CN102861590A - Hydrodemetallization catalyst and preparation method thereof - Google Patents
Hydrodemetallization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrodemetallization catalyst and a preparation method of the hydrodemetallization catalyst. The hydrodemetallization catalyst uses alumina to serve as a carrier and uses MoO3 and NiO to serve as active components. The hydrodemetallization catalyst comprises the following active components by weight: 1.0-15.0% of the MoO3 and 0.5-6.0% of NiO, a pore volume of the catalyst is 0.6-1.40ml/g, a specific surface area is 130.0-250.0m<2>/g, a pore diameter is 10-20 nanometers and is 80%-90% of a total pore volume, and a crushing strength is 120-150N/cm. The preparation method of the hydrodemetallization catalyst comprises the steps of adopting a sol gelatin method to prepare an alumina supporter; adopting an immersing method to load metal components of Mo and Ni, drying and roasting, adding a sugar solution in a concentration of 1-5mol/L in a sol system in a process of preparing the alumina supporter by using the sol gelatin method, and enabling a molar ratio of sugar and aluminum in the sol system to be 1-6. The hydrodemetallization catalyst prepared by using the preparation method has high-activity stability, has a big pore volume and a pore diameter, and is concentrated in pore distribution and moderate in mechanical strength.
Description
Technical field
The present invention relates to a kind of Hydrodemetalation catalyst and preparation method thereof.
Background technology
Along with the continuous aggravation of the continuous minimizing of petroleum resources and crude oil heaviness, in poor quality trend, the mink cell focus deep process technology is subject to the worker's that refines oil great attention both at home and abroad always.Have hold metal and hold the charcoal ability than the catalyst of large pore volume and larger bore dia strong, can slow down catalyst inactivation, prolonged the service cycle of catalyst.Aluminium oxide is class catalyst carrier commonly used, is widely used in the fields such as PETROLEUM PROCESSING, chemical industry, environmental protection.The bore dia that is generally used for preparing the aluminium oxide of hydrotreating catalyst and commercial alumina is less, can not satisfy the needs of preparation heavy oil, residuum hydrogenating and metal-eliminating and/or heavy oil hydrodesulfurization catalyst, therefore, preparation to have the carrier than large pore volume and larger bore dia be preparation residual oil, especially for the preparation of the key of the higher decompression residuum Hydrodemetalation catalyst of tenor.
US4448896 discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, and this catalyst loads on a kind of large-pore alumina carrier take at least a VIII family and/or VI B family metallic element as active component.The specific area of this aluminium oxide is 100 ~ 350 meters
2/ gram, preferred 200 ~ 300 meters
2/ gram, pore volume is 0.5 ~ 1.5 ml/g, preferred 0.7 ~ 1.2 ml/g, the aperture be the pore volume in the hole of 3.75 ~ 100 nanometers account for total pore volume 90%.The preparation method of this residuum hydrogenating and metal-eliminating catalyst is that boehmite and carbon powder kneading is even, moulding, drying, roasting makes alumina support in oxygen containing atmosphere, then at this carrier dipping VIII family and VI B family active metal component, or with boehmite, carbon powder and contain VIII family and the compound kneading of VI B family active metal component even, moulding, drying, roasting makes Hydrodemetalation catalyst in oxygen containing atmosphere.Use separately the physics expanding agent in the method carrier preparation process, in order to reach often expanding agent large usage quantity of desirable reaming effect, cause the bad mechanical strength of final carrier, the pore size distribution disperse.
CN92112511.9 proposes to add Ludox in the kneading, extrusion process at boehmite can play the reaming effect.In addition, adding simultaneously silicon and phosphorus compound in alumina support, also can to play the reaming effect of reaming effect, particularly phosphorus compound more obvious.This expanding agent and boehmite generation chemical action are so can be described as the chemical enlargement agent.When using the chemical enlargement agent separately, because chemical enlargement agent and boehmite generation chemical action reduce the pore volume of carrier, specific area.
