CN115501891B - N-carbon tetra-alkane isomerization catalyst and preparation method and application thereof - Google Patents
N-carbon tetra-alkane isomerization catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an n-tetraalkane isomerization catalyst and a preparation method and application thereof. The catalyst composition is MO x /SO 4 2‑ /ZrO 2 /Al 2 O 3 Wherein MO is x Is a group VIII metal oxide, x is 1 or 2, and the total acid amount is 0.25 to 1.0mmol NH 3 And/g. The preparation method comprises the following steps: immersing alumina into a zirconium sulfate solution, standing, drying and roasting to obtain an intermediate; immersing the intermediate into a metal salt solution, standing, drying and roasting to obtain the catalyst. The catalyst is used in the reaction of isomerizing n-tetraalkane to prepare isomerized tetraalkane, and can obviously improve the isomerization catalytic activity and stability of n-butane skeleton at low temperature.
Description
Technical Field
The invention belongs to the field of heterogeneous catalyst preparation, and relates to a catalyst for an isobutane preparation reaction by n-tetraalkane skeleton isomerization, a preparation method and application thereof.
Background
The carbon four resources are important petrochemical raw materials, and the sources of the carbon four resources are mainly catalytic cracking devices and vapor decomposition ethylene production devices of oil refineries, wherein n-butane resources are rich, and an isomerism product isobutane of the carbon four resources has better industrial application value and can be used for alkylation and other reactions. The hydrocarbon alkylate has the advantages of higher octane number, low volatility, no aromatic hydrocarbon and olefin, almost no sulfur and the like, and is very suitable for blending gasoline. Therefore, the development of the isobutane catalyst prepared by n-butane skeleton isomerization has great significance for clean gasoline production.
The isomerization catalyst is typically a platinum halide/alumina catalyst, in the form of gamma-Al 2 O 3 As a carrier, a proper amount of chloride auxiliary agent is required to be continuously added into the raw materials in the operation process. The main problem of the technology is that the content of water and sulfur in raw materials is strictly required to be less than 0.1ppm, and meanwhile, chlorine-containing substances generated in the reaction process are corrosive to equipment, so that the material cost and maintenance cost of the equipment are increased, and the environment is polluted. The sulfated solid super acid catalyst is chlorine-free, has loose requirements on the moisture and sulfur content of raw materials, can be regenerated, and is the development direction of the isomerization catalyst at present.
CN1660973a discloses a process for isomerising C5, C6 alkanes, the catalyst of which contains a mixed oxide of a group VIII metal (platinum, palladium or nickel) and a sulfate-loaded oxide of zirconium oxide, aluminum oxide and silicon oxide, the process for its preparation comprising: the zirconium salt solution reacts with the alkali solution to prepare zirconium hydroxide precipitate, and the zirconium hydroxide precipitate is subjected to hydrothermal treatment, filtration and drying; mixing aluminum hydroxide with silica sol and drying; mixing the above two materials, and adding SO-containing agent 4 2- Dipping, drying and roasting the solution to obtain a carrier; the catalyst is prepared by impregnating the carrier with a solution of a group VIII metal salt, drying and calcining.
CN106732676a discloses a solid acid catalyst for catalyzing n-butane isomerization and a preparation method thereof. The catalyst consists of zirconia sulfated by sulfur-containing compounds, gallium oxide and a transition metal element, wherein the transition metal element is selected from IB groups, and the catalyst comprises the following components: 0.1-5% of IB group transition metal element, 0.1-10% of gallium oxide, 0.1-10% of sulfur and the balance of zirconium oxide. The preparation method comprises the following steps: dissolving zirconium salt in a solvent to prepare a zirconium salt solution, clarifying, adding a III A group metal gallium compound, preparing a mixed solution of the zirconium salt and the metal gallium compound after dissolving, adding an alkaline solution until the pH value is 7-10 to obtain hydroxide precipitate, filtering, washing and drying the precipitate to obtain a precursor; and (3) adding the precursor into a solution containing sulfate radical for soaking, drying, soaking with a copper salt solution, drying and roasting to obtain the catalyst. CN109772287a discloses an alkane isomerization catalyst carrier, catalyst and method for preparing the same. The method comprises the following steps: dissolving zirconium salt, dropwise adding dilute ammonia water under stirring to adjust the pH to 7-10, and then carrying out hydrothermal reaction; after the reaction is completed and cooled to room temperature, washing and filtering are carried out until the reaction is neutral, and after no chloride ions are detected by using silver nitrate, the washing is finished; drying the obtained filter cake, adding yttrium salt solution, stirring and impregnating, washing, filtering and drying; continuously adding cerium salt solution, stirring and soaking, washing, filtering and drying; then adopting an isovolumetric impregnation method to sequentially load sulfate radical and tungstate radical, and finally roasting for 2-4 hours at 350-750 ℃, kneading and extruding to form the catalyst.
