N-alkane hydroisomerization catalyst, preparation method thereof, composition containing n-alkane hydroisomerization catalyst and application of n-alkane hydroisomerization catalyst

Abstract

The invention provides an n-alkane hydroisomerization catalyst and a preparation method thereof, a composition containing the n-alkane hydroisomerization catalyst and application of the n-alkane hydroisomerization catalyst, and the n-alkane hydroisomerization catalyst is prepared by the following steps: mixing a metal mixed solution containing a modified metal precursor and an active metal precursor with a carrier, heating according to a program, and carrying out equivalent-volume vacuum impregnation and modification to obtain a catalyst precursor; the catalyst precursor is subjected to homogenization treatment and roasting in sequence, and the catalyst is obtained. The modified metal comprises first modified metal and second modified metal, the first modified metal comprises one or more of alkali metal, alkaline earth metal and first transition metal, and the second modified metal comprises one or more of IIIA group metal and IVA group metal; the active metal comprises a group VIII metal. The n-alkane hydroisomerization catalyst composition comprises two or three n-alkane hydroisomerization catalysts. The composition has higher isoselectivity and target product yield, better pour point depression and cloud point depression effects and better raw material adaptability.

Description

Technical Field

[0001] The invention relates to a normal alkane hydrogenation isomerization catalyst and a preparation method thereof, a composition containing the catalyst and application thereof, and belongs to the technical field of petrochemical industry and molecular sieve catalysts. Background Art

[0002] The hydroisomerization of normal alkanes is an important technical means to produce high-octane gasoline, low-viscosity diesel, and high-grade lubricant base oils. The hydroisomerization catalyst is the core of the technology. The molecular sieve, as a carrier of the hydroisomerization catalyst, takes into account multiple functions such as providing acidic active centers, spatially confined pores, and supporting metal active centers. For the raw materials for the production of the above products, especially lubricant raw materials, their carbon number distribution is wide and the composition is complex. During the hydroisomerization conversion process, the difficulty of converting molecules with different carbon numbers and structures is different. Therefore, there are differences in the requirements for the active center and pore structure of the catalyst. The catalyst prepared by a single molecular sieve is difficult to meet the conversion requirements of different molecules due to the singleness of the acidity and pore structure, and thus has shortcomings such as poor activity, low conversion rate, and low selectivity.

[0003] In the prior art, in order to achieve pore and acid diversity and meet the conversion requirements of different molecules in the raw materials, the following methods are used: mixing two molecular sieves to prepare hydroisomerization catalysts; preparing composite molecular sieve materials and hydroisomerization catalysts with symbiotic crystals of different structures; combining different molecular sieve catalyst components, etc. However, the above methods all have the disadvantages of complex molecular sieve preparation process, difficult to control properties, high gas yield, and substandard quality of hydroisomerization heavy products.

[0004] CN105728023A and CN102942958A use one or more molecular sieves to prepare catalysts. Although the mixture of multiple molecular sieves can prepare different pore structures and acid centers in the same catalyst, the preparation process of multiple molecular sieves is complicated, and the disorder of the pore and acid site distribution still cannot achieve a good conversion effect in the hydroisomerization process of wide-fraction heavy raw materials. The cloud point of the medium-quality lubricating oil obtained in CN105728023A can only reach -6°C, and the viscosity of 10mm at 100°C is 10mm. 2 / s or more heavy base oil is difficult to meet the index requirements. When CN102942958A is used for the conversion of different raw materials, it has the disadvantages of high gas yield, low base oil yield, and low pour point depression.

[0005] CN114713281A, CN1762594A and CN1792451A respectively prepare and use TON / *MRE composite, silicon aluminum molecular sieve and SAPO-11 composite, ZSM-22 / ZSM-23 or ZSM-23 / ZSM-22 composite and other materials to prepare hydrogenation isomerization catalysts. Although different pore structures and acid centers can be prepared in the same catalyst, the preparation process of the composite molecular sieve is complicated, and it is necessary to add seed induction or use a variety of templates to guide the synthesis. It is not easy to control the proportion of each component. For the conversion of different raw materials, it is necessary to adjust the molecular sieve synthesis formula to achieve it. The catalytic performance of the molecular sieve is unstable, which is not conducive to stable production.

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

[0007] In addition, although the hydrogen-type molecular sieve used in the above-mentioned prior art as a catalyst carrier has a high initial activity, impurities in the actual reaction raw materials, such as metals and nitrides, will cause rapid poisoning of the medium and strong acid centers, causing the catalyst acid centers and metal centers to quickly be in a mismatched state, thereby reducing the catalyst activity stability and service life.

[0008] Therefore, providing a novel n-alkane hydroisomerization catalyst and a preparation method thereof, a composition comprising the catalyst and an application thereof has become a technical problem that needs to be solved urgently in the art. Summary of the invention

[0009] For the hydroisomerization conversion of heavy and waxy raw materials, the isomerization selectivity of a single molecular sieve component catalyst is not high, and the ability to reduce the pour point and cloud point is insufficient; when using multi-component mixing or grading, different molecular sieve materials need to be prepared. Since the synthesis and treatment methods of different materials are quite different, the preparation process is complicated and the efficiency is low. In order to solve the above shortcomings and deficiencies, one object of the present invention is to provide a catalyst for the hydroisomerization of normal alkanes.

[0010] Another object of the present invention is to provide a method for preparing the above-mentioned normal alkane hydroisomerization catalyst.

[0011] Another object of the present invention is to provide a normal alkane hydroisomerization catalyst composition, which comprises two or three or more normal alkane hydroisomerization catalysts.

[0012] Another object of the present invention is to provide the use of the above-mentioned normal alkane hydroisomerization catalyst or the above-mentioned normal alkane hydroisomerization catalyst composition in the hydroisomerization of waxy feedstock.

[0013] The last object of the present invention is to provide a method for hydroisomerization of waxy feedstock, which utilizes the above-mentioned n-alkane hydroisomerization catalyst or the above-mentioned n-alkane hydroisomerization catalyst composition to catalyze the hydroisomerization of waxy feedstock.

[0014] In order to achieve the above objectives, on the one hand, the present invention provides a normal alkane hydroisomerization catalyst, wherein the normal alkane hydroisomerization catalyst is obtained by first mixing a metal 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 under a certain vacuum condition to obtain a catalyst precursor, and then sequentially homogenizing and calcining the catalyst precursor;

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

[0016] Active metals include Group VIII metals and the like.

