CN104226322B - Heavy-oil hydrotreatment catalyst and preparation and application thereof - Google Patents
Heavy-oil hydrotreatment catalyst and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a heavy-oil hydrotreatment catalyst and preparation and application thereof. The catalyst comprises an aluminium oxide carrier containing a group IVB metal composition, and a hydrogenation active metal composition, wherein the carrier has a double-peak pore structure, and by employing a mercury intrusion method, the carrier is characterized to have the pore volume of 0.9-1.2 mL/g and the specific area of 50-300 m＜2＞/g, and the pore volume of pores with the diameter of 10-30 nm accounts for 55-80% of the total pore volume, and the pore volume of pores with the diameter of 300-500 nm accounts for 10-35%. A preparation method of the carrier comprises mixing aluminium oxide hydrate P1 containing pseudo-boehmite and a P1 modifier P2, introducing a compound containing a group IVB metal into the mixture, and then performing shaping, drying and roasting. The kappa value of P2 is in the range of 0≤kappa≤0.9, and kappa=DI2/DI1, DI1 is the acidic dispersion index of the aluminium oxide hydrate P1 containing pseudo-boehmite, and DI2 is the acidic dispersion index of the P1 modifier P2. Compared with the prior art, the provided catalyst has relatively good hydrogenation deasphalting and demetalization performances when being applied to hydrotreatment of heavy oil.
Description
Technical field
The present invention relates to a kind of hydrotreating 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 sulfur, 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 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, 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 active center 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 are low（Armaticity are 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 includes mixing a kind of precursor of aluminium oxide with the nitrogen-containing compound beyond a kind of deacidification, molding roasting.
Catalyst for heavy oil fixed bed hydrogenating treatment disclosed in CN1233795C and preparation method etc..
But, the asphaltene removal of these catalyst is generally relatively low.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of new, catalysis with preferably hydrogenation depitching matter performance
Agent, the preparation method of the catalyst and application.
The present invention relates to herein below：
1st, a kind of heavy oil hydrogenating treatment catalyst, containing carrier and hydrogenation active metals component, wherein, the carrier is one
The bimodal porous aluminum oxide containing group ivb metal is planted, is characterized with mercury injection method, the pore volume of the carrier is 0.9-1.2 ml/g,
Specific surface area is 50-300 rice2/ gram, the pore volume in a diameter of 10-30nm holes accounts for the 55-80% of total pore volume, a diameter of 300-
The pore volume in 500nm holes accounts for the 10-35% of total pore volume.
2nd, the catalyst according to 1, it is characterised in that the pore volume of the carrier is 0.95-1.15 ml/g, compares table
Area is 80-200 rice2/ gram, the pore volume in a diameter of 10-30nm holes accounts for the 60-75% of total pore volume, a diameter of 300-500nm holes
Pore volume account for the 15-30% of total pore volume.
3rd, the catalyst according to 1, it is characterised in that the group ivb metal component in titanium, zirconium, hafnium
Plant or several, on the basis of the carrier and in terms of oxide, in the carrier, the content of the IVth race's metal is 0.1-6 weight %.
4th, the catalyst according to 3, it is characterised in that the group ivb metal component is titanium, with the carrier as base
Accurate and in terms of oxide, in the carrier, the content of group ivb metal is 0.3-4 weight %.
5th, the catalyst according to 4, it is characterised in that on the basis of the carrier and in terms of oxide, the carrier
The content of middle group ivb metal is 0.5-2.5 weight %.
6th, 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 metal component of group VIB, are counted by oxide and on the basis of catalyst, the group VIII metal group
The content divided 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 %.
7th, the catalyst according to 6, 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 %.
8th, the preparation method of the heavy oil hydrogenating treatment catalyst according to 1, it is bimodal containing group ivb metal including preparing
The carrier of porous aluminum oxide simultaneously loads hydrogenation active metals component on this carrier, wherein, the preparation method of the carrier include by
The modifier P2 mixing of hydrated alumina P1 and P1 containing boehmite simultaneously introduces metal containing group ivb in the mixture
Compound, aftershaping, drying roasting, the Mixing ratio by weight of the P1 and P2 is 20-95：The κ values of 5-80, P2 be 0 to
Less than or equal to 0.9, the κ=DI2/DI1, DI1It is the sour peptization index of the hydrated alumina P1 containing boehmite, DI2For
The sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite.
