CN104338539B - A hydrogenation demetalization catalyst for heavy oil, and preparation and applications thereof - Google Patents
A hydrogenation demetalization catalyst for heavy oil, and preparation and applications thereof Download PDFInfo
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Abstract
A hydrogenation demetalization catalyst, and preparation and applications thereof are disclosed. The catalyst comprises an aluminum oxide carrier and hydrogenation active metal components. The carrier has a double-peak pore structure. By representation by a mercury intrusion method, the pore volume of the carrier is 0.6-1.4 mL/g, the specific surface area is 80-400 m＜2＞/g, the pore volume of pores having a diameter of 5-20 nm is 30-60% of the total pore volume, and the pore volume of pores having a diameter of 100-300 nm is 15-45% of the total pore volume. Compared with the prior art, the catalyst provided by the invention has better hydrogenation deasphalting and demetallation properties when the catalyst is used for hydrogenation processing of residual oil.
Description
Technical field
The present invention relates to a kind of Hydrodemetalation catalyst and its preparation and application.
Background technology
Not only contribute to improve the utilization rate of crude oil to deep processing being carried out including the mink cell focus including residual oil, alleviate the energy
The nervous trend of supply, while environmental pollution can also be reduced, reaches the clean utilization of the energy.Compared with distillate, in mink cell focus
Containing the macromolecular reaction thing such as substantial amounts of asphalitine, colloid, and the heteroatomic compound such as sulphur, nitrogen, oxygen in mink cell focus and nickel and
The heavy metals such as vanadium and condensed-nuclei aromatics are largely focused in asphalitine, and these impurity and heavy metal can be in follow-up process
In corresponding catalyst is polluted, thus the hydro-conversion of asphalitine is a critical step during residual hydrogenation.And
In the conversion and subtractive process of asphalitine, the characteristic according to asphalitine is needed, select active high and the performance of good stability is excellent
Good catalyst.
For the hydrogenation catalyst of depitching matter, its pore-size distribution is of great significance to catalyst performance tool.
The molecular size of asphalitine be about it is tens of to hundreds of nanometers, if catalyst active center is smaller than asphaltene molecules,
Asphaltene molecules are difficult to contact with the activated centre of catalyst by diffusion, and mainly adsorb in outer surface or the hole of catalyst
Mouthful, as the carrying out of reaction can only form coke because of thermal condensation, cause catalyst to inactivate.Macroporous catalyst is conducive to asphalitine
Remove, but the aperture of catalyst is negatively correlated each other with specific surface, be i.e. the big catalyst of average pore size, its specific surface area is just little.Cause
, in order to take into account this property, catalyst needs rational pore size distribution for this.
Existing Heavy oil hydrogenation catalyst is disadvantageous in that its S, N removal rate, heavy metal removing rate and asphalitine take off
Except matching well can not be reached between rate, for example, often S, N removal rate and asphalitine take off to remove the high catalyst of metal active
Except rate it is not high.The reason for producing problems is very complicated.Raw material is first consisted in, is molecular weight the characteristics of each component in residual oil
Greatly, complex structure, saturation degree are low（Armaticity is high）, S, N content are high.And beyond sulphur removal, impurity most and be present in more
In asphalitine, therefore it is intended to remove such S, N, it is necessary to carry out appropriate conversion to asphaltene molecules（Including saturation, open loop and hydrogenolysis
Deng）.Next is catalyst.In prior art, it is guard catalyst with the catalyst for being suitable for carrying out such reaction aperture
And catalyst for demetalation, for example：
A kind of Hydrodemetalation catalyst with relatively low carbon deposition quantity and greater activity disclosed in CN1267537C and its
Preparation method.
A kind of residuum hydrogenating and metal-eliminating catalyst disclosed in CN1796500A, the catalyst is by a kind of load with double-hole
Body and load molybdenum on this carrier and/or tungsten and cobalt and/or nickel metal component composition.The preparation side of the carrier that catalyst is used
Method is included being mixed a kind of precursor of aluminum oxide with the nitrogen-containing compound beyond a kind of deacidification, is molded and roasting.
Catalyst for heavy oil fixed bed hydrogenating treatment disclosed in CN1233795C and preparation method etc..
But, the metal of these catalyst, asphaltene removal are generally relatively low.
The content of the invention
The technical problem to be solved in the present invention be to provide it is a kind of it is new, with preferable HDM and depitching matter performance
Catalyst, the preparation method of the catalyst and application.
The present invention relates to herein below：
1. a kind of Hydrodemetalation catalyst, containing alumina support and hydrogenation active metals component, wherein, the carrier
With structure of double peak holes, characterized with mercury injection method, the pore volume of the carrier is 0.6-1.4 ml/g, and specific surface area is 80-400
Rice2/ gram, the pore volume in a diameter of 5-20nm holes accounts for the 30-60% of total pore volume, and the pore volume in a diameter of 100-300nm holes accounts for total hole
The 15-45% of appearance.
2. the catalyst according to 1, it is characterised in that the pore volume of the carrier is 0.7-1.3 ml/g, specific surface
Product is 100-300 rice2/ gram, the pore volume in a diameter of 5-20nm holes accounts for the 35-50% of total pore volume, a diameter of 100-300nm holes
Pore volume accounts for the 20-40% of total pore volume.
3. the catalyst according to 1, it is characterised in that the hydrogenation active metals component is selected from least one VIIIth race
Metal component and at least one vib metals component, are counted by oxide and on the basis of catalyst, VIII race metal component
Content more than 0.8 to less than or equal to 3 weight %, the content of metal component of group VIB is more than 3 to less than or equal to 10 weight %.
