A residue oil hydrogenation catalyst and its synthesis method and application

Abstract

The present invention discloses a residual oil hydrogenation catalyst and a synthesis method and application thereof. The synthesis method comprises the following steps: (1) mixing activated carbon with boric acid, heating and treating, and synthesizing a boron-doped carbon carrier; (2) impregnating active metal C1 onto the boron-doped carbon carrier described in step (1) to obtain an impregnated boron-doped carbon carrier; (3) preparing silicon-containing pseudo-boehmite; (4) mixing the impregnated boron-doped carbon carrier in step (2) with the silicon-containing pseudo-boehmite powder in step (3), forming, and obtaining a catalyst precursor; (5) mixing the catalyst precursor in step (4) with active metal C2 for a second impregnation, drying, and roasting to obtain a catalyst. The catalyst provided by the present invention has a high metal loading, is evenly dispersed, has high mechanical strength, has suitable pore distribution and specific surface area, and has suitable surface acidity, and is suitable for residual oil hydrogenation.

Description

Technical Field

[0001] The present invention relates to a hydrogenation catalyst and a synthesis method and application thereof, in particular to a residual oil hydrogenation catalyst and a synthesis method and application thereof. Background Art

[0002] At present, the residual oil hydrogenation catalyst mainly uses alumina or silica as a carrier, and the active metal components such as Ni, Mo, and Co are loaded on the carrier by impregnation or kneading, and then the hydrogenation catalyst is obtained by high-temperature roasting. In the existing method, when the active metal loading is large, the metal particles are easily agglomerated or unevenly distributed. In addition, during the roasting process, due to the strong interaction between the metal and the carrier, the metal-oxygen-aluminum bond is formed, which affects the catalytic efficiency of the catalyst and ultimately leads to a decrease in the hydrogenation activity of the catalyst.

[0003] In addition, the catalyst carrier commonly used in the petroleum refining process is usually made of alumina or γ-Al containing a small amount of one or more other elements such as Si, P, Ti, B, Mg, F, etc. 2 O 3 The introduction of an appropriate amount of silicon oxide is beneficial to improving the acidity and specific surface area of ​​alumina, and is beneficial to polymerization and hydrogenation reactions. Therefore, silicon can be introduced during the carrier synthesis stage to adjust the acidity of the catalyst and / or improve the interaction between the active component and the carrier.

[0004] CN103055908A discloses a method for preparing a hydroprocessing catalyst. The method firstly pulps aluminum hydroxide or aluminum oxide to form a slurry, adds concentrated phosphoric acid to react and obtains a sol; then uses the sol as a binder, kneads with macroporous aluminum oxide and microporous aluminum oxide, forms, dries and roasts to obtain an aluminum oxide carrier; then uses an active metal component impregnation solution to impregnate the aluminum oxide carrier, and dries and roasts to obtain a hydroprocessing catalyst. The method uses concentrated phosphoric acid as a structural additive, which is introduced into the aluminum oxide carrier to improve the active metal load dispersion and reduce the total acid content of the carrier, and can also improve the pore structure of the aluminum oxide carrier. However, the method is complicated to operate, and the introduction of acidic sites will promote the bonding between the active metal and the carrier. The use of a large amount of concentrated acid will cause environmental pollution, and industrial production is relatively dangerous.

[0005] CN105582945A discloses a method for preparing a hydroprocessing catalyst. The method is to first impregnate an alumina carrier with an aqueous solution of urea, and then spray an aqueous solution of a polyol or monosaccharide on the alumina carrier in a descending order of concentration, so that the concentration of the polyol and / or monosaccharide forms a gradient distribution from low to high from outside to inside on the carrier, and then loads the active metal component. This method makes the subsequent active metal center show the characteristics of gradually increasing activity from outside to inside due to the gradient distribution of the carbide shell, which greatly reduces the pore blockage rate. However, this method requires multi-step spray impregnation to form a polymer carbide shell, and has high requirements for solution concentration, and the actual operation process is relatively complicated.

[0006] CN1257754A discloses a method for preparing a silica-alumina catalyst carrier, wherein a silica-alumina precursor is prepared by introducing water glass and aluminum sulfate, and the prepared carrier has a pore volume of 0.45-0.75 mL / g and an average pore size of 5-10 nm. However, the final synthesized silica-alumina carrier has a small pore size and is not suitable for use as a hydrogenation catalyst for heavy oil or residual oil with a large molecular weight.

[0007] CN1169614C discloses a method for preparing silicon-containing aluminum hydroxide. By introducing a certain amount of sodium silicate in the process of preparing aluminum hydroxide gel by carbonization, and continuing to add a certain amount of sodium silicate in the subsequent aging process, silicon-containing aluminum oxide can be prepared. The average pore size is 6-13nm. Although it is suitable for heavy oil or residual oil hydrodesulfurization or hydrodenitrogenation catalysts, its pore size is relatively small for residual oil hydrodemetallization catalysts, and further improvement is needed. Summary of the invention

[0008] In view of the shortcomings of the prior art, the present invention provides a residual oil hydrogenation catalyst and a synthesis method and application thereof. The catalyst provided by the present invention has a high metal loading, is evenly dispersed, has high mechanical strength, has suitable pore distribution and specific surface area, and has suitable surface acidity, and is suitable for residual oil hydrogenation treatment.