9th, the method according to 8, it is characterised in that the Mixing ratio by weight of the P1 and P2 is 70-95：5-25；It is described
The k value of P2 is 0 to less than or equal to 0.6.
10th, the method according to 8 or 9, it is characterised in that the hole of the hydrated alumina P1 containing boehmite
Hold for 0.9-1.4 ml/g, specific surface is 100-350 rice2/ gram, most can and bore dia 8-30nm.
11st, the method according to 10, it is characterised in that the pore volume of the hydrated alumina P1 containing boehmite
For 0.95-1.3 ml/g, specific surface is 120-300 rice2/ gram, most can and bore dia 10-25nm.
12nd, the method according to 8 or 9 any one, it is characterised in that particulate matters of the P2 for 80-300 mesh.
13rd, the method according to 12, it is characterised in that particulate matters of the P2 for 100-200 mesh.
14th, the method according to 8, 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.
15th, the method according to 14, 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.
16th, the method according to 8, it is characterised in that by P1 be modified as one of method of P2 be will it is described containing intend it is thin
Its all or part is ground, is sieved by the hydrated alumina P1 molding of diaspore, drying afterwards, and it is P2 to obtain powder thing,
The condition of the drying includes：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are the molding for obtaining method one
Thing roasting, sintering temperature are that roasting time is 1-8 hours, afterwards by its all or part more than 350 to less than or equal to 1400 DEG C
Be ground, sieve, powder thing is obtained for P2；The three of method are that the hydrated alumina P1 containing boehmite is dodged dry, are dodged
Dry temperature is that flash-off time is 0.05-1 hours more than 150 to less than or equal to 1400 DEG C, obtains powder thing for P2；The four of method
Be by one of method, method two and with the three of the method modifier for obtaining in one or more be mixed to get.
17th, the method according to 16, 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.
18th, the method according to 16, it is characterised in that the P2 is the particulate matter of 80-300 mesh in P1 modifiers.
19th, the method according to 18, it is characterised in that the P2 is the particulate matter of 100-200 mesh in P1 modifiers.
20th, the method according to 8, it is characterised in that described to bear in the Bimodal-pore alumina support of metal containing group ivb
The method for carrying hydrogenation active metals component is infusion process, including the solution for preparing the compound containing hydrogenation active metals and molten with this
Liquid impregnated carrier, is dried, roasting or not roasting afterwards, and the hydrogenation active metals component is selected from least one vib
Metal component and at least one VIIIth race metal component, counted by oxide and on the basis of catalyst, it is described containing hydrogenation live
The metal group of vib of the compound of property metal in the concentration of the solution and the consumption of the solution make final catalyst
The content divided is more than 0.8 to less than or equal to 3 weights more than 3 to the content less than or equal to 10 weight %, the metal component of the VIIIth race
Amount %.The drying condition includes：Temperature is 100-250 DEG C, and the time is 1-10 hours；The roasting condition includes：Temperature is
360-500 DEG C, the time is 1-10 hours.
21st, the method according to 20, it is characterised in that the metal component of the group 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 group 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.
22nd, application of the catalyst in claim 1-7 described in any one in heavy-oil hydrogenation process.
Depending on different requirements, the Bimodal-pore alumina support of metal containing group ivb described in heretofore described catalyst can be with
Make arbitrary easily operated article shaped, such as spherical, cellular, nest like, tablet or bar shaped（Herba Trifolii Pratentis, butterfly, cylinder
Shape etc.）.The molding can be carried out according to a conventional method, such as a kind of method in spin, tabletting and extruded moulding or several method
With reference to.In molding, such as extruded moulding is to ensure that the molding is smoothed out, can to described bimodal porous aluminum oxide and/
Or add in the precursor of aluminium oxide and the mixture containing group ivb metallic compound water, extrusion aid and/or adhesive, containing or
Without expanding agent, then extrusion molding, it is dried afterwards and roasting.Can also will prepare containing the IVth B races metallic compound
Into aqueous solution, the aqueous solution is mixed into or changing in the P1 and P1 while the modifier P2 of the P1 and P1 mixes
Property thing P2 mixing after again the aqueous solution is mixed into, aftershaping, drying roasting.
