CN106140182B - A kind of preparation method of heavy oil hydrogenating treatment catalyst - Google Patents
A kind of preparation method of heavy oil hydrogenating treatment catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of heavy oil hydrogenating treatment catalyst, including following content：（1）Physics expanding agent I is impregnated respectively with hydrogenation active component maceration extract I and titaniferous solution I, impregnates physics expanding agent II respectively with hydrogenation active component maceration extract II and titaniferous solution II, and the physics expanding agent I and physics expanding agent II after dipping are through drying for standby；（2）By step（1）Into plastic, modified aluminium oxide supports are made in extrusion, drying, roasting for physics expanding agent I, physics expanding agent II and the boehmite dry glue powder of gained, chemical enlargement agent, extrusion aid, peptizing agent kneading；（3）With hydrogenation active component maceration extract III impregnation steps（2）Through drying, roasting, heavy oil hydrogenating treatment catalyst is made in obtained modified aluminium oxide supports.Catalyst activity metal prepared by this method content at macropore is relatively high, content is relatively low at aperture, and for multicomponent reactive component at macropore, the utilization rate of macropore significantly improves, which has preferable hydrodesulfurization and hydrodenitrogenationactivity activity.
Description
Technical field
The present invention relates to a kind of preparation methods of heavy oil hydrogenating treatment catalyst.
Background technology
With the raising that raw material deep processing requires in world wide, main energy sources structure is gradually to macromolecular and high-carbon direction
Development, it is even more so for China of the universal heaviness of crude oil.Impurity such as S, N, carbon residue and a huge sum of money in heavy oil particularly residual oil
Category etc. must effectively remove the requirement that could meet catalytic cracking feeds, if impurity content is excessively high to lead to downstream catalytic cracking
Catalyst poisoning.Hydrocarbon hydrogenizing treamtent catalyst is mostly using aluminium oxide as carrier at present, using Mo and/or W and Ni and/or Co as activity
Component.
CN1289822A discloses a kind of heavy oil hydrogenating treatment catalyst and preparation method thereof, and the catalyst is using aluminium oxide as load
Body matrix, with vib metals and group VIII metallic element, particularly Mo-Ni for active component, addition Ti is helped for activity
Agent.The preparation method of catalyst uses full kneading method, process roasting will can be converted into the aluminum hydroxide solid elastomer powder of aluminium oxide,
A kind of alkaline solution containing vib metals, abundant kneading are first added in, until aluminium hydrate powder is soaked completely by alkalies, then is added
Enter the acid solution of a kind of group VIII and vib metals element, kneading to material is into plastic, extruded moulding, drying, roasting
It burns to get catalyst.
CN1110304A discloses a kind of heavy oil hydrogenating treatment catalyst, using siliceous and phosphorus aluminium oxide as carrier, particularly
The carrier being mixed by a kind of siliceous and phosphorus macroporous aluminium oxide and small porous aluminum oxide, supports molybdenum, nickel, P elements.Due to carrying
Silicon and phosphorus in body are added in substep plastic method, and silicon and phosphorus is made largely to be dispersed in oxidation aluminium surface, can give full play to work
With, while catalyst has suitable surface nature, has good nitrogen removal performance.
CN1854260A discloses a kind of catalyst for hydrotreating heavy fraction of oil and preparation method thereof.Catalyst of the present invention carries
Body is made of, and support at least one vib metals and group VIII siliceous and boron macroporous aluminium oxide and small porous aluminum oxide
Metallic element.Silicon and boron in carrier are added in macroporous aluminium oxide by substep plastic method, and silicon and boron largely disperse
In oxidation aluminium surface, synergistic effect can be more fully played.Simultaneously catalyst have suitable Acidity, thus surface go out it is higher
Hydrodenitrogenationactivity activity and activity stability.
