A residue hydrotreating protective catalyst and its preparation method

Abstract

The present invention discloses a residual oil hydrogenation protection catalyst and a preparation method thereof. The residual oil hydrogenation protection catalyst comprises a volcanic rock-based porous carrier material and a hydrogenation active component loaded on the carrier; the volcanic rock-based porous carrier material is volcanic rock particles containing flaky aluminum oxide in the pores, with the volcanic rock accounting for 75wt% to 95wt% and the flaky aluminum oxide accounting for 5wt% to 25wt% based on the weight of the carrier; the flaky aluminum oxide is about 60-200nm long, about 50-150nm high, and about 10-20nm thick. The preparation method comprises: (1) impregnating the volcanic rock-based porous carrier material with an impregnation solution containing the hydrogenation active component, drying and roasting the impregnated material to obtain a hydrogenation protection catalyst precursor material; immersing the hydrogenation protection agent precursor material in a propylene oxide solution for sealed hydrothermal treatment, drying and roasting the hydrothermally treated material to obtain a hydrogenation protection agent. The hydrogenation protective agent prepared with the porous material as a carrier has the characteristics of strong impurity tolerance and high demetallization activity, and is particularly suitable for the residual oil hydroprocessing process.

Description

Technical Field

[0001] The present invention relates to the field of catalytic material preparation, and in particular to a residual oil hydrogenation protection catalyst and a preparation method thereof. Background Art

[0002] In recent years, crude oil has become increasingly heavier and inferior worldwide, market demand for lighter oil products has increased year by year, and environmental regulations have become increasingly stringent. Improving product quality at the lowest possible cost has become a critical issue for refineries.

[0003] Residue oil contains numerous impurities such as metals (Ni, V, Na, Fe), sulfur, nitrogen, and non-ideal components such as colloids and asphaltenes. During the hydrotreating process, various chemical reactions occur, each with its own distinct species and characteristics. Using a single catalyst alone is unlikely to achieve optimal results. Therefore, during the fixed-bed hydrotreating of residue oil, different catalysts with varying functions must be used simultaneously. These catalysts can be broadly categorized into four main categories: protective agents, demetallization catalysts, desulfurization catalysts, and denitrification catalysts.

[0004] Hydrogenation protectants and demetallization catalysts are key components of hydroprocessing technology. During processing, metallic impurities (such as V, Ni, Ca, and Fe) and scale in the raw materials easily deposit on the catalyst surface and in the spaces between catalyst particles. These impurities can clog the catalyst orifices, leading to catalyst deactivation. Furthermore, they can cause a rapid increase in bed pressure drop, leading to frequent plant shutdowns and catalyst replacements. This significantly reduces the efficiency of industrial plants and the lifespan of the catalyst, resulting in significant economic losses. Therefore, to ensure long-term, normal operation of production plants, hydrogenation protectants and demetallization catalysts must be installed before the main catalyst (such as hydrodesulfurization and hydrodenitrogenation catalysts).

[0005] CN1966616A discloses a hydrogenation protective agent and a preparation method thereof, wherein the protective agent comprises an alumina carrier, an effective amount of a hydrogenation active metal component and a halogen loaded on the carrier, and the carrier is prepared by mixing, shaping and calcining one or more alumina and / or alumina precursors with at least one halogen-containing compound.

[0006] CN102649070A discloses a hydrogenation active protective agent using alkali metal alumina as a carrier, its preparation and application. The protective agent contains an alkali metal alumina carrier and a hydrogenation active component loaded on the carrier.

[0007] The hydrogenation protective agents prepared by the prior art mainly use alumina and / or modified alumina as carriers, which results in a relatively high price of the catalyst. On the other hand, the activity of the current hydrogenation protective agents in removing metal Ni and V needs to be further improved. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention provides a residual oil hydroprocessing protected catalyst and its preparation method. This hydroprocessing protected catalyst utilizes a volcanic rock-based porous material containing flaky alumina as a carrier. The porous material is simple to prepare and uses inexpensive raw materials. The hydroprocessing protected catalyst prepared using this porous material as a carrier exhibits strong impurity tolerance and high demetallization activity, making it particularly suitable for use in residual oil hydroprocessing processes.