[0017] As a specific embodiment of the above n-alkane hydroisomerization catalyst of the present invention, the first modified metal includes one or a combination 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 In, Ga and Sn, preferably In;

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

[0019] As a specific embodiment of the above-mentioned n-alkane hydroisomerization catalyst of the present invention, wherein, in the n-alkane hydroisomerization catalyst, the content of the first modified metal calculated as oxide is 0.1-5wt%, preferably 0.5-3wt%, 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. Wherein, the content of the first modified metal calculated as oxide is calculated based on the total weight of the n-alkane hydroisomerization catalyst as 100%.

[0020] As a specific embodiment of the n-alkane hydroisomerization catalyst described above in the present invention, the modified metal precursor includes at least one of the modified metal phosphates, acetates, formates, oxalates, nitrates and sulfonates, etc., preferably at least one of the modified metal phosphates, acetates, formates, oxalates, etc., and more preferably the modified metal acetate.

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

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

[0023] As a specific embodiment of the above-mentioned n-alkane hydroisomerization catalyst of the present invention, the vacuum degree is 0.01-1 bar.

[0024] As a specific embodiment of the above-mentioned n-alkane hydroisomerization catalyst of the present invention, the temperature program of the programmed temperature increase is: at room temperature-30°C and pressure of 0.5-1 bar, immersion for 0.5-5h, at 40-60°C and pressure of 0.1-0.5 bar, immersion for 0.5-5h, at 70-90°C and pressure of 0.01-0.1 bar, immersion for 0.5-5h;

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

[0026] As a specific embodiment of the above-mentioned 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 n-alkane hydroisomerization catalyst of the present invention, the calcination is performed at 300-500° C. for 1-12 h, preferably, the calcination is performed at 400-480° C. for 8-10 h.

[0028] As a specific embodiment of the above n-alkane hydroisomerization catalyst of the present invention, the carrier is a molecular sieve carrier, which is prepared by a preparation method comprising the following specific steps:

[0029] Step 1): calcining the molecular sieve raw powder at 550-600°C for 10-24h;

[0030] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place it in 0.5-5 mol / L, preferably 1 mol / L ammonium salt solution and stir at 70-90° C. for 1-2 h;

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

[0032] Step 4): crush the dried molecular sieve obtained in step 3) to 200-300 mesh and mix it evenly with the inorganic porous material, extrusion aid, acid solution and deionized water, then knead the mixture and extrude it into strips, dry the shaped material at 100-120°C for 12-24h, and finally calcine it at 550-600°C for 6-12h to obtain the carrier.

[0033] As a specific embodiment of the above-mentioned n-alkane hydroisomerization catalyst of the present invention, wherein, in step 1), the molecular sieve includes any one of a ten-membered ring or twelve-membered ring one-dimensional channel molecular sieve and the like.

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

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

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

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

[0038] The extrusion aid comprises at least one of sesbania powder, methyl cellulose and soluble starch, and is preferably sesbania powder;

[0039] The acid solution comprises one of hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, preferably nitric acid, and its mass concentration is 5-50%, preferably 10-20%.

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

[0041] In the present invention, when preparing the n-alkane hydrogenation isomerization catalyst, the diffusion degree of the modified metal can be accurately controlled by adjusting the amount of modified metal and the equal volume vacuum impregnation and roasting procedures, the acidity of the catalyst can be adjusted, and the pore size can be adjusted by utilizing the distribution degree of the modified metal element at the pore mouth and in the pores of the molecular sieve carrier, thereby obtaining catalyst components with different properties.

[0042] In the present invention, when preparing the n-alkane hydrogenation isomerization catalyst, a metal mixed solution containing a modified metal precursor and an active metal precursor is first mixed with a one-dimensional pore carrier, and the carrier is modified and loaded with active metals simultaneously under a certain vacuum condition according to a program temperature control. The main purpose of this operation is to use the modified metal to simultaneously accurately control the acid position / acid center and pore size of the carrier to obtain catalyst components with different isomerization properties. At the same time, the modified metal element assists in anchoring and dispersing the active metal active center during the loading process, and can effectively prevent the active metal from aggregating, realize the synergy between the active metal active center and the acid center, and improve the selectivity and service life 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-mentioned n-alkane hydroisomerization catalyst, wherein the preparation method comprises:

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

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

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

[0047] Step 4: calcining the dried catalyst precursor to obtain a normal alkane hydroisomerization catalyst.

[0048] As a specific embodiment of the preparation method described above in the present invention, wherein, 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, formic acid, etc.

[0049] As a specific embodiment of the above preparation method of the present invention, in step 1, the pH value of the modified solution is 2-6.

[0050] In yet another aspect, the present invention further provides a normal alkane hydroisomerization catalyst composition, wherein the normal alkane hydroisomerization catalyst composition comprises 2 or more than 3 normal alkane hydroisomerization catalysts.

[0051] As a specific embodiment of the above composition of the present invention, when the n-alkane hydroisomerization catalyst composition comprises 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 recorded as catalyst A, catalyst B and catalyst C;

[0052] Wherein, 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 comprises two n-alkane hydroisomerization catalysts, the n-alkane hydroisomerization reactor is loaded 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 1:10-10:1, preferably 1:5-5:1.

[0054] As a specific embodiment of the above composition of the present invention, the weak B acid content of catalyst A at 150°C is 0.01-0.20 mmol / g, and the medium-strong B acid content at 350°C is 0.01-0.20 mmol / g;

[0055] The weak B acid content of catalyst B at 150°C is 0.05-0.70 mmol / g, and the medium-strong B acid content at 350°C is 0.05-0.70 mmol / g;

[0056] Catalyst C has a weak B acid content of 0.05-0.30 mmol / g at 150°C and a medium-strong B acid content of 0.05-0.30 mmol / g at 350°C, wherein the content ratio of weak B acid to medium-strong B acid is 5:1-1:1;

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

[0058] Catalyst B has a weak B acid content of 0.30-0.60 mmol / g at 150°C and a medium-strong B acid content of 0.30-0.60 mmol / g at 350°C;

[0059] Catalyst C has a weak B acid content of 0.10-0.20 mmol / g at 150°C and a medium-strong B acid content of 0.10-0.20 mmol / g at 350°C;

[0060] In the catalyst A, catalyst B and catalyst C, the content ratio of weak B acid to medium-strong B acid is 2:1-1:1.

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

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

[0063] In another aspect, the present invention also provides the use of the above-mentioned n-alkane hydroisomerization catalyst or the above-mentioned n-alkane hydroisomerization catalyst composition in the hydroisomerization of waxy feedstocks. Among them, by using the n-alkane hydroisomerization catalyst or the above-mentioned n-alkane hydroisomerization catalyst composition to catalyze the hydroisomerization reaction of waxy feedstocks, high-quality lubricating oil base oil, low-condensing diesel, high-octane gasoline, biofuel and other products can be obtained.

