Hydrogenation catalyst, preparation method thereof and method for producing hydrogenated coal tar

Abstract

The invention relates to a hydrogenation catalyst. The hydrogenation catalyst comprises a carrier and an active metal component, the carrier is a carbon-based carrier, and active metal elements in the active metal component are one or more of Fe, Co and Ni; active metal elements in the hydrogenation catalyst exist in the form of metal sulfide; the metal sulfide comprises at least one of FeS, CoS and NiS. According to the hydrogenation catalyst provided by the invention, the carbon-based carrier is used as a carrier, and active metal elements in the active metal component exist in the form of metal sulfide, so that the reaction activity of hydrogenation reaction can be improved and the coking rate can be reduced under the condition that a vulcanizing agent is not added; and the metal removal rate, the mechanical impurity removal rate and the liquid yield are kept at a relatively high level. In addition, the active metal elements in the hydrogenation catalyst are one or more of Fe, Co and Ni, so that the cost of the hydrogenation catalyst can be reduced.

Description

Technical Field

[0001] The invention relates to the technical field of petrochemical industry, in particular to a hydrogenation catalyst and a preparation method thereof and a method for producing hydrogenated coal tar. Background Art

[0002] The traditional processing route of coal tar is to extract target products such as anthracene oil, naphthalene, crude phenol and light oil from coal tar by extraction or distillation, but there are problems such as few high value-added components, difficulty in using low value-added components, complex process flow, high energy consumption and serious pollution, and poor economic benefits. Coal tar hydrogenation technology can improve resource utilization and product added value while reducing pollution, and is the main direction for the development of new coal tar clean utilization technology.

[0003] CN102380396A discloses a method for preparing a bimetallic or multimetallic composite suspended bed coal tar hydrogenation catalyst, which comprises the steps of firstly loading ferrous salt on coal powder to prepare a γ-FeOOH coal powder filter cake, then spraying highly active metal components such as molybdenum, nickel, and cobalt water-soluble salts on the coal powder filter cake, and then dehydrating to obtain a composite coal tar hydrogenation catalyst.

[0004] CN111420671A discloses a method for preparing a coal tar suspended bed hydrocracking catalyst, wherein the catalyst is prepared by mixing solid powders containing blue coke, iron compounds and cobalt-molybdenum-nickel hydrocracking catalyst regeneration waste agent, and then mixing the solid powders with red mud powder.

[0005] CN109701537A discloses a pre-hydrogenation catalyst and its preparation method and application. The pre-hydrogenation catalyst comprises activated carbon and an active substance supported on the activated carbon, wherein the active substance comprises a metal oxide or a salt thereof, wherein the metal oxide is one or more of the oxides of Co, Mo, Ni, W, Fe, and Mg; and the metal oxide accounts for 0.1-25wt% of the activated carbon.

[0006] However, the existing coal tar hydrogenation catalyst needs to add a sulfiding agent 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 the present invention is to provide a hydrogenation catalyst and a preparation method thereof and a method for producing hydrogenated coal tar, which can solve the problem of low catalytic reaction activity of coal tar hydrogenation catalyst in the prior art without adding a sulfiding agent in the coal tar hydrogenation reaction.

[0008] In order to achieve the above-mentioned object, the first aspect of the present invention provides a hydrogenation catalyst, which includes a carrier and an active metal component; the carrier is a carbon-based carrier, 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 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 10-1000m 2 / g, preferably 20-600m 2 / g; pore diameter is 2-20nm, preferably 5-15nm; pore volume is 0.01-3cm 3 / g, preferably 0.1-1cm 3 / g.

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

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

[0015] S1. Mixing a carrier and an active metal source solution, adding sulfide to carry out precipitation reaction, and then performing solid-liquid separation to obtain a solid material; S2. Drying and roasting the solid material to obtain a roasted product; the roasting is carried out in an inert atmosphere; the carrier is a carbon-based carrier; the active metal source solution is selected from a sulfate solution and / or a 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 active metal elements 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 conditions of the precipitation reaction include: a reaction temperature of 10-100°C, a reaction time of 30-300 min, a stoichiometric ratio of the amount of the sulfide to the amount of the active metal element in the active metal source solution of (1-2.5):1; a drying temperature of 90-120°C, a time of 60-360 min; a calcination temperature of 300-700°C, a time of 90-360 min.

