CN110935469B - Preparation method of high-activity hydrodemetallization catalyst - Google Patents
Preparation method of high-activity hydrodemetallization catalyst Download PDFInfo
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- CN110935469B CN110935469B CN201811114218.4A CN201811114218A CN110935469B CN 110935469 B CN110935469 B CN 110935469B CN 201811114218 A CN201811114218 A CN 201811114218A CN 110935469 B CN110935469 B CN 110935469B
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- 239000000243 solution Substances 0.000 claims abstract description 43
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
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- 239000000843 powder Substances 0.000 claims abstract description 16
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
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- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 2
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- 241000219782 Sesbania Species 0.000 description 2
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a high-activity hydrodemetallization catalyst, which comprises the following steps: (1) immersing alumina powder into an ammonium bicarbonate aqueous solution for sealing heat treatment, carrying out solid-liquid separation on the heat-treated material, and drying the solid-phase material to obtain a rod-shaped alumina cluster body; (2) loading a hydrogenation active component I on a rod-shaped alumina cluster body, then kneading and molding the rod-shaped alumina cluster body and pseudo-boehmite, and drying to obtain a carrier I; (3) spraying and soaking the carrier I by using a carbon-containing precursor solution, and sequentially drying, roasting in a nitrogen atmosphere and roasting in an oxygen-containing atmosphere after spraying and soaking to obtain a carrier II; (4) and loading the hydrogenation active component II on a carrier II to obtain the high-activity hydrogenation demetalization catalyst. The hydrodemetallization catalyst has high macroporous content, and the pore channels are communicated with each other, so that mass transfer and diffusion of macromolecular reactants are facilitated, the catalyst is ensured to have high activity and good stability, and the running period of the device is prolonged.
Description
Technical Field
The invention relates to a preparation method of a high-activity hydrodemetallization catalyst, which is suitable for a heavy oil hydrotreating process.
Background
In the production process of heavy oil hydrodemetallization, because a large amount of sulfur and nitrogen in heavy oil exist in asphaltene micelles, the diameter of asphaltene molecules is 4-5nm, and the formed asphaltene micelles exist in heavy oil under the action of colloid serving as a stabilizer and have the diameter of 10nm to hundreds of nm. In heavy oil hydrogenation series catalysts, even if a hydrodemetallization catalyst is arranged in front of a heavy oil hydrodesulfurization, denitrification and carbon residue removal catalyst, macromolecular asphaltene is partially crushed to form small asphaltene micelles, but the small asphaltene micelles cannot enter the catalyst and can react on the outer surface of the denitrification and carbon residue removal catalyst to block the pores on the outer surface by impurities such as metal and the like due to the fact that the pores of the hydrodemetallization and carbon residue removal catalyst are not suitable and are concentrated at about 10nm, so that the catalyst is inactivated, and industrial application is influenced.
In order to realize the long-period operation of the desulfurization, denitrification and carbon residue removal catalyst, the metal capacity of the catalyst must be improved and the pore channel proportion of 30nm to micron order must be improved while the desulfurization, denitrification and carbon residue removal of the catalyst are ensured. The existing hole expanding method is mainly a physical hole forming method, and can obtain 30nm to micron-sized macroporous channels, but the channels are discontinuously penetrated, the channels are in a dispersed state, and the orifices are of an ink bottle type, so that the diffusion effect on reactants is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a high-activity hydrodemetallization catalyst. The hydrodemetallization catalyst has high macroporous content, and the pore channels are communicated with each other, so that mass transfer and diffusion of macromolecular reactants are facilitated, the catalyst is ensured to have high activity and good stability, and the running period of the device is prolonged.
