CN105749925B - A kind of heavy oil hydrogenating treatment catalyst and its application - Google Patents
A kind of heavy oil hydrogenating treatment catalyst and its application Download PDFInfo
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Abstract
The present invention provides a kind of heavy oil hydrogenating treatment catalyst, which includes siliceous or fluorine shaped alumina alumina supporter, metal component molybdenum and metal component cobalt and nickel；Wherein, the atomic ratio of the cobalt and the nickel is 24；Based on the element and on the basis of described siliceous or fluorine shaped alumina alumina supporter total weight, the content of silicon or fluorine is 0.5 10 heavy % in described siliceous or fluorine shaped alumina alumina supporter；It is counted by oxide and on the basis of unit carrier surface load capacity, the content of metal component molybdenum described in the catalyst is 4.8 μm of ol/m2‑9.0μmol/m2, the total content of the metal component cobalt and nickel is 1.5 μm of ol/m2‑4.0μmol/m2；When the catalyst uses XRD characterization, there is no MoO in 2 θ=26 ° ± 2 ° of the angle of diffraction3Characteristic peak occurs.Compared with existing heavy oil hydrogenating treatment catalyst, heavy oil hydrogenating treatment catalyst using the present invention carries out having better hydrodesulfurization, denitrogenation and de- carbon residue effect during heavy-oil hydrogenation processing.
Description
Technical field
The present invention relates to a kind of heavy oil hydrogenating treatment catalyst and heavy oil is carried out using the heavy oil hydrogenating treatment catalyst to add
The method of hydrogen processing.
Background technology
Processing of heavy oil, particularly to residual oil carry out deep processing, not only contribute to improve crude oil utilization rate, alleviate the energy
The nervous trend of supply, while can also reduce environmental pollution, realize the efficient clean utilization of the energy.
Heavy oil is enriched the impurity such as sulphur, nitrogen, metal and the carbon residue of crude oil, these impurity are to subsequent process and production
Moral character matter has serious adverse effect, thus must be removed.Since the impurity such as sulfur in heavy oil, nitrogen are mostly enriched in big point
Among the multiring aromatic hydrocarbon species of son, it is more difficult to remove, therefore it is required that carrying out the catalysis of the correlated responses such as desulfurization, denitrogenation and de- carbon residue
Agent has higher catalytic activity.Catalyst reaction activity is directly related with calculation in catalyst surface active, surface have compared with
More activated centres is beneficial to the promotion of catalyst reaction activity.The increase at catalyst surface active center can not pass through raising
(i.e. the load capacity of metal component) and simple realization are measured on the active metal of catalyst, because increasing in conventional catalyst preparation method
Add amount on metal that can lead to accumulation of metal, reduce the utilization rate of active metal instead.Therefore improve the dispersity of active metal,
The aggregation of active metal is avoided, improves the utilization rate of active metal, is the pass developed high-performance heavy oil desulfurization, take off carbon residue catalyst
Key.
Patent ZL201110187353.3 discloses a kind of Hydrobon catalyst, which is modified oxygen to be supported on titanium
Change molybdenum, cobalt, three component catalyst of nickel on alumina supporter, wherein, by weight, oxidation molybdenum content is 4~18%, nickel oxide content
It is 0.2~5%, cobalt oxide content is 2.0~7.5%.Specific preparation method is to be impregnated by the total immersion solution containing molybdenum, nickel and cobalt
Dry and calcination for activation is made after carrier.
Nickel molybdenum or cobaltmolybdate catalyst disclosed in the prior art are not easy have higher activity due to the aggregation between metal
Tenor, the especially content of active oxidation molybdenum can not improve, and the activated centre quantity which results in catalyst surface is limited,
Affect the raising of catalyst reaction activity.
Invention content
The technical problem to be solved by the present invention is to, for the prior art provide heavy oil hydrogenating treatment catalyst with compared with
It the drawbacks of aggregation of active metal can not be avoided during high metal content, is reduced so as to cause catalyst surface active center, provides
A kind of new have more preferable desulfurization, denitrification effect and the excellent heavy oil hydrogenating treatment catalyst of carbon residue conversion performance and its should
With.
