A hydrogenation catalyst, a method for preparing the same, and a method for hydroprocessing coal tar

Abstract

The present application relates to a kind of hydrogenation catalyst, its preparation method and the method for hydrogenating coal tar, which includes carrier and active metal component;The carrier is carbon-based carrier, and the active metal element in the active metal component is selected from one or several of Fe, Co and Ni;With the total weight of the hydrogenation catalyst as basis, the loading of the active metal component is 1-50 wt% in the amount of metal element.The hydrogenation catalyst provided by the present application uses carbon-based carrier, which can improve the reaction activity of hydrogenation reaction and reduce the coking rate while maintaining the metal removal rate, machine miscellaneous removal rate and liquid yield at a high level.And the active metal element in the hydrogenation catalyst is one or several of Fe, Co and Ni, which can reduce the price of hydrogenation catalyst, and the preparation is simple.

Description

Technical Field

[0001] This invention relates to the field of petrochemicals, specifically to a hydrogenation catalyst, its preparation method, and a method for hydrogenating coal tar. Background Technology

[0002] Traditional coal tar processing involves extraction or distillation to extract target products such as anthracene oil, naphthalene, crude phenols, and light oil. However, this method suffers from drawbacks including low levels of high-value-added components, difficulty in utilizing low-value-added components, complex processes, high energy consumption, severe pollution, and poor economic efficiency. Coal tar hydrogenation technology can improve resource utilization and product added value while reducing pollution, making it a major direction for exploring new clean coal tar utilization technologies.

[0003] Patent ZL201010272981.7 discloses a method for preparing a bimetallic or multimetallic composite suspended bed coal tar hydrogenation catalyst. The method involves first loading ferrous salts onto coal powder to prepare a γ-FeOOH coal powder filter cake, then spraying highly active metal components such as water-soluble salts of molybdenum, nickel, and cobalt onto the coal powder filter cake, and finally dehydrating the mixture to obtain the composite coal tar hydrogenation catalyst.

[0004] Patent 202010265211.3 discloses a method for preparing a coal tar suspension bed hydrocracking catalyst. The catalyst is prepared by mixing solid powder containing semi-coke, iron-based compounds and cobalt-molybdenum-nickel-based hydrocracking catalyst regeneration waste, and then mixing the above solid powder with red mud powder.

[0005] Experiments have shown that the catalytic activity of existing coal tar hydrogenation catalysts still needs to be further improved. Summary of the Invention

[0006] The purpose of this invention is to provide a hydrogenation catalyst, its preparation method, and a method for hydrogenating coal tar, thereby solving the problem of low catalytic activity in existing coal tar hydrogenation catalysts.

[0007] To achieve the above objectives, a first aspect of the present invention provides a hydrogenation catalyst comprising a support and an active metal component; the support is a carbon-based support, and the active metal element in the active metal component is selected from one or more of Fe, Co, and Ni; the active metal element in the hydrogenation catalyst exists in the form of a metal oxide; the metal oxide includes at least one of Fe3O4, Fe2O3, CoO, and NiO; and the particle size of the active metal component in the hydrogenation catalyst is 5-40 nm.

[0008] Optionally, the carbon-based support includes one or more of carbon black, activated carbon, semi-coke, graphite, and petroleum coke; the particle size of the carbon-based support is 10-100 μm, preferably 20-60 μm.

[0009] Optionally, the specific surface area of ​​the hydrogenation catalyst is 10-1000 m². 2 / g, preferably 20-600m 2 / g.

[0010] Optionally, based on the total weight of the hydrogenation catalyst, the content of the active metal element is 1-50% by weight, preferably 10-50% by weight.

[0011] Optionally, the particle size of the active metal component in the hydrogenation catalyst is 8-35 nm, preferably 10-30 nm.

[0012] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising: mixing a support and an active metal source solution, adding an alkaline substance to perform a precipitation reaction and then performing solid-liquid separation to obtain a solid material; drying and calcining the solid material to obtain a calcined product; the calcination being carried out in an inert atmosphere; the support being a carbon-based support; the active metal source solution being selected from one or more of nitrate solutions, sulfate solutions, and chloride solutions; and the active metal element in the active metal source solution being selected from one or more of Fe, Co, and Ni.

[0013] Optionally, the alkaline substance is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia solution; the content of the active metal element in the active metal source solution is 0.5-5g relative to 100mL of the active metal source solution; the inert atmosphere is selected from one or more of nitrogen, argon and helium.

