阅读说明：本技术 一种石脑油重整催化剂及其制备方法与应用 (Naphtha reforming catalyst and preparation method and application thereof ) 是由 刘建良 马爱增 王春明 潘锦程 刘辰 于 2019-10-29 设计创作，主要内容包括：一种石脑油重整催化剂,包括无机氧化物载体和以无机氧化物载体为基准计的含量如下的组分：0.1-3质量％的Pt,0.01-3质量％的IVA族金属,0.1-5质量％的氯,以及,0.01-1质量％的Li或0.25-1质量％的ⅡA族金属。本发明的催化剂用于石脑油催化重整,具有良好的选择性和抗积炭能力,可明显提高液体产物收率,降低液体产物芳烃含量。(A naphtha reforming catalyst comprising an inorganic oxide support and the following components in amounts based on the inorganic oxide support: 0.1-3 mass% of Pt, 0.01-3 mass% of a group IVA metal, 0.1-5 mass% of chlorine, and 0.01-1 mass% of Li or 0.25-1 mass% of a group IIA metal. The catalyst of the invention is used for catalytic reforming of naphtha, has good selectivity and carbon deposit resistance, can obviously improve the yield of liquid products and reduce the content of aromatic hydrocarbon in the liquid products.)

1. A naphtha reforming catalyst comprising an inorganic oxide support and the following components in amounts based on the inorganic oxide support:

0.1 to 3 mass% of Pt, 0.01 to 3 mass% of a group IVA metal, 0.1 to 5 mass% of chlorine, and 0.01 to 1 mass% of Li or 0.25 to 1 mass% of a group IIA metal.

2. The catalyst of claim 1, wherein the catalyst comprises the following components in amounts:

0.15 to 1 mass% of Pt, 0.1 to 1 mass% of a group IVA metal, 0.5 to 2.5 mass% of chlorine, and 0.02 to 0.6 mass% of Li or 0.3 to 0.9 mass% of a group IIA metal.

3. The catalyst according to claim 1 or 2, wherein the Li/Pt atomic ratio in the catalyst is 1 to 30;

the IIA group metal is Ca and/or Ba, and the atomic ratio of the IIA group metal to Pt is 0.5-5.

4. The catalyst of claim 1 or 2, wherein the group IVA metal is Ge or Sn.

5. The catalyst of claim 1, wherein the inorganic oxide support is one or more of alumina, magnesia, titania, zinc oxide, zirconia, ceramic, alumina, bauxite, silica, silicon carbide, silicates, clay, crystalline alumino-silicate zeolites, and non-zeolitic molecular sieves.

6. A process for preparing a catalyst according to any one of claims 1 to 5, comprising the steps of:

(1) impregnating an inorganic oxide carrier containing IVA group metals with a solution containing lithium compounds or IIA group metal compounds, and carrying out first drying and roasting on the impregnated solid to obtain a first carrier;

(2) impregnating the first carrier with a solution containing a platinum compound, and carrying out secondary drying on the impregnated solid;

(3) and (3) carrying out water-chlorine activation on the solid obtained in the step (2).

7. The method according to claim 6, wherein the temperature of the first drying in the step (1) is 50-300 ℃ and the time is 2-48 hours; the roasting is carried out in an oxygen-containing atmosphere at the temperature of 350-700 ℃ for 2-24 hours; the temperature of the second drying in the step (2) is 50-300 ℃, and the time is 2-48 hours.

8. The method according to claim 6 or 7, wherein the impregnated solid in step (1) is subjected to the first drying and then calcined with air having a water content of 1 to 10 mass%.

9. The method of claim 6, wherein the water-chlorine activation comprises: treating the solid obtained in the step (2) in air containing water and HCl, wherein the water-chlorine activation temperature is 370 ℃ and 700 ℃, the time is 1-16 hours, and the molar ratio of water to HCl contained in the air is (10-100): 1.

10. the method of claim 6, wherein the method further comprises: reducing the solid obtained in the step (3); the reduction is carried out in a reducing atmosphere at a temperature of 250-650 ℃ for 0.5-16 hours.