To achieve these goals, the present invention provides a kind of heavy oil hydrogenating treatment catalyst, the catalyst include it is siliceous or
Fluorine shaped alumina alumina supporter, metal component molybdenum and metal component cobalt and nickel；Wherein, the atomic ratio of the cobalt and the nickel is 2-
4；Based on the element and on the basis of described siliceous or fluorine shaped alumina alumina supporter total weight, described siliceous or fluorine formed alumina
The content of silicon or fluorine is 0.5-10 weights % in carrier；It is counted by oxide and on the basis of unit carrier surface load capacity, it is described to urge
The content of metal component molybdenum described in agent is 4.8 μm of ol/m2-9.0μmol/m2, the total content of the metal component cobalt and nickel is
1.5μmol/m2-4.0μmol/m2；When the catalyst uses XRD characterization, there is no MoO in 2 θ=26 ° ± 2 ° of the angle of diffraction3Feature
Peak occurs.
Preferably, it wherein, is counted by oxide and on the basis of unit carrier surface load capacity, it is golden described in the catalyst
The content for belonging to component molybdenum is 5.4 μm of ol/m2-8.0μmol/m2, the total content of the metal component cobalt and nickel is 1.8 μm of ol/m2-
3.6μmol/m2。
Preferably, it wherein, is counted by oxide and on the basis of unit carrier surface load capacity, it is golden described in the catalyst
The content for belonging to component molybdenum is 5.9 μm of ol/m2-7.5μmol/m2, the total content of the metal component cobalt and nickel is 2.0 μm of ol/m2-
3.1μmol/m2。
Preferably, wherein, described siliceous or fluorine shaped alumina alumina supporter is loading the metal component molybdenum and the gold
Before belonging to component cobalt and nickel, by hydro-thermal process in confined conditions.
Preferably, wherein, the temperature of the hydro-thermal process is 60-180 DEG C, and the time is 1-24 hours；By weight, it is described
The dosage of water is siliceous or fluorine formed alumina vehicle weight 100-300 weights % in hydro-thermal process.
Preferably, wherein, the described siliceous or fluorine shaped alumina alumina supporter by the hydro-thermal process is loading the gold
Before belonging to component molybdenum and the metal component cobalt and nickel, by being dried；The temperature of the drying process is 60-350 DEG C, is done
The time of dry processing is 1-48 hours.
Preferably, wherein, described siliceous or fluorine shaped alumina alumina supporter preparation process includes：To the predecessor of aluminium oxide
Then the siliceous or fluorine element compound of middle introducing will introduce described siliceous or fluorine element compound aluminum oxide precursor object and carry out
Molding, and aluminum oxide precursor object after molding is roasted.
Preferably, wherein, described siliceous or fluorine shaped alumina alumina supporter has selected from γ-, η-, θ-, δ-and χ-aluminium oxide
At least one of crystalline phase crystalline phase.
Preferably, wherein, described siliceous or fluorine shaped alumina alumina supporter is selected from spherical, cylindrical, annular, clover
At least one of shape, quatrefoil, honeycombed and butterfly shape.
Preferably, wherein, the metal component molybdenum and the metal component cobalt and nickel are contained by dip loading described in
On silicon or fluorine shaped alumina alumina supporter.
Preferably, wherein, by the dipping described siliceous or fluorine shaped alumina alumina supporter through drying process and
Calcination process or non-calcination process；The temperature of the drying process is 60-150 DEG C, and the time of drying process is 1-5 hours；The roasting
The temperature for burning processing is 350-550 DEG C, and the time of calcination process is 1-6 hours.
The present invention also provides a kind of heavy oil hydrogenation treatment method, this method includes：Under heavy-oil hydrogenation treatment conditions, by weight
It is oily to be contacted with heavy oil hydrogenating treatment catalyst provided by the invention and carry out heavy-oil hydrogenation processing.
Preferably, heavy oil hydrogenation treatment method according to the present invention, wherein, the heavy oil be selected from crude oil, reduced crude,
At least one of decompression residuum, deep drawing wax oil, frivolous coal tar and wax tailings.
Preferably, heavy oil hydrogenation treatment method according to the present invention, wherein, the heavy-oil hydrogenation treatment conditions include：Instead
It is 300-550 DEG C to answer temperature, and hydrogen partial pressure is 4-20 megapascal, and liquid hourly space velocity (LHSV) is 0.1-3 hours-1, hydrogen to oil volume ratio 200-2500.
