CN109718863B - Carrier and catalyst for hydrogenation protective agent and preparation method thereof - Google Patents
Carrier and catalyst for hydrogenation protective agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carrier and a catalyst for a hydrogenation protective agent and a preparation method thereof. The carrier is an alumina carrier and comprises main alumina and rod-shaped alumina, wherein the main alumina is alumina with micron-sized pore channels, and at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina and in the micron-sized pore channels. The preparation method of the carrier comprises the steps of firstly preparing a carrier intermediate, then immersing the carrier intermediate into an ammonium bicarbonate solution, then carrying out sealing heat treatment, drying and roasting the heat-treated material to prepare the carrier. The carrier is used as residual oil hydrogenation protection catalyst, has the characteristics of good macromolecular diffusion performance, strong impurity capacity, high demetalization activity and the like, and is particularly suitable for residual oil hydrotreating process.
Description
Technical Field
The invention relates to an alumina carrier, a catalyst and a preparation method thereof, in particular to a carrier and a catalyst for a residual oil hydrogenation protective agent and a preparation method thereof.
Background
Currently, hydrotreating is still the most important means for producing high quality, environmentally friendly petroleum products. The core of the hydrotreating technology is the catalyst, and for hydrotreating heavy components of petroleum (such as VGO, especially residual oil), the size of the pore diameter and the pore volume of the catalyst directly influence the exertion of the activity of the catalyst.
The residual oil hydrogenation protecting catalyst has the main function of eliminating iron, calcium, nickel, vanadium and other matters from residual oil. The carrier material used by the existing residual oil hydrogenation protection catalyst is generally macroporous alumina and modified products thereof. The common preparation method of the macroporous alumina comprises the following steps: physical pore-forming method and high-temperature roasting method.
US4448896, US4102822 and the like use physical pore-expanding agents such as carbon black, starch and the like to be mixed and kneaded with active alumina or precursors of the alumina to expand the pore diameter of the alumina carrier, and the dosage of the physical pore-expanding agent is more than 10wt% of the alumina.
CN102861617A discloses a preparation method of an alumina carrier with a double-pore structure. Weighing a certain amount of pseudo-boehmite dry glue powder, uniformly mixing the pseudo-boehmite dry glue powder with a proper amount of peptizer and extrusion aid, then adding a proper amount of ammonium bicarbonate aqueous solution into the materials, kneading the obtained materials into a plastic body, extruding the plastic body into strips, and placing the formed materials into a sealed container to be subjected to hydrothermal treatment and then roasting to obtain the alumina carrier. The alumina carrier prepared by the technology has double pore distribution, but the content of pores with the diameter of more than 1000nm is low, which is not beneficial to the precipitation and removal of substances such as iron, calcium, nickel, vanadium and the like in residual oil.
CN1120971A discloses a preparation method of an alumina carrier with a bimodal pore structure. The method uniformly mixes two or more than two pseudo-boehmite dry glue prepared by different raw material route methods, and then carries out peptization, molding, drying and roasting treatment to obtain the alumina with the specific surface area of 100-200 m-2The pore volume is 0.7-1.6mL/g, the double-peak pores are respectively concentrated in the areas of 3.5-35nm and more than 100nm, wherein the pore volume occupied by the pores with the diameter of more than 100nm is 10% -56% of the total pore volume. But the content of pores with the diameter of more than 1000nm is low, which is not beneficial to the precipitation and removal of substances such as iron, calcium, nickel, vanadium and the like in the residual oil.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a hydrogenation protection catalyst carrier, a hydrogenation protection catalyst and a preparation method thereof. The hydrogenation protection catalyst prepared by the carrier has the characteristics of good macromolecule diffusion performance, strong impurity-containing capacity, high demetalization activity and the like, and is particularly suitable for a residual oil hydrotreating process.
The hydrogenation protection catalyst carrier is an alumina carrier and comprises main alumina and rod-shaped alumina, wherein the main alumina is alumina with micron-sized pore channels, at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina and in the micron-sized pore channels with the pore diameter D of 5-10 mu m, the length of the rod-shaped alumina is 1-12 mu m, and the diameter of the rod-shaped alumina is 100-300 nm; the pore distribution of the carrier is as follows: the pore volume occupied by the pores with the pore diameter of less than 10nm is less than 10 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 15-35nm is 30-50 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-800nm is 30-45 percent of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 1000nm is 10-26 percent of the total pore volume, preferably 10-24 percent.
