CN109718863A - A kind of carrier for hydrogenation protecting agent, catalyst and preparation method thereof - Google Patents
A kind of carrier for hydrogenation protecting agent, catalyst and preparation method thereof Download PDFInfo
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- CN109718863A CN109718863A CN201711039334.XA CN201711039334A CN109718863A CN 109718863 A CN109718863 A CN 109718863A CN 201711039334 A CN201711039334 A CN 201711039334A CN 109718863 A CN109718863 A CN 109718863A
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Abstract
The carrier that the invention discloses a kind of for hydrogenation protecting agent, catalyst and preparation method thereof.The carrier is alumina support, including main body aluminium oxide and rod-like aluminum oxide, and the main body aluminium oxide is the aluminium oxide with micron order duct, and wherein at least part rod-like aluminum oxide is distributed in the outer surface and micron order duct of main body aluminium oxide.The preparation method of the carrier is to prepare support intermediate first, then immerses support intermediate in ammonium bicarbonate soln, then sealing heat treatment, and carrier is made through drying, roasting in material after heat treatment.The carrier has the characteristics such as solid tumor performance is good, appearance impurity ability is strong, metal removal activity is high, especially suitable in residual hydrocracking technique as hydrotreating guard catalyst for residual oil.
Description
Technical field
The present invention relates to a kind of alumina supports, catalyst and preparation method thereof, add more particularly to one kind for residual oil
The protectant carrier of hydrogen, catalyst and preparation method thereof.
Background technique
Currently, hydrotreating is still to produce the most important means of high-quality, environmental-friendly oil product.Hydrotreating techniques
Core be catalyst, for heavy constituent (such as VGO, especially residual oil) hydrotreating of petroleum, the aperture of catalyst
The performance of catalyst activity will be directly affected with the size of Kong Rong.
The major function of hydrotreating guard catalyst for residual oil is the substances such as iron, calcium, nickel and vanadium in removing residual oil.Existing residual hydrogenation
Carrier material used in guard catalyst is generally macroporous aluminium oxide and its modified product.The common side of preparation of macroporous aluminium oxide
Method has: physics port-creating method and high-temperature roasting method etc..
The predecessor of the physics expanding agents such as the carbon black such as US4448896, US4102822, starch and activated alumina or aluminium oxide
Kneading expands the aperture of alumina support, and the dosage of physics expanding agent is aluminium oxide 10wt% or more, and the above method is to aoxidize
Physics expanding agent is added in aluminium predecessor, and the dosage of expanding agent is big, causes the pore size distribution disperse of aluminium oxide, macroperforation is not
It can be formed and be continuous through duct, duct is ink bottle-type, and aperture is smaller, and intensity is poor.
CN102861617A discloses a kind of preparation method of double-hole-structuralumina alumina supporter.This method includes weighing one
Quantitative boehmite dry glue powder, is uniformly mixed with appropriate peptizing agent, extrusion aid, states appropriate carbon is added in material then up
Sour hydrogen aqueous ammonium, by resulting material kneading at plastic, extruded moulding, molding materials are placed in sealing container at through hydro-thermal
It is roasted after reason and alumina support is made.Although the alumina support of technology preparation has dual pore size distribution, 1000nm or more
Hole content it is lower, be unfavorable for the precipitating and removing of the substances such as iron in residual oil, calcium, nickel, vanadium.
CN1120971A discloses a kind of preparation method of alumina supporter.This method is by two kinds or two kinds
The boehmite dry gum method of the above different material route methods preparation uniformly mixes, and then carries out peptization, molding, drying and roasting
It burns processing and is made, the specific surface area of gained aluminium oxide is 100-200m2/ g, Kong Rongwei 0.7-1.6mL/g, bimodal hole collect respectively
In in 3.5-35nm and 100nm area above, the wherein 10%-56% of Kong Rongwei total pore volume shared by the hole of 100nm or more.But hole
Diameter is that the hole content of 1000nm or more is lower, is unfavorable for the precipitating and removing of the substances such as iron in residual oil, calcium, nickel and vanadium.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of hydrogenation protecting catalyst carriers plus hydrogen to protect
Protect catalyst and preparation method thereof.Good with solid tumor performance using the hydrogenation protecting catalyst of carrier of the present invention preparation,
Hold the characteristics such as impurity ability is strong, metal removal activity is high, especially suitable in residual hydrocracking technique.