[0009] The residual oil hydrogenation protection catalyst of the present invention comprises a volcanic rock-based porous support material and a hydrogenation-active component supported on the support. The volcanic rock-based porous support material comprises volcanic rock particles containing flaky alumina in their pores. Based on the weight of the support, the volcanic rock accounts for 75% to 95% by weight, and the flaky alumina accounts for 5% to 25% by weight. The flaky alumina grows in situ within the pores of the volcanic rock and interweaves and accumulates. The flaky alumina is approximately 60-200 nm long, 50-150 nm high, and 10-20 nm thick. The hydrogenation-active component is selected from at least one Group VIB metal component and at least one Group VIII metal component. Based on the total weight of the catalyst and calculated as oxide, the Group VIB metal component accounts for 2.0% to 7.5%, preferably 3.5% to 6.5%, and the Group VIII metal component accounts for 0.5% to 3.5%, preferably 1.5% to 2.5%. The Group VIB metal component is W and / or Mo. The Group VIII metal component is Co and / or Ni.

[0010] The specific surface area of the hydrogenation protection catalyst of the present invention is 40-130m 2 / g, pore volume is 0.1-0.4mL / g, pores with a diameter greater than 1μm account for 20%-40% of the total pore volume, pores with a diameter of 30-200nm account for 30%-60% of the total pore volume, and the crushing strength is 100-300N / particle.

[0011] In the hydrogenation protected catalyst of the present invention, the particle size of the carrier particles is 1-10 mm, preferably 3-5 mm.

[0012] The preparation method of the residual oil hydrogenation protection catalyst of the present invention comprises:

[0013] (1) Preparation of aluminum-loaded volcanic rock-based porous carrier materials;

[0014] (2) Impregnating the volcanic rock-based porous support material obtained in step (1) with an impregnation solution containing hydrogenation active components

[0015] The impregnated material is dried and calcined to obtain a hydrogenation protection catalyst precursor material;

[0016] (3) Immersing the hydrogenation protection agent precursor material in step (2) in a sealed propylene oxide solution for hydrothermal treatment, and drying and calcining the hydrothermal treated material to obtain a hydrogenation protection catalyst.

[0017] In the method of the present invention, the aluminum-loaded volcanic rock-based porous carrier material described in step (1) is obtained by impregnating volcanic rock with an aluminum salt solution, followed by drying and roasting. The volcanic rock is in granular form, with a particle size of 1-10 mm, preferably 3-5 mm. The volcanic rock particles are commercially available products, and the particle size can be sieved as needed. The volcanic rock particles have internal pores of micron size, and the pore diameter is preferably 1-30 microns. The aluminum-containing solution is an aqueous solution of one or more aluminum salts such as aluminum sulfate, aluminum chloride, and aluminum nitrate, or an ethanol solution of aluminum isopropoxide, preferably an aqueous solution of aluminum nitrate. The mass percentage concentration of the aluminum salt solution is 15%-55%, preferably 20%-50%, and the volume ratio of the aluminum-containing solution to the volcanic rock is 3:1-10:1. The impregnation time is 0.5-2 hours. The impregnation can be performed once or multiple times as needed, preferably multiple times, and the number of impregnations is preferably 3 or more. When multiple impregnations are used, drying and roasting treatments are required after each impregnation; the drying temperature is 100-160°C, the drying time is 2-10 hours, the roasting temperature is 450-750°C, and the roasting time is 4-10 hours.

[0018] In the method of the present invention, the impregnation solution containing hydrogenation-active metals in step (2) is a solution containing Group VIB and / or Group VIII metals, and can be an acid solution, an alkaline solution, or an aqueous solution. The Group VIB metal is selected from W and / or Mo, and the Group VIII metal is selected from Co and / or Ni. The content of the Group VIB metal oxide in the solution is 1.5-6.5 g / 100 mL, and the content of the Group VIII metal oxide is 0.5-2.5 g / 100 mL.