Catalyst for hydrotreatment of residual oil active metal component prepared by the above method punishes cloth in the macropore and aperture of carrier
More uniform, the utilization rate for leading to macropore is relatively low.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of heavy oil hydrogenating treatment catalyst.This method
The catalyst activity metal of preparation content at macropore is relatively high, and content is relatively low at aperture, and is polynary work at macropore
Property component, the utilization rate of macropore significantly improves, which has preferable hydrodesulfurization and hydrodenitrogeneration
Activity.
The preparation method of the heavy oil hydrogenating treatment catalyst of the present invention, including following content：
（1）Physics expanding agent I is impregnated respectively with hydrogenation active component maceration extract I and titaniferous solution I, uses hydrogenation active component
Maceration extract II and titaniferous solution II impregnates physics expanding agent II respectively, physics expanding agent I and physics expanding agent II warps after dipping
Drying for standby；
（2）By step（1）Physics expanding agent I, the physics expanding agent II and boehmite dry glue powder, chemical enlargement of gained
Into plastic, modified aluminium oxide supports are made in extrusion, drying, roasting for agent, extrusion aid, peptizing agent kneading；
（3）With hydrogenation active component maceration extract III impregnation steps（2）Obtained modified aluminium oxide supports, through drying, roasting
It burns, heavy oil hydrogenating treatment catalyst is made.
In the method for the present invention, the hydrogenation active component is VIB and/or group VIII metal, and vib metals are molybdenum
And/or tungsten, the metal of group VIII is cobalt and/or nickel；Hydrogenation active component maceration extract can be to contain hydrogenation active component
One kind in acid solution, aqueous solution or ammonia solution.
In the method for the present invention, step（1）The hydrogenation active component I is at least containing a kind of and step（3）Hydrogen is added to live
Property component III form different active components, such as step（3）Hydrogenation active component III be molybdenum/nickel, step（1）The activity
Component I can be the mixing of one or more of molybdenum/cobalt, tungsten/cobalt, tungsten/nickel, molybdenum/cobalt/nickel, tungsten/cobalt/nickel, tungsten/molybdenum/cobalt/nickel.
In the method for the present invention, step（1）The hydrogenation active component II is at least containing a kind of and step（3）Hydrogen is added to live
Property component III form different active components, such as step（3）Hydrogenation active component III be molybdenum/nickel, step（1）Described plus hydrogen
Active component II can be one or more of molybdenum/cobalt, tungsten/cobalt, tungsten/nickel, molybdenum/cobalt/nickel, tungsten/cobalt/nickel, tungsten/molybdenum/cobalt/nickel
Mixing.
In the method for the present invention, step（1）In the hydrogenation active component maceration extract I, vib metals weight content with
Oxide is calculated as the 0.8wt%-1.0wt% of final catalyst weight, and group VIII weight metal content is calculated as finally with oxide
The 0.5wt%-0.7wt% of catalyst weight.Hydrogenation active component maceration extract I dosages are the saturated water adsorptive value of physics expanding agent I.
In the method for the present invention, step（1）In the hydrogenation active component maceration extract II, vib metals weight content
The 0.3wt%-0.5wt% of final catalyst weight is calculated as with oxide, group VIII weight metal content is calculated as most with oxide
The 0.2wt%-0.4wt% of whole catalyst weight.The saturation that hydrogenation active component maceration extract II dosages are physics expanding agent II absorbs water
Amount.
In the method for the present invention, step（1）The titaniferous solution can be butyl titanate, isopropyl titanate or metatitanic acid four
The ethanol solution or titanium tetrachloride solution of ethyl ester etc., the dosage of titaniferous solution I are the saturated water adsorptive value of physics expanding agent I, dipping
Ti content accounts for the 0.6%-0.8% of catalyst weight in terms of oxide in physics expanding agent I afterwards；The dosage of titaniferous solution II is physics
The saturated water adsorptive value of expanding agent II, the content of titanium accounts for catalyst weight in terms of oxide in physics expanding agent II after dipping
0.1%-0.3%。
In the method for the present invention, step（1）The physics expanding agent is mixed for one or more of carbon black powder, charcoal or sawdust
It closes, the grain size of physics expanding agent I is 600-1000 mesh, and the grain size of physics expanding agent II is 300-500 mesh.
