A normal paraffin hydroisomerization catalyst, a preparation method thereof, a composition containing the same, and an application thereof

Abstract

The present application provides a normal paraffin hydroisomerization catalyst and a preparation method thereof, a composition containing the same and an application, wherein the catalyst is obtained by mixing a mixed solution containing a modified metal precursor and an active metal precursor with a carrier, performing equal-volume vacuum impregnation and modification according to programmed temperature rising, and then sequentially performing homogenization treatment and calcination on the catalyst precursor; the modified metal includes a first modified metal and a second modified metal, the first modified metal includes one or more of alkali metals, alkaline earth metals and first transition series metals, and the second modified metal includes one or more of group IIIA metals and group IVA metals; the active metal includes group VIII metals. The normal paraffin hydroisomerization catalyst composition contains two or three normal paraffin hydroisomerization catalysts. The composition has higher isomerization selectivity and target product yield, and has better effects of pour point depression and cloud point depression, and better raw material adaptability.

Description

Technical Field

[0001] This invention relates to a catalyst for the hydrogenation isomerization of n-alkanes, its preparation method, compositions comprising the catalyst, and its applications, belonging to the fields of petrochemical and molecular sieve catalyst technology. Background Technology

[0002] Hydroisomerization of n-alkanes is a crucial technology for producing high-octane gasoline, low-pour-point diesel, and high-grade lubricating oil base oils. The hydroisomerization catalyst is the core of this technology. Molecular sieves, serving as catalyst supports, provide multiple functions, including providing acidic active centers, spatially confined pores, and supporting metal active centers. For the raw materials used in producing these products, especially lubricating oil feedstocks, the carbon number distribution is wide and the composition is complex. During the hydroisomerization process, molecules with different carbon numbers and structures face varying degrees of transformation difficulty. Therefore, the requirements for the catalyst's active centers and pore structure differ. Catalysts prepared from single molecular sieves, due to their limited acidity and pore structure, struggle to meet the transformation requirements of different molecules, resulting in poor activity, low conversion rates, and low selectivity.

[0003] In existing technologies, to achieve pore and acidity diversity and meet the conversion requirements of different molecules in the raw materials, the following methods are used: preparing hydroisomerization catalysts by mixing two types of molecular sieves; preparing composite molecular sieve materials and hydroisomerization catalysts with coexisting crystals of different structures; and combining different molecular sieve catalyst components. However, all of the above methods have shortcomings such as complex molecular sieve preparation processes, difficulty in controlling properties, high gas yields, and substandard quality of hydroisomerized heavy products.

[0004] CN105728023A and CN102942958A, among others, employ a mixture of one or more molecular sieves to prepare catalysts. While mixing multiple molecular sieves can produce catalysts with different pore structures and acid sites within the same catalyst, the preparation process using multiple molecular sieves is complex, and the disordered distribution of pores and acid sites still fails to achieve satisfactory conversion in the hydroisomerization process of wide-fraction heavy feedstocks. The medium-strength lubricating oil obtained from CN105728023A has a cloud point as low as -6℃, which is insufficient for a 100℃ viscosity of 10mm... 2 Heavy base oil with a yield of more than 1 / s is difficult to meet the requirements. When used for conversion of different feedstocks, CN102942958A has shortcomings such as high gas yield, low base oil yield, and low pour point depressing.

[0005] CN114713281A, CN1762594A, and CN1792451A, among others, prepared hydroisomerization catalysts using materials such as TON / *MRE composites, silica-alumina molecular sieves combined with SAPO-11 composites, and ZSM-22 / ZSM-23 or ZSM-23 / ZSM-22 composites. While different pore structures and acid centers can be prepared in the same catalyst, the preparation process of composite molecular sieves is complex, requiring seed crystal induction or the use of multiple template agents for directed synthesis. It is difficult to control the proportions of each component, and the molecular sieve synthesis formula needs to be adjusted for different feedstock conversions. Furthermore, the catalytic performance of the molecular sieves is unstable, which is detrimental to stable production.

[0006] CN105214717A uses macromolecular organic amines and alkaline earth metals to adjust the acidity of the catalyst. First, the support needs to be modified and dried before the metal is loaded. The preparation process is complicated. The single component has limited effect on the conversion of heavy raw materials. Moreover, the use of additional organic amines increases the emission of nitrogen wastewater and exhaust gas during wastewater treatment and roasting, which causes serious environmental pollution.

[0007] Furthermore, although the hydrogen-type molecular sieves used in the above-mentioned prior art have high initial activity, impurities in the actual reaction raw materials, such as metals and nitrides, can cause rapid poisoning of the medium-strong acid centers, causing the acid centers and metal centers of the catalyst to quickly become mismatched, thus reducing the catalyst's activity stability and service life.

[0008] Therefore, providing a catalyst for the hydrogenation isomerization of n-alkanes, its preparation method, compositions comprising it, and its applications have become urgent technical problems to be solved in this field. Summary of the Invention

[0009] For the hydroisomerization conversion of heavy, high-wax feedstocks, single-component molecular sieve catalysts exhibit low isomerization selectivity and insufficient ability to lower pour point and turbidity. Furthermore, using multi-component mixing or gradation requires the preparation of different molecular sieve materials, which are complex and inefficient due to significant differences in synthesis and processing methods. To address these shortcomings, one objective of this invention is to provide a hydroisomerization catalyst for n-alkanes.

[0010] Another object of the present invention is to provide a method for preparing the above-described n-alkane hydrogenation isomerization catalyst.

[0011] Another object of the present invention is to provide a n-alkane hydroisomerization catalyst composition comprising two or more of the aforementioned n-alkane hydroisomerization catalysts.

[0012] Another object of the present invention is to provide the application of the above-described n-alkane hydroisomerization catalyst or the n-alkane hydroisomerization catalyst composition in the hydroisomerization of wax-containing feedstocks.

[0013] A final objective of this invention is to provide a method for the hydroisomerization of waxy raw materials, which utilizes the above-described n-alkane hydroisomerization catalyst or the n-alkane hydroisomerization catalyst composition to catalyze the hydroisomerization of waxy raw materials.

[0014] To achieve the above objectives, on the one hand, the present invention provides a catalyst for the hydrogenation isomerization of n-alkane, wherein the catalyst is obtained by first mixing a metal mixed solution containing a modified metal precursor and an active metal precursor with a support, and then performing equal-volume vacuum impregnation and modification under a certain vacuum condition according to a programmed temperature increase to obtain a catalyst precursor, and then performing homogenization treatment and calcination on the catalyst precursor in sequence.

[0015] The modified metal includes a first modified metal and a second modified metal, etc. The first modified metal includes one or more of alkali metals, alkaline earth metals and first transition metals, etc., and the second modified metal includes one or more of group IIIA metals and group IVA metals, etc.

[0016] Active metals include Group VIII metals, etc.

[0017] As a specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, the first modified metal includes one or a combination of several of Na, K, Mg, Ca, Ba, Fe and Zn, preferably Mg and / or Ca, and the second modified metal includes one or a combination of several of In, Ga and Sn, preferably In;

[0018] The active metal includes one or a combination of several of Ru, Rh, Pd, Os, Ir and Pt, preferably Pd and / or Pt.

[0019] In a specific embodiment of the n-alkane hydroisomerization catalyst described above, the content of the first modified metal, calculated as oxide, in the n-alkane hydroisomerization catalyst is 0.1-5 wt%, preferably 0.5-3 wt%, and the molar ratio of the first modified metal to the second modified metal is 0.5:1-5:1, preferably 1:1-3:1. The content of the first modified metal, calculated as oxide, is obtained based on 100% of the total weight of the n-alkane hydroisomerization catalyst.

[0020] As a specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, the modified metal precursor includes at least one of modified metal phosphate, acetate, formate, oxalate, nitrate and sulfonate, preferably at least one of modified metal phosphate, acetate, formate and oxalate, more preferably modified metal acetate.

[0021] As a specific embodiment of the n-alkane hydroisomerization catalyst described above in this invention, the active metal content in the n-alkane hydroisomerization catalyst, based on elemental composition, is 0.05-1 wt%, preferably 0.1-1 wt%. The active metal content, based on elemental composition, is calculated as 100% of the total weight of the n-alkane hydroisomerization catalyst.

[0022] As a specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, the active metal precursor includes at least one of the acid and salt of the active metal, preferably an aminosulfonate or nitrate of the active metal.