Hydrogenation protecting catalyst carrier of the invention, the carrier are alumina support, including main body aluminium oxide and rodlike
Aluminium oxide, the main body aluminium oxide are the aluminium oxide with micron order duct, and wherein at least part rod-like aluminum oxide is distributed in
In the micron order duct that the outer surface of main body aluminium oxide and bore dia D are 5-10 μm, rod-like aluminum oxide length is 1-12 μm, diameter
For 100-300 nm；The pore size distribution of the carrier is as follows: bore dia is 10% of Kong Rongwei total pore volume shared by the hole below 10nm
Hereinafter, bore dia is the 30%-50% of Kong Rongwei total pore volume shared by the hole of 15-35nm, bore dia is shared by the hole of 100-800nm
Kong Rongwei total pore volume 30%-45%, bore dia greater than 1000nm hole shared by Kong Rongwei total pore volume 10%-26%, preferably
For 10%-24%.
Micron order duct involved in the present invention refers to that bore dia D is 5-10 μm of micron order duct
In carrier of the present invention, rod-like aluminum oxide is substantially distributed in the outer surface and micron order duct of main body aluminium oxide.It is distributed in
Rod-like aluminum oxide in the outer surface and micron order duct of main body aluminium oxide accounts for 95% or more of all rod-like aluminum oxide total weights,
Preferably 97% or more.
In carrier of the present invention, the length of rod-like aluminum oxide is that micron order duct is straight with 0.3D-0.9D(in micron order duct
0.3-0.9 times of diameter) based on, i.e., rod-like aluminum oxide in micropore by weight about 85% or more length be 0.3D-0.9D；Outside
The length of surface rod-like aluminum oxide based on 3-8 μm, i.e., rod-like aluminum oxide on outer surface by weight about 85% or more length
It is 3-8 μm.
Wherein, in the micron order duct of main body aluminium oxide, rod-like aluminum oxide is distributed with unordered interlaced state.
Wherein, at least one end of at least partly rod-like aluminum oxide is attached in the micron order cell walls of main body, preferably at least part
At least one end of rod-like aluminum oxide combines in cell walls in the micron-scale, forms one with main body aluminium oxide.Further preferably, micron
At least one end of rod-like aluminum oxide in grade duct combines in cell walls in the micron-scale, forms one with main body aluminium oxide.
Wherein, on the outer surface of main body aluminium oxide, rod-like aluminum oxide is distributed with unordered interlaced state.
Wherein, one end of at least partly rod-like aluminum oxide is attached on the outer surface of main body aluminium oxide, preferably at least part
One end of rod-like aluminum oxide is incorporated on the outer surface of main body aluminium oxide, and the other end is protruding, forms one with main body aluminium oxide
Body.Further preferably, one end of the rod-like aluminum oxide on the outer surface of main body aluminium oxide is incorporated in the outer surface of main body aluminium oxide
On, the other end is protruding, forms one with main body.
In carrier of the present invention, the coverage rate of rod-like aluminum oxide accounts for 70%-95% in the micron order duct of main body aluminium oxide, wherein
The surface that the coverage rate refers to that the inner surface in the micron order duct of main body aluminium oxide is accounted for by rod-like aluminum oxide accounts for main body
The percentage of micron order inner surfaces of pores.The coverage rate of rod-like aluminum oxide accounts for 70%-95% on the outer surface of main body aluminium oxide, wherein
The coverage rate refers to that the surface accounted on the outer surface of main body aluminium oxide by rod-like aluminum oxide accounts for the outer of main body aluminium oxide
The percentage on surface.
Carrier of the present invention, property are as follows: specific surface area 140-290m2/ g, Kong Rong 0.6-1.5mL/g, crushing strength
For 9-18N/mm.
In carrier of the present invention, concentrated between 100-800nm by rod-like aluminum oxide with the hole of unordered interlaced formation.