The preparation method of the hydrodemetallization catalyst comprises the following steps:
(1) immersing alumina powder into an ammonium bicarbonate aqueous solution for sealing heat treatment, carrying out solid-liquid separation on the heat-treated material, and drying the solid-phase material to obtain a rod-shaped alumina cluster body;
(2) loading a hydrogenation active component I on a rod-shaped alumina cluster body, then kneading and molding the rod-shaped alumina cluster body and pseudo-boehmite, and drying to obtain a carrier I;
(3) spraying and soaking the carrier I by using a carbon-containing precursor solution, and sequentially drying, roasting in a nitrogen atmosphere and roasting in an oxygen-containing atmosphere after spraying and soaking to obtain a carrier II;
(4) and loading the hydrogenation active component II on a carrier II to obtain the high-activity hydrogenation demetalization catalyst.
In the method of the invention, the alumina powder in the step (1) is gamma-alumina powder which is prepared according to the prior art or is commercially available. The preparation method is generally a method for roasting pseudo-boehmite, wherein the roasting temperature is 450-600 ℃, the roasting time is 4-8 hours, and the pseudo-boehmite can be prepared by a precipitation method, an aluminum alkoxide hydrolysis method, an inorganic salt sol-gel method, a hydrothermal method, a vapor deposition method and the like.
In the method, the mass ratio of the amount of the ammonium bicarbonate aqueous solution in the step (1) to the alumina powder is 5:1-10:1, and the mass concentration of the ammonium bicarbonate aqueous solution is 10% -20%.
In the method, the sealing heat treatment temperature in the step (1) is 120-160 ℃, and the treatment time is 4-8 hours.
In the method of the present invention, the solid-liquid separation in step (1) may be performed by filtration, centrifugation, or the like, and the solid-liquid separation process generally includes a washing process.
In the method, the rod-shaped alumina cluster body obtained in the step (1) is a cluster body structure formed by disordered and staggered rod-shaped alumina, the outer diameter of the rod-shaped alumina cluster body is 5-20 mu m, wherein the rod-shaped alumina accounts for more than 85% of the rod-shaped alumina cluster body, preferably more than 90%, the rest is spherical or ellipsoidal alumina, the length of a single rod-shaped alumina is 1-5 mu m, and the diameter is 100-300 nm.
In the method, the hydrogenation active component I in the step (2) is VIB and/or VIII group metal, the VIB group metal is molybdenum and/or tungsten, and the VIII group metal is cobalt and/or nickel. The loading mode can adopt an immersion mode, and immersion liquid can be one of acid solution, water solution or ammonia solution containing hydrogenation active components; the content of VIB group metal in the impregnating solution is 1.2-2.3g/100ml calculated by oxide, the content of VIII group metal is 0.1-0.4g/100ml calculated by oxide, and the load is completed through the drying process after impregnation.
In the method of the present invention, the pseudoboehmite described in the step (2) may be a pseudoboehmite prepared by any method, for example, prepared by a precipitation method, an aluminum alkoxide hydrolysis method, an inorganic salt sol-gel method, a hydrothermal method, a vapor deposition method, and the like.
In the method, the weight ratio of the addition amount of the modified rodlike alumina cluster bodies to the pseudo-boehmite is 1:6.5-1: 3.
In the method of the invention, the kneading molding in the step (2) is carried out by adopting the conventional method in the field, and in the molding process, the conventional molding auxiliary agent, such as one or more of peptizer, extrusion assistant and the like, can be added according to the requirement. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like; the extrusion aid is sesbania powder.
In the method, the carbon-containing precursor in the step (3) can be polyalcohol and/or saccharide, wherein the polyalcohol is one or more of xylitol, sorbitol, mannitol and arabitol; the saccharide is one or more of glucose, ribose, fructose, triose, tetrose, pentose, hexose and unsaccharide; the mass concentration of the carbon-containing precursor water solution is 15-30 wt%, and the dosage of the solution is 15-25% of the saturated water absorption capacity of the carrier I.
In the method, the nitrogen roasting condition in the step (3) is roasting: the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours; the roasting condition of the oxygen-containing atmosphere is as follows: the roasting temperature is 600-750 ℃, the roasting time is 0.5-6 hours, the oxygen content in the oxygen-containing atmosphere is more than 60wt%, preferably more than 75wt%, and pure oxygen is more preferably used. .