[0023] In one specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, the vacuum degree is 0.01-1 bar.

[0024] As a specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, the temperature program of the programmed temperature rise is as follows: room temperature - 30°C, pressure 0.5-1 bar, impregnation for 0.5-5 h; 40-60°C, pressure 0.1-0.5 bar, impregnation for 0.5-5 h; 70-90°C, pressure 0.01-0.1 bar, impregnation for 0.5-5 h.

[0025] Preferably, the temperature program is as follows: immersion for 0.5-1 h at room temperature -30°C and pressure 0.5-0.6 bar, immersion for 1-2 h at 50°C and pressure 0.1-0.2 bar, and immersion for 2-3 h at 70°C and pressure 0.01-0.05 bar.

[0026] As a specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, the homogenization treatment is a homogenization treatment at 100-120°C for 10-40 hours, preferably 20-30 hours.

[0027] As a specific embodiment of the above-described n-alkane hydrogenation isomerization catalyst of the present invention, the calcination is carried out at 300-500°C for 1-12 hours, preferably at 400-480°C for 8-10 hours.

[0028] In a specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, the support is a molecular sieve support, which is prepared by a method including the following specific steps:

[0029] Step 1): Calcine the molecular sieve powder at 550-600℃ for 10-24 hours;

[0030] Step 2): After calcining the molecular sieve in step 1), pulverize it to 100-200 mesh and place it in a 0.5-5 mol / L, preferably 1 mol / L, ammonium salt solution and stir at 70-90℃ for 1-2 hours.

[0031] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 100-120℃ for 10-24h. After drying, the water content of the molecular sieve is <2wt%.

[0032] Step 4): After drying the molecular sieve in step 3), crush it to 200-300 mesh and mix it evenly with inorganic porous material, extrusion aid, acid solution and deionized water. Then, knead the mixture into strips and shape them. Dry the shaped material at 100-120℃ for 12-24 hours and finally calcine it at 550-600℃ for 6-12 hours to obtain the carrier.

[0033] As a specific embodiment of the above-described n-alkane hydrogenation isomerization catalyst of the present invention, in step 1), the molecular sieve includes any one of ten-membered ring or twelve-membered ring one-dimensional channel molecular sieves.

[0034] As a specific embodiment of the above-described n-alkane hydrogenation isomerization catalyst of the present invention, the molecular sieve includes ZSM-22, ZSM-23, ZSM-48 or ZSM-12, etc.

[0035] In a specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, the SiO2 / Al2O3 molar ratio of the molecular sieve is 20-100, preferably 30-60.

[0036] In a specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, in step 2), the ammonium salt includes one or a combination of several of ammonium chloride, ammonium nitrate, and ammonium sulfate, preferably ammonium chloride.

[0037] As a specific embodiment of the above-described n-alkane hydroisomerization catalyst of the present invention, in step 4), the inorganic porous material includes at least one of alumina, amorphous aluminum silicate, boehmite, and silica; preferably alumina or a mixture of alumina and amorphous aluminum silicate.

[0038] The extrusion aid includes at least one of guar gum powder, methylcellulose, and soluble starch; preferably guar gum powder.

[0039] The acid solution includes one of hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, preferably nitric acid, with a mass concentration of 5-50%, more preferably 10-20%.

[0040] As a specific embodiment of the n-alkane hydroisomerization catalyst described above in this invention, the average pore size of the HK micropores of the n-alkane hydroisomerization catalyst is adjustable from 0.50 to 0.75 nm, and the contents of weak Brønsted acid and moderately strong Brønsted acid are adjustable from 0.01 to 0.70 mmol / g, respectively.

[0041] In this invention, when preparing the n-alkane hydroisomerization catalyst, the diffusion degree of the modified metal can be precisely controlled by adjusting the amount of modified metal, the equal volume vacuum impregnation, and the calcination process, thereby adjusting the acidity of the catalyst and adjusting the pore size by utilizing the distribution degree of the modified metal elements at the pore openings and inside the molecular sieve support, thus obtaining catalyst components with different properties.

[0042] In this invention, when preparing the n-alkane hydroisomerization catalyst, a metal mixed solution containing a modified metal precursor and an active metal precursor is first mixed with a one-dimensional porous support. Under a certain vacuum condition and with programmed temperature control, the support is modified and the active metal is loaded simultaneously. The main purpose of this operation is to utilize the modified metal to precisely control both the acid sites / acid centers and the pore size of the support, thereby obtaining catalyst components with different isomerization properties. Simultaneously, the modified metal elements assist in anchoring and dispersing the active metal centers during loading, effectively preventing active metal aggregation, achieving synergy between the active metal centers and acid centers, and improving the selectivity and lifespan of the catalyst. By controlling the amount of modified metal and the preparation procedure, catalyst components with different properties can be obtained.

[0043] On the other hand, the present invention also provides a method for preparing the above-described n-alkane hydroisomerization catalyst, wherein the preparation method includes:

[0044] Step 1: Mix the modified metal precursor with acid to obtain a modified solution, and then mix the active metal precursor with the modified solution to obtain a metal mixed solution;

[0045] Step 2: Based on the water absorption rate of the carrier, the metal mixed solution is mixed with the carrier and subjected to equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0046] Step 3: Homogenize the catalyst precursor to obtain a dry catalyst precursor;

[0047] Step 4: Calcining the dried catalyst precursor to obtain a n-alkane hydrogenation isomerization catalyst.

[0048] As a specific embodiment of the preparation method described above in this invention, in step one, the acid solution includes at least one of phosphoric acid, formic acid, acetic acid, oxalic acid, boric acid, citric acid and tartaric acid, preferably at least one of phosphoric acid, formic acid, acetic acid, boric acid, citric acid and tartaric acid, and more preferably at least one of acetic acid, citric acid and formic acid.

[0049] In one specific embodiment of the preparation method described above in this invention, in step one, the pH value of the modified solution is 2-6.

[0050] In another aspect, the present invention also provides a n-alkane hydroisomerization catalyst composition, wherein the n-alkane hydroisomerization catalyst composition comprises two or more of the n-alkane hydroisomerization catalysts.

[0051] As a specific embodiment of the composition described above in this invention, when the n-alkane hydroisomerization catalyst composition contains three kinds of n-alkane hydroisomerization catalysts, the three kinds of n-alkane hydroisomerization catalysts are loaded from top to bottom in the n-alkane hydroisomerization reactor and are respectively labeled as catalyst A, catalyst B and catalyst C.

[0052] The volume ratio of catalyst A to catalyst B is 1:10-10:1, preferably 1:5-5:1; the volume ratio of catalyst A to catalyst C is 1:10-10:1, preferably 1:5-5:1.

[0053] When the n-alkane hydroisomerization catalyst composition contains two of the n-alkane hydroisomerization catalysts, catalyst A and catalyst B or catalyst C are loaded from top to bottom in the n-alkane hydroisomerization reactor, and the volume ratio of catalyst A and catalyst B or catalyst C is 1:10-10:1, preferably 1:5-5:1.

[0054] As a specific embodiment of the composition described above in this invention, the catalyst A has a weak Brønsted acid content of 0.01-0.20 mmol / g at 150°C and a moderately strong Brønsted acid content of 0.01-0.20 mmol / g at 350°C.

[0055] Catalyst B has a weak Brønsted acid content of 0.05-0.70 mmol / g at 150℃ and a moderately strong Brønsted acid content of 0.05-0.70 mmol / g at 350℃.

[0056] The content of weak Brønsted acid in catalyst C at 150℃ is 0.05-0.30 mmol / g, and the content of moderately strong Brønsted acid at 350℃ is 0.05-0.30 mmol / g, wherein the content ratio of weak Brønsted acid to moderately strong Brønsted acid is 5:1-1:1.

[0057] Preferably, catalyst A has a weak Brønsted acid content of 0.05-0.15 mmol / g at 150°C and a moderately strong Brønsted acid content of 0.05-0.15 mmol / g at 350°C;

[0058] Catalyst B has a weak Brønsted acid content of 0.30-0.60 mmol / g at 150℃ and a moderately strong Brønsted acid content of 0.30-0.60 mmol / g at 350℃.

[0059] The content of weak Brønsted acid in catalyst C at 150℃ is 0.10-0.20 mmol / g, and the content of moderately strong Brønsted acid at 350℃ is 0.10-0.20 mmol / g.