Second aspect of the present invention provides a kind of preparation method of hydrogenation protecting catalyst carrier, comprising:
(1) support intermediate is prepared；
(2) by support intermediate immerse ammonium bicarbonate soln in, then sealing heat treatment, after heat treatment material through drying, roasting,
Carrier is made.
In the preparation method of carrier of the present invention, the property of step (1) described support intermediate is as follows: specific surface area 120-
280m2/ g, Kong Rongwei 0.7-1.4mL/g, pore size distribution are as follows: bore dia is Kong Rongwei total pore volume shared by the hole of 15-35nm
25%-45%, bore dia are the 15%-45% of Kong Rongwei total pore volume shared by the hole of 100-800nm, the hole that bore dia is 5 μm or more
Kong Rongwei total pore volume 10%-20% shared by (preferably bore dia is 5-10 μm of hole).
In the preparation method of carrier of the present invention, step (1) described support intermediate can be prepared using conventional method, such as
Physics expanding agent method, detailed process is as follows: by boehmite and physics expanding agent kneading and compacting, molding through drying, roasting,
Obtain support intermediate.The physics expanding agent can be one or more of active carbon, sawdust, polyvinyl alcohol, it is added
The partial size of physics expanding agent is selected according to the micron order duct of alumina support intermediate, wherein the physics expanding agent
Partial size is preferably about 5-10 μm, and physics expanding agent additional amount is the 21wt%-35wt% of body weight among alumina support.Described
Kneading and compacting can be carried out using conventional method in that art, in forming process, can according to need and conventional shaping assistant is added,
Such as one of peptizing agent, extrusion aid etc. or a variety of.The peptizing agent is in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc.
One or more, the extrusion aid refer to the substance for being conducive to extrusion forming, such as sesbania powder.The drying of the molding and
Roasting condition is as follows: drying temperature is 100-160 DEG C, and drying time is 6-10 hours, and the maturing temperature is 600-750
DEG C, calcining time is 4-6 hours, roasts in oxygen-containing atmosphere, preferably carries out in air atmosphere.
The dosage of ammonium bicarbonate soln described in step (2) and the mass ratio of step (1) resulting vehicle intermediate are 4:1-
10:1, the mass concentration of ammonium bicarbonate soln are 15%-25%.
Sealing heat treatment temperature described in step (2) is 120-170 DEG C, and the processing time is 4-8 hours, heating rate 5
DEG C/min-20 DEG C/min, it seals heat treatment and generally carries out in a high pressure reaction kettle.
In the preparation method of alumina support of the present invention, step (2) preferably, is sealed pre- place before sealing heat treatment
Reason, pretreatment temperature are 60-100 DEG C, and it is 2-4 hour that constant temperature, which handles the time, heating rate before pretreatment for 10-20 DEG C/
Min, pretreated heating rate be 5-10 DEG C/min, and pretreated heating rate than pretreatment before it is low at least
3 DEG C/min, preferably at least 5 DEG C/min.
In the method for the present invention, drying temperature described in step (2) is 100-160 DEG C, and drying time is 6-10 hours, described
Maturing temperature be 600-750 DEG C, calcining time be 4-6 hours.
In the method for the present invention, alumina support made from step (2) is right compared with step (1) alumina support intermediate
In the pore size distribution that bore dia is 15-35nm and 100-800nm, distribution of the alumina support than support intermediate is more concentrated.
Third aspect present invention provides a kind of hydrogenation protecting catalyst, including carrier and active metal component, wherein carrying
Body uses above-mentioned carrier.
In the hydrogenation protecting catalyst, active metal component is group VIB and/or group VIII metal.Group VIB
Metal is selected from one of W, Mo or a variety of, and group VIII metal is selected from one of Co, Ni or a variety of.With the weight of catalyst
On the basis of, the content of reactive metal oxides is 2.5%-10.0%, preferably 2.5%-9.0%, further preferably group VIB gold
The content for belonging to oxide is 2.0%-.8.5%, and the content of group VIII metal oxide is 0.3%-2.5%.
