Residue hydrodemetallization catalyst and method for making same

Abstract

The application discloses a residual oil hydrodemetallization catalyst and a preparation method thereof. The catalyst comprises a carrier component, an active metal component and carbon distributed on the surface of the catalyst, the active metal component comprises molybdenum and a group 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 0.15-0.35. The residual oil hydrodemetallization catalyst provided by the application has excellent channel smoothness, concentrated pore distribution, suitable pore volume and pore size, and the activity and stability of the reaction are obviously improved in the application process of the residual oil hydrodemetallization reaction.

Description

TECHNICAL FIELD

[0001] The present application relates to a residue hydrodemetallization catalyst, in particular to a residue hydrodemetallization catalyst and a preparation method thereof. BACKGROUND

[0002] It is known that the traditional residue hydrodemetallization catalyst is mostly a supported hydrodemetallization catalyst, and the active metal component is generally supported on the surface of the carrier. Generally, under the action of the catalyst, various metal compounds react with H2S to form metal sulfides, and the generated metal sulfides are then deposited on the catalyst, so as to be removed. Therefore, the specific surface area of the catalyst not only affects the distribution of the active metal when the active metal is supported, but also affects the deposition of metal impurities after the reaction.

[0003] CN110773185A discloses a silicon-containing residue hydroprocessing catalyst and a preparation method thereof, the catalyst has mesopores, the mesopores are concentrated and uniform in size, the pore size of the mesopores ranges from 10nm to 30nm, and the channel surface of the mesopores is uniformly distributed with a strong acidic carrier; the total pore volume of the catalyst carrier is 0.6mL / g to 1.2mL / g, the specific surface area is 180m 2 / g to 350m 2 / g, and the mesopore pore volume accounts for 60% to 95% of the total pore volume of the catalyst carrier. CN105983417A discloses a preparation method of a residue hydrodemetallization catalyst, which comprises the following steps: one or more selected from aluminum oxide trihydrate, boehmite, pseudo-boehmite and amorphous aluminum hydroxide are uniformly mixed with a peptizing agent, a extrusion aid and an organic solution, and then are formed, dried and calcined to obtain a carrier. The obtained carrier is impregnated with a solution containing nickel and molybdenum and is dried and calcined to obtain the final catalyst. The catalyst obtained by the method has a pore volume of 0.80mL / g to 1.20mL / g and a specific surface area of 100m 2 / g to 180m

[0004] The pore size distribution range of the alumina carrier prepared by the above method is limited, and the pores of the carrier are not effectively protected in the process of impregnating active metals on the carrier, so that the dispersion degree of the active metals is insufficient, which is not conducive to the effective play of the hydrogenation activity of the subsequent catalyst. Therefore, the activity and stability of the alumina carrier and the hydrodemetallization catalyst prepared by the above method still need to be further improved. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a residue hydrodemetallization catalyst and a preparation method thereof. The residue hydrodemetallization catalyst provided by the present application has excellent pore openness, and has a relatively concentrated pore distribution as well as suitable pore volume and pore size. In the application process of the catalyst in residue hydrodemetallization reaction, the activity and stability of the reaction are significantly improved.

[0006] The present application provides a residue hydrodemetallization catalyst in the first aspect, comprising a carrier component, an active metal component and carbon distributed on the surface of the catalyst, the active metal component comprising molybdenum and a group VIII metal, and the carrier component being alumina; wherein the mass ratio of the carbon distributed on the surface of the catalyst to the alumina in the catalyst is 0.15-0.35.

[0007] In the present application, the active metal component comprises molybdenum and a group VIII metal, and the group VIII metal is preferably nickel.

[0008] In the present application, the content of MoO3 is 5.0%-20.0% and the content of group VIII metal oxide is 2.0%-6.0% based on the mass of the catalyst.

[0009] In the present application, the specific surface area of the catalyst is 180-220m 2 / g, and the pore volume is 0.70-1.00mL / g.

[0010] In the present application, preferably, the specific surface area of the catalyst is 190-200m 2 / g, and the pore volume is 0.85-0.95mL / g.