4. the catalyst according to 3, it is characterised in that the metal component of group VIII is selected from cobalt and/or nickel, VIB
Race's metal component is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of catalyst, and the content of VIII race metal component is 1-
2 weight %, the content of metal component of group VIB are more than 4 to less than or equal to 8 weight %.
5. according to 1 catalyst preparation method, including preparing carrier and load hydrogenation active metals on this carrier
Component, wherein, the preparation of the carrier includes containing the hydrated alumina PA and PB containing boehmite with one kind intends thin
The modifier PC mixing of the hydrated alumina of diaspore, shaping, dry and roasting, wherein, the weight mixing of described PA, PB and PC
Than for 20-60：20-50：The κ values of 5-50, PC are the κ=DI 0 to less than or equal to 0.92/DI1, DI1For PC hydrations before modified
The sour peptization index of aluminum oxide, DI2For the sour peptization index of the PC.
6. the method according to 5, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50：35-50：
10-30。
7. the method according to 5, it is characterised in that the k values of the PC are 0 to less than or equal to 0.6.
8. the method according to 5 or 6, it is characterised in that the hole of the hydrated alumina PA containing boehmite
Hold for 0.75-1 ml/g, specific surface is 200-450 rice2/ gram, most can and bore dia 3-10nm；It is described containing boehmite
Hydrated alumina PB pore volume be 0.9-1.4 ml/g, specific surface be 100-350 rice2/ gram, most can and bore dia be more than 10
To less than or equal to 30nm.
9. the method according to 8, it is characterised in that the pore volume of the hydrated alumina PA containing boehmite is
0.80-0.95 ml/g, specific surface is 200-400 rice2/ gram, most can and bore dia 5-10nm；It is described containing boehmite
Hydrated alumina PB pore volume be 0.95-1.3 ml/g, specific surface be 120-300 rice2/ gram, most can and bore dia be more than
10 to less than or equal to 25nm.
10. the method according to 5,6 or 7 any one, it is characterised in that particulate matters of the PC for 80-300 mesh.
11. methods according to 10, it is characterised in that particulate matters of the PC for 100-200 mesh.
12. methods according to 5, it is characterised in that the condition of the drying includes：Temperature is 40-350 DEG C, the time
For 1-24 hours, the condition of the roasting includes：Temperature is that the time is 1-8 hours more than 500 to less than or equal to 1200 DEG C.
13. methods according to 12, it is characterised in that the condition of the drying includes：Temperature is 100-200 DEG C, when
Between be 2-12 hours, the condition of the roasting includes：Temperature is that roasting time is 2-6 more than 800 to less than or equal to 1000 DEG C
Hour.
14. methods according to 5, it is characterised in that the hydrated alumina containing boehmite is modified as into PC's
One of method is by the shaping of the hydrated alumina containing boehmite, is dried, and grinds its all or part afterwards
Mill, screening, the condition of the drying include：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are to obtain method one
The article shaped roasting arrived, sintering temperature are that roasting time is 1-8 hours, afterwards which is complete more than 350 to less than or equal to 1400 DEG C
Portion or part are ground, sieve；The three of method are that the hydrated alumina containing boehmite is dodged dry, and it is big to dodge dry temperature
In 150 to less than or equal to 1400 DEG C, flash-off time is 0.05-1 hours；The four of method be by one of method, method two and with
One or more in the modifier that the three of method obtain are mixed to get.
15. methods according to 14, it is characterised in that the condition of the drying in methods described one includes：Temperature is
100-200 DEG C, the time is 2-12 hours；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is that 0.1-6 is little
When；The dry temperature of sudden strain of a muscle in the three of method is 200-1000 DEG C, and flash-off time is 0.1-0.5 hours.
16. methods according to 14, it is characterised in that the PC is changing for the hydrated alumina containing boehmite
The particulate matter of 80-300 mesh in property thing.
17. methods according to 16, it is characterised in that the PC is changing for the hydrated alumina containing boehmite
The particulate matter of 100-200 mesh in property thing.
18. methods according to 5, it is characterised in that the method in supported on carriers hydrogenation active metals component
For infusion process, simultaneously the solution impregnating carrier is used including the solution for preparing the compound containing hydrogenation active metals, be dried afterwards,
Roasting or not roasting, metal component and at least one VIIIth of the hydrogenation active metals component selected from least one vib
The metal component of race, is counted by oxide and on the basis of catalyst, and the compound containing hydrogenation active metals is in the solution
Concentration and the solution consumption make the vib in final catalyst metal component content more than 3 to being less than or equal to
10 weight %, the content of the metal component of the VIIIth race are more than 0.8 to less than or equal to 3 weight %；The drying condition includes：Temperature
Spend for 100-250 DEG C, the time is 1-10 hours；The roasting condition includes：Temperature is 360-500 DEG C, and the time is 1-10 hours.
19. methods according to 18, it is characterised in that the metal component of the vib is selected from molybdenum and/or tungsten, the
The metal component of VIII race is selected from cobalt and/or nickel, is counted by oxide and on the basis of catalyst, the change containing hydrogenation active metals
The content of the metal component of vib of the compound in the concentration of the solution and the consumption of the solution make final catalyst is big
It is 1-2 weight % in 4 to the content less than or equal to 8 weight %, the metal component of the VIIIth race；The drying condition includes：Temperature is
100-140 DEG C, the time is 1-6 hours；The roasting condition includes：Temperature is 360-450 DEG C, and the time is 2-6 hours.
Application of the catalyst in 20. claims 1-4 described in any one in hydrocarbon oil hydrogenation process.