[0014] Optionally, the precipitation reaction conditions include: a reaction temperature of 20-100℃, a reaction time of 30-300 min, and a stoichiometric ratio of the alkaline substance to the active metal element in the active metal source solution of (0.8-3):1; a drying temperature of 90-120℃ and a drying time of 60-360 min; and a calcination temperature of 300-700℃ and a calcination time of 90-360 min.

[0015] The third aspect of the present invention uses a hydrogenation catalyst obtained by the method for preparing a hydrogenation catalyst described in the second aspect of the present invention.

[0016] The fourth aspect of the present invention provides a method for hydrogenating coal tar, the method comprising: in the presence of hydrogen and a sulfiding agent, contacting the coal tar feedstock and the hydrogenation catalyst described in the first or third aspect of the present invention in a slurry bed reactor to carry out a hydrogenation reaction, to obtain a hydrogenated material; and subjecting the hydrogenated material to solid-liquid separation to obtain hydrogenated coal tar.

[0017] Through the above technical solution, the hydrogenation catalyst provided by this invention uses a carbon-based support as the carrier, which can improve the reactivity of the hydrogenation reaction and reduce the coking rate while ensuring that the metal removal rate, mechanical impurity (hereinafter referred to as mechanical impurity) removal rate, and liquid yield are maintained at a high level. Furthermore, the active metal element in the hydrogenation catalyst is one or more of Fe, Co, and Ni, which can reduce the price of the hydrogenation catalyst and simplify its preparation.

[0018] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0019] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0020] The first aspect of this invention provides a hydrogenation catalyst comprising a support and an active metal component; the support is a carbon-based support, and the active metal element in the active metal component is selected from one or more of Fe, Co, and Ni; the active metal element in the hydrogenation catalyst exists in the form of a metal oxide; the metal oxide includes at least one of Fe3O4, Fe2O3, CoO, and NiO; and the particle size of the active metal component in the hydrogenation catalyst is 5-40 nm.

[0021] Through the above technical solution, the hydrogenation catalyst provided by the present invention uses a carbon-based support as the support, which can improve the reactivity of the hydrogenation reaction and reduce the coking rate while ensuring that the metal removal rate, the mechanical impurity removal rate and the liquid yield are maintained at a high level; in addition, the active metal element in the hydrogenation catalyst is one or more of Fe, Co and Ni, which can reduce the price of the hydrogenation catalyst and simplify its preparation.

[0022] The hydrogenation catalyst is obtained by a precipitation reaction between a support and an active metal component.

[0023] To further improve the performance of the hydrogenation catalyst, the particle size of the active component in the hydrogenation catalyst is optimized. Specifically, the particle size of the active metal component in the hydrogenation catalyst is preferably 8-35 nm, and more preferably 10-30 nm. Since the hydrogenation catalyst is obtained by precipitation reaction of the support and the active metal component followed by calcination, the particle size of the active metal component is smaller than that of the traditional impregnation method. This increases the surface area in contact with the material and enhances the activity of the hydrogenation catalyst.

[0024] The carbon-based support for the hydrogenation catalyst can be selected from one or more of carbon black, activated carbon, semi-coke, graphite, and petroleum coke. The particle size of the carbon-based support is 10-100 μm, preferably 20-60 μm, and more preferably 20-40 μm.

[0025] The specific surface area of ​​the hydrogenation catalyst is 10-1000 m². 2 / g, preferably 20-600m 2 / g, further preferably 30-400m 2 / g.

[0026] In order to reduce costs while ensuring the performance of the hydrogenation catalyst, the content of the active metal component in the hydrogenation catalyst needs to be limited. Specifically, based on the total weight of the hydrogenation catalyst, the content of the active metal element is 1-60% by weight, preferably 10-50% by weight, and more preferably 12-45% by weight.

[0027] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising: mixing a support and an active metal source solution, adding an alkaline substance to perform a precipitation reaction and then performing solid-liquid separation to obtain a solid material; drying and calcining the solid material to obtain a calcined product; the calcination being carried out in an inert atmosphere; the support being a carbon-based support; the active metal source solution being selected from one or more of nitrate solutions, sulfate solutions, and chloride solutions; and the active metal element in the active metal source solution being selected from one or more of Fe, Co, and Ni.

