CN117899900B - Hydrodemetallization catalyst for residue oil and its preparation method - Google Patents
Hydrodemetallization catalyst for residue oil and its preparation methodInfo
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- CN117899900B CN117899900B CN202211235022.7A CN202211235022A CN117899900B CN 117899900 B CN117899900 B CN 117899900B CN 202211235022 A CN202211235022 A CN 202211235022A CN 117899900 B CN117899900 B CN 117899900B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
本发明公开了一种渣油加氢脱金属催化剂及其制备方法。本发明催化剂的制备方法，包括：将硝酸铝、尿素及模板剂溶于水，得到溶液X；转移至晶化釜中进行第一次晶化，取下层浆液，得到物料Y；物料Y、硝酸铝、尿素及模板剂溶于水，得到溶液Z；转移至晶化釜中进行第二次晶化，焙烧，得到载体A；载体A浸入碳酸氢铵水溶液后密封热处理，干燥，得到载体B；载体B和第一活性金属组分源进行混捏、成型，焙烧，得到载体C；载体C浸入碳酸氢铵水溶液后密封处理，干燥，得到载体D；载体D浸渍负载含水溶性高聚物J的第二活性金属组分，焙烧，得到催化剂。本发明催化剂应用于渣油加氢脱金属反应中，反应活性和稳定性均得到明显提高。This invention discloses a catalyst for the hydrodemetallization of residual oil and its preparation method. The preparation method of the catalyst includes: dissolving aluminum nitrate, urea, and a template agent in water to obtain solution X; transferring the solution to a crystallization kettle for a first crystallization, removing the lower slurry layer to obtain material Y; dissolving material Y, aluminum nitrate, urea, and the template agent in water to obtain solution Z; transferring the solution to a crystallization kettle for a second crystallization and calcining to obtain support A; immersing support A in an ammonium bicarbonate aqueous solution, sealing and heat-treating, and drying to obtain support B; mixing and molding support B with a first active metal component source, and calcining to obtain support C; immersing support C in an ammonium bicarbonate aqueous solution, sealing and drying to obtain support D; impregnating support D with a second active metal component containing a water-soluble polymer J, and calcining to obtain the catalyst. When applied to the hydrodemetallization reaction of residual oil, the catalyst of this invention exhibits significantly improved reactivity and stability.
Description
Technical Field
The invention relates to a residual oil hydrodemetallization catalyst, in particular to a residual oil hydrodemetallization catalyst and a preparation method thereof.
Background
As is well known, most of the conventional residuum hydrogenation catalysts are supported hydrogenation catalysts, and the active metal component is generally supported on the surface of the carrier. In general, various metal compounds react with H 2 S under the action of a catalyst to form metal sulfides, which are then deposited on the catalyst to be removed. Therefore, the specific surface area of the catalyst not only influences the distribution of the active metal when the active metal is loaded, but also influences the deposition of metal impurities after the reaction.
CN111001424A discloses a phosphorus-containing residuum hydrotreating catalyst and a preparation method thereof, wherein mesopores are arranged on the catalyst, the mesopores are intensively distributed and uniform in size, the pore diameter range of the mesopores is 10-30 nm, strong acid carriers are uniformly distributed on the pore channel surfaces of the mesopores, the total pore volume of the catalyst carrier is 0.6-1.2 mL/g, the specific surface area is 180-350 m 2/g, and the pore volume of the mesopores accounts for 60-95% of the total pore volume of the catalyst carrier. CN101880049B discloses a method for preparing alumina nano-rod with grade mesoporous channel. Under the combined action of biological small molecules such as sucrose and macromolecules such as polyalcohol, aluminum nitrate is used as a precursor, ammonium carbonate or ammonium bicarbonate is used as a precipitator, and the hydrothermal crystallization method is utilized to synthesize the hierarchical mesoporous alumina nano rod with high specific surface area and large pore volume. The smaller mesopores of the alumina obtained by the method are concentrated at about 3nm, the larger mesopores can be regulated and controlled within 10-30 nm, the length-diameter ratio of the nanorods is less than 50, and the specific surface is up to 500m 2/g. CN103785400a discloses a preparation method of a high-activity residual oil hydrodemetallization catalyst, which comprises the steps of impregnating an alumina carrier with a polyalcohol and/or monosaccharide aqueous solution, carrying out hydrothermal carbonization treatment in a sealed container after the impregnation is finished, then loading active metal components Mo and Ni on the carrier, and finally roasting the alumina loaded with the active components in a nitrogen atmosphere, and then roasting in an air atmosphere to obtain the residual oil hydrodemetallization catalyst.