[0019] In the method of the present invention, the impregnation in step (2) can be carried out by spray impregnation, saturated impregnation, or supersaturated impregnation. The drying conditions are 100-160°C for 1-5 hours; the calcination conditions are 400-550°C for 2-10 hours.

[0020] In the method of the present invention, the mass percentage concentration of the propylene oxide aqueous solution in step (3) is 2.5%-12%, preferably 4%-8%, and the mass ratio of the propylene oxide aqueous solution to the hydrogenation protective agent precursor material is 3:1-10:1, preferably 4:1-8:1. More preferably, polyethylene glycol 2000-20000 is added to the propylene oxide aqueous solution at a mass ratio of the polyethylene glycol 2000-20000 to the hydrogenation protective agent precursor material of 0.01:1-0.05:1.

[0021] In the method of the present invention, the sealed hydrothermal treatment in step (3) is carried out in a sealed container, which is preferably an autoclave. The treatment temperature is 110-180°C, preferably 120-160°C, and the treatment time is 4-8 hours. The pressure in the sealed container during the hydrothermal treatment is autogenous pressure.

[0022] In the method of the present invention, the drying temperature in step (3) is 100-160°C, and the drying time is 2-10 hours; the roasting temperature is 450-550°C, and the roasting time is 4-10 hours.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] (1) The carrier material used in the hydrogenation protective agent of the present invention is a volcanic rock-based aluminum-supported material. Since volcanic rock particles are cheap and readily available, the production cost of the catalyst can be effectively reduced;

[0025] (2) The present invention uses an aluminum-containing solution to impregnate volcanic rock and then dry and roast it. Since the surface of the micron-sized pores of the volcanic rock is coated with aluminum oxide, the pore volume and specific surface area of the material are increased while ensuring the smooth flow of the volcanic rock pores, so that the carrier has the ability to remove impurities such as calcium and iron and impurities such as nickel and vanadium;

[0026] (3) When the precursor of the hydrogenation protective agent is hydrothermally treated in a propylene oxide solution, the aluminum oxide undergoes secondary growth under weakly alkaline and sealed hydrothermal conditions and forms flaky particles. The flaky particles are interwoven and accumulated on the surface of the micron-scale pores of the volcanic rock to form a large number of 30-200 nm pores. This pore structure is conducive to the diffusion of residual oil reactant molecules and the removal of impurities such as calcium, iron, nickel, and vanadium, so that the final catalyst has a higher impurity tolerance and a higher demetallization activity, effectively reducing the load of the downstream hydrodemetallization catalyst.

[0027] (4) When the hydrogenation protective agent precursor is hydrothermally treated in propylene oxide solution, the active metal components grow epitaxially along with the alumina. On the one hand, this improves the interaction between the active metal and the alumina support, thereby increasing the activity of the catalyst; on the other hand, it increases the contact opportunity between the active metal and the residual oil molecules, thereby increasing the number of active sites. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is the SEM image of volcanic rock raw material.

[0029] FIG2 is an SEM image of the surface of micron-sized pores of the aluminum-loaded volcanic rock in Example 1.

[0030] Figure 3 This is a low-magnification SEM image of the hydrogenation protective agent prepared in Example 1

[0031] Figure 4This is an SEM image of the micron-scale pore surface of the hydrogenation protective agent prepared in Example 1.

[0032] Figure 5 This is the SEM image of the micron-scale pore surface of the hydrogenation protective agent prepared in Comparative Example 3. DETAILED DESCRIPTION

[0033] The technical solutions and effects of the present invention are further described below with reference to the following embodiments, but are not limited to the following embodiments.

[0034] The pore structure of the samples from the examples and comparative examples was characterized using N2 physical adsorption-desorption. The specific procedure was as follows: The pore structure of the samples was characterized using an ASAP-2420 N2 physical adsorption-desorption instrument. A small amount of sample was vacuum-treated at 300°C for 3-4 hours. Finally, the product was subjected to nitrogen adsorption-desorption testing at a low temperature of liquid nitrogen (-200°C). The specific surface area was calculated using the BET equation, and the pore size distribution and pore volume were calculated using the BJH model.

