Catalyst as well as preparation method and application thereof

Abstract

The invention provides a catalyst as well as a preparation method and application thereof. The catalyst comprises a carrier, the carrier comprises at least one pore channel, the pore channel is a hierarchical pore, and the size of the pore channel is 0.3-10 nanometers; at least part of the first active material is located in the pore channel, and the first active material comprises platinum and / or iridium. When the catalyst disclosed by the embodiment of the invention is applied to hydrogenation of coal tar and / or direct coal liquefaction oil, the coal tar and / or direct coal liquefaction oil enters the pore channels, so that the coal tar and / or direct coal liquefaction oil can be subjected to a ring-opening reaction, fuel with high heat sink can be obtained, and the obtained fuel can have high density, high freezing point and thermal stability at the same time and can be applied to hydrogenation of coal tar and / or direct coal liquefaction oil. The method is suitable for aerospace crafts.

Description

Technical Field

[0001] This application relates to the field of catalytic technology, and particularly to a catalyst, its preparation method and application. Background Art

[0002] The process of preparing aviation fuel from coal tar and direct coal liquefied oil usually includes steps such as phenol removal, hydrodesulfurization, hydrogen saturation and fractionation, etc., to obtain a naphthene mixture with a boiling range of 150 - 300 °C. However, the molecular cyclization degree of coal tar and direct coal liquefied oil is too high, resulting in a reduction in the vibratable chemical bonds of fuel molecules and a significant decrease in physical heat capacity. Therefore, the heat sink of these fuels is low and cannot meet the high heat sink requirements of new aircraft. Summary of the Invention

[0003] In view of this, embodiments of this application provide a catalyst, its preparation method and application.

[0004] The first aspect of this application provides a catalyst, including:

[0005] A carrier, the carrier includes at least one pore, and the size of the pore is 0.3 - 10 nanometers;

[0006] A first active material, at least part of the first active material is located in the pore, and the active material includes platinum and / or iridium.

[0007] In one embodiment, the size of the pore is 4 - 10 nm;

[0008] Preferably, the carrier includes molecular sieve;

[0009] Preferably, the molecular sieve includes HY molecular sieve and / or SAPO molecular sieve;

[0010] Preferably, the molecular sieve is HY molecular sieve.

[0011] In one embodiment, the first active material includes first active material particles, and the particle size of the first active material particles is 2 - 5 nanometers.

[0012] In one embodiment, it further includes: a second active material, located on the surface of the carrier;

[0013] Preferably, the second active material includes second active material particles, and the particle size of the second active material particles is 2 - 10 nanometers;

[0014] Preferably, the total mass of the first active material and the second active material accounts for 0.5 - 1.5% of the mass of the carrier.

[0015] The second aspect of this application provides a preparation method of the aforementioned catalyst, including:

[0016] Pretreat the carrier so that the size of at least one pore in the carrier is 0.3 to 10 nanometers;

[0017] Load a first active material into the pores of the pretreated carrier to obtain the catalyst.

[0018] In one embodiment, the step of pretreating the carrier includes:

[0019] Soak the carrier with an acid solution;

[0020] Preferably, the concentration of the acid solution is 0.1 to 1 mol / L;

[0021] Preferably, soaking the carrier with an acid solution includes:

[0022] Mix the acid solution with the carrier and soak for 0.5 to 2 h under stirring and under a first heating condition;

[0023] Remove the stirring and the first heating condition and let stand for 0.5 to 1 h;

[0024] Preferably, the temperature of the first heating is 60 to 80 °C;

[0025] Preferably, the step of pretreating the carrier further includes:

[0026] Treat the soaked carrier to neutrality.

[0027] In one embodiment, the step of loading the first active material into the pores of the pretreated carrier includes:

[0028] Mix the pretreated carrier with a precursor of the active material to obtain a first mixture;

[0029] Calcine the first mixture to obtain the catalyst;

[0030] Preferably, the step of mixing the pretreated carrier with the precursor of the active material includes:

[0031] Mix the pretreated carrier, the precursor of the active material and a first solvent to obtain a second mixture;

[0032] Under stirring and under a second heating condition, volatilize the first solvent to obtain the first mixture;

[0033] Preferably, the precursor of the active material includes chloroplatinic acid and / or chloroiridic acid.

[0034] In one embodiment, the step of calcining the first mixture includes:

[0035] The first stage: calcine the first mixture at 500 - 600 °C for 1 - 3 h;

[0036] The second stage: calcine and reduce in a 5% H2 / N2 atmosphere at 150 - 250 °C for 1 - 3 h;

[0037] Preferably, in the first stage, heat up from room temperature to 500 - 600 °C at a heating rate of 4 - 6 °C / min;

[0038] Preferably, in the second stage, heat up from room temperature to 150 - 250 °C at a heating rate of 4 - 6 °C / min.

[0039] The third aspect of the present application provides an application of the aforementioned catalyst in the hydro - reaction of coal tar and / or directly liquefied coal oil.

[0040] In one embodiment, mix coal tar and / or directly liquefied coal oil, the catalyst and a second solvent to obtain a third mixture;

[0041] Hydro - react coal tar and / or directly liquefied coal oil under the third heating condition;

[0042] Preferably, in the third mixture, the concentration of coal tar and / or directly liquefied coal oil is 0.5 - 2 wt%, preferably 1 wt%;

[0043] Preferably, the second solvent is mesitylene;

[0044] Preferably, the temperature of the third heating is 300 - 420 °C, preferably 400 °C.

[0045] Preferably, hydro - react coal tar and / or directly liquefied coal oil in the third mixture in a flowing state, and the flow rate of the third mixture is 0.5 - 4 mL / min, preferably 1 mL / min.

[0046] According to the catalyst provided by the embodiments of the present application, the pore size in the carrier is appropriate, and the hydrogenation activity of the active material is excellent; when the catalyst of the embodiments of the present application is applied to the hydrogenation of coal tar and / or directly liquefied coal oil, coal tar and / or directly liquefied coal oil enter the pores, which is beneficial to the ring - opening reaction of coal tar and / or directly liquefied coal oil: the pore structure restricts the intermolecular interaction, promotes the anthracene molecule to carry out the ring - opening reaction along a specific path, thereby improving the reaction selectivity. At the same time, carrying out the ring - opening reaction in the pores can improve the selectivity and yield of specific products (such as naphthalene compounds), and reduce the generation of by - products. It is beneficial to obtain a fuel with a high heat sink, and the obtained fuel can take into account high density, high freezing point and thermal stability, and is suitable for aerospace vehicles. Brief Description of the Drawings

[0047] Figure 1 XRD patterns of the acid-treated HY zeolites in Examples 1 to 9 of this application.

[0048] Figure 2 XRD patterns of the catalysts in Examples 1 to 4, and Comparative Example 1 of this application.

[0049] Figure 3 Elution order of the products and raw materials in Examples 1 to 16 of this application in the chromatogram.

[0050] Figure 4 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 1 of this application.

[0051] Figure 5 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 2 of this application.

[0052] Figure 6 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 3 of this application.

[0053] Figure 7 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 4 of this application.

[0054] Figure 8 XRD patterns of the catalysts in Examples 5 to 8, and Comparative Example 3 of this application.