[0060] In catalysts A, B, and C, the ratio of weak Brønsted acid to moderately strong Brønsted acid is 2:1 to 1:1.

[0061] As a specific embodiment of the composition described above in this invention, the average pore size of the HK micropores of catalyst A is 0.60-0.75 nm, the average pore size of the HK micropores of catalyst component B is 0.50-0.65 nm, and the average pore size of the HK micropores of catalyst C is 0.55-0.70 nm.

[0062] Preferably, the average pore size of the HK micropores in catalyst A is 0.65-0.70 nm, the average pore size of the HK micropores in catalyst B is 0.55-0.60 nm, and the average pore size of the HK micropores in catalyst C is 0.60-0.65 nm.

[0063] Furthermore, this invention also provides the application of the above-described n-alkane hydroisomerization catalyst or the above-described n-alkane hydroisomerization catalyst composition in the hydroisomerization of waxy feedstocks. Specifically, by utilizing the above-described n-alkane hydroisomerization catalyst or the above-described n-alkane hydroisomerization catalyst composition to catalyze the hydroisomerization reaction of waxy feedstocks, high-quality lubricating oil base oils, low-pour-point diesel oil, high-octane gasoline, and biofuels can be obtained.

[0064] As a specific embodiment of the application described above in this invention, the wax-containing raw material includes biodeoxidized oil, hydrocracking tail oil or FT synthetic wax, etc., and the wax content is 10-100% by mass.

[0065] As a specific embodiment of the application described above in this invention, wax-containing feedstocks such as biodeoxidized oil, hydrocracking tail oil, or FT-synthesized wax are sequentially converted through catalysts A, B, and C under certain reaction pressure, reaction temperature, and volume hourly space velocity. For biodeoxidized oil, subsequent vacuum distillation after fractional conversion yields biojet fuel and biodiesel, wherein the freezing point of the biojet fuel is ≤ -40℃. For hydrocracking tail oil, subsequent vacuum distillation after fractional conversion yields light base oil and medium base oil, wherein the kinematic viscosity of the medium base oil at 100℃ is 4-8 mm. 2 / s, pour point ≤ -18℃, cloud point ≤ -15℃; for FT synthetic waxes, after graded conversion and subsequent vacuum distillation, light base oils, medium base oils, and heavy base oils can be obtained, wherein the heavy base oil has a kinematic viscosity > 10 mm at 100℃. 2 / s, viscosity index >150, pour point ≤ -15℃, cloud point ≤ -5℃.

[0066] Finally, the present invention also provides a method for hydroisomerization of waxy raw materials, wherein the method utilizes the above-described n-alkane hydroisomerization catalyst or the above-described n-alkane hydroisomerization catalyst composition to catalyze the hydroisomerization of waxy raw materials.

[0067] Compared with the prior art, the beneficial technical effects achieved by the present invention include:

[0068] (1) In preparing the n-alkane hydroisomerization catalyst, this invention utilizes a modified metal precursor to prepare a buffer solution, i.e., a modified solution, and forms a composite impregnation solution, i.e., a metal mixed solution, with a noble metal precursor, i.e., an active metal precursor. This completes catalyst modification and noble metal loading in one step, resulting in a simple preparation process. By utilizing the steric hindrance and competitive adsorption of the modified metal, the dispersion of the noble metal is improved, while the migration and aggregation of the active centers of the noble metal during calcination and use are effectively blocked and controlled, thereby improving the dispersion and anti-migration ability of the noble metal, and thus enhancing the catalyst activity and service life.

[0069] (2) This invention controls the amount of modified metal and the modification process, namely, the equal-volume vacuum impregnation process. By utilizing the migration, selective coverage, and deposition of the modified metal at acid sites and the changes in pore structure caused by the change in charge density of the metal, it is possible to prepare different functional catalyst components from a single molecular sieve material. The average pore size of the micropores is adjustable from 0.50 to 0.75 nm, and the contents of weak Brønsted acid and moderately strong Brønsted acid are adjustable from 0.01 to 0.70 mmol / g, respectively. By grading multiple catalyst components, the acidity and pore size differences can be used to achieve the graded conversion of different raw materials, thereby improving the isomer selectivity and the yield of the target product, realizing the high-selectivity graded isomerization conversion of raw materials, and solving the problem of the complex preparation process using multiple molecular sieve materials.

[0070] (3) The hydroisomerization catalyst composition of n-alkane provided by the present invention is used to catalyze the hydroisomerization reaction of complex mixed long-chain n-alkanes in heavy, high-wax feedstock. It has higher isomerization selectivity and target product yield, and better pour point and turbidity point reduction effects. It also has better feedstock adaptability. That is, the hydroisomerization catalyst composition of n-alkane can effectively control cracking side reactions, reduce gas and naphtha yield, increase base oil yield, obtain base oil products with low pour point and turbidity point, and is generally applicable to the hydroisomerization reaction of waxy feedstock. Attached Figure Description

[0071] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0072] Figure 1 The NH3-TPD curves are for the n-alkane hydroisomerization catalysts provided in Examples 1-4 of the present invention, the n-alkane hydroisomerization catalyst composition provided in Comparative Example 1, and the n-alkane hydroisomerization catalyst composition provided in Comparative Example 7.

[0073] Figure 2 This is an aberration-corrected transmission electron microscope image of the n-alkane hydrogenation isomer catalyst provided in Example 2 of the present invention.

[0074] Figure 3 Aberration-corrected transmission electron microscope image of the n-alkane hydrogenation isomerization catalyst provided for Comparative Example 1.

[0075] Figure 4 Aberration-corrected transmission electron microscope image of the n-alkane hydrogenation isomerization catalyst provided for Comparative Example 1. Detailed Implementation

[0076] It should be noted that the term "comprising" and any variations thereof in the specification, claims, and accompanying drawings of this invention are intended to cover non-exclusive inclusion. 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 explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or devices.

[0077] The "range" disclosed in this invention is given in the form of a lower limit and an 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 and upper limits define the boundaries of the particular range. All ranges defined in this way are composable, meaning that any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for specific parameters, it is also expected that ranges of 60-110 and 80-120 are also expected. Furthermore, if the listed minimum range values ​​are 1 and 2, and the listed maximum range values ​​are 3, 4, and 5, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0078] In this invention, unless otherwise specified, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this invention, and "0-5" is simply a shortened representation of these numerical combinations.

[0079] In this invention, unless otherwise specified, all embodiments and preferred embodiments mentioned in this invention can be combined with each other to form new technical solutions.

[0080] In this invention, unless otherwise specified, all technical features and preferred features mentioned in this invention can be combined with each other to form new technical solutions.

[0081] In this invention, unless otherwise specified, the term "two kinds" as used in this specification means "at least two kinds".

[0082] In this invention, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it 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 it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0083] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying tables, drawings, and embodiments. The embodiments described below are some, but not all, embodiments of this invention, and are only used to illustrate the invention, and should not be considered as limiting the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0084] Examples and comparative examples of catalysts for the hydroisomerization of n-alkane

[0085] Example 1

[0086] This embodiment provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0087] Preparation of catalyst support:

[0088] Step 1): The ZSM-22 raw powder with a silicon-to-aluminum ratio of 60 is calcined at 595℃ for 12 hours;

[0089] Step 2): After calcining the molecular sieve in Step 1), pulverize it to 100-200 mesh and place it in a 1 mol / L ammonium nitrate solution, then stir at 80°C for 1.5 h.

[0090] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0091] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 595℃ for 6h to obtain the catalyst support.

[0092] Catalyst preparation:

[0093] Step 1: Mix 3.3g magnesium acetate and 2.79g indium nitrate with 17.42g acetic acid with a concentration of 1mol / L to obtain a modified solution with a pH of 2-4. Dissolve 0.31g tetraammineplatinum nitrate in 3.58g water to obtain an active solution. Then mix the active solution with the modified solution to obtain a metal mixed solution.

[0094] Step 2: Mix the metal mixed solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0095] The conditions for vacuum impregnation and modification of equal volume were as follows: impregnation for 4 hours at room temperature -30℃ and pressure of 0.5 bar; impregnation for 4 hours at temperature of 40℃ and pressure of 0.1 bar; and impregnation for 4 hours at temperature of 70℃ and pressure of 0.01 bar.