[0011] In the present application, the pore distribution of the catalyst is as follows: the pore volume of the pores with a pore diameter of <30nm accounts for 25%-35% of the total pore volume, the pore volume of the pores with a pore diameter of 30-100nm accounts for 33%-42% of the total pore volume, and the pore volume of the pores with a pore diameter of 100-300nm accounts for 32%-35% of the total pore volume.

[0012] In the present application, the strength of the catalyst is 11.0-22.0N / mm.

[0013] In the present application, the catalyst further comprises an auxiliary component selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus. The content of the auxiliary component in terms of oxide is 1.0% to 5.0% based on the mass of the catalyst.

[0014] The present application provides a preparation method of the above-mentioned residue hydrodemetallization catalyst, comprising the following steps:

[0015] (1) dissolving aluminum nitrate, urea and a template agent in water to obtain a solution X;

[0016] (2) crystallizing the solution X obtained in step (1), drying and calcining to obtain an alumina carrier A;

[0017] (3) sealing and heat-treating the carrier A obtained in step (2) after being immersed in an ammonium bicarbonate aqueous solution, and drying to obtain a carrier B;

[0018] (4) kneading and shaping the carrier B obtained in step (3) and a first active metal component source, drying and calcining to obtain a carrier C;

[0019] (5) sealing and treating the carrier C obtained in step (4) after being immersed in an ammonium bicarbonate aqueous solution, and drying to obtain a carrier D;

[0020] (6) impregnating the carrier D obtained in step (5) with a second active metal component containing a water-soluble polymer J, and drying and calcining to obtain the residue hydrodemetallization catalyst.

[0021] In the present application, the water used is preferably deionized water.

[0022] In step (1) of the present application, the aluminum nitrate, urea and template agent are sequentially dissolved in deionized water to obtain the solution X.

[0023] In step (1) of the present application, the molar ratio of Al(NO3)3 to the template agent is 160 to 240.

[0024] In step (1) of the present application, the molar ratio of urea to Al(NO3)3 is 7 to 14. Within this range, the OH - amount generated by the decomposition of urea is just right for the hydrolysis rate of Al 3+ and the alumina can grow uniformly on the surface of the template agent.

[0025] In step (1) of the present application, the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose, and is preferably polyethylene glycol; the viscosity of the template agent (20℃) is 10 to 1000 mPa·s, and the viscosity of the solution X after the template agent is uniformly stirred and added is 120 to 660 mPa·s.

[0026] In step (2) of the present application, the crystallization temperature is 80-200℃, and the crystallization time is 25-35h. The crystallization is carried out in a crystallization kettle.

[0027] In step (2) of the present application, the filtration and washing can be carried out according to conventional known methods before drying. The washing can be carried out using deionized water until the pH value of the filtrate is close to neutral. After drying, the dry basis content of the obtained dry product is 50wt%-80wt%.

[0028] In step (2) of the present application, the drying temperature is 120-200℃, and the drying time is 2-12h.

[0029] In step (2) of the present application, the calcination temperature is 500-750℃, the calcination time is 2-6h, and the calcination atmosphere is air.

[0030] In step (3) of the present application, the mass concentration of the ammonium bicarbonate aqueous solution is 10%-20%. The sealing heat treatment temperature is 80-140℃, preferably 90-140℃, and the treatment time is 6-12h. The drying temperature is 120-180℃, and the drying time is 2-10h.

[0031] In step (4) of the present application, the source of the first active metal component is a soluble compound of metallic molybdenum and a soluble compound containing a Group VIII metal. The Group VIII metal is preferably nickel.

[0032] In step (4) of the present application, the soluble compound of metallic molybdenum is at least one of molybdenum oxide and ammonium molybdate, and the soluble compound of the Group VIII metal (preferably Ni) is at least one of basic nickel carbonate and nickel nitrate.

[0033] In step (4) of the present application, the amount of MoO3 introduced into the catalyst by the first active metal component is 50%-65% of the total MoO3 loading in the catalyst, and the amount of the Group VIII metal oxide introduced into the catalyst by the first active metal component is 50%-65% of the total Group VIII metal oxide loading in the catalyst.