[0009] The first aspect of the present invention provides a method for synthesizing a residue oil hydrogenation catalyst, comprising the following steps:

[0010] (1) Mixing activated carbon with boric acid, and heating the mixture to synthesize a boron-doped carbon carrier;

[0011] (2) impregnating the active metal Cl onto the boron-doped carbon support described in step (1), drying, and calcining to obtain an impregnated boron-doped carbon support;

[0012] (3) preparing a silicon-containing pseudo-boehmite wet filter cake, and drying the wet cake to obtain silicon-containing pseudo-boehmite;

[0013] (4) mixing the boron-doped carbon support impregnated in step (2) with the silicon-containing pseudo-boehmite powder in step (3), forming, drying, and calcining to obtain a catalyst precursor;

[0014] (5) The catalyst precursor of step (4) is mixed with active metal C2 for a second impregnation, drying, and calcining to obtain a catalyst.

[0015] Furthermore, in the silicon-containing pseudo-boehmite of step (3), silicon is in the form of SiO 2 Aluminum is Al 2 O 3 The mass content of silicon is 5% to 40%.

[0016] Furthermore, in step (3), the method for preparing silicon-containing pseudo-boehmite wet filter cake comprises:

[0017] (A) adding a first alkaline solution into a first reaction kettle, introducing a mixed gas containing carbon dioxide to react, and making the pH value of the system be 2 to 4;

[0018] (B) adding bottom water to the second reaction kettle, heating to the reaction temperature, and then adding the second alkaline solution and the material obtained in step (A) to the second reaction kettle in parallel to react;

[0019] (C) aging the slurry obtained after the reaction in step (B), filtering and washing after the aging to obtain a silicon-containing pseudo-boehmite filter cake.

[0020] Furthermore, in step (A), the first alkaline solution is a mixed solution of water glass and an aluminum-containing alkaline solution; the aluminum-containing alkaline solution is one or both of a sodium aluminate solution or a potassium aluminate solution, preferably a sodium aluminate solution. The modulus of the water glass is 2.5 to 3.0, and the caustic ratio of the sodium aluminate solution or the potassium aluminate solution is 1.35 to 1.65.

[0021] Furthermore, in step (A), the concentration of water glass in the first alkaline solution is SiO 2 5~90gSiO 2 / L, the concentration of sodium aluminate and / or potassium aluminate in the first alkaline solution is Al 2 O 3 10~30gAl 2 O 3 / L.

[0022] Furthermore, in step (A), the volume of the first alkaline solution added to the first reactor is 2 / 3 to 3 / 4 of the volume of the first reactor; the volume fraction of carbon dioxide in the carbon dioxide-containing mixed gas is 30% to 70%; and the carbon dioxide-containing mixed gas can be a mixed gas of carbon dioxide and air.

[0023] Furthermore, in step (A), the initial reaction temperature of the reaction of introducing the mixed gas containing carbon dioxide is 15-65°C. The reaction is an exothermic reaction, and the system temperature gradually increases. The entire reaction process does not require cooling to maintain a low temperature. Generally, the temperature of the slurry at the end of the reaction is 40-75°C.

[0024] Furthermore, in step (B), the second alkaline solution is one or both of a sodium aluminate solution and a potassium aluminate solution, preferably a sodium aluminate solution; the concentration of the sodium aluminate solution and / or the potassium aluminate solution is Al 2 O 3 130~350g Al 2 O 3 / L, preferably 150 to 250 g Al 2 O 3 The caustic ratio of the second alkaline solution is 1.10 to 1.40, preferably 1.15 to 1.35.

[0025] Furthermore, in step (B), the bottom water added to the second reaction kettle is 1 / 10 to 1 / 5 of the volume of the second reaction kettle.

[0026] Furthermore, in step (B), the material obtained in step (A) is added to the second reaction kettle, and the material addition time is controlled to be 60 to 150 minutes.

[0027] Furthermore, in step (B), the second alkaline solution and the material obtained in step (A) are added to the second reactor in parallel to react, and the pH value is controlled to be 7.5-9.0.

[0028] Furthermore, in step (B), the reaction temperature of the reaction is 40°C to 70°C, preferably 45°C to 65°C.

[0029] Furthermore, in step (B), the reaction is carried out under stirring.

[0030] Furthermore, in step (C), the aging conditions are: temperature of 50°C to 95°C, and time of 30min to 120min.

[0031] Furthermore, in step (C), the washing can be carried out by conventional washing methods in the art, preferably by washing with deionized water at 50° C. to 80° C. until neutral.

