CN104338527B - A kind of heavy-oil hydrogenation depitching matter catalyst and preparation and application thereof - Google Patents
A kind of heavy-oil hydrogenation depitching matter catalyst and preparation and application thereof Download PDFInfo
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Abstract
A kind of heavy-oil hydrogenation depitching matter catalyst and preparation and application thereof, this catalyst contains carrier and hydrogenation active metals component, described hydrogenation active metals component is selected from the metal component of at least one group vib and the metal component of at least one VB race, wherein, described carrier is a kind of Bimodal-pore alumina support containing group ivb metal component, characterizing with mercury injection method, the pore volume of described carrier is 0.6 1.4 mls/g, and specific surface area is 80 400 meters2/ 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 the 15 45% of total pore volume.Compared with prior art, the catalyst that the present invention provides has preferably hydrogenation depitching matter and demetalization performance when for residual hydrocracking.
Description
Technical field
The present invention relates to a kind of hydrogenation depitching matter catalyst and preparation and application thereof.
Background technology
Mink cell focus including residual oil is carried out deep processing and not only contributes to improve the utilization rate of crude oil, alleviate the energy
The nervous trend of supply, can also reduce environmental pollution simultaneously, reach the clean utilization of the energy.Compared with distillate, in mink cell focus
Containing macromolecular reaction things such as substantial amounts of asphalitine, colloids, and the heteroatomic compounds such as sulfur in mink cell focus, nitrogen, oxygen 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 the follow-up courses of processing
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, need the characteristic according to asphalitine, select active high and the performance of good stability is excellent
Good catalyst.
For the hydrogenation catalyst of depitching matter, catalyst performance tool is of great significance by its pore-size distribution.
The molecular size of asphalitine is about tens of to hundreds of nanometer, if catalyst active center be smaller than asphaltene molecules, then
Asphaltene molecules is difficult to be contacted with the active center of catalyst by diffusion, and mainly adsorbs in the outer surface of catalyst or hole
Mouthful, along with the carrying out of reaction can only form coke because of thermal condensation, cause catalysqt deactivation.Macroporous catalyst is conducive to asphalitine
Removing, but the aperture of catalyst and specific surface negative correlation each other, the catalyst that i.e. average pore size is big, its specific surface area is the least.Cause
This is in order to take into account this character, and catalyst needs rational pore size distribution.
Existing Heavy oil hydrogenation catalyst is disadvantageous in that its S, N removal rate, heavy metal removing rate and asphalitine are de-
Except not reaching between rate well to mate, such as, removing metal active is high catalyst often S, N removal rate and asphalitine are de-
Except rate is the highest.The reason producing problems is the most complicated.First consisting in raw material, in residual oil, the feature of each component is molecular weight
Greatly, structure is complicated, and saturation low (armaticity is high), S, N content are high.And beyond sulphur removal, the overwhelming majority of impurity again more to be present in
In asphalitine, therefore it is intended to remove this type of S, N, it is necessary to the conversion that asphaltene molecules carries out appropriateness (includes saturated, open loop and hydrogenolysis
Deng).Next is catalyst.In prior art, having the catalyst being suitable for carrying out this type of reaction aperture is guard catalyst
And catalyst for demetalation, such as:
Disclosed in CN1267537C a kind of have relatively low carbon deposition quantity and the Hydrodemetalation catalyst of greater activity and
Preparation method.
A kind of residuum hydrogenating and metal-eliminating catalyst disclosed in CN1796500A, this 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 uses
Method includes mixing the precursor of a kind of aluminium oxide with the nitrogen-containing compound beyond a kind of deacidification, molding roasting.
Catalyst for heavy oil fixed bed hydrogenating treatment and preparation method etc. disclosed in CN1233795C.
But, the asphaltene removal of these catalyst is the most relatively low.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalysis new, that have preferably hydrogenation depitching matter performance
Agent, the preparation method of this catalyst and application.
The present invention relates to herein below:
1. a heavy-oil hydrogenation depitching matter catalyst, containing carrier and hydrogenation active metals component, described hydrogenation activity
Metal component is selected from the metal component of at least one group vib and the metal component of at least one VB race, and wherein, described carrier is one
Planting the Bimodal-pore alumina support containing group ivb metal component, characterize with mercury injection method, the pore volume of described carrier is 0.6-1.4
Ml/g, specific surface area is 80-400 rice2/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 30-60% of total pore volume, a diameter of
The pore volume in 100-300nm hole accounts for the 15-45% of total pore volume.
2. according to the catalyst described in 1, it is characterised in that the pore volume of described carrier is 0.7-1.3 ml/g, specific surface
Amass as 100-300 rice2/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-50% of total pore volume, a diameter of 100-300nm hole
Pore volume accounts for the 20-40% of total pore volume.
3, according to the catalyst described in 1, it is characterised in that described group ivb metal component is selected from titanium, zirconium, hafnium
Planting or several, on the basis of described carrier and in terms of oxide, in described carrier, the content of the IVth race's metal is 0.1-6 weight %.
4, according to the catalyst described in 3, it is characterised in that described group ivb metal component is titanium, with described carrier as base
Accurate and in terms of oxide, in described carrier, the content of group ivb metal is 0.3-4 weight %.
5, according to the catalyst described in 4, it is characterised in that on the basis of described carrier and in terms of oxide, described carrier
The content of middle group ivb metal is 0.5-2.5 weight %.
6. according to the catalyst described in 1, it is characterised in that described hydrogenation active metals component is selected from least one group vib
Metal component and the combination of metal component of at least one VB race, count and on the basis of catalyst by oxide, described group vib
The content of metal component is 0.2-15 weight %, and the content of VB race metal component is 0.2-12 weight %.