[0055] Figure 9 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 5 of this application.

[0056] Figure 10 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 6 of this application.

[0057] Figure 11 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 7 of this application.

[0058] Figure 12 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 8 of this application.

[0059] Figure 13 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 9 of this application.

[0060] Figure 14 XRD patterns of the acid-treated zeolites in Examples 10 to 12 of this application.

[0061] Figure 15 XRD patterns of the catalysts in Examples 10 to 12, and Comparative Example 4 of this application.

[0062] Figure 16 Anthracene hydrogenation reaction performance diagram of the catalyst in Example 10 of this application.

[0063] Figure 17 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Example 11 of this application.

[0064] Figure 18 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Example 12 of this application.

[0065] Figure 19 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Example 13 of this application.

[0066] Figure 20 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Example 14 of this application.

[0067] Figure 21 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Example 15 of this application.

[0068] Figure 22 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Example 16 of this application.

[0069] Figure 23 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Comparative Example 1.

[0070] Figure 24 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Comparative Example 2.

[0071] Figure 25 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Comparative Example 3.

[0072] Figure 26 It is the anthracene hydrogenation reaction performance diagram of the catalyst in Comparative Example 4. Detailed implementation manners

[0073] Next, the technical solutions in the embodiments of this application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of this application. Obviously, the described embodiments are only a part of the embodiments of this application, rather than all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of this application.

[0074] In addition, in order to better illustrate this application, numerous specific details are given in the following detailed implementation manners. Those skilled in the art should understand that this application can be implemented without some specific details. In some instances, methods and means well-known to those skilled in the art are not described in detail so as to highlight the gist of this application.

[0075] It should be noted that similar reference numerals and letters indicate similar items in the following drawings. Therefore, once an item is defined in one drawing, it does not need to be further defined and explained in subsequent drawings.

[0076] In addition, terms such as "first" and "second" are only used for distinguishing descriptions and should not be construed as indicating or implying relative importance.

[0077] The first aspect of the present application provides a catalyst, comprising: a carrier and a first active material. The carrier includes at least one pore, and the size of the pore is 0.3 to 10 nanometers, for example, it can be 0.3 nanometers, 2 nanometers, 4 nanometers, 6 nanometers, 8 nanometers or 10 nanometers, etc.; at least part of the first active material is located in the pore, and the first active material includes platinum and / or iridium.

[0078] According to the catalyst provided by the embodiments of the present application, the size of the pores in the carrier is appropriate, and the first active material has excellent hydrogenation activity; when the catalyst of the embodiments of the present application is applied to the hydrogenation of coal tar and / or direct coal liquefaction oil, the coal tar and / or direct coal liquefaction oil enter the pores, which is beneficial to the ring-opening reaction of coal tar and / or direct coal liquefaction oil, beneficial to obtaining a fuel with high heat sink, and the obtained fuel can take into account high density, high freezing point and thermal stability, and is suitable for aerospace vehicles.

[0079] In a preferred embodiment, the size of the pore is 4 to 10 nm.

[0080] Exemplarily, compared with the above pore size, when the pore size is less than 0.3 nanometers, the active metal sites are likely to accumulate on the surface of the catalyst, and it is difficult for the reaction raw materials to enter the pores. While the effective surface area of the reaction decreases, the pore effect is not utilized, which is not conducive to improving the selectivity of a certain type of product directionally. When the pore size is between 0.3 and 10 nanometers, the hydrogenation active sites can fall into the effective pores, and the appropriate pore size promotes the high conversion rate and high selectivity of a certain type of product.

[0081] It can be understood that the pore can be a through-hole penetrating the carrier or a blind hole not penetrating the carrier. The pore can extend in a straight line or in a curve.

[0082] Optionally, when the first active material is located in the pore, the first active material is loaded on the side wall of the pore.

[0083] In one embodiment, the carrier includes a molecular sieve. Thus, the molecular sieve has a rich pore structure, which is beneficial to the loading of the active material in the pores.

[0084] It should be noted that the molecular sieve in the embodiments of the present application can be an untreated molecular sieve or a pretreated molecular sieve. Optionally, the pretreatment includes performing a pore expansion treatment on the molecular sieve to enlarge the original pore size of the molecular sieve so that the pore size meets 0.3 to 10 nanometers.

[0085] In one embodiment, the molecular sieve includes HY molecular sieve and / or SAPO molecular sieve; exemplarily, the molecular sieve is HY molecular sieve. Thus, the HY molecular sieve has hierarchical pores and a relatively large pore size.

[0086] It can be understood that the pore size refers to the size of the pore in the cross-section perpendicular to the extension direction of the pore, which can be the maximum distance between any two points in the cross-section.

[0087] In one embodiment, the first active material includes first active material particles with a particle size of 2 to 5 nanometers, for example, it can be 2 nanometers, 3 nanometers, 4 nanometers, or 5 nanometers, etc. Thus, the particle size of the first active material particles matches the pore size, which is conducive to the first active material particles being loaded in the pores, and further conducive to hydrogenating the reactants in the pores.

[0088] In one embodiment, the catalyst further includes a second active material located on the surface of the carrier. Optionally, the second active material includes second active material particles with a particle size of 2 to 10 nanometers, for example, it can be 2 nanometers, 3 nanometers, 4 nanometers, 5 nanometers, 6 nanometers, 7 nanometers, 8 nanometers, 9 nanometers, or 10 nanometers, etc. Thus, the second active particles located on the surface of the carrier can first perform preliminary hydrogenation treatment on the reaction substrate. After the hydrogenation treatment, the intermediate product enters the pores and undergoes a hydrogenation ring-opening reaction with the first active material to obtain the target product.

[0089] In one embodiment, the total mass of the first active material and the second active material accounts for 0.5 to 1.5% of the mass of the carrier, for example, it can be 0.5%, 0.8%, 1%, 1.2%, or 1.5%, etc. The loading amount of the first active material is appropriate, and the hydrogenation effect is excellent.

[0090] The second aspect of the present application provides a preparation method of the aforementioned catalyst, and this preparation method includes the following steps.

[0091] S100: Pretreat the carrier so that the size of at least one pore in the carrier is 0.3 to 10 nanometers.

[0092] In one embodiment, the step of pretreating the carrier includes: soaking the carrier with an acid solution. Thus, the acid solution can corrode the pores in the carrier, making the pore size larger.

[0093] In one embodiment, the concentration of the acid solution is 0.1 - 1 mol / L. For example, it can be 0.1 mol / L, 0.3 mol / L, 0.5 mol / L, 0.7 mol / L, 1 mol / L, etc.

[0094] In one embodiment, using the acid solution to soak the carrier includes: mixing the acid solution with the carrier, soaking for 0.5 - 2 h (for example, it can be 0.5 h, 1 h, 1.5 h, 2 h, etc.) under stirring and the first heating condition, removing the stirring and the first heating condition, and standing for 0.5 - 1 h (for example, it can be 0.5 h, 0.6 h, 0.8 h, 1 h, etc.). Thus, the acid solution can effectively corrode the pores in the carrier, making the pore size larger.