[0064] As a specific implementation of the above application of the present invention, the wax-containing raw material includes bio-deoxygenated oil, hydrocracking tail oil or FT synthetic wax, and the mass content of the wax is 10-100%.

[0065] As a specific embodiment of the above application of the present invention, wherein, biodeoxygenated oil, hydrocracking tail oil or FT synthetic wax and other wax-containing raw materials are sequentially converted by catalyst A, catalyst B and catalyst C under certain reaction pressure, reaction temperature and volume space velocity. For biodeoxygenated oil, after the graded conversion, it is frequently distilled under reduced pressure to obtain bio-jet kerosene and biodiesel, and the freezing point of the bio-jet kerosene is ≯-40°C; for hydrocracking tail oil, after the graded conversion, it is frequently distilled under reduced pressure to obtain light base oil and medium base oil, and the kinematic viscosity of the medium base oil at 100°C is 4-8mm 2 / s, pour point ≯-18℃, cloud point ≯-15℃; for FT synthetic wax, after graded conversion and frequent vacuum distillation, light base oil, medium base oil and heavy base oil can be obtained, and the heavy base oil has a kinematic viscosity of >10mm at 100℃ 2 / s, viscosity index>150, pour point≯-15℃, cloud point≯-5℃.

[0066] In the last aspect, the present invention also provides a method for hydroisomerization of a waxy feedstock, wherein the method utilizes the above-mentioned n-alkane hydroisomerization catalyst or the above-mentioned n-alkane hydroisomerization catalyst composition to catalyze the hydroisomerization of the waxy feedstock.

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

[0068] (1) When preparing a catalyst for hydrogenation isomerization of normal alkanes, the present invention uses 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, to complete catalyst modification and noble metal loading in one step, and the preparation process is simple. By utilizing the steric hindrance and competitive adsorption of the modified metal to improve the dispersion of the noble metal, the migration and agglomeration of the active centers of the noble metal during calcination and use can also be effectively blocked and controlled, thereby improving the dispersion and anti-migration ability of the noble metal, thereby improving the activity and service life of the catalyst.

[0069] (2) The present invention controls the amount of modified metal and the modification procedure, i.e., the equal volume vacuum impregnation procedure, and utilizes the migration of the modified metal at the acid position, the selective coverage, the deposition in the catalyst pores, and the change in the pore structure caused by the change in charge density, so as to realize the preparation of catalyst components with different functions with one molecular sieve material, wherein the average pore diameter of the micropores is adjustable from 0.50 to 0.75 nm, and the contents of weak B acid and medium-strong B acid are adjustable from 0.01 to 0.70 mmol / g, respectively. By grading the various catalyst components, the differences in acidity and pore size can be utilized to realize the graded conversion of different raw materials, thereby improving the isomerization selectivity and the yield of the target product, realizing the high-selectivity graded isomerization conversion of raw materials, and solving the problem of the complicated preparation process of using various molecular sieve materials.

[0070] (3) The n-alkane hydroisomerization catalyst composition provided by the present invention is used to catalyze the hydroisomerization reaction of complex mixed long-chain n-alkanes in heavy high-wax content feedstocks, which has higher isomerization selectivity and target product yield, and has better pour point and cloud point lowering effects and better feedstock adaptability. That is, the n-alkane hydroisomerization catalyst composition can effectively control cracking side reactions, reduce gas and naphtha yields, increase base oil yields, obtain base oil products with low pour point and cloud point, and can be generally applied to the hydroisomerization reaction of waxy feedstocks. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

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

[0073] Figure 2 This is a spherical aberration corrected transmission electron microscopy image of the normal alkane hydroisomerization catalyst provided in Example 2 of the present invention.

[0074] Figure 3 This is a spherical aberration corrected transmission electron microscope image of the normal alkane hydroisomerization catalyst provided in Comparative Example 1.

[0075] Figure 4 This is a spherical aberration corrected transmission electron microscope image of the normal alkane hydroisomerization catalyst provided in Comparative Example 3. DETAILED DESCRIPTION

[0076] It should be noted that the term "comprises" and any variations thereof in the specification and claims of the present invention and the above-mentioned drawings are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0077] "Scope" disclosed in the present invention is given in the form of lower limit and upper limit. It can be one or more lower limits, and one or more upper limits respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower limit and upper limit define the boundaries of a particular range. All ranges defined in this way are combinable, i.e. any lower limit can be combined with any upper limit to form a range. For example, for a specific parameter, a range of 60-120 and 80-110 is listed, and it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​listed are 1 and 2, and the maximum range values ​​listed are 3, 4 and 5, then the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.

[0078] In the present invention, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in the present invention, and "0-5" is just an abbreviation of these numerical combinations.

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

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

[0081] In the present invention, if not specifically stated, the term "two" used in this specification means "at least two".

[0082] In the present invention, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0083] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the attached table, drawings and examples. The following described embodiments are some embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. If the specific conditions are not specified in the embodiments, they are carried out according to the normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0084] Examples of normal alkane hydroisomerization catalysts and related comparative examples

[0085] Example 1

[0086] This embodiment provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0087] Preparation of catalyst carrier:

[0088] Step 1): calcining ZSM-22 raw powder with a silicon-aluminum ratio of 60 at 595° C. for 12 h;

[0089] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 1 mol / L ammonium nitrate solution and stir at 80° C. for 1.5 h;

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

[0091] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 595°C for 6h to obtain a catalyst carrier;

[0092] Preparation of catalyst:

[0093] Step 1: 3.3 g of magnesium acetate and 2.79 g of indium nitrate are mixed with 17.42 g of 1 mol / L acetic acid to obtain a modified solution having a pH value of 2-4, 0.31 g of tetraamine platinum nitrate is dissolved in 3.58 g of water to obtain an active solution, and the active solution is then mixed with the modified solution to obtain a metal mixed solution;

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

[0095] The conditions for equal volume vacuum impregnation and modification are: impregnation for 4 h at room temperature -30 °C and pressure of 0.5 bar, impregnation for 4 h at temperature 40 °C and pressure of 0.1 bar, and impregnation for 4 h at temperature 70 °C and pressure of 0.01 bar.

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

[0097] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the first modified metal calculated as oxide, that is, magnesium content is 2.84%, the second modified metal calculated as oxide, that is, indium content is 3.9%, and the active metal calculated as a single substance, that is, platinum content is 0.48%, wherein the above contents are all calculated based on the total weight of the normal alkane hydroisomerization catalyst as 100%.