[0028] In the above embodiments, the hydroxide formed by the active metal component in the active metal source solution under alkaline conditions is precipitated on a carbon-based support, and then calcined to convert the hydroxide coated on the surface of the carbon-based support into an oxide form. Compared with the conventional impregnation method for preparing supported catalysts, the method of this application can obtain active metal components with smaller particle sizes, thereby increasing the contact area between the active metal components and the reactants, and thus enhancing the activity of the hydrogenation catalyst. The hydrogenation catalyst provided by this invention uses a carbon-based support, which can improve the reactivity of the hydrogenation reaction and reduce the coking rate while maintaining a high level of metal removal rate, organic impurity removal rate, and liquid yield; furthermore, the active metal element in the hydrogenation catalyst is one or more of Fe, Co, and Ni, which can reduce the price of the hydrogenation catalyst and reduce the preparation difficulty.

[0029] To improve the precipitation reaction, the carbon-based support needs to be pretreated before the precipitation reaction. The pretreatment method is a conventional choice in the art and is not specifically required in this application. For example, the carbon-based support is dried at a temperature of 100-130°C to remove moisture and some impurities.

[0030] To further enhance the activity of the precipitation reaction, the alkaline material can be added directly as a solid powder to the mixture or prepared as a solution before being added. The alkaline material is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and an aqueous ammonia solution with a concentration of 25%-28%.

[0031] The amount of active metal component added can be relative to 100 mL of the active metal source solution, and the content of active metal element in the active metal source solution is 0.5-5 g, preferably 0.8-4 g, and more preferably 1-3 g.

[0032] The precipitation reaction conditions include: a reaction temperature of 20-100℃, preferably 30-95℃, and more preferably 40-90℃; a reaction time of 30-300 min, preferably 45-200 min, and more preferably 60-90 min; and a stoichiometric ratio of the alkaline substance to the active metal element in the active metal source solution of (0.8-3):1, preferably (0.9-1.5):1, and more preferably (1-1.2):1.

[0033] In the above embodiments, by placing the carbon-based support in an active metal source solution and adding an alkaline substance thereto, the active metal elements in the active metal source solution can react with the alkaline substance to generate a precipitate, which will coat the carbon-based support in the mixture; therefore, the precipitate coating the surface of the carbon-based support is uniform, which can further enhance the performance of the hydrogenation catalyst.

[0034] After the precipitation reaction is complete, the reactants exist in a state where solid and liquid coexist. Therefore, it is necessary to separate the precipitation reaction products into solid and liquid components. The solid-liquid separation method used in this invention is a conventional choice in the art, and this application does not make any special requirements. For example, the precipitation reaction products can be filtered to obtain a filter cake, which is a solid material.

[0035] To further remove liquid from the solid material, it is necessary to dry the solid material at a temperature of 90-120℃ for 60-360 minutes.

[0036] To avoid the influence of moisture, oxygen, and impurities in the air on the catalyst and thus improve the performance of the hydrogenation catalyst, the present invention sends the dried solid material into a tube furnace and performs calcination under an inert atmosphere, wherein the inert atmosphere is selected from one or more of nitrogen, argon, and helium.

[0037] The roasting temperature is 300-700℃, preferably 400-650℃, and more preferably 450-600℃; the roasting time is 90-360min, preferably 150-330min, and more preferably 200-300min.

[0038] In one embodiment, the method for preparing the hydrogenation catalyst includes:

[0039] (1) Preparation of the carrier: The carbon-based carrier is dried and dehydrated at 100-130℃ and then pulverized into powder with a particle size of 20-60μm;

[0040] (2) After the metal source solution and the carrier are mixed evenly, an alkaline substance is added while stirring to carry out a precipitation reaction; the conditions for the precipitation reaction are: reaction temperature of 20-100℃ and reaction time of 30-300min; after the precipitation is washed, the obtained precipitation reaction product is separated into solid and liquid to obtain solid material.

[0041] (3) After drying the solid material at 90-120℃ for 60-360 min, place it in a tube furnace and calcine it at 300-700℃ for 90-360 min under an inert atmosphere. The calcined product is the hydrogenation catalyst.

[0042] The third aspect of the present invention uses a hydrogenation catalyst obtained by the method for preparing a hydrogenation catalyst described in the second aspect of the present invention.

