CN106140183A - A kind of preparation method containing zirconium Hydrodemetalation catalyst - Google Patents
A kind of preparation method containing zirconium Hydrodemetalation catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method containing zirconium Hydrodemetalation catalyst, including following content: (1) impregnates physics expanding agent I respectively with hydrogenation active component impregnation liquid I with containing zirconium solution I, impregnating physics expanding agent II respectively with hydrogenation active component impregnation liquid II with containing zirconium solution II, physics expanding agent I and physics expanding agent II drying after dipping are standby；(2) the physics expanding agent I of step (1) gained is become plastic with physics expanding agent II with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, be dried, the first roasting in a nitrogen atmosphere of dried material, roasting prepares modified aluminium oxide supports the most in air atmosphere；(3) with the modified aluminium oxide supports of hydrogenation active component impregnation liquid III impregnation steps (2), drying, roasting, prepare the Hydrodemetalation catalyst Han zirconium.Catalyst activity metal content at macropore prepared by the method is of a relatively high, and at aperture, content is relatively low, and the utilization rate of macropore significantly improves, and this Hydrodemetalation catalyst has high activity and long-term operation stability.
Description
Technical field
The present invention relates to a kind of preparation method containing zirconium Hydrodemetalation catalyst.
Background technology
The raising required along with raw material deep processing in world wide, main energy sources structure gradually develops to macromole and high-carbon direction, and China of heaviness universal for crude oil is all the more so.For effectively solving that heavy oil component is excessive at catalyst duct inside diffusional resistance, beavy metal impurity deposition and coking and the problem such as the catalyst activity reduction that causes or inactivation, an urgent demand possesses big pore volume and wide-aperture characteristic at the widely used alumina support of the industries such as petrochemical industry.Large aperture is conducive to macromolecular compound to catalyst granules diffusion inside, and big pore volume is then conducive to improving holding metal or coke ability.
The open a kind of residuum hydrogenating and metal-eliminating catalyst of CN1206037A, the method is simultaneously introduced physics expanding agent and chemical enlargement agent in carrying alumina production procedure, in the way of spray dipping, active component is loaded on carrier again, the pore volume of this catalyst is 0.80-1.20ml/g, and specific surface area is 110-200m2/ g, can several apertures be 15-20nm, and bulk density is 0.50-0.60g/ml.
CN1289640A discloses the preparation method of a kind of carried catalyst for hydrogenation and demetalation.Have employed unsaturation in the method and spray technology, the catalyst after spraying does not does dried, is directly placed in roaster.The method is effectively prevented in follow-up dry run metal salt solution by material lower floor to upper strata or the migration on surface, reduces production cost.
US4,448,896 disclose the catalyst of a kind of hydrodesulfurization and heavy metal, and the preparation method of this catalyst is that active component loads to specific surface area is 100-350m2/ g, pore radius is on the alumina support that pore volume is 0.5-1.5ml/g of 3.75-7500nm, the preparation method of this carrier be activated alumina or activated alumina precursor are mixed with white carbon black, molding, roasting.
CN102989493A discloses a kind of heavy-oil hydrogenation and processes the preparation method of composite catalyst, the method with the aluminium oxide of one or more in the silicon oxide containing vehicle weight 2.5%-12%, titanium oxide, zirconium oxide, chromium oxide, boron oxide, lithium oxide, phosphorous oxide, F as carrier, the sulfide of supported active metals cobalt, molybdenum, nickel or tungsten, phosphide and the composite catalyst of sulfur phosphide；Active metal accounts for the 5%-50% of catalyst weight.
Residuum hydrogenating and metal-eliminating catalyst active metal component prepared by said method is distribution uniform at the macropore and aperture of carrier, and the utilization rate causing macropore is relatively low.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of preparation method containing zirconium Hydrodemetalation catalyst.Catalyst activity metal content at macropore prepared by the method is of a relatively high, and at aperture, content is relatively low, and the utilization rate of macropore significantly improves, and this Hydrodemetalation catalyst has high activity and long-term operation stability.