[0032] Furthermore, in step (C), the solid content of the obtained silicon-containing pseudo-boehmite wet filter cake is 35wt% to 45wt%.

[0033] Furthermore, in step (3), the drying temperature is 60 to 150° C., and the drying time is 4 to 10 hours.

[0034] Furthermore, in step (1), the specific surface area of ​​the activated carbon is 350 to 480 m 2 / g. The water absorption rate of the activated carbon is in the range of 0.7 to 1.5 mL / g.

[0035] Furthermore, in step (1), the specific surface area of ​​the activated carbon is 350 to 450 m 2 / g.

[0036] Furthermore, in step (1), the mass ratio of the activated carbon to the boric acid is 0.1 to 4.

[0037] Furthermore, in step (1), the heat treatment is carried out in an inert atmosphere and / or nitrogen, and the calcination is carried out at a temperature of 600-700° C. for 150-250 min. The inert atmosphere is selected from at least one of Ar and He.

[0038] Furthermore, in step (2), the active metal C1 is at least one of the metals of group VIB and at least one of the metals of group VIII. The metal of group VIB is selected from at least one of Mo and W, and the metal of group VIII is selected from at least one of Ni and Co. The amount of the active metal introduced into the catalyst by step (2) is 30% to 50% by mass of the total active metal in the catalyst in terms of oxide.

[0039] Furthermore, in step (2), the impregnation method adopts a saturated impregnation method.

[0040] Furthermore, in step (2), the drying temperature is 80-120°C and the time is 4-6 hours. The calcination temperature is 400-600°C and the time is 3-5 hours. The drying and calcination atmosphere is an inert gas and / or nitrogen. The inert gas is selected from at least one of Ar and He.

[0041] Furthermore, in step (4), the mass ratio of the boron-doped carbon carrier to pseudo-boehmite is 0.05 to 0.5.

[0042] Furthermore, in step (4), the molding can be performed by extrusion molding. An extrusion aid can be added during the molding process, and the extrusion aid can be sesbania powder, and the added amount is 1% to 6% of the mass of the pseudo-boehmite.

[0043] Furthermore, in step (4), the drying temperature is 80-120°C and the time is 4-6 hours. The calcination temperature is 450-800°C and the time is 3-6 hours. The drying and calcination atmosphere is an inert gas and / or nitrogen. The inert gas is selected from at least one of Ar and He.

[0044] Furthermore, in step (5), the impregnation is carried out by saturation impregnation, and the active metal C2 is at least one of the metals of Group VIB and at least one of the metals of Group VIII. The metal of Group VIB is at least one of Mo and W, and the metal of Group VIII is at least one of Ni and Co, preferably Mo and Ni.

[0045] Furthermore, the amount of active metal introduced into the catalyst in step (5) is 50% to 70% by mass of the total active metal in the catalyst in terms of oxide.

[0046] Furthermore, after the impregnation in step (5), the mass ratio of the Group VIB metal to the Group VIII metal in the total active metals of the catalyst, calculated as oxides, is 1.8 to 30.

[0047] Furthermore, in step (5), the drying temperature is 100-120° C., and the time is 4-6 hours; the calcination temperature is 430-600° C., and the time is 3-5 hours.

[0048] The second aspect of the present invention provides a residue oil hydrogenation catalyst obtained by the synthesis method described in the first aspect.

[0049] Furthermore, in the catalyst, the active metal loading is 15% to 40% by mass of the oxide, wherein the active metal is at least one of the metals of Group VIB and at least one of the metals of Group VIII, and preferably, the active metal is molybdenum and nickel.

[0050] Furthermore, in the catalyst, the active metal loading is calculated based on the mass of the oxide, the mass content of the VIB group metal is 15% to 30%, and the mass content of the VIII group metal is 1% to 8%.

[0051] Furthermore, the catalyst also contains boron, and the mass content of boron is 0.2% to 3.5%.

[0052] Furthermore, in the catalyst, the active metal dispersion is: VIB / I Al (×100) is 6 to 10, I VIII / I Al (×100) is 2 to 5.

[0053] Furthermore, the specific surface area of ​​the catalyst is 110 to 270 m2 / g, preferably 175 to 230 m 2 / g, pore volume is 0.8~1.4cm 3 / g, mechanical strength>20N / mm, preferably 21-24N / mm, the pore volume of pores with a pore diameter>15nm accounts for 5.5%-24% of the total pore volume, preferably 6%-14%, and the pore volume of pores with a pore diameter<8nm accounts for less than 7.5% of the total pore volume, preferably 2%-7%.

[0054] Furthermore, the acid content of the catalyst is 0.1 to 0.9 mmol / g, preferably 0.5 to 0.65 mmol / g. The ratio of the acid content of B acid to the acid content of L acid is C B / C L It is 0.03 to 0.085, preferably 0.05 to 0.07.

[0055] The third aspect of the present invention provides use of the residue oil hydrogenation catalyst described in the second aspect in a residue oil hydrogenation process.