In the method for the present invention, step（1）The drying condition dries in the shade or 1-10 hours dry in 50-120 DEG C for nature.
In the method for the present invention, step（2）The boehmite dry glue powder can be prepared using any one method
Boehmite dry glue powder.
In the method for the present invention, step（2）Described in physics expanding agent I addition be boehmite dry glue powder weight
3%-5%, the addition of physics expanding agent II is the 4%-8% of boehmite dry glue powder weight.
In the method for the present invention, step（2）Mass concentration is preferably added in the kneading process as 1%-5% polyethylene glycol water
The average molecular weight of solution, wherein polyethylene glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 grams/100
Gram boehmite dry glue powder.
In the method for the present invention, step（2）The chemical enlargement agent is one or more of phosphoric acid or phosphate, preferably
Phosphate, wherein phosphate are selected from one or more of ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate, and chemical enlargement agent adds in
Measure the 3%-5% for boehmite dry glue powder weight.
In the method for the present invention, step（2）The extrusion aid is one kind or several in sesbania powder, starch or methylcellulose
Kind, preferably sesbania powder, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
In the method for the present invention, step（2）The peptizing agent is one kind or several in formic acid, acetic acid, citric acid or nitric acid
Kind mixing, addition is the 3%-10% of boehmite dry glue powder weight, depending on last molding effect.
In the method for the present invention, step（2）The drying condition is 1-10 hours dry at 100-130 DEG C；Roasting process
To be roasted 2-4 hours at 500-650 DEG C.
In the method for the present invention, step（3）The hydrogenation active component maceration extract III is to form to count according to final catalyst
It calculates and prepares.In hydrogenation active component maceration extract III, vib metals content is calculated as 7-15g/100ml, Section VII race with oxide
Tenor is calculated as 0.8-3g/100ml with oxide, and volume impregnation, incipient impregnation or spray impregnating side may be used
Formula, dip time are 1-5 hours.
In the method for the present invention, step（3）The drying condition is 6-10 hours dry at 80-120 DEG C；The roasting
Condition is roasts 3-6 hours at 400-600 DEG C.
Suitable titaniferous solution and active metallic element are impregnated on physics expanding agent by the method for the present invention, and with intending thin water
Alumina support is made in aluminium stone kneading, molding, drying, roasting, and catalyst is finally made in dipping active component.Physics expanding agent is pre-
The active component of dipping and at least a kind of difference of active component of later stage dipping, form after the roasting of physics expanding agent in this way
Multicomponent reactive component is formed at macropore, improves the catalytic activity of active component.Physics expanding agent of the selection with different-grain diameter,
Make to form the macroporous structure accordingly with different pore size in final catalyst, be conducive to mass transfer and the diffusion of reactant.In addition,
Active metal component is loaded at corresponding macropore, is significantly increased the active component content in final catalyst at macropore, is carried
The high utilization rate of macropore.The presence of titanium has adjusted the surface nature of carrier at macropore, improves the phase of active component and carrier
Interaction improves the catalytic activity of active metal.The addition of polyethylene glycol makes physics expanding agent and boehmite during kneading
It is uniformly mixed, improves the uniformity coefficient of macropore.
Specific embodiment
The effect further illustrated the present invention with reference to embodiment and effect, but it is not limited to following embodiment.
Embodiment 1
Grain size is weighed as 800 mesh（Particle by 800 mesh sieve pores but can can't pass 1000 mesh sieve pores）Carbon black powder I4.3 put
It rolls in pot in spray, under rotary state, is sprayed with carbon black powder of the atomizing type into rolling pot containing 0.8 gram of molybdenum oxide, cobalt oxide
0.6 gram of active metal maceration extract makes carbon black powder adsorption saturation, and the carbon black powder after dipping is 3 hours dry in 110 DEG C.After dry
Carbon black powder be replaced in spray rolling pot in, under rotary state, with atomizing type to rolling pot in carbon black powder spray containing oxidation
The ethanol solution for the butyl titanate that 0.6 gram of titanium makes carbon black powder adsorption saturation, and the carbon black powder after dipping is 3 hours dry in 110 DEG C
It is spare.