[0098] Example 2

[0099] This embodiment provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0100] Preparation of catalyst carrier:

[0101] Step 1): calcining ZSM-23 raw powder with a silicon-aluminum ratio of 60 at 575° C. for 18 h;

[0102] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 1 mol / L ammonium nitrate solution and stir at 80° C. for 1.5 h;

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

[0104] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 575°C for 8h to obtain a catalyst carrier;

[0105] Preparation of catalyst:

[0106] Step 1: 1.7 g of magnesium formate and 3.78 g of indium sulfamate are mixed with 13.4 g of formic acid having a concentration of 1 mol / L to obtain a modified solution having a pH value of 2-4, 0.31 g of tetraamine platinum nitrate is dissolved in 9.88 g of water to obtain an active solution, and the active solution is then mixed with the modified solution to obtain a metal mixed solution;

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

[0108] The conditions for equal volume vacuum impregnation and modification are: room temperature -30 ° C, pressure 0.7 bar, impregnation for 2 h, temperature 50 ° C, pressure 0.3 bar, impregnation for 2 h, temperature 80 ° C, pressure 0.07 bar, impregnation for 2 h;

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

[0110] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the first modified metal calculated as oxide, that is, magnesium content is 3.0%, the second modified metal calculated as oxide, that is, indium content is 4.0%, and the active metal calculated as a single substance, that is, platinum content is 0.48%, wherein the above contents are all calculated based on the total weight of the normal alkane hydroisomerization catalyst as 100%.

[0111] Example 3

[0112] This embodiment provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0113] Preparation of catalyst carrier:

[0114] Step 1): calcining ZSM-23 raw powder with a silicon-aluminum ratio of 40 at 550° C. for 24 h;

[0115] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 1 mol / L ammonium nitrate solution and stir at 80° C. for 1.5 h;

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

[0117] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 550°C for 12h to obtain a catalyst carrier;

[0118] Preparation of catalyst:

[0119] Step 1: 0.6 g of magnesium formate and 1.34 g of indium sulfamate are mixed with 4.5 g of formic acid having a concentration of 1 mol / L to obtain a modified solution having a pH value of 2-4, 0.31 g of tetraamine platinum nitrate is dissolved in 17.25 g of water to obtain an active solution, and the active solution is then mixed with the modified solution to obtain a metal mixed solution;

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

[0121] The conditions for equal volume vacuum impregnation and modification are: room temperature -30 ° C, pressure 1.0 bar, impregnation for 1 h, temperature 60 ° C, pressure 0.5 bar, impregnation for 1 h, temperature 90 ° C, pressure 0.1 bar, impregnation for 1 h;

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

[0123] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the first modified metal calculated as oxide, that is, magnesium content is 1.1%, the second modified metal calculated as oxide, that is, indium content is 1.5%, and the active metal calculated as a single substance, that is, platinum content is 0.5%, wherein the above contents are all calculated based on the total weight of the normal alkane hydroisomerization catalyst as 100%.

[0124] Example 4

[0125] This embodiment provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0126] Preparation of catalyst carrier:

[0127] Step 1): calcining ZSM-23 raw powder with a silicon-aluminum ratio of 40 at 550° C. for 24 h;

[0128] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 1 mol / L ammonium nitrate solution and stir at 80° C. for 1.5 h;

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

[0130] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 550°C for 8h to obtain a catalyst carrier;

[0131] Preparation of catalyst:

[0132] Step 1: 1.1 g of magnesium formate and 2.45 g of indium sulfamate are mixed with 8.9 g of 1 mol / L formic acid to obtain a modified solution having a pH value of 2-4, 0.31 g of tetraamine platinum nitrate is dissolved in 13.6 g of water to obtain an active solution, and the active solution is then mixed with the modified solution to obtain a metal mixed solution;

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

[0134] The conditions for equal volume vacuum impregnation and modification are: room temperature -30 ° C, pressure 0.5 bar, impregnation for 1 h, temperature 50 ° C, pressure 0.1 bar, impregnation for 2 h, temperature 70 ° C, pressure 0.01 bar, impregnation for 2 h;

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

[0136] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the first modified metal calculated as oxide, that is, magnesium content is 1.9%, the second modified metal calculated as oxide, that is, indium content is 2.7%, and the active metal calculated as a single substance, that is, platinum content is 0.49%, wherein the above contents are all calculated based on the total weight of the normal alkane hydroisomerization catalyst as 100%.

[0137] Example 5

[0138] This embodiment provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0139] Preparation of catalyst carrier:

[0140] Step 1): calcining ZSM-23 raw powder with a silicon-aluminum ratio of 40 at 550° C. for 24 h;

[0141] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 2 mol / L ammonium nitrate solution and stir at 70° C. for 2 h;

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

[0143] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 550°C for 8h to obtain a catalyst carrier;

[0144] Preparation of catalyst:

[0145] Step 1: 1.1 g potassium acetate and 1.14 g stannous chloride are mixed with 8.9 g formic acid having a concentration of 1 mol / L to obtain a modified solution having a pH value of 2-4, 0.31 g tetraamine platinum nitrate is dissolved in 13.6 g water to obtain an active solution, and the active solution is then mixed with the modified solution to obtain a metal mixed solution;

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

[0147] The conditions for equal volume vacuum impregnation and modification are: room temperature -30 ° C, pressure 0.5 bar, impregnation for 1 h, temperature 50 ° C, pressure 0.1 bar, impregnation for 2 h, temperature 70 ° C, pressure 0.01 bar, impregnation for 2 h;

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

[0149] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the first modified metal calculated as oxide, that is, potassium content is 1.6%, the second modified metal calculated as oxide, that is, tin content is 2.9%, and the active metal calculated as a single substance, that is, platinum content is 0.49%, wherein the above contents are all calculated based on the total weight of the normal alkane hydroisomerization catalyst as 100%.

[0150] Example 6

[0151] This embodiment provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0152] Preparation of catalyst carrier:

[0153] Step 1): calcining ZSM-23 raw powder with a silicon-aluminum ratio of 40 at 550° C. for 24 h;

[0154] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 4 mol / L ammonium nitrate solution and stir at 70° C. for 1 hour;

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

[0156] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 550°C for 8h to obtain a catalyst carrier;

[0157] Preparation of catalyst:

[0158] Step 1: 1.44 g of zinc acetate and 2.45 g of indium sulfamate are mixed with 8.9 g of formic acid having a concentration of 1 mol / L to obtain a modified solution having a pH value of 2-4, 0.31 g of tetraamine platinum nitrate is dissolved in 13.6 g of water to obtain an active solution, and the active solution is then mixed with the modified solution to obtain a metal mixed solution;

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

[0160] The conditions for equal volume vacuum impregnation and modification are: room temperature -30 ° C, pressure 0.5 bar, impregnation for 1 h, temperature 50 ° C, pressure 0.1 bar, impregnation for 2 h, temperature 70 ° C, pressure 0.01 bar, impregnation for 2 h;

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

[0162] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the first modified metal calculated as oxide, i.e., zinc content, is 2.0%, the second modified metal calculated as oxide, i.e., indium content, is 2.7%, and the active metal calculated as a single substance, i.e., platinum content, is 0.49%, wherein the above contents are all calculated based on the total weight of the normal alkane hydroisomerization catalyst as 100%.