Hydrogenation protecting catalyst of the present invention can be prepared using conventional method, such as infusion process, kneading method etc., it is preferred to use
Infusion process.The carrier using infusion process supported active metals component can be used and be sprayed using conventional infusion process preparation
Method, saturation infusion process or supersaturated infusion process.After impregnating active metal component, through dry and roasting, obtains of the invention plus hydrogen and protect
Protect catalyst.The drying condition is to be dried at a temperature of 100-130 DEG C 1-5 hours；The roasting condition be
400-550 DEG C roasting 2-10 hours.
Hydrogenation protecting catalyst of the present invention is suitable for residual hydrocracking technique, can effectively remove iron in residual oil, calcium,
The substances such as nickel and vanadium.
Compared with prior art, the present invention having the advantage that
1. carrier of the present invention makes full use of the micron order duct of aluminium oxide intermediate, in the micron-scale in duct, rod-like aluminum oxide without
On the one hand the interlaced distribution of sequence, keeps the penetrability in the micron order duct in this way, at the same improve the specific surface area of carrier with
And mechanical strength is enhanced, on the other hand play the role of certain reaming to alumina support intermediate nanoscale duct, into one
Step promotes logical the wearing property and the uniformity in nanoscale duct.Therefore, alumina support of the invention overcomes using physics expanding agent
The problem of bring large aperture and specific surface area and mechanical strength must not be taken into account.
2. the present invention during preparing alumina support, first passes through the pretreatment of certain temperature before sealing heat treatment,
Condition is relatively mild when pretreatment, the mixing atmosphere of the outer surface of alumina support in sealing, hydro-thermal and carbon dioxide and ammonia
NH is slowly formed under enclosing4Al(OH)2CO3Nucleus improves reaction temperature NH in Post isothermal treatment4Al(OH)2CO3Continue nucleus
Homoepitaxial makes rodlike NH4Al(OH)2CO3Rodlike NH is improved with mono-disperse and length while4Al(OH)2CO3In oxygen
Change the coverage rate of external surface and micron order inner surfaces of pores among aluminium.
3. hydrogenation protecting catalyst of the invention is conducive to the mass transfer of macromolecule reactant when being used for residual hydrocracking
With diffusion, the diffusion of the macromolecular especially containing vanadium, iron, calcium and nickel etc., hydrodemetallization activity with higher and appearance are miscellaneous
Mass-energy power, activity and stability with higher.
Detailed description of the invention
Fig. 1 is that the SEM of the resulting alumina support cut surface of embodiment 1 schemes；
Wherein, appended drawing reference is as follows: 1- main body aluminium oxide, 2- rod-like aluminum oxide, 3- micron order duct.
Specific embodiment
Below with reference to embodiment to further illustrate the technical scheme of the present invention, but it is not limited to following embodiment.This
In invention, wt% is mass fraction.
Using N2Physics suction-desorption characterization embodiment and comparative example carrier pore structure, concrete operations are as follows: using ASAP-
2420 type N2Physics is inhaled-is desorbed instrument and characterizes to sample pore structure.A small amount of sample is taken to be vacuum-treated 3-4 hours at 300 DEG C,
Finally product is placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) and carries out nitrogen suction-desorption test.Wherein specific surface area is according to the side BET
Journey obtains, and Kong Rong and bore dia are obtained in 40nm distributive law below according to BJH model.
Mercury injection method: as follows using mercury injection apparatus characterization embodiment and comparative example carrier pore diameter distribution, concrete operations: using beauty
The full-automatic mercury injection apparatus of state Mike AutoPore9500 type characterizes sample pore size distribution.Dilatometer is weighed into after sample drying
It is interior, and deaerate 30 minutes under the vacuum condition for maintaining instrument given, fill mercury.Then dilatometer is put into autoclave, is vented.
Then it boosted, be depressured test.Mercury contact angle 130o, mercury interfacial tension 0.485N.cm-1, bore dia is 100nm's or more
Distributive law is measured with mercury injection method.