[0035] Scanning electron microscopy was used to characterize the microstructure of the samples. The specific operation was as follows: a JSM-7500F scanning electron microscope was used to characterize the microstructure of the samples with an accelerating voltage of 5 KV, an accelerating current of 20 μA, and a working distance of 8 mm.

[0036] Mercury intrusion method: A mercury intrusion instrument was used to characterize the pore diameter distribution of the samples in the examples and comparative examples. The specific operation was as follows: The sample pore distribution was characterized using a Micromeritics AutoPore 9500 fully automatic mercury intrusion instrument. After drying, the sample was weighed and placed into a dilatometer. The sample was degassed for 30 minutes while maintaining the vacuum conditions specified by the instrument, and then mercury was added. The dilatometer was then placed in an autoclave and vented. Then, pressure increase and pressure reduction tests were performed. The mercury contact angle was 130°, and the mercury interfacial tension was 0.485 N.cm. -1 The distribution rate of pores with a diameter of 100 nm or more is measured by mercury intrusion method.

[0037] The volcanic rock particles were purchased from Dunhua Zhongxing Stone Factory. The particle size is 3-6 mm and the specific surface area is 7 m 2 / g, the pore volume is 0.04mL / g, pores larger than 1µm account for 45% of the total pore volume, and pores between 100-1000nm account for 23% of the total pore volume.

[0038] Example 1

[0039] Weigh 70 g of volcanic rock matrix material (see SEM image Figure 1), 500mL of 32.5% aluminum nitrate solution was added and impregnated under magnetic stirring for 1.5 hours to saturate the volcanic rock with adsorption. The impregnated material was dried at 120℃ for 6 hours and calcined at 600℃ for 6 hours. The calcined material was impregnated, dried and calcined twice using the same method to obtain aluminum-loaded volcanic rock. The scanning electron microscope image of the micron-scale pore surface is shown in Figure 2 .

[0040] Weigh 50 g of the above-mentioned aluminum-loaded volcanic rock and use an equal volume spray impregnation method to spray the support material with a Mo-Ni-P impregnation solution with a MoO3 concentration of 4.8 g / 100 mL and a NiO concentration of 1.4 g / 100 mL. After impregnation, the material is dried at 120°C for 5 hours and calcined at 500°C for 5 hours to obtain a hydrogenation protective agent precursor.

[0041] Weigh 20 grams of the above hydrogenation protective agent precursor, add 126 grams of 5.6% propylene oxide solution, transfer the mixture into an autoclave, seal it, and heat it at 130°C for 6 hours. After treatment, the material is filtered and dried at 110°C for 6 hours, and calcined at 500°C for 5 hours to obtain hydrogenation protective agent Cat-1. The catalyst properties are shown in Table 1. The low-magnification scanning electron micrograph of the catalyst is shown in Figure 3 , SEM images of micron-scale pore surface are shown in Figure 4 shown.

[0042] Example 2

[0043] The same method as in Example 1 was used, except that the mass concentration of aluminum nitrate was 41.5%, the amount of propylene oxide used during the sealed heat treatment was 110 g, and the mass concentration of the solution was 6.8%. The heat treatment temperature was 140°C and the treatment time was 5 hours. Hydrogenation protective agent Cat-2 was obtained. Catalyst properties are shown in Table 1.

[0044] Example 3

[0045] The same method as in Example 1 was used, except that the mass concentration of aluminum nitrate was 47.5%, the amount of propylene oxide used during the sealed heat treatment was 145 g, and the mass concentration of the solution was 4.2%. The heat treatment temperature was 120°C and the treatment time was 6.5 hours. Hydrogenation protective agent Cat-3 was obtained. Catalyst properties are shown in Table 1.

[0046] Example 4

[0047] The same method as in Example 1 was used, except that the mass concentration of aluminum nitrate was 24.5%, the amount of propylene oxide used during the sealed heat treatment was 85 g, the mass concentration of the solution was 7.7%, and 0.3 g of polyethylene glycol-20000 was added to the propylene oxide solution. The heat treatment temperature was 150°C and the treatment time was 4 hours. Hydrogenation protective agent Cat-4 was obtained. Catalyst properties are shown in Table 1.