The preparation method containing zirconium Hydrodemetalation catalyst of the present invention, including following content:
(1) impregnating physics expanding agent I respectively with hydrogenation active component impregnation liquid I with containing zirconium solution I, impregnate physics expanding agent II respectively with hydrogenation active component impregnation liquid II with containing zirconium solution II, physics expanding agent I and physics expanding agent II drying after dipping are standby；
(2) the physics expanding agent I of step (1) gained is become plastic with physics expanding agent II with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, be dried, the first roasting in a nitrogen atmosphere of dried material, roasting prepares modified aluminium oxide supports the most in air atmosphere；
(3) with the modified aluminium oxide supports of hydrogenation active component impregnation liquid III impregnation steps (2), drying, roasting, prepare the Hydrodemetalation catalyst Han zirconium.
In the inventive method, described hydrogenation active component is VIB and/or group VIII metal, and vib metals is molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Hydrogenation active component impregnation liquid can be the one in acid solution, aqueous solution or ammonia solution containing hydrogenation active component.
In the inventive method, in step (1) described hydrogenation active component impregnation liquid I, vib metals weight content is calculated as the 0.4wt%-0.6wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.1wt%-0.3wt% of final catalyst weight with oxide.The consumption of active metal impregnation liquid is physics expanding agent I saturated water adsorptive value.
In the inventive method, in step (1) described hydrogenation active component impregnation liquid II, vib metals weight content is calculated as the 0.1wt%-0.3wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.03wt%-0.5wt% of final catalyst weight with oxide.The consumption of active metal impregnation liquid is physics expanding agent II saturated water adsorptive value.
In the inventive method, described in step (1) containing the aqueous solution that zirconium solution I is solubility zirconates, solubility zirconates can be one or more mixing in zirconium nitrate, zirconium chloride, Disulfatozirconic acid., the consumption of solution is the saturated water adsorptive value of physics expanding agent I, and after dipping, in physics expanding agent I, the content of zirconium accounts for the 0.4%-0.6% of catalyst weight in terms of oxide.
In the inventive method, described in step (1) containing the aqueous solution that zirconium solution II is solubility zirconates, solubility zirconates can be one or more mixing in zirconium nitrate, zirconium chloride, Disulfatozirconic acid., the consumption of solution is the saturated water adsorptive value of physics expanding agent II, and after dipping, in physics expanding agent II, the content of zirconium accounts for the 0.1%-0.3% of catalyst weight in terms of oxide.
In the inventive method, step (1) described physics expanding agent is one or more mixing in carbon black powder, Linesless charcoal, wood flour, starch, and the particle diameter of physics expanding agent I is 600-1000 mesh, and the particle diameter of physics expanding agent II is 300-500 mesh.
In the inventive method, the drying condition described in step (1) is that nature dries in the shade or dry 1-10 hour in 50-120 DEG C.
In the inventive method, the boehmite dry glue powder described in step (2) can be the boehmite dry glue powder using any one method to prepare.
In the inventive method, the 4%-8% that addition is boehmite dry glue powder weight of the 3%-5% that addition is boehmite dry glue powder weight of the physics expanding agent I described in step (2), physics expanding agent II.
In the inventive method, being preferably added to mass concentration in kneading process described in step (2) is 1%-5% Aqueous Solutions of Polyethylene Glycol, wherein the mean molecule quantity of Polyethylene Glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 gram/100 grams boehmite dry glue powders.
In the inventive method, chemical enlargement agent described in step (2) is one or more in phosphoric acid or phosphate, preferably phosphate, wherein one or more in ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate of phosphate, chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, the extrusion aid described in step (2) is one or more in sesbania powder, starch or methylcellulose, preferably sesbania powder, and extrusion aid addition is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, the peptizer described in step (2) is one or more mixing in formic acid, acetic acid, citric acid or nitric acid, and addition is the 3%-10% of boehmite dry glue powder weight, depending on last molding effect.
In the inventive method, step (2) described drying condition is to be dried 1-10 hour at 100-130 DEG C；Under nitrogen atmosphere, roasting process is 500-650 DEG C of roasting 2-4 hour, and under air atmosphere, roasting process is 450-550 DEG C of roasting 2-4 hour.
In the inventive method, the hydrogenation active component impregnation liquid III described in step (3) is to calculate preparation according to final catalyst composition.In hydrogenation active component impregnation liquid III, vib metals content is calculated as 7-15g/100ml with oxide, VII race tenor is calculated as 0.8-3g/100ml with oxide, can be to use volume impregnation, incipient impregnation or spray impregnating mode, and dip time is 1-5 hour.