It is 300 to weigh grain size（Particle by 300 mesh sieve pores but can can't pass 325 mesh sieve pores）II11.4 grams of purpose carbon black powder
It is placed in spray rolling pot, under rotary state, is sprayed with carbon black powder of the atomizing type into rolling pot containing 0.4 gram of molybdenum oxide, oxidation
The active metal maceration extract of 0.2 gram of cobalt makes carbon black powder adsorption saturation, and the carbon black powder after dipping is 3 hours dry in 110 DEG C.By drying
Carbon black powder afterwards is replaced in spray rolling pot, under rotary state, is sprayed with carbon black powder of the atomizing type into rolling pot oxygen-containing
Changing the ethanol solution of the butyl titanate of 0.2 gram of titanium makes carbon black powder adsorption saturation, and the carbon black powder after dipping is in 110 DEG C dry 3 small
When it is spare.
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 fields
Cyanines powder, 3 grams of ammonium phosphate are uniformly mixed, and it is 3% to add in mass concentration, and average molecular weight is 4,000 43 grams of Aqueous Solutions of Polyethylene Glycol
Kneading, then adds in that continue kneading dissolved with the aqueous solution of 5 grams of nitric acid in right amount uniform, is extruded on screw rod banded extruder a diameter of
The cloverleaf pattern item of 1.8mm dries 3 hours in 120 DEG C, dried molding is roasted 4 hours at a temperature of 550 DEG C.
Above-mentioned material is placed in beaker, contains MoO with 150 milliliters310 grams/100 milliliters, NiO1.2 grams/100 milliliters
Molybdenum-nickel-ammonia active metal salt solution impregnated carrier 5 hours filters off redundant solution, and 120 DEG C dry 2 hours, then roasted at 550 DEG C
Burn 5 hours obtained catalyst C1, catalyst MoO3Mass percentage is 11.2wt%, and NiO mass percentages are
1.1wt%, CoO mass percentages are 0.8wt%, and titanium oxide percentage composition is 0.8wt%.
Embodiment 2
With embodiment 1, only carbon black powder I weight is 7.2 grams, and grain size is 600 mesh（Particle can be by 600 mesh sieve pores but logical
But 800 mesh sieve pore）, containing 0.9 gram of tungsten oxide in hydrogenation active component maceration extract I, 0.5 gram of nickel oxide is oxygen-containing in titaniferous solution I
Change 0.7 gram of titanium, titanium solution is tetraethyl titanate ethanol solution, and carbon black powder II weight is 5.7 grams, and grain size is 400 mesh（Particle can lead to
It crosses 400 mesh sieve pores but can't pass 500 mesh sieve pores）, containing 0.3 gram of tungsten oxide, nickel oxide 0.4 in hydrogenation active component maceration extract II
Gram, containing 0.1 gram of titanium oxide in titaniferous solution II, titanium solution is tetraethyl titanate ethanol solution, the addition of polyglycol solution
Restrain to obtain catalyst C2 of the present invention, catalyst MoO for 433Mass percentage is 10wt%, WO3Mass percentage is
1.2wt%, NiO mass percentage are 1.2wt%, and titanium oxide mass percentage is 0. 8wt%.