The micron-sized pore canal refers to a micron-sized pore canal with the pore diameter D of 5-10 mu m
In the carrier, the rod-shaped alumina is basically distributed on the outer surface of the main alumina and in the micron-sized pore channel. The rod-shaped alumina distributed on the outer surface of the main alumina and in the micron-sized pore channels accounts for more than 95 percent of the total weight of all the rod-shaped alumina, and preferably more than 97 percent.
In the carrier, the length of the rod-shaped alumina in the micron-sized pore channels is mainly 0.3D-0.9D (which is 0.3-0.9 time of the diameter of the micron-sized pore channels), namely the length of more than 85 percent of the rod-shaped alumina in the micropores is 0.3D-0.9D; the length of the rod-shaped alumina on the outer surface is mainly 3-8 μm, that is, the length of more than 85% of the rod-shaped alumina on the outer surface is 3-8 μm.
Wherein, in the micron-scale pore channels of the main alumina, the rod-shaped alumina is distributed in a disordered and mutually staggered state.
Wherein at least one end of at least part of the rod-shaped alumina is attached to the micron-sized pore channel wall of the main body, and preferably at least one end of at least part of the rod-shaped alumina is bonded to the micron-sized pore channel wall and is integrated with the main body alumina. Further preferably, at least one end of the rod-shaped alumina in the micron-sized pore channel is bonded to the wall of the micron-sized pore channel, and is integrated with the main alumina.
Wherein the rod-like aluminas are distributed on the outer surface of the main alumina in a disordered and staggered state.
Wherein one end of at least part of the rod-shaped alumina is attached to the outer surface of the main alumina, and preferably, one end of at least part of the rod-shaped alumina is combined on the outer surface of the main alumina, and the other end of the rod-shaped alumina extends outwards and is integrated with the main alumina. Further preferably, one end of the rod-shaped alumina on the outer surface of the main body alumina is bonded to the outer surface of the main body alumina, and the other end thereof is protruded outward to be integrated with the main body.
In the carrier, the coverage rate of the rod-shaped alumina in the micron-sized pore channels of the main alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface of the inner surface of the micron-sized pore channels of the main alumina, which is occupied by the rod-shaped alumina, in the inner surface of the micron-sized pore channels of the main alumina. The coverage rate of the rod-shaped alumina on the outer surface of the main body alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface of the outer surface of the main body alumina, which is occupied by the rod-shaped alumina, on the outer surface of the main body alumina.
The carrier of the invention has the following properties: specific surface area of 140-2(iv) g, pore volume of 0.6-1.5mL/g, crush strength of 9-18N/mm.
In the carrier of the present invention, the pores formed by the rod-shaped alumina in a disordered mutual staggering manner are concentrated between 100-800 nm.
In a second aspect, the present invention provides a method for preparing a hydrogenation protection catalyst carrier, comprising:
(1) preparing a carrier intermediate;
(2) and (3) immersing the carrier intermediate into an ammonium bicarbonate solution, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain the carrier.
The preparation method of the carrier of the present invention comprises the following steps1) The carrier intermediate had the following properties: the specific surface area is 120-280m2The pore volume is 0.7-1.4mL/g, and the pore distribution is as follows: the pore volume occupied by the pores with the pore diameters of 15-35nm is 25% -45% of the total pore volume, the pore volume occupied by the pores with the pore diameters of 100-800nm is 15% -45% of the total pore volume, and the pore volume occupied by the pores with the pore diameters of more than 5 mu m (preferably the pores with the pore diameters of 5-10 mu m) is 10% -20% of the total pore volume.