The compound containing group ivb metal can be their arbitrarily known compounds, for example, group ivb metal
Oxide and the salt containing group ivb metal, the preferred water soluble salt of group ivb metal.The kind of the extrusion aid, peptizer
Class and consumption are known to those skilled in the art, such as common extrusion aid can be selected from sesbania powder, methylcellulose, shallow lake
One or more in powder, polyvinyl alcohol, PVOH, the peptizer can be mineral acid and/or organic acid, described reaming
Agent can be one or more in starch, synthetic cellulose, polymeric alcohol and surfactant.Synthetic cellulose therein is preferred
For one or more in hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, gather
One or more in alcohol preferably Polyethylene Glycol, poly- propanol, polyvinyl alcohol are closed, surfactant is preferably fatty alcohols polyethylene
Ether, fatty alkanol amide and its derivant, molecular weight are in the propylene alcohol copolymer and maleic acid copolymer of 200-10000
Plant or several.
Sour peptization index D I in prepared by the carrier refers to the hydrated alumina containing boehmite by certain sour aluminum
Than adding after nitric acid, by the hydrated alumina containing boehmite of peptization with Al within certain response time2O3The hundred of meter
Fraction, DI=（1-W2/W1) × 100%, W1And W2Before respectively intending thin water aluminum and acid reaction and with acid reaction after with Al2O3The weight of meter
Amount.
The measure of DI includes：(1) the calcination base content of the hydrated alumina containing boehmite is determined（Calcination base（Also referred to as
For butt）Content referred to quantitative boehmite in 600 DEG C of roastings 4 hours, after its burning weight with burn before weight ratio）,
It is calculated as a；(2) the hydrated alumina W containing boehmite is weighed with analytical balance0Gram, W0Amount meet with Al2O3The W of meter1For 6
Gram（W1/a=W0）, weigh W gram of deionized water, W=40.0-W0, by the hydrated alumina containing boehmite for weighing under stirring
Add in beaker with deionized water and mix；(3) the dilute nitric acid solution that 20mL, concentration are 0.74N is pipetted with 20mL pipets, should
Acid solution is added to step（2）Beaker in, the lower reaction of stirring 8 minutes；(4) by step（3）Reacted serosity is in centrifuge
It is centrifuged, precipitate is inserted in the crucible weighed, afterwards, by which in 125 DEG C of dryings 4 hours, 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 aluminium oxide P1 not specially require, can be the boehmite, or boehmite of any prior art preparation
With the mixture of other hydrated aluminas, other hydrated aluminas are selected from a water aluminium oxide, gibbsite and nothing
One or more in hydrated amorphous alumina.For example, pore volume is 0.9-1.4 ml/g, and specific surface is 100-350 rice2/ gram,
Most can and bore dia 8-30nm；It is preferred that pore volume is 0.95-1.3 ml/g, specific surface is 120-300 rice2/ gram, most can and Kong Zhi
The hydrated alumina containing boehmite of footpath 10-25nm is just particularly suitable for the present invention.In the present invention, containing the thin water of plan
The pore volume of the hydrated alumina of aluminum stone, specific surface area and most can and aperture, be by the aqua oxidation containing boehmite
Aluminum 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, in the hydrated alumina containing boehmite
Boehmite content is not less than 50%, more preferably not less than 60%.