[0096] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0097] Step 4: The dried catalyst precursor is calcined at 480°C for 10 hours to obtain a n-alkane hydroisomerization catalyst. In the n-alkane hydroisomerization catalyst, the content of the first modified metal (magnesium) based on oxides is 2.84%, the content of the second modified metal (indium) based on oxides is 3.9%, and the content of the active metal (platinum) based on elemental composition is 0.48%. All of the above contents are calculated based on the total weight of the n-alkane hydroisomerization catalyst as 100%.

[0098] Example 2

[0099] This embodiment provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0100] Preparation of catalyst support:

[0101] Step 1): The ZSM-23 raw powder with a silicon-to-aluminum ratio of 60 was calcined at 575℃ for 18 hours;

[0102] Step 2): After calcining the molecular sieve in Step 1), pulverize it to 100-200 mesh and place it in a 1 mol / L ammonium nitrate solution, then stir at 80°C for 1.5 h.

[0103] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0104] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 575℃ for 8h to obtain the catalyst support.

[0105] Catalyst preparation:

[0106] Step 1: Mix 1.7g magnesium formate and 3.78g indium aminosulfonate with 13.4g of 1mol / L formic acid to obtain a modified solution with a pH of 2-4. Dissolve 0.31g tetraammineplatin nitrate in 9.88g of water to obtain an active solution. Then mix the active solution with the modified solution to obtain a metal mixed solution.

[0107] Step 2: Mix the metal mixed solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0108] The conditions for vacuum impregnation and modification of equal volume were as follows: impregnation for 2 hours at room temperature -30℃ and pressure of 0.7 bar; impregnation for 2 hours at temperature of 50℃ and pressure of 0.3 bar; and impregnation for 2 hours at temperature of 80℃ and pressure of 0.07 bar.

[0109] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0110] Step 4: The dried catalyst precursor is calcined at 480°C for 10 hours to obtain a n-alkane hydroisomerization catalyst. The n-alkane hydroisomerization catalyst contains 3.0% magnesium (calculated as oxide), 4.0% indium (calculated as oxide), and 0.48% platinum (calculated as elemental). All of the above contents are calculated based on 100% of the total weight of the n-alkane hydroisomerization catalyst.

[0111] Example 3

[0112] This embodiment provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0113] Preparation of catalyst support:

[0114] Step 1): The ZSM-23 raw powder with a silicon-to-aluminum ratio of 40 is calcined at 550℃ for 24 hours;

[0115] Step 2): After calcining the molecular sieve in Step 1), pulverize it to 100-200 mesh and place it in a 1 mol / L ammonium nitrate solution, then stir at 80°C for 1.5 h.

[0116] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0117] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 550℃ for 12h to obtain the catalyst support.

[0118] Catalyst preparation:

[0119] Step 1: Mix 0.6g magnesium formate and 1.34g indium aminosulfonate with 4.5g of 1mol / L formic acid to obtain a modified solution with a pH of 2-4. Dissolve 0.31g tetraammineplatin nitrate in 17.25g of water to obtain an active solution. Then mix the active solution with the modified solution to obtain a metal mixed solution.

[0120] Step 2: Mix the metal mixed solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0121] The conditions for vacuum impregnation and modification of equal volume were as follows: impregnation for 1 hour at room temperature -30℃ and pressure of 1.0 bar; impregnation for 1 hour at temperature of 60℃ and pressure of 0.5 bar; and impregnation for 1 hour at temperature of 90℃ and pressure of 0.1 bar.

[0122] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0123] Step 4: The dried catalyst precursor is calcined at 480°C for 10 hours to obtain a n-alkane hydroisomerization catalyst. The n-alkane hydroisomerization catalyst contains 1.1% magnesium (calculated as oxide), 1.5% indium (calculated as oxide), and 0.5% platinum (calculated as elemental). All of the above contents are calculated based on 100% of the total weight of the n-alkane hydroisomerization catalyst.

[0124] Example 4

[0125] This embodiment provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0126] Preparation of catalyst support:

[0127] Step 1): The ZSM-23 raw powder with a silicon-to-aluminum ratio of 40 is calcined at 550℃ for 24 hours;

[0128] Step 2): After calcining the molecular sieve in Step 1), pulverize it to 100-200 mesh and place it in a 1 mol / L ammonium nitrate solution, then stir at 80°C for 1.5 h.

[0129] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0130] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 550℃ for 8h to obtain the catalyst support.

[0131] Catalyst preparation:

[0132] Step 1: Mix 1.1g magnesium formate and 2.45g indium aminosulfonate with 8.9g of 1mol / L formic acid to obtain a modified solution with a pH of 2-4. Dissolve 0.31g tetraammineplatin nitrate in 13.6g of water to obtain an active solution. Then mix the active solution with the modified solution to obtain a metal mixed solution.

[0133] Step 2: Mix the metal mixed solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0134] The conditions for vacuum impregnation and modification of equal volume were as follows: impregnation for 1 hour at room temperature -30℃ and pressure of 0.5 bar; impregnation for 2 hours at temperature of 50℃ and pressure of 0.1 bar; and impregnation for 2 hours at temperature of 70℃ and pressure of 0.01 bar.

[0135] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0136] Step 4: The dried catalyst precursor is calcined at 480°C for 10 hours to obtain a n-alkane hydroisomerization catalyst. In the n-alkane hydroisomerization catalyst, the content of the first modified metal (magnesium) based on oxides is 1.9%, the content of the second modified metal (indium) based on oxides is 2.7%, and the content of the active metal (platinum) based on elemental composition is 0.49%. All of the above contents are calculated based on the total weight of the n-alkane hydroisomerization catalyst as 100%.

[0137] Example 5

[0138] This embodiment provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0139] Preparation of catalyst support:

[0140] Step 1): The ZSM-23 raw powder with a silicon-to-aluminum ratio of 40 is calcined at 550℃ for 24 hours;

[0141] Step 2): After calcining the molecular sieve in step 1), pulverize it to 100-200 mesh and place it in a 2 mol / L ammonium nitrate solution and stir at 70°C for 2 hours.

[0142] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0143] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 550℃ for 8h to obtain the catalyst support.

[0144] Catalyst preparation:

[0145] Step 1: Mix 1.1g potassium acetate and 1.14g stannous chloride with 8.9g of 1mol / L formic acid to obtain a modified solution with a pH of 2-4. Dissolve 0.31g tetraammineplatinum nitrate in 13.6g of water to obtain an active solution. Then mix the active solution with the modified solution to obtain a metal mixed solution.

[0146] Step 2: Mix the metal mixed solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0147] The conditions for vacuum impregnation and modification of equal volume were as follows: impregnation for 1 hour at room temperature -30℃ and pressure of 0.5 bar; impregnation for 2 hours at temperature of 50℃ and pressure of 0.1 bar; and impregnation for 2 hours at temperature of 70℃ and pressure of 0.01 bar.

[0148] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0149] Step 4: The dried catalyst precursor is calcined at 480°C for 10 hours to obtain a n-alkane hydroisomerization catalyst. The n-alkane hydroisomerization catalyst contains 1.6% potassium (calculated as oxide), 2.9% tin (calculated as oxide), and 0.49% platinum (calculated as elemental). All of the above contents are calculated based on 100% of the total weight of the n-alkane hydroisomerization catalyst.

[0150] Example 6

[0151] This embodiment provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0152] Preparation of catalyst support:

[0153] Step 1): The ZSM-23 raw powder with a silicon-to-aluminum ratio of 40 is calcined at 550℃ for 24 hours;

[0154] Step 2): After calcining the molecular sieve in Step 1), pulverize it to 100-200 mesh and place it in a 4 mol / L ammonium nitrate solution and stir at 70℃ for 1 h.

[0155] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0156] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 550℃ for 8h to obtain the catalyst support.

[0157] Catalyst preparation:

[0158] Step 1: Mix 1.44g zinc acetate and 2.45g indium aminosulfonate with 8.9g of 1mol / L formic acid to obtain a modified solution with a pH of 2-4. Dissolve 0.31g tetraammineplatin nitrate in 13.6g of water to obtain an active solution. Then mix the active solution with the modified solution to obtain a metal mixed solution.

[0159] Step 2: Mix the metal mixed solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0160] The conditions for vacuum impregnation and modification of equal volume were as follows: impregnation for 1 hour at room temperature -30℃ and pressure of 0.5 bar; impregnation for 2 hours at temperature of 50℃ and pressure of 0.1 bar; and impregnation for 2 hours at temperature of 70℃ and pressure of 0.01 bar.