[0043] The fourth aspect of the present invention provides a method for hydrogenating coal tar, the method comprising: in the presence of hydrogen and a sulfiding agent, contacting the coal tar feedstock and the hydrogenation catalyst described in the first aspect or the third aspect of the present invention in a slurry bed reactor to carry out a hydrogenation reaction, to obtain a hydrogenated material; and subjecting the hydrogenated material to solid-liquid separation to obtain hydrogenated coal tar.

[0044] The coal tar used in this invention is preferably medium-low temperature coal tar and / or high temperature coal tar. High temperature coal tar has a lower saturated content than medium-low temperature coal tar, but a higher residual carbon value. High temperature coal tar has a higher tendency to coke during processing, making it more difficult to process.

[0045] The reaction conditions for the hydrogenation reaction of coal tar are as follows: reaction temperature is 360-420℃; reaction time is 30-360 min; initial hydrogen pressure is 3-9 MPa; relative to 1g of coal tar raw material, the amount of hydrogenation catalyst (calculated as metal element) added is 500-6000 μg, preferably 500-3000 μg, and more preferably 800-2000 μg; the molar ratio of the sulfiding agent (calculated as sulfur) to the hydrogenation catalyst (calculated as metal) is (1-2):1, preferably (1-1.5):1, and more preferably (1-1.2):1.

[0046] In one embodiment, the method for hydrogenating coal tar includes:

[0047] Coal tar feedstock, hydrogenation catalyst, and sublimed sulfur are added to a slurry bed reactor. The air inside the reactor is first replaced with nitrogen at room temperature, then the nitrogen is replaced with hydrogen and pressurized to 3-9 MPa. The reaction temperature is 360-420℃, and the hydrogenation reaction is carried out for 30-360 minutes. After the reaction, the resulting hydrogenated material is cooled to 25-35℃, and the gas is collected using a gas bag for analysis. The solid residue and liquid product are separated to obtain hydrogenated coal tar.

[0048] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0049] Examples 1-7 and Comparative Examples 1-3 are for the preparation of hydrogenation catalysts.

[0050] Example 1

[0051] (1) Preparation of carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm;

[0052] (2) Using Fe2(SO4)3 to prepare an aqueous solution of ferric sulfate as the metal source solution, the Fe content in the aqueous solution of ferric sulfate is 2.4g relative to 100mL of active metal source solution; after mixing 125mL of aqueous solution of ferric sulfate with 5g of carrier evenly, 20.16g of 28wt% ammonia solution is added while stirring to carry out precipitation reaction; the precipitation reaction conditions are: reaction temperature of 60℃ and reaction time of 60min; after the precipitation is washed, the obtained precipitation reaction product is separated into solid and liquid to obtain solid material;

[0053] (3) After drying the solid material at 110°C for 300 min, it is placed in a tube furnace and calcined at 490°C for 300 min under N2 gas protection. The calcined product is the hydrogenation catalyst A1.

[0054] The properties of the hydrogenation catalysts are shown in Table 1.

[0055] Example 2

[0056] (1) Preparation of carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm;

[0057] (2) Using Fe2(SO4)3 to prepare an aqueous solution of ferric sulfate as the metal source solution, the Fe content in the aqueous solution of ferric sulfate is 2g relative to 100mL of active metal source solution; after mixing 150mL of aqueous solution of ferric sulfate with 5g of carrier evenly, 20.16g of 28wt% ammonia solution is added while stirring to carry out precipitation reaction; the precipitation reaction conditions are: reaction temperature of 40℃ and reaction time of 60min; after the precipitation is washed, the obtained precipitation reaction product is separated into solid and liquid to obtain solid material;

[0058] (3) After drying the solid material at 110°C for 300 min, place it in a tube furnace and calcine it at 600°C for 300 min under N2 gas protection. The calcined product is the hydrogenation catalyst A2.

[0059] The properties of the hydrogenation catalysts are shown in Table 1.

[0060] Example 3

[0061] (1) Preparation of carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm;

[0062] (2) Using Fe2(SO4)3 to prepare an aqueous solution of ferric sulfate as the metal source solution, the Fe content in the aqueous solution of ferric sulfate is 2g relative to 100mL of active metal source solution; after mixing 150mL of aqueous solution of ferric sulfate with 5g of carrier evenly, 8.54g of sodium carbonate powder is added while stirring to carry out precipitation reaction; the precipitation reaction conditions are: reaction temperature is 90℃ and reaction time is 60min; after the precipitation is washed, the obtained precipitation reaction product is separated into solid and liquid to obtain solid material;

[0063] (3) After drying the solid material at 110°C for 300 min, it is placed in a tube furnace and calcined at 450°C for 300 min under N2 gas protection. The calcined product is the hydrogenation catalyst A3.