[0056] Furthermore, the residual oil and the hydrogen-containing gas are contacted and reacted under hydrogenation reaction conditions in the presence of the residual oil hydrogenation catalyst or the residual oil hydrogenation catalyst obtained according to the above synthesis method.

[0057] Furthermore, the residual oil raw material is selected from at least one of atmospheric residue oil, vacuum residue oil and deasphalted oil.

[0058] Furthermore, the hydrogen-containing gas is hydrogen, or a mixture of hydrogen and other gases, and the volume content of hydrogen in the mixture is generally not less than 80%, preferably not less than 85%, and further preferably not less than 95%.

[0059] Furthermore, the operating conditions of the residual oil hydrogenation are as follows: reaction temperature is 340-400°C, reaction pressure is 6.0-20.0 MPa, hydrogen-oil volume ratio is 200:1-1200:1, liquid hourly volume space velocity is 0.1-2.0 h -1 .

[0060] Furthermore, the hydrogenated oil obtained by hydrotreating the residual oil is used as feed for a catalytic cracking unit, or as feed for a hydrocracking unit, or as feed for a heavy oil deep catalytic cracking unit (DCC).

[0061] Compared with the prior art, the present invention has the following advantages:

[0062] First, in the synthesis method of the catalyst of the present invention, during the first metal impregnation process, the active phase metal is first loaded on the boron-doped carbon carrier, and the heteroatom boron belongs to the electron-poor heteroatom. During the composite process with the carbon carrier, the band gap of the pure carbon carrier is opened to become a semiconductor. After the metal is loaded, due to the different work functions, electrons will flow from the metal with a high work function to the carrier with a low work function until the Fermi level of the two reaches equilibrium, thereby forming a metal-semiconductor heterojunction. The existence of the heterojunction enhances the interaction force between the boron-carbon carrier and the metal. When the silicon-containing pseudo-boehmite is calcined and converted into silicon-containing alumina, the interaction force between the silicon-containing alumina carrier and the metal can be effectively weakened, and the prepared catalyst has better catalytic performance in the residual oil hydrogenation process. On the other hand, the metal-semiconductor heterojunction promotes the trend of uniform distribution of the metal on the surface of the carbon carrier. After being mixed and formed with the silicon-containing pseudo-boehmite, after calcination, the metal and the carbon carrier in the catalyst precursor are uniformly dispersed inside the silicon-containing alumina, and the prepared catalyst is not easy to coke and deactivate.

[0063] Secondly, the silicon-containing pseudo-boehmite wet filter cake prepared by the present invention has low gibbsite content, high crystallinity, and easily adjustable silicon content, and the silicon-containing alumina obtained by calcination has a large pore volume and pore diameter; at the same time, the silicon-containing pseudo-boehmite wet filter cake prepared by the present invention has a high peptization index, which provides a guarantee for preparing a carrier with high lateral pressure strength.

[0064] Furthermore, the residue oil hydrogenation catalyst obtained by the present invention is used for residue oil hydrogenation reaction, and has good desulfurization, denitrification and residual carbon removal performance, and has a high demetallization ability, with a metal removal rate of more than 80%. DETAILED DESCRIPTION

[0065] The following examples are used to further illustrate the preparation method and effects of the present invention. The examples are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to the following examples.

[0066] In the present invention, the ASAP2020 fully automatic physical adsorption instrument produced by Micromeritics Corporation of the United States is used to test the nitrogen adsorption-desorption curve of the sample at -196°C to determine the specific surface area, pore volume and pore size distribution.

[0067] In the present invention, the mechanical strength is tested by using a ZQJ-Ⅲ intelligent particle strength testing machine manufactured by Dalian Zhiqu Testing Machine Factory to measure the average mechanical strength of a group of samples with a length of 4-6 mm.

[0068] In the present invention, the metal dispersion is measured by XRS (the instrument is Kratos Axis Ultra DLD model) to measure the XPS peak intensity ratio of active metals and aluminum element.

[0069] In the present invention, the infrared acid content is measured using a Nicolet 870 Fourier transform infrared spectrometer produced by Nicolet Company of the United States.

[0070] The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.

[0071] Example 1

[0072] (1) Add 3500 mL of SiO with a modulus of 2.8 and a concentration of 50 g into the 5000 mL first reactor. 2 / L water glass and caustic ratio is 1.45, concentration is 25g Al 2 O 3 / L of sodium aluminate mixed solution, and then introduce a mixed gas of carbon dioxide and air containing 55% by volume of carbon dioxide to reduce the pH value of the system to 3.4. The temperature of the material at the end of the reaction is 55°C;

[0073] Add 1500mL of bottom water to the 10000mL second reactor, start the stirring and heating device, and when the temperature rises to 65°C, add the above materials to the second reactor at a flow rate of 35mL / min for 90min, and add 180gAl 2 O 3 / L, a sodium aluminate solution with a caustic ratio of 1.25, the pH value of the slurry in the second reactor is controlled to be 8.0 by adjusting the flow rate of the sodium aluminate solution, and the temperature of the slurry in the second reactor is kept constant. The reaction ends after the above materials are used up, and the slurry is aged at 90°C for 80 minutes. After the aging, it is washed with deionized water at a temperature of 70°C to neutrality, and a silicon-containing pseudo-boehmite wet filter cake with a solid content of 42% is obtained after filtration, and then dried at 120°C for 6 hours to obtain the silicon-containing pseudo-boehmite required by the present invention.