Inventors of the present invention have surprisingly found that, the hydrated alumina P1 containing boehmite is carried out into heat treatment and is modified
Afterwards, the peptization index of its modifier changes, by this modifier is with not thermally treated P1 mixed-formings, drying and roasts
After burning, resulting carrier has obvious bimodal pore distribution.Particularly by the granule of 80-300 mesh therein, preferably 100-
After the granule of 200 mesh and not thermally treated part mixed-forming, drying roasting, resulting carrier it is bimodal in each
Unimodal pore size distribution is especially concentrated.Here, the granule of the 80-300 mesh, the granule of preferably 100-200 mesh refer to described being modified
Thing is through sieve（The step of including broken or grinding if necessary）, its screening thing（Siftage）Meet the granule of 80-300 mesh, preferably
The particulate matter of 100-200 mesh accounts for the percent of total amount（By weight）Not less than 60%, further preferably not less than 70%.
In being embodied as, the P2 can be conveniently obtained by following method：
(1) based on P2 is dried to obtain, including by the hydrated alumina P1 containing boehmite, according to a conventional method prepared by molding
During regular oxidation alumina supporter, the tailing of drying by-product, for example：In extruded moulding, bar shaped article shaped is being dried, integer
The tailing of process by-product（Traditionally it is referred to as being dried waste material）, the tailing is milled, is sieved and is obtained P2.
(2) obtained based on roasting, including by the hydrated alumina P1 containing boehmite, molding is often prepared according to a conventional method
During rule alumina support, the tailing of fired by-product（Traditionally it is referred to as roasting waste material）, for example, in roller forming, ball
The tailing of shape granule by-product in roasting process, the tailing is milled, is sieved and is obtained P2；Or directly P1 sudden strains of a muscle are done
Arrive, when P1 is dodged dry directly, flash-off time is preferably 0.05-1 hours, more preferably 0.1-0.5 hours.
(3) two or more in the modifier P2 for being obtained based on preceding method are mixed to get.When being obtained using mixed method
When obtaining P2, the mixed proportion of the modifier P2 respectively obtained to aforementioned several method is not limited.
According to the present invention provide catalyst, wherein, the hydrogenation active metals component by those skilled in the art public affairs
The species known and its content, preferred metal component of group VIII are cobalt and/or nickel, and metal component of group VIB is molybdenum and/or tungsten,
Counted by oxide and on the basis of catalyst, the content preferably greater than 0.8 of the metal component of group VIII is to less than or equal to 3 weights
Amount %, more preferably 1-2 weight %, the content preferably greater than 3 of the metal component of group VIB is to less than or equal to 10 weights
Amount %, 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, cobaltous acetate, basic cobaltous carbonate, cobaltous 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 dichloride. 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 and are metallized containing Group IVB
Solution mixing, molding the roasting of compound；Can be by the compound containing the component such as the phosphorus with contain hydrogenation active metals
The compound of component impregnates the carrier after being configured to mixed solution；Can also be and the compound containing components such as phosphorus is individually matched somebody with somebody
The carrier roasting is impregnated after solution processed.It is when the addO-on therapies such as phosphorus introduce the carrier respectively with hydrogenation active metals, excellent
Choosing with carrier roasting described in the solution impregnation containing the addO-on therapy compound, is used containing hydrogenation activity gold first afterwards again
The solution impregnation of category component composition.Wherein, the sintering temperature be 400-600 DEG C, preferably 420-500 DEG C, roasting time
For 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 raw 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 sulfur, 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.
Compared with the catalyst that prior art is provided, the bimodal of carrier that the catalyst that the present invention is provided is adopted is concentrated on
10nm-30nm and 300nm-500nm.When processing of heavy oil is used it for, the catalyst shows preferably to be hydrogenated with depitching matter
Performance.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 especially fitted
Share and poor residuum is particularly in heavy oil and carries out hydrotreating, so as to for subsequent technique（Such as catalytic cracking process）It is qualified to provide
Raw oil.
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：
P1-1：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）.
P1-2：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）.
The explanation of embodiment 1-5 prepares modifier P2 of the P1 of carrier of the present invention and preparation method thereof.
Embodiment 1
1000 grams of P1-1 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of 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 P2A of P1-1.The k value of P2A is shown in Table 1.
Embodiment 2
1000 grams of P1-1 are weighed, is dodged dry 6 minutes in 240 DEG C, is obtained the modifier P2B of P1-1.The k value of P2B is shown in Table 1.