[0064] The properties of the hydrogenation catalysts are shown in Table 1.

[0065] Example 4

[0066] (1) Preparation of carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm;

[0067] (2) Using Fe2(SO4)3 to prepare an aqueous solution of ferric sulfate as the metal source solution, the Fe content in the aqueous solution of ferric sulfate is 1g relative to 100mL of active metal source solution; after mixing 100mL of aqueous solution of ferric sulfate with 5g of carrier evenly, 2.85g of sodium carbonate powder is added while stirring to carry out precipitation reaction; the precipitation reaction conditions are: reaction temperature is 90℃ and reaction time is 75min; after the precipitation is washed, the obtained precipitation reaction product is separated into solid and liquid to obtain solid material;

[0068] (3) After drying the solid material at 110°C for 300 min, it is placed in a tube furnace and calcined at 550°C for 240 min under N2 gas protection. The calcined product is the hydrogenation catalyst A4.

[0069] The properties of the hydrogenation catalysts are shown in Table 1.

[0070] Example 5

[0071] (1) Preparation of carrier: The gasification ash residue is dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm;

[0072] (2) Using Fe(NO3)3·9H2O to prepare an aqueous solution of ferric nitrate as the metal source solution, the Fe content in the aqueous solution of ferric nitrate is 1.25g relative to 100mL of active metal source solution; after mixing 100mL of aqueous solution of ferric nitrate with 5g of carrier evenly, 3.56g of sodium carbonate powder is added while stirring to carry out precipitation reaction; the precipitation reaction conditions are: reaction temperature is 90℃ and reaction time is 75min; after the precipitation is washed, the obtained precipitation reaction product is separated into solid and liquid to obtain solid material;

[0073] (3) After drying the solid material at 110°C for 300 min, it is placed in a tube furnace and calcined at 600°C for 300 min under Ar gas protection. The calcined product is the hydrogenation catalyst A5.

[0074] The properties of the hydrogenation catalysts are shown in Table 2.

[0075] Example 6

[0076] (1) Preparation of carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm;

[0077] (2) Co(NO3)2 was used to prepare a cobalt nitrate aqueous solution as a metal source solution. The content of Co in the cobalt nitrate aqueous solution was 1g relative to 100mL of active metal source solution. After 100mL of cobalt nitrate aqueous solution was mixed evenly with 5g of carrier, 1.82g of sodium carbonate powder was added while stirring to carry out precipitation reaction. The precipitation reaction conditions were: reaction temperature of 90℃ and reaction time of 60min. After the precipitation was washed, the obtained precipitation reaction product was separated into solid and liquid to obtain solid material.

[0078] (3) After drying the solid material at 120°C for 300 min, it is placed in a tube furnace and calcined at 500°C for 300 min under N2 gas protection. The calcined product is the hydrogenation catalyst A6.

[0079] The properties of the hydrogenation catalysts are shown in Table 2.

[0080] Example 7

[0081] (1) Preparation of carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm;

[0082] (2) A nickel nitrate aqueous solution was prepared using Ni(NO3)2 as the metal source solution. The content of Ni in the nickel nitrate aqueous solution was 1g relative to 100mL of active metal source solution. After mixing 100mL of nickel nitrate aqueous solution with 5g of carrier evenly, 1.82g of sodium carbonate powder was added while stirring to carry out the precipitation reaction. The precipitation reaction conditions were: reaction temperature of 90℃ and reaction time of 60min. After the precipitation was washed, the obtained precipitation reaction product was separated into solid and liquid to obtain solid material.

[0083] (3) After drying the solid material at 120°C for 300 min, place it in a tube furnace and calcine it at 500°C for 300 min under N2 gas protection. The calcined product is the hydrogenation catalyst A7.

[0084] The properties of the hydrogenation catalysts are shown in Table 2.

[0085] Comparative Example 1

[0086] (1) Preparation of carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm;

[0087] (2) Using Fe(NO3)3·9H2O to prepare an aqueous solution of ferric nitrate as a metal source solution, the Fe content in the aqueous solution of ferric nitrate is 1g relative to 100mL of active metal source solution; 50mL of the aqueous solution of ferric nitrate is immersed on 5g of the above carrier at an immersion temperature of 60℃ for 180min; after immersion, the precipitated reaction product is separated into solid and liquid to obtain a solid material.

