CN115501891A - N-tetracarbon hydrocarbon isomerization catalyst and preparation method and application thereof - Google Patents
N-tetracarbon hydrocarbon isomerization catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a normal carbon-tetra-alkane isomerization catalyst, a preparation method and application thereof. The catalyst composition is MO x /SO 4 2‑ /ZrO 2 /Al 2 O 3 In which MO is x Is a VIII group metal oxide, x is 1 or 2, and the total acid amount is 0.25 to 1.0mmol NH 3 (iv) g. The preparation method comprises the following steps: immersing aluminum oxide into a zirconium sulfate solution, standing, drying and roasting to obtain an intermediate; and 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-carbon-tetra-alkane to prepare isomerized carbon-tetra-alkane, and can obviously improve the catalytic activity and stability of isomerization 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 a reaction of preparing isobutane through skeletal isomerization of n-carbon and tetraalkyl hydrocarbon, a preparation method and application thereof.
Background
The carbon four resource is an important petrochemical raw material, the source of the carbon four resource is mainly a catalytic cracking device and a steam ethylene decomposing device of an oil refinery, wherein the n-butane resource is rich, and the isomeric product isobutane has better industrial application value and can be used for alkylation and other reactions. The hydrocarbon alkylated oil has the advantages of higher octane value, 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 catalyst for preparing isobutane by skeletal isomerization of n-butane is of great significance to the production of clean gasoline.
The isomerization catalyst is generally of the platinum halide/alumina type, with gamma-Al 2 O 3 Used as a carrier, and a proper amount of chloride auxiliary agent is required to be continuously added into the raw materials in the operation process. The main problems of the technology are that the content of water and sulfur in the 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 the maintenance cost of the equipment are increased, and the environment is polluted. The sulfated solid super acidic catalyst not only does not contain chlorine, but also has loose requirements on the content of water and sulfur in raw materials, and can be regenerated, thus being the development direction of the current isomerization catalyst.
CN1660973A discloses a process for isomerizing C5, C6 alkanes by oxidation of a catalyst containing a group VIII metal (platinum, palladium or nickel) and a supported sulfateMixed oxides of zirconium, alumina and silica, prepared by a process comprising: reacting the zirconium salt solution with an alkali solution to prepare zirconium hydroxide precipitate, carrying out hydrothermal treatment, filtering and drying; mixing aluminum hydroxide and silica sol, and drying; mixing the above two, and adding SO 4 2- Dipping, drying and roasting the solution to obtain a carrier; the carrier is impregnated by VIII family metal salt solution, and the catalyst is prepared after drying and roasting.
CN106732676A discloses a solid acid catalyst for catalyzing isomerization of n-butane and a preparation method thereof. The catalyst consists of zirconium oxide sulfated by sulfur-containing compounds, gallium oxide and a transition metal element selected from IB groups, and the catalyst comprises the following components: 0.1-5% of IB 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 the solution, adding a III A group metal gallium compound, dissolving the solution to prepare a mixed solution of the zirconium salt and the metal gallium compound, adding an alkaline solution until the pH value is 7-10 to obtain a hydroxide precipitate, and filtering, washing and drying the precipitate to obtain a precursor; and adding the precursor into a solution containing sulfate radicals for dipping, drying, dipping by using a copper salt solution, drying and roasting to obtain the catalyst. CN109772287A discloses a paraffin isomerization catalyst carrier, a catalyst and a preparation method thereof. The method comprises the following steps: dissolving zirconium salt, dropwise adding diluted ammonia water under stirring to adjust the pH value to 7-10, and then carrying out hydrothermal reaction; after the reaction is finished and the temperature is reduced to room temperature, washing and filtering are carried out until the reaction is neutral, and after chloride ions cannot be detected by silver nitrate, the washing is finished; drying the obtained filter cake, then adding yttrium salt solution, stirring and dipping, washing, filtering and drying; adding the cerium salt solution continuously, stirring and dipping, washing, filtering and drying; then loading sulfate radicals and tungstate radicals in turn by adopting an isometric impregnation method, finally roasting for 2-4 h at 350-750 ℃, kneading and extruding to form to obtain the catalyst.
