between Examples 2 and 3 and Comparative Examples 2 and 3 shows that the specific surface area and pore volume of the composite material synthesized by using ZSM-23 and ZSM-48 molecular sieves instead of ZSM-22 are reduced.

[0120] The composite molecular sieve prepared by other composite methods in Comparative Example 4 also has lower specific surface area and pore volume than that in Example 1.

[0121] Example 4

[0122] The catalysts of the embodiments and comparative examples were used, and furfural refined oil and propane deasphalted oil were used as raw materials. The properties of the raw materials are shown in Table 2. When furfural refined oil was used as raw material, the reaction temperature was 380°C, the hydrogen partial pressure was 12 MPa, and the volume space velocity was 0.8 h -1 The hydroisomerization reaction was carried out under the process conditions, and the pour point and cloud point of the VHVI 10 base oil product are shown in Table 3.

[0123] When propane deasphalted oil is used as raw material, the reaction temperature is 350°C, the hydrogen partial pressure is 15 MPa, and the volume space velocity is 1.2 h -1 The hydroisomerization reaction was carried out under the process conditions, and the pour point and cloud point of the VHVI 14 base oil product are shown in Table 4.

[0124] Table 2

[0125] Furfural refined oil Propane deasphalted oil <![CDATA[Density, g / cm 3 > 0.8637 0.8745 Sulfur, μg / g ＜1 ＜1 Nitrogen, μg / g ＜1.1 ＜1.1 <![CDATA[Viscosity at 100 °C, mm 2 / s]]> 5.123 8.988 Sticky Fingers 136 135 Pour point, ℃ 25 42 Distillation range, ℃ 285～499 243～570 Saturated hydrocarbon content, wt% 96.34 96.45

[0126] Table 3

[0127] VHVI 10 Pour point,℃ Cloud point,℃ Example 1 -23 -16 Example 2 -21 -16 Example 3 -23 -16 Comparative Example 1 -20 -8 Comparative Example 2 -20 -8 Comparative Example 3 -20 -6 Comparative Example 4 -20 -5

[0128] Table 4

[0129] VHVI 14 Pour point,℃ Cloud point,℃ Example 1 -18 -5 Example 2 -21 -6 Example 3 -18 -5 Comparative Example 1 -16 -4 Comparative Example 2 -14 -3 Comparative Example 3 -10 -1 Comparative Example 4 -16 -4

[0130] In the data of Table 3 and Table 4, it can be seen from the comparison between Example 1 and Comparative Example 1 that, compared with the conventional base oil with ZSM-22 molecular sieve as the carrier, under the same process conditions, the base oil produced by the scheme of the present invention has better low-temperature properties; the catalyst prepared by the present invention forms a spherical mesoporous foam material with ultra-large mesopores and a three-dimensional through-pore system, which provides a more ideal mass transfer channel for polymer diffusion.

[0131] From the comparison between Example 2 and Comparative Example 2 and between Example 3 and Comparative Example 3, it can be seen that the composite material prepared by using ZSM-22 molecular sieve is more conducive to the isomerization of macromolecular long-chain alkanes.

[0132] From the comparison between Comparative Example 4 and Example 1, it can be seen that the catalyst exhibits better isomerization performance by adopting the composite method of the present invention.

[0133] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A method for preparing a carrier for producing lubricating oil base oil by hydroisomerization, wherein: The carrier is a ZSM-22 / MCFs composite material, and the preparation method comprises the following steps: Using water, aluminum source, alkali source, template agent and silicon source as raw materials, a ZSM-22 molecular sieve precursor is prepared by a hydrothermal crystallization method; The MCFs precursor was prepared by hydrothermal crystallization method using nonionic surfactant triblock copolymer P123, hydrochloric acid solution, water, 1,3,5-trimethylbenzene and tetraethyl orthosilicate as raw materials. The ZSM-22 molecular sieve precursor is added to the MCFs precursor to obtain a mixture; the mixture is crystallized, heated, filtered, washed, dried and calcined in sequence to obtain the ZSM-22 / MCFs composite material.

2. The preparation method according to claim 1, wherein The preparation steps of the ZSM-22 molecular sieve precursor include: After mixing water, aluminum source and alkali source evenly, stir at room temperature; then add template agent dropwise, continue stirring at room temperature, and finally add silicon source and continue stirring; then hydrothermally crystallize the obtained mixture at 155-165° C. for 30h-50h to obtain ZSM-22 molecular sieve precursor.