Application scanning Electronic Speculum characterizes the microstructure of alumina support, and concrete operations are as follows: using JSM-7500F scanning electricity
Mirror characterizes carrier microstructure, acceleration voltage 5KV, accelerates 20 μ A of electric current, operating distance 8mm.
Embodiment 1
Weigh 260 grams of boehmite dry glue powder (production of Wenzhou essence crystal alumina Co., Ltd), the activity that partial size is 10 microns
It is 60 grams of charcoal, 8 grams of sesbania powder, above-mentioned physical mixed is uniform, the aqueous acetic acid kneading that appropriate mass concentration is 1.5% is added, squeezes
Item molding, molding is 6 hours dry in 100 DEG C, and dried object in air atmosphere, roasts 5 hours in 700 DEG C, obtains aluminium oxide
Support intermediate ZA1.
Above-mentioned 100 grams of alumina support intermediate ZA1 are weighed, is placed in 800 grams of ammonium bicarbonate solns, the ammonium hydrogen carbonate
In the aqueous solution that the mass concentration of solution is 20%, mixed material is transferred to after being sealed in autoclave with the speed liter of 15 DEG C/min
Then temperature was warming up to 160 DEG C of constant temperature 6 hours with the speed of 10 DEG C/min, then by carrier in 100 to constant temperature 3 hours after 100 DEG C
DEG C dry 6 hours, 700 DEG C were made alumina support A1 of the present invention in roasting 5 hours, and the property of carrier is shown in Table 1.The carrying alumina
In body A1, rodlike oxygen of the length of rod-like aluminum oxide based on 3.0-9.0 μm, on main body aluminium oxide outer surface in micron order duct
Change the length of aluminium based on 3-8 μm, the coverage rate of rod-like aluminum oxide accounts for about 85% on the outer surface of main body aluminium oxide, main body micron
The coverage rate of rod-like aluminum oxide accounts for about 81% in grade duct；It is concentrated on by rod-like aluminum oxide with the hole of unordered interlaced formation
400-700nm。
Embodiment 2
With embodiment 1, only active carbon is changed to the polyvinyl alcohol that partial size is 6 microns, and polyvinyl alcohol additional amount is 50 grams, obtains oxygen
Change alumina supporter intermediate ZA2.The quality of ammonium bicarbonate soln is 600 grams, and the mass concentration of ammonium bicarbonate soln is 17.5%.It is close
Sealing pretreatment temperature is 90 DEG C, and the processing time is 2 hours, and heat treatment temperature is 140 DEG C, and the processing time is 8 hours, and oxidation is made
The property of alumina supporter A2, carrier are shown in Table 1.In the alumina support A2, in micron order duct the length of rod-like aluminum oxide with
Based on 2.0-5.5 μm, the length of the rod-like aluminum oxide on main body aluminium oxide outer surface based on 3-8 μm, main body aluminium oxide it is outer
The coverage rate of rod-like aluminum oxide accounts for about 80% on surface, and the coverage rate of rod-like aluminum oxide accounts for about 78% in main body micron order duct；By
Rod-like aluminum oxide concentrates on 400-600nm with the hole of unordered interlaced formation.
Embodiment 3
With embodiment 1, only active carbon is changed to the sawdust that partial size is 10 microns, and sawdust additional amount is 75 grams and obtains alumina support
Intermediate ZA3.The quality of ammonium bicarbonate soln is 1000 grams, and the mass concentration of ammonium bicarbonate soln is 15%.Before sealing pretreatment
Heating rate be 11 DEG C/min, sealing pretreated heating rate is 5 DEG C/min, and heat treatment temperature is 170 DEG C, when processing
Between be 4 hours, alumina support A3 is made, the property of carrier is shown in Table 1.In the alumina support A3, stick in micron order duct
Based on 3.0-9.0 μm, the length of the rod-like aluminum oxide on main body aluminium oxide outer surface is the length of shape aluminium oxide with 3-8 μm
Main, the coverage rate of rod-like aluminum oxide accounts for about 89% on the outer surface of main body aluminium oxide, rod-like aluminum oxide in main body micron order duct
Coverage rate accounts for about 81%；500-800nm is concentrated on the hole of unordered interlaced formation by rod-like aluminum oxide.