[0161] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0162] Step 4: The dried catalyst precursor is calcined at 480°C for 10 hours to obtain a n-alkane hydroisomerization catalyst. The n-alkane hydroisomerization catalyst contains 2.0% zinc (calculated as oxide), 2.7% indium (calculated as oxide), and 0.49% platinum (calculated as elemental). All of the above contents are calculated based on 100% of the total weight of the n-alkane hydroisomerization catalyst.

[0163] Example 7

[0164] This embodiment provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0165] Preparation of catalyst support:

[0166] Step 1): The ZSM-23 raw powder with a silicon-to-aluminum ratio of 40 is calcined at 550℃ for 24 hours;

[0167] Step 2): After calcining the molecular sieve in step 1), pulverize it to 100-200 mesh and place it in a 1 mol / L ammonium nitrate solution and stir at 90℃ for 1 h.

[0168] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0169] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 550℃ for 8h to obtain the catalyst support.

[0170] Catalyst preparation:

[0171] Step 1: Mix 1.1g magnesium formate and 2.45g indium aminosulfonate with 8.9g of 1mol / L formic acid to obtain a modified solution with a pH of 2-4. Dissolve 0.44g tetraamminepalladium nitrate in 13.6g of water to obtain an active solution. Then mix the active solution with the modified solution to obtain a metal mixed solution.

[0172] Step 2: Mix the metal mixed solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0173] The conditions for vacuum impregnation and modification of equal volume were as follows: impregnation for 1 hour at room temperature -30℃ and pressure of 0.5 bar; impregnation for 2 hours at temperature of 50℃ and pressure of 0.1 bar; and impregnation for 2 hours at temperature of 70℃ and pressure of 0.01 bar.

[0174] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0175] Step 4: The dried catalyst precursor is calcined at 480°C for 10 hours to obtain a n-alkane hydroisomerization catalyst. The n-alkane hydroisomerization catalyst contains 2.0% magnesium (calculated as oxide), 2.7% indium (calculated as oxide), and 0.49% palladium (calculated as elemental). All of the above contents are calculated based on 100% of the total weight of the n-alkane hydroisomerization catalyst.

[0176] Comparative Example 1

[0177] This comparative example provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0178] Preparation of catalyst support:

[0179] Step 1): The ZSM-23 raw powder with a silicon-to-aluminum ratio of 40 is calcined at 550℃ for 24 hours;

[0180] Step 2): After calcining the molecular sieve in step 1), pulverize it to 100-200 mesh and place it in a 1 mol / L ammonium nitrate solution and stir at 80°C for 1 hour.

[0181] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0182] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 550℃ for 8h to obtain the catalyst support.

[0183] Catalyst preparation:

[0184] Step 1: Dissolve 0.31g of tetraammineplatin nitrate in 21g of water to obtain an active solution;

[0185] Step 2: Mix the active solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature rise to obtain the catalyst precursor;

[0186] The conditions for vacuum impregnation and modification of equal volume were as follows: impregnation for 1 hour at room temperature -30℃ and pressure of 0.5 bar; impregnation for 2 hours at temperature of 50℃ and pressure of 0.1 bar; and impregnation for 2 hours at temperature of 70℃ and pressure of 0.01 bar.

[0187] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0188] Step 4: The dried catalyst precursor is calcined at 480°C for 10 hours to obtain a n-alkane hydroisomerization catalyst. The active metal content, namely platinum, in the n-alkane hydroisomerization catalyst is 0.49% based on elemental composition. All of the above contents are calculated based on the total weight of the n-alkane hydroisomerization catalyst as 100%.

[0189] Comparative Example 2

[0190] This comparative example provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0191] Preparation of catalyst support:

[0192] Step 1): The ZSM-23 raw powder with a silicon-to-aluminum ratio of 40 is calcined at 550℃ for 24 hours;

[0193] Step 2): After calcining the molecular sieve in step 1), pulverize it to 100-200 mesh and place it in a 1 mol / L ammonium nitrate solution and stir at 80°C for 1 hour.

[0194] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0195] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 550℃ for 8h to obtain the catalyst support.

[0196] Catalyst preparation:

[0197] Step 1: Mix 1.1g magnesium formate and 2.45g indium aminosulfonate with 8.9g of 1mol / L formic acid to obtain a modified solution with a pH of 2-4. Dissolve 0.31g tetraammineplatin nitrate in 13.6g of water to obtain an active solution. Then mix the active solution with the modified solution to obtain a metal mixed solution.

[0198] Step 2: Mix the metal mixed solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0199] The conditions for vacuum impregnation and modification of equal volume were: impregnation for 2 hours at room temperature and pressure of 0.1 bar, and impregnation for 2 hours at temperature of 70℃ and pressure of 0.1 bar.

[0200] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0201] Step 4: The dried catalyst precursor is calcined at 480°C for 10 hours to obtain a n-alkane hydroisomerization catalyst. In the n-alkane hydroisomerization catalyst, the content of the first modified metal (magnesium) based on oxides is 1.9%, the content of the second modified metal (indium) based on oxides is 2.7%, and the content of the active metal (platinum) based on elemental composition is 0.49%. All of the above contents are calculated based on the total weight of the n-alkane hydroisomerization catalyst as 100%.

[0202] Comparative Example 3

[0203] This comparative example provides a catalyst for the hydrogenation isomerization of n-alkanes, which is prepared by a method including the following specific steps:

[0204] Preparation of catalyst support:

[0205] Step 1): The ZSM-23 raw powder with a silicon-to-aluminum ratio of 40 is calcined at 550℃ for 24 hours;

[0206] Step 2): After calcining the molecular sieve in step 1), pulverize it to 100-200 mesh and place it in a 1 mol / L ammonium nitrate solution and stir at 80°C for 1 hour.

[0207] Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 120℃ for 24h. After drying, the water content of the molecular sieve is <2wt%.

[0208] Step 4): After drying in Step 3), the molecular sieve is pulverized to 200-300 mesh. Then, 40g of the pulverized molecular sieve is mixed evenly with 10g of boehmite, 3g of guar gum powder, 19g of 15% nitric acid solution and 16g of deionized water. The mixture is then kneaded and extruded into strips, and the strips are dried at 120℃ for 24h. Finally, the strips are calcined at 550℃ for 8h to obtain the catalyst support.

[0209] Catalyst preparation:

[0210] Step 1: Mix 1.1g of magnesium formate with 8.9g of 1mol / L formic acid to obtain a modified solution with a pH of 2-4. Dissolve 0.31g of tetraammineplatin nitrate in 13.6g of water to obtain an active solution. Then mix the active solution with the modified solution to obtain a metal mixed solution.

[0211] Step 2: Mix the metal mixed solution with 30g of catalyst support and perform equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor;

[0212] The conditions for vacuum impregnation and modification of equal volume were as follows: impregnation for 1 hour at room temperature -30℃ and pressure of 0.5 bar; impregnation for 2 hours at temperature of 50℃ and pressure of 0.1 bar; and impregnation for 2 hours at temperature of 70℃ and pressure of 0.01 bar.

[0213] Step 3: Homogenize the catalyst precursor at 120°C for 24 hours to obtain a dry catalyst precursor;

[0214] Step 4: The dried catalyst precursor is calcined at 480°C for 10 h to obtain a n-alkane hydroisomerization catalyst. The n-alkane hydroisomerization catalyst contains 1.9% modified magnesium metal as oxide and 0.49% active metal, i.e., platinum, as element. The above contents are calculated based on 100% of the total weight of the n-alkane hydroisomerization catalyst.

[0215] The pyridine-IR analysis data of the n-alkane hydroisomerization catalysts provided in Examples 1-4 and Comparative Examples 1-3 and Comparative Example 7 of this invention are shown in Table 1 below.

[0216] Table 1

[0217]

[0218] The pore structure analysis data of the n-alkane hydrogenation isomer catalysts provided in Examples 1-4 and Comparative Examples 1-3 of this invention are shown in Table 2 below.