7. according to the catalyst described in 3, it is characterised in that the metal component of described group vib is selected from molybdenum and/or tungsten, VB race
Metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, and the content of described group vib metal component is
0.5-12 weight %, the content of VB race metal component is 0.5-9 weight %.
8. according to the preparation method of catalyst described in 1, including prepare have structure of double peak holes containing the IVth B race metal component
Alumina support, the preparation method of described carrier includes containing hydrated alumina PA and PB containing boehmite with one
There is the modifier PC mixing of the hydrated alumina of boehmite and introduce the change containing the IVth B race metal component in the mixture
Compound, molding, dry and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is the κ value of 20-60:20-50:5-50, PC
It is 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1For the sour peptization index of PC hydrated alumina before modified, DI2For described
The sour peptization index of PC.
9. according to the method described in 8, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50:35-50:
10-30。
10. according to the method described in 8, it is characterised in that described IVth B race metal one in titanium, zirconium, the hafnium and
Mixture, counts and on the basis of carrier by oxide, and the described introduction volume containing the IVth B race metallic compound makes in final carrier
The content of IV B race metal is 0.1-6 weight %.
11. according to the method described in 10, it is characterised in that described IVth B race metal is titanium, in terms of oxide and with carrier
On the basis of, the described introduction volume containing the IVth B race metallic compound makes the content of the IVth B race metal in final carrier be 0.3-4 weight
Amount %.
12. according to the method described in 8, it is characterised in that the k value of described PC is 0 to less than or equal to 0.6.
13. according to the method described in 8 or 9, it is characterised in that the hole of the described hydrated alumina PA containing boehmite
Holding for 0.75-1 ml/g, specific surface is 200-450 rice2/ gram, can and bore dia 3-10nm；Described containing boehmite
The pore volume of hydrated alumina PB be 0.9-1.4 ml/g, specific surface is 100-350 rice2/ gram, can and bore dia more than 10
To less than or equal to 30nm.
14. according to the method described in 13, it is characterised in that the pore volume of the described hydrated alumina PA containing boehmite
For 0.80-0.95 ml/g, specific surface is 200-400 rice2/ gram, can and bore dia 5-10nm；Described containing intending thin water aluminum
The pore volume of the hydrated alumina PB of stone is 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, can and bore dia big
In 10 to less than or equal to 25nm.
15. according to the method described in 8 or 9, it is characterised in that described PC is the particulate matter of 80-300 mesh.
16. according to the method described in 15, it is characterised in that described PC is the particulate matter of 100-200 mesh.
17. according to the method described in 8, it is characterised in that described dry condition includes: temperature is 40-350 DEG C, the time
For 1-24 hour, the condition of described roasting included: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500.
18. according to the method described in 17, it is characterised in that described dry condition includes: temperature is 100-200 DEG C, time
Between be 2-12 hour, the condition of described roasting includes: temperature for more than 800 to less than or equal to 1000 DEG C, roasting time is 2-6
Hour.
19. according to the method described in 8, it is characterised in that the hydrated alumina containing boehmite is modified as PC's
One of method is by described hydrated alumina molding containing boehmite, is dried, and it is completely or partially ground afterwards
Mill, screening, described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are method one to be obtained
The article shaped roasting arrived, sintering temperature is that roasting time is 1-8 hour, afterwards that it 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 to dodge the hydrated alumina containing boehmite to do, and it is big for dodging dry temperature
In 150 to less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour；The four of method be by one of method, the two of method and with
One or more in the modifier that the three of method obtain are mixed to get.
20. according to the method described in 19, it is characterised in that the condition being dried in described method one includes: temperature is
100-200 DEG C, the time is 2-12 hour；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is that 0.1-6 is little
Time；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour.
21. according to the method described in 19, it is characterised in that described PC is changing of the hydrated alumina containing boehmite
The particulate matter of 80-300 mesh in property thing.
22. according to the method described in 21, it is characterised in that described PC is changing of the hydrated alumina containing boehmite
The particulate matter of 100-200 mesh in property thing.
23. according to the method described in 8, it is characterised in that described method is included in described supported on carriers hydrogenation active metals
Component, the method for load hydrogenation active metals component is infusion process on the carrier, including preparation containing hydrogenation active metals
The solution of compound also uses this solution impregnating carrier, is dried afterwards, roasting or not roasting, described hydrogenation active metals component
Selected from metal component and at least one Group VB metal component of at least one vib, in terms of oxide and with catalyst it is
Benchmark, the concentration of described impregnation liquid and consumption make the content of group vib metal component described in final catalyst be 0.2-15 weight
The content of amount %, VB race metal component is 0.2-12 weight %, and described drying condition is: temperature 80-200 DEG C, 1-8 hour time,
Roasting condition is: temperature 400-600 DEG C, 2-8 hour time.
24. according to the method described in 23, it is characterised in that the metal component of described group vib is selected from molybdenum and/or tungsten, VB race
Metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, and concentration and the consumption of described impregnation liquid make
Described in whole catalyst, the content of group vib metal component is 0.5-12 weight %, and the content of VB race metal component is 0.5-9 weight
Amount %, described drying condition is: temperature 100-150 DEG C, 2-6 hour time, and roasting condition is: temperature 420-500 DEG C, time 3-6
Hour.
25. according to the method described in 24, it is characterised in that count and on the basis of catalyst by oxide, described impregnation liquid
Concentration and consumption make the content of group vib metal component described in final catalyst be 5-12 weight %, VB race metal component
Content is 1-9 weight %.
Catalyst described in any one application in hydrocarbon oil hydrogenation processes in 26. claim 1-7.