The alumina carrier prepared by the method has a narrow pore size distribution range, has limited effect in the diffusion process of macromolecules in residual oil raw materials, and cannot avoid aggregation of active metals in and around carrier pore channels in the process of impregnating the active metals, so that the activity and stability of the alumina carrier and hydrodemetallization catalyst prepared by the method still need to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a residual oil hydrodemetallization catalyst and a preparation method thereof. The residual oil hydrodemetallization catalyst provided by the invention has larger pore volume and pore diameter, has more regular pore channel structure, is applied to residual oil hydrodemetallization reaction, and obviously improves the reactivity and stability.
The invention provides a preparation method of a residual oil hydrodemetallization catalyst, which comprises the following steps:
(1) Dissolving aluminum nitrate, urea and a template agent in water to obtain a solution X;
(2) Performing primary crystallization on the solution X obtained in the step (1), and taking out the lower slurry to obtain a material Y;
(3) Dissolving the material Y, aluminum nitrate, urea and a template agent obtained in the step (2) in water to obtain a solution Z;
(4) Performing secondary crystallization, drying and roasting on the solution Z obtained in the step (3) to obtain an alumina carrier A;
(5) Immersing the carrier A obtained in the step (4) into an ammonium bicarbonate aqueous solution, sealing, performing heat treatment, and drying to obtain a carrier B;
(6) Kneading, molding, drying and roasting the carrier B obtained in the step (5) and a first active metal component source to obtain a carrier C;
(7) Immersing the carrier C obtained in the step (6) into an ammonium bicarbonate aqueous solution, sealing, and drying to obtain a carrier D;
(8) And (3) impregnating the carrier D obtained in the step (7) with a second active metal component containing a water-soluble high polymer J, drying and roasting to obtain the residual oil hydrodemetallization catalyst.
In the present invention, the water used is preferably deionized water. The crystallization is carried out in a crystallization kettle.
In the step (1), aluminum nitrate, urea and a template agent are dissolved in deionized water successively according to the sequence and mixed to obtain a solution X.
In the step (1), the molar ratio of Al (NO 3)3) to the template agent is 160-240.
In the step (1) of the invention, the molar ratio of urea to Al (NO 3)3) is 7-14, in the range, the hydrolysis rate of OH - generated by urea decomposition and Al 3+ is just right, and alumina can uniformly grow on the surface of the template agent.
In the step (1), the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose, preferably polyethylene glycol, the viscosity (20 ℃) of the template agent is 10-1000 mPa.s, and the viscosity (20 ℃) of the solution X is 120-660 mPa.s after the template agent is added and stirred uniformly.
In the step (2), the condition of the first crystallization is that the crystallization temperature is 90-140 ℃ and the crystallization time is 5-30 h.
In the step (3), the materials Y, aluminum nitrate, urea and a template agent are dissolved in deionized water successively according to the sequence, and then mixed to obtain a solution Z.
In the step (3) of the invention, the proportion of Al (NO 3)3, template agent and urea is the same as that in the step (1).
In the step (3), the addition amount of the material Y accounts for 10% -40% of the total mass of the material Y and urea used for the second crystallization.
In the step (4), the condition of the second crystallization is that the crystallization temperature is 100-200 ℃ and the crystallization time is 25-35 h. Wherein the temperature of the second crystallization is 60-100 ℃ higher than the temperature of the first crystallization.
In step (4) of the present invention, filtration and washing may be performed before drying according to conventionally known methods. The washing can be carried out by adopting deionized water until the pH value of the filtrate is close to neutral. The dry matter content of the dried product is 50-80 wt%.
In the step (4), the drying temperature is 120-200 ℃ and the drying time is 2-12 h.
In the step (4), the roasting temperature is 500-750 ℃, the roasting time is 2-6 h, and the air atmosphere is the roasting atmosphere.
In the step (5), the mass percentage concentration range of the ammonium bicarbonate aqueous solution is 10% -20%. The sealing heat treatment temperature is 80-140 ℃, preferably 85-130 ℃ and the treatment time is 6-12 h. The drying temperature is 120-180 ℃, and the drying time is 2-10 h.
In step (6) of the present invention, the first active metal component source is a soluble compound of metallic molybdenum and a soluble compound containing a group VIII metal. The group VIII metal is preferably nickel.
In the step (6) of the invention, the soluble compound of the metallic molybdenum is at least one of molybdenum oxide and ammonium molybdate, and the soluble compound of the VIII group metal (preferably Ni) is at least one of basic nickel carbonate and nickel nitrate.