3. The preparation method according to claim 1, wherein The molar ratio of the silicon source, aluminum source, alkali source, template and water is 1.0: (0.005-0.05): (0.002-0.1): (0.03-0.4): (7-15); wherein the molar ratio of the aluminum source, silicon source and alkali source is calculated as Al2O3, SiO2 and K2O respectively.

4. The preparation method according to claim 1, wherein The aluminum source is selected from at least one of aluminum sulfate 18hydrate, sodium aluminate, and pseudo-boehmite; Preferably, the silicon source is selected from at least one of silica sol, white carbon black, fumed silica, ethyl orthosilicate, propyl orthosilicate, and silica gel; Preferably, the alkali source is potassium hydroxide; Preferably, the template is 1,6-hexanediamine.

5. The preparation method according to claim 1, wherein The preparation steps of the MCFs precursor include: At 38-42° C., the nonionic surfactant triblock copolymer P123 was dissolved in a hydrochloric acid solution, and then 1,3,5-trimethylbenzene was added and mixed evenly, and then tetraethyl orthosilicate was added to obtain an MCFs precursor through a hydrothermal crystallization method.

6. The preparation method according to claim 1, wherein The molar ratio of the nonionic surfactant triblock copolymer P123, 1,3,5-trimethylbenzene, tetraethyl orthosilicate, HCl, and water is (0.003-0.01): (0.3-0.5): 1.0: (3.0-7.0): (120-140).

7. The preparation method according to claim 1, wherein In the step of mixing the ZSM-22 molecular sieve precursor and the MCFs precursor for treatment: the crystallization temperature is 100 to 120° C. and the time is 18 hours to 45 hours; Preferably, the heating temperature is 80-100°C and the heating time is 48h-72h; Preferably, the drying temperature is 80-120°C and the drying time is 3h-8h; Preferably, the calcination temperature is 450-650° C. and the calcination time is 4-8 hours.

8. The preparation method according to claim 1, wherein In the step of mixing the ZSM-22 molecular sieve precursor and the MCFs precursor for treatment, the added mass of the ZSM-22 molecular sieve precursor is controlled to be 0.5 to 1.0 times the added mass of tetraethyl orthosilicate in the preparation of the MCFs precursor.

9. A carrier for producing lubricating oil base oil by hydroisomerization, wherein: The carrier is a ZSM-22 / MCFs composite material, which is obtained by the preparation method according to any one of claims 1 to 8.

10. A catalyst for producing lubricating oil base oil by hydroisomerization, wherein: The catalyst comprises a carrier and an active component; the carrier is the carrier according to claim 9, and the active component is platinum and / or palladium.

11. The catalyst according to claim 10, wherein The specific surface area of ​​the catalyst is 350 m 2 / g~650m 2 / g, total pore volume is 0.5cm 3 / g~1.5cm 3 / g, the total acid content is 0.3mmol / g~0.5mmol / g; Preferably, the content of the active component in the catalyst is 0.1 wt% to 5 wt%.

12. A method for preparing the catalyst for producing lubricating oil base oil by hydroisomerization according to claim 10 or 11, wherein: The preparation method comprises the following steps: The carrier according to claim 9 is impregnated in a salt impregnation solution corresponding to the active component, and then dried and calcined to obtain the catalyst; The salt corresponding to the active component is selected from at least one of chloroplatinic acid, platinum nitrate, tetraamineplatinum acetate, tetraamineplatinum nitrite, tetraamineplatinum sulfate and tetraamineplatinum chloride.

13. A method for producing lubricating oil base oil by hydroisomerization, wherein: The method comprises the following steps: The high wax content crude oil is subjected to isomerization dewaxing reaction under the action of the catalyst according to claim 10 or 11 to obtain a lubricating oil base oil product; The high wax content feedstock oil is selected from at least one of petroleum-based wax oil, FT synthetic oil, propane deasphalted oil, and wax-derived oil; Preferably, the isodewaxing reaction conditions include: hydrogen partial pressure of 12-15 MPa, reaction temperature of 350-380°C, volume liquid hourly space velocity of 0.7-1.5 h -1 , hydrogen to oil volume ratio (500~800):1.

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