Embodiment 3
With embodiment 1, only carbon black powder I weight is 5.7 grams, and grain size is 1000 mesh（Particle can by 1000 mesh sieve pores but
It can't pass 1340 mesh sieve pores）, containing 1.0 grams of tungsten oxide in hydrogenation active component maceration extract I, 0.7 gram of cobalt oxide, in titaniferous solution I
Containing 0.8 gram of titanium oxide, carbon black powder II weight is 8.6 grams, and grain size is 500 mesh（Particle by 500 mesh sieve pores but can can't pass 600
Mesh sieve pore）, containing 0.5 gram of tungsten oxide in hydrogenation active component maceration extract II, 0.3 gram of cobalt oxide contains titanium oxide in titaniferous solution II
0.3 gram, the addition of polyglycol solution restrains to obtain catalyst C3 of the present invention, catalyst MoO for 1003Mass percentage
For 10wt%, WO3Mass percentage is 1.5wt%, and NiO mass percentages are 1.2wt%, and CoO mass percentages are
1.0wt%, titanium oxide mass percentage are 1.1wt%.
Embodiment 4
With embodiment 1, only carbon black powder changes charcoal into, and charcoal I weight is 5 grams, oxygen-containing in hydrogenation active component maceration extract I
Change 0.85 gram of tungsten, 0.55 gram of nickel oxide, charcoal II weight is 7.2 grams, contains molybdenum oxide 0.45 in hydrogenation active component maceration extract II
Gram, 0.3 gram of cobalt oxide, activity component impregnation liquid is containing 0.3 gram of molybdenum oxide, 0.4 gram of tungsten oxide, nickel oxide 0.05 when impregnating charcoal
Gram.The addition of polyglycol solution restrains to obtain catalyst C4 of the present invention, catalyst MoO for 1003Mass percentage is
10.5wt%, WO3Mass percentage is 0.85wt%, and NiO mass percentages are 1.7wt%, and CoO mass percentages are
0.3wt%, titanium oxide mass percentage are 0.8wt%.
Embodiment 5
With embodiment 1, only carbon black powder I weight is 6.4 grams, and carbon black powder II weight is 10 grams, and polyglycol solution adds
Enter amount for 86 grams, with 150 milliliters containing MoO during dipping38 grams/100 milliliters, NiO0.9 grams/100 milliliters of molybdenum-nickel-ammonia activity gold
Belong to salt solution impregnated carrier and catalyst C5 of the present invention, catalyst MoO is made3Mass percentage is 9.2wt%, NiO mass hundred
It is 0.9wt% to divide content, and CoO mass percentages are 0.8wt%, and titanium oxide mass percentage is 0.8wt%.
Embodiment 6
With embodiment 1, polyglycol solution is not added in when only boehmite is mixed with carbon black powder the present invention is made and urged
Agent C6, catalyst MoO3Mass percentage is 11.2wt%, and NiO mass percentages are 1.1wt%, CoO mass percentages
Content is 0.8wt%, and titanium oxide percentage composition is 0.8wt%.
Comparative example 1
With example 1, only active metal is unsupported on carbon black powder, but is added in when kneading, prepare have with
The comparative catalyst C7 of 1 same composition of embodiment.
Comparative example 2
With example 1, only titanium is unsupported on carbon black powder, but is added in when kneading, and preparing has and 1 phase of embodiment
With the catalyst C8 of composition.
Comparative example 3
With example 1, only active metal and titanium are unsupported on carbon black powder, but are added in when kneading, and preparation has
The catalyst C9 of composition same as Example 1.
Comparative example 4
Grain size is weighed as 800 mesh（Particle by 800 mesh sieve pores but can can't pass 1000 mesh sieve pores）Carbon black powder I15.6 put
It rolls in pot in spray, under rotary state, is sprayed with carbon black powder of the atomizing type into rolling pot containing 1.2 grams of molybdenum oxide, cobalt oxide
0.8 gram of active metal maceration extract makes carbon black powder adsorption saturation, and the carbon black powder after dipping is 3 hours dry in 110 DEG C.After dry
Carbon black powder be replaced in spray rolling pot in, under rotary state, with atomizing type to rolling pot in carbon black powder spray containing oxidation
The ethanol solution for the butyl titanate that 0.8 gram of titanium makes carbon black powder adsorption saturation, and the carbon black powder after dipping is 3 hours dry in 110 DEG C
It is spare.