Embodiment 3
The each 200 grams of uniform mixing of P2B that the P2A and embodiment 2 that embodiment 1 is obtained is obtained, obtain the modifier of P1-1
P2C.The k value of P2C is shown in Table 1.
Embodiment 4
1000 grams of P1-2 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）10 milliliters of 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 P2D of P1-2.The k value of P2D is shown in Table 1.
Embodiment 5
1000 grams of P1-2 are weighed, is dodged dry 10 minutes in 650 DEG C, is obtained the modifier P2E of P1-2.The k value of P2E is shown in Table 1.
Table 1
| Embodiment | Raw material | k |
| 1 | P2A | 0.5 |
| 2 | P2B | 0.4 |
| 3 | P2C | 0.4 |
| 4 | P2D | 0 |
| 5 | P2E | 0.3 |
The explanation of embodiment 6-13 prepares the preparation side of the catalyst of the present invention Bimodal-pore alumina support of metal containing group ivb
Method.Comparative example 1-3 illustrates the preparation method of conventional catalyst carrier.
Embodiment 6
800 grams of P1-1 are weighed, after uniformly mixing with 1 obtained 200 gram of raw material P2A of embodiment, is added containing nitric acid（Tianjin
Learn three factory's product of reagent）10 milliliters, 1440 milliliters of the aqueous solution containing titanium tetrachloride 16.6g, are extruded on double screw banded extruder outer
The butterfly bar of footpath φ 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 obtained
To carrier Z1.The property of carrier Z1 is listed in table 2.
Embodiment 7
200 grams of P1-1 are weighed, after uniformly mixing with 2 obtained 800 grams of raw material P2B of embodiment, Tianjin containing nitric acid is added
Learn three factory's product of reagent）10 milliliters, 1440 milliliters of the aqueous solution containing titanium tetrachloride 16.6g, are extruded on double screw banded extruder outer
The butterfly bar of footpath φ 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 obtained
To carrier Z2.The property of carrier Z2 is listed in table 2.
Embodiment 8
500 grams of P1-1 are weighed, after uniformly mixing with 3 obtained 500 grams of raw material P2C of embodiment, Tianjin containing nitric acid is added
Learn three factory's product of reagent）10 milliliters, 1440 milliliters of the aqueous solution containing titanium tetrachloride 16.6g, are extruded on double screw banded extruder outer
The butterfly bar of footpath φ 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 obtained
To carrier Z3.The property of carrier Z3 is listed in table 2.
Comparative example 1
1000 grams of P1-1 are weighed, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）10 milliliters, 16.6g containing titanium tetrachloride
1440 milliliters of aqueous solution, be 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.
Embodiment 9
800 grams of P1-2 are weighed, after uniformly mixing with 4 obtained 200 grams of raw material P2D of embodiment, is added containing nitric acid（Tianjin
Learn three factory's product of reagent）10 milliliters, 1440 milliliters of the aqueous solution containing titanium tetrachloride 29.9g, are extruded on double screw banded extruder outer
The butterfly bar of footpath φ 1.4mm.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,
Obtain carrier Z4.The property of carrier Z4 is listed in table 2.
Embodiment 10
900 grams of P1-1 are weighed, after uniformly mixing with 5 obtained 100 grams of raw material P2E of embodiment, Tianjin containing nitric acid is added
Learn three factory's product of reagent）10 milliliters, 1440 milliliters of the aqueous solution containing titanium tetrachloride 29.9g, are extruded on double screw banded extruder outer
The butterfly bar of footpath φ 1.4mm.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,
Obtain carrier Z5.The property of carrier Z5 is listed in table 2.
Embodiment 11
850 grams of P1-2 are weighed, after uniformly mixing with 3 obtained 150 grams of raw material P2C of embodiment, Tianjin containing nitric acid is added
Learn three factory's product of reagent）10 milliliters, 1440 milliliters of the aqueous solution containing titanium tetrachloride 29.9g, are extruded on double screw banded extruder outer
The butterfly bar of footpath φ 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 obtained
To carrier Z6.The property of carrier Z6 is listed in table 2.
