A hydrogenation catalyst, its preparation method, and a method for producing hydrogenated coal tar.

Abstract

This invention relates to a hydrogenation catalyst comprising a support and an active metal component. The support is a carbon-based support, and the active metal component comprises one or more of Fe, Co, and Ni. The active metal component exists in the form of a metal sulfide, which includes at least one of FeS, CoS, and NiS. The hydrogenation catalyst provided by this invention uses a carbon-based support, and the active metal component exists in the form of a metal sulfide. This allows for improved reactivity of the hydrogenation reaction and reduced coking rate without the addition of a sulfiding agent, while maintaining high levels of metal removal rate, mechanical impurity removal rate, and liquid yield. Furthermore, the active metal component in the hydrogenation catalyst is one or more of Fe, Co, and Ni, which reduces the cost of the hydrogenation catalyst.

Description

Technical Field

[0001] This invention relates to the field of petrochemical technology, specifically to a hydrogenation catalyst, its preparation method, and a method for producing hydrogenated 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 a low concentration of high-value-added components, difficulty in utilizing low-value-added components, and complex processing procedures. Coal tar hydrogenation technology can improve resource utilization and product added value while reducing pollution, making it a key area for exploring new clean coal tar utilization technologies.

[0003] CN102380396A 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] CN111420671A 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] CN109701537A discloses a pre-hydrogenation catalyst, its preparation method, and its application. The pre-hydrogenation catalyst comprises activated carbon and an active material supported on the activated carbon. The active material includes metal oxides or their salts, wherein the metal oxides are one or more oxides of Co, Mo, Ni, W, Fe, and Mg; the metal oxides account for 0.1-25 wt% of the activated carbon.

[0006] However, existing coal tar hydrogenation catalysts require the addition of sulfiding agents during the reaction, which increases the operating cost of the reaction, and the reaction activity of the catalyst still needs to be further improved. Summary of the Invention

[0007] The purpose of this invention is to provide a hydrogenation catalyst, its preparation method, and a method for producing hydrogenated coal tar. This method solves the problem of low catalytic activity in existing coal tar hydrogenation catalysts without the need to add a sulfiding agent during the coal tar hydrogenation reaction.

[0008] 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 one or more of Fe, Co, and Ni; the active metal element in the hydrogenation catalyst exists in the form of a metal sulfide; the metal sulfide includes at least one of FeS, CoS, and NiS.

[0009] Optionally, based on the total weight of the hydrogenation catalyst, the content of the active metal element in the active metal component is 1-60% by weight, preferably 10-50% by weight.

[0010] Optionally, the particle size of the active metal component in the hydrogenation catalyst is 5-40 nm.

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

[0012] Optionally, the specific surface area of ​​the hydrogenation catalyst is 10-1000 m². 2 / g, preferably 20-600m 2 / g; pore size is 2-20nm, preferably 5-15nm; pore volume is 0.01-3cm³. 3 / g, preferably 0.1-1cm 3 / g.

[0013] Optionally, the carbon-based support includes one or more of carbon black, activated carbon, semi-coke, graphite, gasification ash, and petroleum coke; the particle size of the carbon-based support is 10-100 μm, preferably 20-60 μm; and the specific surface area of ​​the carbon-based support is 20-1200 m². 2 / g, pore size 1-20nm, pore volume 0.1-10cm³ 3 / g.

[0014] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:

[0015] S1. The carrier and the active metal source solution are mixed, and a sulfide is added to carry out a precipitation reaction, followed by solid-liquid separation to obtain a solid material; S2. The solid material is dried and calcined to obtain a calcined product; the calcination is carried out in an inert atmosphere; the carrier is a carbon-based carrier; the active metal source solution is selected from sulfate solution and / or chloride solution; the active metal element in the active metal source solution is one or more of Fe, Co and Ni.

[0016] Optionally, relative to 100 mL of the active metal source solution, the content of the active metal element in the active metal source solution is 0.5-5 g; the sulfide is one or more of sodium sulfide, potassium sulfide and ammonium sulfide; and the inert atmosphere is one or more of nitrogen, argon and helium.