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 fields
Cyanines powder, 3 grams of ammonium phosphate are uniformly mixed, and it is 3% to add in mass concentration, and average molecular weight is 4,000 43 grams of Aqueous Solutions of Polyethylene Glycol
Kneading, then adds in that continue kneading dissolved with the aqueous solution of 5 grams of nitric acid in right amount uniform, is extruded on screw rod banded extruder a diameter of
The cloverleaf pattern item of 1.8mm dries 3 hours in 120 DEG C, dried molding is roasted 4 hours at a temperature of 550 DEG C.
Above-mentioned material is placed in beaker, contains MoO with 150 milliliters310 grams/100 milliliters, NiO1.2 grams/100 milliliters
Molybdenum-nickel-ammonia active metal salt solution impregnated carrier 5 hours filters off redundant solution, and 120 DEG C dry 2 hours, then roasted at 550 DEG C
Burn 5 hours obtained catalyst C10, catalyst MoO3Mass percentage is 11.2wt%, and NiO mass percentages are
1.1wt%, CoO mass percentages are 0.8wt%, and titanium oxide percentage composition is 0.8wt%.
The catalyst prepared to examples detailed above and comparative example carries out activity rating, more above-mentioned each catalyst activity.Raw material
Oil nature is shown in Table 1.When evaluating catalyst, catalyst bed is passed through after hydrogen and feedstock oil mixing, first passes through and adds hydrogen
Catalyst for demetalation, using above each example catalyst.The process conditions all same used during evaluation, respectively：Reaction pressure,
14.6MPa, 400 DEG C of reaction temperature, total liquid hourly space velocity (LHSV), 0.6 h-1, hydrogen to oil volume ratio, 1000.Reactor volume is：Ф25mm×
2000mm.Loaded catalyst is respectively：Catalyst for demetalation 80cm3, more than each example catalyst, 120 cm3.Operate 200h's
Activity evaluation is shown in Table 2.
Table 1.
Table 2.
Catalyst provided by the invention adds hydrogen to take off compared with reference catalyst with higher it can be seen from 2 data of table
Sulphur and hydrodenitrogenationactivity activity.
Claims (10)
1. a kind of preparation method of heavy oil hydrogenating treatment catalyst, it is characterised in that including following content：（1）With hydrogenation activity group
Maceration extract I and titaniferous solution I is divided to impregnate physics expanding agent I respectively, with II points of hydrogenation active component maceration extract II and titaniferous solution
Not Jin Zi physics expanding agent II, the physics expanding agent I and physics expanding agent II after dipping are through drying for standby；（2）By step（1）Institute
Physics expanding agent I, physics expanding agent II and boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizing agent kneading into
Modified aluminium oxide supports are made in plastic, extrusion, drying, roasting；（3）With hydrogenation active component maceration extract III impregnation steps
（2）Through drying, roasting, heavy oil hydrogenating treatment catalyst is made in obtained modified aluminium oxide supports；The hydrogenation active component
For VIB and/or group VIII metal, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Hydrogen is added to live
Property component maceration extract be one kind in the acid solution containing hydrogenation active component, aqueous solution or ammonia solution；Step（1）Described adds
Hydrogen activity component I is at least containing a kind of and step（3）Hydrogenation active component III forms different active components；Step（1）Institute
The hydrogenation active component II stated is at least containing a kind of and step（3）Hydrogenation active component III forms different active components；Step
Suddenly（1）In the hydrogenation active component maceration extract I, vib metals weight content is calculated as final catalyst weight with oxide
The 0.8wt%-1.0wt% and/or group VIII weight metal content of amount are calculated as final catalyst weight with oxide
0.5wt%-0.7wt%；Hydrogenation active component maceration extract I dosages are the saturated water adsorptive value of physics expanding agent I；Step（1）Described
In hydrogenation active component maceration extract II, vib metals weight content is calculated as the 0.3wt%- of final catalyst weight with oxide