Comparative example 2
1000 grams of P1-2 are weighed, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）10 milliliters, 29.9g containing titanium tetrachloride
1440 milliliters of aqueous solution, be 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 1000 DEG C of the article shaped, carrier DZ2 is obtained.The property of carrier DZ2 is listed in table 2.
Embodiment 12
900 grams of P1-2 are weighed, after uniformly mixing with 4 obtained 100 grams of raw material P2D of embodiment, Tianjin containing nitric acid is added
Learn three factory's product of reagent）10 milliliters, 1440 milliliters of the aqueous solution containing titanium tetrachloride 41.6g, are extruded on double screw banded extruder outer
The butterfly bar of footpath φ 1.4mm.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,
Obtain carrier Z7.The property of carrier Z7 is listed in table 2.
Embodiment 13
850 grams of P1-2 are weighed, after uniformly mixing with 5 obtained 150 grams of raw material P2E of embodiment, Tianjin containing nitric acid is added
Learn three factory's product of reagent）10 milliliters, 1440 milliliters of the aqueous solution containing titanium tetrachloride 41.6g, are extruded on double screw banded extruder outer
The butterfly bar of footpath φ 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 obtained
To carrier 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 double screw banded 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.
Table 2
Catalyst that the embodiment 14-16 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 14
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 4
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 15
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 5
200 carrier DZ2 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 16
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 6
200 grams of carrier DZ3 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 17
200 grams of carrier Z4 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 18
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.
Table 3
Embodiment 19-23
The residuum hydrogenating and metal-eliminating performance of the catalyst that the embodiment 19-23 explanation present invention is provided.
The granule 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 Colophonium 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：
Raw 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 7-9
Method according to embodiment 19-23 evaluates demetallization per and the depitching matter rate of catalyst DC1, DC2 and DC3, knot
Fruit is shown in Table 4.
Table 4
| Embodiment | Catalyst is numbered | Depitching matter rate/% | Demetallization per/% |
| 19 | C1 | 87 | 72.9 |
| Comparative example 7 | DC1 | 66 | 65.5 |
| 20 | C2 | 88 | 71.1 |
| Comparative example 8 | DC2 | 63 | 65.1 |
| 21 | C3 | 92 | 73.1 |
| Comparative example 9 | DC3 | 68 | 68.1 |
| 22 | C4 | 90 | 75.1 |
| 23 | C5 | 88 | 74.2 |
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 (22)
1. a kind of heavy oil hydrogenating treatment catalyst, containing carrier and hydrogenation active metals component, wherein, the carrier contains for one kind
There is the bimodal porous aluminum oxide of group ivb metal, characterized with mercury injection method, the pore volume of the carrier is 0.9-1.2 ml/g, compares table
Area is 50-300 rice2/ gram, the pore volume in a diameter of 10-30nm holes accounts for the 55-80% of total pore volume, a diameter of 300-500nm holes
Pore volume account for the 10-35% of total pore volume.
2. catalyst according to claim 1, it is characterised in that the pore volume of the carrier is 0.95-1.15 ml/g,
Specific surface area is 80-200 rice2/ gram, the pore volume in a diameter of 10-30nm holes accounts for the 60-75% of total pore volume, a diameter of 300-
The pore volume in 500nm holes accounts for the 15-30% of total pore volume.
3. catalyst according to claim 1, it is characterised in that the group ivb metal component is in titanium, zirconium, hafnium
One or more, on the basis of the carrier and in terms of oxide, in the carrier content of the IVth B races metal be 0.1-6
Weight %.
4. catalyst according to claim 3, it is characterised in that the group ivb metal component is titanium, with the carrier
On the basis of and in terms of oxide, in the carrier content of group ivb metal be 0.3-4 weight %.
5. catalyst according to claim 4, it is characterised in that on the basis of the carrier and in terms of oxide, described
In carrier, the content of group ivb metal is 0.5-2.5 weight %.
6. 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 metal component of group VIB, 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 %.