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

[0019] Through the above technical scheme, the hydrogenation catalyst provided by the present invention uses a carbon-based carrier as a carrier, and the active metal element in the active metal component exists in the form of metal sulfide, which can improve the reaction activity of the hydrogenation reaction and reduce the coking rate without adding a sulfiding agent, while ensuring that the metal removal rate, mechanical impurity (abbreviated as mechanical impurities) removal rate and 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 cost of the hydrogenation catalyst.

[0020] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:

[0022] Figure 1 It is an electron microscope image of the hydrogenation catalyst of Example 1 of the present invention. DETAILED DESCRIPTION

[0023] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0024] The first aspect of the present invention provides a hydrogenation catalyst, which includes a carrier and an active metal component; the carrier is a carbon-based carrier, 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 metal sulfide; the metal sulfide includes at least one of FeS, CoS and NiS.

[0025] In the present invention, the hydrogenation catalyst is obtained by precipitation reaction between a carrier and an active metal component. The hydrogenation catalyst uses a carbon-based carrier as a carrier, and the active metal element in the active metal component exists in the form of metal sulfide. By introducing metal sulfide on the carbon-based carrier to make them interact with each other, the reaction activity of the hydrogenation reaction can be improved and the coking rate can be reduced without adding a sulfiding agent, while ensuring that the metal removal rate, organic impurity removal rate and liquid yield are maintained at a high level; and 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 enable the hydrogenation catalyst to exert excellent catalytic performance while reducing costs, it is necessary to limit the content of active metal components in the hydrogenation catalyst to a certain extent. Specifically, based on the total weight of the hydrogenation catalyst, the content of active metal elements in the active metal components 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 calcining the carrier and the active metal component after precipitation reaction, the particle size of the active metal component is smaller than that of the traditional 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 10-1000m 2 / g, preferably 20-600m 2 / g; pore diameter is 2-20nm, preferably 5-15nm; pore volume is 0.01-3cm 3 / g, preferably 0.1-1cm 3 / g.

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

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

[0032] S1. Mixing a carrier and an active metal source solution, adding sulfide to carry out precipitation reaction, and then performing solid-liquid separation to obtain a solid material; S2. Drying and roasting the solid material to obtain a roasted product; the roasting is carried out in an inert atmosphere; the carrier is a carbon-based carrier; the active metal source solution is selected from a sulfate solution and / or a chloride solution; the active metal element in the active metal source solution is one or more of Fe, Co and Ni.

[0033] In the present invention, the metal sulfide formed by the active metal component and the sulfide in the active metal source solution is precipitated on a carbon-based carrier as a carrier, and then subjected to a roasting treatment, so that the metal sulfide and the carrier interact with each other. Compared with the method of preparing a supported catalyst by a conventional impregnation method, the method of the present invention can obtain an active metal component with a smaller particle size, thereby increasing the contact area between the active metal component and the reaction material, and thus can enhance the activity of the hydrogenation catalyst.

[0034] According to the present invention, optionally, in order to make the precipitation reaction more effective, the carbon-based carrier needs to be pretreated before the precipitation reaction; the pretreatment method is conventionally selected in the art, and this application does not make special requirements. For example, the carbon-based carrier is dried at a temperature of 100-130°C to remove moisture and some impurities therein.

[0035] According to the present invention, optionally, in order to further enhance the activity of the precipitation reaction, when adding the sulfide material, the present invention can directly add solid powder to the mixed material, or can prepare the sulfide into a solution and then add it to the mixed material. The sulfide is one or more of sodium sulfide, potassium sulfide and ammonium sulfide.