0.5wt% and/or group VIII weight metal content are calculated as the 0.2wt%-0.4wt% of final catalyst weight with oxide；Add
Hydrogen activity component maceration extract II dosages are the saturated water adsorptive value of physics expanding agent II；Step（1）The titaniferous solution is metatitanic acid
One kind in the ethanol solution or titanium tetrachloride solution of four butyl esters, isopropyl titanate or tetraethyl titanate；Step（1）Described contains
The dosage of titanium solution I is the saturated water adsorptive value of physics expanding agent I, and Ti content is accounted in terms of oxide in physics expanding agent I after dipping
The 0.6%-0.8% of catalyst weight；Step（1）The saturation that the dosage of the titaniferous solution II is physics expanding agent II absorbs water
It measures, the content of titanium accounts for the 0.1%-0.3% of catalyst weight in terms of oxide in physics expanding agent II after dipping；Step（1）It is described
Physics expanding agent is the mixing of one or more of carbon black powder, charcoal or sawdust, and the grain size of physics expanding agent I is 600-1000
Mesh, the grain size of physics expanding agent II is 300-500 mesh.
2. according to the method for claim 1, it is characterised in that：Step（1）The drying condition for nature dry in the shade or in
50-120 DEG C 1-10 hours dry.
3. according to the method for claim 1, it is characterised in that：Step（2）Described in the addition of physics expanding agent I be
The addition of the 3%-5% of boehmite dry glue powder weight, physics expanding agent II are the 4%- of boehmite dry glue powder weight
8%。
4. according to the method for claim 1, it is characterised in that：Step（2）Mass concentration is added in the kneading process
For 1%-5% Aqueous Solutions of Polyethylene Glycol, the wherein average molecular weight of polyethylene glycol is 1000-4000, and Aqueous Solutions of Polyethylene Glycol adds
Enter amount for 30-70 grams/100 grams boehmite dry glue powders.
5. according to the method for claim 1, it is characterised in that：Step（2）The chemical enlargement agent is phosphoric acid or phosphoric acid
One or more of salt, chemical enlargement agent addition are the 3%-5% of boehmite dry glue powder weight.
6. according to the method for claim 1, it is characterised in that：Step（2）The extrusion aid is sesbania powder, starch or first
One or more of base cellulose, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
7. according to the method for claim 1, it is characterised in that：Step（2）The peptizing agent is formic acid, acetic acid, lemon
The mixing of one or more of acid or nitric acid, addition are the 3%-10% of boehmite dry glue powder weight.
8. according to the method for claim 1, it is characterised in that：Step（2）The drying condition is to be done at 100-130 DEG C
It is 1-10 hours dry；Roasting process is to be roasted 2-4 hours at 500-650 DEG C.
9. according to the method for claim 1, it is characterised in that：Step（3）The hydrogenation active component maceration extract III
In, vib metals content is calculated as 7-15g/100mL with oxide and/or group VIII tenor is calculated as with oxide
0.8-3g/100mL。
10. according to the method for claim 1, it is characterised in that：Step（3）The drying condition is at 80-120 DEG C
It is 6-10 hours dry；The roasting condition is roasts 3-6 hours at 400-600 DEG C.
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| CN110935462B (en) * | 2018-09-25 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
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| CN111375401B (en) * | 2018-12-29 | 2022-08-12 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN111821988B (en) * | 2019-04-17 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN112717949B (en) * | 2019-10-28 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrofining 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 |
| CN114433109B (en) * | 2020-10-19 | 2023-05-30 | 中国石油化工股份有限公司 | Hydrogenation pretreatment catalyst and preparation method and application thereof |
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| CN116328782B (en) * | 2021-12-24 | 2024-10-15 | 中国石油天然气股份有限公司 | Hydrodemetallization catalyst for titanium-containing residual oil and preparation method thereof |
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