According to the catalyst that the present invention is provided, require that carrier therein can be made into various easily operated shapings depending on difference
Thing, such as spherical, cellular, nest like, tablet or bar shaped（Clover, butterfly, cylinder etc.）.Shaping can be entered according to a conventional method
The combination of a kind of method or several method OK, for example, in spin, compressing tablet and extruded moulding.Shaping when, such as extrusion into
Type, be ensure it is described shaping be smoothed out, can add in described mixture water, extrusion aid and/or adhesive, containing or not
Containing expanding agent, then extrusion molding, it is dried afterwards and roasting.The extrusion aid, the species of peptizing agent and consumption are ability
Well known to field technique personnel, such as common extrusion aid can be selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol, poly- second
One or more in alcohol, the peptizing agent can be inorganic acid and/or organic acid, and described expanding agent can be starch, conjunction
Into one or more in cellulose, polymeric alcohol and surfactant.Synthetic cellulose therein be preferably hydroxymethyl cellulose,
One or more in methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol are preferably poly- second two
One or more in alcohol, poly- propyl alcohol, polyvinyl alcohol, surfactant be preferably fat alcohol polyethylene ether, fatty alkanol amide and
Its derivative, molecular weight are one or more in the propylene alcohol copolymer and maleic acid copolymer of 200-10000.
In the present invention, sour peptization index D I refers to the hydrated alumina containing boehmite and containing the thin water of plan
The hydrated alumina modifier of aluminium stone is added after nitric acid, by peptization containing plan within certain reaction time by certain acid aluminum ratio
The hydrated alumina of boehmite is with Al2O3The percentage of meter, DI=（1-W2/W1) × 100%, W1And W2Respectively containing the thin water of plan
Before the hydrated alumina of aluminium stone and acid reaction and with acid reaction after with Al2O3The weight of meter.
The measure of DI includes：(1) the calcination base of the hydrated alumina containing boehmite is determined（Also referred to as butt）Content
（Calcination base content referred to quantitative boehmite in 600 DEG C of roastings 4 hours, after its burning weight with burn before weight ratio, with
Percentage is represented）, it is calculated as a；(2) the hydrated alumina W containing boehmite is weighed with assay balance0Gram, W0Amount meet with
Al2O3The W of meter1For 6 grams（W1/a=W0）, weigh deionized water W gram, W=40.0-W0, will weigh under stirring containing the thin water aluminium of plan
The hydrated alumina of stone and deionized water mix in adding beaker；(3) it is the dilute of 0.74N to pipette 20mL, concentration with 20mL pipettes
The acid solution is added to step by salpeter solution（2）Beaker in, the lower reaction of stirring 8 minutes；(4) by step（3）It is reacted
Slurries are centrifuged in centrifuge, sediment are inserted in the crucible weighed, afterwards, and which is little in 125 DEG C of dryings 4
When, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W2Gram；（5）According to formula DI=(1-W2/W1)×
100% is calculated.
On the premise of it be enough to make final carrier meet application claims, the present invention is to the water containing boehmite
Close aluminum oxide PA and PB not specially require, can be the boehmite, or the thin water of plan of any prior art preparation
The mixture of aluminium stone and other hydrated aluminas, other hydrated aluminas are selected from a water aluminum oxide, gibbsite
And one or more in amorphous hydrated aluminum oxide.
In a detailed embodiment, the preferred pore volumes of hydrated alumina PA containing boehmite are 0.75-1
Ml/g, specific surface is 200-450 rice2/ gram, most can and bore dia 3-10nm, further preferred pore volume be 0.80-0.95 milli
Rise/gram, specific surface is 200-400 rice2/ gram, most can and bore dia 5-10nm；The hydrated alumina containing boehmite
The preferred pore volumes of PB are 0.9-1.4 ml/g, and specific surface is 100-350 rice2/ gram, most can and bore dia more than 10 to being less than or equal to
30nm, further preferred pore volume are 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, most can and bore dia be more than 10
To less than or equal to 25nm.
In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and most can and aperture, be by institute
The hydrated alumina containing boehmite is stated after 600 DEG C of roastings 4 hours, is characterized by BET N2 adsorptions and is obtained.
In further preferred embodiment, characterized with X diffraction, the hydrated alumina PA containing boehmite
It is not less than 50% with the boehmite content in PB, more preferably not less than 60%.
Inventors of the present invention have surprisingly found that, the hydrated alumina containing boehmite is carried out being thermally treated resulting in changing
Property thing PC, relative to the original hydrated alumina containing boehmite, the peptization index of modifier PC changes, will
After this modifier and PA and PB mixed-formings, drying roasting, resulting carrier has obvious bimodal pore distribution.Especially
It is by the particle of 80-300 mesh therein, preferably after the particle of 100-200 mesh and PA and PB mixed-formings, drying roasting,
Resulting carrier it is bimodal in each unimodal pore size distribution especially concentrate.Here, the particle of the 80-300 mesh, preferably
The particle of 100-200 mesh refers to the modifier through sieve（The step of including broken or grinding if necessary）, its screening thing（Under sieve
Thing）Meet the particle of 80-300 mesh, the particulate matter of preferably 100-200 mesh accounts for the percentage of total amount（By weight）Not less than 60%,
Further preferably it is not less than 70%.Here the hydrated alumina containing boehmite can be prepared by any prior art
The mixture of boehmite, or boehmite and other hydrated aluminas, other hydrated aluminas
One or more in a water aluminum oxide, gibbsite and amorphous hydrated aluminum oxide.In a preferred embodiment,
Modifiers of the PC for PA and/or PB.
In the present invention, during the Mixing ratio by weight of described PA, PB and PC refers to the mixture of described PA, PB and PC parts per hundred parts
The ratio of parts by weight shared by PA, PB and PC difference.Wherein, PA：PB：PC is preferably 20-60：20-50：5-50, further preferably
For 30-50：35-50：10-30.
In the present invention, described PC can be conveniently obtained by following method：
Hereinafter, the method for obtaining PC is illustrated by initiation material of the PA and PB.