The catalyst provided according to the present invention, one or more in titanium, zirconium, hafnium of described group ivb metal component,
Being preferably titanium, count and on the basis of described carrier by oxide, the content of described group ivb metal is 0.1-0.6 weight %, excellent
Elect 0.3-4 weight %, more preferably 0.5-2.5 weight % as.
Optionally, described carrier can make the most easily operated article shaped, the most spherical, cellular, nest like,
Tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.).Wherein, the method described PA, PB and PC mixed is conventional method, example
As, PA, PB and PC of powder body are put in stirring-type batch mixer according to ingredient proportion and mixes.To described PA, PB and PC mixture
The method of the middle introducing compound containing the IVth B race metal is conventional method, for example, it may be directly contain the IVth B by the desired amount of
The compound of race's metal is mixed in aforesaid PA, PB and PC mixed process.
In a concrete embodiment preparing carrier, introduce containing the IVth B in the mixture of described PA, PB and PC
The method of the compound of race's metal is by being configured to aqueous solution containing the IVth B race metallic compound, by this aqueous solution at described PA, PB
With PC mix while be mixed into or described PA, PB and PC mix after again this aqueous solution is mixed into, aftershaping, be dried also
Roasting.Described contain the IVth B race metal compound can be arbitrary IVth B race metal water soluble compound in one or
Several.Such as, one or more in the water-soluble inorganic salt of the IVth B race metal.
In the present invention, described molding is carried out according to a conventional method, such as, and a kind of method in spin, tabletting and extruded moulding
Or the combination of several method.When molding, such as extruded moulding, for ensureing that described molding is smoothed out, can mix to described
Compound adds water, extrusion aid and/or adhesive, with or without expanding agent, then extrusion molding, be dried afterwards and roast
Burn.Described extrusion aid, the kind of peptizer and consumption are known to those skilled in the art, and the most common extrusion aid can select
One or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH, described peptizer can be mineral acid
And/or organic acid, described expanding agent can be the one in starch, synthetic cellulose, polymeric alcohol and surfactant or several
Kind.Synthetic cellulose therein is preferably hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl fiber poly alkyl alcohol
One or more in vinyl Ether, polymeric alcohol is preferably one or more in Polyethylene Glycol, poly-propanol, polyvinyl alcohol, surface
Activating agent preferably fat alcohol polyethylene ether, fatty alkanol amide and derivant thereof, molecular weight are the propenyl copolymerization of 200-10000
One or more in thing and maleic acid copolymer.
In the present invention, described acid peptization index D I refers to the hydrated alumina containing boehmite and containing intending thin water
After the hydrated alumina modifier of aluminum stone adds nitric acid by certain acid aluminum ratio, intended by containing of peptization within certain response time
The hydrated alumina of boehmite is with Al2O3The percent of meter, DI=(1-W2/W1) × 100%, W1And W2It is respectively containing intending thin water
Before the hydrated alumina of aluminum stone and acid reaction and with acid reaction after with Al2O3The weight of meter.
The mensuration of DI includes: (1) measure calcination base (also referred to as butt) content of the hydrated alumina containing boehmite
(calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours, weight weight ratio front with burning after its burning, with
Percent represents), it is calculated as a；(2) weigh the hydrated alumina W containing boehmite with analytical balance0Gram, W0Amount meet with
Al2O3The W of meter1It is 6 grams of (W1/a=W0), weigh deionized water W gram, W=40.0-W0, under stirring, contain the thin water aluminum of plan by weigh
The hydrated alumina of stone and deionized water add in beaker and mix；With 20mL pipet pipette 20mL, concentration is the dilute of 0.74N
Salpeter solution, joins in the beaker of step (2) by this acid solution, the lower reaction of stirring 8 minutes；(4) by reacted for step (3)
Serosity is centrifuged separating in centrifuge, is inserted by precipitate in the crucible weighed, and afterwards, in 125 DEG C, it is dried 4 little
Time, 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 being enough to make final carrier meet application claims, the present invention is to the described water containing boehmite
Close aluminium oxide PA and PB not specially require, can be the boehmite prepared of any prior art, it is also possible to be to intend thin water
The mixture of aluminum stone and other hydrated alumina, other hydrated alumina described is selected from a water aluminium oxide, gibbsite
And one or more in amorphous hydrated aluminium oxide.
In a detailed description of the invention, the described preferred pore volume of hydrated alumina PA containing boehmite is 0.75-1
Ml/g, specific surface is 200-450 rice2/ gram, can and bore dia 3-10nm, further preferred pore volume is 0.80-0.95 milli
Rise/gram, specific surface is 200-400 rice2/ gram, can and bore dia 5-10nm；The described hydrated alumina containing boehmite
The preferred pore volume of PB is 0.9-1.4 ml/g, and specific surface is 100-350 rice2/ gram, can and bore dia more than 10 to being less than or equal to
30nm, further preferred pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, can and bore dia 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 can and aperture, be by institute
State the hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours, BET N2 adsorption characterize and obtain.
In further preferred embodiment, characterize with X diffraction, the described hydrated alumina PA containing boehmite
With the boehmite content in PB not less than 50%, more preferably not less than 60%.
Inventors of the present invention have surprisingly found that, carry out being thermally treated resulting in changing by the hydrated alumina containing boehmite
Property thing PC, relative to the original hydrated alumina containing boehmite, the peptization index of modifier PC changes, will
This modifier and PA and PB mixed-forming, it is dried and after roasting, obtained carrier has obvious bimodal pore distribution.Especially
It is at the granule by 80-300 mesh therein, the granule of preferably 100-200 mesh and PA and PB mixed-forming, is dried and after roasting,
Obtained by carrier bimodal in each unimodal pore size distribution concentrate especially.Here, the granule of described 80-300 mesh, preferably
The granule of 100-200 mesh refers to that described modifier (includes step that is broken or that grind) if desired through sieving, and its screening thing is (under sieve
Thing) meet the granule of 80-300 mesh, the particulate matter of preferably 100-200 mesh accounts for the percent (by weight) of total amount not less than 60%,
Further preferably not less than 70%.Here the hydrated alumina containing boehmite can any prior art be prepared
Boehmite, it is also possible to be boehmite and the mixture of other hydrated alumina, other hydrated alumina described
One or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide.In a preferred embodiment,
Described PC is the modifier of PA and/or PB.