In the preparation method of the carrier, the carrier intermediate in the step (1) can be prepared by a conventional method, such as a physical pore-expanding agent method, and the specific process is as follows: kneading the pseudoboehmite and the physical pore-enlarging agent for molding, drying and roasting the molded product to obtain the carrier intermediate. The physical pore-enlarging agent can be one or more of activated carbon, sawdust and polyvinyl alcohol, the particle size of the added physical pore-enlarging agent is selected according to the micron-sized pore canal of the alumina carrier intermediate, the particle size of the physical pore-enlarging agent is preferably about 5-10 mu m, and the addition amount of the physical pore-enlarging agent is 21-35 wt% of the weight of the alumina carrier intermediate. The kneading molding can be carried out by adopting a conventional method in the field, and in the molding process, conventional molding aids, such as one or more of peptizing agents, extrusion aids and the like can be added according to needs. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like, and the extrusion assistant agent is a substance which is beneficial to extrusion forming, such as sesbania powder and the like. The drying and roasting conditions of the formed product are as follows: the drying temperature is 100-160 ℃, the drying time is 6-10 hours, the roasting temperature is 600-750 ℃, the roasting time is 4-6 hours, and the roasting is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.
The mass ratio of the using amount of the ammonium bicarbonate solution in the step (2) to the carrier intermediate obtained in the step (1) is 4:1-10:1, and the mass concentration of the ammonium bicarbonate solution is 15% -25%.
The sealing heat treatment temperature in the step (2) is 120-170 ℃, the treatment time is 4-8 hours, the heating rate is 5-20 ℃/min, and the sealing heat treatment is generally carried out in a high-pressure reaction kettle.
In the preparation method of the alumina carrier, the step (2) is preferred, sealing pretreatment is carried out before sealing heat treatment, the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is at least 3 ℃/min, preferably at least 5 ℃/min lower than that before the pretreatment.
In the method of the invention, the drying temperature in the step (2) is 160 ℃ for 6-10 hours, the roasting temperature is 600 ℃ for 750 ℃ for 4-6 hours.
In the method, compared with the alumina carrier intermediate in the step (1), the alumina carrier prepared in the step (2) has more concentrated distribution than the carrier intermediate for the pore diameter distribution of 15-35nm and 100-800 nm.
The third aspect of the invention provides a hydrogenation protection catalyst, which comprises a carrier and an active metal component, wherein the carrier adopts the carrier.
In the hydrogenation protection catalyst, the active metal component is VIB group and/or VIII group metal. The VIB group metal is selected from one or more of W, Mo, and the VIII group metal is selected from one or more of Co and Ni. Based on the weight of the catalyst, the content of the active metal oxide is 2.5% -10.0%, preferably 2.5% -9.0%, more preferably the content of the VIB group metal oxide is 2.0% -8.5%, and the content of the VIII group metal oxide is 0.3% -2.5%.
The hydrogenation protection catalyst of the invention can be prepared by conventional methods, such as an impregnation method, a kneading method and the like, and the impregnation method is preferably adopted. The carrier is prepared by a conventional impregnation method by adopting an impregnation method to load the active metal component, and can adopt a spray impregnation method, a saturated impregnation method or a supersaturated impregnation method. After the active metal components are impregnated, the hydrogenation protection catalyst is obtained after drying and roasting. The drying condition is that the drying is carried out for 1 to 5 hours at the temperature of 100-130 ℃; the roasting condition is roasting at 400-550 ℃ for 2-10 hours.
The hydrogenation protection catalyst is suitable for a residual oil hydrotreating process, and can effectively remove substances such as iron, calcium, nickel, vanadium and the like in residual oil.
Compared with the prior art, the invention has the following advantages:
1. the carrier of the invention makes full use of micron-scale pore channels of the alumina intermediate, and the rod-shaped alumina is distributed in the micron-scale pore channels in a staggered way in a disorder way, so that on one hand, the penetrability of the micron-scale pore channels is maintained, the specific surface area of the carrier is improved, the mechanical strength is enhanced, on the other hand, a certain hole expanding effect is performed on the nanometer-scale pore channels of the alumina carrier intermediate, and the penetrability and the uniformity of the nanometer-scale pore channels are further promoted. Therefore, the alumina carrier of the invention overcomes the problem that the large aperture, the specific surface area and the mechanical strength are not compatible caused by adopting a physical pore-expanding agent.