[0034] In step (4) of the present application, one or more conventional forming aids such as a peptizing agent and an extrusion aid can be added as needed during the forming process. The peptizing agent is one or more of nitric acid, sulfuric acid, and oxalic acid, and is preferably nitric acid. The extrusion aid is one or more of amaranth powder, cellulose, and resin, and is preferably amaranth powder.

[0035] In step (4) of the present application, the addition amount (mass percentage) of the peptizing agent is 1.0%-5.0% of the carrier B, and the addition amount (mass percentage) of the extrusion aid is 0.2%-5.0% of the carrier B.

[0036] In step (4) of the present application, the drying temperature is 20-200℃, and the drying time is 2-12h.

[0037] In step (4) of the present application, the calcination temperature is 500-800℃, the calcination time is 2-6h, and the calcination atmosphere is air.

[0038] In step (5) of the present application, the mass concentration of the ammonium bicarbonate aqueous solution is 20-30%. The sealing treatment temperature is 10-60℃, preferably 20-50℃, and the treatment time is 6-12h. The heat treatment temperature in step (5) is 70-80℃ lower than that in step (3). The drying temperature is 10-40℃, the drying time is 2-10h, and the drying method is static drying.

[0039] In step (5) of the present application, the mass concentration of the ammonium bicarbonate aqueous solution is 8-15% higher than that in step (3).

[0040] In step (6) of the present application, the impregnation is performed by saturation impregnation, and the standing time after impregnation is 4-14h.

[0041] In step (6) of the present application, when the carrier D is impregnated with the second active metal component containing the water-soluble polymer J, an impregnation solution containing the second active metal component containing the water-soluble polymer J is used. The impregnation solution contains Mo and Group VIII metal (preferably Ni), wherein the active metal component Mo is derived from one or both of molybdenum oxide and ammonium heptamolybdate, and the active metal component Ni is derived from one or both of basic nickel carbonate and nickel nitrate. The content of MoO3 and Group VIII metal oxide in the impregnation solution containing the second active metal component containing the water-soluble polymer J is 10.0-60.0g / 100mL and 2.0-40.0g / 100mL, respectively.

[0042] In step (6) of the present application, the amount of MoO3 introduced into the catalyst by the second active metal component is 35%-50% of the total MoO3 loading in the catalyst, and the amount of Group VIII metal oxide introduced into the catalyst by the second active metal component is 35%-50% of the total Group VIII metal oxide loading in the catalyst.

[0043] In step (6) of the present application, the water-soluble polymer J is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose, and is preferably polyethylene glycol. The viscosity of the water-soluble polymer J (20℃) is 10-1000mPa·s, and the viscosity of the impregnation solution after the addition of the water-soluble polymer J (20℃) is 150-800mPa·s.

[0044] In step (6) of the present application, at least one additive containing fluorine, phosphorus, silicon or boron can be introduced into the impregnation solution of the second active metal component, and the additive (calculated as an oxide) is added in an amount of 6% to 18% of the total mass of the molybdenum oxide in the second active metal component impregnation solution containing the water-soluble polymer J, preferably 8% to 15%.

[0045] In step (6) of the present application, the drying temperature is 120 to 200°C, and the drying time is 2 to 12 hours.

[0046] In step (6) of the present application, the calcination temperature is 350 to 600°C, the calcination time is 2 to 6 hours, the calcination atmosphere is a mixed atmosphere of an inert atmosphere and another atmosphere, and the volume ratio of the inert atmosphere to the other atmosphere is 0.5 to 5:1. The inert atmosphere is one or both of nitrogen and helium, and the other atmosphere is one or both of water vapor and air.