As is known, the preparation process of the catalyst generally generates 'three wastes' pollution, thereby bringing environmental protection pressure and increasing the cost of the catalyst, so that the simple, efficient and clean preparation of the catalyst is an important proposition for industrial catalysis. As can be seen from the above-mentioned publication, the SO used in the isomerization of normal tetra-alkane is currently 4 2- /ZrO 2 The catalyst is generally prepared by reacting zirconium salt with ammonia water to generate zirconium hydroxide precipitate, filtering, washing and drying to obtain a catalyst precursor, and respectively impregnating the catalyst precursor with SO-containing solution 4 2- And (3) solution and metal salt solution, and finally drying and roasting to obtain the catalyst. The method has the advantages of multiple preparation steps, long flow, production of alkaline wastewater containing ammonia and the like, consumption of a large amount of water for washing the precipitate to be neutral, and more energy consumption for repeated drying.
Disclosure of Invention
The invention provides an n-tetraalkane isomerization catalyst, a preparation method and application thereof, and aims to solve the problems that the existing solid superacid catalyst is long in preparation flow and possibly causes environmental pollution and the like. The catalyst has simple preparation process and can obviously improve the isomerization catalytic activity and stability of the normal carbon tetra-alkane skeleton.
The first aspect of the invention provides an n-tetraalkane isomerization catalyst which comprises MO x /SO 4 2- /ZrO 2 /Al 2 O 3 Wherein MO is x Is a group VIII metal oxide, x is 1 or 2, and the total acid amount is 0.25 to 1.0mmol NH 3 Preferably 0.28 to 0.60mmol NH/g 3 /g。
In the technical scheme, the strong acid accounts for 45-70% of the total acid, and the medium strong acid accounts for 30-55% of the total acid.
In the above technical scheme, M is at least one selected from platinum, palladium and nickel, preferably platinum.
In the technical proposal, the mass of the catalyst is taken as the reference, and MO is calculated by mass fraction x The content of (C) is 0.1-4.0%, preferably 0.1-3.0%, al 2 O 3 The content of S is 60% -94%, preferably 65% -85%, S is SO 3 The calculated content is 0.5 to 7 percent, preferably 2 to 6 percent, and ZrO 2 The content is 5% -30%, preferably 10% -26%.
The second aspect of the invention provides a preparation method of an n-tetraparaffin isomerization catalyst, which comprises the following steps:
(1) Immersing alumina into a zirconium sulfate solution, standing, drying and roasting to obtain an intermediate;
(2) Immersing the intermediate into a metal salt solution, standing, drying and roasting to obtain the catalyst.
In the technical proposal, the alumina in the step (1) is gamma-Al 2 O 3 。
In the above technical solution, the zirconium sulfate in step (1) may be zirconium sulfate or a hydrate thereof. The concentration of the zirconium sulfate solution is 0.2-2.1 mol/L.
In the above technical scheme, the amount of the zirconium sulfate substance in the step (1) is 3% -30% of the amount of the alumina substance, preferably 10% -20%.
In the technical scheme, the soaking in the step (1) adopts an isovolumetric soaking method or an excessive soaking method, and the standing time is 1-48h.
In the above technical solution, the drying in step (1) may use a forced air drying oven, and drying conditions are as follows: drying at 100-150 deg.c for 10-20 hr.
In the above technical solution, the baking in step (1) may use a muffle furnace, where the baking condition is that the baking is performed in an oxygen-containing atmosphere (such as air), the baking temperature is 550-800 ℃, and the baking time is 3-8 hours, where the baking temperature is preferably 650-750 ℃.
In the above technical solution, the metal in step (2) is at least one selected from platinum, palladium and nickel. The metal salt is selected from at least one of chloroplatinic acid, palladium chloride, palladium nitrate, nickel sulfate and hydrates thereof. The amount of the metal salt is different according to different types, and when the metal salt is palladium salt or platinum salt, the metal salt is calculated as Pd or Pt element and is 0.1-0.5% of the mass of the intermediate, and when the metal salt is nickel salt, the metal salt is calculated as Ni element and is 0.5-3% of the mass of the intermediate.
In the technical scheme, the soaking in the step (2) adopts an isovolumetric soaking method or an excessive soaking method, and the standing time is 1-48h.
In the above technical solution, the drying in step (2) may use a forced air drying oven, and drying conditions are as follows: drying at 100-150 deg.c for 10-20 hr.