[0088] (3) After drying the solid material at 110℃ for 240 min, it was placed in a tube furnace and calcined at 600℃ for 300 min under N2 gas protection to prepare coal tar hydrogenation catalyst B1.

[0089] The properties of the hydrogenation catalysts are shown in Table 2.

[0090] Comparative Example 2

[0091] The method for preparing the hydrogenation catalyst is the same as in Example 1, except that the catalyst is an organic acid molybdenum catalyst B2. The properties of the hydrogenation catalyst are shown in Table 2.

[0092] Comparative Example 3

[0093] The method for preparing the hydrogenation catalyst is the same as in Example 1, except that no calcination treatment is performed, resulting in catalyst B3. The properties of the hydrogenation catalyst are shown in Table 2.

[0094] Table 1 Properties of hydrogenation catalysts

[0095]

[0096] Table 2 Properties of hydrogenation catalysts

[0097]

[0098]

[0099] The parameters of the hydrogenation catalyst were tested as follows:

[0100] Metal composition of hydrogenation catalyst: determined using a Thermo Scientific iCAP7000 inductively coupled plasma atomic emission spectrometer.

[0101] Metallic phase: Characterized on a D8 ADVANCE X-ray diffractometer, Cu Kα rays, λ=0.15418nm, 2θ scan range of 5°~70°, scan rate of 4(°) / min.

[0102] Particle size of active metal component: calculated using the Scherrer formula based on data of hydrogenation catalyst measured by X-ray diffraction.

[0103] Hydrogenation catalyst particle size: measured using an MS3000 laser particle size analyzer.

[0104] Specific surface area of ​​hydrogenation catalyst: determined by ASAP2460 physical BET adsorption analyzer.

[0105] Examples 8-15 and Comparative Examples 4-6 are evaluations of hydrogenation catalysts. The coal tar used was both low-temperature and high-temperature coal tar, the properties of which are shown in Table 3.

[0106] Table 3 Properties of Coal Tar

[0107]

[0108]

[0109] Example 8

[0110] 200 g of medium-low temperature coal tar, 0.565 g of hydrogenation catalyst Al (Fe content 1000 μg / g), and 0.115 g of sublimed sulfur were added to a 1.8 L high-pressure reactor. The air inside the reactor was first replaced with nitrogen at room temperature, then the nitrogen was replaced with hydrogen, and the reactor was pressurized to 4.0 MPa. The hydrogenation reaction was carried out for 60 min at 380 °C. After the reaction, the hydrogenated product was cooled to room temperature, and the gas was collected using a gas bag for analysis. The solid residue and liquid product were separated to obtain hydrogenated coal tar and liquid product. The operating conditions and reaction results are shown in Tables 4 and 5.

[0111] Example 9

[0112] The method for hydrogenating coal tar is the same as in Example 8, except that the hydrogenation catalyst is hydrogenation catalyst A5, and the amount added is 1.04 g (Fe addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 4 and 5.

[0113] Example 10

[0114] The method for hydrotreating coal tar is the same as in Example 8, except that the hydrotreating catalyst is hydrotreating catalyst A6, and the amount added is 1.182 g (Co addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 4 and 5.

[0115] Example 11

[0116] The method for hydrogenating coal tar is the same as in Example 8, except that the hydrogenation catalyst is hydrogenation catalyst A7, and the amount added is 1.286 g (Ni addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 4 and 5.

[0117] Example 12

[0118] The method for hydrogenating coal tar is the same as in Example 8, except that the coal tar feedstock is 200g of high-temperature coal tar, the amount of hydrogenation catalyst A1 added is 0.565g (Fe added is 1000μg / g), the reaction temperature is 420℃, the initial hydrogen pressure is 7.0MPa, and the reaction time is 150min. The operating conditions and reaction results are shown in Tables 6 and 7.

[0119] Example 13

[0120] The method for hydrotreating coal tar is the same as in Example 12, except that the hydrotreating catalyst is hydrotreating catalyst A5 and the amount added is 0.565g (Fe addition amount is 1000μg / g), the reaction temperature is 420℃, the initial hydrogen pressure is 9.0MPa, and the reaction time is 300min. The operating conditions and reaction results are shown in Tables 6 and 7.

