Coal tar hydrogenation catalyst, its preparation method and application

Abstract

The application discloses a coal tar hydrogenation catalyst and a preparation method and application thereof. The catalyst comprises a carrier and an active metal component distributed on the carrier, wherein the carrier comprises alumina, carbon and hydrogen; and the active metal component is one or more of group VIII metal and / or group VIB metal. The preparation method of the coal tar hydrogenation catalyst comprises the following steps: (a) preparing a carrier material; (b) performing surface modification treatment on the carrier material to obtain a modified carrier; and (c) introducing the active metal into the modified carrier to obtain the coal tar hydrogenation catalyst. Through the modification treatment on the carrier, the dispersion of the active metal is strengthened, the hydrogenation performance of the catalyst is improved, and the coal tar hydrogenation catalyst with good water resistance is provided.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of petroleum chemical industry, and relates to a preparation method and application of a coal tar hydrogenation catalyst. BACKGROUND

[0002] Coal chemical industry has great potential, and key core technology research should be accelerated, and coal-based special fuel should be actively developed. Coal tar is a liquid product obtained in the process of coal dry distillation and gasification. At room temperature, coal tar is a black viscous liquid with high density, high metal, high mechanical impurities, high gum and asphaltene, high oxygen content, high aromatic hydrocarbon and high carbon-hydrogen ratio, and belongs to a poor quality raw material which is difficult to process. Coal tar hydrogenation technology is a main direction of clean utilization technology exploration of coal tar, can extend the industrial chain, improve resource utilization rate, reduce pollution and extract high value-added products.

[0003] Coal tar raw material contains a certain amount of water and is rich in oxygen elements. In the hydrogenation process, oxygen is hydrogenated to form water, which has a serious impact on the mechanical properties of the catalyst under high temperature and high pressure conditions, and even causes the catalyst to be pulverized, resulting in shutdown of the device. Therefore, the focus of coal tar catalyst research and development should be to improve the water resistance of the catalyst under the premise of ensuring the hydrogenation performance of the catalyst.

[0004] CN201210308751.0 relates to a coal tar hydrocracking catalyst and a preparation method thereof. Amorphous silicon aluminum is made into a slurry with a pH value of 3.0-5.5, modified Y molecular sieve solid powder is uniformly mixed with the amorphous silicon aluminum slurry, and then dehydrated to form a paste that can be formed. The catalyst carrier is prepared by forming, drying and calcining, and finally the final hydrocracking catalyst is obtained by loading hydrogenation metal components by impregnation. In the present application, one of the cracking components, amorphous silicon aluminum, is made into a slurry with a certain acidity. Due to the peptizing effect of acid, the slurry has a certain adhesive property of thin paste. After the modified molecular sieve powder is uniformly mixed with the slurry, the modified molecular sieve particles are wrapped with the amorphous silicon aluminum slurry to form a covering layer, i.e. a composite layer structure of the modified molecular sieve inside and the amorphous silicon aluminum outside. The patent first prepares amorphous silicon aluminum material, and realizes water resistance by using silicon aluminum material, but the preparation process is complex.

[0005] CN201810203515.X discloses a hydrophobic modified hydrogenation catalyst and its preparation method and application. The preparation method comprises: providing an active component solution containing Group VIII metal and / or Group IB metal ammonia complex ions; impregnating and drying the TiO2-Al2O3 composite oxide carrier in the active component solution to prepare a catalyst precursor; contacting the catalyst precursor with a carrier gas carrying a silane modifier for hydrophobic modification treatment; and heating the hydrophobic modified catalyst precursor in a hydrogen atmosphere to prepare the hydrogenation catalyst. The application utilizes multiple ammonia molecules complexed on the surface of Group VIII metal and / or Group IB metal to realize space occupation, thereby being capable of adjusting the subsequent hydrophobic modification process, so as to obtain a hydrogenation catalyst with reduced catalytic activity due to the covering of active sites by the silane modifier. The patent uses a surface modification method to prepare a hydrogenation catalyst with high water resistance, but the preparation process is relatively complex, and the activity of the catalyst is lost, which is not suitable for improving the activity and stability of the catalyst. SUMMARY

[0006] The application provides a coal tar hydrogenation catalyst with good water resistance and a preparation method thereof. In the preparation method, a flexible material is added to an existing alumina-based catalyst carrier, the flexible material is combined with alumina efficiently by using the multifunctional groups of the flexible material, the flexibility of the high-temperature material is used to weaken the gasification of water, the strength of the carrier is maintained, and the water resistance of the catalyst is improved. Meanwhile, the modification of the carrier is combined to strengthen the dispersion of the active metal and improve the hydrogenation performance of the catalyst.