In the above technical solution, the baking in step (2) may use a muffle furnace, where the baking condition is that the baking is performed in an inert atmosphere (such as nitrogen), the baking temperature is 300-500 ℃, and the baking time is 3-8 hours, and the baking temperature is preferably 350-450 ℃.
In the technical scheme, the roasting material obtained in the step (2) can be formed to prepare the formed normal-carbon tetra-alkane isomerization catalyst. Wherein the molding can be performed by adopting a tabletting method.
In a third aspect, the present invention provides a method for preparing isomerised tetra-alkane by isomerising normal tetra-alkane, wherein the catalyst according to the first aspect or the catalyst prepared by the preparation method according to the second aspect is used.
In the technical scheme, the catalyst needs to be activated before use, and is activated by a method of heating in a nitrogen stream containing 5-20% of hydrogen by volume fraction, wherein the activation temperature is 350-450 ℃, and the activation time is 2-6 h.
In the above technical scheme, the reaction conditions for preparing the isomerized tetraalkane by isomerizing the normal tetraalkane are as follows: under the condition of hydrogen, the reaction temperature is 180-220 ℃, the pressure is 0.5-2.0 MPa, and the volume space velocity of normal carbon tetra-alkane is 0.2-2.0 h -1 The molar ratio of hydrogen to hydrocarbon is 0.1-1.0.
The beneficial effects of the invention are as follows:
1. the invention uses gamma-Al 2 O 3 The zirconium sulfate is used as a carrier, the zirconium sulfate is used as a sulfating reagent, the solid super acid catalyst is simply prepared, then metal is introduced, and different roasting conditions are controlled, so that not only can enough active acid catalyst centers be formed, but also the coking resistance of the catalyst can be improved, and the activity and stability of the catalyst are obviously improved.
2. The catalyst is used in the reaction of isomerizing normal tetra-alkane to prepare isomerized tetra-alkane, and can obviously improve the isomerization catalytic activity and stability of normal tetra-alkane skeleton at low temperature.
Drawings
FIG. 1 shows ammonia temperature programmed desorption (NH) of the catalysts obtained in example 5, comparative example 1 and comparative example 2 3 -TPD) map.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
In the invention, NH is used 3 Surface acidity of catalyst was measured for probe molecules, ammonia temperature programmed desorption (NH 3 TPD) experiment in Tianjin Pengxiang Co NH 3 -on TPD instrument. The sample amount was 0.2000g, the pretreatment temperature was 550℃and the sample amount contained 10vol.% NH 3 The ammonia helium gas mixture is adsorption gas, and the flow rate of carrier gas helium gas is 30mL/min. The desorption temperature is raised from 100 ℃ to 640 ℃ with the temperature rising rate of 10 ℃/min. Total acid quantity standardAnd (3) calibrating the ammonia with the standard content, wherein the total acid amount is the sum of the medium strong acid amount and the strong acid amount, the medium strong acid refers to the acid with the desorption temperature less than 380 ℃, and the strong acid refers to the acid with the desorption temperature of 380-640 ℃.
[ example 1 ]
Taking 1mol of gamma-Al 2 O 3 Adding 100mL of 0.4mol/L zirconium sulfate solution, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air at 720 ℃ for 5h.
100g of the roasted sample is taken and added into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, the mixture is stirred uniformly, and is kept stand for 48 hours, then the mixture is dried for 12 hours at 110 ℃, and is roasted in nitrogen atmosphere after grinding, the roasting temperature is 400 ℃ and the roasting time is 4 hours, so that the solid super acid catalyst is recorded as PtSZA-1.
[ example 2 ]
Taking 1mol of gamma-Al 2 O 3 Adding 100mL of 0.8mol/L zirconium sulfate solution, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air at 720 ℃ for 5h.
100g of the roasted sample is taken and added into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, the mixture is stirred uniformly, kept stand for 48h, then dried for 12h at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4h to obtain the solid super acid catalyst which is marked as PtSZA-2.
[ example 3 ]
Taking 1mol of gamma-Al 2 O 3 Adding the mixture into 100mL of 1.2mol/L zirconium sulfate solution, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air at 720 ℃ for 5h.
100g of the roasted sample is taken and added into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, the mixture is stirred uniformly, kept stand for 48h, then dried for 12h at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4h to obtain the solid super acid catalyst which is marked as PtSZA-2.
[ example 4 ]
Taking 1mol of gamma-Al 2 O 3 Adding the mixture into 100mL of 1.6mol/L zirconium sulfate solution, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air at 720 ℃ for 5h.