[0121] Example 14

[0122] The method for hydrogenating coal tar is the same as in Example 12, except that the hydrogenation catalyst is hydrogenation catalyst A6 and the amount added is 1.182 g (Co addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 6 and 7.

[0123] Example 15

[0124] The method for hydrogenating coal tar is the same as in Example 12, except that the hydrogenation catalyst is hydrogenation catalyst A7 and the amount added is 1.285 g (Co addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 6 and 7.

[0125] Comparative Example 4

[0126] The method for hydrogenating coal tar is the same as in Example 8, except that the hydrogenation catalyst is hydrogenation catalyst B1 and the amount added is 1.068 g (Fe addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 4 and 5.

[0127] Comparative Example 5

[0128] The method for hydrotreating coal tar is the same as in Example 8, except that the hydrotreating catalyst is hydrotreating catalyst B2 and the amount added is 1.359 g (Mo added amount is 1000 μg / g), and the mass of sublimed sulfur added is 0.1333 g. The operating conditions and reaction results are shown in Tables 4 and 5.

[0129] Comparative Example 6

[0130] The method for hydrotreating coal tar is the same as in Example 13, except that the hydrotreating catalyst is hydrotreating catalyst B2 and the amount added is 1.359 g (Mo added amount is 1000 μg / g), and the mass of sublimed sulfur added is 0.1333 g. The operating conditions and reaction results are shown in Tables 6 and 7.

[0131] Comparative Example 7

[0132] The method for hydrogenating coal tar is the same as in Example 8, except that the hydrogenation catalyst is hydrogenation catalyst B3 and the amount added is 0.721 g (Fe addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 4 and 5.

[0133] Table 4 Operating conditions and reaction results

[0134]

[0135]

[0136] Table 5 Properties of Liquid Products

[0137]

[0138]

[0139] Table 6 Operating conditions and reaction results

[0140] Example 12 Example 13 Example 14 Example 15 Comparative Example 6 catalyst A1 A1 A6 A7 B2 Metals (μg / g) 1000 1000 1000 1000 1000 Catalyst (μg / g) 2825 2825 5910 6426 6793 Temperature / °C 420 420 420 420 420 Hydrogen partial pressure / MPa 7 9 7 7 9 Time / min 150 300 150 150 300 Hydrogen consumption / % 1.02 2.60 2.04 2.03 2.81 Liquid yield / % 88.07 92.15 93.21 94.63 93.78 Coking rate / % 8.40 3.21 4.60 4.10 3.50 Metal removal rate / % 91.00 97.69 96.93 95.81 97.74 Mechanical impurity removal rate / % 82.52 93.18 97.11 96.98 90.05

[0141] Table 7 Properties of Liquid Products

[0142]

[0143] The hydrogen consumption, liquid yield, metal removal rate, mechanical impurity removal rate, and coke production rate of the hydrotreating coal tar method are calculated using the following formulas:

[0144]

[0145]

[0146]

[0147]

[0148]

[0149] A comparison of Examples 8 and 9 and Comparative Examples 4 and 5 in Tables 4 and 5 shows that, in the medium- and low-temperature coal tar hydrogenation system, the activated carbon-precipitated iron catalyst outperforms the activated carbon-supported impregnated iron catalyst and the uncalcined catalyst in terms of liquid yield, coking rate, and demetallization rate. Its performance is comparable to that of commercially available oil-soluble organic molybdenum catalysts, and it features a low catalyst addition amount. This indicates that the catalyst prepared by this invention has advantages such as high reactivity, high metal and organic impurity removal rate, high liquid yield, and low coking rate. Furthermore, it can significantly reduce the catalyst addition amount, thereby reducing pretreatment operation costs. A comparison of Example 8 and Comparative Example 7 shows that calcination treatment can improve the performance of the hydrogenation catalyst. Examples 10 and 11 demonstrate that the Fe, Co, and Ni supported catalysts prepared by the activated carbon-supported precipitation method also have the advantages of high metal and organic impurity removal rate and high liquid yield.

[0150] A comparison of Examples 12-15 and Comparative Example 6 in Tables 6 and 7 shows that, in high-temperature coal tar systems, under relatively high pressure (9 MPa), both the Fe catalyst and the organic Mo catalyst prepared by the activated carbon-supported precipitation method exhibit high metal and organic impurity removal rates and high liquid yields. However, under lower pressure (7 MPa), compared to the Fe catalyst, the Co and Ni catalysts show stronger hydrogenation activity, better resistance to coking, and higher metal and organic impurity removal rates. Considering that nickel is 30 times more expensive than iron, cobalt is 70 times more expensive than iron, and molybdenum is 40 times more expensive than iron, iron is the preferred metal component for this catalyst considering economic costs. This catalyst also has the advantages of low cost, simple preparation, and efficient pretreatment of coal tar.