In the present invention, described PA, PB refer in the most described PA, PB mixture with PC with the Mixing ratio by weight of PC
The ratio of the most shared parts by weight of PA, PB and PC.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 conveniently can be obtained by following method:
Hereinafter, the method illustrating to obtain PC with described PA and PB for initiation material.
(1) based on being dried to obtain PC, including by hydrated alumina PA and/or PB containing boehmite according to a conventional method
During regular oxidation alumina supporter is prepared in molding, the tailing of drying by-product, such as: in extruded moulding, bar shaped article shaped exists
Dry, the tailing (being referred to as traditionally being dried waste material) of integer process by-product, mills this tailing, sieves and obtain PC.
(2) obtain based on roasting, become according to a conventional method including by hydrated alumina PA and/or PB containing boehmite
During regular oxidation alumina supporter prepared by type, the tailing (being referred to as roasting waste material traditionally) of fired by-product, such as, become in spin
In type, spheroidal particle is the tailing of by-product in roasting process, is milled by this tailing, sieves and obtain PC；Or directly will
PA and/or PB dodges and dry obtains, and when directly dodging dry by PA and/or PB, flash-off time is preferably 0.05-1 hour, further preferably
For 0.1-0.5 hour.
(3) two or more be mixed to get in the modifier PC obtained based on preceding method.Obtain when using mixed method
When obtaining C, the mixed proportion of the modifier PC respectively obtaining aforementioned several method does not limit.
The catalyst provided according to the present invention, wherein, described group vib metal component is preferably molybdenum and/or tungsten, the most excellent
Electing molybdenum or tungsten as, VB race metal component is preferably vanadium and/or niobium, more preferably vanadium.In terms of oxide and with catalyst it is
Benchmark, the content of described vib metals component is preferably 0.2-15 weight %, more preferably 0.5-12 weight %, more
It is preferably 5-12 weight %；The content of Group VB metal component is preferably 0.2-12 weight %, more preferably 0.5-9 weight %,
It is more preferably 1-9 weight %.
On the premise of being enough to be carried on described carrier described hydrogenation active metals component, the present invention is to described negative
Support method is not particularly limited, and preferred method is infusion process, including the dipping solution of the preparation compound containing described metal, it
Afterwards with the carrier described in this solution impregnation.Described dipping method is conventional method, for example, it may be excess immersion stain, hole satisfy
With method infusion process.The described one being selected from the soluble compound in them containing the metal component compound selected from VI B race
Or it is several, such as one or more 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.One or more in the described soluble compound being selected from them containing the compound selected from VB race metal component, with VB
As a example by the vanadium of race, can be selected from such as the one or several in vanadic anhydride, ammonium vanadate, ammonium metavanadate, Sulfovanadic acid, vanada polyacid
Kind, ammonium metavanadate preferably wherein, ammonium vanadate.
The catalyst provided according to the present invention, it is also possible to provide catalyst performance maybe can change containing any present invention that do not affects
The addO-on therapy of the catalytic performance of the catalyst that rare book invention provides.As the addO-on therapy such as phosphorus can be contained, in terms of oxide also
On the basis of catalyst, the content of described addO-on therapy is less than 10 weight %, preferably 0.1-4 weight %.
When in described catalyst possibly together with addO-on therapy such as phosphorus, the introducing method of described addO-on therapy can be arbitrary
Method, can be by containing as described in the component such as phosphorus compound directly with as described in boehmite mix, molding roasting；Permissible
It is that the compound containing components such as described phosphorus and the compound containing hydrogenation active metals component are configured to leaching after mixed solution
Carrier described in stain；Can also is that and after the compound containing components such as phosphorus is individually prepared solution, impregnate described carrier roasting.When
When the addO-on therapy such as phosphorus and hydrogenation active metals introduce described carrier respectively, first with containing described addO-on therapy compound
Solution impregnation described in carrier roasting, the most again by the solution impregnation containing hydrogenation active metals component composition.Wherein, institute
Stating sintering temperature and be 400-600 DEG C, preferably 420-500 DEG C, roasting time is 2-6 hour, preferably 3-6 hour.
According to hydrocarbon ils provided by the present invention (including residual oil) hydrotreating method, anti-to the hydrotreating of described hydrocarbon ils
Answering condition to be not particularly limited, in a preferred embodiment, described 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
Time-1, further preferred 0.15-2 hour-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.
The device of described hydrogenation reaction can any be enough to make described raw oil at hydrotreating reaction conditions with institute
State in the catalytic reactor of catalyst and carry out, such as, anti-at described fixed bed reactors, moving-burden bed reactor or ebullated bed
Answer in device and carry out.
According to the conventional method in this area, described hydrotreating catalyst before the use, generally can exist at hydrogen
Under, at a temperature of 140-370 DEG C, carrying out presulfurization with sulfur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outside device
Also can be In-situ sulphiding in device, the active metal component it loaded is converted into metal sulfide component.
The catalyst that the present invention provides can be used alone, it is also possible to is applied in combination with other catalyst, and this catalyst is special
It is not suitable for heavy oil particularly poor residuum and carries out hydrotreating, in order to provide for subsequent technique (such as catalytic cracking process) and close
The raw oil of lattice.Compared with prior art, the catalyst that the present invention provides has when for residual hydrocracking and preferably adds
Hydrogen depitching matter and demetalization performance.