[0007] The technical scheme provided by the application mainly includes the following aspects:

[0008] The application provides a coal tar hydrogenation catalyst. The catalyst comprises a carrier and an active metal component distributed on the carrier, wherein the carrier comprises alumina, carbon and hydrogen, H is in the form of C-H bond, and the active metal component is one or more of Group VIII metal and / or Group VIB metal.

[0009] Further, in the coal tar hydrogenation catalyst, the content of alumina is 55-90wt%, the content of carbon is 3.5-19.0wt%, and the content of H is 0.28-1.72wt% based on the weight of the catalyst.

[0010] Further, in the coal tar hydrogenation catalyst, the content of Group VIII metal is 0.5%-5% and preferably 0.5%-4.5% based on the weight of the catalyst; and the content of Group VIB metal is 4%-25% and preferably 4%-20% based on the weight of the catalyst.

[0011] Further, in the coal tar hydrogenation catalyst, the pore volume of the catalyst is not less than 0.45 mL / g, preferably more than 0.50 mL / g, and generally can be 0.50-0.75 mL / g.

[0012] Further, in the coal tar hydrogenation catalyst, the specific surface area of the catalyst is 150-250 m 2 / g, preferably 150-220 m 2 / g.

[0013] Further, in the coal tar hydrogenation catalyst, the total acid content of the catalyst is 0.2-0.6 mmol / g, preferably 0.25-0.55 mmol / g.

[0014] Further, in the catalyst material, as a preferred embodiment, the lateral pressure strength of the catalyst is more than 6 N / mm, preferably more than 8 N / mm.

[0015] The second aspect of the present application provides a preparation method of a coal tar hydrogenation catalyst, which comprises the following steps:

[0016] (a) preparing a carrier material;

[0017] (b) performing surface modification treatment on the carrier material to obtain a modified carrier;

[0018] (c) introducing active metal onto the modified carrier obtained in step (b) to obtain a coal tar hydrogenation catalyst.

[0019] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the surface modification treatment in step (b) is as follows: the carrier material obtained in step (a) is contacted with a high-molecular organic alcohol solution, and then subjected to calcination treatment; the calcination treatment temperature is 150-300°C, and the calcination treatment time is 0.5-2 h; the calcination treatment is generally performed in an air atmosphere.

[0020] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the high-molecular organic alcohol solution is one or several of polyethylene glycol and polyvinyl alcohol, and the molecular weight of the high-molecular organic alcohol is not more than 6000, preferably not more than 2000.

[0021] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the concentration of the high-molecular organic alcohol solution is 10 wt%-40 wt%, preferably 15 wt%-30 wt%.

[0022] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the mass ratio of the high-molecular organic alcohol solution to the carrier material obtained in step (a) is 0.8:1-1.1:1.

[0023] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the preparation method of the carrier material in step (a) comprises the following steps:

[0024] (1) uniformly mixing the first additive with the first solvent to obtain a first stream;

[0025] (2) uniformly mixing the first carrier and the first stream, then adding the second carrier, the second additive and the second solvent, and uniformly mixing to obtain a second stream;

[0026] (3) carbonizing the second stream in the presence of an inert atmosphere;

[0027] (4) oxidizing the material after the carbonization treatment in the presence of an oxygen-containing atmosphere to obtain the carrier.

[0028] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the first additive in step (1) is a polymer, and the specific first additive is selected from one or more of resins, rubbers, plastics and the like, preferably one or more of C5 petroleum resin, C9 petroleum resin, silicone rubber, polyethylene and polyester (PET), and further preferably C9 petroleum resin.

[0029] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the first solvent in step (1) is an organic solvent, and the organic solvent is one or more of benzene and derivatives thereof, cycloalkanes, ketones, alcohols and chlorinated hydrocarbons, and the specific organic solvent can be one or more of benzene, toluene, xylene, cyclohexane, acetone, N-methyl pyrrolidone and trichloromethane; further, the selection of the first solvent is generally based on the selection of the type of the first additive to select a suitable solvent, for example, when the resin is selected as the first additive, cyclohexane can be used as the solvent, when the rubber is selected as the first additive, toluene can be used as the solvent, and when the polyester (PET) is selected as the first additive, N-methyl pyrrolidone can be used as the solvent.

[0030] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the weight ratio of the first solvent to the first additive is 4:1 to 10:1, and preferably 4:1 to 8:1.