In step (6) of the invention, the amount of MoO 3 introduced into the catalyst by the first active metal component is 45% -70% of the total MoO 3 loading in the catalyst, and the amount of the VIII group metal oxide introduced into the catalyst by the first active metal component is 45% -70% of the total VIII group metal oxide loading in the catalyst.
In the step (6), conventional forming aids such as one or more of peptizers, extrusion aids and the like can be added according to the need in the forming process, wherein the peptizers are one or more of nitric acid, sulfuric acid and oxalic acid, preferably nitric acid, and the extrusion aids are one or more of sesbania powder, cellulose and resin, preferably sesbania powder.
In the step (6), the addition amount of the peptizing agent accounts for 0.5% -6.0% of the carrier B, and the addition amount of the extrusion assisting agent accounts for 0.1% -5.5% of the carrier B.
In the step (6), the drying temperature is 20-200 ℃ and the drying time is 2-12 h.
In the step (6), the roasting temperature is 500-750 ℃, the roasting time is 2-6 h, and the air atmosphere is the roasting atmosphere.
In the step (7), the mass percentage concentration range of the ammonium bicarbonate aqueous solution is 20% -30%. The sealing treatment temperature is 10-60 ℃, preferably 20-50 ℃ and the treatment time is 6-12 h. Wherein the heat treatment temperature in the step (7) is 70-95 ℃ lower than the heat treatment temperature in the step (5). The drying temperature is 10-40 ℃, the drying time is 2-10 h, and the drying mode is standing drying.
In the step (7), the mass concentration of the ammonium bicarbonate aqueous solution is 8-15 percent higher than that of the ammonium bicarbonate aqueous solution in the step (5).
In the step (8), the saturated impregnation method is adopted for impregnation, and the standing time after impregnation is 4-14 hours.
In the step (8) of the present invention, the carrier D is impregnated with the impregnation liquid containing the second active metal component of the water-soluble polymer J. The impregnating solution is an impregnating solution containing Mo and a group VIII metal (preferably Ni), wherein the active metal component molybdenum is one or two of molybdenum oxide and ammonium heptamolybdate, and the nickel is one or two of basic nickel carbonate and nickel nitrate. The contents of MoO 3 and group VIII metal oxide in the impregnation liquid containing the second active metal component are respectively 10.0-80.0 g/100mL and 2.0-40.0 g/100mL.
In step (8) of the invention, the amount of MoO 3 introduced into the catalyst by the second active metal component is 30% -55% of the total MoO 3 loading in the catalyst, and the amount of the VIII group metal oxide introduced into the catalyst by the second active metal component is 30% -55% of the total VIII group metal oxide loading in the catalyst.
In the step (8), the water-soluble polymer J is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, methylcellulose and the like, and is preferably polyethylene glycol. The viscosity (20 ℃) of the water-soluble polymer J is 10-1000 mPa.s, and the viscosity (20 ℃) of the impregnating solution after the water-soluble polymer J is added is 150-800 mPa.s.
In the step (8), at least one auxiliary agent containing fluorine, phosphorus, silicon or boron can be introduced into the impregnating solution containing the second active metal component, wherein the addition amount of the auxiliary agent (calculated by oxide) is 2% -20% of the total mass of molybdenum oxide in the impregnating solution containing the second active metal component, and is preferably 2% -15%.
In the step (8), the drying temperature is 120-200 ℃ and the drying time is 2-12 h.
In the step (8), the roasting temperature is 350-500 ℃, the roasting time is 2-6 h, the roasting atmosphere is a mixed atmosphere of an inert atmosphere and other atmospheres, and the volume ratio of the inert atmosphere to the other atmospheres is 0.5-5:1. Wherein, the inert atmosphere is mainly one or two of nitrogen and helium, and the other atmosphere is one or more of steam and air.
The invention provides a residual oil hydrodemetallization catalyst prepared by the preparation method, which comprises a carrier component, an active metal component and carbon distributed on the surface of the catalyst, wherein the active metal component comprises molybdenum and VIII metal, and the carrier component is alumina, wherein the mass ratio of the carbon distributed on the surface of the catalyst to the alumina in the catalyst is 0.20-0.40.
In the present invention, the active metal component includes a first active metal component distributed inside the alumina and a second active metal component distributed on the surface of the alumina.
In the present invention, the active metal component comprises molybdenum and a group VIII metal, preferably nickel.
In the present invention, the first active metal component comprises molybdenum and a group VIII metal, preferably nickel.
In the present invention, the second active metal component comprises molybdenum and a group VIII metal, preferably nickel.