As is well known, the preparation process of the catalyst generally produces 'three wastes' pollution, which not only brings pressure on environmental protection, but also increases the cost of the catalyst, thereby accelerating the production of the catalystThe simple, efficient and clean preparation of the catalyst is an important proposition of industrial catalysis. From the above publications, it is known that SO is currently used for the isomerization of n-tetrakaolefins 4 2- /ZrO 2 The catalyst is prepared through the reaction of zirconium salt and ammonia water to produce zirconium hydroxide precipitate, filtering, washing and drying to obtain catalyst precursor, and soaking in SO-containing solution 4 2- Solution and metal salt solution, and finally drying and roasting to obtain the catalyst. The method has multiple preparation steps and long flow, alkaline wastewater containing ammonia and the like is generated, a large amount of water is consumed when the precipitate is washed to be neutral, and the energy consumption is high after multiple drying.
Disclosure of Invention
The invention provides a normal carbon-tetralkyl hydrocarbon isomerization catalyst and a preparation method and application thereof, aiming at solving the problems that the existing solid super acidic catalyst has long preparation flow and can cause 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-alkyl hydrocarbon skeleton.
In a first aspect, the present invention provides a catalyst for isomerizing a normal carbon-tetracarbon hydrocarbon, which comprises MO x /SO 4 2- /ZrO 2 /Al 2 O 3 In which MO is x Is a VIII group metal oxide, x is 1 or 2, and the total acid amount is 0.25 to 1.0mmol NH 3 A/g, preferably 0.28 to 0.60mmol NH 3 /g。
In the technical scheme, the strong acid accounts for 45-70% of the total acid amount, and the medium-strong acid accounts for 30-55% of the total acid amount.
In the above technical solution, M is at least one selected from platinum, palladium and nickel, and is preferably platinum.
In the technical scheme, the mass of the catalyst is taken as a reference, and the mass fraction is MO x Is 0.1 to 4.0%, preferably 0.1 to 3.0%, and Al 2 O 3 In an amount of 60% to 94%, preferably 65% to 85%, S is SO 3 The content is 0.5-7%, preferably 2-6%, zrO 2 The content is 5 to 30 percent, preferably 10 to 26 percent.
In a second aspect, the present invention provides a method for preparing a n-tetracarbon isomerization catalyst, comprising:
(1) Immersing aluminum oxide into a zirconium sulfate solution, standing, drying and roasting to obtain an intermediate;
(2) And immersing the intermediate into a metal salt solution, standing, drying and roasting to obtain the catalyst.
In the technical scheme, the alumina in the step (1) is gamma-Al 2 O 3 。
In the above technical solution, the zirconium sulfate in the 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 solution, the amount of the zirconium sulfate substance in the step (1) is 3% to 30%, preferably 10% to 20% of the amount of the alumina substance.
In the technical scheme, the impregnation in the step (1) adopts an isometric impregnation method or an excess impregnation method, and the standing time is 1-48h.
In the above technical solution, the drying in step (1) may use an air-blast drying oven, and the drying conditions are as follows: drying for 10-20 h at 100-150 ℃.
In the above technical scheme, the roasting in step (1) may use a muffle furnace, and the roasting condition is that the roasting is performed in an oxygen-containing atmosphere (such as air), the roasting temperature is 550-800 ℃, the roasting time is 3-8 h, and the roasting 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 dosage of the metal salt is different according to different types, when the metal salt is palladium salt or platinum salt, the dosage is 0.1-0.5 percent of the mass of the intermediate based on Pd or Pt element, and when the metal salt is nickel salt, the dosage is 0.5-3 percent of the mass of the intermediate based on Ni element.
In the technical scheme, the impregnation in the step (2) adopts an isometric impregnation method or an excess impregnation method, and the standing time is 1-48h.
In the above technical solution, the drying in step (2) may use an air-blast drying oven, and the drying conditions are as follows: drying for 10-20 h at 100-150 ℃.
In the above technical scheme, the roasting in step (2) may use a muffle furnace, and the roasting condition is that roasting is performed in an inert atmosphere (such as nitrogen), the roasting temperature is 300-500 ℃, the roasting time is 3-8 h, and the roasting temperature is preferably 350-450 ℃.