[0163] Example 7

[0164] This embodiment provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0165] Preparation of catalyst carrier:

[0166] Step 1): calcining ZSM-23 raw powder with a silicon-aluminum ratio of 40 at 550° C. for 24 h;

[0167] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 1 mol / L ammonium nitrate solution and stir at 90° C. for 1 h;

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

[0169] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 550°C for 8h to obtain a catalyst carrier;

[0170] Preparation of catalyst:

[0171] Step 1: 1.1 g of magnesium formate and 2.45 g of indium sulfamate are mixed with 8.9 g of formic acid having a concentration of 1 mol / L to obtain a modified solution having a pH value of 2-4, 0.44 g of tetraammine palladium nitrate is dissolved in 13.6 g of water to obtain an active solution, and the active solution is then mixed with the modified solution to obtain a metal mixed solution;

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

[0173] The conditions for equal volume vacuum impregnation and modification are: room temperature -30 ° C, pressure 0.5 bar, impregnation for 1 h, temperature 50 ° C, pressure 0.1 bar, impregnation for 2 h, temperature 70 ° C, pressure 0.01 bar, impregnation for 2 h;

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

[0175] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the first modified metal calculated as oxide, that is, magnesium content is 2.0%, the second modified metal calculated as oxide, that is, indium content is 2.7%, and the active metal calculated as a single substance, that is, palladium content is 0.49%, wherein the above contents are all calculated based on the total weight of the normal alkane hydroisomerization catalyst as 100%.

[0176] Comparative Example 1

[0177] This comparative example provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0178] Preparation of catalyst carrier:

[0179] Step 1): calcining ZSM-23 raw powder with a silicon-aluminum ratio of 40 at 550° C. for 24 h;

[0180] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 1 mol / L ammonium nitrate solution and stir at 80° C. for 1 h;

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

[0182] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 550°C for 8h to obtain a catalyst carrier;

[0183] Preparation of catalyst:

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

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

[0186] The conditions for equal volume vacuum impregnation and modification are: room temperature -30 ° C, pressure 0.5 bar, impregnation for 1 h, temperature 50 ° C, pressure 0.1 bar, impregnation for 2 h, temperature 70 ° C, pressure 0.01 bar, impregnation for 2 h;

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

[0188] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the content of active metal, i.e. platinum, in the normal alkane hydroisomerization catalyst is 0.49% on a simple basis, wherein the above contents are calculated based on the total weight of the normal alkane hydroisomerization catalyst being 100%.

[0189] Comparative Example 2

[0190] This comparative example provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0191] Preparation of catalyst carrier:

[0192] Step 1): calcining ZSM-23 raw powder with a silicon-aluminum ratio of 40 at 550° C. for 24 h;

[0193] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 1 mol / L ammonium nitrate solution and stir at 80° C. for 1 h;

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

[0195] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 550°C for 8h to obtain a catalyst carrier;

[0196] Preparation of catalyst:

[0197] Step 1: 1.1 g of magnesium formate and 2.45 g of indium sulfamate are mixed with 8.9 g of 1 mol / L formic acid to obtain a modified solution having a pH value of 2-4, 0.31 g of tetraamine platinum nitrate is dissolved in 13.6 g of water to obtain an active solution, and the active solution is then mixed with the modified solution to obtain a metal mixed solution;

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

[0199] The conditions for equal volume vacuum impregnation and modification are: impregnation for 2 h at room temperature and pressure of 0.1 bar, and impregnation for 2 h at temperature of 70 °C and pressure of 0.1 bar;

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

[0201] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the first modified metal calculated as oxide, that is, magnesium content is 1.9%, the second modified metal calculated as oxide, that is, indium content is 2.7%, and the active metal calculated as a single substance, that is, platinum content is 0.49%, wherein the above contents are all calculated based on the total weight of the normal alkane hydroisomerization catalyst as 100%.

[0202] Comparative Example 3

[0203] This comparative example provides a normal alkane hydroisomerization catalyst, which is prepared by a preparation method comprising the following specific steps:

[0204] Preparation of catalyst carrier:

[0205] Step 1): calcining ZSM-23 raw powder with a silicon-aluminum ratio of 40 at 550° C. for 24 h;

[0206] Step 2): crush the molecular sieve calcined in step 1) to 100-200 mesh, place in 1 mol / L ammonium nitrate solution and stir at 80° C. for 1 h;

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

[0208] Step 4): crush the molecular sieve after drying in step 3) to 200-300 mesh, and then mix 40g of the crushed molecular sieve with 10g of pseudo-boehmite, 3g of sesbania powder, 19g of 15% nitric acid solution and 16g of deionized water, and then knead the mixture to form a strip, and then dry the molded product at 120°C for 24h, and finally calcine at 550°C for 8h to obtain a catalyst carrier;

[0209] Preparation of catalyst:

[0210] Step 1: 1.1 g of magnesium formate and 8.9 g of 1 mol / L formic acid are mixed to obtain a modified solution having a pH value of 2-4, 0.31 g of tetraamine platinum nitrate is dissolved in 13.6 g of water to obtain an active solution, and the active solution is then mixed with the modified solution to obtain a metal mixed solution;

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

[0212] The conditions for equal volume vacuum impregnation and modification are: room temperature -30 ° C, pressure 0.5 bar, impregnation for 1 h, temperature 50 ° C, pressure 0.1 bar, impregnation for 2 h, temperature 70 ° C, pressure 0.01 bar, impregnation for 2 h;

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

[0214] Step 4: calcining the dried catalyst precursor at 480° C. for 10 hours to obtain a normal alkane hydroisomerization catalyst, wherein the content of modified metal magnesium in terms of oxide is 1.9% and the content of active metal, i.e. platinum, in terms of elemental substance is 0.49%, wherein the above contents are calculated based on the total weight of the normal alkane hydroisomerization catalyst being 100%.

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

[0216] Table 1

[0217]

[0218] The pore structure analysis data of the n-alkane hydroisomerization catalysts provided by Examples 1 to 4 and Comparative Examples 1 to 3 of the present 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 to 4 of the present invention and in Comparative Example 1 and the n-alkane hydroisomerization catalyst composition provided in Comparative Example 7 are shown in FIG. Figure 1 The infrared data of pyridine are shown in Table 1 above. Figure 1 As can be seen from Table 1, the present invention can regulate the distribution of acid centers through bimetallic programmed temperature impregnation modification, and the ratio of weak acid to medium-strong acid is significantly improved compared with the unmodified catalyst in Comparative Example 1; for the catalyst prepared by single metal 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 in Comparative Example 1, the effect is not significant compared with Examples 2 to 4; for the catalyst prepared by Comparative Example 2 without programmed temperature impregnation modification, its ratio of weak acid to medium-strong acid is lower than that of the unmodified catalyst in Comparative Example 1, and of course lower than that of the catalysts prepared in Examples 2 to 4.