In the invention, the content of MoO 3 is 2.0-20.0% and the content of the VIII group metal oxide is 1.0-6.0% based on the mass of the catalyst.
In the invention, the content of MoO 3 in the first active component is 45% -70% and the content of MoO 3 in the second active component is 30% -55% based on the total mass of MoO 3 in the catalyst.
In the invention, the content of the VIII metal oxide in the first active component is 45% -70% and the content of the VIII metal oxide in the second active component is 30% -55% based on the mass of the total VIII metal oxide in the catalyst.
In the invention, the specific surface area of the catalyst is 185-225 m 2/g, and the pore volume is 0.75-1.05 mL/g.
In the invention, preferably, the specific surface area of the catalyst is 190-210 m 2/g, and the pore volume is 0.80-0.95 mL/g.
The catalyst has the pore distribution that the pore volume occupied by the pores with the diameter of less than 30nm is 27% -36% of the total pore volume, the pore volume occupied by the pores with the diameter of 30-100 nm is 31% -37% of the total pore volume, and the pore volume occupied by the pores with the diameter of 100-300 nm is 33% -36% of the total pore volume.
In the invention, the strength of the catalyst is 8.0-18.0N/mm.
In the invention, the catalyst also comprises an auxiliary component, wherein the auxiliary component is at least one selected from fluorine, phosphorus, silicon or boron, and preferably phosphorus. The mass of the catalyst is taken as a reference, and the content of the auxiliary agent component calculated by oxide is 1.0% -8.0%.
Compared with the prior art, the invention has the following beneficial effects:
For hydrodemetallization catalysts, good pore channel structure and reasonable active metal distribution on the catalyst are of great significance for the exertion of the catalytic performance of the catalyst. On one hand, the catalyst has smooth pore canal structure because of the existence of large macromolecules in heavy oil material, and on the other hand, the active metal component has good dispersion in the catalyst and on the surface to prevent the active metal component from accumulating in the outer pore opening of the catalyst to block the molecular diffusion channel. The inventors have found through a great deal of research that the pore canal structure of the prepared alumina carrier is more regular and smooth by introducing seed crystals (material Y) in the process of preparing the alumina carrier by a uniform precipitation method, then the pore canal smoothness is further adjusted after sealing heat treatment after passing through ammonium bicarbonate aqueous solution, and then the alumina carrier is kneaded and molded with nitric acid, sesbania powder, part of active metals and deionized water, and then the alumina carrier with large specific surface area and smooth pore canal can be obtained through drying and roasting. And then, carrying out sealing treatment after carrying out ammonium bicarbonate aqueous solution on the molded carrier again, so that the carrier is filled with the ammonium bicarbonate aqueous solution to fill the external pore canal and the pore opening of the carrier, and active metal components are prevented from accumulating around the pore opening in the impregnation process. Finally, impregnating the carrier with impregnating solution prepared by the residual active metal in a saturated impregnation mode, and drying and roasting to obtain the hydrodemetallization catalyst. In addition, the impregnating solution is added with water-soluble high polymer, and the final roasting atmosphere is mixed atmosphere roasting, so that the pore canal and pore opening structure on the surface of the catalyst are released, the blocking phenomenon of the pore opening in the impregnation process is prevented, the high polymer is incompletely decomposed to form carbon points distributed in a punctiform manner, the acidity of the catalyst can be properly regulated, the interaction between the active metal and the carrier is reduced, and the dispersion degree of the active metal on the surface of the catalyst is promoted. Through comprehensive coordination of the steps, the activity and stability of the catalyst prepared by the method are obviously improved.
Detailed Description
In the invention, the pore Structure (SVD) and specific surface area of the catalyst are characterized by using an ASAP-2420 physical adsorption instrument of Michael company.
In the invention, a ZQJ-III intelligent particle strength tester is used for detecting the crushing resistance of the catalyst particles.
In the invention, a thermal gravimetric-mass spectrometry analyzer (TG-MS) of STA409PC-QMS403C of NETZSCH company is adopted to measure the mass ratio of carbon to alumina on the surface of the catalyst.
The technical scheme and effect of the present invention will be further described with reference to the following examples, but is not limited to the following examples.