CN1206037A discloses a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof, and this catalyst loads on a kind of large-pore alumina carrier take VIII family and/or VI B family metallic element as active component.The pore volume of this carrier is 0.80 ~ 1.20 ml/g (mercury injection method), and specific area is 110 ~ 200 meters
2/ gram can several bore dias be 15 ~ 20 nanometers, and bulk density is 0.50 ~ 0.60 gram/millimeter.The preparation method of this residuum hydrogenating and metal-eliminating catalyst is in the boehmite kneading process, add simultaneously physics expanding agent and chemical enlargement agent, kneading becomes plastic, extruded moulding, dry, roasting makes carrier, again with the spray impregnation method with active constituent loading to carrier, drying, roasting make catalyst.Use simultaneously physics expanding agent and chemical enlargement agent in the carrier preparation process, can bring into play the synergy of two kinds of expanding agents, reduce its each plant demand, can overcome certain negative effect, but preparation process is complicated, and the pore size distribution of carrier centrality needs further to improve.
CN200510003776.X discloses a kind of preparation method of mesoporous aluminas, the method is take aluminium colloidal sol as precursor, add surfactant, high molecular polymer or carboxylic acid and make structure directing agent, add alkali regulation system pH value 8～11,80～100 ℃ of lower Hydrothermal Synthesiss form in 500 ℃ of roastings after separation, washing, drying; Or directly with the mixture of aluminium colloidal sol and structure directing agent in 30～100 ℃ of dryings, obtain mesoporous aluminas 500 ℃ of roastings again.Although the alumina support of the method preparation has larger specific area, its pore volume and aperture are less, are not suitable for use in the Hydrodemetalation catalyst carrier.
Summary of the invention
For the deficiencies in the prior art, the invention provides and a kind ofly have than large pore volume and aperture, concentrate the Hydrodemetalation catalyst and preparation method thereof of the high-activity stable of pore size distribution, moderate mechanical strength.
A kind of Hydrodemetalation catalyst is take aluminium oxide as carrier, with MoO
3, NiO is active component, by the catalyst weight content meter, active component MoO
3Be that 1.0 ~ 15.0 %, NiO are 0.5 ~ 6.0 %, the pore volume of this catalyst is 0.6 ~ 1.40ml/g, and specific area is 130.0 ~ 250.0m
2/ g, bore dia be the hole of 10 ~ 20 nanometers account for total pore volume 80% ~ 90%, crushing strength 120 ~ 150N/cm.
Active component MoO among the present invention
3Weight content be preferably 4.0 ~ 10.0 %, the weight content of NiO is preferably 1.0 ~ 3.0 %.
A kind of preparation method of Hydrodemetalation catalyst comprises and adopts sol-gal process to prepare the alumina support process; Infusion process supported active metal component Mo and Ni and drying, roasting process, it prepares in the alumina support process at sol-gal process, and to have added concentration in the sol system be the sugar juice of 1～5mol/L, the mol ratio of aluminium is 1～6 in sugar and the sol system.
The sugar juice concentration that adds in the sol system described in the inventive method is preferably 2～4mol/L, and the mol ratio of aluminium is 1～3 in sugar and the sol system.Described sugar juice is the aqueous solution of sugar.
Sugar described in the inventive method is monose or disaccharide, the preferred glucose of monose or fructose, disaccharide preferably sucrose or maltose.
Concrete sol-gel process described in the inventive method is as follows: take by weighing an amount of aluminum nitrate and be dissolved in the water, drip ammonia spirit, filter and washing leaching cake, add in the filter cake after the washing and add an amount of salpeter solution after suitable quantity of water stirs, obtained aluminium colloidal sol at least 2 hours in continuation stirring more than 70 ℃, add sugar juice in the aluminium colloidal sol, under room temperature, wore out 1～5 hour after stirring, gel is dry in 100～130 ℃ of baking ovens, then moulding, roasting.
The mass concentration of described ammonia spirit is 1%～5%, and addition is the pH that makes system〉9.0; The concentration of described salpeter solution is 0.5mol/L～2mol/L, and addition is for making H
+/ Al
3+=0.05～0.15; Described being shaped to mixed aluminium oxide dry powder with suitable quantity of water, peptizing agent, extrusion aid, kneading evenly after extruded moulding, shaping carrier in 100～130 ℃ of baking ovens dry 2～4 hours; Described extrusion aid can be one or more mixing in starch, methylcellulose, the sesbania powder; Peptizing agent can be one or more mixing in formic acid, acetic acid, citric acid, malonic acid, the nitric acid; Roasting rises to 600～800 ℃ with the programming rate of 0.5～2 ℃/min, and constant temperature calcining made alumina support in 2～4 hours.