[0095] In one embodiment, the temperature of the first heating is 60 - 80 °C. For example, it can be 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, etc. Compared with the above heating temperature, when the temperature of the first heating is less than 60 °C, it is not conducive to the rapid formation of the pore diameter, resulting in a hierarchical pore molecular sieve carrier with similar pore diameters obtained by treating with different acid concentrations; when the temperature of the first heating is greater than 80 °C, it is easy for the molecular sieve to react excessively, forming products such as amorphous silica.

[0096] In one embodiment, the step of pre-treating the carrier further includes: treating the soaked carrier to be neutral. Thus, it is beneficial to avoid further corrosion of the pores in the carrier.

[0097] S200: Loading a first active material into the pores of the pre-treated carrier to obtain the catalyst.

[0098] In one embodiment, the step of loading the first active material into the pores of the pre-treated carrier includes: mixing the pre-treated carrier with a precursor of the active material to obtain a first mixture; calcining the first mixture to obtain the catalyst. Exemplarily, the precursor of the active material includes chloroplatinic acid and / or chloroiridic acid.

[0099] It can be understood that after mixing the pre-treated carrier with the precursor of the active material, part of the precursor of the active material enters the pores of the carrier, and part of the precursor of the active material coats the surface of the carrier. After calcination, in the obtained catalyst, there is a first active material in the pores, and a second active material on the surface of the carrier; and the first active material and the second active material are consistent with the previous description, and will not be elaborated here too much.

[0100] In one embodiment, the step of mixing the pretreated support with the active material precursor includes: mixing the pretreated support, the active material precursor, and a first solvent to obtain a second mixture; and volatilizing the first solvent under stirring and under a second heating condition to obtain the first mixture. Thus, the active material precursor can enter the pore structure of the support, which is conducive to obtaining the first active material particles loaded in the pores.

[0101] In one embodiment, the step of calcining the first mixture includes: a first stage: calcining the first mixture at 500 - 600 °C

[0102] (such as 500 °C, 520 °C, 550 °C, 580 °C, or 600 °C, etc.) for 1 - 3 h (such as 1 h, 2 h, or 3 h, etc.); when the temperature in the first stage is too high, metal active sites are prone to agglomeration and problems such as pore blockage may occur. When the heating temperature in the first stage is relatively low, the interaction between the metal site system and the molecular sieve is not strong. A second stage: calcining and reducing in a 5% H2 / N2 atmosphere at 150 - 250 °C (such as 150 °C, 180 °C, 200 °C, 230 °C, or 250 °C, etc.) for 1 - 3 h (such as 1 h, 2 h, or 3 h, etc.). When the temperature in the second stage is relatively high, the metal is prone to agglomeration and pore blockage may occur; when the temperature in the second stage is relatively low, the active metal is not completely reduced to the metallic state, and there is a dynamic imbalance during performance evaluation, resulting in inaccurate test data.

[0103] It can be understood that the calcination treatments in the first stage and the second stage can be carried out in the same device or in different devices respectively. For example, the first - stage calcination is carried out in a muffle furnace, taken out after cooling to room temperature, and then the second - stage calcination is carried out in an atmosphere furnace.

[0104] In one embodiment, in the first stage, the temperature is raised from room temperature (such as 15 - 35 °C) to 500 - 600 °C at a heating rate of 4 - 6 °C / min (such as 4 °C / min, 5 °C / min, or 6 °C / min, etc.).

[0105] In one embodiment, in the second stage, the temperature is raised from room temperature (such as 15 - 35 °C) to 150 - 250 °C at a heating rate of 4 - 6 °C / min (such as 4 °C / min, 5 °C / min, or 6 °C / min, etc.).

[0106] The third aspect of the present application provides an application of the foregoing catalyst in the hydro - reaction of coal tar and / or direct coal liquefaction oil.

[0107] Exemplarily, the catalyst is applied to the hydro - reaction of anthracene.

[0108] In one embodiment, coal tar and / or directly liquefied coal oil, the catalyst, and a second solvent are mixed to obtain a third mixture; the coal tar and / or directly liquefied coal oil is hydrogenated under a third heating condition. Thus, the coal tar and / or directly liquefied coal oil can enter the pores of the support, and the active material in the pores catalyzes the hydrogenation of the coal tar and / or directly liquefied coal oil, facilitating the ring-opening reaction of the coal tar and / or directly liquefied coal oil to obtain a fuel with a higher heat sink.

[0109] In one embodiment, in the third mixture, the concentration of coal tar and / or directly liquefied coal oil is 0.5 - 2 wt%, preferably 1 wt%.

[0110] In one embodiment, the second solvent is mesitylene.

[0111] In one embodiment, the temperature of the third heating is 300 - 420 °C (for example, it can be 300 °C, 320 °C, 340 °C, 360 °C, 380 °C, 400 °C or 420 °C, etc.), preferably 400 °C.

[0112] In one embodiment, the coal tar and / or directly liquefied coal oil in the third mixture is hydrogenated in a flowing state, and the flow rate of the third mixture is 0.5 - 4 mL / min, for example, it can be 0.5 mL / min, 1 mL / min, 2 mL / min, 3 mL / min or 4 mL / min, etc., preferably 1 mL / min.

[0113] The following further elaborates on the present application in combination with specific embodiments. It should be noted that the following embodiments are only used to explain the present application and should not be construed as a limitation to the present application.

[0114] It should be noted that in the following embodiments, unless otherwise specified, in the reaction products, 8H-anthracene (hydrogenated) represents the hydrogenation product 8H-anthracene, 2H-anthracene (hydrogenated) represents the hydrogenation product 2H-anthracene, 6H-anthracene (hydrogenated) represents the hydrogenation product 6H-anthracene, 4H-anthracene (hydrogenated) represents the hydrogenation product 4H-anthracene, and 8H-anthracene (ring-opening) represents the ring-opening product 8H-anthracene.

[0115] Example 1

[0116] The preparation method of the catalyst includes the following steps:

[0117] Weigh 10 g of commercial HY zeolite (Si / Al ratio is 5.3), and add it together with 100 mL of 0.1 mol / L hydrochloric acid solution into a round-bottom flask, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices, and let it stand for half an hour. Then, wash and centrifuge the treated HY zeolite with deionized water until it is neutral, and dry it overnight at room temperature. The finally collected zeolite sample will be labeled as HY(0.1M). The XRD (X-ray diffraction) of HY(0.1M) is shown in Figure 1 .

[0118] Put 3 g of HY(0.1M) and 0.064 g of H2PtCl6 (the theoretical mass of platinum is 1 wt% of the support) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to make the zeolite and the platinum precursor evenly mixed. Transfer the obtained powder to a muffle furnace, calcine it at 550 °C for 2 hours, and the heating rate is 5 °C / min. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours, and the heating rate is 5 °C / min to obtain a catalyst, labeled as Pt / HY(0.1M)-1%, and its XRD is shown in Figure 2 . Performance test of the catalyst:

[0119] Load 1 g of Pt / HY(0.1M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the performance of the anthracene hydrogenation reaction in the range of 300 - 420 °C, and the heating rate is 10 °C / min. Test one data point for every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, conduct qualitative and quantitative data analysis of the products with GC-MS (gas chromatography-mass spectrometry) to calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst. The products obtained from this reaction are as shown in Figure 3 , and the main products obtained are 8H-anthracene (hydrogenation), 2H-anthracene (hydrogenation), 6H-anthracene (hydrogenation), 4H-anthracene (hydrogenation), 8H-anthracene (ring opening), and iso-anthracene. After GC-MS analysis of the products, the results are as shown in Figure 4The conversion rate and selectivity shown. The conversion rate of anthracene basically remains between 98% and 100% as the temperature increases. The main products of the catalytic conversion of anthracene are the ring-opening products of anthracene and 4H-anthracene products. Among them, the selectivity of 4H-anthracene products decreases as the temperature increases, indicating that with the increase of temperature, the deep hydrogenation of anthracene is promoted. The selectivity of which remains almost unchanged, while the selectivity of ring-opening products increases as the temperature increases and reaches 46.70% at 380 °C, indicating that high temperature is beneficial to the formation of ring-opening products, but too high temperature will affect the performance of the catalyst.