[0219] Table 2

[0220]

[0221] The NH3-TPD curves of the n-alkane hydroisomerization catalysts provided in Examples 1-4, Comparative Example 1, and Comparative Example 7 are shown in the figure. Figure 1 As shown in Table 1 above, the pyridine infrared data are as follows. Figure 1 As can be seen from Table 1, the present invention, through bimetallic programmed temperature impregnation modification, can regulate the distribution of acid centers. Compared with the unmodified catalyst of Comparative Example 1, the ratio of weak acid to medium-strong acid is significantly improved. For the catalyst prepared by monometallic programmed temperature impregnation modification in Comparative Example 3, although the ratio of weak acid to medium-strong acid is improved compared with the unmodified catalyst of Comparative Example 1, the effect is not significant compared with Examples 2-4. For the catalyst prepared by unmodified programmed temperature impregnation in Comparative Example 2, the ratio of weak acid to medium-strong acid is lower than that of the unmodified catalyst of Comparative Example 1, and also lower than that of the catalysts prepared in Examples 2-4.

[0222] As can be seen from Table 1 above, Comparative Example 2 did not follow the temperature-progression procedure claimed in this application for impregnation modification during catalyst preparation. Compared with the n-alkane hydroisomerization catalyst provided in Example 4, the catalyst prepared in Comparative Example 2 showed a significant decrease in the amount of weak acid and a relatively small change in the amount of strong acid, resulting in a weak acid to strong acid ratio of only 0.956. This indicates that the specific temperature-progression procedure used in this invention can improve the diffusivity of the modified metal during the modification process and achieve precise control of the amount of strong acid. More importantly, it can increase the ratio of weak acid to strong acid.

[0223] In the isomerization reaction of n-alkane, a high content of weak acid is beneficial to the isomerization reaction, while a low content of medium-strong acid can reduce the occurrence of cracking side reactions and reduce the yield of gas and light hydrocarbons. Therefore, the present invention can effectively increase the ratio of weak acid to medium-strong acid, thereby improving the isomerization selectivity of the catalyst and the yield of the target product.

[0224] For the ZSM-23 molecular sieve used in the examples and comparative examples, its elliptical channel diameter is 0.45 × 0.52 nm, and the average pore size of the HK micropores of catalysts prepared from it is generally around 0.5-0.6 nm. However, as can be seen from the experimental data in Table 2 above, the n-alkane hydroisomerization catalyst prepared by bimetallic temperature-programmed impregnation modification in the examples of the present invention can significantly increase the upper limit of the average pore size of the HK micropores of the n-alkane hydroisomerization catalyst. For example, the average pore size of the HK micropores of the n-alkane hydroisomerization catalysts provided in Examples 1, 2, 3 and 4 can reach 0.69 nm, 0.74 nm, 0.65 nm and 0.68 nm, respectively, while the average pore size of the HK micropores of the n-alkane hydroisomerization catalysts provided in Comparative Examples 1, 2 and 3 is only 0.49 nm, 0.53 nm and 0.62 nm.

[0225] The aberration-corrected transmission electron microscope image of the n-alkane hydroisomerization catalyst provided in Example 2 of this invention is shown below. Figure 2 As shown, the aberration-corrected transmission electron microscope (TEM) image of the n-alkane hydroisomerization catalyst provided in Comparative Example 1 is as follows: Figure 3 As shown, the aberration-corrected transmission electron microscope (TEM) image of the n-alkane hydroisomerization catalyst provided in Comparative Example 3 is as follows: Figure 4 As shown. From Figure 2 , Figure 3 and Figure 4 As can be seen from the above, in the n-alkane hydroisomerization catalyst provided in Example 2 of this invention, all the noble metals are in a highly dispersed atomic state. In contrast, Comparative Example 1, which did not use metal modification, showed obvious metal agglomeration in its n-alkane hydroisomerization catalyst, with agglomerated particles reaching approximately 2 nm in size. Comparative Example 3, which used single-metal modification, did not show obvious metal particles in its n-alkane hydroisomerization catalyst, but... Figure 4 As can be seen, clusters of about 1 nm appear in the n-alkane hydroisomerization catalyst. In contrast, the steric hindrance and anchoring effect of the dual-modified metals result in atomic-level high dispersion of noble metals in the n-alkane hydroisomerization catalyst provided by this invention.

[0226] Examples and comparative examples of n-alkane hydroisomerization catalyst compositions

[0227] Example 8

[0228] This embodiment provides a n-alkane hydroisomerization catalyst composition, which includes the n-alkane hydroisomerization catalysts provided in Examples 2, 3 and 4. These three catalysts are referred to as catalyst A, catalyst B and catalyst C, respectively. They are loaded from top to bottom in a fixed-bed reactor at a volume ratio of 4:3:3 to form the n-alkane hydroisomerization catalyst composition. The waxy feedstock passes through the three catalyst beds from top to bottom to complete the staged conversion.

[0229] Comparative Example 4

[0230] This comparative example provides a n-alkane hydroisomerization catalyst composition comprising the n-alkane hydroisomerization catalysts provided in Examples 2, 3, and 4, referred to as catalyst A, catalyst B, and catalyst C, respectively. The catalysts are loaded from top to bottom in a fixed-bed reactor at a volume ratio of 12:1:1 to form the n-alkane hydroisomerization catalyst composition. The waxy feedstock passes through the three catalyst beds sequentially from top to bottom to complete the staged conversion.

[0231] Comparative Example 5

[0232] This comparative example provides a n-alkane hydroisomerization catalyst composition comprising the n-alkane hydroisomerization catalysts provided in Examples 2, 3, and 4, referred to as catalyst A, catalyst B, and catalyst C, respectively. The catalysts are loaded from top to bottom in a fixed-bed reactor at a volume ratio of 1:12:12 to form the n-alkane hydroisomerization catalyst composition. The waxy feedstock passes through the three catalyst beds sequentially from top to bottom to complete the staged conversion.

[0233] Comparative Example 6

[0234] This comparative example provides a n-alkane hydroisomerization catalyst composition comprising the n-alkane hydroisomerization catalysts provided in Examples 3, 2, and 4, referred to as catalyst A, catalyst B, and catalyst C, respectively. The catalysts are loaded from top to bottom in a fixed-bed reactor at a volume ratio of 4:3:3 to form the n-alkane hydroisomerization catalyst composition. The waxy feedstock passes through the three catalyst beds sequentially from top to bottom to complete the staged conversion.

[0235] Comparative Example 7

[0236] This comparative example provides a n-alkane hydroisomerization catalyst composition, which is obtained by mechanically mixing the n-alkane hydroisomerization catalysts provided in Examples 2, 3 and 4 at a volume ratio of 4:3:3, and then packing it into a fixed-bed reactor to form a n-alkane hydroisomerization catalyst system.

[0237] Application examples and comparative application examples

[0238] Application Example 1

[0239] This application example uses FT-synthesized wax as raw material, the properties of which are shown in Table 3. It employs the n-alkane hydroisomerization catalyst composition provided in Example 8, with a reaction temperature of 360°C, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 5.

[0240] Application Example 2

[0241] This application example uses biodeoxidized oil as feedstock, the properties of which are shown in Table 4. It employs the n-alkane hydroisomerization catalyst composition provided in Example 8, with reaction temperatures of 330°C and 300°C, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 300:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 6.

[0242] Application Example 3

[0243] This application example uses FT-synthesized wax as raw material, the properties of which are shown in Table 3. The catalyst for the hydroisomerization of n-alkanes provided in Example 1 is used, with a reaction temperature of 360°C, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 5.

[0244] Application Example 4

[0245] This application example uses FT-synthesized wax as raw material, the properties of which are shown in Table 3. The n-alkane hydroisomerization catalyst provided in Example 2 is used, with a reaction temperature of 360°C, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 5.

[0246] Comparative Application Example 1

[0247] This application example uses FT-synthesized wax as raw material, the properties of which are shown in Table 3. The catalyst for the hydroisomerization of n-alkanes provided in Comparative Example 1 is employed. The reaction conditions are: a reaction temperature of 360°C, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 5.

[0248] Comparative Application Example 2

[0249] This application example uses FT-synthesized wax as raw material, the properties of which are shown in Table 3. It employs the n-alkane hydroisomerization catalyst composition provided in Comparative Example 4, with a reaction temperature of 360℃, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 5.

[0250] Comparative Application Example 3

[0251] This application example uses FT-synthesized wax as raw material, the properties of which are shown in Table 3. It employs the n-alkane hydroisomerization catalyst composition provided in Comparative Example 5, with a reaction temperature of 360°C, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 5.