[0074] (2) Weigh the specific surface area of ​​400m 2 100 g of activated carbon powder with a water absorption rate of 0.8 mL / g was fully mixed with 100 g of boric acid and ground, placed in a tubular furnace, and calcined to 600 °C in a nitrogen atmosphere for 180 min to prepare MoO 3 The boron-doped carbon support is saturated with an impregnation solution having a molybdenum content of 0.497 g / mL and a NiO content of 0.0994 g / mL. After the impregnation is complete, the carbon support is dried at 120° C. for 5 hours and calcined at 500° C. under nitrogen protection for 3 hours to obtain an impregnated boron-doped carbon support, wherein the amount of Mo and Ni introduced into the catalyst in step (2) accounts for 33% of the total Mo and Ni in the catalyst, based on the mass of the oxides.

[0075] (3) Weigh 100 g of the impregnated boron-doped carbon support, 500 g of the silicon-containing pseudo-boehmite powder and 15 g of sesbania powder, mix them evenly and squeeze them into strips. After drying at 120° C. for 5 hours, calcinate them at 600° C., pass nitrogen protection, and keep the temperature constant for 3 hours to prepare MoO-containing 3 The catalyst was saturated with an impregnation solution of 0.181 g / mL of NiO and 0.036 g / mL of NiO, dried at 120°C for 5 hours, and calcined at 500°C for 3 hours to obtain the final residue hydrogenation catalyst A. Its physical and chemical properties are shown in Table 1.

[0076] Example 2

[0077] The other synthetic processes were the same as those in Example 1, except that the amount of boric acid added was changed to 200 g. The final residue oil hydrogenation catalyst B was obtained. Its physicochemical properties are shown in Table 1.

[0078] Example 3

[0079] The other synthesis processes were the same as in Example 1, except that the MoO 3 The concentration was changed to 0.71 g / mL, the NiO concentration was changed to 0.142 g / mL, and the MoO 3 The concentration was changed to 0.144 g / mL, the NiO concentration was changed to 0.029 g / mL, and the calcination temperature after impregnation was changed to 450°C to obtain the final residue oil hydrogenation catalyst C. Its physicochemical properties are shown in Table 1. Among them, the amount of Mo and Ni introduced into the catalyst in step (2) accounted for 46.5% of the total Mo and Ni in the catalyst, based on the mass of the oxides.

[0080] Example 4

[0081] The other conditions were the same as those in Example 1, except that the SiO 2 The concentration of Al in the mixed solution was changed to 75g / L. 2 O 3 The concentration is changed to 15 g / L, the volume fraction of carbon dioxide in the mixed gas of carbon dioxide and air is 45%, and the aging temperature is changed to 95° C. to obtain the silicon-containing pseudo-boehmite required by the present invention, and finally the hydrogenation catalyst D (physical and chemical properties are shown in Table 1).

[0082] Comparative Example 1

[0083] (1) Add 3500 mL of SiO with a modulus of 2.8 and a concentration of 50 g into the 5000 mL first reactor. 2 / L water glass and caustic ratio is 1.45, concentration is 25g Al 2 O 3 / L of sodium aluminate mixed solution, and then introduce a mixed gas of carbon dioxide and air containing 55% by volume of carbon dioxide to reduce the pH value of the system to 3.4. The temperature of the material at the end of the reaction is 55°C;

[0084] Add 1500mL of bottom water to the 10000mL second reactor, start the stirring and heating device, and when the temperature rises to 65°C, add the above materials to the second reactor at a flow rate of 35mL / min. The addition time is 90min, and add 180gAl 2 O 3 / L, a sodium aluminate solution with a caustic ratio of 1.25, the pH value of the slurry in the second reactor is controlled to be 8.0 by adjusting the flow rate of the sodium aluminate solution, and the temperature of the slurry in the second reactor is kept constant. The reaction is completed after the above materials are used up, and the slurry is aged at 90°C for 80 minutes. After the aging, it is washed with deionized water at a temperature of 70°C to neutrality, and a silicon-containing pseudo-boehmite wet filter cake with a solid content of 42% is obtained after filtration, and then dried at 120°C for 6 hours to obtain silicon-containing pseudo-boehmite.