11. The method of claim 10, wherein the content of hydrogen in the reducing atmosphere is not less than 60 vol%.

12. A method for catalytically reforming naphtha, wherein naphtha is contacted with the catalyst of any one of claims 1 to 11 to react under the reaction conditions of naphtha catalytic reforming.

13. The method of claim 12, wherein the reaction conditions comprise: the temperature is 360-600 ℃, the pressure is 0.1-2.5MPa, and the volume space velocity of liquid feeding is 1-20h^-1The hydrogen/hydrocarbon volume ratio was 500-.

Technical Field

The invention relates to a hydrocarbon conversion catalyst, a preparation method and application thereof, in particular to a naphtha reforming catalyst, a preparation method thereof and a naphtha catalytic reforming method.

Background

Catalytic reforming processes are widely used to increase the quality of heavy gasolines (paraffins and naphthenes) in which hydrocarbons containing from 6 to 12 carbon atoms per molecule form aromatics or branched paraffins in the reforming process. The reforming reaction is carried out at high temperature (500 deg.C), low to medium pressure (3.5X 10)⁵Pa-25×10⁵Pa) and in the presence of a catalyst. The catalytic reformed oil can be used for improving the octane number of oil components, and the reformed oil mainly comprises C₅ ⁺A hydrocarbon compound (containing at least 5 carbon atoms). The process also produces H₂Fuel gas (from C)₁-C₂Hydrocarbon formation) and liquefied gas (from C)₃-C₄Hydrocarbon formation). In addition, coke deposited on the active sites of the catalyst is also formed by condensation of the aromatic rings.

In the catalytic reforming process, competing reactions occur simultaneously, including dehydrogenation of cyclohexane to aromatics, dehydrogenation and isomerization of alkylcyclohexane to aromatics, and dehydrogenation and cyclization of cycloalkanes to aromatics. In these reactions, the yield of gasoline is reduced due to the production of light hydrocarbon gases by hydrocracking, the rate of catalyst deactivation is accelerated by coking reactions, and the operating costs of the plant are increased by frequent catalyst regeneration. Meanwhile, with the increasingly strict national environmental regulations, the aromatic hydrocarbon content in the gasoline pool is further required, so that the development of a catalytic reforming catalyst with high selectivity, low aromatic hydrocarbon content and low carbon deposition rate and a process thereof are always targets of people. The method for preparing the multi-metal reforming catalyst by adding the third metal component and the fourth metal component into the bimetallic catalyst is one of the more modification methods applied at present.

The reforming catalyst is a porous solid in the form of a strip, bead or granule, and is a bifunctional catalyst. The metal function provides mainly the dehydrogenation of naphthenes and paraffins as well as the hydrogenation of coke precursors. The acidic function provides for the isomerization of naphthenes and paraffins as well as the cyclization of paraffins. The acidic function is provided by the support itself, typically a halogenated alumina. The metal function is provided by a noble metal of the platinum group and at least one additional metal, the additional metal being tin in a continuous process (moving bed) and rhenium in a semi-regenerative process (fixed bed).

The conventional method for preparing the reforming catalyst of Pt and Sn is to introduce the required metal components into the carrier at one time, and the introduced metal components usually contain rare earth elements besides the metals of VIII group and IVA group. USP 3915845 discloses catalysts comprising a group viii metal, a group iva metal, a halogen and a lanthanide, wherein the atomic ratio of lanthanide to group viii metal is from 0.1 to 1.25: preferred lanthanides are Nd, La or Ce 1.

CN1234455C introduces a multi-metal catalyst and a preparation method thereof, wherein the catalyst comprises the following components in percentage by mass: 0.01-2.0 of VIII group metal, 0.01-5.0 of IVA group metal, 0.01-10.0 of Eu, 0.01-10.0 of Ce, 0.10-10.0 of halogen and 63.00-99.86 of high-temperature resistant inorganic oxide. The catalyst has high activity and selectivity when used for reforming naphtha, low carbon deposition rate and long service life.