In the inventive method, the drying condition described in step (3) is to be dried 6-10 hour at 80-120 DEG C；Described roasting condition is roasting 3-6 hour at 400-600 DEG C.
Appropriate is impregnated on physics expanding agent by the inventive method containing zirconium solution and active metallic element, and with boehmite kneading, molding, be dried, roasting prepares alumina support, dipping active component finally prepares catalyst.In a nitrogen atmosphere during roasting, the active metal being carried in physics expanding agent is first responsible for zirconium surface, forms molybdenum-nickel/zirconium oxide active thing, improves the catalysis activity of active component.In roasting process, oxidized removing of physics expanding agent forms macropore in air atmosphere, and the molybdenum-nickel/zirconium oxide in physics expanding agent is loaded on corresponding macropore, makes the active component content increase at macropore in final catalyst.Select the physics expanding agent with different-grain diameter, make final catalyst is formed mass transfer and the diffusion of the macroporous structure accordingly with different pore size, beneficially reactant.The existence of zirconium have adjusted the surface nature of carrier at macropore, improves the interaction of active component and carrier, improves the catalysis activity of active metal.Active metallic content at macropore is higher simultaneously, and activity increases, and improves the utilization rate of macropore.During kneading, the addition of Polyethylene Glycol makes carbon black powder mix homogeneously with boehmite, improves the uniformity coefficient of macropore.Catalyst of the present invention is applicable to heavy resid HDM field, and this catalyst has higher activity and activity stability.
Detailed description of the invention
Further illustrate effect and the effect of the present invention below in conjunction with embodiment, but be not limited to following example.
Embodiment 1
Take industry ammonium heptamolybdate 55g to be placed in ammonia, be stirred, till insoluble matter, add industry basic nickel carbonate 25g, be stirred, till insoluble matter, make containing MoO310 grams/100 milliliters, the molybdenum-nickel-ammonia active metal salt solution of NiO1.2 gram/100 milliliters.The impregnation liquid of the addition preparation variable concentrations of ammonium heptamolybdate and basic nickel carbonate can be regulated as required.
Weigh carbon black powder I4.3 gram that particle diameter is 800 mesh (granule can pass through 800 mesh sieve holes but can't pass 1000 mesh sieve holes) to be placed in spray rolling pot, under rotary state, spray containing molybdenum oxide 0.5 gram in the way of atomizing type carbon black powder in rolling pot is with saturated spraying, the active metal impregnation liquid of nickel oxide 0.2 gram, the carbon black powder after dipping is dried 3 hours in 110 DEG C.Dried carbon black powder is replaced in spray rolling pot in, under rotary state, by atomizing type to rolling pot in carbon black powder with saturated spraying in the way of spray the zirconium nitrate aqueous solution containing zirconium oxide 0.4 gram, the carbon black powder after dipping in 110 DEG C be dried 3 hours standby.
Weigh particle diameter be 300(granule can by 300 mesh sieve holes but can't pass 325 mesh sieve holes) II11.4 gram of mix homogeneously of purpose carbon black powder, it is placed in spray rolling pot, under rotary state, spray containing molybdenum oxide 0.1 gram in the way of atomizing type carbon black powder in rolling pot is with saturated spraying, the active metal impregnation liquid of nickel oxide 0.03 gram, the carbon black powder after dipping is dried 3 hours in 110 DEG C.Dried carbon black powder is replaced in spray rolling pot in, under rotary state, by atomizing type to rolling pot in carbon black powder with saturated spraying in the way of spray the zirconium nitrate aqueous solution containing zirconium oxide 0.3 gram, the carbon black powder after dipping in 110 DEG C be dried 3 hours standby.