[0047] Compared with the prior art, the present application has the following beneficial effects:

[0048] For a hydrodemetallization catalyst, on the one hand, the catalyst should have a large pore size because there are many macromolecules in heavy oil feedstock; on the other hand, the catalytic performance of the catalyst is greatly related to the dispersion state of the active metal component on the surface of the catalyst. The present inventors have found through a large number of studies that, by using a uniform precipitation method, an alumina carrier with a large specific surface area and a regular pore structure can be prepared, and by performing a sealed heat treatment after the alumina carrier is treated with an aqueous ammonium bicarbonate solution, the pore openness of the carrier is adjusted. Then, by mixing and kneading the carrier with nitric acid, sesbania powder, part of the active metal component and deionized water, and by forming the mixture, drying and calcining, a carrier containing part of the active metal component with appropriate pore openness and specific surface area can be obtained. Then, the formed carrier is again treated with an aqueous ammonium bicarbonate solution to fill the pores and pore openings of the carrier with the aqueous ammonium bicarbonate solution, so as to prevent the pore openings from being blocked by the active metal component during the impregnation process. Finally, the carrier is impregnated with an impregnation solution containing the remaining active metal component in a saturated manner, and then dried and calcined to obtain a residual oil hydrodemetallization catalyst. In addition, a water-soluble polymer is added to the impregnation solution, and the final calcination atmosphere is a mixed atmosphere. This process not only causes the water-soluble polymer to be incompletely decomposed to form carbon dots in a dot-like distribution, but also appropriately adjusts the acidity of the surface of the catalyst, which is beneficial to weakening the interaction between the active metal component and the carrier. This distribution form also promotes the dispersion degree of the active metal component on the surface of the catalyst. In addition, the ammonium bicarbonate decomposes during the high-temperature drying and calcination process, and the pore openings can be restored to be open. Through the comprehensive coordination of the steps, the catalyst prepared by the present application has high mechanical strength, concentrated pore distribution, appropriate pore volume and pore size, and the activity and stability of the catalyst are greatly improved. DETAILED DESCRIPTION

[0049] In the present application, ASAP-2420 physical adsorption instrument of Mike Company is used to characterize the pore structure (SVD) and specific surface area of the catalyst.

[0050] In the present application, ZQJ-III intelligent particle strength tester is used to detect the crushing resistance of the catalyst particles.

[0051] In the present application, STA409PC-QMS403C thermal gravimetric-mass spectrometer (TG-MS) of NETZSCH Company is used to determine the carbon / alumina mass ratio on the surface of the catalyst.

[0052] The technical solutions and effects of the present application are further illustrated below in combination with examples, but are not limited to the following examples.

[0053] Example 1

[0054] (1) A proper amount of aluminum nitrate, urea and template agent polyethylene glycol (viscosity of 500 mPa·s) are weighed, wherein the molar ratio of Al(NO3)3 to polyethylene glycol is 180, and the molar ratio of urea to Al(NO3)3 is 9. The above substances are sequentially dissolved in a certain amount of deionized water, and then magnetically stirred for 5 h to obtain solution X (viscosity of 350 mPa·s);

[0055] (2) The obtained solution X is transferred to a crystallization kettle, and the crystallization kettle is placed in an oven at 180℃. After 32 h of reaction, the crystallization kettle is taken out and cooled. A mixed slurry containing white precipitate is obtained in the reaction kettle. The obtained white precipitate is filtered and washed several times until the pH value of the filtrate approaches 7. The white precipitate is placed in an oven for drying, the drying temperature is 120℃, and the drying time is 6 h. Then, the white precipitate is calcined in a muffle furnace, the calcination temperature is 600℃, and the calcination time is 4 h. Thus, the alumina carrier A is prepared;

[0056] (3) The obtained alumina carrier A is immersed in an ammonium bicarbonate aqueous solution and then sealed for heat treatment to obtain carrier B. The mass percentage concentration of the ammonium bicarbonate aqueous solution is 18%, the sealed heat treatment temperature is 90℃, the treatment time is 6 h, and the drying temperature is 140℃, and the drying time is 4 h.