In the method of the present invention, the properties of the vector II in step (3) are as follows: the specific surface area is 170-255m2The pore volume is 0.75-1.5mL/g, and the pore distribution is as follows: the pore volume occupied by the pores with the pore diameter of 20-50nm is 40-60% of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-300nm is 20-30% of the total pore volume, and the crushing strength is 10-20N/mm.
In the method, the hydrogenation active component I in the step (4) is VIB and/or VIII group metal, the VIB group metal is molybdenum and/or tungsten, and the VIII group metal is cobalt and/or nickel. The loading mode can adopt an immersion mode, and immersion liquid can be one of acid solution, water solution or ammonia solution containing hydrogenation active components; the hydrogenation active component impregnating solution II contains 7-15g/100ml of VIB group metal calculated by oxide and 0.8-3g/100ml of VII group metal calculated by oxide, and can adopt the modes of over-volume impregnation, equal-volume impregnation or spray impregnation and the like, and the impregnation time is 1-5 hours.
In the method, the drying is generally carried out until the material has no obvious weight loss phenomenon, and the drying condition can be drying for 6-10 hours at 80-160 ℃. The roasting condition of the step (4) is that the roasting is carried out for 3-6 hours at the temperature of 400-600 ℃ and the roasting is carried out in the air atmosphere.
Compared with the prior art, the invention has the following advantages:
(1) in the hydrodemetallization catalyst, the rod-shaped alumina cluster bodies are integrally dispersed in the carrier, and the rod-shaped aluminas in the rod-shaped alumina cluster body structure are mutually staggered, so that the catalyst has high macroporous content and the pore channels are mutually communicated, and mass transfer and diffusion of macromolecular reactants are facilitated; meanwhile, the rod-shaped alumina cluster body is modified by the active component impregnating solution, the content of the active metal component is increased after modification, the active metal component is well matched with the macropores, the utilization rate of the macropores is improved, and the macropores have higher metal capacity and carbon deposition resistance, so that the catalyst has higher activity, good stability and the running period of the device can be prolonged.
(2) The surface of the alumina carrier is unsaturated and sprayed with the polyol or the carbohydrate, when the carrier is roasted in the nitrogen atmosphere, the polyol or the carbohydrate is carbonized on the surface of the alumina carrier, and when the carrier is roasted in the oxygen-containing atmosphere, the formed carbon is quickly oxidized and burnt and releases heat, so that the temperature on the surface of the alumina carrier is quickly raised to be higher than the roasting temperature, the crystal grains on the surface of the alumina carrier are further grown, the pore channel on the surface of the carrier is improved, and macromolecular reactants can enter the catalyst easily.
Drawings
FIG. 1 is a low-magnification SEM photograph of the rod-like alumina cluster prepared in example 1.
FIG. 2 is a high-magnification SEM photograph of the rod-shaped alumina cluster prepared in example 1.
Detailed Description
The technical solutions and effects of the present invention are further described below with reference to the following examples, but the present invention is not limited to the following examples. Wherein, in the present invention, wt% represents a mass fraction.
The BET method: 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 30nm 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, the mercury interfacial tension is 0.485N/cm, and the distribution rate of the pore diameter of more than 100nm is measured by a 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.
The preparation method of the alumina powder used in the examples and comparative examples of the present invention: calcining pseudo-boehmite at 500 ℃ for 6 hours to prepare alumina powder; wherein the pseudoboehmite is produced by Yixin chemical company Limited in Shanghai, and the dry basis weight content is 73 percent. The hydrogenation active component impregnation liquid in the examples and the comparative examples of the invention adopts a Mo-Ni-P solution which is well known in the field, and the contents of Mo and Ni are calculated by oxides.