[0252] Comparative Application Example 4

[0253] This application example uses FT-synthesized wax as raw material, the properties of which are shown in Table 3. It employs the n-alkane hydroisomerization catalyst composition provided in Comparative Example 6, with a reaction temperature of 360°C, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 5.

[0254] Comparative Application Example 5

[0255] This application example uses FT-synthesized wax as raw material, the properties of which are shown in Table 3. It employs the n-alkane hydroisomerization catalyst composition provided in Comparative Example 7, with a reaction temperature of 360°C, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 5.

[0256] Application ratio 6

[0257] This application example uses FT-synthesized wax as raw material, the properties of which are shown in Table 3. It employs the n-alkane hydroisomerization catalyst composition provided in Comparative Example 2, with a reaction temperature of 360℃, a pressure of 5 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume hourly space velocity of 1.0 h⁻¹. -1 Hydroisomerization reaction was carried out under certain conditions, and the product yield and properties were obtained by fractionation, as shown in Table 5.

[0258] Table 3

[0259]

[0260]

[0261] Table 4

[0262] project raw material Carbon number distribution 15-18 <![CDATA[Density, g / cm 3 > 0.88 Sulfur content, ppm <2 Nitrogen content, ppm <2 IBP / 5% 238.0 / 272.4 10％ / 30％ 277.9 / 283.6 50％ / 70％ 287.7 / 292.4 90％ / 95％ 302.3 / 323.7 FBP 336.3

[0263] Table 5

[0264]

[0265] Note: The yields in Table 5 are all weight yields, which are calculated based on: product mass / raw material mass × 100%.

[0266] As can be seen from the experimental data in Table 5 above, the n-alkane hydroisomerization catalyst composition provided in the embodiments of the present invention can effectively reduce the yield of light hydrocarbons and naphtha, obtain a higher base oil yield and a lower product pour point and cloud point, and is suitable for high-yield production of biofuels.

[0267] Specifically, Application Examples 3 and 4, and Comparative Application Examples 1 and 6 all used a single n-alkane hydroisomerization catalyst to catalyze the hydroisomerization reaction of FT-synthesized wax. Application Example 1, however, used the n-alkane hydroisomerization catalyst composition provided in Example 8 to catalyze the hydroisomerization reaction of FT-synthesized wax. Compared to Application Examples 3 and 4, and Comparative Application Examples 1 and 6, Application Example 1 showed lower yields of light hydrocarbons and naphtha, but higher yields of base oils, especially medium and heavy base oils. Furthermore, the pour point and cloud point of the heavy base oil were significantly reduced, reaching only -21°C and -5°C, respectively. Comparative Application Examples 3, 4, and 1 also showed that the higher yields of light hydrocarbons and naphtha, and lower yields of medium and heavy base oils, were due to the lack of metal modification in the n-alkane hydroisomerization catalyst used in Comparative Application Example 1. Because the heating process for the n-alkane hydroisomerization catalyst used in Comparative Application Example 6 was not performed according to the procedure claimed in this invention, the yields of light hydrocarbons and naphtha were lower than those in Comparative Application Example 1, while the yield of base oil was higher. However, the pour point and cloud point of the heavy base oil were higher. Compared to Application Examples 3 and 4, the pour point and cloud point of the heavy base oil in Comparative Application Example 6 were lower than those in Application Example 3 and roughly equivalent to those in Application Example 4, but the yields of light hydrocarbons and naphtha remained relatively high. Therefore, the specific temperature-programmed modification used in the embodiments of this invention can significantly improve the isomer selectivity of the catalyst and reduce the yields of light hydrocarbons and naphtha.

[0268] Although comparative application examples 2-4 also used a n-alkane hydroisomerization catalyst composition to catalyze the hydroisomerization reaction of FT-synthesized wax, the n-alkane hydroisomerization catalyst composition, such as the volume ratio of the three catalysts or the weak or medium-strong Brønsted acid content of the three catalysts, did not meet the requirements of this application. The yields of light hydrocarbons, naphtha, and base oil in comparative application examples 2-4 were either close to or significantly higher than those in application example 1, but the pour point and cloud point of the heavy base oil obtained were significantly higher than those in application example 1.

[0269] Comparative Application Example 5 also used a n-alkane hydroisomerization catalyst composition to catalyze the hydroisomerization reaction of FT-synthesized wax. However, the n-alkane hydroisomerization catalyst composition was obtained by mechanically mixing three n-alkane hydroisomerization catalysts. In Comparative Application Example 5, the yields of light hydrocarbons and naphtha were significantly higher than in Application Example 1, while the yield of heavy base oil was significantly lower. Furthermore, the pour point and cloud point of the heavy base oil were also significantly higher in Comparative Application Example 5 than in Application Example 1.

[0270] Table 6

[0271]

[0272]

[0273] As can be seen from the experimental data in Table 6 above, the use of the n-alkane hydroisomerization catalyst composition provided in the embodiments of the present invention to catalyze the hydroisomerization reaction of biodeoxygenated oil can achieve a high jet fuel yield of up to 55% in the jet fuel scheme, and the jet fuel freezing point can be as low as -47°C; similarly, a high diesel fuel yield of up to 85% can be achieved in the diesel fuel scheme, and the diesel fuel pour point is only -5°C.

[0274] The above description is merely a specific embodiment of the present invention and should not be construed as limiting the scope of the invention. Therefore, any substitution of equivalent components or equivalent changes and modifications made within the scope of protection of this patent should still fall within the scope of this patent. Furthermore, the technical features, technical features and technical inventions, and technical inventions in this invention can be freely combined and used.

Claims

1. A catalyst for the hydroisomerization of n-alkane, characterized in that, The n-alkane hydrogenation isomer catalyst is obtained by first mixing a metal mixed solution containing a modified metal precursor and an active metal precursor with a support, and then performing equal-volume vacuum impregnation and modification under a certain vacuum condition and according to a programmed temperature increase to obtain a catalyst precursor. The catalyst precursor is then subjected to homogenization treatment and calcination in sequence. The carrier is a one-dimensional porous molecular sieve; The temperature program for the programmed temperature rise is as follows: immersion for 0.5-5 hours at room temperature -30℃ and pressure of 0.5-1 bar; immersion for 0.5-5 hours at 40-60℃ and pressure of 0.1-0.5 bar; and immersion for 0.5-5 hours at 70-90℃ and pressure of 0.01-0.1 bar. The modified metal includes a first modified metal and a second modified metal. The first modified metal includes one or more of alkali metals, alkaline earth metals and first transition metals, and the second modified metal includes one or more of group IIIA metals and group IVA metals. Active metals include Group VIII metals.

2. The catalyst for the hydroisomerization of n-alkanes according to claim 1, characterized in that, The first modified metal includes one or a combination of several of Na, K, Mg, Ca, Ba, Fe and Zn, and the second modified metal includes one or a combination of several of In, Ga and Sn; The active metal includes one or a combination of several of Ru, Rh, Pd, Os, Ir, and Pt.

3. The catalyst for the hydroisomerization of n-alkanes according to claim 1 or 2, characterized in that, In the catalyst for the hydroisomerization of n-alkane, the content of the first modified metal, calculated as oxide, is 0.1-5 wt%, and the molar ratio of the first modified metal to the second modified metal is 0.5:1-5:

1.

4. The catalyst for the hydroisomerization of n-alkanes according to claim 1 or 2, characterized in that, Modified metal precursors include at least one of the following: phosphate, acetate, formate, oxalate, nitrate, and sulfonate of modified metals.

5. The catalyst for the hydroisomerization of n-alkane according to claim 1 or 2, characterized in that, In the catalyst for the hydroisomerization of n-alkane, the content of active metal, calculated as elemental, is 0.05-1 wt%.

6. The catalyst for the hydroisomerization of n-alkane according to claim 1 or 2, characterized in that, Active metal precursors include at least one of the acids and salts of active metals.

7. The catalyst for the hydroisomerization of n-alkanes according to claim 1, characterized in that, The vacuum level is 0.01-1 bar.

8. The catalyst for the hydroisomerization of n-alkanes according to claim 1 or 2, characterized in that, The homogenization treatment is performed at 100-120℃ for 10-40 hours.

9. The catalyst for the hydroisomerization of n-alkane according to claim 1, characterized in that, The roasting is carried out at 300-500℃ for 1-12 hours.