Embodiment 4
With embodiment 1, there is no preprocessing process before heat treatment only, directly with the speed of 15 DEG C/min be warming up to 120 DEG C into
Row heat treatment.Alumina support A4 of the present invention is made, the property of carrier is shown in Table 1.In the alumina support A4, micron order duct
The length of interior rod-like aluminum oxide is based on 3.0-9.0 μm, and the length of the rod-like aluminum oxide on main body aluminium oxide outer surface is with 3-8 μm
Based on, the coverage rate of rod-like aluminum oxide accounts for about 76% on the outer surface of main body aluminium oxide, rod-like aluminum oxide in main body micron order duct
Coverage rate account for about 79%；400-700nm is concentrated on the hole of unordered interlaced formation by rod-like aluminum oxide.
Comparative example 1
With embodiment 1, only alumina support intermediate ZA1 is not heat-treated in ammonium bicarbonate aqueous solution, but in distilled water
The ammonium hydrogen carbonate of middle heat treatment, phase homogenous quantities is added when carrying alumina is body formed, and comparative example alumina support A5, carrier is made
Property be shown in Table 1.
Comparative example 2
With embodiment 1, only ammonium hydrogen carbonate is changed to ammonium carbonate identical in quality, and comparative example alumina support A6 is made, carrier
Property is shown in Table 1.
The property of 1 alumina support intermediate of table and alumina support
| Embodiment 1 | Embodiment 1 | Embodiment 2 | Embodiment 2 | Embodiment 3 | Embodiment 3 | |
| Number | ZA1 | A1 | ZA2 | A2 | ZA3 | A3 |
| Specific surface area, m2/g | 175 | 198 | 186 | 205 | 171 | 203 |
| Kong Rong, mL/g | 0.86 | 1.09 | 0.89 | 1.03 | 0.87 | 1.04 |
| Pore size distribution *, v% | ||||||
| < 10nm | - | 4 | - | 6 | - | 5 |
| 15-35nm | 30 | 36 | 28 | 34 | 30 | 40 |
| 100-800nm | 21 | 35 | 18 | 36 | 19 | 35 |
| > 1000nm | - | 15 | - | 14 | - | 16 |
| 5 μm or more | 14 | Nothing | 12 | Nothing | 16 | Nothing |
| Crushing strength, N/mm | 11.0 | 12.9 | 11.4 | 13.1 | 10.8 | 12.5 |
The property of 1 alumina support intermediate of continued and alumina support
| Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| Number | A4 | A5 | A6 |
| Specific surface area, m2/g | 194 | 181 | 179 |
| Kong Rong, mL/g | 1.03 | 0.87 | 0.89 |
| Pore size distribution *, v% | |||
| < 10nm | 3 | ||
| 15-35nm | 41 | 33 | 35 |
| 100-800nm | 31 | 20 | 19 |
| > 1000nm | 13 | 5 | 4 |
| 5 μm or more | Nothing | 13 | 13.5 |
| Crushing strength, N/mm | 12.6 | 10.4 | 10.7 |
Note: * pore size distribution refers to that the Kong Rong of certain diameter range inner hole in carrier accounts for the percentage of total pore volume.
Embodiment 5
The present embodiment is to prepare hydrogenation protecting agent using aluminium oxide obtained by above-mentioned embodiment and comparative example as carrier.
Each 100 grams of alumina support A1-A6 of embodiment 1-4 and comparative example 1-2 are weighed, 150mL Mo- is separately added into
Ni-NH3Solution (is pressed and contains MoO in final catalyst36.0wt%, NiO1.5 wt%) dipping 2 hours, elimination redundant solution, 120 DEG C
Drying 5 hours, then 550 DEG C roasting temperature 5 hours, respectively obtain hydrogenation protecting agent C1-C6.
Embodiment 6
The following examples illustrate the catalytic performance of hydrogenation protecting agent C1-C6.