[0017] Optionally, the precipitation reaction conditions include: a reaction temperature of 10-100℃, a reaction time of 30-300 min, and a stoichiometric ratio of the sulfide to the active metal element in the active metal source solution of (1-2.5):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.

[0018] A third aspect of the present invention provides a method for producing hydrogenated coal tar, the method comprising: in the presence of hydrogen, contacting a coal tar feedstock and a hydrogenation catalyst provided in the first aspect of the present invention in a slurry bed reactor to carry out a hydrogenation reaction.

[0019] Through the above technical solution, the hydrogenation catalyst provided by this invention uses a carbon-based support as the carrier, and the active metal element in the active metal component exists in the form of metal sulfides. This allows for improved reactivity of the hydrogenation reaction and reduced coking rate without the addition of sulfiding agents, while maintaining high levels of metal removal rate, mechanical 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 reduces the cost of the hydrogenation catalyst.

[0020] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0021] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0022] Figure 1 This is an electron microscope image of the hydrogenation catalyst in Example 1 of the present invention. Detailed Implementation

[0023] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0024] The 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 one or more of Fe, Co, and Ni; the active metal element in the hydrogenation catalyst exists in the form of a metal sulfide; the metal sulfide includes at least one of FeS, CoS, and NiS.

[0025] In this invention, the hydrogenation catalyst is obtained by precipitation reaction between a support and an active metal component. The hydrogenation catalyst uses a carbon-based support as the support, and the active metal element in the active metal component exists in the form of metal sulfides. By introducing metal sulfides onto the carbon-based support to enable their interaction, the reactivity of the hydrogenation reaction can be improved and the coking rate reduced without the addition of a sulfiding agent, while maintaining high levels 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 cost of the hydrogenation catalyst.

[0026] According to the present invention, optionally, in order to reduce the cost while enabling the hydrogenation catalyst to exhibit excellent catalytic performance, it is necessary to limit the content of the active metal component in the hydrogenation catalyst. Specifically, based on the total weight of the hydrogenation catalyst, the content of the active metal element in the active metal component is 1-60% by weight, preferably 10-50% by weight, and more preferably 12-45% by weight.

[0027] According to the present invention, optionally, the particle size of the active metal component in the hydrogenation catalyst is 5-40 nm.

[0028] According to the present invention, optionally, in order to further improve the performance of the hydrogenation catalyst, the particle size of the active metal 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 conventional impregnation method, thereby increasing the surface area in contact with the material and enhancing the activity of the hydrogenation catalyst.

[0029] According to the present invention, optionally, the specific surface area of ​​the hydrogenation catalyst is 10-1000 m². 2 / g, preferably 20-600m 2 / g; pore size is 2-20nm, preferably 5-15nm; pore volume is 0.01-3cm³. 3 / g, preferably 0.1-1cm 3 / g.

[0030] According to the present invention, optionally, the carbon-based support includes one or more of carbon black, activated carbon, semi-coke, graphite, gasification ash, and petroleum coke; the particle size of the carbon-based support is 10-100 μm, preferably 20-60 μm; and the specific surface area of ​​the carbon-based support is 20-1200 m². 2 / g, pore size 1-20nm, pore volume 0.1-10cm³ 3 / g.

[0031] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:

[0032] S1. The carrier and the active metal source solution are mixed, and a sulfide is added to carry out a precipitation reaction, followed by solid-liquid separation to obtain a solid material; S2. The solid material is dried and calcined to obtain a calcined product; the calcination is carried out in an inert atmosphere; the carrier is a carbon-based carrier; the active metal source solution is selected from sulfate solution and / or chloride solution; the active metal element in the active metal source solution is one or more of Fe, Co and Ni.