[0085] (2) Weigh the specific surface area of ​​400m 2 100 g of activated carbon powder with a water absorption rate of 0.8 mL / g was placed in a tube furnace without adding boric acid and calcined to 600 °C in a nitrogen atmosphere for 180 min to prepare MoO 3 The pure carbon support is saturated with an impregnation solution having a molybdenum content of 0.497 g / mL and a NiO content of 0.0994 g / mL. After complete impregnation, the carbon support is dried at 120° C. for 5 hours and calcined at 500° C. under nitrogen protection for 3 hours to obtain an impregnated carbon support, wherein the amount of Mo and Ni introduced into the catalyst in step (2) accounts for 33% of the total Mo and Ni in the catalyst, based on the mass of the oxides.

[0086] (3) Weigh 100 g of the impregnated carbon support, 500 g of the silicon-containing pseudo-boehmite powder and 15 g of sesbania powder, mix them evenly and squeeze them into strips. After drying at 120° C. for 5 hours, calcine them at 600° C., pass nitrogen protection, and keep the temperature constant for 3 hours to prepare MoO-containing 3 The catalyst was saturated with an impregnation solution containing 0.181 g / mL of Ni and 0.036 g / mL of NiO. After the impregnation was complete, the catalyst was dried at 120°C for 5 hours and calcined at 500°C for 3 hours to obtain the final residue oil hydrogenation catalyst E. Its physicochemical properties are shown in Table 1.

[0087] Comparative Example 2

[0088] (1) Add 3500 mL of SiO with a modulus of 2.8 and a concentration of 50 g into the 5000 mL first reactor. 2 / L water glass and caustic ratio is 1.45, concentration is 25g Al2 O 3 / L of sodium aluminate mixed solution, and then introduce a mixed gas of carbon dioxide and air containing 55% by volume of carbon dioxide to reduce the pH value of the system to 3.4. The temperature of the material at the end of the reaction is 55°C;

[0089] Add 1500mL of bottom water to the 10000mL second reactor, start the stirring and heating device, and when the temperature rises to 65°C, add the above materials to the second reactor at a flow rate of 35mL / min. The addition time is 90min, and add 180gAl 2 O 3 / L, a sodium aluminate solution with a caustic ratio of 1.25, the pH value of the slurry in the second reactor is controlled to be 8.0 by adjusting the flow rate of the sodium aluminate solution, and the temperature of the slurry in the second reactor is kept constant. The reaction is completed after the above materials are used up, and the slurry is aged at 90°C for 80 minutes. After the aging, it is washed with deionized water at a temperature of 70°C to neutrality, and a silicon-containing pseudo-boehmite wet filter cake with a solid content of 42% is obtained after filtration, and then dried at 120°C for 6 hours to obtain silicon-containing pseudo-boehmite.

[0090] (2) Weigh the specific surface area of ​​400m 2 100 g of activated carbon powder with a water absorption rate of 0.8 mL / g was fully mixed with 100 g of boric acid and ground, placed in a tubular furnace, and calcined to 600 °C in a nitrogen atmosphere for 180 min to prepare MoO 3 The boron-doped carbon support is saturated with an impregnation solution having a molybdenum content of 0.994 g / mL and a NiO content of 0.1989 g / mL. After the impregnation is complete, the carbon support is dried at 120° C. for 5 hours and calcined at 500° C. under nitrogen protection for 3 hours to obtain an impregnated boron-doped carbon support, wherein the amount of Mo and Ni introduced into the catalyst in step (2) accounts for 65% of the total Mo and Ni in the catalyst, based on the mass of the oxides.

[0091] (3) Weigh 100 g of the impregnated boron-doped carbon support, 500 g of the silicon-containing pseudo-boehmite powder and 15 g of sesbania powder, mix them evenly and squeeze them into strips. After drying at 120° C. for 5 hours, calcinate them at 600° C., pass nitrogen protection, and keep the temperature constant for 3 hours to prepare MoO-containing 3 The catalyst was saturated with an impregnation solution of 0.094 g / mL of NiO and 0.188 g / mL of NiO, dried at 120°C for 5 hours, and calcined at 500°C for 3 hours to obtain the final residue hydrogenation catalyst F. Its physicochemical properties are shown in Table 1.

[0092] Comparative Example 3

[0093] (1) Add 3500 mL of SiO with a modulus of 2.8 and a concentration of 50 g into the 5000 mL first reactor. 2 / L water glass and caustic ratio is 1.45, concentration is 25g Al 2 O 3 / L of sodium aluminate mixed solution, and then introduce a mixed gas of carbon dioxide and air containing 55% by volume of carbon dioxide to reduce the pH value of the system to 3.4. The temperature of the material at the end of the reaction is 55°C;

[0094] Add 1500mL of bottom water to the 10000mL second reactor, start the stirring and heating device, and when the temperature rises to 65°C, add the above materials to the second reactor at a flow rate of 35mL / min. The addition time is 90min, and add 180gAl 2 O 3 / L, a sodium aluminate solution with a caustic ratio of 1.25, the pH value of the slurry in the second reactor is controlled to be 8.0 by adjusting the flow rate of the sodium aluminate solution, and the temperature of the slurry in the second reactor is kept constant. The reaction is completed after the above materials are used up, and the slurry is aged at 90°C for 80 minutes. After the aging, it is washed with deionized water at a temperature of 70°C to neutrality, and a silicon-containing pseudo-boehmite wet filter cake with a solid content of 42% is obtained after filtration, and then dried at 120°C for 6 hours to obtain silicon-containing pseudo-boehmite.