[0036] According to the present invention, 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, preferably 0.8-4 g, and more preferably 1-3 g.

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

[0038] In the present invention, the carbon-based carrier is placed in an active metal source solution and a suitable amount of sulfide is added thereto, so that the active metal element in the active metal source solution can react with the sulfide to generate a precipitate, and the precipitate will coat the carbon-based carrier in the mixed material. Therefore, the surface of the carbon-based carrier is coated with a uniform precipitate, which can further enhance the performance of the hydrogenation catalyst.

[0039] According to the present invention, optionally, after the precipitation reaction is completed, the reaction mass is in a state where solid and liquid coexist, and therefore, the precipitation reaction product needs to be subjected to solid-liquid separation. The method of solid-liquid separation used in the present invention is conventionally selected in the art, and this application does not make special requirements. For example, the precipitation reaction product can be filtered, and the obtained filter cake is a solid material. In order to further remove the liquid in the solid material, the solid material needs to be dried at a temperature of 90-120° C. for 60-360 min.

[0040] According to the present invention, optionally, in order to avoid the influence of moisture, oxygen and impurities in the air on the catalyst, thereby improving the performance of the hydrogenation catalyst, the present invention sends the dried solid material to a tubular furnace and performs a 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°C, preferably 400-650°C, and more preferably 450-600°C; the time is 90-360min, preferably 150-330min, and more preferably 200-300min.

[0041] The third aspect of the present invention provides a method for producing hydrogenated coal tar, which comprises: in the presence of hydrogen, contacting a coal tar raw material with the hydrogenation catalyst provided by the first aspect of the present invention in a slurry bed reactor for a hydrogenation reaction to obtain a material after the hydrogenation reaction; and subjecting the material after the hydrogenation reaction to solid-liquid separation to obtain hydrogenated coal tar.

[0042] In the present invention, the coal tar used is preferably medium-low temperature coal tar, and the reaction conditions of the hydrogenation reaction of coal tar are: reaction temperature is 360-420°C, reaction time is 30-360min, and initial hydrogen pressure is 3-9MPa; relative to 1g of coal tar raw material, the addition amount of hydrogenation catalyst (in terms of metal element) 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 comprises: adding coal tar raw material and hydrogenation catalyst to a slurry bed reactor, and replacing the air in the kettle with nitrogen at room temperature, and then replacing the nitrogen in the kettle with hydrogen and pressurizing it to 3-9MPa. The reaction temperature is 360-420°C, and the hydrogenation reaction is carried out for 30-360min. After the reaction is completed, the obtained hydrogenation reaction material is cooled to 25-35°C, and the gas is collected with an air bag for analysis, and the solid residue and the liquid product are separated by solid-liquid separation to obtain hydrogenated coal tar.

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

[0045] Examples 1-6 and Comparative Examples 1-3 are preparations of hydrogenation catalysts.

[0046] Example 1

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

[0048] (2) FeSO4·7H2O is used to prepare an aqueous ferrous sulfate solution as a metal source solution, wherein the Fe content in the aqueous ferrous sulfate solution is 2.4 g relative to 100 mL of the active metal source solution; after 125 mL of the aqueous ferrous sulfate solution is uniformly mixed with 5 g of the carrier, 12.92 g of sodium sulfide nonahydrate powder is added during stirring to perform a precipitation reaction; wherein the conditions of the precipitation reaction are: a reaction temperature of 70° C. and a reaction time of 60 min; after the precipitate is washed, the obtained precipitation reaction product is subjected to solid-liquid separation to obtain a solid material;

[0049] (3) The solid material was dried at 110° C. for 300 min, placed in a tube furnace, and calcined at 500° C. for 300 min under N2 gas protection to obtain a calcined product, which was 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 was 32.39% by weight.