[0033] In this invention, the active metal component in the active metal source solution and the sulfide form a metal sulfide precipitate on a carbon-based support, followed by calcination, which allows the metal sulfide to interact with the support. Compared with the traditional impregnation method for preparing supported catalysts, the method of this invention can obtain active metal components with smaller particle sizes, thereby increasing the contact area between the active metal component and the reactants, and thus enhancing the activity of the hydrogenation catalyst.

[0034] According to the present invention, optionally, in order to improve the precipitation reaction effect, the carbon-based support needs to be pretreated before the precipitation reaction is carried out; wherein the pretreatment method is conventionally selected in the art and is not specifically required in this application, for example, drying the carbon-based support at a temperature of 100-130°C to remove moisture and some impurities.

[0035] According to the present invention, optionally, to further enhance the activity of the precipitation reaction, when adding sulfide materials, the solid powder can be added directly to the mixture, or the sulfide can be prepared as a solution and added to the mixture. The sulfide is one or more of sodium sulfide, potassium sulfide, and ammonium sulfide.

[0036] According to the present invention, optionally, the content of active metal element in the active metal source solution is 0.5-5g, preferably 0.8-4g, and more preferably 1-3g, relative to 100mL of the active metal source solution.

[0037] According to the present invention, optionally, the conditions for the precipitation reaction include: a reaction temperature of 10-100°C, a reaction time of 30-300 min, and a stoichiometric ratio of the sulfide to the active metal element in the active metal source solution of (1-2.5):1, preferably (1-1.5):1, and more preferably (1-1.2):1.

[0038] In this invention, a carbon-based support is placed in an active metal source solution, and an appropriate amount of sulfide is added. This allows the active metal elements in the source solution to react with the sulfides, forming a precipitate that coats the carbon-based support in the mixture. Therefore, the precipitate coating on the surface of the carbon-based support is uniform, further enhancing the performance of the hydrogenation catalyst.

[0039] According to the present invention, optionally, after the precipitation reaction is completed, the reactants exist in a state where solid and liquid coexist. Therefore, it is necessary to perform solid-liquid separation on the precipitation reaction product. The solid-liquid separation method used in the present invention is a conventional choice in the art, and this application does not make any special requirements. For example, the precipitation reaction product can be filtered, and the resulting filter cake is the solid material. In order to further remove the liquid from the solid material, the solid material needs to be dried at a temperature of 90-120°C for 60-360 minutes.

[0040] According to the present invention, optionally, in order 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 feeds the dried solid material into a tubular furnace and performs calcination treatment under an inert atmosphere, wherein the inert atmosphere is one or more of nitrogen, argon and helium; the calcination temperature is 300-700℃, preferably 400-650℃, more preferably 450-600℃; the time is 90-360 min, preferably 150-330 min, more preferably 200-300 min.

[0041] A third aspect of the present invention provides a method for producing hydrogenated coal tar, the method comprising: in the presence of hydrogen, contacting coal tar feedstock and hydrogenation catalyst provided in the first 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.

[0042] In this invention, the coal tar used is preferably medium-low temperature coal tar, and the reaction conditions for the hydrogenation reaction of the coal tar are: reaction temperature of 360-420℃, reaction time of 30-360min, and initial hydrogen pressure of 3-9MPa; relative to 1g of coal tar raw material, the amount of hydrogenation catalyst (calculated as metal element) added is 500-6000μg, preferably 500-3000μg, and more preferably 800-2000μg.

[0043] According to the present invention, optionally, the method for producing hydrogenated coal tar specifically includes: adding coal tar feedstock and hydrogenation catalyst to a slurry bed reactor, and first replacing the air in the reactor with nitrogen at room temperature, then replacing the nitrogen in the reactor with hydrogen and pressurizing to 3-9 MPa. The reaction temperature is 360-420℃, and the hydrogenation reaction is carried out for 30-360 min. After the reaction is completed, the obtained hydrogenated material is cooled to 25-35℃, the gas is collected using a gas bag for analysis, and the solid residue and liquid product are separated to obtain hydrogenated coal tar.

[0044] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0045] Examples 1-6 and Comparative Examples 1-3 describe the preparation of hydrogenation catalysts.