CN100338189C describes a preparation method of a Pt, Sn catalyst, which comprises a refractory inorganic oxide and the following active components in the following content calculated by taking a carrier as a reference: 0.01-5.0 group VIII metal, 0.01-5.0 group IVA metal, 0-10.0 lanthanide and 0.10-10.0 halogen. The method comprises the steps of firstly preparing a high-temperature-resistant inorganic oxide carrier containing IVA group metals, enabling the content of the IVA group metals in the carrier to be 50-70% of the content of the IVA group metals in a catalyst, and then preparing an impregnating solution containing the IVA group metal compounds and lanthanide series metal compounds or not. Impregnating a carrier containing IVA group metals, drying and roasting the impregnated carrier after impregnation, preparing impregnation liquid containing VIII group metal compounds, impregnating the carrier, and drying and roasting the impregnated carrier, wherein the impregnation liquid contains 2-15% of monobasic inorganic acid calculated by taking the carrier as a standard. The catalyst prepared by the method has low carbon deposition rate, and has high activity and aromatic selectivity.

CN103372454B describes a multi-metal reforming catalyst, which comprises a high-temperature resistant inorganic oxide carrier and the following components calculated by taking the carrier as a reference: 0.01-2.0 mass% of platinum group metal, 0.01-5.0 mass% of IVA group metal, 0.01-3.0 mass% of Sm, 0.01-3.0 mass% of Ce and 0.1-5.0 mass% of halogen.

US20170266646 describes a naphtha reforming catalyst comprising an alumina support, noble metals Pt, Pd, Rh, Ru, Os or Ir, one or more alkaline earth metals for use in reforming reactions to significantly increase the aromatics content of the produced oil.

Disclosure of Invention

The invention aims to provide a naphtha reforming catalyst, a preparation method and application thereof.

In order to achieve the above object, the present invention provides a catalytic reforming catalyst comprising an inorganic oxide support and the following components in amounts based on the inorganic oxide support: 0.1 to 3 mass% of Pt, 0.01 to 3 mass% of a group IVA metal, 0.1 to 5 mass% of chlorine, and 0.01 to 1 mass% of Li or 0.25 to 1 mass% of a group IIA metal.

Through the technical scheme, the catalyst is used for naphtha catalytic reforming reaction, has good selectivity and carbon deposit resistance, can obviously improve the yield of liquid products of the reaction, and reduces the content of aromatic hydrocarbon of the liquid products.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a graph of the selectivity of catalyst A, B, C versus comparative catalyst b as a function of reaction time;

FIG. 2 is a graph of the activity of catalyst A, B, C versus comparative catalyst b as a function of reaction time;

FIG. 3 is a graph of selectivity versus reaction time for catalyst D, E, F and comparative catalyst b;

fig. 4 is a graph of the activity of catalyst D, E, F versus comparative catalyst b as a function of reaction time.

Detailed Description

The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The invention provides a naphtha reforming catalyst, which comprises an inorganic oxide carrier and the following components in percentage by weight based on the inorganic oxide carrier:

0.1 to 3 mass% of Pt, 0.01 to 3 mass% of a group IVA metal, 0.1 to 5 mass% of chlorine, and 0.01 to 1 mass% of Li or 0.25 to 1 mass% of a group IIA metal.

Wherein, Pt can be a metal simple substance, a Pt-containing compound or exist in a form of chemical combination with one or more components in the catalyst, and the Pt-containing compound can be an oxide, a sulfide or a chloride containing Pt. The catalyst contains lithium or alkaline earth metal, can adjust the acidity of the catalyst, obviously improve the yield of liquid products of reforming reaction, reduce the aromatic hydrocarbon content of the liquid products and reduce the carbon deposition rate of the catalyst.