Example 1
(1) Weighing 100 g of alumina powder, placing the alumina powder into 530 g of ammonium bicarbonate aqueous solution with the mass concentration of 13.7wt%, sealing the alumina powder in a closed high-pressure kettle, carrying out heat treatment at 140 ℃ for 5.5 hours, filtering and washing the alumina powder, and drying the alumina powder at 110 ℃ for 6 hours to obtain a rod-shaped alumina cluster body;
（2）with a catalyst containing MoO3Dipping the rod-shaped alumina cluster body by using 1.54g/100ml of dipping solution I and NiO0.23g/100ml of dipping solution I, filtering the dipped materials, and drying the materials for 6 hours at 120 ℃ to prepare a modified rod-shaped alumina cluster body;
(3) 105g of pseudo-boehmite, 16.5g of modified rodlike alumina cluster and 1.5g of sesbania powder are uniformly mixed, a proper amount of aqueous solution in which 3g of acetic acid is dissolved is added, the mixture is kneaded, extruded and formed, the formed product is dried for 6 hours at 140 ℃ to prepare a carrier I, then 23ml of 22.5wt% xylitol aqueous solution is used for unsaturated spray impregnation of the carrier, and then the carrier II is prepared by drying for 6 hours at 140 ℃, roasting for 5 hours at 750 ℃ in nitrogen atmosphere and roasting for 1 hour at 750 ℃ in oxygen atmosphere in sequence, wherein the property of the carrier II is shown in Table 1.
Example 2 the same as example 1 except that the ammonium bicarbonate solution was used in an amount of 820 g and the solution had a mass concentration of 11.5%. The heat treatment temperature was 150 ℃ and the treatment time was 6.5 hours.
MoO in active metal impregnation liquid I3The concentration was 1.89g/100ml and the NiO concentration was 0.17g/100 ml. The addition amount of the modified rod-like alumina cluster body was 26.5 g, the mass concentration of the xylitol solution was 27.5%, the amount was 20ml, and the calcination temperature in a nitrogen atmosphere and an oxygen-containing atmosphere was 720 ℃ to prepare an alumina carrier, the properties of which are shown in table 1.
Example 3
The same as example 1, except that 650 g of ammonium bicarbonate solution was used and the mass concentration of the solution was 19.3%. The heat treatment temperature was 160 ℃ and the treatment time was 4.5 hours. MoO in active metal impregnation liquid I3The concentration was 2.25 g/100ml and the NiO concentration was 0.2g/100 ml. The addition amount of the modified rod-like alumina cluster body is 21.5 g, the mass concentration of the xylitol solution is 18.5 percent, and the dosage is 17.5ml, so that the alumina carrier is prepared, and the properties of the carrier are shown in Table 1.
Example 4
The same as example 1, except that the amount of the ammonium bicarbonate solution was 960 g, the mass concentration of the solution was 16.6%. The heat treatment temperature was 125 ℃ and the treatment time was 7.5 hours. MoO in active metal impregnation liquid I3The concentration was 1.44g/100ml and the NiO concentration was 0.38g/100 ml. The adding amount of the modified rod-shaped alumina cluster body is 29.5 g, and the mass concentration of the xylitol solution is15.5%, in an amount of 24.5ml, an alumina carrier was prepared, the properties of which are shown in table 1.
Comparative example 1
Comparative alumina supports were prepared as in example 1 except that the ammonium bicarbonate solution was changed to ammonium carbonate solution, and the properties of the supports are shown in Table 1.
Comparative example 2
In the same manner as in example 1, except that the rod-like alumina cluster was not subjected to the modification treatment with the active metal impregnation solution, the same amount of the active metal impregnation solution was added in a kneaded form at the time of molding, and the properties of the carrier were as shown in Table 1.
Comparative example 3
As in example 1, except that the carrier was not sprayed with the xylitol solution, the same amount of xylitol solution was added in kneaded form during molding, and the properties of the carrier are shown in Table 1.