[0057] (4) knead, shape, dry and calcine carrier B, nitric acid (68wt%), sesbania powder, the first active metal component source (the active metal source is nickel nitrate and ammonium molybdate), deionized water to obtain carrier C; wherein the mass content of nitric acid (68wt%) added is 2.0% of carrier B, the mass content of sesbania powder added is 3.0% of carrier B, the addition content of deionized water is adjusted in real time according to the material state during shaping, the drying temperature is 120°C, the drying time is 6h, the calcination temperature is 800°C, and the calcination time is 4h (the heating rate is 2.5°C / min); wherein the amount of MoO3 introduced into the catalyst by the first active metal component is 60% of the total MoO3 loading in the catalyst, and the amount of NiO is 60% of the total NiO loading in the catalyst;

[0058] (5) seal the obtained carrier C after immersing in an ammonium bicarbonate aqueous solution, and dry to obtain carrier D, wherein the mass percentage concentration of the ammonium bicarbonate aqueous solution ranges from 28%, the sealing treatment temperature is 20°C, the treatment time is 8h, the drying temperature is 20°C, the drying time is 6h, and the drying method is static drying;

[0059] (6) immerse carrier D in an impregnation solution containing the second active component metal component (the content of MoO3 is 29.05g / 100mL, the content of NiO is 4.88g / 100mL, and the addition amount of P (as an oxide) in the additive phosphoric acid is 9.0% of the total mass of molybdenum oxide in the impregnation solution) in a saturated impregnation manner, wherein the amount of MoO3 introduced into the catalyst by the second active metal component is 40% of the total MoO3 loading in the catalyst, and the amount of NiO is 40% of the total NiO loading in the catalyst; the impregnation solution contains water-soluble polymer J polyethylene glycol (viscosity is 500mPa·s), and the viscosity (20°C) of the impregnation solution after adding water-soluble polymer J polyethylene glycol is 340mPa·s; after the impregnated sample is placed at room temperature (25°C) for 6h, it is dried (temperature is 120°C, drying time is 6h), calcined at a temperature of 550°C for 3h (heating rate is 2.0°C / min), and the calcination atmosphere is a mixed gas atmosphere of nitrogen and air (volume ratio of nitrogen to air is 3:1) to obtain the residual oil hydrodemetallization catalyst. The above-prepared residual oil hydrodemetallization catalyst is named CAT-1. The physicochemical properties of the catalyst are shown in Table 1.

[0060] Example 2

[0061] The example is different from example 1 in that: in step (1), the molar ratio of Al(NO3)3 to polyethylene glycol is 200, and the molar ratio of urea to Al(NO3)3 is 11; in step (2), the obtained solution X is transferred to a crystallization kettle, and the crystallization kettle is placed in an oven at 160°C; after 30h, the crystallization kettle is taken out, and the white precipitate is placed in the oven for drying at a temperature of 140°C for 8h; then, the precipitate is calcined in a muffle furnace at a temperature of 650°C for 3h; and a residue oil hydrodemetallization catalyst CAT-2 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0062] Example 3

[0063] The example is different from example 1 in that: in step (3), the mass percentage concentration of the first ammonium bicarbonate aqueous solution ranges from 16%, the sealed heat treatment temperature is 110°C, the treatment time is 7h, the drying temperature is 130°C, and the drying time is 5h; in step (5), the mass percentage concentration of the second ammonium bicarbonate aqueous solution ranges from 26%, the sealed treatment temperature is 30°C, the treatment time is 7h, the drying temperature is 30°C, and the drying time is 8h; and a residue oil hydrodemetallization catalyst CAT-3 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0064] Example 4