10. The catalyst for the hydroisomerization of n-alkanes according to claim 1 or 2, characterized in that, The carrier is prepared by a method including the following specific steps: Step 1): Calcine the molecular sieve powder at 550-600℃ for 10-24 hours; Step 2): After calcining the molecular sieve in Step 1), pulverize it to 100-200 mesh and place it in a 0.5-5 mol / L ammonium salt solution and stir at 70-90℃ for 1-2 hours. Step 3): Filter the solution after step 2), then wash the obtained filter cake with deionized water, filter the washing solution to obtain the filter cake, and then dry the finally obtained filter cake at 100-120℃ for 10-24h. After drying, the water content of the molecular sieve is <2wt%. Step 4): After drying the molecular sieve in step 3), crush it to 200-300 mesh and mix it evenly with inorganic porous material, extrusion aid, acid solution and deionized water. Then, knead the mixture into strips and shape them. Dry the shaped material at 100-120℃ for 12-24 hours and finally calcine it at 550-600℃ for 6-12 hours to obtain the carrier.

11. The catalyst for the hydroisomerization of n-alkane according to claim 10, characterized in that, In step 1), the molecular sieve includes any one of ten-membered ring or twelve-membered ring one-dimensional porous molecular sieves.

12. The catalyst for the hydroisomerization of n-alkanes according to claim 11, characterized in that, The molecular sieves include ZSM-22, ZSM-23, ZSM-48, or ZSM-12.

13. The catalyst for the hydroisomerization of n-alkanes according to claim 11 or 12, characterized in that, The SiO2 / Al2O3 molar ratio of the molecular sieve is 20-100.

14. The catalyst for the hydroisomerization of n-alkane according to claim 10, characterized in that, In step 2), the ammonium salt includes one or a combination of several of ammonium chloride, ammonium nitrate, and ammonium sulfate.

15. The catalyst for the hydroisomerization of n-alkanes according to claim 10, characterized in that, In step 4), the inorganic porous material includes at least one of alumina, amorphous aluminum silicate, boehmite, and silica. The extrusion aid includes at least one of guar gum powder, methylcellulose, and soluble starch; The acid solution includes one of hydrochloric acid, nitric acid, phosphoric acid, or sulfuric acid, with a mass concentration of 5-50%.

16. The catalyst for the hydroisomerization of n-alkane according to claim 1 or 9, characterized in that, The average pore size of the HK micropores in the n-alkane hydroisomerization catalyst is adjustable from 0.50 to 0.75 nm, and the contents of weak Brønsted acid and moderately strong Brønsted acid are adjustable from 0.01 to 0.70 mmol / g, respectively.

17. A method for preparing the n-alkane hydroisomerization catalyst according to any one of claims 1-16, characterized in that, The preparation method includes: Step 1: Mix the modified metal precursor with acid to obtain a modified solution, and then mix the active metal precursor with the modified solution to obtain a metal mixed solution; Step 2: Based on the water absorption rate of the carrier, the metal mixed solution is mixed with the carrier and subjected to equal-volume vacuum impregnation and modification under a certain vacuum degree and according to a programmed temperature increase to obtain the catalyst precursor; Step 3: Homogenize the catalyst precursor to obtain a dry catalyst precursor; Step 4: Calcining the dried catalyst precursor to obtain a n-alkane hydrogenation isomerization catalyst.

18. The preparation method according to claim 17, characterized in that, In step one, the acid solution includes at least one of phosphoric acid, formic acid, acetic acid, oxalic acid, boric acid, citric acid, and tartaric acid.

19. The preparation method according to claim 17 or 18, characterized in that, In step one, the pH value of the modified solution is 2-6.

20. A catalyst composition for the hydroisomerization of n-alkanes, characterized in that, The n-alkane hydroisomerization catalyst composition comprises two or three n-alkane hydroisomerization catalysts according to any one of claims 1-16.

21. The composition according to claim 20, characterized in that, When the n-alkane hydroisomerization catalyst composition contains three n-alkane hydroisomerization catalysts, the three n-alkane hydroisomerization catalysts are loaded from top to bottom in the n-alkane hydroisomerization reactor and are respectively labeled as catalyst A, catalyst B and catalyst C. The volume ratio of catalyst A to catalyst B is 1:10-10:1; the volume ratio of catalyst A to catalyst C is 1:10-10:

1. When the n-alkane hydroisomerization catalyst composition contains two of the n-alkane hydroisomerization catalysts, catalyst A and catalyst B or catalyst C are loaded from top to bottom in the n-alkane hydroisomerization reactor, and the volume ratio of catalyst A and catalyst B or catalyst C is 1:10-10:

1.

22. The composition according to claim 21, characterized in that, When the n-alkane hydroisomerization catalyst composition contains three n-alkane hydroisomerization catalysts, the three n-alkane hydroisomerization catalysts are loaded from top to bottom in the n-alkane hydroisomerization reactor and are respectively labeled as catalyst A, catalyst B and catalyst C, wherein the volume ratio of catalyst A and catalyst B is 1:5-5:

1.

23. The composition according to claim 21, characterized in that, When the n-alkane hydroisomerization catalyst composition contains three n-alkane hydroisomerization catalysts, the three n-alkane hydroisomerization catalysts are loaded from top to bottom in the n-alkane hydroisomerization reactor and are respectively labeled as catalyst A, catalyst B and catalyst C, wherein the volume ratio of catalyst A and catalyst C is 1:5-5:

1.

24. The composition according to claim 21, characterized in that, When the n-alkane hydroisomerization catalyst composition contains two of the n-alkane hydroisomerization catalysts, the n-alkane hydroisomerization reactor is filled with catalyst A and catalyst B or catalyst C from top to bottom, and the volume ratio of catalyst A to catalyst B or catalyst C is 1:5-5:

1.

25. The composition according to any one of claims 20-24, characterized in that, Catalyst A has a weak Brønsted acid content of 0.01-0.20 mmol / g at 150℃ and a moderately strong Brønsted acid content of 0.01-0.20 mmol / g at 350℃; Catalyst B has a weak Brønsted acid content of 0.05-0.70 mmol / g at 150℃ and a moderately strong Brønsted acid content of 0.05-0.70 mmol / g at 350℃. The catalyst C has a weak Brønsted acid content of 0.05-0.30 mmol / g at 150℃ and a moderately strong Brønsted acid content of 0.05-0.30 mmol / g at 350℃, with the ratio of weak Brønsted acid to moderately strong Brønsted acid being 5:1-1:

1.

26. The composition according to claim 25, characterized in that, Catalyst A has a weak Brønsted acid content of 0.05-0.15 mmol / g at 150℃ and a moderately strong Brønsted acid content of 0.05-0.15 mmol / g at 350℃. Catalyst B has a weak Brønsted acid content of 0.30-0.60 mmol / g at 150℃ and a moderately strong Brønsted acid content of 0.30-0.60 mmol / g at 350℃. The content of weak Brønsted acid in catalyst C at 150℃ is 0.10-0.20 mmol / g, and the content of moderately strong Brønsted acid at 350℃ is 0.10-0.20 mmol / g. In catalysts A, B, and C, the ratio of weak Brønsted acid to moderately strong Brønsted acid is 2:1 to 1:

1.

27. The composition according to any one of claims 20-24, characterized in that, The average pore size of the HK micropores in catalyst A is 0.60-0.75 nm, the average pore size of the HK micropores in catalyst component B is 0.50-0.65 nm, and the average pore size of the HK micropores in catalyst C is 0.55-0.70 nm.

28. The composition according to claim 27, characterized in that, The average pore size of the HK micropores in catalyst A is 0.65-0.70 nm, the average pore size of the HK micropores in catalyst B is 0.55-0.60 nm, and the average pore size of the HK micropores in catalyst C is 0.60-0.65 nm.

29. The use of the n-alkane hydroisomerization catalyst according to any one of claims 1-16 or the n-alkane hydroisomerization catalyst composition according to any one of claims 20-28 in the hydroisomerization of waxy feedstocks.

30. The application according to claim 29, characterized in that, The wax-containing raw materials include biodeoxidized oil, hydrocracking tail oil, or FT synthetic wax.

31. A method for hydroisomerization of wax-containing raw materials, characterized in that, The method utilizes the n-alkane hydroisomerization catalyst according to any one of claims 1-16 or the n-alkane hydroisomerization catalyst composition according to any one of claims 20-28 to catalyze the hydroisomerization of waxy feedstock.

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