2. In the process of preparing the alumina carrier, the alumina carrier is pretreated at a certain temperature before sealing heat treatment, the pretreatment condition is relatively mild, and NH is slowly formed on the outer surface of the alumina carrier in a sealed and hydrothermal mixed atmosphere of carbon dioxide and ammonia gas4Al(OH)2CO3Crystal nuclei, raising the reaction temperature NH during the post-heat treatment4Al(OH)2CO3The crystal nucleus continues to grow evenly to make rod-shaped NH4Al(OH)2CO3Having uniform diameter and length while increasing rod-like NH4Al(OH)2CO3Coverage on the outer surface of the alumina intermediate and the inner surface of the micron-sized pore channel.
3. The hydrogenation protection catalyst of the invention is beneficial to mass transfer and diffusion of macromolecular reactants when being used for residual oil hydrogenation treatment, especially for the diffusion of macromolecules containing vanadium, iron, calcium, nickel and the like, has higher hydrogenation demetalization activity and impurity capacity, and has higher activity and stability.
Drawings
FIG. 1 is an SEM image of a cut surface of an alumina support obtained in example 1;
wherein the reference numbers are as follows: 1-main alumina, 2-rod-shaped alumina and 3-micron pore canal.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples. In the present invention, wt% is a mass fraction.
Application N2Physical adsorption-desorption characterization of the pore structures of the carriers of the examples and the comparative examples, the specific operations are as follows: adopting ASAP-2420 type N2And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter below 40nm is obtained according to a BJH model.
Mercury pressing method: the pore diameter distribution of the carriers of the examples and the comparative examples is characterized by applying a mercury porosimeter, and the specific operation is as follows: and characterizing the distribution of sample holes by using an American microphone AutoPore9500 full-automatic mercury porosimeter. The samples were dried, weighed into an dilatometer, degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and filled with mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm-1The distribution ratio of pore diameter of 100nm or more is measured by mercury intrusion method.
A scanning electron microscope is used for representing the microstructure of the alumina carrier, and the specific operation is as follows: and a JSM-7500F scanning electron microscope is adopted to represent the microstructure of the carrier, the accelerating voltage is 5KV, the accelerating current is 20 muA, and the working distance is 8 mm.
Example 1
Weighing 260 g of pseudo-boehmite dry glue powder (produced by Wenzhou refined crystal alumina Co., Ltd.), 60 g of active carbon with the particle size of 10 microns and 8 g of sesbania powder, uniformly mixing the materials physically, adding an appropriate amount of acetic acid aqueous solution with the mass concentration of 1.5%, kneading, extruding into strips, forming, drying the formed product at 100 ℃ for 6 hours, and roasting the dried product at 700 ℃ for 5 hours in an air atmosphere to obtain an alumina carrier intermediate ZA 1.
Weighing 1100 g of the alumina carrier intermediate ZA, placing the alumina carrier intermediate ZA in 800 g of ammonium bicarbonate solution, sealing the ammonium bicarbonate solution in an autoclave, heating to 100 ℃ at a speed of 15 ℃/min, keeping the temperature for 3 hours, heating to 160 ℃ at a speed of 10 ℃/min, keeping the temperature for 6 hours, drying the carrier at 100 ℃ for 6 hours, and roasting at 700 ℃ for 5 hours to obtain the alumina carrier A1, wherein the properties of the carrier are shown in Table 1. In the alumina carrier A1, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 3.0-9.0 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 85%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 81%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 400-700 nm.
Example 2
In the same manner as in example 1 except that the activated carbon was changed to polyvinyl alcohol having a particle size of 6 μm, the amount of polyvinyl alcohol added was 50 g, to obtain an alumina support intermediate ZA 2. The mass of the ammonium bicarbonate solution is 600 grams, and the mass concentration of the ammonium bicarbonate solution is 17.5 percent. The sealing pretreatment temperature is 90 ℃, the treatment time is 2 hours, the heat treatment temperature is 140 ℃, and the treatment time is 8 hours, so that the alumina carrier A2 is prepared, and the properties of the carrier are shown in Table 1. In the alumina carrier A2, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 2.0-5.5 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 80%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 78%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 400-600 nm.