Detailed description of the invention
The present invention will be further described for the following examples, but should be therefore understands that be not limitation of the invention.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
The boehmite used below in an example includes:
(pore volume is 0.9 ml/g to the dry glue powder that PA-1: Chang Ling catalyst branch company produces, and specific surface is 280 meters2/ gram,
Can and bore dia 8.5nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %, surplus
For amorphous alumina, DI value 34.6).
(pore volume is 0.9 ml/g to the dry glue powder of PA-2: Zibo limited production of neat cyclopentadienyl catalyst, and specific surface is 290 meters2/
Gram, can and bore dia 8.3nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %,
Surplus is amorphous alumina, DI value 33.2).
(pore volume is 1.2 mls/g to the dry glue powder that PB-1: Chang Ling catalyst branch company produces, and specific surface is 280 meters2/ gram,
Can and bore dia 15.8nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %, remaining
Amount is amorphous alumina, DI value 15.8).
(pore volume is 1.1 mls/g to the dry glue powder that PB-2: Yantai Heng Hui Chemical Co., Ltd. produces, and specific surface is 260
Rice2/ gram, can and bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 weights
Amount %, surplus is amorphous alumina, DI value 17.2).
Embodiment 1-10 illustrates PC of the present invention and preparation method thereof.
Embodiment 1
Weigh 1000 grams of PA-1, add the aqueous solution 1000 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains dried strip,
By dried strip shaping, sieve, the length dried strip material (commonly referred to as industrially drying bar waste material) less than 2mm milled,
Sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier PC-A1 of PA-1.The k value of PC-A1 is shown in Table 1.
Embodiment 2
Weigh 1000 grams of PA-1, add the aqueous solution 1000 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, 800 DEG C of roastings 4
Hour, obtain carrier, by carrier strip shaping, sieve, by the length carrier strip material less than 2mm, (commonly referred to as industry carrier gives up
Material) mill, sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier PC-A2 of PA-1.The k value of PC-A2 is shown in Table 1.
Embodiment 3
Weigh 1000 grams of PA-2, dodge dry 6 minutes in 400 DEG C, obtain the modifier PC-A3 of PA-2.The k value of PC-A3 is shown in Table
1。
Embodiment 4
The each 200 grams of uniform mixing of PC-A3 that PC-A1 embodiment 1 obtained and embodiment 3 obtain, obtain PA-1 and PA-
The modifier PC-A4 of 2.The k value of PC-A4 is shown in Table 1.
Embodiment 5
Weigh 1000 grams of PB-1, add the aqueous solution 1440 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, 1200 DEG C of roastings 4
Hour, obtain carrier, by carrier strip shaping, sieve, by the length carrier strip material less than 2mm, (commonly referred to as industry carrier gives up
Material) mill, sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier PC-B1 of PB-1.The k value of PC-B1 is shown in Table 1.
Embodiment 6
Weigh 1000 grams of PB-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier PC-B2 of PB-2.The k value of PC-B2 is shown in Table
1。
Embodiment 7
Weigh 1000 grams of PB-2, add the aqueous solution 1440 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards
Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains dried strip,
By dried strip shaping, sieve, the length dried strip material (commonly referred to as industrially drying bar waste material) less than 2mm milled,
Sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier PC-B3 of PB-2.The k value of PC-B3 is shown in Table 1.
Embodiment 8
The each 200 grams of uniform mixing of PC-B2 that PC-B1 embodiment 5 obtained and embodiment 6 obtain, obtain PB-1 and PB-
The modifier PC-B4 of 2.The k value of PC-B4 is shown in Table 1.
Embodiment 9
150 grams of PC-B3 that 100 grams of PC-A1 embodiment 1 obtained and embodiment 7 obtain uniformly mix, obtain PA-1 and
The modifier PC-B5 of PB-2.The k value of PC-B5 is shown in Table 1.
Embodiment 10
The each 150 grams of uniform mixing of PC-B1 that PC-A3 embodiment 3 obtained and embodiment 5 obtain, obtain PA-2 and PB-
The modifier PC-B6 of 1.The k value of PC-B6 is 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 11-18 explanation present invention provides and preparation method thereof.Comparative example 1-4 explanation routine is urged
Agent carrier and preparation method thereof.
Embodiment 11
Weighing each 400 grams of PA-1 and PB-1, after the 200 grams of raw material PC-A2 prepared with embodiment 2 uniformly mix, addition contains
10 milliliters of nitric acid (Tianjin chemical reagent three factory product), aqueous solution 1300 milliliters containing titanium tetrachloride 16.6g, in plunger type extrusion
The Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm it is extruded on machine.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, should
900 DEG C of roastings of article shaped 3 hours, obtain carrier Z1.The character of carrier Z1 is listed in table 2.
Embodiment 12
Weigh 300 grams of PA-2,200 grams of PB-2, after the 500 grams of raw material PC-B2 prepared with embodiment 6 uniformly mix, add
Containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1300 milliliters containing titanium tetrachloride 16.6g, squeeze at twin screw
The butterfly bar of external diameter φ 1.4mm it is extruded on bar machine.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 900 DEG C
Roasting 3 hours, obtains carrier Z2.The character of carrier Z2 is listed in table 2.
Embodiment 13
Weigh 500 grams of PA-2,300 grams of PB-2, after the 200 grams of raw material PC-B4 prepared with embodiment 8 uniformly mix, add
Containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1300 milliliters containing titanium tetrachloride 16.6g, squeeze in plunger type
The Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm it is extruded on bar machine.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, will
950 DEG C of roastings of this article shaped 3 hours, obtain carrier Z3.The character of carrier Z3 is listed in table 2.