In a preferred embodiment, the catalyst may comprise the following components in the amounts: 0.15 to 1 mass% of Pt, 0.1 to 1 mass% of a group IVA metal, 0.5 to 2.5 mass% of chlorine, and 0.02 to 0.6 mass% of Li or 0.3 to 0.9 mass% of a group IIA metal, and further, the Li content is preferably 0.02 to 0.3 mass%.

According to the invention, the atomic ratio of Li to Pt in the catalyst can vary within a wide range, preferably (1-30): 1, more preferably (2-25): 1. li may be present in the catalyst in various forms, for example, in the form of oxides, sulfides, chlorides, nitrates, carbonates, and the like; or independently in a carrier; or may be present in physical or chemical association with the carrier or other component.

According to the invention, the group IIA metal may be Ca and/or Ba, preferably Ba, and the atomic ratio of the group IIA metal to Pt may vary within a wide range, preferably (0.5-5): 1, more preferably (1-5): 1. the group IIA metal may be present in the catalyst in a variety of forms, for example, as an oxide, sulfide, chloride, nitrate, carbonate, etc.; or independently in a carrier; or may be present in physical or chemical association with the carrier or other component.

In one embodiment, the group IVA metal may be Ge or Sn, preferably Sn. The group IVA metal may be present in various forms, for example, in the metallic state; or in the form of oxides, sulfides, chlorides; or independently in a carrier; or may be present in physical or chemical association with the carrier or other component.

According to the present invention, the inorganic oxide support may be one conventionally used by those skilled in the art, for example, may be a high-temperature resistant inorganic oxide, may be an adsorbent having a porous structure, and the composition of the porous support may be uniform without a fixed concentration gradient. The inorganic oxide support may be a refractory inorganic oxide such as alumina, magnesia, titania, zinc oxide, zirconia, and may be one or more of ceramic, alumina, bauxite, silica, silicon carbide, silicates, clay, crystalline alumino-silicate zeolites, and non-zeolitic molecular sieves. Among them, crystalline alumino-silicate zeolites such as X-zeolite, Y-zeolite, mordenite, L-zeolite, which may be in the hydrogen form or in the non-hydrogen ionic form, preferably in the ionic form; non-zeolitic molecular sieves such as aluminum phosphate, silico-aluminum phosphate. The inorganic oxide is preferably alumina, the alumina is preferably high-purity alumina obtained by hydrolyzing aluminum alkoxide, and the crystal form of the alumina is not particularly limited and may be, for example, γ -Al₂O₃、η-Al₂O₃Or theta-Al₂O₃Preferably gamma-Al₂O₃。

The shape of the inorganic oxide support is also not limited, and may be, for example, a sphere, a tablet, a bar, or a clover. The spherical inorganic oxide carrier can be prepared by oil ammonia column, oil heat column or water column molding, and the strip-shaped or clover-shaped inorganic oxide carrier can be prepared by a conventional extrusion molding method. The inorganic oxide support is preferably alumina, which may have an apparent bulk density of 0.3-1.0g/mL, pore volume of 0.3-1.2g/mL, and specific surface area of 50-300m²Per g, preferably 100-²/g。

In a second aspect, the present invention provides a method for preparing the catalyst provided in the first aspect, the method comprising the steps of:

(1) impregnating an inorganic oxide carrier containing IVA group metals with a solution containing lithium compounds or IIA group metal compounds, and carrying out first drying and roasting on the impregnated solid to obtain a first carrier;

(2) impregnating the first carrier with a solution containing a platinum compound, and carrying out secondary drying on the impregnated solid;

(3) and (3) carrying out water-chlorine activation on the solid obtained in the step (2).

According to the present invention, inorganic oxide supports containing group IVA metals may be prepared by methods well known to those skilled in the art. The group IVA metal may be incorporated into the support by one of coprecipitation, ion exchange and impregnation with the porous support. The impregnation method is a method in which a carrier is impregnated with a solution of a soluble compound of a group IVA metal to disperse the solution in a porous carrier material, and the coprecipitation method is a method in which a soluble compound of a group IVA metal is added at the time of forming the carrier. Preferably, the group IVA metal is introduced by co-precipitation. The soluble compound of the group IVA metal is not particularly limited in form, and may be, for example, an oxide, chloride, nitrate or alkoxide of the group IVA metal. Preferably, the compound is a soluble compound containing tin, such as stannous bromide, stannous chloride, stannic chloride pentahydrate, preferably stannic chloride, stannous chloride.