Example 3
In the same manner as in example 1 except that the activated carbon was changed to wood chips having a particle size of 10 μm, 75 g of the wood chips were added to obtain an alumina support intermediate ZA 3. The mass of the ammonium bicarbonate solution is 1000 g, and the mass concentration of the ammonium bicarbonate solution is 15%. The heating rate before the sealing pretreatment is 11 ℃/min, the heating rate after the sealing pretreatment is 5 ℃/min, the heat treatment temperature is 170 ℃, and the treatment time is 4 hours, so that the alumina carrier A3 is prepared, wherein the properties of the carrier are shown in Table 1. In the alumina carrier A3, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 3.0-9.0 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 89%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 81%; the pores formed by the rod-shaped alumina crossing each other in a random order were concentrated at 500-800 nm.
Example 4
As in example 1, the temperature was raised to 120 ℃ at a rate of 15 ℃/min, except that no pretreatment was carried out prior to the heat treatment. The alumina carrier A4 of the present invention was prepared, and the properties of the carrier are shown in Table 1. In the alumina carrier A4, the length of the rod-shaped alumina in the micron-sized pore channel is mainly 3.0-9.0 μm, the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is about 76%, and the coverage rate of the rod-shaped alumina in the micron-sized pore channel of the main alumina is about 79%; the pores formed by the rod-shaped alumina staggered with each other in a random order are concentrated at 400-700 nm.
Comparative example 1
A comparative alumina support a5 was prepared as in example 1 except that the alumina support intermediate ZA1 was not heat treated in aqueous ammonium bicarbonate solution, but in distilled water, and the same mass of ammonium bicarbonate was added as the alumina support was shaped, the properties of the support being shown in table 1.
Comparative example 2
A comparative alumina support A6 was prepared as in example 1 except that the ammonium bicarbonate was changed to ammonium carbonate of the same mass, and the properties of the support are shown in Table 1.
TABLE 1 Properties of the alumina support intermediate and the alumina support
| Example 1 | Example 1 | Example 2 | Example 2 | Example 3 | Example 3 | |
| Numbering | ZA1 | A1 | ZA2 | A2 | ZA3 | A3 |
| Specific surface area, m2/g | 175 | 198 | 186 | 205 | 171 | 203 |
| Pore volume, mL/g | 0.86 | 1.09 | 0.89 | 1.03 | 0.87 | 1.04 |
| Pore distribution:, v% | ||||||
| ＜10nm | - | 4 | - | 6 | - | 5 |
| 15-35nm | 30 | 36 | 28 | 34 | 30 | 40 |
| 100-800nm | 21 | 35 | 18 | 36 | 19 | 35 |
| ＞1000nm | - | 15 | - | 14 | - | 16 |
| Over 5 mu m | 14 | Is free of | 12 | Is free of | 16 | Is free of |
| Crush strength, N/mm | 11.0 | 12.9 | 11.4 | 13.1 | 10.8 | 12.5 |
TABLE 1 Properties of the alumina support intermediate and the alumina support
| Example 4 | Comparative example 1 | Comparative example 2 | |
| Numbering | A4 | A5 | A6 |
| Specific surface area, m2/g | 194 | 181 | 179 |
| Pore volume, mL/g | 1.03 | 0.87 | 0.89 |
| Pore distribution:, v% | |||
| ＜ |
3 | ||
| 15-35nm | 41 | 33 | 35 |
| 100-800nm | 31 | 20 | 19 |
| ＞1000nm | 13 | 5 | 4 |
| Over 5 mu m | Is free of | 13 | 13.5 |
| Crush strength, N/mm | 12.6 | 10.4 | 10.7 |
Note: pore distribution refers to the percentage of the pore volume of pores within a certain diameter range in the support to the total pore volume.
Example 5
In this example, the alumina obtained in the above examples and comparative examples was used as a carrier to prepare a hydrogenation protecting agent.
The alumina carriers A1-A6 of examples 1-4 and comparative examples 1-2 were weighed to 100 g each, and 150mL of Mo-Ni-NH were added3Solution (according to MoO content in the final catalyst)36.0wt% and NiO1.5 wt%) for 2 hours, filtering out the redundant solution, drying at 120 ℃ for 5 hours, and roasting at 550 ℃ for 5 hours to respectively obtain hydrogenation protective agents C1-C6.
Example 6
The following examples illustrate the catalytic performance of the hydroprotectants C1-C6.