Compared with existing heavy oil hydrogenating treatment catalyst, heavy oil hydrogenating treatment catalyst using the present invention carries out heavy oil and adds
There is better hydrodesulfurization, denitrogenation and de- carbon residue effect during hydrogen processing.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention, but be not construed as limiting the invention together.In the accompanying drawings：
Fig. 1 is the XRD spectrums of heavy oil hydrogenating treatment catalyst C1 provided by the invention (catalyst i.e. prepared by embodiment 3)
Figure；
Fig. 2 is the heavy oil hydrogenating treatment catalyst DC1 (catalyst i.e. prepared by comparative example 1) using prior art preparation
XRD spectra.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of heavy oil hydrogenating treatment catalyst, the catalyst include siliceous or fluorine shaped alumina alumina supporter,
Metal component molybdenum and metal component cobalt and nickel；Wherein, the atomic ratio of the cobalt and the nickel is 2-4；Based on the element and with institute
On the basis of stating siliceous or fluorine shaped alumina alumina supporter total weight, silicon or fluorine contains in described siliceous or fluorine shaped alumina alumina supporter
It measures as 0.5-10 weights %；It is counted by oxide and on the basis of unit carrier surface load capacity, metal group described in the catalyst
The content for dividing molybdenum is 4.8 μm of ol/m2-9.0μmol/m2, preferably 5.4 μm of ol/m2-8.0μmol/m2, further preferably 5.9 μ
mol/m2-7.5μmol/m2, the total content of the metal component cobalt and nickel is 1.5 μm of ol/m2-4.0μmol/m2, preferably 1.8 μ
mol/m2-3.6μmol/m2, further preferably 2.0 μm of ol/m2-3.1μmol/m2；When the catalyst uses XRD characterization,
2 θ=26 ° ± 2 ° of the angle of diffraction do not have MoO3Characteristic peak occurs.Wherein, the unit carrier surface load capacity refers to unit carrier table
The ratio between the load capacity of metal component and carrier total surface area in load capacity on area, i.e. catalyst, carrier described herein are
Refer to the siliceous or fluorine shaped alumina alumina supporter before carried metal component, if the described siliceous or carrier loaded gold of fluorine formed alumina
Pass through hydro-thermal process before belonging to component, then the carrier refers to the siliceous or fluorine shaped alumina alumina supporter before hydro-thermal process.It is described
The size of carrier total surface area is measured according to RIPP151-90 standard methods using BET method.
Present inventors discovered unexpectedly that when the heavy oil hydrogenating treatment catalyst of the present invention is carried out XRD characterization,
2 θ=26 ° ± 2 ° of the angle of diffraction do not have MoO3Characteristic peak occur.This explanation and the heavy-oil hydrogenation processing of existing high molybdenum content are catalyzed
Unlike agent, the molybdenum trioxide in catalyst of the present invention is in the well dispersed of catalyst surface, not a large amount of aggregations, so as to nothing
Method detects MoO3Characteristic peak, and such catalyst have higher reactivity.
Heavy oil hydrogenating treatment catalyst according to the present invention, described siliceous or fluorine shaped alumina alumina supporter are loading the gold
Before belonging to component molybdenum and the metal component cobalt and nickel, hydro-thermal process in confined conditions can be passed through.At the hydro-thermal
It manages unlike being handled from conventional catalyst high-temperature vapor, in the present invention at siliceous or fluorine shaped alumina alumina supporter hydro-thermal
Reason refers to siliceous or fluorine shaped alumina alumina supporter and water being put into the closed containers such as reaction kettle, is heated to one in confined conditions
Then constant temperature degree carries out hydro-thermal process at a temperature of the hydro-thermal process.Siliceous or fluorine shaped alumina alumina supporter after hydro-thermal process
It can make the metal component of load that better dispersity be presented, the number of active center and catalysis for improving prepared catalyst are lived
Property.Wherein, the hydro-thermal process temperature can be 60-180 DEG C, preferably 90-150 DEG C；The time of the hydro-thermal process can be with
It is 1-24 hours, preferably 4-12 hours；By weight, in the hydro-thermal process water dosage can be described siliceous or fluorine into
100-300 the weights %, preferably described siliceous or fluorine formed alumina vehicle weight 150-250 of type carrying alumina body weight
Weight %.In the present invention, the pressure of hydro-thermal process is self-generated pressure under confined conditions, when the hydro-thermal process carries out at a constant temperature
When, hydro-thermal process temperature is the thermostat temperature, and the time of the hydro-thermal process is reaches at the hydro-thermal from the closed container
Start timing when managing temperature；The heating rate of temperature-rise period before hydro-thermal process is not particularly limited, preferably 5-15 DEG C/
Minute, more preferably 8-12 DEG C/min.