[0048] Comparative Example 1

[0049] The same method as Example 1 was used, except that volcanic rock was directly used as the carrier to prepare the comparative hydrogenation protective agent Cat-5. The catalyst properties are shown in Table 1.

[0050] Comparative Example 2

[0051] The same method as Example 1 was used, except that the hydrogenation protective agent precursor was not subjected to hydrothermal treatment, to prepare a comparative hydrogenation protective agent Cat-6. The catalyst properties are shown in Table 1.

[0052] Comparative Example 3

[0053] The same as Example 1, except that the propylene oxide was replaced with the same amount of ethylene oxide during the hydrothermal treatment, to prepare a comparative hydrogenation protective agent Cat-7. The catalyst properties are shown in Table 1. No flaky particles were observed on the surface of the micron-sized pores of the catalyst. The scanning electron microscope photo is shown in Figure 5 .

[0054] Comparative Example 4

[0055] The same as Example 1, except that all carriers of the hydrogenation protective agent are conventional alumina carriers. The alumina carriers are prepared according to the method of Example 1 of patent CN1488441A to obtain comparative hydrogenation protective agent Cat-8. The catalyst properties are shown in Table 1.

[0056] Table 1 Properties of hydrogenation protective agents

[0057]

[0058] Example 5

[0059] The following examples illustrate the catalytic performance of hydrogenation protectants Cat-1-Cat-8.

[0060] The hydrogenation protection catalysts Cat-1 to Cat-4 of the present invention and the hydrogenation protection catalysts Cat-5 to Cat-8 of the comparative example were respectively loaded into a fixed-bed hydrogenation reactor. The raw materials to be treated (see Table 2) were tested under the following conditions: reaction temperature 380°C, hydrogen to oil volume ratio 800, liquid hourly volume space velocity 0.6h -1 , hydrogen partial pressure 14.5MPa, continuous operation for 500 hours, the evaluation results of the catalyst are shown in Table 3.

[0061]

[0062] Table 3 Catalyst evaluation results

[0063]

[0064] The results in Table 3 show that the hydrogenation protectant prepared using the method of the present invention has comparable calcium and iron removal rates, but higher nickel and vanadium removal rates, compared to hydrogenation protectants based on conventional alumina. It also has higher removal rates of Ca, Fe, Ni, and V than other comparative hydrogenation protectants.

Claims

1. A residual oil hydrogenation protection catalyst, characterized in that: The invention comprises a volcanic rock-based porous carrier material and a hydrogenation active component supported on the carrier; the volcanic rock-based porous carrier material is volcanic rock particles containing flaky alumina in the pores, and based on the weight of the carrier, the volcanic rock accounts for 75wt% to 95wt% and the flaky alumina accounts for 5wt% to 25wt%; the flaky alumina grows in situ in the pores of the volcanic rock itself and interweaves and stacks with each other, and the flaky alumina is 60-200nm long, 50-150nm high, and 10-20nm thick; the hydrogenation active component is selected from at least one Group VIB metal component and at least one Group VIII metal component, and based on the total weight of the catalyst and calculated as oxide, the Group VIB metal component accounts for 2.0% to 7.5% and the Group VIII metal component accounts for 0.5% to 3.5%; the Group VIII metal component is 0.5% to 3.5%. The Group VIB metal component is W and / or Mo; the Group VIII metal component is Co and / or Ni; the preparation method of the residual oil hydrogenation protection catalyst comprises: (1) preparing an aluminum-loaded volcanic rock-based porous carrier material; (2) impregnating the volcanic rock-based porous carrier material obtained in step (1) with an impregnation solution containing a hydrogenation active component, and drying and roasting the impregnated material to obtain a hydrogenation protection catalyst precursor material; (3) immersing the hydrogenation protection agent precursor material in step (2) in a propylene oxide aqueous solution for sealed hydrothermal treatment, and drying and roasting the material after the hydrothermal treatment to obtain a hydrogenation protection catalyst; the sealed hydrothermal treatment in step (3) is carried out in a sealed container, the treatment temperature is 110-180°C, the treatment time is 4-8 hours, and the pressure in the sealed container during the hydrothermal treatment is autogenous pressure.