According to the invention, the lithium-containing compound or group IIA metal-containing compound may be a water-soluble compound, preferably a nitrate, chloride, fluoride, organic alkoxide of Li or group IIA metal, preferably chloride. The above compounds can be dissolved in water to obtain soaking solution, preferably containing acid such as HCl and HNO₃Oxalic acid, maleic acid or citric acid.

In the step (1), the method for introducing lithium or group IIA metal into the catalyst is not limited, and in one embodiment, the inorganic oxide support containing group IVA metal is impregnated with a solution containing a lithium compound or a group IIA metal compound, and the impregnated support is subjected to first drying and calcination, and more preferably, the impregnated support is calcined using air containing water vapor.

According to the present invention, the platinum compound-containing solution in step (2) may be a solution containing a soluble platinum compound, and the platinum compound may be at least one of chloroplatinic acid, ammonium chloroplatinate, bromoplatinic acid, platinum trichloride, platinum tetrachloride hydrate, dichlorocarbonylplatinum dichloride, dinitrodiaminoplatinum and tetranitroplatinic acid, preferably chloroplatinic acid. Preferably, the impregnated support is subjected to a second drying after platinum has been introduced by impregnation. Optionally, the platinum-containing compound solution contains acid, which can be HCl or HNO₃Oxalic acid, maleic acid or citric acid.

According to the invention, the impregnation method in step (1) and step (2) is well known to those skilled in the art, the impregnation method in both steps may be the same or different, preferably, a supersaturated impregnation method may be used in each of the two steps, the liquid/solid mass ratio of the impregnation solution is preferably greater than 1, more preferably (1-3): the temperature of the impregnation can be 10-50 ℃, and the excess liquid after the impregnation can be removed by adopting an evaporation method.

According to the present invention, the first drying, the second drying and the firing may employ a method well known to those skilled in the art. Wherein, the temperature and time of the first drying, the second drying and the roasting can be changed in a large range, preferably, the temperature of the first drying can be 50-300 ℃, and the time can be 2-48 hours; the roasting can be carried out in an oxygen-containing atmosphere, the temperature can be 350-700 ℃, and the time can be 2-24 hours; preferably, the solid after the first drying in step (1) is calcined with air containing water vapor, the content of water vapor in the air being preferably 1 to 10% by mass, more preferably 1 to 5% by mass. The temperature of the second drying may be 50-300 deg.C and the time may be 2-48 hours.

According to the present invention, the water-chlorine activation of step (3) may include: treating the solid obtained in the step (2) in air containing water and HCl. Chlorine can be introduced into the catalyst by water-chlorine activation to render the catalyst suitably acidic.

In one embodiment, the conditions for water-chlorine activation may include: the temperature is 370 ℃ and 700 ℃, the time can be 1-16 hours, and the molar ratio of water to HCl in the air can be (10-100): 1. preferably, the temperature is 450-650 ℃, the time is 2-8 hours, and the molar ratio of water to HCl in the air (10-80): 1.

according to the invention, the method may further comprise: reducing the solid obtained in the step (3); the conditions of the reduction treatment may include: the reduction is carried out in a reducing atmosphere at a temperature of 250 ℃ and 650 ℃ for a time of 0.5 to 16 hours. Preferably, the temperature is 400-600 ℃ and the time is 2-8 hours. The reducing atmosphere may contain a reducing gas or a mixed gas of a reducing gas and an inert gas, and preferably, the reducing gas may be H₂The inert gas may be nitrogen, argon or helium. The content of hydrogen in the mixed gas is not less than 60% by volume, preferably 70 to 100% by volume.