[0095] (2) Weigh the specific surface area of ​​400m 2 100 g of activated carbon powder with a water absorption rate of 0.8 mL / g was placed in a tubular furnace and calcined to 600 °C in a nitrogen atmosphere for 180 min to prepare MoO 3 The carbon support is saturated with an impregnation solution containing 0.497 g / mL Mo and 0.0994 g / mL NiO. After complete impregnation, the carbon support is dried at 120° C. for 5 hours and calcined at 500° C. under nitrogen protection for 3 hours to obtain an impregnated carbon support. The dried carbon support is further impregnated in 50 mL of an aqueous solution containing 100 g boric acid. After impregnation, the carbon support is dried in an oven at 120 degrees for 5 hours. The amount of Mo and Ni introduced into the catalyst in step (2) accounts for 33% of the total Mo and Ni in the catalyst, based on the mass of the oxides.

[0096] (3) Weigh 100 g of the impregnated carbon support, 500 g of the silicon-containing pseudo-boehmite powder and 15 g of sesbania powder, mix them evenly and squeeze them into strips. After drying at 120° C. for 5 hours, calcine them at 600° C., pass nitrogen protection, and keep the temperature constant for 3 hours to prepare MoO-containing 3The catalyst was saturated with an impregnation solution containing 0.181 g / mL of NiO and 0.036 g / mL of NiO, dried at 120°C for 5 hours, and calcined at 500°C for 3 hours to obtain the final residue hydrogenation catalyst G. Its physicochemical properties are shown in Table 1.

[0097] Comparative Example 4

[0098] (1) Add 3000 mL of 65 gAl into a 5.0 L reactor. 2 O 3 / L, a sodium aluminate solution with a caustic ratio of 1.35, and then a mixture of carbon dioxide and air with a carbon dioxide content of 80% (volume fraction), the initial reaction temperature is 25°C, the slurry temperature is maintained constant by cooling, the reaction time is controlled to be 45 minutes, and the pH value of the sodium aluminate solution is reduced to 8.8. The slurry is filtered, washed with 75°C deionized water, and dried at 120°C for 6 hours after washing to obtain pseudo-boehmite.

[0099] (2) Weigh the specific surface area of ​​400m 2 100 g of activated carbon powder with a water absorption rate of 0.8 mL / g was fully mixed with 100 g of boric acid and ground, placed in a tubular furnace, and calcined to 600 °C in a nitrogen atmosphere for 180 min to prepare MoO 3 The boron-doped carbon support is saturated with an impregnation solution having a molybdenum content of 0.497 g / mL and a NiO content of 0.0994 g / mL. After the impregnation is complete, the carbon support is dried at 120° C. for 5 hours and calcined at 500° C. under nitrogen protection for 3 hours to obtain an impregnated boron-doped carbon support, wherein the amount of Mo and Ni introduced into the catalyst in step (2) accounts for 33% of the total Mo and Ni in the catalyst, based on the mass of the oxides.

[0100] (3) Weigh 100 g of the impregnated boron-doped carbon support, 500 g of the pseudo-boehmite powder and 15 g of sesbania powder, mix them evenly and squeeze them into strips. After drying at 120° C. for 5 hours, calcinate them at 600° C., pass nitrogen protection, and keep the temperature constant for 3 hours to prepare MoO-containing 3 The catalyst was saturated with an impregnation solution of 0.181 g / mL of NiO and 0.036 g / mL of NiO, dried at 120°C for 5 hours, and calcined at 500°C for 3 hours to obtain the final residue oil hydrogenation catalyst H. Its physicochemical properties are shown in Table 1.

[0101] Example 5

[0102] The catalysts obtained in Examples 1-4 and Comparative Examples 1-4 were used in residual oil hydrogenation reactions. The properties of the raw materials are shown in Table 2, and the evaluation conditions and results are shown in Table 3.

[0103] Table 1 Physicochemical properties of the residue hydrogenation catalysts obtained in each example

[0104]

[0105]

[0106] Table 2 Raw oil properties

[0107] <![CDATA[Density (20 °C), kg / m 3 > 987.5 S,wt% 3.56 N,ppm 2426 CCR,wt% 12.5 Ni,ppm 23.6 V,ppm 73.1

[0108] Table 3 Evaluation conditions and evaluation results of the residue hydrogenation catalysts obtained in each example

[0109]