Weigh boehmite dry glue powder (aluminium oxide contents on dry basis 70%) 143 grams and above-mentioned steps carbon black powder, 7.5 grams of sesbania powder, 3 grams of ammonium phosphate mix homogeneously, adding mass concentration is 3%, mean molecule quantity is 43 grams of kneadings of Aqueous Solutions of Polyethylene Glycol of 4000, it is subsequently adding uniform dissolved with 5 grams of nitre aqueous acids continuation kneadings in right amount, screw rod banded extruder is extruded into the cloverleaf pattern bar of a diameter of 1.8mm, dry 3 hours in 120 DEG C, by dried article shaped in a nitrogen atmosphere in 600 DEG C of roastings 3 hours, the most in air atmosphere in 500 DEG C of roastings 4 hours.
Above-mentioned material is placed in beaker, with 150 milliliters containing MoO310 grams/100 milliliters, the molybdenum-nickel of NiO1.2 gram/100 milliliters-ammonia active metal salt solution dipping carrier 5 hours, filter off redundant solution, dry 2 hours for 120 DEG C, then 5 hours prepared catalyst C1 of roasting, this catalyst MoO at 550 DEG C3Weight/mass percentage composition be 10.6wt%, NiO weight/mass percentage composition be 1.4wt%, zirconium oxide percentage composition is 0.7wt%.
Embodiment 2
With embodiment 1, simply carbon black powder I weight is 7.2 grams, particle diameter is 600 mesh (granule can pass through 600 mesh sieve holes but can't pass 800 mesh sieve holes), containing molybdenum oxide 0.6 gram in active component I, nickel oxide 0.3 gram, containing zirconium solution I contains zirconium oxide 0.5 gram, carbon black powder II weight is 5.7 grams, particle diameter is 400 mesh (granule can pass through 400 mesh sieve holes but can't pass 500 mesh sieve holes), containing molybdenum oxide 0.2 gram in active component II, nickel oxide 0.04 gram, containing zirconium solution II contains zirconium oxide 0.2 gram, the addition of polyglycol solution is 43 to restrain to obtain catalyst C2 of the present invention, this catalyst MoO3Weight/mass percentage composition be 10.8wt%, NiO weight/mass percentage composition be 1.44wt%, zirconium oxide weight/mass percentage composition is 0. 7wt%.
Embodiment 3
With embodiment 1, simply carbon black powder I weight is 5.7 grams, particle diameter is 1000 mesh (granule can pass through 1000 mesh sieve holes but can't pass 1340 mesh sieve holes), containing molybdenum oxide 0.4 gram in active component I, nickel oxide 0.1 gram, containing zirconium solution I contains zirconium oxide 0.6 gram, carbon black powder II weight is 8.6 grams, particle diameter is 500 mesh (granule can pass through 500 mesh sieve holes but can't pass 600 mesh sieve holes), containing molybdenum oxide 0.3 gram in active component II, nickel oxide 0.05 gram, containing zirconium solution II contains zirconium oxide 0.1 gram, the addition of polyglycol solution is 100 to restrain to obtain catalyst C3 of the present invention, this catalyst MoO3Weight/mass percentage composition be 10.7wt%, NiO weight/mass percentage composition be 1.35wt%, zirconium oxide weight/mass percentage composition is 0.7wt%.
Embodiment 4
With embodiment 1, simply carbon black powder changes Linesless charcoal into, and the addition of polyglycol solution is 100 to restrain to obtain catalyst C4 of the present invention, this catalyst MoO3Weight/mass percentage composition be 10.6wt%, NiO weight/mass percentage composition be 1.4wt%, zirconium oxide percentage composition is 0.7wt%.
Embodiment 5
With embodiment 1, with 150 milliliters containing MoO during dipping38 grams/100 milliliters, the molybdenum-nickel of NiO0.9 gram/100 milliliters-ammonia active metal salt solution dipping carrier prepares catalyst C5 of the present invention, this catalyst MoO3Weight/mass percentage composition be 8.6wt%, NiO weight/mass percentage composition be 1.1wt%, zirconium oxide weight/mass percentage composition is 0.7wt%.
Embodiment 6
With embodiment 1, simply boehmite does not adds polyglycol solution and prepares catalyst C6 of the present invention, this catalyst MoO when mixing with carbon black powder3Weight/mass percentage composition be 10.6wt%, NiO weight/mass percentage composition be 1.4wt%, zirconium oxide percentage composition is 0.7wt%.
Comparative example 1
With example 1, simply active metal is unsupported on carbon black powder, but adds kneading when, and preparation has the comparative catalyst C7 of composition same as in Example 1.