Example 1
(1) Weighing a proper amount of aluminum nitrate, urea and template agent polyethylene glycol (viscosity is 500 mPa.s), wherein the molar ratio of Al (NO 3)3 to polyethylene glycol is 180, the molar ratio of urea to Al (NO 3)3 is 9), dissolving the substances in a certain amount of deionized water according to the sequence of the aluminum nitrate, urea and polyethylene glycol, and magnetically stirring for 5 hours to uniformly mix to obtain a solution X (viscosity is 350 mPa.s);
(2) Transferring the obtained solution X into a crystallization kettle, placing the crystallization kettle into a 100 ℃ oven, taking out the crystallization kettle after reacting for 8 hours, and taking out a lower slurry of the crystallization kettle with a certain mass as a material Y;
(3) Weighing a material Y, metered aluminum nitrate, urea and template agent polyethylene glycol (viscosity is 500 mPa.s), wherein the molar ratio of Al (NO 3)3 to polyethylene glycol is 180, the molar ratio of urea to Al (NO 3)3 is 9), dissolving in a certain amount of deionized water successively, wherein the mass of the material Y accounts for 15% of the total mass of the material Y and urea used for the second crystallization, and uniformly mixing through magnetic stirring to obtain a solution Z;
(4) Transferring the solution Z obtained in the step (3) into a crystallization kettle, placing the crystallization kettle into a 200 ℃ oven, taking out the crystallization kettle after reacting for 35 hours, cooling, and obtaining mixed slurry containing white precipitate in the reaction kettle, filtering and washing the obtained white precipitate for several times until the pH value of filtrate is close to 7, drying the white precipitate in the oven at 130 ℃ for 7 hours, roasting the white precipitate in a muffle furnace at 550 ℃ for 4 hours, and obtaining a carrier A;
(5) Immersing the obtained alumina carrier A into an ammonium bicarbonate aqueous solution, and then carrying out sealing heat treatment to obtain a carrier B, wherein the mass percentage concentration range of the ammonium bicarbonate aqueous solution is 18%, the sealing heat treatment temperature is 120 ℃, the treatment time is 4 hours, the drying temperature is 150 ℃, and the drying time is 6 hours;
(6) Kneading and molding a carrier B, 68wt% of nitric acid, 68wt% of sesbania powder, 700 ℃ of a first active metal component source (ammonium molybdate and nickel nitrate) and deionized water, drying and roasting to obtain a carrier C, wherein the mass content of the nitric acid (68 wt%) added is 2.5% of that of the carrier B, the mass content of the sesbania powder added is 3.5% of that of the carrier B, the adding content of the deionized water is adjusted in real time according to the material state in the forming process, the drying temperature is 120 ℃, the drying time is 6h, the roasting temperature is 700 ℃, and the roasting time is 6h (the heating rate is 2.5 ℃ per minute), wherein the amount of MoO 3 introduced into the catalyst by the first active metal component is 60% of the total MoO 3 loading amount in the catalyst, and the amount of NiO is 60% of the total NiO loading amount in the catalyst;
(7) Immersing the obtained carrier C into an ammonium bicarbonate aqueous solution, sealing, and drying to obtain a carrier D, wherein the mass percentage concentration range of the ammonium bicarbonate aqueous solution is 28%, the sealing treatment temperature is 25 ℃, the treatment time is 7 hours, the drying temperature is 25 ℃, the drying time is 5 hours, and the drying mode is standing and drying;
(8) And (3) impregnating the carrier D in a saturated impregnation mode by using a second active component-containing metal component impregnating solution (the content of MoO 3 is 30.68g/100mL, the content of NiO is 5.07g/100mL, the addition amount of P (calculated as oxide) in auxiliary phosphoric acid is 8.87% of the total mass of molybdenum oxide in the impregnating solution), wherein the amount of MoO 3 introduced into the catalyst by the second active component is 40% of the total MoO 3 loading amount in the catalyst, the amount of NiO is 40% of the total NiO loading amount in the catalyst, the impregnating solution contains water-soluble high polymer J polyethylene glycol, the viscosity (20 ℃) of the impregnating solution is 320 mPa.s after the water-soluble high polymer J polyethylene glycol is added, the impregnated sample is subjected to standing at room temperature (25 ℃) for 6 hours, drying (the temperature is 120 ℃) for 6 hours), the roasting temperature is 500 ℃, the roasting time is 4 hours (the temperature rising rate is 2.0 ℃ per minute), and the roasting atmosphere is the mixed atmosphere of nitrogen and air (the volume ratio of nitrogen to air is 3:1), so as to obtain the residual oil hydrodemetallization catalyst. The catalyst for hydrodemetallization of the residual oil is named CAT-1. The physicochemical properties of this catalyst are shown in Table 1.