[0065] The difference between this example and Example 1 is that in step (4), carrier B and nitric acid (68 wt%), sesbania powder, a first active metal component source (the active metal sources are nickel nitrate and ammonium molybdate), and deionized water are mixed and kneaded, shaped, dried, and calcined to obtain carrier C, the drying temperature is 140°C, the drying time is 8h, the calcination temperature is 750°C, and the calcination time is 5h (the temperature rising rate is 3.0°C / min); the amount of MoO3 introduced into the catalyst by the first active metal component is 55% of the total MoO3 loading in the catalyst, and the amount of NiO is 55% of the total NiO loading in the catalyst; finally, the carrier D is impregnated with a second active component metal component impregnation solution (the content of MoO3 is 32.68g / 100mL, the content of NiO is 5.49g / 100mL, and the amount of P (as an oxide) in the additive phosphoric acid is 10.13% of the total mass of molybdenum oxide in the impregnation solution) in a saturated impregnation manner, wherein the amount of MoO3 introduced into the catalyst by the second active metal component is 45% of the total MoO3 loading in the catalyst, and the amount of NiO is 45% of the total NiO loading in the catalyst; the impregnation solution contains a water-soluble high polymer J polyacrylamide, the viscosity of the impregnation solution after adding the water-soluble high polymer J polyacrylamide (viscosity 900mPa·s) is 400mPa·s, and the impregnated sample is placed at room temperature for 8h, then dried (drying temperature 140°C, drying time 5h), calcined at a temperature of 500°C for 4h (temperature rising rate 3.0°C / min), and calcined in a mixed gas atmosphere of nitrogen and air (volume ratio of nitrogen to air 1:1) to obtain a hydrodemetallization catalyst CAT-4. The physicochemical properties of the catalyst are shown in Table 1.

[0066] Comparative Example 1

[0067] The difference compared with Example 1 is that in step (1), the molar ratio of Al (NO3) 3 to polyethylene glycol is 245, and the molar ratio of urea to Al (NO3) 3 is 6, the above substances are dissolved in a certain amount of deionized water in the order of aluminum nitrate, urea, and polyethylene glycol, and after being mixed uniformly by magnetic stirring for 8h, a solution X is obtained; in step (2), the obtained solution X is transferred to a crystallization kettle, the crystallization kettle is placed in an oven at 180°C, and after 18h, the crystallization kettle is taken out; a residual oil hydrodemetallization catalyst dCAT-1 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0068] Comparative Example 2

[0069] The difference compared with Example 1 is that in step (5), the mass percentage concentration of the second ammonium bicarbonate aqueous solution is in the range of 35%, the sealed treatment temperature is 70°C, the treatment time is 6h, the drying temperature is 120°C, and the drying time is 6h; a residual oil hydrodemetallization catalyst dCAT-2 is prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0070] Comparative Example 3

[0071] Comparative Example 3 is the same as Example 1 except that in step (4) no active metal is added during the kneading process, and in step (6) the support D is impregnated with an impregnation solution containing a water-soluble polymer J, polyethylene glycol (viscosity 500 mPa-s) in a saturated impregnation manner. The viscosity of the impregnation solution after adding the water-soluble polymer J, polyethylene glycol is 400 mPa-s at 20°C. The impregnated sample is allowed to stand at room temperature for 6 h, then dried (drying temperature 120°C, drying time 6 h), and calcined at 600°C for 3 h (heating rate 3.0°C / min) in a mixed gas atmosphere of nitrogen and water vapor to obtain a residue oil hydrodemetallization catalyst dCAT-3. The physicochemical properties of the catalyst are shown in Table 1.

[0072] Comparative Example 4

[0073] Comparative Example 4 is the same as Example 1 except that in step (5) no water-soluble polymer J, polyethylene glycol is added to the impregnation solution containing the second active metal component, and the calcination atmosphere is air. A residue oil hydrodemetallization catalyst dCAT-4 is obtained. The surface of the catalyst dCAT-4 does not contain carbon. The physicochemical properties of the catalyst are shown in Table 1.

[0074] Table 1 Physicochemical properties of residue oil hydrodemetallization catalysts

[0075]

[0076] Evaluation Test

[0077] The activity stability tests of the residue oil hydrodemetallization catalysts CAT-1 to 4 and dCAT-1 to 4 were carried out in a 200 mL fixed bed hydrogenation test apparatus, and the catalysts used were in the form of strips having a length of 2 to 3 mm. The reaction conditions were: reaction temperature 390°C, hydrogen partial pressure 13.0 MPa, liquid hourly space velocity 1.0 h -1 , hydrogen to oil volume ratio 850, and the demetallization rate (Ni + V) of each catalyst after 1500 h of reaction is shown in Table 3. The properties of the feed oil are shown in Table 2.