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

[0051] Example 2

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

[0053] (2) FeCl2·4H2O is used to prepare an aqueous ferrous chloride solution as a metal source solution, wherein the content of Fe in the aqueous ferrous chloride solution is 2 g relative to 100 mL of the active metal source solution; after 150 mL of the aqueous ferrous chloride solution is uniformly mixed with 5 g of the carrier, 12.92 g of sodium sulfide nonahydrate powder is added during stirring to perform a precipitation reaction; wherein the conditions of the precipitation reaction are: a reaction temperature of 40° C. and a reaction time of 60 min; after the precipitate is washed, the obtained precipitation reaction product is subjected to solid-liquid separation to obtain a solid material;

[0054] (3) The solid material was dried at 110° C. for 300 min, placed in a tube furnace, and calcined at 550° C. for 300 min under Ar gas protection to obtain a calcined product, which 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 catalyst are shown in Table 1.

[0056] Example 3

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

[0058] (2) FeSO4·7H2O is used to prepare an aqueous ferrous sulfate solution as a metal source solution, wherein the content of Fe in the aqueous ferrous sulfate solution is 1 g relative to 100 mL of the active metal source solution; after 100 mL of the aqueous ferrous sulfate solution is uniformly mixed with 5 g of the carrier, 4.31 g of sodium sulfide nonahydrate powder is added during stirring to perform a precipitation reaction; wherein the conditions of the precipitation reaction are: a reaction temperature of 80° C. and a reaction time of 75 min; after the precipitate is washed, the obtained precipitation reaction product is subjected to solid-liquid separation to obtain a solid material;

[0059] (3) The solid material was dried at 110° C. for 300 min, placed in a tube furnace, and calcined at 500° C. for 240 min under N2 gas protection to obtain a calcined product, which 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 catalyst are shown in Table 1.

[0061] Example 4

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

[0063] (2) FeSO4·7H2O is used to prepare an aqueous ferrous sulfate solution as a metal source solution, wherein the content of Fe in the aqueous ferrous sulfate solution is 1 g relative to 100 mL of the active metal source solution; after 100 mL of the aqueous ferrous sulfate solution is uniformly mixed with 5 g of the carrier, 4.31 g of sodium sulfide nonahydrate powder is added during stirring to perform a precipitation reaction; wherein the conditions of the precipitation reaction are: a reaction temperature of 80° C. and a reaction time of 75 min; after the precipitate is washed, the obtained precipitation reaction product is subjected to solid-liquid separation to obtain a solid material;

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

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

[0066] Example 5

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

[0068] (2) CoSO4·7H2O is used to prepare a cobalt sulfate aqueous solution as a metal source solution, wherein the content of Co in the cobalt sulfate aqueous solution is 1 g relative to 100 mL of the active metal source solution; after 100 mL of the cobalt sulfate aqueous solution is evenly mixed with 5 g of the carrier, 4.31 g of sodium sulfide nonahydrate powder is added during stirring to perform a precipitation reaction; wherein the conditions of the precipitation reaction are: a reaction temperature of 70° C. and a reaction time of 60 min; after the precipitate is washed, the obtained precipitation reaction product is subjected to solid-liquid separation to obtain a solid material;

[0069] (3) The solid material was dried at 110° C. for 300 min, placed in a tube furnace, and calcined at 500° C. for 300 min under N2 gas protection to obtain a calcined product, which was 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 was 16.79 wt%.

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

[0071] Example 6

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

[0073] (2) preparing a nickel sulfate aqueous solution with NiSO4·6H2O as a metal source solution, wherein the content of Ni in the nickel sulfate aqueous solution is 1 g relative to 100 mL of the active metal source solution; after uniformly mixing 100 mL of the nickel sulfate aqueous solution with 5 g of the carrier, 4.31 g of sodium sulfide nonahydrate powder is added during stirring to perform a precipitation reaction; wherein the conditions of the precipitation reaction are: a reaction temperature of 70° C. and a reaction time of 60 min; after the precipitation is washed, the obtained precipitation reaction product is subjected to solid-liquid separation to obtain a solid material;

[0074] (3) The solid material was dried at 110° C. for 300 min, placed in a tube furnace, and calcined at 500° C. for 300 min under N2 gas protection to obtain a calcined product, which was 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 was 16.96% by weight.