In the technical scheme, the roasted material obtained in the step (2) can be molded to prepare the molded n-tetraalkyl carbon isomerization catalyst. Wherein the molding can be performed by a tabletting method.
In a third aspect of the present invention, there is provided a process for isomerizing a normal tetraalkylhydrocarbon to an isomerized tetraalkylhydrocarbon, wherein the catalyst of the first aspect or the catalyst prepared by the process of the second aspect is used.
In the technical scheme, the catalyst needs to be activated before use, and is activated by a heating method in nitrogen flow 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 solution, the reaction conditions for isomerizing the normal tetraalkyl hydrocarbons to prepare the isomerized tetraalkyl hydrocarbons 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 the n-carbon tetralkyl hydrocarbon is 0.2-2.0 h -1 The hydrogen-hydrocarbon molar ratio is 0.1 to 1.0.
The invention has the following beneficial effects:
1. the invention uses gamma-Al 2 O 3 As a carrier, zirconium sulfate is used as a sulfating reagent, a solid super acidic catalyst is simply and conveniently 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 anti-coking capability of the catalyst can be improved, and the activity and the stability of the catalyst are obviously improved.
2. The catalyst is used in the reaction of isomerizing n-carbon-tetrahydrocarbon to prepare isomerized carbon-tetrahydrocarbon, and can obviously improve the isomerization catalytic activity and stability of the n-carbon-tetrahydrocarbon skeleton at low temperature.
Drawings
FIG. 1 shows temperature programmed desorption (NH) of ammonia gas in 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 present invention, NH is used 3 Determination of the surface acidity of the catalyst for the probe molecules, temperature programmed desorption of ammonia (NH) 3 TPD) experiments in the Tianjin Pengxiang NH 3 -on a TPD instrument. The amount of the sample was 0.2000g, the pretreatment temperature was 550 ℃ to contain 10vol.% NH 3 The ammonia helium mixed gas is the adsorption gas, and the flow rate of the carrier gas helium gas is 30mL/min. The desorption temperature is increased from 100 ℃ to 640 ℃, and the temperature increase rate is 10 ℃/min. The total acid amount is calibrated by ammonia with standard content, and the total acid amount is the sum of medium-strength acid and strong acid, wherein the medium-strength acid refers to acid with the desorption temperature of less than 380 ℃, and the strong acid refers to acid with the desorption temperature of 380-640 ℃.
[ example 1 ]
1mol of gamma-Al is taken 2 O 3 Adding 100mL of zirconium sulfate solution with the concentration of 0.4mol/L, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace filled with air at the roasting temperature of 720 ℃ for 5h.
And adding 100g of roasted sample into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 4h to obtain the solid super acidic catalyst, which is marked as PtSZA-1.
[ example 2 ]
1mol of gamma-Al is taken 2 O 3 Adding 100mL of zirconium sulfate solution with the concentration of 0.8mol/L, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace filled with air at the roasting temperature of 720 ℃ for 5h.
And adding 100g of roasted sample into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 4h to obtain the solid super acidic catalyst, which is marked as PtSZA-2.
[ example 3 ] A method for producing a polycarbonate
1mol of gamma-Al is taken 2 O 3 Adding 100mL of zirconium sulfate solution with the concentration of 1.2mol/L, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace filled with air at the roasting temperature of 720 ℃ for 5h.
Adding 100g of roasted sample into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 4h to obtain the solid super acidic catalyst, which is marked as PtSZA-2.
[ example 4 ]
1mol of gamma-Al is taken 2 O 3 Adding 100mL of zirconium sulfate solution with the concentration of 1.6mol/L, stirring uniformly, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace filled with air at the roasting temperature of 720 ℃ for 5h.
Adding 100g of roasted sample into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 4h to obtain the solid super acidic catalyst, which is marked as PtSZA-4.
[ example 5 ]
1mol of gamma-Al is taken 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 filled with air at the roasting temperature of 720 ℃ for 5h.
Adding 100g of roasted sample into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 4h to obtain the solid super acidic catalyst, which is marked as PtSZA-5.