(1) based on being dried to obtain PC, including by hydrated alumina PA and/or PB containing boehmite according to a conventional method
During shaping prepares regular oxidation alumina supporter, the tailing of drying by-product, for example：In extruded moulding, bar shaped article shaped exists
The dry, tailing of integer process by-product（Traditionally it is referred to as being dried waste material）, the tailing is milled, is sieved and is obtained PC.
(2) obtained based on roasting, including by hydrated alumina PA and/or PB containing boehmite according to a conventional method into
During type prepares regular oxidation alumina supporter, the tailing of fired by-product（Traditionally it is referred to as roasting waste material）, for example, spin into
In type, the tailing is milled, sieves and obtain PC by the tailing of spheric granules by-product in roasting process；Or directly will
PA and/or PB dodge it is dry obtains, directly will PA and/or PB dodge dry when, flash-off time is preferably 0.05-1 hours, further preferably
For 0.1-0.5 hours.
(3) two or more in the modifier PC for being obtained based on preceding method are mixed to get.When being obtained using mixed method
When obtaining C, the mixed proportion of the modifier PC respectively obtained to aforementioned several method is not limited.
According to the catalyst that the present invention is provided, wherein, the preferred VIII race metal component of the hydrogenation active metals component is
Cobalt and/or nickel, VI B races metal component are molybdenum and/or tungsten, are counted by oxide and on the basis of catalyst, the VIII race metal group
The content divided preferably greater than 0.8 is to less than or equal to 3 weight %, more preferably 1-2 weight %, the VI B races metal component
Content preferably greater than 3 to less than or equal to 10 weight %, further preferably greater than 4 to less than or equal to 8 weight %.
On the premise of it be enough to described hydrogenation active metals component is carried on the carrier, the present invention is to described negative
Support method is not particularly limited, and preferred method is infusion process, including the dipping solution for preparing the compound containing the metal, it
Afterwards with the carrier described in the solution impregnation.Described dipping method is conventional method, for example, it may be excessive immersion stain, hole are satisfied
With method infusion process.Described one kind containing the metal component compound selected from VI B races in the soluble compound in them
Or several, one or more such as in molybdenum oxide, molybdate, paramolybdate, molybdenum oxide preferably wherein, ammonium molybdate, para-molybdic acid
Ammonium；One or more in tungstates, metatungstate, ethyl metatungstate, ammonium metatungstate preferably wherein, ethyl metatungstic acid
Ammonium.The described compound containing selected from VIII race's metal component one or more in their soluble compound, such as nitre
One or more in the soluble complexes of sour cobalt, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt, preferably cobalt nitrate, alkali
Formula cobalt carbonate；One or more in the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel, preferably
For nickel nitrate, basic nickel carbonate.
According to the catalyst that the present invention is provided, the present invention can not also be affected to provide catalyst performance or can change containing any
The addO-on therapy of the catalytic performance of the catalyst that rare book invention is provided.The addO-on therapies such as phosphorus can such as be contained, in terms of oxide simultaneously
On the basis of catalyst, the content of the addO-on therapy is less than 10 weight %, preferably 0.1-4 weight %.
When in the catalyst also containing addO-on therapies such as phosphorus, the introducing method of the addO-on therapy can be arbitrary
Method, the compound of the component such as phosphorus as described in can be to contain directly are mixed with the boehmite, are molded and roasting；Can be with
It is to be configured to soak after mixed solution by the compound containing components such as the phosphorus and the compound containing hydrogenation active metals component
Carrier described in stain；Can also be individually to prepare the compound containing components such as phosphorus and after solution, impregnate the carrier roasting.When
When the addO-on therapies such as phosphorus introduce the carrier respectively with hydrogenation active metals, preferably first with containing the addO-on therapy compound
Solution impregnation described in carrier roasting, afterwards again with the solution impregnation containing hydrogenation active metals component composition.Wherein, institute
Sintering temperature is stated for 400-600 DEG C, preferably 420-500 DEG C, roasting time is 2-6 hours, preferably 3-6 hours.
According to hydrocarbon ils provided by the present invention（Including residual oil）Hydrotreating method, to the anti-of the hydrotreating of the hydrocarbon ils
Condition is answered to be not particularly limited, in a preferred embodiment, the hydrotreating reaction condition is：Reaction temperature 300-550
DEG C, further preferred 330-480 DEG C, hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3.0 is little
When-1, further preferred 0.15-2 hours-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.
The device of the hydrogenation reaction can it is any be enough to make the feedstock oil at hydrotreating reaction conditions with institute
Carry out in stating the catalytic reactor of catalyst, for example, in the fixed bed reactors, moving-burden bed reactor or ebullated bed are anti-
Carry out in answering device.
According to the conventional method in this area, the hydrotreating catalyst before the use, generally can be present in hydrogen
Under, presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140-370 DEG C, this presulfurization can be carried out outside device
Also can be In-situ sulphiding in device, the active metal component loaded by which is converted into metal sulfide component.
The catalyst that the present invention is provided can be used alone, it is also possible to use with other catalyst combinations, and the catalyst is special
It is not suitable for heavy oil and is particularly poor residuum carrying out hydrotreating, so as to for subsequent technique（Such as catalytic cracking process）There is provided and close
The feedstock oil of lattice.Compared with prior art, the catalyst for providing of the invention has when for residual hydrocracking and preferably adds
Hydrogen depitching matter and demetalization performance.
Specific embodiment
The present invention will be further described for the following examples, but should be therefore understands that being not limitation of the invention.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
The boehmite for using below in an example includes：
PA-1：The dry glue powder of Chang Ling catalyst branch company production（Pore volume is 0.9 ml/g, and specific surface is 280 meters2/ gram,
Most can and bore dia 8.5nm.Butt is 73%, wherein boehmite content be 68%, gibbsite content be 5 weight %, surplus
For amorphous alumina, DI values 34.6）.