[0046] Example 1

[0047] (1) Preparation of the carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm; the specific surface area of ​​the activated carbon carrier was 137.8m². 2 / g, pore size 15.9nm, pore volume 0.68cm³ 3 / g;

[0048] (2) A ferrous sulfate aqueous solution was prepared using FeSO4·7H2O as the metal source solution. The Fe content in the ferrous sulfate aqueous solution was 2.4g relative to 100mL of active metal source solution. After mixing 125mL of ferrous sulfate aqueous solution with 5g of carrier evenly, 12.92g of sodium sulfide nonahydrate powder was added while stirring to carry out the precipitation reaction. The precipitation reaction conditions were: reaction temperature of 70℃ 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.

[0049] (3) After drying the solid material at 110℃ for 300 min, it is placed in a tube furnace and calcined at 500℃ for 300 min under N2 gas protection. The calcined product is the hydrogenation catalyst A1. Based on the total weight of the hydrogenation catalyst A1, the content of the active metal element Fe in the active metal component FeS is 32.39% by weight.

[0050] The properties of the hydrogenation catalysts are shown in Table 1.

[0051] Example 2

[0052] (1) Preparation of the carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm; the specific surface area of ​​the activated carbon carrier was 137.8m². 2 / g, pore size 15.9nm, pore volume 0.68cm³ 3 / g;

[0053] (2) A ferrous chloride aqueous solution was prepared using FeCl2·4H2O as the metal source solution. The Fe content in the ferrous chloride aqueous solution was 2g relative to 100mL of active metal source solution. After mixing 150mL of ferrous chloride aqueous solution with 5g of carrier evenly, 12.92g of sodium sulfide nonahydrate powder was added while stirring to carry out the precipitation reaction. The precipitation reaction conditions were: reaction temperature of 40℃ 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.

[0054] (3) After drying the solid material at 110℃ for 300 min, it was placed in a tube furnace and calcined at 550℃ for 300 min under Ar gas protection. The calcined product obtained was the hydrogenation catalyst A2. Based on the total weight of the hydrogenation catalyst A2, the content of the active metal element Fe in the active metal component FeS was 30.72% by weight.

[0055] The properties of the hydrogenation catalysts are shown in Table 1.

[0056] Example 3

[0057] (1) Preparation of the carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm; the specific surface area of ​​the activated carbon carrier was 137.8m². 2 / g, pore size 15.9nm, pore volume 0.68cm³ 3 / g;

[0058] (2) A ferrous sulfate aqueous solution was prepared using FeSO4·7H2O as the metal source solution. The Fe content in the ferrous sulfate aqueous solution was 1g relative to 100mL of active metal source solution. After mixing 100mL of ferrous sulfate aqueous solution with 5g of carrier evenly, 4.31g of sodium sulfide nonahydrate powder was added while stirring to carry out the precipitation reaction. The precipitation reaction conditions were: reaction temperature of 80℃ and reaction time of 75min. After the precipitation was washed, the obtained precipitation reaction product was separated into solid and liquid to obtain solid material.

[0059] (3) After drying the solid material at 110°C for 300 min, it was placed in a tube furnace and calcined at 500°C for 240 min under N2 gas protection. The calcined product obtained was the hydrogenation catalyst A3. Based on the total weight of the hydrogenation catalyst A3, the content of the active metal element Fe in the active metal component FeS was 17.42% by weight.

[0060] The properties of the hydrogenation catalysts are shown in Table 1.

[0061] Example 4

[0062] (1) Preparation of the carrier: The gasification ash was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm; the specific surface area of ​​the gasification ash carrier was 719.6m². 2 / g, pore size 8.3nm, pore volume 1.50cm³ 3 / g;

[0063] (2) A ferrous sulfate aqueous solution was prepared using FeSO4·7H2O as the metal source solution. The Fe content in the ferrous sulfate aqueous solution was 1g relative to 100mL of active metal source solution. After mixing 100mL of ferrous sulfate aqueous solution with 5g of carrier evenly, 4.31g of sodium sulfide nonahydrate powder was added while stirring to carry out the precipitation reaction. The precipitation reaction conditions were: reaction temperature of 80℃ and reaction time of 75min. After the precipitation was washed, the obtained precipitation reaction product was separated into solid and liquid to obtain solid material.