Infusion process described in the inventive method can adopt saturated infusion process, also can adopt unsaturated infusion process, the solution that contains Mo can be a kind of or mixture in ammonium molybdate and the ammonium paramolybdate, and the solution that contains Ni can be one or more mixing in nickel nitrate, nickel acetate and the basic nickel carbonate; Drying behind the dipping active metal component is generally at 80 ~ 140 ℃ to descend dry 1 ~ 5 hour, and roasting is generally 500 ~ 600 ℃ of lower roastings 1 ~ 5 hour.
Active aluminum oxide carrier is actually by the particulate cohesion than its little several order of magnitude and forms, and particulate is to form by less primary particle is coalescent than it.The hole of active aluminum oxide carrier can be divided into three types: primary particle is piled up and the micropore that differs in size or the mesopore of formation, i.e. the intercrystalline hole of primary particle; Particulate is piled up the macropore that forms, i.e. particulate intercrystalline hole; And the defective hole that forms during the aluminium oxide moulding.Therefore interparticle space is exactly the source of alumina pore, and further the size in hole and shape depend on particle size, shape and accumulation mode fully.The aluminium colloidal sol that is evenly distributed with particle diameter in the Hydrodemetalation catalyst preparation process of the present invention is as the aluminium source, and glucide is as structure directing agent Borolon carrier.Contain a plurality of hydroxyls in the carbohydrate molecule structure, it is intermolecular can to form aggregation with hydrogen bond action.These aggregations can with inorganic species with hydrogen bond action, thereby guide the arrangement mode of inorganic species.The aluminium colloidal sol that particle diameter is evenly distributed is the accumulation of rule, arrangement centered by the carbohydrate aggregation under hydrogen bond action, the accumulation of this rule, arranges and to make gained Hydrodemetalation catalyst of the present invention have larger pore volume, concentrated pore-size distribution, higher specific area and suitable mechanical strength.The Hydrodemetalation catalyst of preparation has higher activity and activity stability take this aluminium oxide as carrier.
In a word, a kind of Hydrodemetalation catalyst of the present invention and preparation method thereof has following advantage:
(1) use glucide as structure directing agent among the present invention, accumulation, the arrangement of aluminium colloidal sol rule under the effect of structure directing agent, make the gained Hydrodemetalation catalyst have larger pore volume, aperture, the pore size distribution of concentrating and suitable mechanical strength, this catalyst has high activity and stability in the residuum hydrogenating and metal-eliminating course of reaction;
(2) the inventive method do not need to use the physics expanding agent and or the chemical enlargement agent just can make carrier have higher specific area;
(3) raw materials used such as carbohydrate, aluminum nitrate, cheap in the inventive method, environmental protection, pollution-free;
(4) the inventive method does not need to change existing catalyst preparation flow, and preparation process is simple, is suitable for commercial Application.
The specific embodiment
Further specify effect of the present invention below in conjunction with embodiment, but be not limited to following examples.
The concrete preparation process of Hydrodemetalation catalyst of the present invention is as follows:
(1) takes by weighing an amount of Al (NO
3)
3Be dissolved in the deionized water, drip mass concentration and be 2.5% ammonia spirit to system pH〉9.0, the sediment that obtains is carried out suction filtration, with deionized water Washing of Filter Cake is transferred in the beaker to neutrality, add appropriate amount of deionized water and stir an amount of salpeter solution of dropping after 0.5 hour, stir in continuation more than 70 ℃ and obtained aluminium colloidal sol at least in 2 hours; The aqueous solution of proper amount of sugar is added in the gained aluminium colloidal sol, stirred after 0.5 hour under room temperature aging 3 hours, gel drying 3 hours in 120 ℃ of baking ovens; Gained dry powder and suitable quantity of water, peptizing agent, extrusion aid kneading is even, extruded moulding, shaping carrier in 120 ℃ of baking ovens dry 2～4 hours; Dry support changes in the Muffle furnace, rises to 700 ℃ with the programming rate of 1 ℃/min, constant temperature calcining 2～4 hours final alumina support.(2) take by weighing an amount of above-mentioned carrier, add an amount of Mo-Ni-NH
3Solution (contains MoO
35 wt%～15.0wt%, NiO 2.0 wt%～6.0wt%) flooded 2～4 hours, the elimination redundant solution was dried 1～4 hour, and was made Hydrodemetalation catalyst of the present invention in 1～5 hour at 550 ℃ of roasting temperatures again for 120 ℃.
The preparation method of example 1-4 explanation Hydrodemetalation catalyst of the present invention.