[0031] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the first carrier in step (2) is at least one of alumina and silicon-containing alumina, and preferably the alumina is alumina obtained by calcining pseudo-boehmite, the calcining temperature is 550 to 900°C, and the calcining time is 2 to 5 h, and the calcining is generally performed in an air atmosphere; the specific surface area of the alumina is 200 to 350 m2 / g, and the pore volume is 0.6 to 1.0 mL / g.2 / g, preferably 220-330 m 2 / g, and a pore volume of 0.8-1.4 mL / g, preferably 0.8-1.2 mL / g.

[0032] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the ratio of the first carrier in step (2) to the first stream is 1:1.5-8:1, preferably 1:1.5-4:1, in g / mL, and they are mixed uniformly on a mixer. More specifically, the mixing time can be controlled to be 10-60 min, preferably 20-50 min.

[0033] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the second carrier in step (2) is pseudo-boehmite, which can be one or more of large-pore pseudo-boehmite and small-pore pseudo-boehmite, and is preferably small-pore pseudo-boehmite. The large-pore pseudo-boehmite has a specific surface area greater than 260 m 2 / g after being calcined at 600°C, and a pore volume greater than 0.95 mL / g. The small-pore pseudo-boehmite has a specific surface area greater than 300 m 2 / g after being calcined at 600°C, and a pore volume greater than 0.50 mL / g. The second carrier is added in an amount of 5-10 wt% based on the amount of alumina.

[0034] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the shaping in step (2) is not particularly limited, and can be any one of a sphere, a strip, a trilobal shape, a quadrilobal shape, etc. The shaping method can be any one of the existing shaping methods in the art.

[0035] In the preparation method of the coal tar hydrogenation catalyst, as a specific embodiment, the second solvent is an alcohol solution, specifically at least one of an ethanol solution and a glycol solution, etc. The concentration of the alcohol solution is greater than 50 wt%, preferably 50 wt%-80 wt%. The amount of the alcohol solution added is 1-15 wt%, preferably 2-15 wt%, based on the amount of alumina added to the final carrier.

[0036] As a specific embodiment of the preparation method of the coal tar hydrogenation catalyst, the second additive can be starch and / or cellulose; the starch can be one or more of mung bean starch, cassava starch, sweet potato starch, sweet potato starch, potato starch, wheat starch, water caltrop starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch. The cellulose can be one or more of sesbania gum, methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose. The amount of the second additive added is 3wt% to 10wt% of the alumina in the final carrier material, preferably 3wt% to 8wt%.

[0037] As a specific embodiment of the preparation method of the coal tar hydrogenation catalyst, the mixing in step (2) is not particularly limited and any of the existing methods that can achieve uniform mixing of two or more materials can be used, such as kneading, which can be performed on a mixer.

[0038] As a specific embodiment of the preparation method of the coal tar hydrogenation catalyst, the carbonization treatment temperature in step (3) is 450 to 600°C, and the carbonization treatment time is 2 to 5h; the inert gas atmosphere can be nitrogen and / or an inert gas, and the inert gas can be at least one of helium, neon, argon, krypton, and xenon.

[0039] As a specific embodiment of the preparation method of the coal tar hydrogenation catalyst, the oxidation treatment temperature in step (4) is 400 to 500°C, and the oxidation treatment time is 0.5 to 1.5h. The oxygen-containing atmosphere can be oxygen, air, or a mixture of oxygen and an inert atmosphere, the inert gas atmosphere can be nitrogen and / or an inert gas, and the volume content of oxygen in the mixture is 15% to 30%.

[0040] As a specific embodiment of the preparation method of the coal tar hydrogenation catalyst, the active metal in step (c) is a Group VIII metal and / or a Group VIB metal, and the content of the Group VIII metal as calculated as an oxide is 0.5% to 5% by weight of the catalyst, preferably 0.5% to 4.5%, and the content of the Group VIB metal as calculated as an oxide is 4% to 25%, preferably 4% to 20%.

[0041] As a specific embodiment of the preparation method of the coal tar hydrogenation catalyst, the introduction of the active metal in step (c) can use any of the existing methods in the art, which can be selected by those skilled in the art according to actual needs.

[0042] In the above-mentioned method for preparing the coal tar hydrogenation catalyst, as a specific embodiment, if the impregnation method is used for loading in step (c), firstly, a metal salt containing the active metal component is prepared into an impregnation solution, then the modified support is contacted with the impregnation solution, and finally, the coal tar hydrogenation catalyst is obtained after separation, washing, drying, and calcination. Typically, the drying temperature is 100℃~150℃, and calcination is carried out in an air atmosphere at a temperature of 400~500℃ for 1~3 hours.

[0043] A third aspect of the present invention also provides a coal tar hydrogenation catalyst obtained by the above preparation method.

[0044] The fourth aspect of the present invention provides the application of the above-described coal tar hydrogenation catalyst or the coal tar hydrogenation catalyst obtained by the above preparation method in the coal tar hydrogenation process.