Comparative example 4
In the same manner as in example 1 except that the alumina was not hydrothermally treated with the ammonium bicarbonate solution, the same amount of the ammonium bicarbonate solution was added to the carrier during kneading and molding to obtain an alumina carrier for comparative example, and the properties of the carrier are shown in Table 1.
Comparative example 5
Comparative alumina supports were prepared as in example 1 except that the modified rod-like alumina cluster carriers were added in an amount of 7.5g, and the properties of the supports are shown in Table 1.
Comparative example 6
A comparative example alumina support was prepared as in example 1, except that the heat treatment temperature was 220 ℃.
Comparative example 7
A comparative example alumina support was prepared as in example 1, except that the heat treatment temperature was 80 ℃.
Comparative example 8
In the same manner as in example 1 except that the ammonium bicarbonate aqueous solution was at a mass concentration of 5%, a comparative alumina carrier was prepared.
Comparative example 9
The comparative alumina carrier was prepared in the same manner as in example 1 except that the ammonium bicarbonate aqueous solution had a mass concentration of 35%.
In the rod-shaped alumina clusters obtained in examples 1 to 4 and comparative examples 2, 3 and 5, the rod-shaped alumina had a length of 1 to 5 μm, a diameter of 100-300nm, and an outer diameter of 5 to 20 μm. In contrast, the alumina carriers obtained in comparative examples 1 and 4 and comparative examples 6 to 9 had no rod-like alumina cluster formed.
Table 1 alumina carrier properties.
Preparation of hydrodemetallization catalyst (C1-):
the alumina carriers obtained in the examples 1 to 4 and the alumina carriers obtained in the comparative examples 1 to 5 are respectively prepared into hydrodemetallization catalysts (C1-C9) by the following specific method:
the alumina supports prepared in examples 1 to 4 and comparative examples 1 to 5 were weighed to 100 g each, and 150mL of Mo-Ni-P solution (containing MoO) was added38.1g/100ml and NiO2.7g/100 ml), filtering to remove the redundant solution, drying at 120 ℃, and roasting at 550 ℃ for 5 hours to respectively obtain the hydrodemetallization catalyst C1-C9.
Evaluation of catalytic performance:
the hydrodemetallization catalyst (C1-C9) prepared above was evaluated for its catalytic performance by the following method: the residues listed in Table 2 were used as raw materials, and the catalytic performances of C1-C9 were evaluated on a fixed bed residue hydrogenation reactor, the catalyst was a strip 2-3 mm long, and the reaction conditions were as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 15MPa, and the liquid hourly volume space velocity is 1.0 hour-1The volume ratio of hydrogen to oil is 800, the content of each impurity in the generated oil is determined after 200 hours of reaction, and the metal and sulfur removal rate is calculated according to the following method: the demetallization ratio (HDM,%) = (feed oil metal (Ni + V) content-product metal (Ni + V) content)/feed oil metal (Ni + V) content × 100%, and the relative removal rate of other catalyst metals was calculated with the removal rate of catalyst C1 metal being 100%, and the evaluation results are shown in table 3.
TABLE 2 Properties of the feed oils
TABLE 3 comparison of catalyst hydrogenation performance
As can be seen from the data in Table 3, the catalyst prepared by using the alumina of the present invention as the carrier has higher hydrodemetallization activity compared with the alumina of the comparative example.
The activity of the catalysts prepared in the above examples and comparative examples was evaluated, and the temperature rise at 2000 hours of operation is shown in Table 4.
TABLE 4 reaction temperature increase values
From the results in table 4, it is seen that after 2000 hours of reaction, the hydrodemetallization catalyst provided by the present invention is adopted, and in order to maintain high demetallization rate, the required reaction temperature is increased by a much smaller extent than that of the comparative catalyst, which indicates that the hydrodemetallization catalyst provided by the present invention has higher activity stability.