Example 2
Compared with the example 1, the method is characterized in that Al (NO 3)3 and polyethylene glycol) in the step (1) have a molar ratio of 200, urea and Al (NO 3)3) have a molar ratio of 11, a material Y in the step (3) accounts for 20% of the total mass of urea used for secondary crystallization, the obtained solution Z in the step (4) is transferred to a crystallization kettle, the crystallization kettle is placed in a 160 ℃ oven, the crystallization kettle is taken out after the reaction for 30 hours, the white precipitate is placed in the oven for drying at 140 ℃ for 8 hours, and then is roasted by a muffle furnace at 650 ℃ for 3 hours, so that the residual oil hydrodemetallization catalyst CAT-2 is prepared, and the physicochemical properties of the catalyst are shown in the table 1.
Example 3
Compared with the embodiment 1, the method is characterized in that the mass percentage concentration range of the first ammonium bicarbonate aqueous solution in the step (5) is 16%, the sealing heat treatment temperature is 110 ℃, the treatment time is 7 hours, the drying temperature is 130 ℃, the drying time is 5 hours, the mass percentage concentration range of the second ammonium bicarbonate aqueous solution in the step (7) is 26%, the sealing treatment temperature is 30 ℃, the treatment time is 7 hours, the drying temperature is 30 ℃, and the drying time is 8 hours, so that the residual oil hydrodemetallization catalyst CAT-3 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Example 4
In the step (6), the carrier B, nitric acid (68 wt%), sesbania powder, a first active metal component source (ammonium molybdate and nickel nitrate) and deionized water are kneaded, molded, dried and roasted to obtain a carrier C, wherein the drying temperature is 140 ℃, the drying time is 8 hours, the roasting temperature is 750 ℃, and the roasting time is 5 hours (the heating rate is 3.0 ℃ per minute); wherein the amount of MoO 3 introduced into the catalyst from the first active metal component is 70% of the total MoO 3 load in the catalyst, the amount of NiO is 70% of the total NiO load in the catalyst, the impregnating solution (23.01 g/100mL of MoO 3 and 3.80g/100mL of NiO) containing the second active metal component is used for impregnating the carrier D in a saturated impregnating mode in the step (8), the addition amount of P (calculated as oxide) in the auxiliary phosphoric acid is 6.65% of the total mass of molybdenum oxide in the impregnating solution, the amount of MoO 3 introduced into the catalyst from the second active metal component is 30% of the total MoO 3 load in the catalyst, the amount of NiO is 30% of the total NiO load in the catalyst, the impregnating solution contains water-soluble high polymer J polyvinyl alcohol, the viscosity (20 ℃) of the impregnating solution after the adding of the water-soluble high polymer J polyvinyl alcohol is 400 mPa.s, the impregnated sample is left stand for 8 hours after the impregnating, the sample is dried (the drying temperature is 140 ℃ and the drying time is 5 hours), the temperature is raised and the air temperature is 1:500 ℃ and the air is mixed with the nitrogen atmosphere (the air is 1:1 vol.), the hydrodemetallization catalyst CAT-4 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Comparative example 1
Compared with the embodiment 1, the method is characterized in that Al (NO 3)3 and polyethylene glycol are in a molar ratio of 260 and urea and Al (NO 3)3 are in a molar ratio of 6) in the step (1), the substances are dissolved in a certain amount of deionized water sequentially according to the sequence of aluminum nitrate, urea and polyethylene glycol, solution X is obtained after magnetic stirring for 8 hours and mixing uniformly, the obtained solution X in the step (2) is transferred into a crystallization kettle, the crystallization kettle is placed in an oven at 160 ℃ and is taken out after reacting for 20 hours, and the residual oil hydrogen demetallization catalyst dCAT-1 is prepared, wherein the physicochemical properties of the catalyst are shown in the table 1.
Comparative example 2
Compared with the embodiment 1, the method is characterized in that the mass percentage concentration range of the second ammonium bicarbonate aqueous solution in the step (7) is 35%, the sealing treatment temperature is 80 ℃, the treatment time is 5 hours, the drying temperature is 140 ℃ and the drying time is 5 hours, and the residual oil hydrodemetallization catalyst dCAT-2 is prepared. The physicochemical properties of this catalyst are shown in Table 1.
Comparative example 3
Compared with the embodiment 1, the method is characterized in that in the step (6), active metal is not added in the kneading process, but the carrier D is impregnated in the step (8) in a saturated impregnation mode by an active metal component impregnation liquid, the impregnation liquid contains water-soluble high polymer J polyethylene glycol, the viscosity (20 ℃) of the impregnation liquid is 400 mPa.s after the water-soluble high polymer J polyethylene glycol is added, the impregnated sample is dried (the drying temperature is 120 ℃ and the drying time is 6 h) after standing for 6h at room temperature, the roasting temperature is 650 ℃ and the roasting time is 4h (the heating rate is 3.0 ℃ per minute), and the roasting atmosphere is a mixed atmosphere of nitrogen and water vapor, so that the residual oil hydrodemetallization catalyst dCAT-3 is prepared. The physicochemical properties of this catalyst are shown in Table 1.