In a third aspect of the present invention, there is provided a process for catalytic reforming of naphtha, wherein naphtha is contacted with the catalyst provided in the first aspect of the present invention to perform a reaction under reaction conditions for catalytic reforming of naphtha.

The naphtha may be selected from at least one of straight run naphtha, hydrocracked naphtha, coker naphtha, catalytically cracked naphtha, and ethylene cracked naphtha. Naphtha generally contains paraffins, naphthenes and aromatics, which may have carbon numbers in the range of 5 to 12. The initial boiling point of the naphtha as determined by ASTM D-86 may be in the range of 40 to 100 ℃ and preferably in the range of 70 to 90 ℃ and the final boiling point may be in the range of 140 ℃ to 220 ℃ and preferably in the range of 160 ℃ to 180 ℃. The catalyst of the invention is preferably used in a sulfur-free or low-sulfur environment, and the naphtha sulfur content may be not higher than 1.0. mu.g/g, preferably not higher than 0.5. mu.g/g. To achieve the desired sulfur content, the naphtha can be desulfurized by a variety of methods including adsorption desulfurization, catalytic desulfurization, which are well known to those skilled in the art and will not be described further herein.

The water content of the naphtha as it enters the reforming reaction zone (vessel) may be less than 50ppm, preferably less than 20 ppm. The dehydration of naphtha can be carried out by conventional adsorption dehydration, such as molecular sieve and alumina dehydration, or by a suitable stripping operation in a fractionation unit, or by a combination of adsorption drying and gas drying to remove water from naphtha. The specific steps of the above method are well known to those skilled in the art and will not be described herein.

According to an embodiment of the present invention, the reaction conditions for catalytic reforming of naphtha may include: the temperature is 360-600 ℃, the pressure is 0.1-2.5MPa, and the volume space velocity of liquid feeding is 1-20h^-1The hydrogen/hydrocarbon volume ratio was 500-. Preferably, the temperature is 450-550 ℃, the pressure is 0.15-1MPa, and the volume space velocity of liquid feeding is 1-10h^-1The hydrogen/hydrocarbon volume ratio is 700-.

The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.

Example 1

(1) Preparation of spherical Sn-containing gamma-Al₂O₃Carrier

137.4g of pseudo-boehmite powder (manufactured by Condea, Germany, trade name SB, alumina content 72.8 mass%) and 0.60g of SnCl₂·2H₂O and 350g of deionized water are mixed and stirred for 0.5h, 14g of nitric acid solution with the concentration of 22 mass percent is added dropwise, the mixture is stirred for 2h at the temperature of 20 ℃, 30g of kerosene and 3g of fatty alcohol-polyoxyethylene ether are added, and dropping balls are formed in an oil-ammonia column. Solidifying the wet ball in ammonia water for 1h, then filtering, washing with deionized water, drying at 60 ℃ for 6h, drying at 120 ℃ for 10h, and roasting at 600 ℃ for 4h to obtain the Sn-containing gamma-Al₂O₃Carrier of N₂The specific surface area of the adsorption test (BET) support was 210m²Pore volume was 0.6 mL/g.

(2) Introduction of Li

0.4321g of LiCl. H were taken₂O, the amount of lithium contained is gamma-Al₂O₃0.05% by mass of the carrier was dissolved in 180mL of a hydrochloric acid solution having an HCl content of 1.5% by mass to prepare an impregnation solution containing Li. 100g of the carrier prepared in the step (1) is taken, dipped for 12h at 30 ℃ by using a dipping solution containing Li, and dippedThe mass ratio of liquid to solid is 1.8, the solid obtained after impregnation is dried at 60 deg.C for 6h, dried at 120 deg.C for 12h, and then calcined at 600 deg.C for 4h with air containing 3 wt% of water to obtain gamma-Al containing Sn and Li₂O₃And (3) a carrier.