[0120] Example 2

[0121] Weigh 10 grams of commercial HY zeolite (Si / Al ratio is 5.3), add it to a round-bottom flask together with 100 mL of 0.3 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. After that, centrifuge the treated HY zeolite with deionized water until it is neutral and dry it overnight at room temperature. The finally collected zeolite sample will be labeled as HY(0.3M), and the XRD of HY(0.3M) is shown in Figure 1 .

[0122] Put 3 grams of the treated HY(0.3M) and 0.064 grams of H2PtCl6 (the theoretical mass of platinum is 1 wt% of the carrier) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to make the zeolite and platinum precursor evenly mixed. Transfer the obtained powder to a muffle furnace and calcine it at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours with a heating rate of 5 °C / min to obtain a catalyst labeled as Pt / HY(0.3M)-1%, and its XRD is shown in Figure 2 .

[0123] Load 1 gram of the Pt / HY(0.3M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the performance of the anthracene hydrogenation reaction in the range of 300 - 420 °C with a heating rate of 10 °C / min. Test one data point every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, conduct qualitative and quantitative data analysis of the products with GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0124] After analyzing the products by GC-MS, the results are as shown in Figure 5The conversion rate and selectivity changes are shown as follows. The conversion rate of anthracene increases with the increase of temperature, and there is a slight decrease in the conversion rate at 400 - 420 °C, and the highest value of the conversion rate reaches 97.68% at 380 °C. The main products of the catalytic conversion of anthracene are 2H-anthracene, 4H-anthracene and the ring-opening products of anthracene. Among them, the selectivity of 2H-anthracene decreases with the increase of temperature, indicating that with the increase of temperature, the deep hydrogenation of anthracene is promoted. The selectivity of the 4H-anthracene product remains almost unchanged, while the selectivity of the ring-opening products increases with the increase of temperature and reaches 33.00% at 400 °C, indicating that high temperature is beneficial to the formation of ring-opening products, but too high temperature will affect the performance of the catalyst.

[0125] Example 3

[0126] Weigh 10 grams of commercial HY molecular sieve (Si / Al ratio is 5.3), add it to a round-bottom flask together with 100 mL of 0.5 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. Then, centrifuge the treated HY-type molecular sieve with deionized water until it is neutral, and dry it overnight at room temperature. The finally collected molecular sieve sample will be labeled as HY(0.5M). The XRD of HY(0.5M) is shown in Figure 1 .

[0127] Put 3 grams of the treated HY(0.5M) and 0.064 grams of H2PtCl6 (the theoretical mass of platinum is 1 wt% of the carrier) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to make the molecular sieve and the platinum precursor evenly mixed. Transfer the obtained powder to a muffle furnace and calcine it at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours with the same heating rate of 5 °C / min to obtain the catalyst, labeled as Pt / HY(0.5M)-1%, and its XRD is shown in Figure 2 .

[0128] Load 1 gram of the Pt / HY(0.5M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the hydrogenation reaction performance of anthracene in the range of 300 - 420 °C with a heating rate of 10 °C / min. Test one data point every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, conduct qualitative and quantitative data analysis of the products with GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0129] After analyzing the product by GC-MS, the conversion rate and selectivity changes as shown in Figure 6 were obtained. The conversion rate of anthracene increased with the increase of temperature and reached 99.98% at 400 °C and 420 °C, almost completely converted. The main products of anthracene catalytic conversion were 2H-anthracene, 4H-anthracene and the ring-opening products of anthracene. Among them, the selectivity of 2H-anthracene and 4H-anthracene generally showed a downward trend with the increase of temperature, indicating that the deep hydrogenation of anthracene was promoted with the increase of temperature. The selectivity of the ring-opening products increased with the increase of temperature and reached 50.85% at 400 °C, indicating that high temperature was beneficial to the formation of ring-opening products, and the types of ring-opening products increased sharply from 380 to 420 °C.

[0130] Example 4

[0131] Weigh 10 g of commercial HY zeolite (Si / Al ratio is 5.3), add it to a round-bottom flask together with 100 mL of 0.7 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. Then, centrifuge the treated HY zeolite with deionized water until it is neutral and dry it overnight at room temperature. The finally collected zeolite sample will be labeled as HY(0.7M). The XRD of HY(0.7M) is shown in Figure 1 .

[0132] Put 3 g of the treated HY(0.7M) and 0.064 g of H2PtCl6 (the theoretical mass of platinum is 1 wt% of the support) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to uniformly mix the zeolite and the platinum precursor. Transfer the obtained powder to a muffle furnace, calcine it at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, reduce it at 200 °C for 2 hours in a 5% H2 / N2 atmosphere with the same heating rate of 5 °C / min to obtain a catalyst, labeled as Pt / HY(0.7M)-1%, and its XRD is shown in Figure 2 .

[0133] Load 1 g of the Pt / HY(0.7M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the performance of anthracene hydrogenation reaction in the range of 300 - 420 °C with a heating rate of 10 °C / min. Test one data point every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, perform qualitative and quantitative data analysis on the product by GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst. The mass spectrum of its product is shown inFigure 3 。

[0134] After performing GC-MS analysis on the product, the conversion rate and selectivity changes as shown in Figure 7 were obtained. The conversion rate of anthracene increased with the increase of temperature and reached 97.60% at 400 °C. The main products of the catalytic conversion of anthracene were 2H-anthracene, 4H-anthracene and the ring-opening products of anthracene. Among them, the selectivities of 2H-anthracene and 4H-anthracene showed a downward trend with the increase of temperature, but the selectivities of 2H and 4H-anthracene products remained above 60%. The selectivity of the ring-opening products increased with the increase of temperature and reached 28.92% at 420 °C, indicating that high temperature is beneficial to the formation of ring-opening products.