100g of the roasted sample is taken and added into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, the mixture is stirred uniformly, kept stand for 48h, then dried for 12h at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4h to obtain the solid super acid catalyst which is marked as PtSZA-4.
[ example 5 ]
Taking 1mol of gamma-Al 2 O 3 Adding the mixture into 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air, wherein the roasting temperature is 720 ℃ and the roasting time is 5h.
100g of the roasted sample is taken and added into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, the mixture is stirred uniformly, kept stand for 48h, then dried for 12h at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4h to obtain a solid super acid catalyst which is marked as PtSZA-5.
[ example 6 ]
Taking 1mol of gamma-Al 2 O 3 Adding the mixture into 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air, wherein the roasting temperature is 680 ℃ and the roasting time is 5h.
100g of roasted sample is taken and added into 100mL of palladium chloride solution containing 0.3g of palladium element, the mixture is stirred uniformly, and is kept stand for 48h, then dried for 12h at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4h, and the solid super acid catalyst is obtained and is marked as PdSZA-6.
[ example 7 ]
Taking 1mol of gamma-Al 2 O 3 Adding into 100mL of 2.0mol/L zirconium sulfate solution, stirringEven, stand for 48 hours, then dry for 12 hours at 110 ℃, bake in muffle furnace with air after grinding, baking temperature is 700 ℃ and baking time is 5 hours.
100g of roasted sample is taken and added into 100mL of palladium nitrate solution containing 0.3g of palladium element, the mixture is stirred uniformly, and is kept stand for 48h, then dried for 12h at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4h, and the solid super acid catalyst is obtained and is marked as PdSZA-7.
[ example 8 ]
Taking 1mol of gamma-Al 2 O 3 Adding the mixture into 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air at 660 ℃ for 5h.
100g of roasted sample is taken and added into 100mL of nickel nitrate solution containing 1.0g of nickel element, the mixture is stirred uniformly, and is kept stand for 48 hours, then dried for 12 hours at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4 hours, and the solid super acid catalyst is obtained and is recorded as NiSZA-8.
[ example 9 ]
Taking 1mol of gamma-Al 2 O 3 Adding the mixture into 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air, wherein the roasting temperature is 720 ℃ and the roasting time is 5h.
100g of roasted sample is taken and added into 100mL of nickel sulfate solution containing 1.0g of nickel element, the mixture is stirred uniformly, and is kept stand for 48 hours, then dried for 12 hours at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4 hours, and the solid super acid catalyst is obtained and is recorded as NiSZA-9.
[ example 10 ]
Taking 1mol of gamma-Al 2 O 3 Adding 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air, wherein the roasting temperature is 400 ℃ and the roasting time is 5h.
100g of the roasted sample is taken and added into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, the mixture is stirred uniformly, kept stand for 48h, then dried for 12h at 110 ℃, ground and roasted in nitrogen atmosphere at 650 ℃ for 4h to obtain a solid super acid catalyst which is marked as PtSZA-10.
Comparative example 1
Taking 1mol of gamma-Al 2 O 3 Adding the mixture into 100mL of sulfuric acid solution with the concentration of 4.0mol/L, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air, wherein the roasting temperature is 720 ℃ and the roasting time is 5h.
100g of the roasted sample is taken and added into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, the mixture is stirred uniformly, the mixture is kept stand for 48h, then the mixture is dried for 12h at 110 ℃, the mixture is roasted in nitrogen atmosphere after grinding, the roasting temperature is 400 ℃ and the roasting time is 4h, and the catalyst is recorded as PtSA-C1.
Comparative example 2
Taking 1mol of gamma-Al 2 O 3 Adding into 100mL of ammonium sulfate solution with the concentration of 4.0mol/L, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace with air, wherein the roasting temperature is 720 ℃ and the roasting time is 5h.
100g of the roasted sample is taken and added into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, the mixture is stirred uniformly, kept stand for 48h, then dried for 12h at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4h to obtain the catalyst, which is marked as PtSA-C2.
[ comparative example 3 ]
Taking 1mol of gamma-Al 2 O 3 100mL of zirconium nitrate solution with the concentration of 2.0mol/L is added, stirred evenly, stood for 48h and then dried for 12h at 110 ℃. Then adding 100mL of ammonium sulfate solution with the concentration of 4.0mol/L, uniformly stirring, standing for 48h, drying at 100 ℃ for 12h, grinding, and roasting in a muffle furnace with air, wherein the roasting temperature is 720 ℃ and the roasting time is 5h.