The hydrogenation protection catalysts of the invention, C1, C2, C3 and C4, and the hydrogenation protection catalysts of the comparative examples, C5 and C6, were respectively loaded into a fixed bed hydrogenation reactor, and the treated feedstock (see table 2) was subjected to the following test conditions: the reaction temperature is 385 ℃, the volume ratio of hydrogen to oil is 1000, and the liquid hourly space velocity is 1.0h-1The hydrogen partial pressure was 14MPa, and the continuous operation was carried out for 4000 hours, and the impurity removal properties are shown in Table 3.
TABLE 2 Properties of the feed oils
| Analysis item | Light sand slag |
| Density (20 ℃ C.), g/cm3 | 0.96 |
| Ni，µg/g | 22.4 |
| V，µg/g | 73.7 |
| Fe，µg/g | 6.8 |
| Ca，µg/g | 7.9 |
TABLE 3 evaluation results of catalysts
| Hydrogenation protection catalyst | C1 | C2 | C3 | C4 | C5 | C6 |
| V + Ni removal ratio, wt% | 49.1 | 51.3 | 50.6 | 45.5 | 27.5 | 28.6 |
| Percent by weight of Ca removed | 65.1 | 69.2 | 67.5 | 61.3 | 36.2 | 35.7 |
| Fe removal rate, wt% | 73.6 | 75.4 | 76.2 | 70.1 | 47.9 | 48.1 |
The results in Table 3 show that the hydrogenation protection catalyst of the invention has higher Ca, Fe, Ni and V removal rate and good stability.
Claims (23)
1. A hydrogenation protection catalyst carrier is an alumina carrier and comprises main alumina and rod-shaped alumina, wherein the main alumina is alumina with micron-sized pore channels, at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina and in the micron-sized pore channels with the pore diameter D of 5-10 mu m, the length of the rod-shaped alumina is 1-12 mu m, and the diameter of the rod-shaped alumina is 100-300 nm; the pore distribution of the carrier is as follows: the pore volume occupied by the pores with the pore diameter of less than 10nm is less than 10 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 15-35nm is 30-50 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-800nm is 30-45 percent of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 1000nm is 10-26 percent of the total pore volume.
2. The carrier of claim 1, wherein: in the carrier, the pore volume occupied by pores with the diameter of more than 1000nm is 10-24% of the total pore volume.
3. The carrier of claim 1, wherein: the rod-shaped alumina is basically distributed on the outer surface of the main alumina and in the micron-sized pore channels.
4. The carrier of claim 1, wherein: the length of the rod-shaped alumina in the micron-sized pore channel is mainly 0.3D-0.9D; the length of the rod-shaped alumina on the outer surface of the main alumina is mainly 3-8 μm.
5. The carrier of claim 1, wherein: in the micron-sized pore channels of the main alumina, the rod-shaped aluminas are distributed in a disordered and mutually staggered state; at least one end of at least part of the rod-shaped alumina is attached to the micron-sized pore channel wall of the main body.
6. The vector of claim 5, wherein: in the micron-sized pore channels of the main alumina, at least one end of at least part of rod-shaped alumina is combined on the wall of the micron-sized pore channel and is integrated with the main alumina.
7. The vector of claim 5, wherein: in the micron-sized pore channels of the main alumina, at least one end of the rod-shaped alumina in the micron-sized pore channels is combined on the wall of the micron-sized pore channel and is integrated with the main alumina.
8. The vector according to claim 1 or 5, wherein: on the outer surface of the main alumina, the rod-shaped aluminas are distributed in a disordered and mutually staggered state; one end of at least part of the rod-shaped alumina is attached to the outer surface of the main alumina.
9. The carrier of claim 8, wherein: on the outer surface of the main alumina, one end of at least partial rod-shaped alumina is combined on the outer surface of the main alumina, and the other end of the rod-shaped alumina extends outwards and is integrated with the main alumina.
10. The carrier of claim 8, wherein: on the outer surface of the main alumina, one end of the rod-shaped alumina on the outer surface of the main alumina is bonded to the outer surface of the main alumina, and the other end of the rod-shaped alumina extends outwards and is integrated with the main body.
11. The vector according to claim 1 or 5, wherein: the coverage rate of the rod-shaped alumina in the micron-sized pore channels of the main alumina is 70-95%, and the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is 70-95%.