[0151] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0152] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0153] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A hydrogenation catalyst, characterized in that, The hydrogenation catalyst comprises a support and an active metal component; the support is a carbon-based support, and the active metal element in the active metal component is selected from one or more of Fe, Co, and Ni; The active metal element in the hydrogenation catalyst exists in the form of a metal oxide; the metal oxide includes at least one of Fe3O4, Fe2O3, CoO, and NiO; The active metal component in the hydrogenation catalyst has a particle size of 5-40 nm; The hydrogenation catalyst is prepared by a method comprising the following steps: mixing a support and an active metal source solution, adding an alkaline substance to perform a precipitation reaction and then performing solid-liquid separation to obtain a solid material; drying and calcining the solid material to obtain a calcined product; the calcination is carried out in an inert atmosphere; the support is a carbon-based support; the active metal source solution is selected from one or more of nitrate solution, sulfate solution and chloride solution; the active metal element in the active metal source solution is selected from one or more of Fe, Co and Ni.

2. The hydrogenation catalyst according to claim 1, characterized in that, The carbon-based support includes one or more of carbon black, activated carbon, semi-coke, graphite, and petroleum coke; the particle size of the carbon-based support is 10-100 μm.

3. The hydrogenation catalyst according to claim 2, characterized in that, The carbon-based support has a particle size of 20-60 μm.

4. The hydrogenation catalyst according to claim 1, characterized in that, The specific surface area of ​​the hydrogenation catalyst is 10-1000 m². 2 / g.

5. The hydrogenation catalyst according to claim 4, characterized in that, The specific surface area of ​​the hydrogenation catalyst is 20-600 m². 2 / g.

6. The hydrogenation catalyst according to claim 1, characterized in that, Based on the total weight of the hydrogenation catalyst, the content of the active metal element is 1-50% by weight.

7. The hydrogenation catalyst according to claim 6, characterized in that, Based on the total weight of the hydrogenation catalyst, the content of the active metal element is 10-50% by weight.

8. The hydrogenation catalyst according to claim 1, characterized in that, The active metal component in the hydrogenation catalyst has a particle size of 8-35 nm.

9. The hydrogenation catalyst according to claim 8, characterized in that, The active metal component in the hydrogenation catalyst has a particle size of 10-30 nm.

10. A method for preparing the hydrogenation catalyst according to any one of claims 1-9, characterized in that, The method includes: The carrier and the active metal source solution are mixed, and an alkaline substance is added to carry out a precipitation reaction and solid-liquid separation to obtain a solid material. The solid material is dried and calcined to obtain a calcined product; the calcination is carried out in an inert atmosphere; the calcination temperature is 450-700℃ and the time is 90-360min. The carrier is a carbon-based carrier; The active metal source solution is selected from one or more of nitrate solution, sulfate solution and chloride solution; the active metal element in the active metal source solution is selected from one or more of Fe, Co and Ni.

11. The method according to claim 10, characterized in that, The alkaline substance is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; The content of the active metal element in the active metal source solution is 0.5~5g relative to 100mL of the active metal source solution; The inert atmosphere is selected from one or more of nitrogen, argon and helium.

12. The method according to claim 11, characterized in that, The conditions for the precipitation reaction include: a reaction temperature of 20-100℃, a reaction time of 30-300 min, and a molar ratio of the alkaline substance to the active metal element in the active metal source solution of (0.8-3):

1. The drying temperature is 90-120℃ and the time is 60-360 min.

13. The method according to claim 10, characterized in that, The alkaline substance is an ammonia solution.

14. The hydrogenation catalyst obtained by the method of any one of claims 11-13.

15. A method for hydrogenating coal tar, characterized in that, The method includes: In the presence of hydrogen and a sulfiding agent, coal tar feedstock and the hydrogenation catalyst according to any one of claims 1-9 or the hydrogenation catalyst according to claim 14 are brought into contact in a slurry bed reactor to carry out a hydrogenation reaction, thereby obtaining the hydrogenated material. The material after the hydrogenation reaction is subjected to solid-liquid separation to obtain hydrogenated coal tar.

Images