Comparative example 4
Compared with the embodiment 1, the difference is that the impregnating solution containing the second active metal component in the step (8) is not added with water-soluble high polymer J polyethylene glycol, and the roasting atmosphere is air. The residuum hydrodemetallization catalyst dCAT-4 is prepared. The surface of catalyst dCAT-4 is free of carbon. The physicochemical properties of this catalyst are shown in Table 1.
Comparative example 5
The difference from example 1 is that the conditions for both crystallization are the same and that crystallization is carried out for 15 hours at 150 ℃. The residuum hydrodemetallization catalyst dCAT-5 is prepared. The physicochemical properties of this catalyst are shown in Table 1.
TABLE 1 physicochemical Properties of residuum hydrodemetallization catalyst
TABLE 1 physicochemical Properties of residuum hydrodemetallization catalyst (follow-up)
Evaluation test
The activity stability test of the residual oil hydrodemetallization catalyst CAT-1-4 and dCAT-1-5 is carried out in a200 mL fixed bed hydrogenation test device, and the used catalyst is in a strip shape with the length of 2-3 mm. The reaction conditions are that the reaction temperature is 395 ℃, the reaction pressure is 15.7MPa, the liquid hourly space velocity is 1.0h- 1, the hydrogen oil volume ratio is 900, the demetallization rate (Ni+V) of each catalyst after 1500h of reaction is shown in table 3, and the properties of the raw oil are shown in table 2.
TABLE 2 oil Properties of raw materials
TABLE 3 results of various residuum hydrodemetallization catalyst runs
As can be seen from tables 1, 2 and 3, the hydrodemetallization catalyst prepared by the method has a smooth pore structure, has a large specific surface area, has high reactivity and stability in the reaction process, and can well meet the hydrodemetallization process of heavy oil, especially residual oil.
Claims (18)
1. The preparation method of the residuum hydrodemetallization catalyst comprises the following steps:
(1) Dissolving aluminum nitrate, urea and a template agent in water to obtain a solution X;
(2) Performing primary crystallization on the solution X obtained in the step (1), and taking out the lower slurry to obtain a material Y;
(3) Dissolving the material Y, aluminum nitrate, urea and a template agent obtained in the step (2) in water to obtain a solution Z;
(4) Performing secondary crystallization, drying and roasting on the solution Z obtained in the step (3) to obtain an alumina carrier A;
(5) Immersing the carrier A obtained in the step (4) into an ammonium bicarbonate aqueous solution, sealing, performing heat treatment, and drying to obtain a carrier B;
(6) Kneading, molding, drying and roasting the carrier B obtained in the step (5) and a first active metal component source to obtain a carrier C;
(7) Immersing the carrier C obtained in the step (6) into an ammonium bicarbonate aqueous solution, sealing, and drying to obtain a carrier D;
(8) Impregnating the carrier D obtained in the step (7) with a second active metal component containing a water-soluble polymer J, drying and roasting to obtain the residual oil hydrodemetallization catalyst
In the step (1), al (the molar ratio of NO 3)3 to the template agent is 160-240, the molar ratio of urea to Al (the molar ratio of NO 3)3 is 7-14; in the step (3), the molar ratio of Al (the molar ratio of NO 3)3 to the template agent is 160-240, and the molar ratio of urea to Al (the molar ratio of NO 3)3 is 7-14);
The temperature of the first crystallization is 90-140 ℃, the temperature of the second crystallization is 100-200 ℃, and the temperature of the second crystallization is 60-100 ℃ higher than the temperature of the first crystallization;
In the step (5), the mass percentage concentration range of the ammonium bicarbonate aqueous solution is 10% -20%, in the step (7), the mass percentage concentration range of the ammonium bicarbonate aqueous solution is 20% -30%, and in the step (7), the mass concentration of the ammonium bicarbonate aqueous solution is 8% -15% higher than that in the step (5);
The sealing heat treatment temperature in the step (5) is 80-140 ℃, the sealing treatment temperature in the step (7) is 10-60 ℃, and the treatment temperature in the step (7) is 70-95 ℃ lower than the heat treatment temperature in the step (5);
In the step (6), the first active metal component source is a soluble compound of metallic molybdenum and a soluble compound containing VIII group metal, in the step (8), when the carrier D is immersed and loaded with the second active metal component containing water-soluble polymer J, an immersion liquid containing the second active metal component of the water-soluble polymer J is adopted, the immersion liquid is an immersion liquid containing Mo and VIII group metal, in the step (8), the water-soluble polymer J is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose, the viscosity of the water-soluble polymer J at 20 ℃ is 10-1000 mPa.s, and the viscosity of the immersion liquid at 20 ℃ after the water-soluble polymer J is added is 150-800 mPa.s.