(3) Lead Pt

And (3) taking 35.0mL of chloroplatinic acid solution with platinum content of 8.3mg/mL, adding 20mL of hydrochloric acid solution with concentration of 100mg/mL and 125mL of deionized water, wherein the amount of HCl accounts for 2% of the mass of the carrier, adding 100g of the alumina carrier prepared in the step (2), oscillating and dipping at 30 ℃ for 1h, wherein the dipping liquid/solid mass ratio is 1.8, and standing for 12 h. Evaporating the filtrate to dryness, drying at 90 ℃ for 10h, introducing air containing HCl and water at 520 ℃ for carrying out water-chlorine activation for 6h, wherein the molar ratio of water to HCl in the air is 60: 1. then reducing the mixture for 6 hours in hydrogen at 500 ℃ to obtain the catalyst A in a reduced state, wherein the active components of the catalyst A are shown in a table 1. In Table 1, the contents of metal components were measured by X-ray fluorescence and the chlorine content was measured by the electrode method.

(4) Catalyst evaluation

A 100mL apparatus was charged with 50mL of catalyst, and the catalyst was evaluated using straight run naphtha after hydrorefining as a raw material, the properties of the naphtha being shown in table 2, and the evaluation conditions were as follows: the reaction temperature is 530 ℃, the reaction pressure is 0.7MPa, the volume ratio of hydrogen to hydrocarbon is 1000, and the hourly space velocity of the feed liquid is 1.8h^-1. The average reaction results of the cumulative 120h reaction are shown in Table 3. After 48h of reaction, sampling every 24h, measuring the bed temperature, plotting the aromatic hydrocarbon content of the liquid product-the yield of the liquid product, and observing the change of the selectivity of the catalyst along with the reaction time, as shown in figure 1. The activity of the catalyst was examined as a function of reaction time by plotting the yield of aromatic hydrocarbon versus the bed temperature, as shown in FIG. 2. The amount of carbon deposited in the catalyst after the reaction was measured by using an EMIA-820V infrared sulfur and carbon measuring instrument manufactured by HORIBA, Japan. Octane number yield ═ C₅ ⁺Liquid product yield x liquid product research octane number.

Example 2

A catalyst was prepared and evaluated in the same manner as in example 1, except that 0.8643g of LiCl. H was used in the step (2)₂Preparing impregnating solution with lithium in the carrier mass0.1 percent, the content of the active component of the prepared catalyst B is shown in Table 1, and the average reaction result of the cumulative reaction for 120 hours is shown in Table 3. After the reaction is started for 48 hours, sampling is carried out every 24 hours, the bed temperature is measured, the selectivity of the catalyst is shown in figure 1 along with the change of the reaction time, and the activity is shown in figure 2 along with the change of the reaction time.

Example 3

A catalyst was prepared and evaluated in the same manner as in example 1, except that 1.7286g of LiCl. H was used in the step (2)₂O, preparing an impregnation solution, wherein the lithium content accounts for 0.2 percent of the mass of the carrier, the active component content of the prepared catalyst C is shown in Table 1, and the average reaction result of the cumulative reaction for 120 hours is shown in Table 3. After the reaction is started for 48 hours, sampling is carried out every 24 hours, the bed temperature is measured, the selectivity of the catalyst is shown in figure 1 along with the change of the reaction time, and the activity is shown in figure 2 along with the change of the reaction time.

Example 4

A catalyst was prepared and evaluated in the same manner as in example 1, except that 0.5521g of BaCl was used in the step (2)₂·2H₂O instead of LiCl. H₂Preparing an impregnating solution by using O, introducing Ba into the carrier, wherein the content of the barium contained in the impregnating solution accounts for 0.31% of the mass of the carrier, the content of the active component of the prepared catalyst D is shown in Table 1, and the average reaction result of the cumulative reaction for 120h is shown in Table 3. After the reaction is started for 48 hours, sampling is carried out every 24 hours, the bed temperature is measured, the selectivity of the catalyst is shown in figure 3 along with the change of the reaction time, and the activity is shown in figure 4 along with the change of the reaction time.