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

[0076] Comparative Example 1

[0077] (1) Preparation of carrier: The activated carbon was dried and dehydrated at 120°C and then crushed into powder with a particle size of 20-60 μm. The specific surface area of ​​the activated carbon carrier was 137.8 m 2 / g, pore diameter is 15.9nm, pore volume is 0.68cm 3 / g.

[0078] (2) preparing an aqueous ferric sulfate solution with Fe2(SO4)3 as a metal source solution, wherein the Fe content in the aqueous ferric sulfate solution is 2.4 g relative to 100 mL of the active metal source solution; after uniformly mixing 125 mL of the aqueous ferric sulfate solution with 5 g of the carrier, sodium carbonate powder is added during stirring to perform a precipitation reaction; wherein the precipitation conditions are: a reaction temperature of 90°C and a reaction time of 60 min; after the impregnation is completed, the obtained precipitation reaction product is subjected to solid-liquid separation to obtain a solid material;

[0079] (3) The solid material was dried at 110° C. for 240 min, placed in a tubular furnace, and calcined at 490° C. for 300 min under N 2 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 that in Example 1, except that no calcination treatment is performed to prepare the 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] Among them, the parameters of the hydrogenation catalyst test are as follows:

[0092] The metal composition of the hydrogenation catalyst was measured using an iCAP7000 inductively coupled plasma emission spectrometer from Thermo Scientific.

[0093] Metal phase: Characterized on a D8ADVANCE X-ray diffractometer, Cu Kα radiation, λ=0.15418 nm, 2θ scanning range of 5° to 70°, and scanning rate of 4 (°) / min.

[0094] Active metal component particle size: calculated using the Scherrer formula based on data of hydrogenation catalyst measured by an X-ray diffractometer.

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

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

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

[0098] Table 3 Properties of medium and low temperature coal tar

[0099]

[0100]

[0101] Example 7

[0102] 200g of medium-low temperature coal tar and 0.617g of hydrogenation catalyst A1 (Fe addition amount is 1000μg / g) were added to a 1.8L autoclave, and the air in the autoclave was replaced with nitrogen at room temperature, and then the nitrogen in the autoclave was replaced with hydrogen and pressurized to 4.0MPa. When the reaction temperature reached 380°C, the hydrogenation reaction was carried out for 60min. After the reaction was completed, the obtained hydrogenation reaction material was cooled to room temperature, and the gas was collected with an air bag for analysis, and the solid residue and the liquid product were separated by solid-liquid separation to obtain hydrogenated coal tar and liquid products. 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 that in Example 7, except that the hydrogenation catalyst is hydrogenation catalyst A5 and the addition amount is 1.192 g (the addition amount of Co 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 that of Example 7, except that the hydrogenation catalyst is hydrogenation catalyst A6 and the addition amount 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 hydrogenating coal tar is the same as that of Example 7, except that the hydrogenation catalyst is hydrogenation catalyst B1 and the addition amount is 0.565 g (the addition amount of Fe is 1000 μg / g) and 0.115 g of sublimated 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 that in Example 7, except that the hydrogenation catalyst is hydrogenation catalyst B2 and the addition amount is 0.741 g (the addition amount of Fe 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 hydrogenating coal tar is the same as that of Example 7, except that the hydrogenation catalyst is hydrogenation catalyst B3 and the added amount is 1.359 g (Mo added amount is 1000 μg / g), and the added mass of sublimated sulfur 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 Liquid product properties

[0117]

[0118]

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

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127] From Tables 4 and 5, it can be seen that the activated carbon precipitated ferrous sulfide catalyst is comparable to the precipitated iron oxide catalyst with activated carbon as the carrier in terms of liquid yield, coking rate and metal removal rate without adding a sulfiding agent, and has a better desulfurization rate and denitrification rate. The denitrification rate of the activated carbon precipitated ferrous sulfide catalyst is better than that of the commercial organic molybdenum catalyst, and is comparable in liquid yield, coking rate and metal removal rate, and has the characteristics of low catalyst addition and low raw material cost, indicating that the catalyst prepared by the present invention still has the advantages of high reaction activity, high metal and organic impurity removal rate, high liquid yield and low coking rate when no sulfiding agent and low catalyst addition are added, thereby reducing the pretreatment operation cost. It can be seen from the comparison of Example 7 and Comparative Example 5 that the roasting treatment can make the hydrogenation catalyst have better performance.