2. The preparation method according to claim 1, wherein in the step (3), the amount of the material Y added is 10% -40% of the total mass of urea used for the second crystallization.
3. The preparation method of claim 1, wherein in the step (1), the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose, and/or the viscosity of the template agent at 20 ℃ is 10-1000 mPa.s, and the viscosity of the solution X20 ℃ is 120-660 mPa.s after the template agent is added and stirred uniformly.
4. The method of claim 3, wherein in step (1), the template is polyethylene glycol.
5. The method according to claim 1, wherein the first crystallization is performed for 5 to 30 hours and the second crystallization is performed for 25 to 35 hours.
6. The preparation method according to claim 1, wherein the sealing heat treatment temperature in the step (5) is 85-130 ℃, the treatment time is 6-12 h, the drying temperature is 120-180 ℃ and the drying time is 2-10 h, and/or the sealing treatment temperature in the step (7) is 20-50 ℃, the treatment time is 6-12 h, the drying temperature is 10-40 ℃ and the drying time is 2-10 h.
7. The method according to claim 1, wherein in the step (6), the first active metal component source is nickel, and/or in the step (8), the second active metal component impregnating solution containing the water-soluble polymer J has contents of MoO 3 and group VIII metal oxide of 10.0 to 80.0g/100mL and 2.0 to 40.0g/100mL, respectively.
8. The process according to claim 1, wherein in the step (8), the water-soluble polymer J is polyethylene glycol.
9. The preparation method of claim 1, wherein in the step (8), at least one auxiliary agent containing fluorine, phosphorus, silicon or boron is introduced into the impregnation liquid of the second active metal component, and the addition amount of the auxiliary agent is 2% -20% of the total mass of molybdenum oxide in the impregnation liquid of the second active metal component.
10. The preparation method according to claim 9, wherein the addition amount of the auxiliary agent is 2% -15% of the total mass of the molybdenum oxide in the impregnation liquid containing the second active metal component.
11. The preparation method of the catalyst according to claim 1, wherein in the step (8), the roasting temperature is 350-500 ℃, the roasting time is 2-6 hours, the roasting atmosphere is a mixed atmosphere of an inert atmosphere and other atmospheres, the inert atmosphere is mainly one or two of nitrogen and helium, and the other atmosphere is one or more of water vapor and air.
12. The residuum hydrodemetallization catalyst prepared by the preparation method according to any one of claims 1-11, which is characterized by comprising a carrier component, an active metal component and carbon distributed on the surface of the catalyst, wherein the active metal component comprises molybdenum and a VIII group metal, the carrier component is alumina, and the mass ratio of the carbon distributed on the surface of the catalyst to the alumina in the catalyst is 0.20-0.40.
13. The catalyst according to claim 12, wherein the content of MoO 3 is 2.0% to 20.0% and the content of group VIII metal oxide is 1.0% to 6.0% based on the mass of the catalyst.
14. The catalyst of claim 12, wherein the catalyst has a specific surface area of 185-225 m 2/g and a pore volume of 0.75-1.05 ml/g.
15. The catalyst of claim 14, wherein the catalyst has a specific surface area of 190-210 m 2/g and a pore volume of 0.80-0.95 ml/g.
16. The catalyst according to claim 12, wherein the catalyst has a pore distribution such that pores with a pore diameter of <30nm occupy 27% -36% of the total pore volume, pores with a pore diameter of 30-100 nm occupy 31% -37% of the total pore volume, pores with a pore diameter of 100-300 nm occupy 33% -36% of the total pore volume, and/or the catalyst has a strength of 8.0-18.0N/mm.
17. The catalyst according to claim 12, wherein the catalyst comprises an auxiliary component, the auxiliary component is selected from at least one of fluorine, phosphorus, silicon or boron, and/or the content of the auxiliary component in terms of oxide is 1.0% -8.0% based on the mass of the catalyst.
18. The catalyst of claim 17 wherein the adjunct component is phosphorus.
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