Example 1
(1) takes by weighing 375gAl (NO
3)
39H
2O is dissolved in the deionized water, drip mass fraction and be 2.5% ammonia spirit to system pH〉9.0, the precipitation suction filtration that obtains is separated, extremely neutral with the deionized water washing, the filter cake that obtains is transferred in the beaker, add appropriate amount of deionized water and stir the salpeter solution 100ml that drips 1mol/L after 0.5 hour, under 70 ℃ of conditions, continue to stir and obtained aluminium colloidal sol in 2 hours, adding 1L concentration is that 1mol/L glucose is in gained aluminium colloidal sol, making the mol ratio of aluminium in sugar and the sol system is 1:1, stirred after 0.5 hour under room temperature gel in 120 ℃ of baking ovens dry 3 hours aging 3 hours; Gained dry powder and suitable quantity of water, nitric acid, sesbania powder kneading is even, extruded moulding, shaping carrier in 120 ℃ of baking ovens dry 2～4 hours; Dry support changes in the Muffle furnace, rises to 700 ℃ with the programming rate of 1 ℃/min, constant temperature calcining 2～4 hours final alumina support.(2) take by weighing above-mentioned alumina support 100 grams, add 150ml Mo-Ni-NH
3Solution (contains MoO
310.0wt%, NiO3.0 wt%) dipping is 2 hours, the elimination redundant solution, and 120 ℃ of oven dry 2 hours 550 ℃ of roasting temperatures 5 hours, obtain Hydrodemetalation catalyst C1 of the present invention again.Catalyst property is listed in the table 1.
Example 2
With example 1, just add 1L concentration and be the mixed solution (sucrose and glucose mol ratio are 1:1) of 3mol/L sucrose and glucose in the alumina support preparation process in gained aluminium colloidal sol, making the mol ratio of aluminium in sugared and the sol system is that 1:3 makes aluminium oxide.Adopt the method with example 1 to make Hydrodemetalation catalyst C2 of the present invention take this aluminium oxide as carrier.Catalyst property is listed in the table 1.
Example 3
With example 1, just in the alumina support preparation process, add 1L concentration and be the 5mol/L sucrose solution in gained aluminium colloidal sol, making the mol ratio of aluminium in sugar and the sol system is that 1:5 makes aluminium oxide.Adopt the method with example 1 to make Hydrodemetalation catalyst C3 of the present invention take this aluminium oxide as carrier.Catalyst property is listed in the table 1.
Example 4
With example 1, just add 2L concentration and be the mixed solution (maltose and fructose mol ratio are 1:1) of 3mol/L maltose and fructose in the alumina support preparation process in gained aluminium colloidal sol, making the mol ratio of aluminium in sugared and the sol system is that 1:6 makes aluminium oxide.Adopt the method with example 1 to make Hydrodemetalation catalyst C4 of the present invention take this aluminium oxide as carrier.Catalyst property is listed in the table 1.
The preparation method of Comparative Examples 1-2 explanation Comparative Examples catalyst.
Comparative Examples 1
This Comparative Examples is the comparative catalyst by the method preparation of describing among the CN1206037A embodiment 1.
Weigh Chinese Qilu Petroleum Chemical Corporation Institute with in the carbon dioxide and the prepared moisture 78g of boehmite dry glue powder 300g(of sheet sodium chlorate), the granular size that weighs again the production of Chinese Fushun Carbon Black Plant is 30 microns carbon black 18g and extrusion aid sesbania powder 10g, mix, the solution that adding is made into by 2.0g phosphoric acid and 400g water, kneading becomes plastic to be extruded into the bar that diameter is 0.9mm at banded extruder, lower dry 4 hours at 120 ℃, then 900 ℃ of lower roastings 2 hours, make carrier, through with containing MoO
3The Mo-Ni-NH of 12.0w% and NiO4.0 w%
3
Solution impregnation, 100 ℃ of dryings 2 hours make comparative catalyst C5.Catalyst property is listed in the table 1.
Comparative Examples 2
This Comparative Examples is by the aluminium oxide of the method preparation of describing among the CN200510003776.X, adopts the dipping method with example 1 to prepare the comparative catalyst take this aluminium oxide as carrier.