[0135] Example 5

[0136] Weigh 10 g of commercial HY zeolite (Si / Al ratio is 5.3), add it to a round-bottom flask together with 100 mL of 0.1 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. Then, centrifuge the treated HY zeolite with deionized water until it is neutral and dry it overnight at room temperature. The finally collected zeolite sample will be labeled as HY(0.1M). The XRD of HY(0.1M) is shown in Figure 1 。

[0137] Put 3 g of the treated HY(0.1M) and 0.0857 g of H2IrCl6 (the theoretical mass of iridium is 1 wt% of the support) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to uniformly mix the zeolite and the iridium precursor. Transfer the obtained powder to a muffle furnace, calcine it at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, reduce it at 200 °C for 2 hours in a 5% H2 / N2 atmosphere with the same heating rate of 5 °C / min to obtain a catalyst, labeled as Ir / HY(0.1M)-1%, and its XRD is shown in Figure 8 。Load 1 g of the Ir / HY(0.1M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the hydrogenation reaction performance of anthracene in the range of 300 - 420 °C with a heating rate of 10 °C / min. Test one data point for every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and perform qualitative and quantitative data analysis on the product with GC-MS after the experiment to calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0138] After analyzing the products by GC-MS, the conversion rate and selectivity changes as shown in Figure 9 were obtained. The conversion rate of anthracene increased with the increase of temperature and reached 79.18% at 420 °C. The main products obtained were 2H-anthracene, 4H-anthracene and the ring-opening products of anthracene (mainly 8H-anthracene). Among them, the selectivity of the hydrogenation products first increased and then decreased slowly with the increase of temperature, and the selectivity of the 8H-anthracene (ring-opening) product was at a relatively low level in the high-temperature section, indicating that the HY did not obtain suitable pores to promote the catalytic conversion of anthracene after being treated with 0.1M acid.

[0139] Example 6

[0140] Weigh 10 g of commercial HY molecular sieve (Si / Al ratio is 5.3), add it to a round-bottom flask together with 100 mL of 0.3 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. Then, centrifuge the treated HY-type molecular sieve with deionized water until it is neutral and dry it overnight at room temperature. The finally collected molecular sieve sample will be labeled as HY(0.3M). The XRD of HY(0.3M) is shown in Figure 1 .

[0141] Put 3 g of the treated HY(0.3M) and 0.0857 g of H2IrCl6 (the theoretical mass of iridium is 1 wt% of the carrier) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to make the molecular sieve and the iridium precursor evenly mixed. Transfer the obtained powder to a muffle furnace and calcine it at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours with the same heating rate of 5 °C / min to obtain a catalyst, labeled as Ir / HY(0.3M)-1%, and its XRD is shown in Figure 8 .

[0142] Load 1 g of the Ir / HY(0.3M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the performance of the anthracene hydrogenation reaction in the range of 300 - 420 °C with a heating rate of 10 °C / min. Test one data point every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, perform qualitative and quantitative data analysis of the products by GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0143] After analyzing the products by GC-MS, the results as shown in Figure 10The shown changes in conversion rate and selectivity. The conversion rate of anthracene increases with the increase in temperature and reaches 97.16% at 420 °C. The main products obtained are 2H-anthracene, 4H-anthracene and anthracene ring-opening products (mainly 8H-anthracene). Among them, the selectivity of the hydrogenation products slowly decreases with the increase in temperature, and the selectivity of the 8H-anthracene (ring-opening) product increases with the increase in temperature and reaches 23.74% at 400 °C.

[0144] Example 7

[0145] Weigh 10 grams of commercial HY zeolite (Si / Al ratio is 5.3), add it to a round-bottom flask together with 100 mL of 0.5 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. After that, centrifuge the treated HY zeolite with deionized water until it is neutral and dry it overnight at room temperature. The finally collected zeolite sample will be labeled as HY(0.5M). The XRD of HY(0.5M) is shown in Figure 1 .

[0146] Put 3 grams of the treated HY(0.5M) and 0.0857 grams of H2IrCl6 (the theoretical mass of iridium is 1 wt% of the support) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to uniformly mix the zeolite and the iridium precursor. Transfer the obtained powder to a muffle furnace, calcine it at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours with the same heating rate of 5 °C / min to obtain a catalyst, labeled as Ir / HY(0.5M)-1%, and its XRD is shown in Figure 8 .

[0147] Load 1 gram of the Ir / HY(0.1M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the performance of the anthracene hydrogenation reaction in the range of 300 - 420 °C with a heating rate of 10 °C / min. Test one data point for every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, perform qualitative and quantitative data analysis of the products with GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0148] After performing GC-MS analysis on the products, we obtain as shown in Figure 11The conversion rate and selectivity shown. The conversion rate of anthracene increases with the increase of temperature and reaches 97.19% at 420 °C. The main products obtained are 2H-anthracene, 4H-anthracene, and anthracene ring-opening products (mainly 8H-anthracene). Among them, the selectivity of the hydrogenation products slowly decreases with the increase of temperature, and the selectivity of the 8H-anthracene (ring-opening) product increases with the increase of temperature and reaches 24.15% at 400 °C.

[0149] Example 8

[0150] Weigh 10 grams of commercial HY zeolite (Si / Al ratio is 5.3), add it to a round-bottom flask together with 100 mL of 0.7 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. Then, centrifuge the treated HY zeolite with deionized water until it is neutral and dry it overnight at room temperature. The finally collected zeolite sample will be labeled as HY(0.7M). The XRD of HY(0.7M) is shown in Figure 1 .

[0151] Put 3 grams of the treated HY(0.7M) and 0.0857 grams of H2IrCl6 (the theoretical mass of iridium is 1 wt% of the carrier) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to make the zeolite and the iridium precursor evenly mixed. Transfer the obtained powder to a muffle furnace and calcine it at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, reduce it at 200 °C for 2 hours in a 5% H2 / N2 atmosphere with the same heating rate of 5 °C / min. The sample obtained is labeled as Ir / HY(0.7M)-1%. Its XRD is shown in Figure 8 .

[0152] Load 1 gram of the Ir / HY(0.7M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the performance of the anthracene hydrogenation reaction in the range of 300 - 420 °C with a heating rate of 10 °C / min. Test one data point every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, conduct qualitative and quantitative data analysis of the products with GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0153] After analyzing the products by GC-MS, we obtain as shown in Figure 12The conversion rate and selectivity shown. The conversion rate of anthracene first increases and then decreases with the increase of temperature. The conversion rate reaches 87.97% at 360 °C. As the conversion rate decreases with the increase of temperature, it indicates that the structure of the HY molecular sieve treated with 0.7M hydrochloric acid may have collapsed and is prone to deactivation at high temperatures. With the increase of temperature, the 2H-anthracene product is further hydrogenated to form the 4H-anthracene product, while the selectivity of the ring-opening product does not increase but decreases, indicating catalyst deactivation in this process.

[0154] Example 9

[0155] Weigh 10 grams of commercial HY molecular sieve (Si / Al ratio is 5.3), add it to a round-bottom flask together with 100 milliliters of 0.5 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. After that, centrifuge the treated HY-type molecular sieve with deionized water until it is neutral and dry it overnight at room temperature. The finally collected molecular sieve sample will be labeled as HY(0.5M). The XRD of HY(0.5M) is shown in Figure 1 .

[0156] Put 3 grams of treated HY(0.7M), 0.032 grams of H2PtCl6, and 0.0428 grams of H2IrCl6 (where the theoretical masses of platinum and iridium are 0.05 wt% of the support respectively) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to uniformly mix the molecular sieve with the platinum and iridium precursors. Transfer the obtained powder to a muffle furnace and calcine it at 550 °C for 2 hours with a heating rate of 5 °C / minute. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours with the same heating rate of 5 °C / minute. The sample obtained is labeled as PtIr / HY(0.5M)-1%.