[ example 6 ]
Taking 1mol of gamma-Al 2 O 3 Adding 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace filled with air at 680 ℃ for 5h.
Adding 100g of roasted sample into 100mL of palladium chloride solution containing 0.3g of palladium element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at 400 ℃ for 4h to obtain the solid super acidic catalyst, which is recorded as PdSZA-6.
[ example 7 ] A method for producing a polycarbonate
1mol of gamma-Al is taken 2 O 3 Adding 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace filled with air at 700 ℃ for 5h.
Adding 100g of roasted sample into 100mL of palladium nitrate solution containing 0.3g of palladium element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at 400 ℃ for 4h to obtain the solid super acidic catalyst, which is recorded as PdSZA-7.
[ example 8 ]
1mol of gamma-Al is taken 2 O 3 Adding 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace filled with air at the roasting temperature of 660 ℃ for 5h.
And adding 100g of the roasted sample into 100mL of nickel nitrate solution containing 1.0g of nickel element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 4h to obtain the solid super acidic catalyst, which is recorded as NiSZA-8.
[ example 9 ] A method for producing a polycarbonate
1mol of gamma-Al is taken 2 O 3 Adding into 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, stirring uniformly, and standing for 4Drying at 110 deg.C for 12h for 8h, grinding, and calcining in muffle furnace with air at 720 deg.C for 5h.
Adding 100g of roasted sample into 100mL of nickel sulfate solution containing 1.0g of nickel element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at 400 ℃ for 4h to obtain the solid super acidic catalyst, which is recorded as NiSZA-9.
[ example 10 ]
1mol of gamma-Al is taken 2 O 3 Adding 100mL of zirconium sulfate solution with the concentration of 2.0mol/L, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a muffle furnace filled with air at the roasting temperature of 400 ℃ for 5h.
And adding 100g of roasted sample into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at 650 ℃ for 4h to obtain the solid super acidic catalyst, which is marked as PtSZA-10.
Comparative example 1
1mol of gamma-Al is taken 2 O 3 Adding into 100mL of 4.0mol/L sulfuric acid solution, stirring, standing for 48h, drying at 110 deg.C for 12h, grinding, and calcining in a muffle furnace filled with air at 720 deg.C for 5h.
Adding 100g of roasted sample into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at 400 ℃ for 4h to obtain the catalyst, which is recorded as PtSA-C1.
Comparative example 2
Taking 1mol of gamma-Al 2 O 3 Adding 100mL of ammonium sulfate 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 filled with air at the roasting temperature of 720 ℃ for 5h.
And adding 100g of the roasted sample into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 4h to obtain the catalyst, which is marked as PtSA-C2.
Comparative example 3
1mol of gamma-Al is taken 2 O 3 Adding into 100mL of zirconium nitrate solution with the concentration of 2.0mol/L, stirring uniformly, standing for 48h, and then drying for 12h at 110 ℃. Adding 100mL of ammonium sulfate solution with the concentration of 4.0mol/L, stirring uniformly, standing for 48h, drying at 100 ℃ for 12h, grinding, and roasting in a muffle furnace filled with air at the roasting temperature of 720 ℃ for 5h.
Adding 100g of roasted sample into 100mL of chloroplatinic acid solution containing 0.3g of platinum element, uniformly stirring, standing for 48h, drying at 110 ℃ for 12h, grinding, and roasting in a nitrogen atmosphere at 400 ℃ for 4h to obtain the catalyst, which is recorded as PtSA-C3.
Application example
The performance evaluation of the n-butane skeletal isomerization catalyst was carried out on a fixed bed continuous flow reaction system, the specification of the reaction tube was 20mm × 70cm, the catalyst loading was 10mL, the particle size was 20-40 mesh, and the catalyst was placed in a constant temperature zone 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 hydrogen-hydrocarbon molar ratio is 1, and the reaction product is analyzed on line by adopting a gas chromatograph. The results of the catalyst performance evaluation are shown in Table 3.