Hydrogenation protecting catalyst C1, C2, C3 and C4 of the present invention and comparative example hydrogenation protecting catalyst C5 and C6 are filled respectively
It fills out in fixed bed hydrogenation reactor, handled raw material (see Table 2), experimental condition is as follows: 385 DEG C of reaction temperature, hydrogen oil body
Product ratio 1000, volume space velocity 1.0h when liquid-1, hydrogen partial pressure 14MPa continuously runs 4000 hours, and de- contaminant characteristics are shown in Table 3.
2 raw material oil nature of table
| Analysis project | Husky light normal slag |
| Density (20 DEG C), g/cm3 | 0.96 |
| Ni, μ g/g | 22.4 |
| V, μ g/g | 73.7 |
| Fe, μ g/g | 6.8 |
| Ca, μ g/g | 7.9 |
The evaluation result of 3 catalyst of table
| Hydrogenation protecting catalyst | C1 | C2 | C3 | C4 | C5 | C6 |
| De- V+Ni rate, wt% | 49.1 | 51.3 | 50.6 | 45.5 | 27.5 | 28.6 |
| De- Ca rate, wt% | 65.1 | 69.2 | 67.5 | 61.3 | 36.2 | 35.7 |
| De- Fe rate, wt% | 73.6 | 75.4 | 76.2 | 70.1 | 47.9 | 48.1 |
From the results shown in Table 3 using hydrogenation protecting catalyst of the present invention Ca, Fe, Ni, V removal efficiency with higher and good
Good stability.
Claims (18)
1. a kind of hydrogenation protecting catalyst carrier, the carrier is alumina support, including main body aluminium oxide and rod-like aluminum oxide,
The main body aluminium oxide is the aluminium oxide with micron order duct, and wherein at least part rod-like aluminum oxide is distributed in main body oxidation
In the micron order duct that the outer surface of aluminium and bore dia D are 5-10 μm, rod-like aluminum oxide length is 1-12 μm, diameter 100-
300 nm；The pore size distribution of the carrier is as follows: bore dia be the hole below 10nm shared by Kong Rongwei total pore volume 10% hereinafter,
Bore dia is the 30%-50% of Kong Rongwei total pore volume shared by the hole of 15-35nm, and bore dia is hole shared by the hole of 100-800nm
Hold the 30%-45% for total pore volume, the 10%-26% of Kong Rongwei total pore volume shared by hole of the bore dia greater than 1000nm, preferably
10%-24%。
2. carrier described in accordance with the claim 1, it is characterised in that: rod-like aluminum oxide is substantially distributed in the appearance of main body aluminium oxide
In face and micron order duct.
3. carrier described in accordance with the claim 1, it is characterised in that: the length of rod-like aluminum oxide is in micron order duct with 0.3D-
Based on 0.9D；The length of the rod-like aluminum oxide of main body aluminium oxide outer surface is based on 3-8 μm.
4. carrier described in accordance with the claim 1, it is characterised in that: in the micron order duct of main body aluminium oxide, rodlike oxidation
Aluminium is with unordered interlaced state distribution；At least one end of at least partly rod-like aluminum oxide is attached to the micron order duct of main body
On wall, preferably at least at least one end of part rod-like aluminum oxide is combined in cell walls in the micron-scale, forms one with main body aluminium oxide
Body；Further preferably, at least one end of the rod-like aluminum oxide in micron order duct combines in cell walls in the micron-scale, with main body oxygen
Change aluminium and forms one.
5. according to carrier described in claim 1 or 4, it is characterised in that: on the outer surface of main body aluminium oxide, rod-like aluminum oxide
With unordered interlaced state distribution；One end of at least partly rod-like aluminum oxide is attached on the outer surface of main body aluminium oxide,
One end of preferably at least part rod-like aluminum oxide is incorporated on the outer surface of main body aluminium oxide, and the other end is protruding, with main body
Aluminium oxide forms one；Further preferably, one end of the rod-like aluminum oxide on the outer surface of main body aluminium oxide is incorporated in main body oxygen
On the outer surface for changing aluminium, the other end is protruding, forms one with main body.