12. The vector according to claim 1 or 5, wherein: the properties of the vector are as follows: specific surface area of 140-2(iv) g, pore volume of 0.6-1.5mL/g, crush strength of 9-18N/mm.
13. The vector according to claim 1 or 5, wherein: in the carrier, the pores formed by the rod-shaped alumina in a disordered and staggered manner are concentrated between 100-800 nm.
14. A process for preparing a hydrogenation protection catalyst support as claimed in any one of claims 1 to 13, comprising:
(1) preparing a carrier intermediate;
(2) immersing the carrier intermediate into an ammonium bicarbonate solution, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain a carrier;
wherein the carrier intermediate in the step (1) has the following properties: the specific surface area is 120-280m2The pore volume is 0.7-1.4mL/g, and the pore distribution is as follows: the pore volume occupied by the pores with the pore diameter of 15-35nm is 25% -45% of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-800nm is 15% -45% of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 5 mu m is 10% -20% of the total pore volume;
the sealing heat treatment temperature in the step (2) is 120-170 ℃, the treatment time is 4-8 hours, and the heating rate is 5-20 ℃/min.
15. The method of claim 14, wherein: the preparation process of the carrier intermediate in the step (1) is as follows: kneading and molding pseudo-boehmite and a physical pore-enlarging agent, and drying and roasting a molded product to obtain a carrier intermediate; the physical pore-expanding agent is one or more of activated carbon, wood chips and polyvinyl alcohol, and the addition amount of the physical pore-expanding agent is 21-35 wt% of the weight of the alumina carrier intermediate; the drying and roasting conditions of the formed product are as follows: the drying temperature is 100-160 ℃, the drying time is 6-10 hours, the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours.
16. The method of claim 14, wherein: the mass ratio of the using amount of the ammonium bicarbonate solution in the step (2) to the carrier intermediate obtained in the step (1) is 4:1-10:1, and the mass concentration of the ammonium bicarbonate solution is 15% -25%.
17. The method of claim 14, wherein: in the step (2), sealing pretreatment is carried out before sealing heat treatment, the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, the temperature rise rate before pretreatment is 10-20 ℃/min, the temperature rise rate after pretreatment is 5-10 ℃/min, and the temperature rise rate after pretreatment is at least 3 ℃/min lower than that before pretreatment.
18. The method of claim 17, wherein: the temperature rise rate after the pretreatment is lower than that before the pretreatment by at least 5 ℃/min.
19. The method of claim 14, wherein: the drying temperature in the step (2) is 160 ℃ and the drying time is 6-10 hours, the roasting temperature is 600 ℃ and 750 ℃ and the roasting time is 4-6 hours.
20. A hydrogenation protection catalyst comprising a support and an active metal component, wherein the support is as defined in any one of claims 1 to 13.
21. The catalyst of claim 20, wherein: the active metal component is VIB group and/or VIII group metal, the VIB group metal is selected from one or more of W, Mo, and the VIII group metal is selected from one or more of Co and Ni; the content of active metal oxide is 2.5-10.0% by weight of the catalyst.
22. The catalyst of claim 21, wherein: based on the weight of the catalyst, the content of the active metal oxide is 2.5-9.0%, wherein the content of the VIB group metal oxide is 2.0-8.5%, and the content of the VIII group metal oxide is 0.3-2.5%.
23. A process for the hydrotreatment of a residual oil characterized by the use of a catalyst as claimed in claim 20 or 21.
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| EP2439253A1 (en) * | 2010-10-05 | 2012-04-11 | Research Institute of Petroleum Industry (RIPI) | Hydrodesulfurization nanocatalyst comprising a support of nanotube / nanorod alumina, method of preparation and application |
| CN102441437A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst |
| CN107159173A (en) * | 2012-03-07 | 2017-09-15 | 切弗朗菲利浦化学公司 | Selective hydrocatalyst and production and preparation method thereof |
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| CN101890378A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof in residue fixed-bed hydrogenation method |
| EP2439253A1 (en) * | 2010-10-05 | 2012-04-11 | Research Institute of Petroleum Industry (RIPI) | Hydrodesulfurization nanocatalyst comprising a support of nanotube / nanorod alumina, method of preparation and application |
| CN102441437A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst |
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