PA-2：The dry glue powder of the limited production of the neat cyclopentadienyl catalyst in Zibo（Pore volume is 0.9 ml/g, and specific surface is 290 meters2/
Gram, most can and bore dia 8.3nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %,
Balance of amorphous alumina, DI values 33.2）.
PB-1：The dry glue powder of Chang Ling catalyst branch company production（Pore volume is 1.2 mls/g, and specific surface is 280 meters2/ gram,
Most can and bore dia 15.8nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %, remaining
Measure as amorphous alumina, DI values 15.8）.
PB-2：The dry glue powder of Yantai Heng Hui Chemical Co., Ltd.s production（Pore volume is 1.1 mls/g, and specific surface is 260
Rice2/ gram, most can and bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 weights
Amount %, balance of amorphous alumina, DI values 17.2）.
Embodiment 1-10 illustrates PC of the present invention and preparation method thereof.
Embodiment 1
1000 grams of PA-1 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of the aqueous solution 1000
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar obtains dried strip in 120 DEG C of dryings 4 hours,
By dried strip shaping, sieve, length is less than into the dried strip material of 2mm（Commonly referred to as industrially drying bar waste material）Milled,
Sieve, take wherein 100～200 mesh sieves point, obtain the modifier PC-A1 of PA-1.The k values of PC-A1 are shown in Table 1.
Embodiment 2
1000 grams of PA-1 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of the aqueous solution 1000
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C of dryings 4 hours, 800 DEG C of roastings 4
Hour, carrier is obtained, carrier strip shaping is sieved, length is less than into the carrier strip material of 2mm（Commonly referred to as industrial carrier gives up
Material）Milled, sieved, taken wherein 100～200 mesh sieves point, obtain final product the modifier PC-A2 of PA-1.The k values of PC-A2 are shown in Table 1.
Embodiment 3
1000 grams of PA-2 are weighed, is dodged dry 6 minutes in 400 DEG C, is obtained the modifier PC-A3 of PA-2.The k values of PC-A3 are shown in Table
1。
Embodiment 4
The each 200 grams of uniform mixing of PC-A3 that the PC-A1 and embodiment 3 that embodiment 1 is obtained is obtained, obtain PA-1 and PA-
2 modifier PC-A4.The k values of PC-A4 are shown in Table 1.
Embodiment 5
1000 grams of PB-1 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of the aqueous solution 1440
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C of dryings 4 hours, 1200 DEG C of roastings 4
Hour, carrier is obtained, carrier strip shaping is sieved, length is less than into the carrier strip material of 2mm（Commonly referred to as industrial carrier gives up
Material）Milled, sieved, taken wherein 100～200 mesh sieves point, obtain final product the modifier PC-B1 of PB-1.The k values of PC-B1 are shown in Table 1.
Embodiment 6
1000 grams of PB-2 are weighed, is dodged dry 10 minutes in 650 DEG C, is obtained the modifier PC-B2 of PB-2.The k values of PC-B2 are shown in Table
1。
Embodiment 7
1000 grams of PB-2 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of the aqueous solution 1440
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar obtains dried strip in 120 DEG C of dryings 4 hours,
By dried strip shaping, sieve, length is less than into the dried strip material of 2mm（Commonly referred to as industrially drying bar waste material）Milled,
Sieve, take wherein 100～200 mesh sieves point, obtain the modifier PC-B3 of PB-2.The k values of PC-B3 are shown in Table 1.
Embodiment 8
The each 200 grams of uniform mixing of PC-B2 that the PC-B1 and embodiment 6 that embodiment 5 is obtained is obtained, obtain PB-1 and PB-
2 modifier PC-B4.The k values of PC-B4 are shown in Table 1.
Embodiment 9
150 grams of PC-B3 that the 100 grams of PC-A1 and embodiment 7 that embodiment 1 is obtained are obtained uniformly mix, obtain PA-1 and
The modifier PC-B5 of PB-2.The k values of PC-B5 are shown in Table 1.
Embodiment 10
The each 150 grams of uniform mixing of PC-B1 that the PC-A3 and embodiment 5 that embodiment 3 is obtained is obtained, obtain PA-2 and PB-
1 modifier PC-B6.The k values of PC-B6 are shown in Table 1.
Table 1
| Embodiment | Raw material | DI | k |
| 1 | PC-A1 | 10.0 | 0.29 |
| 2 | PC-A2 | 0.9 | 0.02 |
| 3 | PC-A3 | 3.6 | 0.11 |
| 4 | PC-A4 | 6.7 | 0.20 |
| 5 | PC-B1 | 0 | 0 |
| 6 | PC-B2 | 2.1 | 0.12 |
| 7 | PC-B3 | 5.3 | 0.31 |
| 8 | PC-B4 | 1.0 | 0.06 |
| 9 | PC-B5 | 7.0 | 0.29 |
| 10 | PC-B6 | 1.6 | 0.07 |
Bimodal hole carrier that the embodiment 9-16 explanation present invention is provided and preparation method thereof.The explanation of comparative example 1-4 is conventional to urge
Agent carrier and preparation method thereof.
Embodiment 11
Weigh PA-1 and PB-1 each 400 grams, after uniformly mixing with 2 obtained 200 grams of raw material PC-A2 of embodiment, addition contains
Nitric acid（Three factory's product of Tianjin chemical reagent）1300 milliliters of 10 milliliters of the aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 900 DEG C of the article shaped is carried
Body Z1.The property of carrier Z1 is listed in table 2.
Embodiment 12
300 grams of PA-2,200 grams of PB-2 are weighed, after uniformly mixing with 6 obtained 500 grams of raw material PC-B2 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1300 milliliters of 10 milliliters of the aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 900 DEG C of the article shaped is carried
Body Z2.The property of carrier Z2 is listed in table 2.