7. catalyst according to claim 6, 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, is counted by oxide and on the basis of catalyst, the content of VIII race metal component
For 1-2 weight %, the content of metal component of group VIB is more than 4 to less than or equal to 8 weight %.
8. the preparation method of heavy oil hydrogenating treatment catalyst according to claim 1, contains group ivb metal including preparing
The carrier of bimodal porous aluminum oxide simultaneously loads hydrogenation active metals component, wherein, the preparation method bag of the carrier on this carrier
Include the modifier P2 mixing of hydrated alumina P1 and P1 containing boehmite and introduced containing group ivb in the mixture
The compound of metal, aftershaping, drying roasting, the Mixing ratio by weight of the P1 and P2 is 20-95：The κ values of 5-80, P2 are
0 to less than or equal to 0.9, and the κ=DI2/DI1, DI1 are the sour peptization index of the hydrated alumina P1 containing boehmite,
DI2 is the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite.
9. method according to claim 8, it is characterised in that the Mixing ratio by weight of the P1 and P2 is 70-95：5-25；
The κ values of the P2 are 0 to less than or equal to 0.6.
10. method according to claim 8 or claim 9, it is characterised in that the hydrated alumina P1 containing boehmite
Pore volume be 0.9-1.4 ml/g, specific surface be 100-350 rice2/ gram, most probable bore dia 8-30nm.
11. methods according to claim 10, it is characterised in that the hydrated alumina P1's containing boehmite
Pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, most probable bore dia 10-25nm.
12. methods according to claim 8 or 9 any one, it is characterised in that granules of the P2 for 80-300 mesh
Thing.
13. methods according to claim 12, it is characterised in that particulate matters of the P2 for 100-200 mesh.
14. methods according to claim 8, 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.
15. methods according to claim 14, 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
For 2-6 hours.
16. methods according to claim 8, it is characterised in that P1 is modified as one of method of P2 is contained described
Its all or part is ground, is sieved, obtains powder thing by the hydrated alumina P1 molding of boehmite, drying afterwards
For P2, the condition of the drying includes：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are to obtain one of method
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, and obtain powder thing for P2；The three of method are by the hydrated alumina P1 containing boehmite
Dodge dry, it is that flash-off time is 0.05-1 hours more than 150 to less than or equal to 1400 DEG C to dodge dry temperature, powder thing is obtained for P2；Side
The four of method are several in three modifiers for obtaining by one of method, the two of method and method being mixed to get.
17. methods according to claim 16, it is characterised in that the condition of the drying in one of methods described includes：Temperature
Spend 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.
18. methods according to claim 16, it is characterised in that the P2 is the granule of 80-300 mesh in P1 modifiers
Thing.
19. methods according to claim 18, it is characterised in that the P2 is the granule of 100-200 mesh in P1 modifiers
Thing.
20. methods according to claim 8, it is characterised in that described in the Bimodal-pore alumina support of metal containing group ivb
The method of upper load hydrogenation active metals component is infusion process, is used in combination including the solution for preparing the compound containing hydrogenation active metals
The solution impregnating carrier, is dried, roasting or not roasting afterwards, and the hydrogenation active metals component is selected from least one the
The metal component of group vib and the metal component of at least one VIIIth race, are counted by oxide and on the basis of catalyst, it is described containing plus
The gold of vib of the compound of hydrogen activity metal in the concentration of the solution and the consumption of the solution make final catalyst
The content of category component more than 3 to less than or equal to 10 weight %, the content of the metal component of the VIIIth race more than 0.8 to less than etc.
In 3 weight %；The drying condition includes：Temperature is 100-250 DEG C, and the time is 1-10 hours；The roasting condition includes：Temperature
Spend for 360-500 DEG C, the time is 1-10 hours.
21. methods according to claim 20, it is characterised in that the metal component of the group 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 group 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；The drying condition includes：
Temperature is 100-140 DEG C, and 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 22. claim 1-7 described in any one in heavy-oil hydrogenation process.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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| JP2008093493A (en) * | 2006-10-05 | 2008-04-24 | Idemitsu Kosan Co Ltd | Demetallization catalyst and method for hydrotreating heavy oil by using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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