[0078] Table 2 Properties of feed oil

[0079] Item Content S, wt% 2.42 N, wt% 0.51 Ni, μg / g 63.6 V, μg / g 114.5 CCR, wt% 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 17.4

[0080] Table 3 Test results of residue oil hydrodemetallization catalysts of each example

[0081]

[0082] As can be seen from Table 1, Table 2 and Table 3, the hydrogenation demetallization catalyst prepared by the method of the present application has a smooth pore structure, and has a large specific surface area, and has high reactivity and stability in the reaction process, and can well meet the hydrogenation demetallization process of heavy oil, especially residual oil.

Claims

1. A residue hydrodemetalization catalyst characterized in that, The catalyst comprises a carrier component, an active metal component and carbon distributed on the surface of the catalyst, the active metal component comprises molybdenum and a Group 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 0.15-0.35; the specific surface area of the catalyst is 180-220 m 2 / g, the pore volume is 0.70-1.00 mL / g; the pore distribution of the catalyst is as follows: the pore volume of the pores with a pore diameter of <30 nm accounts for 25%-35% of the total pore volume, the pore volume of the pores with a pore diameter of 30-100 nm accounts for 33%-42% of the total pore volume, and the pore volume of the pores with a pore diameter of 100 nm-300 nm accounts for 32%-35% of the total pore volume; and the strength of the catalyst is 11.0-22.0 N / mm. The preparation method of the residual oil hydrodemetallization catalyst comprises the following steps: (1) dissolving aluminum nitrate, urea and a template agent in water to obtain a solution X; (2) crystallizing the solution X obtained in step (1), drying and calcining to obtain an alumina carrier A; (3) sealing and heat-treating the carrier A obtained in step (2) after being immersed in an ammonium bicarbonate aqueous solution, and drying to obtain a carrier B; (4) mixing and kneading the carrier B obtained in step (3) and a first active metal component source, shaping, drying and calcining to obtain a carrier C; (5) sealing and treating the carrier C obtained in step (4) after being immersed in an ammonium bicarbonate aqueous solution, and drying to obtain a carrier D; (6) impregnating the carrier D obtained in step (5) with a second active metal component containing a water-soluble polymer J, and drying and calcining to obtain the residual oil hydrodemetallization catalyst. In step (4), the first active metal component source is a soluble compound of metallic molybdenum and a soluble compound containing a Group VIII metal; In step (6), when the carrier D is impregnated with the second active metal component containing the water-soluble polymer J, an impregnation solution of the second active metal component containing the water-soluble polymer J is used, and the impregnation solution is an impregnation solution containing Mo and the Group VIII metal; In step (6), 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 impregnation solution after the water-soluble polymer J is added is 150-800 mPa·s at 20℃.

2. The catalyst according to claim 1, characterized in that, The Group VIII metal is nickel.

3. The catalyst of claim 1, wherein The content of MoO3 is 5.0%-20.0% and the content of the Group VIII metal oxide is 2.0%-6.0% based on the mass of the catalyst.

4. The catalyst of claim 1, wherein The specific surface area of the catalyst is 190 to 200 m 2 / g, and the pore volume is 0.85 to 0.95 mL / g.

5. The catalyst of claim 1, wherein The catalyst comprises an auxiliary component selected from at least one of fluorine, phosphorus, silicon or boron, and the content of the auxiliary component in terms of oxide is 1.0%-5.0% based on the mass of the catalyst.