[0045] Furthermore, in the above applications, the coal tar can be selected from at least one of low-temperature coal tar, medium-low-temperature coal tar, medium-temperature coal tar, and high-temperature coal tar.

[0046] Furthermore, in the above applications, the specific reaction conditions for the hydrogenation process are: reaction pressure of 10–20 MPa, reaction temperature of 280–420 °C, and liquid hourly space velocity of 0.1–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100–1000.

[0047] Compared with the prior art, the coal tar hydrogenation catalyst and its preparation method provided by the present invention have the following advantages:

[0048] 1. In the method for preparing coal tar hydrogenation catalyst provided by the present invention, the surface of the support is hydroxylated by a high molecular weight organic alcohol solution, and more hydroxyl sites are retained by low-temperature calcination, which makes it easier to combine with active metals, facilitates metal dispersion and efficient utilization, and improves the hydrogenation performance of the catalyst.

[0049] 2. In the coal tar hydrogenation catalyst provided by the present invention, a network structure of CH bonds is constructed between alumina particles. During the reaction, due to the stretching and shrinking changes of the CH bonds containing plastic materials, the impact of product volume expansion on the final catalyst is reduced, thus avoiding catalyst breakage and maintaining good catalyst activity stability.

[0050] 3. In the coal tar hydrogenation catalyst preparation method provided by the present invention, a first auxiliary agent combined with alumina is added during the preparation of the support to improve the deformation properties of the material. When used to process oxygen-containing raw materials, the first auxiliary agent has variability under high temperature conditions, which can reduce the influence of water generated by hydrogenation of oxygen in the raw material or water vaporization in the raw material on the strength of the catalyst support, thereby improving the water resistance of the catalyst.

[0051] 4、The coal tar hydrogenation catalyst preparation method provided by the present application, in the carrier material preparation, a two-step mixing method is adopted, the first solvent is mixed with the first additive uniformly, and then mixed with the first carrier, so that the first additive is adsorbed on the first carrier and forms a coating, and a network structure of C-H bond between alumina particles is constructed. Then, the second step is to add the second additive and the second carrier, and the second solvent miscible with water is added at the same time, so that the second carrier containing the first additive is better combined with other viscous substances to improve the mechanical strength of the carrier.

[0052] 5、The coal tar hydrogenation catalyst preparation method provided by the present application, in the carrier material preparation, the drying step is omitted, which not only simplifies the preparation process, but also can control the pore structure of the material by leaving a certain amount of water in the carrier precursor during the subsequent carrier material preparation process, so as to effectively increase the content of large pores.

[0053] 6、The coal tar hydrogenation catalyst preparation method provided by the present application, by carbonizing the surface of the carrier, the first additive material is fixed, the mechanical properties of the catalyst are enhanced, and the interaction between the active metal and the carrier in the subsequent process is weakened; then the surface of the carrier is subjected to shallow oxidation, the adhesion of different materials is enhanced, and the foundation for improving the water resistance of the catalyst is laid. DETAILED DESCRIPTION

[0054] The specific embodiments of the present application will be described in detail below in conjunction with specific examples, but it should be pointed out that the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims.

[0055] In the context of the present specification, the pore volume, specific surface area and pore size distribution are measured by low-temperature nitrogen adsorption method. The total acid is measured by pyridine infrared adsorption method. C, H is measured by elemental analysis method.

[0056] The crushing test of the catalyst is carried out in a constant temperature oil bath, dimethyl silicone oil is used, heated to 200 DEG C, the catalyst is saturated with water, then added to the oil bath, and the Lecia image analysis system is used to count the crushing condition of the sample added to the oil bath. IMo / IAl in Table 1 represents the dispersion degree of metal Mo on the carrier.

[0057] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in the present specification are based on weight.

[0058] In the context of the present specification, any two or more embodiments of the present application can be combined arbitrarily, and the technical solutions formed by the combination belong to the original disclosure of the present specification, and also fall within the protection scope of the present application.

[0059] Example 1

[0060] Take 100 g of C9 petroleum resin, add 400 g of cyclohexane and stir to dissolve. Take 800 g of macroporous pseudo-boehmite and place in a calcination dish and calcine in a high temperature furnace at 800°C for 3 h to obtain calcined alumina (specific surface area 250 m 2 / g, pore volume 0.95 mL / g). Take 300 g of calcined alumina powder and 200 g of C9 petroleum resin solution, add the calcined alumina powder to a kneader, add the C9 petroleum resin solution by spraying, mix for 30 min, then add 40 g of pseudo-boehmite (600°C specific surface area 270 m 2 / g, pore volume 1.03 mL / g), 9.9 g of methyl cellulose, mix, then add 40 g of ethanol solution (ethanol content 80 wt%), mix well, then take out and form into spheres on a sphere forming device. The formed sample is calcined in a nitrogen atmosphere at 550°C for 4 h. After cooling, the sample is lightly oxidized in an air atmosphere at 500°C for 0.5 h to obtain 1.0 mm microsphere carrier Z-1.