[0064] (3) After drying the solid material at 110°C for 300 min, it is placed in a tube furnace and calcined at 500°C for 240 min under N2 gas protection. The calcined product is the hydrogenation catalyst A4. Based on the total weight of the hydrogenation catalyst A4, the content of the active metal element Fe in the active metal component FeS is 16.15% by weight.

[0065] The properties of the hydrogenation catalysts are shown in Table 1.

[0066] Example 5

[0067] (1) Preparation of the carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm; the specific surface area of ​​the activated carbon carrier was 137.8m². 2 / g, pore size 15.9nm, pore volume 0.68cm³ 3 / g;

[0068] (2) Cobalt sulfate aqueous solution was prepared using CoSO4·7H2O as the metal source solution. The content of Co in the cobalt sulfate aqueous solution was 1g relative to 100mL of active metal source solution. After 100mL of cobalt sulfate aqueous solution was mixed evenly with 5g of carrier, 4.31g of sodium sulfide nonahydrate powder was added while stirring to carry out precipitation reaction. The precipitation reaction conditions were: reaction temperature of 70℃ 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.

[0069] (3) After drying the solid material at 110°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 A5. Based on the total weight of the hydrogenation catalyst A5, the content of the active metal element Co in the active metal component CoS is 16.79% by weight.

[0070] The properties of the hydrogenation catalysts are shown in Table 2.

[0071] Example 6

[0072] (1) Preparation of the carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm; the specific surface area of ​​the activated carbon carrier was 137.8m². 2 / g, pore size 15.9nm, pore volume 0.68cm³ 3 / g;

[0073] (2) A nickel sulfate aqueous solution was prepared using NiSO4·6H2O as the metal source solution. The content of Ni in the nickel sulfate aqueous solution was 1g relative to 100mL of active metal source solution. After mixing 100mL of nickel sulfate aqueous solution with 5g of carrier evenly, 4.31g of sodium sulfide nonahydrate powder was added while stirring to carry out the precipitation reaction. The precipitation reaction conditions were: reaction temperature of 70℃ 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.

[0074] (3) After drying the solid material at 110℃ for 300 min, it is placed in a tube furnace and calcined at 500℃ for 300 min under N2 gas protection. The calcined product is the hydrogenation catalyst A6. Based on the total weight of the hydrogenation catalyst A6, the content of the active metal element Ni in the active metal component NiS is 16.96% by weight.

[0075] The properties of the hydrogenation catalysts are shown in Table 2.

[0076] Comparative Example 1

[0077] (1) Preparation of the carrier: The activated carbon was dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm; the specific surface area of ​​the activated carbon carrier was 137.8m². 2 / g, pore size 15.9nm, pore volume 0.68cm³ 3 / g.

[0078] (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, sodium carbonate powder is added while stirring to carry out precipitation reaction; the precipitation conditions are: reaction temperature of 90℃ and reaction time of 60min; after impregnation, the obtained precipitation reaction product is separated into solid and liquid to obtain solid material;

[0079] (3) After drying the solid material at 110℃ for 240 min, it was placed in a tube furnace and calcined at 490℃ for 300 min under N2 gas protection to prepare coal tar hydrogenation catalyst B1.

[0080] The properties of the hydrogenation catalysts are shown in Table 2.

[0081] Comparative Example 2

[0082] The method for preparing the hydrogenation catalyst is the same as in Example 1, except that no calcination treatment is performed, resulting in hydrogenation catalyst B2. The properties of the hydrogenation catalyst are shown in Table 2.