Comparative example 2
With example 1, simply zirconium is unsupported on carbon black powder, but adds the when of kneading, and preparation has the catalyst C8 of composition same as in Example 1.
Comparative example 3
With example 1, simply active metal and zirconium are unsupported on carbon black powder, but add the when of kneading, and preparation has the catalyst C9 of composition same as in Example 1.
Comparative example 4
Weigh the carbon black powder 15.7 grams that particle diameter is 800 mesh (granule can pass through 800 mesh sieve holes but can't pass 1000 mesh sieve holes) to be placed in spray rolling pot, under rotary state, spray containing molybdenum oxide 0.6 gram in the way of atomizing type carbon black powder in rolling pot is with saturated spraying, the active metal impregnation liquid of nickel oxide 0.23 gram, the carbon black powder after dipping is dried 3 hours in 110 DEG C.Dried carbon black powder is replaced in spray rolling pot in, under rotary state, by atomizing type to rolling pot in carbon black powder with saturated spraying in the way of spray the zirconium nitrate aqueous solution containing zirconium oxide 0.7 gram, the carbon black powder after dipping in 110 DEG C be dried 3 hours standby.
Weigh boehmite dry glue powder (aluminium oxide contents on dry basis 70%) 143 grams and above-mentioned steps carbon black powder, 7.5 grams of sesbania powder, 3 grams of ammonium phosphate mix homogeneously, adding mass concentration is 3%, mean molecule quantity is 43 grams of kneadings of Aqueous Solutions of Polyethylene Glycol of 4000, it is subsequently adding uniform dissolved with 5 grams of nitre aqueous acids continuation kneadings in right amount, screw rod banded extruder is extruded into the cloverleaf pattern bar of a diameter of 1.8mm, dry 3 hours in 120 DEG C, by dried article shaped in a nitrogen atmosphere in 600 DEG C of roastings 3 hours, the most in air atmosphere in 500 DEG C of roastings 4 hours.
Above-mentioned material is placed in beaker, with 150 milliliters containing MoO310 grams/100 milliliters, the molybdenum-nickel of NiO1.2 gram/100 milliliters-ammonia active metal salt solution dipping carrier 5 hours, filter off redundant solution, dry 2 hours for 120 DEG C, then 5 hours prepared catalyst C10 of roasting, this catalyst MoO at 550 DEG C3Weight/mass percentage composition be 10.6wt%, NiO weight/mass percentage composition be 1.4wt%, zirconium oxide percentage composition is 0.7wt%.
The catalyst preparing examples detailed above and comparative example carries out activity rating, relatively above-mentioned each catalyst activity and stability.Raw oil character and evaluation process conditions are shown in Tables 1 and 2, the Activity evaluation of operating 200h is shown in Table 3, increase along with the duration of runs, the activity reduction of catalyst, in order to keep the activity of catalyst to meet production requirement, needing beds temperature raising, the rear catalyst bed temperature rise in 5000 hours that operates is shown in Table 4.
Table 1.
Table 2
Table 3.
Table 4.
By table 3 data it can be seen that the catalyst that the present invention provides has higher HDM activity compared with reference catalyst.Finding out from the result of table 4, after reacting 5000 hours, the Hydrodemetalation catalyst using the present invention to provide has higher activity stability.
Claims (18)
1. the preparation method containing zirconium Hydrodemetalation catalyst, it is characterized in that including following content: (1) impregnates physics expanding agent I respectively with hydrogenation active component impregnation liquid I with containing zirconium solution I, impregnating physics expanding agent II respectively with hydrogenation active component impregnation liquid II with containing zirconium solution II, physics expanding agent I and physics expanding agent II drying after dipping are standby；(2) the physics expanding agent I of step (1) gained is become plastic with physics expanding agent II with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, be dried, the first roasting in a nitrogen atmosphere of dried material, roasting prepares modified aluminium oxide supports the most in air atmosphere；(3) with the modified aluminium oxide supports of hydrogenation active component impregnation liquid III impregnation steps (2), drying, roasting, prepare the Hydrodemetalation catalyst Han zirconium.