Claims

1. A method for preparing a residue oil hydrogenation catalyst, comprising the following steps: (1) Mixing activated carbon with boric acid, and heating the mixture to synthesize a boron-doped carbon carrier; (2) impregnating the active metal Cl into the boron-doped carbon support described in step (1), drying, and calcining to obtain an impregnated boron-doped carbon support; (3) preparing a silicon-containing pseudo-boehmite wet filter cake, and drying the wet cake to obtain silicon-containing pseudo-boehmite; (4) mixing the boron-doped carbon support impregnated in step (2) with the silicon-containing pseudo-boehmite powder in step (3), forming, drying, and calcining to obtain a catalyst precursor; (5) mixing the catalyst precursor of step (4) with the active metal C2 for a second impregnation, drying, and calcining to obtain a catalyst; Wherein, in step (2), the active metal C1 is at least one of the metals of Group VIB and at least one of the metals of Group VIII; the metal of Group VIB is at least one of Mo and W, and the metal of Group VIII is at least one of Ni and Co; the amount of the active metal introduced into the catalyst by step (2) is 30% to 50% by mass of the total active metal in the catalyst in terms of oxide. In step (5), the impregnation adopts a saturation impregnation method, and the active metal C2 is at least one of the VIB group metals and at least one of the VIII group metals; the VIB group metal is selected from at least one of Mo and W, and the VIII group metal is selected from at least one of Ni and Co; The amount of active metal introduced into the catalyst in step (5) accounts for 50% to 70% of the total amount of active metal in the catalyst in terms of oxide.

2. The preparation method according to claim 1, characterized in that: In step (3), the method for preparing a silicon-containing pseudo-boehmite wet filter cake comprises: (A) adding a first alkaline solution into a first reaction kettle, introducing a mixed gas containing carbon dioxide to react, and making the pH value of the system be 2 to 4; (B) adding bottom water to the second reaction kettle, heating to the reaction temperature, and then adding the second alkaline solution and the material obtained in step (A) into the second reaction kettle in parallel to react; (C) aging the slurry obtained after the reaction in step (B), filtering and washing after the aging to obtain a silicon-containing pseudo-boehmite filter cake.

3. The preparation method according to claim 1, characterized in that: In step (1), the specific surface area of ​​the activated carbon is 350 to 480 m 2 / g; the water absorption rate of the activated carbon is in the range of 0.7 to 1.5 mL / g; the specific surface area of ​​the activated carbon is in the range of 350 to 450 m 2 / g; the mass ratio of the activated carbon to the boric acid is 0.1 to 4.

4. The preparation method according to claim 1, characterized in that: In step (4), the mass ratio of the boron-doped carbon carrier to the silicon-containing pseudo-boehmite is 0.05 to 0.

5.

5. The preparation method according to claim 1, characterized in that: In step (4), the drying temperature is 80-120°C and the time is 4-6 hours; the calcination temperature is 450-800°C and the time is 3-6 hours; the drying and calcination atmosphere is an inert gas and / or nitrogen; the inert gas is selected from at least one of Ar and He.

6. The preparation method according to claim 1, characterized in that: In step (5), the active metal C2 is Mo and Ni.

7. The preparation method according to claim 1, characterized in that: After the impregnation in step (5), the mass ratio of the VIB group metal to the VIII group metal in the total active metal of the catalyst in terms of oxide is 1.8 to 30; in step (5), the drying temperature is 100 to 120° C. and the time is 4 to 6 hours; the calcination temperature is 430 to 600° C. and the time is 3 to 5 hours.

8. A residue oil hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 7.

9. The residue oil hydrogenation catalyst according to claim 8, characterized in that In the catalyst, the active metal loading is 15% to 40% by mass of the oxide; wherein the active metal is at least one of the metals of Group VIB and at least one of the metals of Group VIII.

10. The residue oil hydrogenation catalyst according to claim 8, characterized in that In the catalyst, the active metals are molybdenum and nickel.

11. The residue hydrogenation catalyst according to claim 8, characterized in that In the catalyst, the active metal loading is calculated based on the mass of the oxide, the mass content of the VIB group metal is 15% to 30%, and the mass content of the VIII group metal is 1% to 8%.

12. The residue hydrogenation catalyst according to claim 8, characterized in that The catalyst also contains boron, and the mass content of boron is 0.2% to 3.5%.

13. The residue hydrogenation catalyst according to claim 8, characterized in that In the catalyst, the active metal dispersion is: VIB / I Al 0.06~0.10, I VIII / I Al It is 0.02~0.

05.

14. The residue hydrogenation catalyst according to claim 8, characterized in that The specific surface area of ​​the catalyst is 110 to 270 m 2 / g, pore volume is 0.8~1.4cm 3 / g, mechanical strength>20N / mm, the pore volume of pores with pore diameter>15nm accounts for 5.5% to 24% of the total pore volume, and the pore volume of pores with pore diameter<8nm accounts for less than 7.5% of the total pore volume; the acid amount of the catalyst is 0.1 to 0.9mmol / g; the ratio of the acid amount of B acid to the acid amount of L acid is C B / C L It is 0.03~0.

085.

15. Use of the residue oil hydrogenation catalyst according to any one of claims 8 to 14 in a residue oil hydrogenation process.

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