[0083] Comparative Example 3

[0084] The catalyst is a liquid oil-soluble organic acid molybdenum catalyst B3. The properties of the hydrogenation catalyst are shown in Table 2.

[0085] Table 1 Properties of hydrogenation catalysts

[0086]

[0087]

[0088] Table 2 Properties of hydrogenation catalysts

[0089]

[0090]

[0091] The parameters of the hydrogenation catalyst were tested as follows:

[0092] Metal composition of hydrogenation catalyst: determined using a Thermo Scientific iCAP7000 inductively coupled plasma atomic emission spectrometer.

[0093] 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.

[0094] Particle size of active metal component: calculated using the Scherrer formula based on data of hydrogenation catalyst measured by X-ray diffraction.

[0095] Hydrogenation catalyst particle size: measured using an MS3000 laser particle size analyzer.

[0096] Specific surface area of ​​hydrogenation catalyst: determined by ASAP2460 physical BET adsorption analyzer.

[0097] Examples 7-9 and Comparative Examples 4-6 evaluate the hydrogenation catalysts. The coal tar used is medium-low temperature coal tar, and the properties of the medium-low temperature coal tar are shown in Table 3.

[0098] Properties of Low-Temperature Coal Tar in Table 3

[0099]

[0100]

[0101] Example 7

[0102] 200g of medium-low temperature coal tar and 0.617g of hydrogenation catalyst Al (Fe content 1000μg / g) were added to a 1.8L high-pressure reactor. The air inside the reactor was first replaced with nitrogen at room temperature, then the nitrogen was replaced with hydrogen and pressurized to 4.0MPa. The hydrogenation reaction was carried out for 60min at 380℃. After the reaction, the hydrogenated material was cooled to room temperature, and the gas was collected and analyzed using a gas bag. 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.

[0103] Example 8

[0104] The method for hydrogenating coal tar is the same as in Example 7, except that the hydrogenation catalyst is hydrogenation catalyst A5 and the amount added is 1.192 g (Co addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 4 and 5.

[0105] Example 9

[0106] The method for hydrogenating coal tar is the same as in Example 7, except that the hydrogenation catalyst is hydrogenation catalyst A6 and the amount added is 1.179 g (Ni addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 4 and 5.

[0107] Comparative Example 4

[0108] The method for hydrotreating coal tar is the same as in Example 7, except that the hydrotreating catalyst is hydrotreating catalyst B1 and the amount added is 0.565 g (Fe addition amount is 1000 μg / g) and 0.115 g sublimed sulfur. The operating conditions and reaction results are shown in Tables 4 and 5.

[0109] Comparative Example 5

[0110] The method for hydrogenating coal tar is the same as in Example 7, except that the hydrogenation catalyst is hydrogenation catalyst B2 and the amount added is 0.741 g (Fe addition amount is 1000 μg / g). The operating conditions and reaction results are shown in Tables 4 and 5.

[0111] Comparative Example 6

[0112] The method for hydrotreating coal tar is the same as in Example 7, except that the hydrotreating catalyst is hydrotreating catalyst B3 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.

[0113] Table 4 Operating conditions and reaction results

[0114]

[0115]

[0116] Table 5 Properties of Liquid Products

[0117]

[0118]

[0119] The hydrogen consumption, liquid yield, metal removal rate, mechanical impurity removal rate, and coking rate of the method for producing hydrogenated coal tar are calculated according to the following formulas:

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127] A comparison of Examples 7 and Comparative Examples 4 and 6 in Tables 4 and 5 shows that the activated carbon-precipitated ferrous sulfide catalyst, without the addition of a sulfiding agent, exhibits comparable liquid yield, coking rate, and metal removal rate to the activated carbon-supported precipitated iron oxide catalyst, but with superior desulfurization and denitrification rates. The activated carbon-precipitated ferrous sulfide catalyst demonstrates a higher denitrification rate than commercial organomolybdenum catalysts, while maintaining comparable liquid yield, coking rate, and metal removal rate. Furthermore, it features low catalyst addition and low raw material costs. This indicates that the catalyst prepared in this invention, even without the addition of a sulfiding agent and with a low catalyst addition, still possesses advantages such as high reactivity, high metal and organic impurity removal rates, high liquid yield, and low coking rate, thereby reducing pretreatment operation costs. A comparison of Example 7 and Comparative Example 5 shows that calcination treatment can improve the performance of the hydrogenation catalyst.