Embodiment 13
500 grams of PA-2,300 grams of PB-2 are weighed, after uniformly mixing with 8 obtained 200 grams of raw material PC-B4 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1300 milliliters of 10 milliliters of the aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 950 DEG C of the article shaped is carried
Body Z3.The property of carrier Z3 is listed in table 2.
Comparative example 1
500 grams of PA-2,500 grams of PB-2 are weighed, after uniform mixing, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）10 millis
1300 milliliters of the aqueous solution for rising, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is little in 120 DEG C of dryings 4
When, article shaped is obtained, by the roasting 3 hours of 900 DEG C of the article shaped, carrier DZ1 is obtained.The property of carrier DZ1 is listed in table 2.
Comparative example 2
400 grams of PA-1,600 grams of PB-1 are weighed, after uniform mixing, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）10 millis
1300 milliliters of the aqueous solution for rising, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is little in 120 DEG C of dryings 4
When, article shaped is obtained, by the roasting 3 hours of 950 DEG C of the article shaped, carrier DZ2 is obtained.The property of carrier DZ2 is listed in table 2.
Embodiment 14
250 grams of PA-1,500 grams of PB-1 are weighed, after uniformly mixing with 9 obtained 250 grams of raw material PC-B5 of embodiment, is added
Containing nitric acid（Three factory's product of Tianjin chemical reagent）1300 milliliters of 10 milliliters of the aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 1000 DEG C of the article shaped is obtained
Carrier Z4.The property of carrier Z4 is listed in table 2.
Embodiment 15
350 grams of PA-2,350 grams of PB-2 are weighed, after uniformly mixing with 10 obtained 300 grams of raw material PC-B6 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1440 milliliters of 10 milliliters of the aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 1000 DEG C of the article shaped is obtained
Carrier Z5.The property of carrier Z5 is listed in table 2.
Embodiment 16
200 grams of PA-1,600 grams of PB-1 are weighed, after uniformly mixing with 5 obtained 200 grams of raw material PC-B1 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1440 milliliters of 10 milliliters of the aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 850 DEG C of the article shaped is carried
Body Z6.The property of carrier Z6 is listed in table 2.
Embodiment 17
200 grams of PA-1,600 grams of PB-1 are weighed, after uniformly mixing with 4 obtained 200 grams of raw material PC-A4 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1440 milliliters of 10 milliliters of the aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 850 DEG C of the article shaped is carried
Body Z7.The property of carrier Z76 is listed in table 2.
Embodiment 18
200 grams of PA-1,600 grams of PB-1 are weighed, after uniformly mixing with 2 obtained 200 grams of raw material PC-A2 of embodiment, is added
Three factory's product of the chemical reagent of Tianjin containing nitric acid）1440 milliliters of 10 milliliters of the aqueous solution, is extruded into external diameter φ on double screw banded extruder
The butterfly bar of 1.4mm.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, and the roasting 3 hours of 850 DEG C of the article shaped is carried
Body Z8.The property of carrier Z8 is listed in table 2.
Comparative example 3
According to the method that patent CN1782031A embodiment 7 is provided, it is extruded into external diameter φ 1.4mm's on plunger type bar extruder
Butterfly bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 900 DEG C of the article shaped, obtains carrier DZ3.
The property of carrier DZ3 is listed in table 2.
Comparative example 4
According to the method that patent CN1120971A embodiment 1 is provided, it is extruded into external diameter φ 1.4mm's on plunger type bar extruder
Butterfly bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 1000 DEG C of the article shaped, obtains carrier DZ3.
The property of carrier DZ3 is listed in table 2.
Comparative example 5
200 grams of PA-1,800 grams of PB-2 are weighed, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）10 milliliters of the aqueous solution
1300 milliliters, the butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar is obtained in 120 DEG C of dryings 4 hours
Type thing, by the roasting 3 hours of 1000 DEG C of the article shaped, obtains carrier DZ5.The property of carrier DZ5 is listed in table 2.
Table 2
Can be seen by the result of table 2, compared with conventional method, the alumina support tool prepared by the method provided by the present invention
There is obvious structure of double peak holes.
Catalyst that the embodiment 19-23 explanation present invention is provided and preparation method thereof.
Wherein, in catalyst, the content of active metal component is determined using Xray fluorescence spectrometer（All appts are Japan
3271 type Xray fluorescence spectrometer of Liue electrical machinery Industrial Co., Ltd, concrete grammar are shown in Petrochemical Engineering Analysis method RIPP133-
90）.
Embodiment 19
200 grams of carrier Z1 are taken, contains MoO with 210 milliliters367.9 g/l, CoO11.3 g/l of molybdenum oxide and basic carbonate
Cobalt mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours obtain catalyst C1.In catalyst C1
The content of molybdenum oxide and cobalt oxide is listed in table 3.
Comparative example 6
200 grams of carrier DZ1 are taken, contains MoO with 180 milliliters379.2 g/l, CoO13.2 g/l of molybdenum oxide and alkali formula carbon
Sour cobalt mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, obtains catalyst DC1.Catalyst DC1
In molybdenum oxide and the content of cobalt oxide be listed in table 3.
Embodiment 20
200 carrier Z2 are taken, contains MoO with 200 milliliters353.1 g/l, NiO10.6 g/l of molybdenum oxide and basic nickel carbonate
Mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours obtain catalyst C2.Oxygen in catalyst C2
The content for changing molybdenum and nickel oxide is listed in table 3.
Comparative example 7
200 carrier DZ3 are taken, contains MoO with 180 milliliters359.0 g/l, NiO11.8 g/l of molybdenum oxide and basic carbonate
Nickel mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours obtain catalyst DC2.In catalyst DC2
Molybdenum oxide and the content of nickel oxide be listed in table 3.