[0157] Load 1 gram of the PtIr / HY(0.5M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the performance of the anthracene hydrogenation reaction in the range of 300 - 420 °C with a heating rate of 10 °C / minute. Test one data point for every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, conduct qualitative and quantitative data analysis of the products with GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0158] After analyzing the products by GC-MS, we obtain as shown in Figure 13The conversion rate and selectivity shown. The conversion rate of anthracene increases with the increase of temperature and reaches 99.01% at 400 °C. Its main products are the ring-opening products of 8H-anthracene and 4H-anthracene products. The selectivity of the ring-opening products increases with the increase of temperature and reaches the highest value of 50.06% at 400 °C. At the same time, with the increase of temperature, the conversion rate of 4H-anthracene products decreases. When the temperature increases to 420 °C, the selectivity of the ring-opening products does not increase but decreases, indicating that this temperature is likely to cause the inactivation of the catalyst.

[0159] Example 10

[0160] Weigh 10 grams of commercial SAPO molecular sieve (Si / Al ratio is 0.5), add it to a round-bottom flask together with 100 mL of 0.1 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. After that, centrifuge the treated SAPO-type molecular sieve with deionized water until it is neutral and dry it overnight at room temperature. The finally collected molecular sieve sample will be labeled as SAPO(0.1M). The XRD of SAPO(0.1M) is shown in Figure 14 .

[0161] Put 3 grams of the treated SAPO(0.1M) and 0.0857 grams of H2IrCl6 (the theoretical mass of iridium is 1 wt% of the carrier respectively) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to make the molecular sieve and the iridium precursor evenly mixed. Transfer the obtained powder to a muffle furnace and calcine it at 550 °C for 2 hours with a heating rate of 5 °C / minute. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours with the same heating rate of 5 °C / minute. The obtained sample is labeled as Ir / SAPO(0.1M)-1%. The XRD results are shown in Figure 15 .

[0162] Load 1 gram of the Ir / SAPO(0.1M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the performance of the anthracene hydrogenation reaction in the range of 300 - 420 °C with a heating rate of 10 °C / minute. Test one data point every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, conduct qualitative and quantitative data analysis of the products with GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0163] After analyzing the products by GC-MS, we get as shown in Figure 16The conversion rate and selectivity shown. The conversion rate of anthracene increases with the increase of temperature and reaches 90.02% at 420 °C. Its main product is the 4H-anthracene product, and its selectivity increases with the increase of temperature, reaching 72.52% at 380 °C, and then decreases with the increase of temperature, with deep hydrogenation to the 6H-anthracene product.

[0164] Example 11

[0165] Weigh 10 grams of commercial SAPO molecular sieve (Si / Al ratio is 0.5), add it to a round-bottom flask together with 100 mL of 0.3 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. After that, centrifuge the treated SAPO-type molecular sieve with deionized water until it is neutral, and dry it overnight at room temperature. The finally collected molecular sieve sample will be labeled as SAPO(0.3M). The XRD results of SAPO(0.3M) are shown in Figure 14 .

[0166] Put 3 grams of the treated SAPO(0.3M) and 0.0857 grams of H2IrCl6 (the theoretical mass of iridium is 1 wt% of the carrier respectively) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to make the molecular sieve and the iridium precursor evenly mixed. Transfer the obtained powder to a muffle furnace and calcine it at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours with the same heating rate of 5 °C / min. The sample obtained is labeled as Ir / SAPO(0.3M)-1%. The XRD results are shown in Figure 15 .

[0167] Load 1 gram of the Ir / SAPO(0.3M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the performance of the anthracene hydrogenation reaction in the range of 300 - 420 °C with a heating rate of 10 °C / min. Test one data point every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, perform qualitative and quantitative data analysis of the products with GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0168] After performing GC-MS analysis on the products, we obtain as shown in Figure 17The conversion rate and selectivity shown. The conversion rate of anthracene increases with the increase of temperature and reaches 73.82% at 420 °C. Its main product is the 4H-anthracene product, and its selectivity increases with the increase of temperature, reaching 75.32% at 380 °C, and then decreases with the increase of temperature, with deep hydrogenation to the 6H-anthracene product.

[0169] Example 12

[0170] Weigh 10 grams of commercial SAPO molecular sieve (Si / Al ratio is 0.5), add it to a round-bottom flask together with 100 mL of 0.5 mol / L hydrochloric acid solution, and stir at 70 °C for 1 hour. Subsequently, turn off the heating and stirring devices and let it stand for half an hour. After that, centrifuge the treated SAPO-type molecular sieve with deionized water until it is neutral, and dry it overnight at room temperature. The finally collected molecular sieve sample will be labeled as SAPO(0.5M). The XRD results of SAPO(0.5M) are shown in Figure 14 .

[0171] Put 3 grams of the treated SAPO(0.5M) and 0.0857 grams of H2IrCl6 (where the theoretical mass of iridium is 1 wt% of the support) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to make the molecular sieve and the iridium precursor evenly mixed. Transfer the obtained powder to a muffle furnace and calcine it at 550 °C for 2 hours with a heating rate of 5 °C / minute. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours with the same heating rate of 5 °C / minute. The obtained sample is labeled as Ir / SAPO(0.5M)-1%. The XRD results of it are shown in Figure 15 .

[0172] Load 1 gram of the Ir / SAPO(0.5M)-1% catalyst into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and block both ends with quartz wool. Install the quartz tube in a high-pressure fixed-bed reactor, set the reaction pressure to 5 MPa, and the hydrogen flow rate to 36 mL / min. Test the hydrogenation reaction performance of anthracene in the range of 300 - 420 °C with a heating rate of 10 °C / minute. Test one data point for every 20 °C increase, and keep each temperature for 20 minutes. The liquid feed is 1% anthracene (the solvent is mesitylene), and the flow rate is 3.5 mL / min. At each temperature point, collect the reaction liquid, and after the experiment, conduct qualitative and quantitative data analysis of the products with GC-MS, and calculate the conversion rate and selectivity of the reaction products to evaluate the performance of the catalyst.

[0173] After analyzing the products by GC-MS, we get as Figure 18The conversion rate and selectivity shown. The conversion rate of anthracene increases with the increase of temperature, reaching 88.40% at 400 °C, and then decreases with the increase of temperature, indicating that the stability of SAPO after treatment with 0.5 M hydrochloric acid has decreased significantly. Its main product is the 4H-anthracene product, and its selectivity increases with the increase of temperature, reaching 74.9% at 400 °C, and then decreases with the increase of temperature, with deep hydrogenation to the 6H-anthracene product.

[0174] Example 13

[0175] The preparation method of the catalyst in this example is basically the same as that in Example 1, except that the flow rate of the raw material liquid in the performance test is adjusted to 1 mL / min. At each temperature point, the reaction liquid is collected, and after the experiment, GC-MS is used to conduct qualitative and quantitative data analysis on the products, and the conversion rate and selectivity of the reaction products are calculated to evaluate the performance of the catalyst.