Comparative example 1
Weigh 500 grams of PA-2,500 grams of PB-2, uniformly add the product in nitric acid Tianjin chemical reagent three factory after mixing) 10 millis
Rise, aqueous solution 1300 milliliters containing titanium tetrachloride 16.6g, plunger type bar extruder is extruded into external diameter 2.5mm, internal diameter 1.0mm's
Raschig ring shape bar.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier
DZ1.The character of carrier DZ1 is listed in table 2.
Embodiment 14
Weigh 250 grams of PA-1,500 grams of PB-1, after the 250 grams of raw material PC-B5 prepared with embodiment 9 uniformly mix, add
Containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), aqueous solution 1300 milliliters containing titanium tetrachloride 29.9g, squeeze at twin screw
The butterfly bar of external diameter φ 1.4mm it is extruded on bar machine.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 1000
DEG C roasting 3 hours, obtains carrier Z4.The character of carrier Z4 is listed in table 2.
Comparative example 2
Weigh 400 grams of PA-1,600 grams of PB-1, uniformly add the product in nitric acid Tianjin chemical reagent three factory after mixing) 10 millis
Rise, aqueous solution 1300 milliliters containing titanium tetrachloride 29.9g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet
Bar is dried 4 hours in 120 DEG C, obtains article shaped, by 950 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ2.Carrier DZ2's
Character is listed in table 2.
Embodiment 15
Weigh 350 grams of PA-2,350 grams of PB-2, after the 300 grams of raw material PC-B6 prepared with embodiment 10 uniformly mix, add
Containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing titanium tetrachloride 29.9g, squeeze at twin screw
The butterfly bar of external diameter φ 1.4mm it is extruded on bar machine.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 1000
DEG C roasting 3 hours, obtains carrier Z5.The character of carrier Z5 is listed in table 2.
Embodiment 16
Weigh 200 grams of PA-1,600 grams of PB-1, after the 200 grams of raw material PC-B1 prepared with embodiment 5 uniformly mix, add
Containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing titanium tetrachloride 29.9g, squeeze in plunger type
The Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm it is extruded on bar machine.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, will
850 DEG C of roastings of this article shaped 3 hours, obtain carrier Z6.The character of carrier Z6 is listed in table 2.
Embodiment 17
Weigh 200 grams of PA-1,600 grams of PB-1, after the 200 grams of raw material PC-A4 prepared with embodiment 4 uniformly mix, add
Containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing titanium tetrachloride 41.6g, squeeze in plunger type
The Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm it is extruded on bar machine.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, will
850 DEG C of roastings of this article shaped 3 hours, obtain carrier Z7.The character of carrier Z76 is listed in table 2.
Embodiment 18
Weigh 200 grams of PA-1,600 grams of PB-1, after the 200 grams of raw material PC-A2 prepared with embodiment 2 uniformly mix, add
Containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, aqueous solution 1440 milliliters containing titanium tetrachloride 41.6g, squeeze in plunger type
The Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm it is extruded on bar machine.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, will
850 DEG C of roastings of this article shaped 3 hours, obtain carrier Z8.The character of carrier Z8 is listed in table 2.
Comparative example 3
The method provided according to patent CN1782031A embodiment 7, is extruded into external diameter 2.5mm on plunger type bar extruder, interior
The Raschig ring shape bar of footpath 1.0mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours,
Obtain carrier DZ3.The character of carrier DZ3 is listed in table 2.
Comparative example 4
The method provided according to patent CN1120971A embodiment 1, is extruded into external diameter 2.5mm on plunger type bar extruder, interior
The Raschig ring shape bar of footpath 1.0mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by little for the 1000 DEG C of roastings 3 of this article shaped
Time, obtain carrier DZ4.The character of carrier DZ4 is listed in table 2.
Comparative example 5
Weigh 200 grams of PA-1,800 grams of PB-2, add the product in nitric acid Tianjin chemical reagent three factory) 10 milliliters, containing tetrachloro
Change the aqueous solution 1300 milliliters of titanium 41.6g, plunger type bar extruder is extruded into the Raschig ring shape of external diameter 2.5mm, internal diameter 1.0mm
Bar.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ5.Carrier
The character of DZ5 is listed in table 2.
Table 2
By the result of table 2 it will be seen that compared with conventional method, provider's method of the present invention the alumina support prepared has
There is obvious structure of double peak holes.
Catalyst that the embodiment 19-23 explanation present invention provides and preparation method thereof.
Wherein, in catalyst the content of active metal component use Xray fluorescence spectrometer to measure (all appts be Japanese
Liue electrical machinery Industrial Co., Ltd 3271 type Xray fluorescence spectrometer, concrete grammar is shown in Petrochemical Engineering Analysis method RIPP133-
90).
Embodiment 19
Take 200 grams of carrier Z1, with 220 milliliters containing MoO380 grams per liters, V2O5The ammonium heptamolybdate of 16 grams per liters and ammonium metavanadate mix
Close solution impregnation 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C1, the composition of C1
It is shown in Table 3.
Comparative example 6
Take 200 grams of DZ1, with 220 milliliters containing MoO380 grams per liters, the ammonium heptamolybdate of NiO16 grams per liter and nickel nitrate mixing are molten
Immersion stain 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 2 hours, obtains Hydrodemetalation catalyst DC1, the composition row of DC1
In table 3.
Embodiment 20
Take 200 grams of carrier Z2, with 220 milliliters containing MoO380 grams per liters, V2O5The ammonium heptamolybdate of 16 grams per liters and ammonium metavanadate mix
Close solution impregnation 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C2, the composition of C2
It is shown in Table 3.