Embodiment 21
200 grams of carrier Z3 are taken, contains MoO with 205 milliliters378.5 g/l, NiO15.7 g/l of ammonium molybdate and nickel nitrate are mixed
Solution impregnation 1 hour is closed, 2 hours are dried in 120 DEG C, 420 DEG C of roastings 3 hours obtain catalyst C3.Oxidation in catalyst C3
The content of molybdenum and nickel oxide is listed in table 3.
Comparative example 8
200 grams of carrier DZ4 are taken, contains MoO with 180 milliliters387.2 g/l, NiO17.4 g/l of molybdenum oxide and alkali formula carbon
Sour nickel mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, obtains catalyst DC3.Catalyst DC3
In molybdenum oxide and the content of nickel oxide be listed in table 3.
Embodiment 22
200 grams of carrier Z6 are taken, contains MoO with 210 milliliters367.9 g/l, NiO11.3 g/l of molybdenum oxide and basic carbonate
Nickel mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours obtain catalyst C4.In catalyst C4
The content of molybdenum oxide and nickel oxide is listed in table 3.
Embodiment 23
200 grams of carrier Z8 are taken, contains MoO with 200 milliliters382.8 g/l, CoO19.1 g/l of molybdenum oxide and basic carbonate
Cobalt mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours obtain catalyst C5.In catalyst C5
The content of molybdenum oxide and cobalt oxide is listed in table 3.
Comparative example 9
200 grams of carrier DZ5 are taken, contains MoO with 200 milliliters382.8 g/l, CoO19.1 g/l of molybdenum oxide and alkali formula carbon
Sour cobalt mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, obtains catalyst DC4.Catalyst DC4
In molybdenum oxide and the content of cobalt oxide be listed in table 3.
Table 3
Embodiment 24-28
The residuum hydrogenating and metal-eliminating performance of the catalyst that the embodiment 24-28 explanation present invention is provided.
The particle that catalyst C1, C2, C3, C4 and C5 are broken into diameter 2-3 millimeters is loaded into reactor respectively.Reaction condition
For：380 DEG C of reaction temperature, 14 MPas of hydrogen dividing potential drop, are determined using inductive coupling plasma emission spectrograph (ICP-AES) and are hydrogenated with
After before processing oil in nickel and vanadium content（Instrument be U.S.'s PE companies PE-5300 type plasma quantometers, concrete grammar
See Petrochemical Engineering Analysis method RIPP124-90）.Using pitch in oil before and after the analysis hydrotreating of asphalt compound mensuration method
Matter mass fraction（Concrete grammar is referring to SH/T0509-92）.Asphalitine and metal removal rate is calculated according to the following formula：
Feedstock oil be nickel content be 29.3ppm, content of vanadium be 83ppm, sulfur content be 4.7%, nitrogen content be 0.3%, it is residual
Carbon is the 15.1% normal slag of Kuwait.
The activity data of each catalyst is shown in Table 4.
Comparative example 10-13
Method according to embodiment 24-28 evaluates demetallization per and the depitching matter of catalyst DC1, DC2, DC3 and DC4
Rate, the results are shown in Table 4.
Table 4
| Embodiment | Catalyst is numbered | Depitching matter rate/% | Demetallization per/% |
| 24 | C1 | 86 | 78 |
| Comparative example 10 | DC1 | 65 | 70 |
| 25 | C2 | 89 | 71 |
| Comparative example 11 | DC2 | 62 | 65 |
| 26 | C3 | 87 | 76 |
| Comparative example 12 | DC3 | 72 | 73 |
| 27 | C4 | 90 | 80 |
| 28 | C5 | 86 | 84 |
| Comparative example 13 | DC4 | 80 | 78 |
Can be seen by 4 result of table, the depitching of catalyst is provided by the present invention in poor residuum hydroprocessing processes
Matter and metal removal activity will be substantially better than existing catalyst, illustrate processing of this technology invention catalyst more suitable for poor residuum
Process.
Claims (20)
1. a kind of Hydrodemetalation catalyst, containing alumina support and hydrogenation active metals component, wherein, the carrier has
Structure of double peak holes, is characterized with mercury injection method, and the pore volume of the carrier is 0.6-1.4 ml/g, and specific surface area is 80-400 rice2/
Gram, the pore volume in a diameter of 5-20nm holes accounts for the 30-60% of total pore volume, and the pore volume in a diameter of 100-300nm holes accounts for total pore volume
15-45%.
2. catalyst according to claim 1, it is characterised in that the pore volume of the carrier is 0.7-1.3 ml/g, than
Surface area is 100-300 rice2/ gram, the pore volume in a diameter of 5-20nm holes accounts for the 35-50% of total pore volume, a diameter of 100-300nm
The pore volume in hole accounts for the 20-40% of total pore volume.
3. catalyst according to claim 1, it is characterised in that the hydrogenation active metals component is selected from least one the
VIII race's metal component and at least one vib metals component, are counted by oxide and on the basis of catalyst, the VIIIth race gold
The content of category component is more than 3 to less than or equal to 10 weights more than 0.8 to the content less than or equal to 3 weight %, metal component of group VIB
Amount %.
4. catalyst according to claim 3, it is characterised in that the metal component of group VIII is selected from cobalt and/or nickel, the
Group vib metal component is selected from molybdenum and/or tungsten, counted by oxide and on the basis of catalyst, and the metal component of group VIII contains
Measure as 1-2 weight %, the content of metal component of group VIB is more than 4 to less than or equal to 8 weight %.