(1) gets 13.67g boehmite powder (Al
2O
3Mass content is 74.6%) be dispersed in the 200ml water, 80 ℃ of lower nitric acid 14ml that add 1M, keep temperature to continue to stir 6 hours, stablized, the 1M boehmite sol of high dispersive, under 30 ℃, with 3.64g CTAB (CTAB), 3.6g urea (or ammoniacal liquor of 60ml2M) joins in the boehmite sol of 40ml 1M, continue after the dissolving fully to stir 12 hours, change 100 ℃ of hydrothermal treatment consists 24 hours over to, go out the pH=9.0 of mixture behind the still, through separating, washing, 30 ℃ lower dry, with gained dry powder and suitable quantity of water, nitric acid, sesbania powder kneading is even, extruded moulding, shaping carrier in 120 ℃ of baking ovens dry 2～4 hours; Dry support changes in the Muffle furnace, rises to 700 ℃ with the programming rate of 1 ℃/min, constant temperature calcining 2～4 hours final alumina support.(2) take by weighing above-mentioned alumina support 100 grams, add 150ml Mo-Ni-NH
3Solution (contains MoO
310.0wt%, NiO3.0 wt%) dipping is 2 hours, the elimination redundant solution, and 120 ℃ of oven dry 2 hours 550 ℃ of roasting temperatures 5 hours, make comparative catalyst C6 again.Catalyst property is listed in the table 1.
Above-mentioned example and Comparative Examples gained catalyst property see Table 1.
Table 1 catalyst property.
| Example number | 1 | 2 | 3 | 4 | Comparative Examples 1 | Comparative Examples 2 |
| Bearer number | C1 | C2 | C3 | C4 | C5 | C6 |
| MoO 3wt% | 8.28 | 8.32 | 8.25 | 8.34 | 8.60 | 8.27 |
| NiO wt% | 2.34 | 2.45 | 2.27 | 2.53 | 2.45 | 2.26 |
| Specific area, m 2/g | 248 | 250 | 227 | 246 | 155 | 285 |
| Pore volume, ml/g | 0.96 | 0.98 | 1.0 | 1.02 | 0.84 | 0.59 |
| Can a few aperture nm | 15 | 16 | 17 | 16 | 17 | 6.1 |
| Pore size distribution, v%＜10nm | 5 | 7 | 6 | 8 | 13 | 36 |
| 10~20nm | 83 | 84 | 84 | 85 | 61 | 31 |
| >20nm | 12 | 9 | 10 | 7 | 26 | 33 |
| Intensity N/cm | 138 | 149 | 139 | 142 | 78 | 98 |
Can find out from the data of table 1, adopt the catalyst of our bright method preparation to have than large pore volume concentrated pore size distribution and moderate mechanical strength.In addition, the hole content of 10 ~ 20nm is higher in the catalyst.
Example 5-8
Following example illustrates the catalytic performance of Hydrodemetalation catalyst provided by the invention.
Take the listed decompression residuum of table 2 as raw material, the catalytic performance of the catalyst C1-C4 of evaluation example 1-4 preparation on 200 milliliters hydrogenation reaction device, catalyst is the bar of 2 ~ 3 millimeters of length, the catalyst loading amount is 100 milliliters, reaction temperature is 385 ℃, the hydrogen dividing potential drop is 15.6 MPas, and liquid hourly space velocity (LHSV) is 1.0 hours
-1, hydrogen to oil volume ratio is 800, reacts and measures the content that generates each impurity in the oil after 200 hours, calculates removal efficiency, evaluation result sees Table 3.
Comparative Examples 3-4
The catalytic performance of following Comparative Examples explanation reference Hydrodemetalation catalyst.
Equally take the listed decompression residuum of table 2 as raw material, estimate Comparative Examples 1, the catalyst C5 of 2 preparations, the catalytic performance of C6 at 100 milliliters hydrogenation reaction devices, catalyst is the bar of 2 ~ 3 millimeters of length, the catalyst loading amount is 200 milliliters, reaction temperature is 385 ℃, the hydrogen dividing potential drop is 15.6 MPas, and liquid hourly space velocity (LHSV) is 1.0 hours
-1, hydrogen to oil volume ratio is 800, reacts and measures the content that generates each impurity in the oil after 200 hours, calculates removal efficiency, evaluation result sees Table 4.