[0176] After analyzing the products by GC-MS, the conversion rate and selectivity as shown in Figure 19 are obtained. Under this reaction condition, the selectivity of the conversion rate of anthracene does not change significantly, and generally shows a tendency to approach 100%. The main product is the 8H-anthracene (ring-opening) product, and the yield of this product first increases and then decreases with the increase of temperature, reaching the highest value of 66.89% at 360 °C, indicating that with the increase of temperature, it is beneficial to the formation of the 8H-anthracene (ring-opening) product, but with the further increase of temperature, the formation of deep hydrogenation products such as C12 - C13 occupies the main position.

[0177] Example 14

[0178] The preparation method of the catalyst in this example is basically the same as that in Example 2, except that the flow rate of the raw material liquid in the performance test is adjusted to 1 mL / min. At each temperature point, the reaction liquid is collected, and after the experiment, GC-MS is used to conduct qualitative and quantitative data analysis on the products, and the conversion rate and selectivity of the reaction products are calculated to evaluate the performance of the catalyst.

[0179] After analyzing the products by GC-MS, the conversion rate and selectivity as shown in Figure 20 are obtained. Under this reaction condition, the selectivity of the conversion rate of anthracene does not change significantly, and generally shows a tendency to approach 100%. The main product is the deep hydrogenation product, indicating that with the increase of temperature, the anthracene entering the pores is more likely to produce deep hydrogenation products.

[0180] Example 15

[0181] The preparation method of the catalyst in this example is basically the same as that in Example 3, except that the flow rate of the raw material liquid in the performance test is adjusted to 1 mL / min. At each temperature point, the reaction liquid is collected, and after the experiment, GC-MS is used to conduct qualitative and quantitative data analysis on the products, and the conversion rate and selectivity of the reaction products are calculated to evaluate the performance of the catalyst.

[0182] After analyzing the products by GC-MS, the conversion rate and selectivity as shown in Figure 21 are obtained. Under this reaction condition, the conversion rate of anthracene shows no obvious change in selectivity, and generally approaches 100%. Among them, the products are mainly deep hydrogenation products, indicating that with the increase of temperature, the anthracene entering the pores is more likely to produce deep hydrogenation products.

[0183] Example 16

[0184] The preparation method of the catalyst in this example is basically the same as that in Example 4, except that the flow rate of the raw material liquid in the performance test is adjusted to 1 mL / min. At each temperature point, the reaction liquid is collected, and after the experiment, GC-MS is used to conduct qualitative and quantitative data analysis on the products, and the conversion rate and selectivity of the reaction products are calculated to evaluate the performance of the catalyst.

[0185] After analyzing the products by GC-MS, the conversion rate and selectivity as shown in Figure 22 are obtained. Under this reaction condition, the conversion rate of anthracene shows no obvious change in selectivity, and generally approaches 100%. Among them, the products are mainly deep hydrogenation products, indicating that with the increase of temperature, the anthracene entering the pores is more likely to produce deep hydrogenation products.

[0186] Comparative Example 1

[0187] Put 3 g of untreated HY and 0.064 g of H2PtCl6 (where the theoretical mass of platinum is 1 wt% of the support) into a beaker, add an appropriate amount of ethanol, heat and stir until the ethanol evaporates to make the molecular sieve and the platinum precursor evenly mixed. Transfer the obtained powder to a muffle furnace and calcine it at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, reduce it in a 5% H2 / N2 atmosphere at 200 °C for 2 hours with the same heating rate of 5 °C / min. The sample obtained is labeled as Pt / HY-1%, and its XRD is shown in Figure 2 .

[0188] 1 g of the Pt / HY-1% catalyst was loaded into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and both ends were blocked with quartz wool. The quartz tube was installed in a high-pressure fixed-bed reactor, and the reaction pressure was set at 5 MPa and the hydrogen flow rate was 36 mL / min. The performance of anthracene hydrogenation reaction was tested in the range of 300 - 420 °C with a heating rate of 10 °C / min. One data point was tested for every 20 °C increase, and each temperature was maintained for 20 minutes. The liquid feed was 1% anthracene (with mesitylene as the solvent) and the flow rate was 3.5 mL / min. At each temperature point, the reaction liquid was collected, and after the experiment, GC-MS was used to perform qualitative and quantitative data analysis on the products, and the conversion rate and selectivity of the reaction products were calculated to evaluate the performance of the catalyst.

[0189] After performing GC-MS analysis on the products, the conversion rate and selectivity as shown in Figure 23 were obtained. The conversion rate of anthracene increased with the increase of temperature and reached 96.32% at 420 °C. Among them, the main product was the 8H-anthracene (ring-opening) product, and its selectivity reached the highest 44.16% at 400 °C. As the temperature decreased, the selectivity also decreased.

[0190] Comparative Example 2

[0191] The preparation method of the catalyst in this comparative example was basically the same as that in Comparative Example 1, except that the flow rate of the raw material liquid in the performance test was adjusted to 1 mL / min. At each temperature point, the reaction liquid was collected, and after the experiment, GC-MS was used to perform qualitative and quantitative data analysis on the products, and the conversion rate and selectivity of the reaction products were calculated to evaluate the performance of the catalyst.

[0192] After performing GC-MS analysis on the products, the conversion rate and selectivity as shown in Figure 24 were obtained. The conversion rate of anthracene increased with the increase of temperature and approached 100.00% when the temperature was greater than 360 °C. Among them, the main products were hydrogenation products with more than 6H, which mainly showed deep hydrogenation products, while the yield of the 8H-anthracene (ring-opening) product was not high under this condition.

[0193] Comparative Example 3

[0194] 3 g of untreated HY and 0.0857 g of H2IrCl6 (where the theoretical mass of iridium was 1 wt% of the support) were placed in a beaker, an appropriate amount of ethanol was added, and heating and stirring were carried out until the ethanol evaporated to uniformly mix the molecular sieve and the iridium precursor. The obtained powder was transferred to a muffle furnace and calcined at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, it was reduced at 200 °C for 2 hours in a 5% H2 / N2 atmosphere with the same heating rate of 5 °C / min. The sample obtained thereby was labeled Ir / HY-1%, and its XRD is shown in Figure 8 .

[0195] 1 g of the Ir / HY-1% catalyst was loaded into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and both ends were blocked with quartz wool. The quartz tube was installed in a high-pressure fixed-bed reactor, and the reaction pressure was set at 5 MPa and the hydrogen flow rate was 36 mL / min. The performance of anthracene hydrogenation reaction was tested in the range of 300 - 420 °C with a heating rate of 10 °C / min. One data point was tested for every 20 °C increase, and each temperature was maintained for 20 minutes. The liquid feed was 1% anthracene (the solvent was mesitylene), and the flow rate was 3.5 mL / min. At each temperature point, the reaction liquid was collected, and after the experiment, GC-MS was used to perform qualitative and quantitative data analysis on the products, and the conversion rate and selectivity of the reaction products were calculated to evaluate the performance of the catalyst.

[0196] After GC-MS analysis of the products, the conversion rate and selectivity as shown in Figure 25 were obtained. The conversion rate of anthracene increased with the increase of temperature, and the conversion rate reached 94.98% at 420 °C. The catalyst with Ir supported on untreated HY zeolite mainly obtained 4H-anthracene products. The conversion rate of anthracene ring-opening products increased with the increase of temperature and reached 18.65% at 420 °C.