[0061] Prepare a 20 wt% solution of polyethylene glycol (molecular weight 400), take 330 g of the solution, and impregnate the Z-1 carrier by spraying. The impregnated sample is calcined at 200°C for 1 h to obtain the treated carrier.

[0062] Catalyst preparation

[0063] Take 15.82 g of phosphoric acid, add 450 mL of distilled water, then add 45.4 g of molybdenum oxide and 20.8 g of basic nickel carbonate in sequence, heat and stir until completely dissolved, then dilute the solution to 500 mL with distilled water to obtain solution L-1. Saturate the carrier Z-1 with solution L-1 and impregnate, dry at 110°C for 2 h, and calcine at 450°C in an air atmosphere for 1.5 h to obtain catalyst C-1. The properties are shown in Table 1.

[0064] Example 2

[0065] Other conditions are the same as in Example 1, except that the C9 petroleum resin is replaced by silicone rubber and the cyclohexane is replaced by toluene. The formed sample is calcined in a nitrogen atmosphere at 600°C for 3 h to obtain 1.0 mm microsphere carrier Z-2. The analysis results are shown in Table 1.

[0066] Example 3

[0067] Other conditions are same as example 1, only C9 petroleum resin is replaced by C5 petroleum resin, take 300g calcined alumina powder and 150g C5 petroleum resin solution, mixing time is changed to 40min, after mixing, add 50g ethylene glycol solution (ethylene glycol content is 50wt%), 20wt% polyethylene glycol (molecular weight is 400) solution is changed to 25wt% polyvinyl alcohol (molecular weight is 5000) to prepare 1.0mm microspherical catalyst C-3, its analysis results are shown in table 1.

[0068] Example 4

[0069] Take 100g silicone rubber, add 500g toluene after stirring to complete dissolution, and wait for use. Take 800g macroporous pseudo-boehmite, put it into a calcining dish and calcine in a high temperature furnace, calcination temperature is 700℃, calcination time is 3h, to obtain calcined alumina (specific surface area is 286m2 / g, pore volume is 0.95mL / g). Take 300g calcined alumina powder and 150g silicone rubber solution, put the calcined alumina powder into a kneader, add silicone rubber solution by spraying, mix for 30min, then add 55g pseudo-boehmite (600℃ specific surface area is 330m2 / g, pore volume is 0.72mL / g), 18g hydroxypropyl methyl cellulose, after mixing, add 50g ethylene glycol solution (ethylene glycol content is 60%), uniformly mix, and then take out to form a ball on a ball forming device. The formed sample is calcined in a nitrogen atmosphere, calcination temperature is 600℃, calcination time is 1.5h. After the sample is cooled, it is lightly oxidized in an air atmosphere, calcination temperature is 550℃, calcination time is 0.5h, to obtain 1.0mm microspherical carrier Z-4.

[0070] Prepare a 25% polyethylene glycol (molecular weight is 200) solution, take 300g solution, and impregnate the Z-4 carrier by spraying. The impregnated sample is calcined at 230℃ for 1.5h to obtain the treated carrier.

[0071] Catalyst preparation

[0072] Take 24.9g phosphoric acid, add 450mL distilled water, then add 87.9g molybdenum oxide, 37.2g basic nickel carbonate, heat and stir until completely dissolved, then use distilled water to make the solution to 500mL, to obtain solution L-2. Saturate the carrier Z-4 with solution L-2 solution, dry at 150℃ for 2h, and calcine at 420℃ in an air atmosphere for 2h to obtain catalyst C-4, its properties are shown in table 1.

[0073] Example 5

[0074] Other conditions are the same as in Example 4, except that the calcination temperature of the large-pore pseudo-boehmite is changed from 700°C to 850°C, to obtain the calcined alumina (specific surface area 225 m2 / g, pore volume 0.96 mL / g). 300 g of the calcined alumina powder and 200 g of the silicone rubber solution are mixed for 50 min, and then 75 g of a propylene glycol solution (propylene glycol content 50%) is added. A 20% polyethylene glycol (molecular weight 400) solution is changed to a 15% polyethylene glycol (molecular weight 1000) solution to prepare 1.0 mm microspherical catalyst C-5. The analysis results are shown in Table 1.