Comparative example 7
Take 200 grams of carrier DZ3, with 220 milliliters containing WO380 grams per liters, V2O5The ammonium heptamolybdate of 16 grams per liters and ammonium metavanadate mix
Close solution impregnation 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst DC2, the group of DC2
One-tenth is shown in Table 3.
Embodiment 21
Take 200 grams of carrier Z3, with 220 milliliters containing MoO380 grams per liters, V2O5The ammonium heptamolybdate of 16 grams per liters and ammonium metavanadate mix
Close solution impregnation 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C3, the composition of C3
It is shown in Table 3.
Comparative example 8
Take 200 grams of carrier DZ4, with 220 milliliters containing WO360 grams per liters, V2O5The ammonium heptamolybdate of 60 grams per liters and ammonium metavanadate mix
Close solution impregnation 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst DC3, the group of DC3
One-tenth is shown in Table 3.
Embodiment 22
Take 200 grams of Z6, with 220 milliliters containing MoO390 grams per liters, V2O5The ammonium heptamolybdate of 20 grams per liters and ammonium metavanadate mixing are molten
Immersion stain 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains Hydrodemetalation catalyst C6.HDM is urged
The composition of agent C6 is shown in Table 2.
Embodiment 23
Take 200 grams of Z8, with 220 milliliters containing WO360 grams per liters, V2O5The ammonium tungstate of 60 grams per liters and ammonium metavanadate mixed solution
Impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C8.Hydrodemetallisation catalyst
The composition of agent C8 is shown in Table 2.
Comparative example 9
Take 200 grams of carrier DZ5, with 500 milliliters containing MoO390 grams per liters, V2O5The ammonium heptamolybdate of 20 grams per liters and ammonium metavanadate
Mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains Hydrodemetalation catalyst DC4, DC4's
Composition is shown 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 provides.
The granule that catalyst C1, C2, C3, C4 and C5 are broken into diameter 2-3 millimeter respectively loads reactor.Reaction condition
For: reaction temperature 380 DEG C, hydrogen dividing potential drop 14 MPas, use inductive coupling plasma emission spectrograph (ICP-AES) to measure hydrogenation
Before and after process in oil the content of nickel and vanadium (instrument is U.S.'s PE company PE-5300 type plasma quantometer, concrete grammar
See Petrochemical Engineering Analysis method RIPP124-90).Asphalt compound mensuration method is used to analyze oil medium pitch before and after hydrotreating
Matter mass fraction (concrete grammar sees SH/T0509-92).Calculating asphalitine and metal removal rate according to the following formula:
Raw oil be nickel content be 29.3ppm, content of vanadium be 83ppm, sulfur content be 4.7%, nitrogen content be 0.3%, residual
Carbon is the normal slag of Kuwait of 15.1%.
The activity data of each catalyst is shown in Table 4.
Comparative example 10-13
Demetallization per and the depitching matter of catalyst DC1, DC2, DC3 and DC4 is evaluated according to the method for embodiment 24-28
Rate, the results are shown in Table 4.
Table 4
| Embodiment | Catalyst is numbered | Depitching matter rate/% | Demetallization per/% |
| 24 | C1 | 89 | 75 |
| Comparative example 10 | DC1 | 65 | 69 |
| 25 | C2 | 91 | 67 |
| Comparative example 11 | DC2 | 62 | 65 |
| 26 | C3 | 88 | 76 |
| Comparative example 12 | DC3 | 68 | 73 |
| 27 | C4 | 89 | 75 |
| 28 | C5 | 89 | 80 |
| Comparative example 13 | DC4 | 76 | 71 |
By table 4 result it will be seen that provided the depitching of catalyst in poor residuum hydroprocessing processes by the present invention
Matter and metal removal activity to be substantially better than existing catalyst, illustrate that this technological invention catalyst is more suitable for the processing of poor residuum
Process.
Claims (24)
1. a heavy-oil hydrogenation depitching matter catalyst, containing carrier and hydrogenation active metals component, described hydrogenation active metals
Component is selected from the metal component of at least one group vib and the metal component of at least one VB race, in terms of oxide and with catalyst
On the basis of, the content of described group vib metal component is 0.2-15 weight %, and the content of VB race metal component is 0.2-12 weight
Amount %, wherein, described carrier is a kind of Bimodal-pore alumina support containing group ivb metal component, characterizes with mercury injection method, institute
The pore volume stating 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 hole accounts for
The 30-60% of total pore volume, the pore volume in a diameter of 100-300nm hole accounts for the 15-45% of total pore volume.
Catalyst the most according to claim 1, it is characterised in that the pore volume of described 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 hole 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.
Catalyst the most according to claim 1, it is characterised in that described group ivb metal component is in titanium, zirconium, hafnium
One or more, on the basis of described carrier and in terms of oxide, in described carrier, the content of the IVth B race metal is 0.1-6
Weight %.
Catalyst the most according to claim 3, it is characterised in that described group ivb metal component is titanium, with described carrier
On the basis of and in terms of oxide, in described carrier, the content of group ivb metal is 0.3-4 weight %.
Catalyst the most according to claim 4, it is characterised in that on the basis of described carrier and in terms of oxide, described
In carrier, the content of group ivb metal is 0.5-2.5 weight %.
Catalyst the most according to claim 1, it is characterised in that the metal component of described vib selected from molybdenum and/or
Tungsten, Group VB metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, described vib metals component
Content be 0.5-12 weight %, the content of Group VB metal component is 0.5-9 weight %.