100g of the roasted sample is taken and added into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, the mixture is stirred uniformly, kept stand for 48h, then dried for 12h at 110 ℃, ground and roasted in nitrogen atmosphere at 400 ℃ for 4h to obtain the catalyst, which is marked as PtSA-C3.
Application example
The performance evaluation of the n-butane skeletal isomerization catalyst is carried out on a fixed bed continuous flow reaction system, the specification of a reaction tube is 20mm multiplied by 70cm, the catalyst loading amount is 10mL, the particle size is 20-40 meshes, and the catalyst is placed in a constant temperature area of a furnace. The reaction temperature is 200 ℃, the hydrogen pressure is 1MPa, and the volume space velocity of n-butane is 1h -1 The molar ratio of hydrogen to hydrocarbon is 1:1, and the reaction product is analyzed on line by gas chromatography. The results of the catalyst performance evaluation are shown in Table 3.
Table 1 composition of the catalysts obtained in each of examples and comparative examples
TABLE 2 Properties of the catalysts obtained in examples and comparative examples
TABLE 3 Performance of the catalysts obtained in the examples and comparative examples to catalyze the skeletal isomerization of n-butane
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (11)
1. An n-tetraalkane isomerization catalyst comprising MO x /SO 4 2- /ZrO 2 /Al 2 O 3 Wherein MO is x Is a group VIII metal oxide, x is 1 or 2, and the total acid amount is 0.28 to 0.60mmolNH 3 The amount of the strong acid accounts for 45-70% of the total acid amount, and the amount of the medium strong acid accounts for 30-55% of the total acid amount; in the catalyst, in mass fraction, al 2 O 3 The content of (3) is 65-85%, zrO 2 The content is 10-26%.
2. The catalyst of claim 1, wherein M is selected from at least one of platinum, palladium, and nickel.
3. The catalyst of claim 2 wherein M is platinum.
4. The catalyst according to claim 1, wherein MO is present in a mass fraction x The content of (2) is 0.1% -3.0%, S is SO 3 The content of the components is 2 to 6 percent.
5. The method for preparing the n-tetraparaffin isomerization catalyst according to any one of claims 1-4, comprising:
(1) Immersing alumina into a zirconium sulfate solution, standing, drying and roasting to obtain an intermediate;
(2) Immersing the intermediate into a metal salt solution, standing, drying and roasting to obtain a catalyst;
in the step (1), the roasting condition is that roasting is carried out in an oxygen-containing atmosphere, the roasting temperature is 650-750 ℃, the roasting time is 3-8 h, and in the step (2), the roasting condition is that roasting is carried out in an inert atmosphere, the roasting temperature is 350-450 ℃, and the roasting time is 3-8 h.
6. The process according to claim 5, wherein the alumina of step (1) is gamma-Al 2 O 3 。
7. The method according to claim 5, wherein in the step (1), the zirconium sulfate is zirconium sulfate or a hydrate thereof; the concentration of the zirconium sulfate solution is 0.2-2.1 mol/L;
and/or the amount of the zirconium sulfate substance is 3% -30% of the amount of the aluminum oxide substance;
and/or, the impregnation adopts an isovolumetric impregnation method or an excessive impregnation method;
and/or, the drying conditions are as follows: drying at 100-150 deg.c for 10-20 hr.
8. The method according to claim 7, wherein the amount of the zirconium sulfate substance is 10% to 20% of the amount of the aluminum oxide substance.
9. The method according to claim 5, wherein in the step (2), the metal salt is at least one selected from the group consisting of chloroplatinic acid, palladium chloride, palladium nitrate, nickel sulfate and hydrates thereof;
and/or, when the metal salt is palladium salt or platinum salt, the metal salt is calculated by Pd or Pt element and is 0.1 to 0.5 percent of the mass of the intermediate, and when the metal salt is nickel salt, the metal salt is calculated by Ni element and is 0.5 to 3 percent of the mass of the intermediate;
and/or, the impregnation adopts an isovolumetric impregnation method or an excessive impregnation method;
and/or, the drying conditions are as follows: drying at 100-150 deg.c for 10-20 hr.
10. A method for preparing isomerised tetra-alkane by isomerising tetra-alkane, characterized in that the catalyst of any one of claims 1-4 or the catalyst prepared by the preparation method of any one of claims 5-9 is used.
11. The method of claim 10, wherein the reaction conditions for isomerizing normal paraffins to produce isoparaffins are as follows: under the condition of hydrogen, the reaction temperature is 180-220 ℃, the pressure is 0.5-2.0 MPa, and the volume space velocity of normal carbon tetra-alkane is 0.2-2.0 h -1 The molar ratio of hydrogen to hydrocarbon is 0.1-1.0.
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