6. The catalyst of claim 5, wherein The auxiliary component is phosphorus.

7. The preparation method of the residual oil hydrodemetallization catalyst according to any one of claims 1-6, comprising the following steps: (1) dissolving aluminum nitrate, urea and a template agent in water to obtain a solution X; (2) crystallizing the solution X obtained in step (1), drying and calcining to obtain an alumina carrier A; (3) sealing and heat-treating the carrier A obtained in step (2) after being immersed in an ammonium bicarbonate aqueous solution, and drying to obtain a carrier B; (4) mixing and kneading the carrier B obtained in step (3) and a first active metal component source, shaping, drying and calcining to obtain a carrier C; (5) sealing and treating the carrier C obtained in step (4) after being immersed in an ammonium bicarbonate aqueous solution, and drying to obtain a carrier D; (6) impregnating the carrier D obtained in step (5) with a second active metal component containing a water-soluble polymer J, and drying and calcining to obtain the residual oil hydrodemetallization catalyst.

8. The production method according to claim 7, characterized by, In step (1), the molar ratio of Al(NO3)3 to the template agent is 160-240, and the molar ratio of urea to Al(NO3)3 is 7-14.

9. The preparation method according to claim 7, characterized in that, In step (1), the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose; the viscosity of the template agent at 20℃ is 10-1000 mPa·s, and the viscosity of the solution X at 20℃ after the template agent is stirred uniformly is 120-660 mPa·s.

10. The method of claim 9, wherein, In step (1), the template agent is polyethylene glycol.

11. The preparation method according to claim 7, characterized in that, In step (2), the crystallization temperature is 80-200℃, and the crystallization time is 25-35 h.

12. The method of claim 6, wherein, In step (3), the mass percentage concentration of the ammonium bicarbonate aqueous solution is 10%-20%; and / or, In step (5), the mass percentage concentration of the ammonium bicarbonate aqueous solution is 20%-30%; and / or, In step (5), the mass concentration of the ammonium bicarbonate aqueous solution is 8-15 percentage points higher than that in step (3).

13. The preparation method according to claim 7, characterized in that, In step (3), the sealing heat treatment temperature is 80-140℃, and the treatment time is 6-12 h; the drying temperature is 120-180℃, and the drying time is 2-10 h; and / or, In step (5), the sealing treatment temperature is 10-60℃, and the treatment time is 6-12 h; the drying temperature is 10-40℃, and the drying time is 2-10 h; and / or, In step (5), the treatment temperature is 70-80℃ lower than that in step (3).

14. The method of claim 13, wherein, In step (3), the sealing heat treatment temperature is 90-140℃; and / or, In step (5), the sealing treatment temperature is 20-50℃.

15. The method of claim 7, wherein the method further comprises, In step (4), the first active metal component source is a soluble compound of metallic molybdenum and a soluble compound containing a Group VIII metal, and the Group VIII metal is nickel; and / or, In step (6), when the carrier D is impregnated with the second active metal component containing the water-soluble high polymer J, an impregnation solution of the second active metal component containing the water-soluble high polymer J is used; the content of MoO3 and Group VIII metal oxide in the impregnation solution is 10.0-60.0 g / 100 mL and 2.0-40.0 g / 100 mL, respectively.

16. The preparation method according to claim 7, characterized in that, In step (6), the water-soluble high polymer J is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose; and / or, The viscosity of the water-soluble high polymer J at 20℃ is 10-1000 mPa·s, and the viscosity of the impregnation solution at 20℃ after the water-soluble high polymer J is added is 150-800 mPa·s.

17. The method of claim 16, wherein the method further comprises, In step (6), the water-soluble high polymer J is polyethylene glycol.

18. The method of claim 15, wherein, In step (6), an additive containing at least one of fluorine, phosphorus, silicon or boron is introduced into the impregnation solution of the second active metal component, and the additive is added in an amount of 6%-18% of the total mass of molybdenum oxide in the impregnation solution of the second active metal component containing the water-soluble high polymer J.

19. The method of claim 18, wherein, The additive is added in an amount of 8%-15% of the total mass of molybdenum oxide in the impregnation solution of the second active metal component containing the water-soluble high polymer J.

20. The method of claim 7, wherein, In step (6), the baking temperature is 350-500 DEG C, the baking time is 2-6h, and the baking atmosphere is a mixed atmosphere of an inert atmosphere and other atmosphere; wherein the inert atmosphere is one or both of nitrogen and helium, and the other atmosphere is one or both of water vapor and air.

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