5. the preparation method of catalyst according to claim 1, including preparing carrier and load hydrogenation activity on this carrier
Metal component, wherein, the preparation of the carrier includes containing the hydrated alumina PA and PB containing boehmite with one kind
The modifier PC mixing of the hydrated alumina of boehmite, shaping, dry and roasting, wherein, the weight of described PA, PB and PC
Mixing ratio is 20-60：20-50：The κ values of 5-50, PC are the κ=DI 0 to less than or equal to 0.92/DI1, DI1For PC before modified
Hydrated alumina sour peptization index, DI2For the sour peptization index of the PC.
6. method according to claim 5, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50：35-
50：10-30.
7. method according to claim 5, it is characterised in that the κ values of the PC are 0 to less than or equal to 0.6.
8. the method according to claim 5 or 6, it is characterised in that the hydrated alumina PA containing boehmite
Pore volume be 0.75-1 ml/g, specific surface area be 200-450 rice2/ gram, most probable bore dia 3-10nm；It is described thin containing intending
The pore volume of the hydrated alumina PB of diaspore is 0.9-1.4 ml/g, and specific surface area is 100-350 rice2/ gram, most probable hole is straight
Footpath is more than 10 to less than or equal to 30nm.
9. method according to claim 8, it is characterised in that the hole of the hydrated alumina PA containing boehmite
Hold for 0.80-0.95 ml/g, specific surface area is 200-400 rice2/ gram, most probable bore dia 5-10nm；It is described thin containing intending
The pore volume of the hydrated alumina PB of diaspore is 0.95-1.3 ml/g, and specific surface area is 120-300 rice2/ gram, most probable hole
With diameter greater than 10 to less than or equal to 25nm.
10. the method according to 5,6 or 7 any one of claim, it is characterised in that particles of the PC for 80-300 mesh
Thing.
11. methods according to claim 10, it is characterised in that particulate matters of the PC for 100-200 mesh.
12. methods according to claim 5, it is characterised in that the condition of the drying includes：Temperature is 40-350 DEG C,
Time is 1-24 hours, and the condition of the roasting includes：Temperature is that the time is that 1-8 is little more than 500 to less than or equal to 1200 DEG C
When.
13. methods according to claim 12, it is characterised in that the condition of the drying includes：Temperature is 100-200
DEG C, the time is 2-12 hours, and the condition of the roasting includes：Temperature is that to less than or equal to 1000 DEG C, roasting time is more than 800
2-6 hours.
14. methods according to claim 5, it is characterised in that the hydrated alumina containing boehmite is modified as
One of method of PC is by the shaping of the hydrated alumina containing boehmite, is dried, and is entered its all or part afterwards
Row grinding, screening, the condition of the drying include：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are by method
The one article shaped roasting for obtaining, sintering temperature are that roasting time is 1-8 hours more than 350 to less than or equal to 1400 DEG C, afterwards will
Its all or part is ground, sieves；The three of method are that the hydrated alumina containing boehmite is dodged dry, dodge dry temperature
It is that flash-off time is 0.05-1 hours more than 150 to less than or equal to 1400 DEG C；The four of method be by one of method, method two
And with the three of the method modifiers for obtaining in several be mixed to get.
15. methods according to claim 14, it is characterised in that the condition of the drying in methods described one includes：Temperature
For 100-200 DEG C, the time is 2-12 hours；The dry temperature of sudden strain of a muscle in the three of method is 200-1000 DEG C, and flash-off time is 0.1-0.5
Hour.
16. methods according to claim 14, it is characterised in that the PC is the hydrated alumina containing boehmite
Modifier in 80-300 mesh particulate matter.
17. methods according to claim 16, it is characterised in that the PC is the hydrated alumina containing boehmite
Modifier in 100-200 mesh particulate matter.
18. methods according to claim 5, it is characterised in that described in supported on carriers hydrogenation active metals component
Method is infusion process, and the solution including compound of the preparation containing hydrogenation active metals simultaneously uses the solution impregnating carrier, carries out afterwards
Dry, roasting or not roasting, metal component and at least one of the hydrogenation active metals component selected from least one vib
The metal component of the VIIIth race, is counted by oxide and on the basis of catalyst, and the compound containing hydrogenation active metals is described
The consumption of the concentration of solution and the solution makes the content of the metal component of the vib in final catalyst more than 3 to being less than
Equal to 10 weight %, the content of the metal component of the VIIIth race is more than 0.8 to less than or equal to 3 weight %；Described pair impregnated
The condition that is dried of carrier include：Temperature is 100-250 DEG C, and the time is 1-10 hours；It is described that impregnated carrier is entered
The condition of row roasting includes：Temperature is 360-500 DEG C, and the time is 1-10 hours.
19. methods according to claim 18, it is characterised in that the metal component of the vib be selected from molybdenum and/or
Tungsten, the metal component of the VIIIth race are selected from cobalt and/or nickel, are counted by oxide and on the basis of catalyst, described containing hydrogenation activity gold
The metal component of vib of the compound of category in the concentration of the solution and the consumption of the solution make final catalyst
More than 4 to 8 weight % are less than or equal to, the content of the metal component of the VIIIth race is 1-2 weight % to content；It is described to impregnated load
The condition that body is dried includes：Temperature is 100-140 DEG C, and the time is 1-6 hours；It is described that roasting is carried out to impregnated carrier
Condition include：Temperature is 360-450 DEG C, and the time is 2-6 hours.
Application of the catalyst in 20. claims 1-4 described in any one in hydrocarbon oil hydrogenation process.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
| CN1796500A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Alumina supporter possessing duplicate orifice, catalyst and preparation method |
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| US7737072B2 (en) * | 2004-09-10 | 2010-06-15 | Chevron Usa Inc. | Hydroprocessing bulk catalyst and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
| CN1796500A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Alumina supporter possessing duplicate orifice, catalyst and preparation method |
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