2. The residual oil hydrogenation protection catalyst according to claim 1, characterized in that: Specific surface area is 40-130m 2 / g, pore volume is 0.1-0.4mL / g, pores with a diameter greater than 1μm account for 20%-40% of the total pore volume, pores with a diameter of 30-200nm account for 30%-60% of the total pore volume, and the crushing strength is 100-300N / particle.

3. A method for preparing a residual oil hydrogenation protection catalyst according to claim 1 or 2, characterized in that include: (1) Preparation of aluminum-loaded volcanic rock-based porous carrier materials; (2) impregnating the volcanic rock-based porous support material obtained in step (1) with an impregnation solution containing a hydrogenation active component, and drying and calcining the impregnated material to obtain a hydrogenation protected catalyst precursor material; (3) The hydrogenation protective agent precursor material of step (2) is immersed in a propylene oxide aqueous solution for sealed hydrothermal treatment. After the hydrothermal treatment, the material is dried and calcined to obtain a hydrogenation protective catalyst; the sealed hydrothermal treatment described in step (3) is carried out in a sealed container at a treatment temperature of 110-180°C and a treatment time of 4-8 hours. The pressure in the sealed container during the hydrothermal treatment is autogenous pressure.

4. The method according to claim 3, wherein: The aluminum-loaded volcanic rock-based porous carrier material in step (1) is obtained by impregnating volcanic rock with an aluminum salt solution, followed by drying and roasting; the volcanic rock is granular with a particle size of 1-10 mm; the volcanic rock particles have micron-sized internal pores with a pore diameter of 1-30 microns; the aluminum salt solution is one or more of an aqueous solution of aluminum sulfate, an aqueous solution of aluminum chloride, an aqueous solution of aluminum nitrate, and an ethanol solution of aluminum isopropoxide; the mass percentage concentration of the aluminum salt solution is 15%-55%, and the volume ratio of the aluminum salt solution to the volcanic rock is 3:1-10:1; and the impregnation time is 0.5-2 hours.

5. The method according to claim 3, wherein: The impregnation solution containing hydrogenation active components in step (2) is a solution containing Group VIB and / or Group VIII metals, wherein the content of Group VIB metal oxide in the solution is 1.5-6.5 g / 100 mL, and the content of Group VIII metal oxide is 0.5-2.5 g / 100 mL.

6. The method according to claim 3, wherein: The impregnation in step (2) is carried out by spray impregnation, saturated impregnation or supersaturated impregnation; the drying condition is to dry at a temperature of 100-160°C for 1-5 hours; The calcination conditions are 400-550°C for 2-10 hours.

7. The method according to claim 3, wherein: The mass percentage concentration of the propylene oxide aqueous solution in step (3) is 2.5%-12%, and the mass ratio of the propylene oxide aqueous solution to the hydrogenation protective agent precursor material is 3:1-10:

1.

8. The method according to claim 3, wherein: The mass percentage concentration of the propylene oxide aqueous solution in step (3) is 4%-8%, and the mass ratio of the propylene oxide aqueous solution to the hydrogenation protective agent precursor material is 4:1-8:

1.

9. The method according to claim 3, wherein: Polyethylene glycol 2000-20000 is added to the propylene oxide aqueous solution, and the mass ratio of the added amount of polyethylene glycol 2000-20000 to the hydrogenation protective agent precursor material is 0.01:1-0.05:

1.

10. The method according to claim 3, wherein: The sealing water heat treatment temperature in step (3) is 120-160°C.

11. The method according to claim 3, wherein: In step (3), the drying temperature is 100-160°C, and the drying time is 2-10 hours; the roasting temperature is 450-550°C, and the roasting time is 4-10 hours.

12. Use of the residual oil hydrogenation protection catalyst according to claim 1 or 2 in heavy oil hydroprocessing.

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