[0222] It can also be seen from Table 1 above that when preparing the catalyst, Comparative Example 2 did not perform impregnation modification according to the programmed temperature required for protection in the present application. Compared with the n-alkane hydroisomerization catalyst provided in Example 4, the weak acid amount of the catalyst prepared in Comparative Example 2 decreased significantly, while the strong acid amount changed slightly, resulting in a weak acid to strong acid ratio of only 0.956, which indicates that the specific programmed temperature used in the present invention can improve the diffusivity of the modified metal during the modification process, and realize precise control of the strong acid amount, and more importantly, can improve the ratio of the weak acid amount to the strong acid amount.

[0223] In the isomerization reaction process of normal alkanes, a high weak acid content is beneficial to the isomerization reaction, and a low medium-strong acid content 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 embodiment and the comparative example, the elliptical channel aperture is 0.45×0.52nm, and the HK micropore average aperture of the catalyst prepared therefrom is generally about 0.5-0.6nm. However, as can be seen from the experimental data in Table 2 above, the embodiment of the present invention prepares the normal alkane hydroisomerization catalyst by bimetallic programmed temperature impregnation modification, which can significantly increase the upper limit of the HK micropore average aperture of the normal alkane hydroisomerization catalyst, such as for the normal alkane hydroisomerization catalyst provided in Example 1, Example 2, Example 3 and Example 4, the HK micropore average aperture can reach 0.69nm, 0.74nm, 0.65nm and 0.68nm respectively, while the HK micropore average aperture of the normal alkane hydroisomerization catalyst provided in Comparative Example 1, Comparative Example 2 and Comparative Example 3 is only 0.49nm, 0.53nm and 0.62nm.

[0225] The spherical aberration corrected transmission electron microscopy image of the normal alkane hydroisomerization catalyst provided in Example 2 of the present invention is as follows Figure 2 As shown, the spherical aberration corrected transmission electron microscopy image of the normal alkane hydroisomerization catalyst provided in Comparative Example 1 is as follows Figure 3 As shown, the spherical aberration corrected transmission electron microscopy image of the normal alkane hydroisomerization catalyst provided in Comparative Example 3 is as follows Figure 4 As shown. Figure 2 , Figure 3 and Figure 4 It can be seen from the figure that in the n-alkane hydroisomerization catalyst provided by Example 2 of the present invention, all the noble metals are in a highly dispersed atomic state, while in Comparative Example 1, no metal modification is used, and metal agglomeration is obvious in the obtained n-alkane hydroisomerization catalyst, and the agglomerated particle size reaches about 2 nm. In Comparative Example 3, single metal modification is used, and although there are no obvious metal particles in the obtained n-alkane hydroisomerization catalyst, Figure 4 It can be seen that clusters of about 1 nm appear in the n-alkane hydroisomerization catalyst. In contrast, the steric hindrance and anchoring effect of the double-modified metals make the noble metals in the n-alkane hydroisomerization catalyst provided by the present invention highly dispersed at the atomic level.

[0226] Examples of normal alkane hydroisomerization catalyst compositions and related comparative examples

[0227] Example 8

[0228] The present embodiment provides a normal alkane hydroisomerization catalyst composition, which comprises the normal alkane hydroisomerization catalysts provided in Embodiment 2, Embodiment 3 and Embodiment 4, wherein the three catalysts are respectively recorded as catalyst A, catalyst B and catalyst C, and are loaded from top to bottom in a fixed bed reactor at a volume ratio of 4:3:3 to form a normal alkane hydroisomerization catalyst composition, and the waxy feedstock passes through three catalyst beds in sequence from top to bottom to complete graded conversion.

[0229] Comparative Example 4

[0230] This comparative example provides a normal alkane hydroisomerization catalyst composition, which comprises the normal alkane hydroisomerization catalysts provided in Example 2, Example 3 and Example 4, wherein the three catalysts are respectively recorded as catalyst A, catalyst B and catalyst C, and are loaded from top to bottom in a fixed bed reactor at a volume ratio of 12:1:1 to form a normal alkane hydroisomerization catalyst composition, and the waxy feedstock passes through three catalyst beds in sequence from top to bottom to complete graded conversion.

[0231] Comparative Example 5

[0232] This comparative example provides a normal alkane hydroisomerization catalyst composition, which comprises the normal alkane hydroisomerization catalysts provided in Example 2, Example 3 and Example 4, wherein the three catalysts are respectively recorded as catalyst A, catalyst B and catalyst C, and are loaded from top to bottom in a fixed bed reactor at a volume ratio of 1:12:12 to form a normal alkane hydroisomerization catalyst composition, and the waxy feedstock passes through three catalyst beds in sequence from top to bottom to complete graded conversion.

[0233] Comparative Example 6

[0234] This comparative example provides a normal alkane hydroisomerization catalyst composition, which comprises the normal alkane hydroisomerization catalysts provided in Example 3, Example 2 and Example 4, wherein the three catalysts are respectively recorded as catalyst A, catalyst B and catalyst C, and are loaded from top to bottom in a fixed bed reactor at a volume ratio of 4:3:3 to form a normal alkane hydroisomerization catalyst composition, and the waxy feedstock passes through three catalyst beds in sequence from top to bottom to complete graded conversion.

[0235] Comparative Example 7

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

[0237] Application examples and comparative application examples

[0238] Application Example 1

[0239] This application example uses FT synthetic wax as raw material. The properties of the raw material are shown in Table 3. The n-alkane hydroisomerization catalyst composition provided in Example 8 is used. The reaction temperature is 360°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 500:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are shown in Table 5.

[0240] Application Example 2

[0241] In this application example, biodeoxygenated oil is used as raw material. The properties of the raw material are shown in Table 4. The normal alkane hydroisomerization catalyst composition provided in Example 8 is used. The reaction temperature is 330°C and 300°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 300:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are shown in Table 6.

[0242] Application Example 3

[0243] This application example uses FT synthetic wax as raw material. The properties of the raw material are shown in Table 3. The normal alkane hydrogenation isomerization catalyst provided in Example 1 is used. The reaction temperature is 360°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 500:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are shown in Table 5.