[0075] Comparative Example 1

[0076] 400 g of a cyclohexane solution is weighed and used as is. 800 g of large-pore pseudo-boehmite is placed in a calcination pan and calcined in a high-temperature furnace at a calcination temperature of 800°C for 3 h to obtain calcined alumina (specific surface area 250 m2 / g, pore volume 0.95 mL / g). 300 g of the calcined alumina powder and 200 g of the cyclohexane solution are placed in a kneader, and the cyclohexane solution is added in a spraying manner. After mixing for 30 min, 40 g of pseudo-boehmite (600°C specific surface area 270 m2 / g, pore volume 1.03 mL / g) and 9.9 g of methyl cellulose are added, and then 40 g of an ethanol solution (ethanol content 80%) is added. After uniform mixing, the mixture is taken out and formed into 1.0 mm microspheres in a sphere forming device. The formed sample is calcined in a nitrogen atmosphere at a calcination temperature of 550°C for 4 h. After cooling, the sample is subjected to shallow oxidation in an air atmosphere at a calcination temperature of 500°C for 0.5 h to obtain 1.0 mm microspherical carrier F-1.

[0077] A 20 wt% polyethylene glycol (molecular weight 400) solution is prepared, and 330 g of the solution is used to impregnate the F-1 carrier in a spraying manner. The impregnated sample is calcined at 200°C for 1 h to obtain the treated carrier.

[0078] The carrier F-1 is saturatedly impregnated with the solution L-1 solution, dried at 110°C for 2 h, and calcined at 450°C for 1.5 h in an air atmosphere to obtain catalyst CF-1. The properties are shown in Table 1.

[0079] Comparative Example 2

[0080] Take 100 g of C9 petroleum resin, add 400 g of cyclohexane and stir to dissolve. Take 800 g of macroporous pseudo-boehmite and place in a calcination dish and calcine in a high temperature furnace at 800°C for 3 h to obtain calcined alumina (specific surface area 250 m2 / g, pore volume 0.95 mL / g). Take 300 g of the calcined alumina powder and 200 g of the C9 petroleum resin solution, add the calcined alumina powder to a kneader, add the C9 petroleum resin solution by spraying, mix for 30 min, then add 40 g of pseudo-boehmite (specific surface area 270 m2 / g at 600°C, pore volume 1.03 mL / g), 9.9 g of methyl cellulose, mix, then add 40 g of an ethanol solution (80% ethanol), mix well, and then take out and form into spheres on a sphere forming device. The formed sample is calcined in a nitrogen atmosphere at 750°C for 4 h. A 1.0 mm microsphere carrier F-2 is prepared, and the analysis results are shown in Table 1.

[0081] Prepare a 20 wt% solution of polyethylene glycol (molecular weight 400), take 330 g of the solution, and impregnate the F-2 carrier by spraying. The impregnated sample is calcined at 200°C for 1 h to obtain a treated carrier.

[0082] The carrier F-2 is saturatedly impregnated with the solution L-1 solution, dried at 110°C for 2 h, and calcined at 450°C for 1.5 h in an air atmosphere to obtain a catalyst CF-2, and the properties are shown in Table 1.

[0083] Comparative Example 3

[0084] Take 400 g of a cyclohexane solution and set aside. Take 800 g of macroporous pseudo-boehmite and place in a calcination dish and calcine in a high temperature furnace at 800°C for 3 h to obtain calcined alumina (specific surface area 250 m2 / g, pore volume 0.95 mL / g). Take 300 g of the calcined alumina powder and 200 g of the cyclohexane solution, add the calcined alumina powder to a kneader, add the cyclohexane solution by spraying, mix for 30 min, then add 40 g of pseudo-boehmite (specific surface area 270 m2 / g at 600°C, pore volume 1.03 mL / g), 9.9 g of methyl cellulose, mix, then add 40 g of an ethanol solution (80% ethanol), mix well, and then take out and form into spheres on a sphere forming device. The formed sample is calcined in a nitrogen atmosphere at 550°C for 4 h. After cooling, the sample is lightly oxidized in an air atmosphere at 500°C for 0.5 h to obtain a 1.0 mm microsphere carrier F-1.

[0085] The carrier F-1 is saturatedly impregnated with solution L-1, dried at 110℃ for 2h, and calcined at 450℃ for 1.5h in air atmosphere to obtain catalyst CF-1, whose properties are shown in Table 1.

[0086] Table 1 Analysis results of samples obtained from examples and comparative examples

[0087]

[0088]

[0089] The catalysts prepared from examples and comparative examples are evaluated for activity on a CSTR device, the raw material used for evaluation is medium-low temperature coal tar, the specific properties of the raw material are shown in Table 2, the evaluation conditions are shown in Table 3, and the oil samples are analyzed after 1000h of operation, and the activity of comparative example C-F1 is taken as 100, and the evaluation results of other examples compared with comparative example C-F1 are shown in Table 4.