The preparation method of catalyst the most according to claim 1, including prepare have structure of double peak holes containing the IVth B race metal
The alumina support of component, the preparation method of described carrier includes hydrated alumina PA and PB and containing boehmite
Plant the modifier PC mixing of the hydrated alumina containing boehmite and introduce in the mixture containing the IVth B race metal component
Compound, molding, be dried and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is 20-60:20-50:5-50, PC
κ value be 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1For the sour peptization index of PC hydrated alumina before modified, DI2
For the sour peptization index of described PC, described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour, described roasting
The condition burnt includes: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500.
Method the most according to claim 7, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50:35-
50:10-30.
Method the most according to claim 7, it is characterised in that described IVth B race metal one in titanium, zirconium, hafnium
And mixture, to count and on the basis of carrier by oxide, the described introduction volume containing the IVth B race metallic compound makes final carrier
In the content of the IVth B race metal be 0.1-6 weight %.
Method the most according to claim 9, it is characterised in that described IVth B race metal is titanium, in terms of oxide and with
On the basis of carrier, the described introduction volume containing the IVth B race metallic compound makes the content of the IVth B race metal in final carrier be 0.3-
4 weight %.
11. methods according to claim 7, it is characterised in that the κ value of described PC is 0 to less than or equal to 0.6.
12. according to the method described in claim 7 or 8, it is characterised in that the described hydrated alumina PA containing boehmite
Pore volume be 0.75-1 ml/g, specific surface area is 200-450 rice2/ gram, most probable bore dia 3-10nm；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.
13. methods according to claim 12, it is characterised in that the described hydrated alumina PA's containing boehmite
Pore volume is 0.80-0.95 ml/g, and specific surface area is 200-400 rice2/ gram, most probable bore dia 5-10nm；Described containing plan
The pore volume of the hydrated alumina PB of boehmite is 0.95-1.3 ml/g, and specific surface area is 120-300 rice2/ gram, most probable
Bore dia is more than 10 to less than or equal to 25nm.
14. according to the method described in claim 7 or 8, it is characterised in that described PC is the particulate matter of 80-300 mesh.
15. methods according to claim 14, it is characterised in that described PC is the particulate matter of 100-200 mesh.
16. methods according to claim 7, it is characterised in that described dry condition includes: temperature is 100-200 DEG C,
Time is 2-12 hour, and the condition of described roasting includes: temperature is that roasting time is 2-6 to less than or equal to 1000 DEG C more than 800
Hour.
17. methods according to claim 7, it is characterised in that the hydrated alumina containing boehmite is modified as
One of method of PC is by described hydrated alumina molding containing boehmite, is dried, and it is completely or partially entered afterwards
Row grinds, screening, and described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are by method
The article shaped roasting that one obtains, sintering temperature is that roasting time is 1-8 hour more than 350 to less than or equal to 1400 DEG C, afterwards will
It is completely or partially ground, sieves；The three of method are to dodge the hydrated alumina containing boehmite to do, and dodge dry temperature
For more than 150 to less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour；The four of method be by one of method, the two of method
With one or more in the modifier obtained with the three of method are mixed to get.
18. methods according to claim 17, it is characterised in that the condition being dried in one of described method includes: temperature
Degree is for 100-200 DEG C, and the time is 2-12 hour；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is 0.1-6
Hour；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour.
19. methods according to claim 17, it is characterised in that described PC is the hydrated alumina containing boehmite
Modifier in the particulate matter of 80-300 mesh.
20. methods according to claim 19, it is characterised in that described PC is the hydrated alumina containing boehmite
Modifier in the particulate matter of 100-200 mesh.
21. methods according to claim 7, it is characterised in that described method is included in described supported on carriers hydrogenation and lives
Property metal component, the method for load hydrogenation active metals component is infusion process on the carrier, including preparation containing hydrogenation activity
The solution of the compound of metal also uses this solution impregnating carrier, is dried afterwards, roasting or not roasting, described hydrogenation activity gold
Belong to component and be selected from metal component and at least one Group VB metal component of at least one vib, in terms of oxide and to urge
On the basis of agent, the concentration of described impregnation liquid and consumption make the content of group vib metal component described in final catalyst to be
0.2-15 weight %, the content of VB race metal component is 0.2-12 weight %, and described drying condition is: temperature 80-200 DEG C, time
Between 1-8 hour, roasting condition is: temperature 400-600 DEG C, 2-8 hour time.
22. methods according to claim 21, it is characterised in that the metal component of described group vib is selected from molybdenum and/or tungsten,
VB race metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, and concentration and the consumption of described impregnation liquid make
Obtaining the content of group vib metal component described in final catalyst is 0.5-12 weight %, and the content of VB race metal component is 0.5-9
Weight %, described drying condition is: temperature 100-150 DEG C, 2-6 hour time, and roasting condition is: temperature 420-500 DEG C, time
3-6 hour.
23. methods according to claim 22, it is characterised in that count and on the basis of catalyst by oxide, described leaching
The concentration of stain liquid and consumption make the content of group vib metal component described in final catalyst be 5-12 weight %, VB race metal
The content of component is 1-9 weight %.
Catalyst described in any one application in hydrocarbon oil hydrogenation processes in 24. claim 1-6.
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| CN109569575B (en) * | 2017-09-29 | 2021-12-17 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and heavy oil hydrogenation asphaltene removal method |
| CN114308090A (en) * | 2022-01-14 | 2022-04-12 | 中化泉州石化有限公司 | Hierarchical pore hydrotreating catalyst and preparation method thereof |
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| CN1488441A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
| CN1727063A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Method for preparing alumina supporter in structure of double peak holes |
| CN102652917A (en) * | 2011-03-03 | 2012-09-05 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst using IVB group metal containing aluminum oxide as carrier as well as preparation and application thereof |
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| CN104338527A (en) | 2015-02-11 |
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