[0244] Application Example 4

[0245] This application example uses FT synthetic wax as raw material. The properties of the raw material are shown in Table 3. The normal alkane hydrogenation isomerization catalyst provided in Example 2 is used. The reaction temperature is 360°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 500:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are shown in Table 5.

[0246] Comparative application example 1

[0247] This application example uses FT synthetic wax as raw material. The properties of the raw material are shown in Table 3. The normal alkane hydrogenation isomerization catalyst provided in Comparative Example 1 is used. The reaction temperature is 360°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 500:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are shown in Table 5.

[0248] Comparative Application Example 2

[0249] This application example uses FT synthetic wax as raw material. The properties of the raw material are shown in Table 3. The normal alkane hydroisomerization catalyst composition provided in Comparative Example 4 is used. The reaction temperature is 360°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 500:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are shown in Table 5.

[0250] Comparative Application Example 3

[0251] This application example uses FT synthetic wax as raw material. The properties of the raw material are shown in Table 3. The normal alkane hydroisomerization catalyst composition provided in Comparative Example 5 is used. The reaction temperature is 360°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 500:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are shown in Table 5.

[0252] Comparative Application Example 4

[0253] This application example uses FT synthetic wax as raw material. The properties of the raw material are shown in Table 3. The normal alkane hydroisomerization catalyst composition provided in Comparative Example 6 is used. The reaction temperature is 360°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 500:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are shown in Table 5.

[0254] Comparative Application Example 5

[0255] This application example uses FT synthetic wax as raw material. The properties of the raw material are shown in Table 3. The normal alkane hydroisomerization catalyst composition provided in Comparative Example 7 is used. The reaction temperature is 360°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 500:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are shown in Table 5.

[0256] Application ratio 6

[0257] This application example uses FT synthetic wax as raw material. The properties of the raw material are shown in Table 3. The normal alkane hydroisomerization catalyst composition provided in Comparative Example 2 is used. The reaction temperature is 360°C, the pressure is 5 MPa, the hydrogen-to-oil volume ratio is 500:1, and the volume space velocity is 1.0 h -1 The hydroisomerization reaction was carried out under the following conditions, and the product yields and properties of the reaction products obtained by fractionation are 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] It can be seen from the experimental data in Table 5 above that 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, 4, Comparative Application Examples 1 and 6 all use a single normal alkane hydroisomerization catalyst to catalyze the FT synthetic wax for hydroisomerization reaction, while Application Example 1 uses the normal alkane hydroisomerization catalyst composition provided in Example 8 to catalyze the FT synthetic wax for hydroisomerization reaction. Compared with Application Examples 3, 4, Comparative Application Examples 1 and 6, the yields of light hydrocarbons and naphtha in Application Example 1 are lower, the yields of base oil, especially the yields of medium base oil and heavy base oil are higher, and the pour point and cloud point of the heavy base oil are significantly reduced, and the pour point and cloud point are only -21°C and -5°C, respectively. And it can be seen from the comparison of Application Examples 3, 4 and 1 that since the normal alkane hydroisomerization catalyst used in Comparative Application Example 1 is not modified by modified metal, the yields of light hydrocarbons and naphtha in Comparative Application Example 1 are higher, while the yields of medium base oil and heavy base oil are lower. Since the normal alkane hydroisomerization catalyst used in Comparative Application Example 6 was not heated according to the procedure claimed in the present invention, compared with Comparative Application Example 1, the yields of light hydrocarbons and naphtha were reduced, the yield of base oil was increased, but the pour point and cloud point of heavy base oil were high. Compared with Application Example 3 and Application Example 4, the pour point and cloud point of heavy base oil in Comparative Application Example 6 were lower than those in Application Example 3, and were basically the same as those in Application Example 4, but the yields of light hydrocarbons and naphtha were still high. Therefore, the specific program temperature increase used in the embodiments of the present invention can significantly improve the isomerization selectivity of the catalyst and reduce the yields of light hydrocarbons and naphtha.

[0268] Although the normal alkane hydroisomerization catalyst composition was used to catalyze the hydroisomerization reaction of FT synthetic wax in Comparative Application Examples 2 to 4, the normal alkane hydroisomerization catalyst composition, such as the volume ratio of the three catalysts or the weak B acid content or medium-strong B acid content of the three catalysts, did not meet the requirements of this application. The light hydrocarbon and naphtha yields and base oil yields in Comparative Application Examples 2 to 4 were close to or significantly higher than those in Application Example 1, but the pour point and cloud point of the heavy base oil obtained therein were significantly higher than those in Application Example 1.

[0269] Comparative Application Example 5 also uses a normal alkane hydroisomerization catalyst composition to catalyze the hydroisomerization reaction of FT synthetic wax, but the normal alkane hydroisomerization catalyst composition is obtained by mechanically mixing three normal alkane hydroisomerization catalysts. The yield of light hydrocarbons and naphtha in Comparative Application Example 5 is significantly higher than that in Application Example 1, the yield of heavy base oil is significantly lower than that in Application Example 1, and the pour point and cloud point of the heavy base oil are also significantly higher than those in Application Example 1.

[0270] Table 6

[0271]

[0272]

[0273] It can be seen from the experimental data in Table 6 above that by using the n-alkane hydroisomerization catalyst composition provided in the embodiment of the present invention to catalyze the hydroisomerization reaction of biodeoxygenated oil, a higher jet fuel yield can be obtained in the jet fuel scheme, the jet fuel yield can reach 55%, and the jet fuel freezing point can be as low as -47°C; in the diesel scheme, a higher diesel yield can also be obtained, the diesel yield is as high as 85%, and the diesel freezing point is only -5°C.

[0274] The above is only a specific embodiment of the present invention, and cannot be used to limit the scope of the invention. Therefore, the replacement of equivalent components, or equivalent changes and modifications made according to the protection scope of the patent of the present invention, should still fall within the scope of this patent. In addition, the technical features of the present invention can be freely combined with each other, with each other and with each other, and with each other.

Claims

1. A catalyst for the hydroisomerization of normal alkanes, characterized in that: The normal alkane hydroisomerization catalyst is obtained by first mixing a metal 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 increase under a certain vacuum condition to obtain a catalyst precursor, and then sequentially homogenizing and calcining the catalyst precursor; The modified metal includes a first modified metal and a second modified metal, wherein the first modified metal includes one or a combination of alkali metals, alkaline earth metals and first transition metals, and the second modified metal includes one or a combination of IIIA group metals and IVA group metals; Reactive metals include Group VIII metals.

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

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

1.

4. The normal alkane hydroisomerization catalyst according to claim 1 or 2, characterized in that: The modified metal precursor includes at least one of phosphate, acetate, formates, oxalates, nitrates and sulfonates of the modified metal.