[0090] Table 2 Properties of raw oil

[0091] Item Feed oil Density (20°C), kg / m 3 ]] 1.03 S, wt% 0.38 CCR, wt% 10.38 O，％ 7.6 (Fe+Ca+Na) pg / g 204 >500°C yield, % 70.1

[0092] Table 3 Evaluation conditions

[0093] Item Feed oil Reaction temperature / °C 380 Reaction pressure / MPa 15 airspeed / h -1 ]]> 0.3 Hydrogen / oil volume ratio 500

[0094] Table 4 Evaluation results

[0095]

[0096]

[0097] In Table 4, HDS represents the activity of hydrodesulfurization; HDCCR represents the activity of hydrodecarbon; HDO represents the activity of hydrodeoxygenation; HD(Fe+Ca+Na) represents the activity of hydrodemetals(Fe+Ca+Na).

[0098] As can be seen from the data in the table, the catalyst prepared by the present application has larger pore volume and specific surface, moderate acidity, higher metal dispersion, mechanical strength and water resistance, thereby having better hydrogenation activity. By using the catalyst prepared by the present application and adding plastic material to reduce the crushing of the catalyst during the hydrodeoxygenation process, the operation cycle of the coal tar hydrogenation device is prolonged under the premise of ensuring the hydrogenation performance of the catalyst.

Claims

1. A coal tar hydroprocessing catalyst, said catalyst comprising a support and an active metal component distributed on the support, wherein the support comprises alumina, carbon and hydrogen, wherein, H is in the form of C-H bond; the active metal component is one or more of Group VIII metal and / or Group VIB metal; the content of alumina is 55-90 wt%, the content of carbon is 3.5-19.0 wt%, and the content of H is 0.28-1.72 wt% based on the weight of the catalyst; the content of Group VIII metal in oxide form is 0.5%-5%, and the content of Group VIB metal in oxide form is 4%-25%; The preparation method of the coal tar hydrogenation catalyst comprises the following steps: (a) preparing a carrier material, the preparation method of the carrier material comprising the following steps: (1) mixing a first additive with a first solvent to obtain a first stream; the first additive is selected from a high molecular polymer, and the first solvent is an organic solvent; the first additive is selected from one or more of C5 petroleum resin, C9 petroleum resin, silicone rubber, polyethylene, and polyester; (2) mixing the first carrier and the first stream, then adding a second carrier, a second additive, and a second solvent, and uniformly mixing to obtain a second stream; the second carrier is pseudo-boehmite, the second solvent is an alcohol solution, and the second additive is starch and / or cellulose; (3) performing carbonization treatment on the second stream in the presence of an inert atmosphere; (4) performing oxidation treatment on the material after the carbonization treatment in the presence of an oxygen-containing atmosphere to obtain a carrier; (b) performing surface modification treatment on the carrier material to obtain a modified carrier; the surface modification treatment process is as follows: contacting the carrier material obtained in step (a) with a high molecular organic alcohol solution, and then performing calcination treatment; the high molecular organic alcohol solution is one or more of polyethylene glycol and polyvinyl alcohol, and the molecular weight of the high molecular organic alcohol is not greater than 6000; (c) introducing an active metal into the modified carrier obtained in step (b) to obtain a coal tar hydrogenation catalyst.

2. The coal tar hydroprocessing catalyst according to claim 1, wherein, The content of Group VIII metal in oxide form is 0.5%-4.5% based on the weight of the catalyst; and the content of Group VIB metal in oxide form is 4%-20%.

3. The coal tar hydroprocessing catalyst according to claim 1, wherein, The pore volume of the catalyst is not less than 0.45 mL / g.

4. The coal tar hydroprocessing catalyst according to claim 1, wherein, The pore volume of the catalyst is greater than 0.50 mL / g.

5. The coal tar hydroprocessing catalyst according to claim 1, wherein, The pore volume of the catalyst is 0.50-0.75 mL / g.

6. The coal tar hydroprocessing catalyst according to claim 1, wherein, The specific surface area of the catalyst is 150-250 m 2 / g.

7. The coal tar hydroprocessing catalyst according to claim 1, wherein, The specific surface area of the catalyst is 150-220 m 2 / g.

8. The coal tar hydroprocessing catalyst according to claim 1, wherein, The total acid content of the catalyst is 0.2-0.6 mmol / g.

9. The coal tar hydroprocessing catalyst according to claim 1, wherein, The total acid content of the catalyst is 0.25-0.55 mmol / g.