Table 2 feedstock oil character.
| Project | Content |
| S，wt% | 4.86 |
| N，wt% | 0.37 |
| Ni，μg/g | 53 |
| V，μg/g | 153 |
| CCR，wt% | 19 |
Table 3 catalyst hydrogenation performance comparison.
| Project | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment | Comparative Examples 3 | Comparative Examples 4 |
| Nickel removal, wt% | 53.5 | 51.4 | 52.3 | 54.1 | 41.3 | 33.1 |
| Vanadium removal, wt% | 67.5 | 68.7 | 68.9 | 66.5 | 56.4 | 39.2 |
| Desulfurization, wt% | 45.3 | 44.8 | 43.9 | 45.0 | 38.4 | 37.6 |
Found out that by table 3 data compare with existing catalyst, catalyst provided by the invention has higher HDM activity and hydrodesulfurization activity.
Claims (10)
1. Hydrodemetalation catalyst, it is characterized in that: this catalyst is take aluminium oxide as carrier, with MoO
3, NiO is active component, by the catalyst weight content meter, active component MoO
3Be that 1.0 ~ 15.0 %, NiO are 0.5 ~ 6.0 %, the pore volume of catalyst is 0.6 ~ 1.40ml/g, and specific area is 130.0 ~ 250.0m
2/ g, bore dia be the hole of 10 ~ 20 nanometers account for total pore volume 80% ~ 90%, crushing strength 120 ~ 150N/cm.
2. according to catalyst claimed in claim 1, it is characterized in that: described active component MoO
3Weight content be 4.0 ~ 10.0 %, the weight content of NiO is 1.0 ~ 3.0 %.
3. the preparation method of the described Hydrodemetalation catalyst of claim 1 comprises and adopts sol-gal process to prepare the alumina support process; Infusion process supported active metal component Mo and Ni and drying, roasting process, it is characterized in that: prepare in the alumina support process at sol-gal process that to have added concentration in the sol system be the sugar juice of 1～5mol/L, the mol ratio of aluminium is 1～6 in sugar and the sol system.
4. method according to claim 3 is characterized in that: the described sugar juice concentration that adds in the sol system is 2～4mol/L, and the mol ratio of aluminium is 1～3 in sugar and the sol system.
5. it is characterized in that according to claim 3 or 4 described methods: described sugar juice is the aqueous solution of sugar.
6. method according to claim 3, it is characterized in that: described sugar is monose or disaccharide.
7. according to claim 3 or 6 described methods, it is characterized in that: described monose is glucose or fructose, and disaccharide is sucrose or maltose.
8. method according to claim 3, it is characterized in that: described sol-gel process is as follows: take by weighing an amount of aluminum nitrate and be dissolved in the water, drip ammonia spirit, filter and washing leaching cake, add in the filter cake after the washing and add an amount of salpeter solution after suitable quantity of water stirs, obtained aluminium colloidal sol at least in 2 hours continuing more than 70 ℃ to stir, add sugar juice in the aluminium colloidal sol, wore out 1～5 hour under room temperature after stirring, gel is dry in 100～130 ℃ of baking ovens, then moulding, roasting.
9. according to claim 3 or 8 described methods, it is characterized in that: the mass concentration of described ammonia spirit is 1%～5%, and addition is the pH that makes system〉9.0; The concentration of described salpeter solution is 0.5mol/L～2mol/L, and addition is for making H
+/ Al
3+=0.05～0.15; Described being shaped to mixed aluminium oxide dry powder with suitable quantity of water, peptizing agent, extrusion aid, kneading evenly after extruded moulding, shaping carrier in 100～130 ℃ of baking ovens dry 2～4 hours; Described extrusion aid is one or more mixing in starch, methylcellulose, the sesbania powder; Peptizing agent can be one or more mixing in formic acid, acetic acid, citric acid, malonic acid, the nitric acid; Roasting rises to 600～800 ℃ with the programming rate of 0.5～2 ℃/min, and constant temperature calcining made alumina support in 2～4 hours.
10. method according to claim 3, it is characterized in that: described infusion process adopts saturated infusion process or unsaturated infusion process, the solution that contains Mo is a kind of or mixture in ammonium molybdate and the ammonium paramolybdate, and the solution that contains Ni is one or more mixing in nickel nitrate, nickel acetate and the basic nickel carbonate; Drying behind the dipping active metal component is to descend dry 1 ~ 5 hour at 80 ~ 140 ℃, and roasting is 500 ~ 600 ℃ of lower roastings 1 ~ 5 hour.
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| CN104646009A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Inferior heavy oil hydrodesulfurization catalyst and preparation method thereof |
| CN104785274A (en) * | 2015-04-13 | 2015-07-22 | 河北工业大学 | Method for preparing bulk Ni-Mo hydrodeoxygenation catalyst with large aperture |
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