5. The normal alkane hydroisomerization catalyst according to claim 1 or 2, characterized in that: The content of active metal in the normal alkane hydroisomerization catalyst is 0.05-1wt% based on the single substance.

6. The normal alkane hydroisomerization catalyst according to claim 1 or 2, characterized in that: The active metal precursor includes at least one of an acid and a salt of the active metal.

7. The normal alkane hydroisomerization catalyst according to claim 1, characterized in that: The vacuum degree is 0.01-1 bar.

8. The normal alkane hydroisomerization catalyst according to claim 1 or 7, characterized in that: The temperature rising program of the programmed temperature rising is: immersion for 0.5-5h at room temperature-30°C and pressure of 0.5-1bar, immersion for 0.5-5h at 40-60°C and pressure of 0.1-0.5bar, immersion for 0.5-5h at 70-90°C and pressure of 0.01-0.1bar.

9. The normal alkane hydroisomerization catalyst according to claim 1 or 2, characterized in that: The homogenization treatment is carried out at 100-120° C. for 10-40 hours.

10. The normal alkane hydroisomerization catalyst according to claim 1, characterized in that: The calcination is performed at 300-500° C. for 1-12 hours.

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

12. The normal alkane hydroisomerization catalyst according to claim 11, characterized in that: In step 1), the molecular sieve comprises any one of a ten-membered ring or twelve-membered ring one-dimensional channel molecular sieve; Preferably, the molecular sieve comprises ZSM-22, ZSM-23, ZSM-48 or ZSM-12; Also preferably, the SiO2 / Al2O3 molar ratio of the molecular sieve is 20-100.

13. The normal alkane hydroisomerization catalyst according to claim 11, characterized in that: In step 2), the ammonium salt includes one or a combination of ammonium chloride, ammonium nitrate and ammonium sulfate.

14. The normal alkane hydroisomerization catalyst according to claim 11, characterized in that: In step 4), the inorganic porous material comprises at least one of alumina, amorphous silica-alumina, pseudo-boehmite and silicon dioxide; The extrusion aid comprises at least one of sesbania powder, methyl cellulose and soluble starch; The acid solution includes one of hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, and its mass concentration is 5-50%.

15. The normal alkane hydroisomerization catalyst according to claim 1 or 10, characterized in that: The average pore size of HK micropores of the normal alkane hydroisomerization catalyst can be adjusted from 0.50 to 0.75 nm, and the contents of weak B acid and medium-strong B acid can be adjusted from 0.01 to 0.70 mmol / g respectively.

16. The method for preparing the normal alkane hydroisomerization catalyst according to any one of claims 1 to 15, characterized in that: The preparation method comprises: Step 1: mixing a modified metal precursor with an acid solution to obtain a modified solution, and then mixing an active metal precursor with the modified solution to obtain a metal mixed solution; Step 2: according to the water absorption rate of the carrier, the metal mixed solution is mixed with the carrier and vacuum impregnation and modification of equal volume are performed according to programmed temperature increase under a certain vacuum condition to obtain a catalyst precursor; Step 3: homogenizing the catalyst precursor to obtain a dry catalyst precursor; Step 4: calcining the dried catalyst precursor to obtain a normal alkane hydroisomerization catalyst.

17. The preparation method according to claim 16, characterized in that: In step 1, the acid solution includes at least one of phosphoric acid, formic acid, acetic acid, oxalic acid, boric acid, citric acid and tartaric acid.

18. The preparation method according to claim 16 or 17, characterized in that: In step 1, the pH value of the modified solution is 2-6.

19. A normal alkane hydroisomerization catalyst composition, characterized in that: The n-alkane hydroisomerization catalyst composition comprises 2 or 3 n-alkane hydroisomerization catalysts according to any one of claims 1 to 15.

20. The composition according to claim 19, characterized in that When the normal alkane hydroisomerization catalyst composition comprises three normal alkane hydroisomerization catalysts, the three normal alkane hydroisomerization catalysts are loaded from top to bottom in the normal alkane hydroisomerization reactor and are respectively recorded as catalyst A, catalyst B and catalyst C; Wherein, 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; When the n-alkane hydroisomerization catalyst composition comprises two n-alkane hydroisomerization catalysts, the n-alkane hydroisomerization reactor is loaded 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 1:10-10:1, preferably 1:5-5:

1.

21. The composition according to claim 19 or 20, characterized in that The weak B acid content of catalyst A at 150°C is 0.01-0.20 mmol / g, and the medium-strong B acid content at 350°C is 0.01-0.20 mmol / g; The weak B acid content of catalyst B at 150°C is 0.05-0.70 mmol / g, and the medium-strong B acid content at 350°C is 0.05-0.70 mmol / g; Catalyst C has a weak B acid content of 0.05-0.30 mmol / g at 150°C and a medium-strong B acid content of 0.05-0.30 mmol / g at 350°C, wherein the content ratio of weak B acid to medium-strong B acid is 5:1-1:1; Preferably, the catalyst A has a weak B acid content of 0.05-0.15 mmol / g at 150°C and a medium-strong B acid content of 0.05-0.15 mmol / g at 350°C; Catalyst B has a weak B acid content of 0.30-0.60 mmol / g at 150°C and a medium-strong B acid content of 0.30-0.60 mmol / g at 350°C; Catalyst C has a weak B acid content of 0.10-0.20 mmol / g at 150°C and a medium-strong B acid content of 0.10-0.20 mmol / g at 350°C; In the catalyst A, catalyst B and catalyst C, the content ratio of weak B acid to medium-strong B acid is 2:1-1:

1.

22. The composition according to claim 19 or 20, characterized in that The average pore size of HK micropores of catalyst A is 0.60-0.75 nm, the average pore size of HK micropores of catalyst component B is 0.50-0.65 nm, and the average pore size of HK micropores of catalyst C is 0.55-0.70 nm; Preferably, the average pore size of HK micropores of catalyst A is 0.65-0.70 nm, the average pore size of HK micropores of catalyst B is 0.55-0.60 nm, and the average pore size of HK micropores of catalyst C is 0.60-0.65 nm.

23. Use of the normal alkane hydroisomerization catalyst according to any one of claims 1 to 15 or the normal alkane hydroisomerization catalyst composition according to any one of claims 19 to 22 in the hydroisomerization of waxy feedstock.

24. The use according to claim 23, characterized in that The wax-containing raw material includes biodeoxygenated oil, hydrocracking tail oil or FT synthetic wax.

25. A method for hydroisomerization of a waxy feedstock, characterized in that: The method utilizes the normal alkane hydroisomerization catalyst described in any one of claims 1 to 15 or the normal alkane hydroisomerization catalyst composition described in any one of claims 19 to 22 to catalyze the hydroisomerization of a waxy feedstock.

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