[0128] From Tables 4 and 5, it can be seen that the activated carbon precipitated ferrous sulfide catalyst, activated carbon precipitated cobalt sulfide and nickel sulfide catalysts all show the advantages of high metal and organic impurity removal rate and high liquid yield. Considering that the price of nickel is 30 times that of iron, the price of cobalt is 70 times that of iron, and the price of molybdenum is 40 times that of iron, iron is preferably used as the catalyst metal component considering economic cost. The catalyst is also cheap, simple to prepare, and can achieve efficient pretreatment of coal tar.

[0129] The preferred embodiments of the present invention are described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to 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 further describe various possible combinations.

[0131] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A hydrogenation catalyst, characterized in that The hydrogenation catalyst comprises a carrier and an active metal component; the carrier is a carbon-based carrier, and the active metal element in the active metal component is one or more of Fe, Co and Ni; The active metal elements in the hydrogenation catalyst exist in the form of metal sulfides; the metal sulfides include 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 the active metal element in the active metal component is 1-60% by weight, preferably 10-50% by weight.

3. The hydrogenation catalyst according to claim 1, wherein The particle size of the active metal component in the hydrogenation catalyst is 5-40 nm.

4. The hydrogenation catalyst according to claim 3, wherein The particle size of the active metal component in the hydrogenation catalyst is 8-35 nm, preferably 10-30 nm.

5. The hydrogenation catalyst according to claim 1, wherein The specific surface area of ​​the hydrogenation catalyst is 10-1000m 2 / g, preferably 20-600m 2 / g; pore diameter is 2-20nm, preferably 5-15nm; pore volume is 0.01-3cm 3 / g, preferably 0.1-1cm 3 / g.

6. The hydrogenation catalyst according to claim 1, wherein The carbon-based carrier includes one or more of carbon black, activated carbon, blue carbon, graphite, gasification ash and petroleum coke; The particle size of the carbon-based carrier is 10-100 μm, preferably 20-60 μm; The specific surface area of ​​the carbon-based carrier is 20-1200m 2 / g, pore diameter is 1-20nm, pore volume is 0.1-10cm 3 / g.

7. A method for preparing a hydrogenation catalyst, characterized in that: The method includes: S1, mixing the carrier and the active metal source solution, adding sulfide to carry out precipitation reaction, and then performing solid-liquid separation to obtain a solid material; S2, drying and roasting the solid material to obtain a roasted product; the roasting is carried out in an inert atmosphere; The carrier is a carbon-based carrier; The active metal source solution is selected from a sulfate solution and / or a chloride solution; the active metal element in the active metal source solution is one or more of Fe, Co and Ni.

8. The method according to claim 7, wherein: The content of the active metal element in the active metal source solution is 0.5-5 g relative to 100 mL 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.

9. The method according to claim 7, wherein: The conditions of the precipitation reaction include: a reaction temperature of 10-100° C., a reaction time of 30-300 min, and a stoichiometric ratio of the amount of the sulfide to the amount of the active metal element in the active metal source solution of (1-2.5):1; The drying temperature is 90-120°C and the drying time is 60-360min; The calcination temperature is 300-700° C. and the calcination time is 90-360 min.

10. A method for producing hydrogenated coal tar, characterized in that: The method comprises: in the presence of hydrogen, bringing coal tar raw material and the hydrogenation catalyst described in any one of claims 1 to 6 into contact in a slurry bed reactor to carry out a hydrogenation reaction.

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