The most in accordance with the method for claim 1, it is characterised in that: described hydrogenation active component is VIB and/or group VIII metal, and vib metals is molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Hydrogenation active component impregnation liquid can be the one in acid solution, aqueous solution or ammonia solution containing hydrogenation active component.
3. according to the method described in claim 1 or 2, it is characterized in that: in step (1) described hydrogenation active component impregnation liquid I, vib metals weight content is calculated as the 0.4wt%-0.6wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.1wt%-0.3wt% of final catalyst weight with oxide；The consumption of active metal impregnation liquid is physics expanding agent I saturated water adsorptive value.
4. according to the method described in claim 1 or 2, it is characterized in that: in step (1) described hydrogenation active component impregnation liquid II, vib metals weight content is calculated as the 0.1wt%-0.3wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.03wt%-0.5wt% of final catalyst weight with oxide；The consumption of active metal impregnation liquid is physics expanding agent II saturated water adsorptive value.
The most in accordance with the method for claim 1, it is characterized in that: described in step (1) containing the aqueous solution that zirconium solution I is solubility zirconates, the consumption of solution is the saturated water adsorptive value of physics expanding agent I, and after dipping, in physics expanding agent I, the content of zirconium accounts for the 0.4%-0.6% of catalyst weight in terms of oxide.
The most in accordance with the method for claim 1, it is characterized in that: described in step (1) containing the aqueous solution that zirconium solution II is solubility zirconates, the consumption of solution is the saturated water adsorptive value of physics expanding agent II, and after dipping, in physics expanding agent II, the content of zirconium accounts for the 0.1%-0.3% of catalyst weight in terms of oxide.
The most in accordance with the method for claim 1, it is characterised in that: step (1) described physics expanding agent is one or more mixing in carbon black powder, Linesless charcoal or wood flour, and the particle diameter of physics expanding agent I is 600-1000 mesh, and the particle diameter of physics expanding agent II is 300-500 mesh.
The most in accordance with the method for claim 1, it is characterised in that: the drying condition described in step (1) is that nature dries in the shade or dry 1-10 hour in 50-120 DEG C.
The most in accordance with the method for claim 1, it is characterised in that: the 4%-8% that addition is boehmite dry glue powder weight of the 3%-5% that addition is boehmite dry glue powder weight of the physics expanding agent I described in step (2), physics expanding agent II.
The most in accordance with the method for claim 1, it is characterized in that: adding mass concentration in the kneading process described in step (2) is 1%-5% Aqueous Solutions of Polyethylene Glycol, wherein the mean molecule quantity of Polyethylene Glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 gram/100 grams boehmite dry glue powders.
11. in accordance with the method for claim 1, it is characterised in that: the chemical enlargement agent described in step (2) is one or more in phosphoric acid or phosphate, and chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
12. in accordance with the method for claim 1, it is characterised in that: the extrusion aid described in step (2) is one or more in sesbania powder, starch or methylcellulose, and excellent extrusion aid addition is the 3%-5% of boehmite dry glue powder weight.
13. in accordance with the method for claim 1, it is characterised in that: the peptizer described in step (2) is one or more mixing in formic acid, acetic acid, citric acid or nitric acid, and addition is the 3%-10% of boehmite dry glue powder weight.
14. in accordance with the method for claim 1, it is characterised in that: step (2) described drying condition is to be dried 1-10 hour at 100-130 DEG C.
15. in accordance with the method for claim 1, it is characterised in that: under the nitrogen atmosphere described in step (2), roasting process is 500-650 DEG C of roasting 2-4 hour.
16. in accordance with the method for claim 1, it is characterised in that: under the air atmosphere described in step (2), roasting process is 450-550 DEG C of roasting 2-4 hour.
17. according to the method described in claim 1 or 2, it is characterised in that: in the hydrogenation active component impregnation liquid III described in step (3), vib metals content is calculated as 7-15g/100ml with oxide, and VII race tenor is calculated as 0.8-3g/100ml with oxide.
18. in accordance with the method for claim 1, it is characterised in that: the drying condition described in step (3) is to be dried 6-10 hour at 80-120 DEG C；Described roasting condition is roasting 3-6 hour at 400-600 DEG C.
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| CN109718797A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN114433053A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN114433053B (en) * | 2020-10-19 | 2023-10-10 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
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