Claims (9)
1. A preparation method of a high-activity hydrodemetallization catalyst is characterized by comprising the following steps: (1) immersing alumina powder into an ammonium bicarbonate aqueous solution for sealing heat treatment, carrying out solid-liquid separation on the heat-treated material, and drying the solid-phase material to obtain a rod-shaped alumina cluster body; (2) loading a hydrogenation active component I on a rod-shaped alumina cluster body, then kneading and molding the rod-shaped alumina cluster body and pseudo-boehmite, and drying to obtain a carrier I; (3) spraying and soaking the carrier I by using a carbon-containing precursor solution, and sequentially drying, roasting in a nitrogen atmosphere and roasting in an oxygen-containing atmosphere after spraying and soaking to obtain a carrier II; (4) loading the hydrogenation active component II on a carrier II to obtain a high-activity hydrogenation demetallization catalyst; the mass ratio of the amount of the ammonium bicarbonate aqueous solution in the step (1) to the alumina powder is 5:1-10: 1; the mass concentration of the ammonium bicarbonate aqueous solution is 10-20%; the sealing heat treatment temperature in the step (1) is 120-160 ℃, and the treatment time is 4-8 hours; the rod-shaped alumina cluster body obtained in the step (1) is a cluster body structure formed by disordered and mutually staggered rod-shaped alumina, the outer diameter of the rod-shaped alumina cluster body is 5-20 mu m, wherein the rod-shaped alumina accounts for more than 85% of the rod-shaped alumina cluster body, and the balance is spherical or ellipsoidal alumina; the length of the single rod-shaped alumina is 1-5 mu m, and the diameter is 100-300 nm.
2. The method of claim 1, wherein: the hydrogenation active component I in the step (2) is VIB and/or VIII group metal, the VIB group metal is molybdenum and/or tungsten, and the VIII group metal is cobalt and/or nickel; the loading mode adopts an immersion mode, and immersion liquid is one of acid solution, water solution or ammonia solution containing hydrogenation active components; the content of VIB group metal in the impregnating solution is 1.2-2.3g/100mL calculated by oxide, and the content of VIII group metal is 0.1-0.4g/100mL calculated by oxide.
3. The method of claim 1, wherein: the weight ratio of the added amount of the modified rod-shaped alumina cluster body to the pseudo-boehmite is 1:6.5-1: 3.
4. The method of claim 1, wherein: the carbon-containing precursor in the step (3) is polyalcohol and/or saccharide; the mass concentration of the carbon-containing precursor water solution is 15-30 wt%, and the dosage of the solution is 15-25% of the saturated water absorption capacity of the carrier I.
5. The method of claim 4, wherein: the polyalcohol is one or more of xylitol, sorbitol, mannitol and arabitol; the saccharide is one or more of glucose, ribose, fructose, triose, tetrose, and pentose.
6. The method of claim 1, wherein: the nitrogen roasting condition in the step (3) is as follows: the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours.
7. The method of claim 1, wherein: the roasting condition of the oxygen-containing atmosphere in the step (3) is as follows: the roasting temperature is 600-750 ℃, the roasting time is 0.5-6 hours, and the oxygen content in the oxygen-containing atmosphere is more than 60 wt%.
8. The method of claim 1, wherein: the carrier II in the step (3) has the following properties: the specific surface area is 170-255m2The pore volume is 0.75-1.5mL/g, and the pore distribution is as follows: the pore volume occupied by the pores with the pore diameter of 20-50nm is 40-60% of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-300nm is 20-30% of the total pore volume, and the crushing strength is 10-20N/mm.
9. The method of claim 1, wherein: the hydrogenation active component I in the step (4) is VIB and/or VIII group metal, the VIB group metal is molybdenum and/or tungsten, and the VIII group metal is cobalt and/or nickel; the loading mode adopts an immersion mode, and immersion liquid is one of acid solution, water solution or ammonia solution containing hydrogenation active components; the content of the VIB group metal in the hydrogenation active component impregnating solution II is 7-15g/100mL calculated by oxide, and the content of the VII group metal is 0.8-3g/100mL calculated by oxide.
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