[0197] Comparative Example 4

[0198] 3 g of untreated SAPO molecular sieve and 0.0857 g of H2IrCl6 (the theoretical mass of iridium was 1 wt% of the support) were placed in a beaker, an appropriate amount of ethanol was added, and heating and stirring were carried out until the ethanol evaporated to make the molecular sieve and the iridium precursor evenly mixed. The obtained powder was transferred to a muffle furnace and calcined at 550 °C for 2 hours with a heating rate of 5 °C / min. Subsequently, it was reduced at 200 °C for 2 hours in a 5% H2 / N2 atmosphere with the same heating rate of 5 °C / min. The sample obtained was labeled Ir / SAPO-1%, and its XRD is shown in Figure 15 .

[0199] 1 g of the Ir / SAPO-1% catalyst was loaded into a quartz tube with an inner diameter of 12 mm and a wall thickness of 1 mm, and both ends were blocked with quartz wool. The quartz tube was installed in a high-pressure fixed-bed reactor, and the reaction pressure was set at 5 MPa and the hydrogen flow rate was 36 mL / min. The performance of anthracene hydrogenation reaction was tested in the range of 300 - 420 °C with a heating rate of 10 °C / min. One data point was tested for every 20 °C increase, and each temperature was maintained for 20 minutes. The liquid feed was 1% anthracene (the solvent was mesitylene), and the flow rate was 3.5 mL / min. At each temperature point, the reaction liquid was collected, and after the experiment, GC-MS was used to perform qualitative and quantitative data analysis on the products, and the conversion rate and selectivity of the reaction products were calculated to evaluate the performance of the catalyst.

[0200] After performing GC-MS analysis on the product, the conversion rate and selectivity as shown in Figure 26 were obtained. The conversion rate of anthracene was at a relatively low level, and its selectivity was no more than 40%, with the main product being the 4H-anthracene product.

[0201] Comparative Example 5

[0202] The preparation method of the catalyst in this comparative example was basically the same as that in Example 1, except that the concentration of hydrochloric acid was replaced with 0.05 mol / L.

[0203] Using the same catalyst performance test conditions as in Example 1, the final reaction product was mainly 8H-anthracene (ring-opening product), with a conversion rate reaching 95% at 420 °C and a selectivity of 23.32% for 8H-anthracene (ring-opening).

[0204] Comparative Example 6

[0205] The preparation method of the catalyst in this comparative example was basically the same as that in Example 1, except that the concentration of hydrochloric acid was replaced with 1.5 mol / L.

[0206] Using the same catalyst performance test conditions as in Example 1, the final reaction product was mainly the 2H-anthracene product, with a conversion rate reaching 46% at 420 °C and a selectivity of 68.00% for the 2H-anthracene product.

[0207] The basic principles of the present application have been described above in conjunction with specific embodiments. However, it should be noted that the advantages, advantages, effects, etc. mentioned in the present application are only examples and not limitations, and it cannot be considered that these advantages, advantages, effects, etc. are essential for each embodiment of the present application. In addition, the above-disclosed specific details are only for the purpose of illustration and easy understanding, rather than limitations. The above details do not limit the present application to necessarily adopt the above specific details to implement.

[0208] The above description has been given for purposes of illustration and description. In addition, this description is not intended to limit the embodiments of the present application to the forms disclosed herein. Although multiple example aspects and embodiments have been discussed above, those skilled in the art will recognize certain variations, modifications, changes, additions, and sub-combinations thereof.

Claims

1. A catalyst, characterized in that, Comprising: A carrier, wherein the carrier includes at least one pore, and the size of the pore is 0.3 to 10 nanometers; A first active material, at least a part of the first active material is located in the pore, and the active material includes platinum and / or iridium.

2. The catalyst according to claim 1, characterized in that, The size of the pore is 4 to 10 nm; Preferably, the carrier includes a molecular sieve; Preferably, the molecular sieve includes HY molecular sieve and / or SAPO molecular sieve; Preferably, the molecular sieve is HY molecular sieve.

3. The catalyst according to claim 1, characterized in that, The first active material includes first active material particles, and the particle size of the first active material particles is 2 to 5 nanometers.

4. The catalyst according to claim 1, wherein Further comprising: A second active material, located on the surface of the carrier; Preferably, the second active material includes second active material particles, and the particle size of the second active material particles is 2 to 10 nanometers; Preferably, the total mass of the first active material and the second active material accounts for 0.5 to 1.5% of the mass of the carrier.

5. A method for preparing the catalyst according to any one of claims 1 to 4, characterized in that, Comprising: Pretreating the carrier to make the size of at least one pore in the carrier be 0.3 to 10 nanometers; Loading a first active material into the pore of the pretreated carrier to obtain the catalyst.

6. The preparation method according to claim 5, characterized in that The step of pretreating the carrier includes: Soaking the carrier with an acid solution; Preferably, the concentration of the acid solution is 0.1 to 1 mol / L; Preferably, soaking the carrier with an acid solution includes: Mixing the acid solution with the carrier, and soaking for 0.5 to 2 h under stirring and under a first heating condition; Removing the stirring and the first heating condition, and standing for 0.5 to 1 h; Preferably, the temperature of the first heating is 60 to 80 °C; Preferably, the step of pretreating the carrier further includes: Treating the soaked carrier to be neutral.

7. The preparation method according to claim 5, characterized in that, The step of loading a first active material into the pore of the pretreated carrier includes: Mixing the pretreated carrier with an active material precursor to obtain a first mixture; Calcining the first mixture to obtain the catalyst; Preferably, the step of mixing the pretreated carrier with an active material precursor includes: Mixing the pretreated carrier, the active material precursor and a first solvent to obtain a second mixture; Under stirring and under a second heating condition, volatilizing the first solvent to obtain the first mixture; Preferably, the active material precursor includes chloroplatinic acid and / or chloroiridic acid.

8. The preparation method according to claim 7, wherein, The step of calcining the first mixture includes: The first stage: calcining the first mixture at 500 to 600 °C for 1 to 3 h; The second stage: calcining and reducing in a 5% H2 / N2 atmosphere at 150 to 250 °C for 1 to 3 h; Preferably, in the first stage, heating from room temperature to 500 to 600 °C, and the heating rate is 4 to 6 °C / minute; Preferably, in the second stage, heating from room temperature to 150 to 250 °C, and the heating rate is 4 to 6 °C / minute.

9. Use of the catalyst according to any one of claims 1 to 4 in the hydrotreating reaction of coal tar and / or directly liquefied coal oil.

10. The application according to claim 9, characterized in that, Mixing coal tar and / or directly liquefied coal oil, the catalyst and a second solvent to obtain a third mixture; Hydrogenate the coal tar and / or directly liquefied coal oil in the third mixture under the third heating condition; Preferably, in the third mixture, the concentration of coal tar and / or directly liquefied coal oil is 0.5 - 2 wt%, preferably 1 wt%; Preferably, the second solvent is mesitylene; Preferably, the temperature of the third heating is 300 - 420 °C, preferably 400 °C; Preferably, hydrogenate the coal tar and / or directly liquefied coal oil in the third mixture in a flowing state, and the flow rate of the third mixture is 0.5 - 4 mL / min, preferably 1 mL / min.

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