Example 5

A catalyst was prepared and evaluated in the same manner as in example 1, except that 0.9796g of BaCl was used in the step (2)₂·2H₂O instead of LiCl. H₂Preparing impregnation liquid by O, introducing Ba into the carrier, wherein the content of the barium in the impregnation liquid accounts for 0.55% of the mass of the carrier, the content of the active component of the prepared catalyst E is shown in table 1, and the average reaction result of the cumulative reaction for 120h is shown in table 3. After the reaction is started for 48 hours, sampling is carried out every 24 hours, the bed temperature is measured, the selectivity of the catalyst is shown in figure 3 along with the change of the reaction time, and the activity is shown in figure 4 along with the change of the reaction time.

Example 6

A catalyst was prepared and evaluated in the same manner as in example 1, except that 1.46g of BaCl was used in the step (2)₂·2H₂O instead of LiCl. H₂Preparing impregnation liquid by O, introducing Ba into the carrier, wherein the content of the barium in the impregnation liquid accounts for 0.82% of the mass of the carrier, the content of the active component of the prepared catalyst F is shown in table 1, and the average reaction result of the cumulative reaction for 120h is shown in table 3. After the reaction is started for 48 hours, sampling is carried out every 24 hours, the bed temperature is measured, the selectivity of the catalyst is shown in figure 3 along with the change of the reaction time, and the activity is shown in figure 4 along with the change of the reaction time.

Comparative example 1

A catalyst was prepared and evaluated in the same manner as in example 1, except that the catalyst was prepared in the same manner as in step (3) without carrying out the step (2), the active component content of the obtained catalyst a was as shown in Table 1, and the average reaction result of the cumulative reaction for 120 hours was as shown in Table 3.

Comparative example 2

A catalyst was prepared and evaluated in the same manner as in example 1, except that 0.1505g of Eu was used in step (2)₂O₃And 0.7448g of CeCl₃·7H₂O instead of LiCl. H₂And O, preparing an impregnation solution, introducing Eu and Ce into the carrier, wherein the amount of the Eu accounts for 0.13% of the mass of the carrier, the amount of the cerium accounts for 0.28% of the mass of the carrier, the active component content of the prepared catalyst b is shown in table 1, and the average reaction result of cumulative reaction for 120h is shown in table 3. After 48h of reaction, sampling is carried out every 24h, and bed temperature is measured, the selectivity of the catalyst is shown in a graph 1 and a graph 3 along with the change of reaction time, and the activity is shown in a graph 3 and a graph 4 along with the change of reaction time.

Comparative example 3

A catalyst was prepared and evaluated in the same manner as in example 1, except that 0.3562g of BaCl was used in the step (2)₂·2H₂O instead of LiCl. H₂Preparing impregnating solution by using O, introducing Ba into the carrier, wherein the content of barium in the impregnating solution is 0.2 percent of the mass of the carrier, the content of active components of the prepared catalyst c is shown in table 1, and the average reaction result of the accumulative reaction for 120 hours is shown in table3。

TABLE 1

TABLE 2

TABLE 3

As can be seen from Table 3, the catalyst of the present invention has a high yield of the reaction liquid product, a low content of aromatic hydrocarbons in the liquid product, a low yield of aromatic hydrocarbons, and a low carbon deposit amount after the reaction, as compared with the catalyst prepared in the comparative example.

As can be seen from FIG. 1, at C₅ ⁺The catalyst A, B, C of the present invention had a higher C than the comparative catalyst b for the same aromatic content of the liquid product₅ ⁺The yield of liquid product shows that the selectivity of the catalyst of the invention is higher. Figure 2 shows that the catalyst of the invention has a reduced activity compared to comparative catalyst b.

As is clear from fig. 3 and 4, the catalyst D, E, F of the present invention has higher selectivity and lower activity than the catalyst b under the same reaction conditions.

The catalyst of the invention has good selectivity and carbon deposit resistance when being applied to naphtha catalytic reforming, can obviously improve the yield of liquid products and reduce the content of aromatic hydrocarbon of the liquid products.

The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.