6. according to carrier described in claim 1 or 4, it is characterised in that: rodlike oxidation in the micron order duct of main body aluminium oxide
The coverage rate of aluminium accounts for 70%-95%, and the coverage rate of rod-like aluminum oxide accounts for 70%-95% on the outer surface of main body aluminium oxide.
7. according to carrier described in claim 1 or 4, it is characterised in that: the property of the carrier is as follows: specific surface area 140-
290m2/ g, Kong Rong 0.6-1.5mL/g, crushing strength 9-18N/mm.
8. according to carrier described in claim 1 or 4, it is characterised in that: in the carrier, by rod-like aluminum oxide with unordered mutual
The hole being staggered to form concentrates between 100-800nm.
9. the preparation method of any hydrogenation protecting catalyst carrier of claim 1-8, comprising:
(1) support intermediate is prepared；
(2) by support intermediate immerse ammonium bicarbonate soln in, then sealing heat treatment, after heat treatment material through drying, roasting,
Carrier is made.
10. according to the method for claim 9, it is characterised in that: the property of step (1) described support intermediate is as follows: ratio
Surface area is 120-280m2/ g, Kong Rongwei 0.7-1.4mL/g, pore size distribution are as follows: bore dia is hole shared by the hole of 15-35nm
Hold the 25%-45% for total pore volume, bore dia is the 15%-45% of Kong Rongwei total pore volume shared by the hole of 100-800nm, bore dia
For Kong Rongwei total pore volume 10%-20% shared by 5 μm or more of holes.
11. according to method described in claim 9 or 10, it is characterised in that: the preparation of support intermediate described in step (1)
Journey is as follows: by boehmite and physics expanding agent kneading and compacting, molding obtains support intermediate through drying, roasting；It is described
Physics expanding agent be one or more of active carbon, sawdust, polyvinyl alcohol, physics expanding agent additional amount be alumina support
The 21wt%-35wt% of intermediate body weight；The drying of the molding and roasting condition are as follows: drying temperature is 100-160 DEG C, is done
The dry time is 6-10 hours, and the maturing temperature is 600-750 DEG C, and calcining time is 4-6 hours.
12. according to method described in claim 9 or 10, it is characterised in that: the dosage of ammonium bicarbonate soln described in step (2)
Mass ratio with step (1) resulting vehicle intermediate is 4:1-10:1, and the mass concentration of ammonium bicarbonate soln is 15%-25%.
13. according to method described in claim 9 or 10, it is characterised in that: sealing heat treatment temperature described in step (2) is
120-170 DEG C, the processing time is 4-8 hours, and heating rate is 5 DEG C/min-20 DEG C/min.
14. according to method described in claim 9,10 or 13, it is characterised in that: in step (2), in the advance of sealing heat treatment
Row sealing pretreatment, pretreatment temperature are 60-100 DEG C, and the constant temperature processing time is 2-4 hours, and the heating rate before pretreatment is
10-20 DEG C/min, before pretreated heating rate is 5-10 DEG C/min, and pretreated heating rate is than pretreatment
Low at least 3 DEG C/min, preferably at least 5 DEG C/min.
15. according to method described in claim 9 or 10, it is characterised in that: drying temperature described in step (2) is 100-160
DEG C, drying time is 6-10 hours, and the maturing temperature is 600-750 DEG C, and calcining time is 4-6 hours.
16. a kind of hydrogenation protecting catalyst, including carrier and active metal component, wherein carrier is any using claim 1-8
The carrier.
17. catalyst according to claim 16, it is characterised in that: active metal component is group VIB and/or Section VIII
Race's metal, vib metals are selected from one of W, Mo or a variety of, and group VIII metal is selected from one of Co, Ni or a variety of；
On the basis of the weight of catalyst, the contents of reactive metal oxides is 2.5%-10.0%, preferably 2.5%-9.0%, further
Preferably the content of vib metals oxide is 2.0%-8.5%, and the content of group VIII metal oxide is 0.3%-2.5%.
18. a kind of residual hydrocracking technique, it is characterised in that using catalyst described in claim 16 or 17.
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| CN113117760A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Protective agent and preparation method and application thereof |
| CN113117687A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Grading method and application of hydrogenation protective agent |
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