TABLE 1 composition of catalysts obtained in examples and comparative examples
TABLE 2 Properties of catalysts obtained in examples and comparative examples
TABLE 3 skeletal isomerization performance of n-butane catalyzed by the catalyst obtained in each example and comparative example
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (12)
1. A catalyst for isomerizing n-tetracarbon hydrocarbon is MO x /SO 4 2- /ZrO 2 /Al 2 O 3 In which MO is x Is a VIII group metal oxide, x is 1 or 2, and the total acid amount is 0.25 to 1.0mmol NH 3 Per g, preferably from 0.28 to 0.60mmol NH 3 /g。
2. The catalyst according to claim 1, wherein the amount of strong acid in the catalyst is 45-70% of the total amount of acid, and the amount of medium strong acid is 30-55% of the total amount of acid.
3. The catalyst according to claim 1, wherein M is at least one selected from the group consisting of platinum, palladium and nickel, preferably platinum.
4. The catalyst according to claim 1, characterized in that MO, in mass fraction x Is 0.1 to 4.0%, preferably 0.1 to 3.0%, and Al 2 O 3 In an amount of 60% to 94%, preferably 65% to 85%, S is SO 3 The content is 0.5-7%, preferably 2-6%, zrO 2 The content is 5 to 30 percent, preferably 10 to 26 percent.
5. A method for preparing the n-tetradecane isomerization catalyst as claimed in any one of claims 1 to 4, comprising:
(1) Immersing aluminum oxide into a zirconium sulfate solution, standing, drying and roasting to obtain an intermediate;
(2) And immersing the intermediate into a metal salt solution, standing, drying and roasting to obtain the catalyst.
6. The method according to claim 5, wherein the alumina in the step (1) is γ -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 to 30 percent, preferably 10 to 20 percent of the amount of the alumina substance;
and/or, the impregnation adopts an equal-volume impregnation method or an excess impregnation method;
and/or, the drying conditions are as follows: drying for 10-20 h at 100-150 ℃.
8. The preparation method according to claim 5, wherein in the step (1), the roasting condition is that the roasting is carried out in an oxygen-containing atmosphere, the roasting temperature is 550-800 ℃, and the roasting time is 3-8 h, wherein the roasting temperature is preferably 650-750 ℃.
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 0.1-0.5% of the intermediate mass calculated by Pd or Pt element, and when the metal salt is nickel salt, the metal salt is 0.5-3% of the intermediate mass calculated by Ni element;
and/or the impregnation adopts an equal-volume impregnation method or an excess impregnation method;
and/or, the drying conditions are as follows: drying for 10-20 h at 100-150 ℃.
10. The method according to claim 5, 8 or 9, wherein in the step (2), the roasting is performed under an inert atmosphere at a roasting temperature of 300 to 500 ℃ for 3 to 8 hours, wherein the roasting temperature is preferably 350 to 450 ℃.
11. A process for isomerizing a n-tetracarbon to an isomerized n-tetracarbon, which comprises using the catalyst as claimed in any one of claims 1 to 4 or the catalyst prepared by the process according to any one of claims 5 to 10.
12. The process of claim 11 wherein said isomerizing of said normal tetraalkyl carbon to produce an isomerized tetraalkyl carbon is carried out under the following conditions: 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 the n-carbon tetralkyl hydrocarbon is 0.2-2.0 h -1 The molar ratio of hydrogen to hydrocarbon is 0.1 to 1.0.
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| CN1094995A (en) * | 1993-05-11 | 1994-11-16 | 中国石油化工总公司 | The preparation method of superstrong acid of carried oxide system |
| CN1541764A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Catalyst for isomerizing low-carbon paraffin and its preparing process |
| CN101108355A (en) * | 2007-07-17 | 2008-01-23 | 华东理工大学 | Method of manufacturing high isomerization active solid super acidic catalyst |
| CN107570182A (en) * | 2016-07-04 | 2018-01-12 | 中国石油大学(华东) | Catalyst for alkane isomerization and preparation method thereof and reaction unit |
| CN107051420A (en) * | 2017-05-22 | 2017-08-18 | 中国石油大学(北京) | A kind of normal butane isomerization catalyst and preparation method thereof |
| CN110385142A (en) * | 2019-07-19 | 2019-10-29 | 河北工业大学 | Anti- applications catalyst of a kind of positive structureization of iso-butane and its preparation method and application |
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