[0128] A comparison of Examples 7-9 in Tables 4 and 5 shows that the activated carbon-precipitated ferrous sulfide catalyst, along with the activated carbon-precipitated cobalt sulfide and nickel sulfide catalysts, exhibits advantages such as high metal and organic impurity removal rates and high liquid yields. 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.

[0129] The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the specific details of 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.

[0130] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0131] 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 one or more of Fe, Co, and Ni; the particle size of the active metal component in the hydrogenation catalyst is 5-40 nm; the carbon-based support comprises one or more of carbon black, activated carbon, semi-coke, graphite, gasification ash, and petroleum coke; the specific surface area of ​​the carbon-based support is 20-1200 m². 2 / g, pore size 1-20nm, pore volume 0.1-10cm³ 3 / g; The carrier and active metal source solution are mixed, and sulfide is added to carry out a precipitation reaction. Then, solid-liquid separation is performed to obtain solid material. The solid material is dried and calcined to obtain a calcined product; the calcination is carried out in an inert atmosphere. The hydrogenation catalyst is subjected to the calcination treatment, and the calcination temperature is 450-600℃ for 90-360 min; The active metal element in the hydrogenation catalyst exists in the form of a metal sulfide; the metal sulfide includes at least one of FeS, CoS and NiS.

2. The hydrogenation catalyst according to claim 1, wherein, Based on the total weight of the hydrogenation catalyst, the content of active metal elements in the active metal component is 1-60% by weight.

3. The hydrogenation catalyst according to claim 2, wherein, Based on the total weight of the hydrogenation catalyst, the content of active metal elements in the active metal component is 10-50% by weight.

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

5. The hydrogenation catalyst according to claim 4, wherein, The active metal component in the hydrogenation catalyst has a particle size of 10-30 nm.

6. The hydrogenation catalyst according to claim 1, wherein, The specific surface area of ​​the hydrogenation catalyst is 10-1000 m². 2 / g; pore size 2-20nm; pore volume 0.01-3cm³ 3 / g.

7. The hydrogenation catalyst according to claim 6, wherein, The specific surface area of ​​the hydrogenation catalyst is 20-600 m². 2 / g; pore size 5-15nm; pore volume 0.1-1cm³ 3 / g.

8. The hydrogenation catalyst according to claim 1, wherein, The carbon-based support has a particle size of 10-100 μm.

9. The hydrogenation catalyst according to claim 8, wherein, The carbon-based support has a particle size of 20-60 μm.

10. A method for preparing the hydrogenation catalyst according to claim 1, characterized in that, The method includes: S1. Mix the carrier and the active metal source solution, add sulfide to carry out precipitation reaction, and then perform solid-liquid separation to obtain solid material; S2. 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 450-600℃ and the time is 90-360min. The active metal source solution is selected from sulfate solution and / or chloride solution; the active metal element in the active metal source solution is one or more of Fe, Co and Ni.

11. The method according to claim 10, wherein, 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 sulfide is one or more of sodium sulfide, potassium sulfide and ammonium sulfide; The inert atmosphere is one or more of nitrogen, argon and helium.

12. The method according to claim 10, wherein, The conditions for the precipitation reaction include: a reaction temperature of 10-100℃, a reaction time of 30-300 min, and a stoichiometric ratio of the sulfide to the active metal element in the active metal source solution of (1-2.5):

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

13. A method for producing hydrogenated coal tar, characterized in that, The method includes: in the presence of hydrogen, contacting a coal tar feedstock and the hydrogenation catalyst according to any one of claims 1-9 in a slurry bed reactor to carry out a hydrogenation reaction.

Images