10. A preparation method of a coal tar hydrogenation catalyst, the preparation method comprising the following steps: (a) preparing a carrier material, the preparation method of the carrier material comprising the following steps: (1) mixing a first additive with a first solvent to obtain a first stream; the first additive is selected from a high molecular polymer, and the first solvent is an organic solvent; the first additive is selected from one or more of C5 petroleum resin, C9 petroleum resin, silicone rubber, polyethylene, and polyester; (2) mixing the first carrier and the first stream, then adding a second carrier, a second additive, and a second solvent, and uniformly mixing to obtain a second stream; the second carrier is pseudo-boehmite, the second solvent is an alcohol solution, and the second additive is starch and / or cellulose; (3) performing carbonization treatment on the second stream in the presence of an inert atmosphere; (4) oxidizing the carbonized material in the presence of an oxygen-containing atmosphere to obtain a carrier; (b) performing surface modification treatment on the carrier material to obtain a modified carrier; The surface modification treatment process is as follows: the carrier material obtained in step (a) is contacted with a high-molecular organic alcohol solution, and then is subjected to calcination treatment; the high-molecular organic alcohol solution is one or more of polyethylene glycol and polyvinyl alcohol, and the molecular weight of the high-molecular organic alcohol is not greater than 6000; (c) introducing active metals onto the modified carrier obtained in step (b) to obtain a coal tar hydrogenation catalyst.

11. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The calcination treatment temperature in step (b) is 150-300°C, and the calcination treatment time is 0.5-2h; the calcination treatment is performed in an air atmosphere.

12. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The molecular weight of the high-molecular organic alcohol is not greater than 2000.

13. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The concentration of the high-molecular organic alcohol solution is 10wt%-40wt%.

14. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The concentration of the high-molecular organic alcohol solution is 15wt%-30wt%.

15. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The mass ratio of the high-molecular organic alcohol solution to the carrier material obtained in step (a) is 0.8:1-1.1:

1.

16. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The first additive in step (1) is C9 petroleum resin.

17. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The organic solvent in step (1) is one or more of benzene and its derivatives, cycloalkanes, ketones, alcohols, and chlorinated hydrocarbons.

18. The method of making a coal tar hydroprocessing catalyst according to claim 10 or 17, wherein, The organic solvent in step (1) is one or more of benzene, toluene, xylene, cyclohexane, acetone, N-methyl pyrrolidone, and trichloromethane.

19. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The weight ratio of the first solvent to the first additive is 4:1-10:

1.

20. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The weight ratio of the first solvent to the first additive is 4:1-8:

1.

21. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The first carrier in step (2) is at least one of alumina and silicon-containing alumina.

22. The method of making a coal tar hydroprocessing catalyst according to claim 21, wherein, The alumina is alumina obtained by calcination of pseudo-boehmite.

23. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The addition ratio of the first carrier to the first stream in step (2) is 1:1.5-8:1 in terms of g / mL.

24. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The addition ratio of the first carrier to the first stream in step (2) is 1:1.5-4:1 in terms of g / mL.

25. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The second solvent is at least one of an ethanol solution and an ethylene glycol solution, and the concentration of the alcohol solution is greater than 50wt%.

26. The method of making a coal tar hydroprocessing catalyst according to claim 25, wherein, The concentration of the alcohol solution is 50wt%-80wt%.

27. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The carbonization treatment temperature in step (3) is 450-600°C, and the carbonization treatment time is 2-5h. The inert gas atmosphere is nitrogen and / or an inert gas, and the inert gas is at least one of helium, neon, argon, krypton, and xenon.

28. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The oxidation treatment temperature in step (4) is 400°C-500°C, and the oxidation treatment time is 0.5-1.5h; the oxygen-containing atmosphere is oxygen, air, or a mixture of oxygen and an inert gas, the inert gas atmosphere is nitrogen and / or an inert gas, and the volume content of oxygen in the mixture is 15%-30%.

29. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The active metals in step (c) are Group VIII metals and / or Group VIB metals, and the content of the Group VIII metals in terms of oxides is 0.5%-5% and the content of the Group VIB metals in terms of oxides is 4%-25% based on the weight of the catalyst.

30. The method of making a coal tar hydroprocessing catalyst according to claim 10, wherein, The active metals in step (c) are Group VIII metals and / or Group VIB metals, the content of the Group VIII metals, calculated as oxides, being 0.5% to 4.5% and the content of the Group VIB metals, calculated as oxides, being 4% to 20%, based on the weight of the catalyst.

31. Use of a coal tar hydroprocessing catalyst according to any one of claims 1 to 9 in a coal tar hydroprocessing process.

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