Heavy oil hydrogenating treatment catalyst according to the present invention, by the described siliceous or fluorine shaped alumina of the hydro-thermal process
Alumina supporter may also pass through drying process, to remove before the metal component molybdenum and the metal component cobalt and nickel is loaded
Moisture in deoxidation aluminium surface and duct.The condition of the drying process is not particularly limited, and can be the routine of this field
Selection, be subject to can remove oxidation aluminium surface and duct in moisture.Usually, the drying process can be at 60-350 DEG C
At a temperature of carry out, carry out preferably at a temperature of 80-200 DEG C, carried out more preferably at a temperature of 100-150 DEG C.It is described dry
The time of dry processing can make appropriate choice according to the temperature of drying process, be not particularly limited.Usually, the drying
The time of processing can be 1-48 hours, preferably 1-24 hours, more preferably 1-8 hours.
Heavy oil hydrogenating treatment catalyst according to the present invention, wherein, described siliceous or fluorine shaped alumina alumina supporter preparation
Step can include：Siliceous or fluorine element compound is introduced into the predecessor of aluminium oxide, then will introduce it is described siliceous or
The aluminum oxide precursor object of fluorine element compound is molded, and aluminum oxide precursor object after molding is roasted.It is described siliceous
Or fluorine element compound can be selected from least one of arbitrary siliceous or fluorine element oxide, acid, alkali and salt.By
The siliceous or fluorine element of institute is less therefore described siliceous in the described siliceous or fluorine shaped alumina alumina supporter of the present invention or fluorine is molded
Alumina support generally also maintains the crystalline phase of pure alumina.The alumina crystalline phase be it is well-known to those skilled in the art,
For example, described siliceous or fluorine shaped alumina alumina supporter can have γ-, η-, θ-, δ-and χ-etc. in alumina crystalline phases at least one
Kind crystalline phase.
Heavy oil hydrogenating treatment catalyst according to the present invention, can be according to the specifically used requirement of catalyst, using extrusion
The shaping jigs such as machine are molded to introducing described siliceous or fluorine element compound aluminum oxide precursor object, this is hydrotreating
Institute is common in catalyst preparation process, such as：Described siliceous or fluorine shaped alumina alumina supporter can be selected from spherical, cylinder
At least one of shape, annular, cloverleaf pattern, quatrefoil, honeycombed and butterfly etc. shape.
Heavy oil hydrogenating treatment catalyst according to the present invention is art technology in the method for supported on carriers metal component
Known to personnel, for example, can be by dipping by the metal component molybdenum and the metal component cobalt and nickel load to institute
It states on siliceous or fluorine shaped alumina alumina supporter, i.e., using the compound of the component containing molybdenum and containing cobalt and nickeliferous metal component
The solution for closing object impregnates siliceous or fluorine shaped alumina alumina supporter.Wherein, the component composition containing molybdenum can selected from it
One or more of soluble compound such as one or more of molybdenum oxide, molybdate and paramolybdate, preferably is selected from therein
One or more of molybdenum oxide, ammonium molybdate and ammonium paramolybdate；The compound of the metal component containing cobalt can be selected from it can
One or more of soluble compound, such as the soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt
One or more of, it preferably is selected from one or both of cobalt nitrate and basic cobaltous carbonate.The chemical combination of the nickeliferous metal component
Object can also be selected from one or more of its soluble compound, such as nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride
One or more of with the soluble complexes of nickel, it preferably is selected from one or both of nickel nitrate and basic nickel carbonate.It is described
Dipping is well-known to those skilled in the art, can be equivalent impregnation or excessive dipping, can be that co-impregnation also may be used
To be step impregnation, such as the solution containing individual various metal component compounds may be used and impregnate the molding of siliceous or fluorine respectively
Alumina support can also use the mixed solution of the component composition containing various metals to impregnate siliceous or fluorine formed alumina and carry
Body.By adjusting the concentration of the dipping solution of metallic components compound described in dipping process and the dosage of dipping solution, sheet
Field technology personnel can control the content for the metal component being introduced into catalyst, and which is not described herein again.
Heavy oil hydrogenating treatment catalyst according to the present invention can also will pass through the siliceous or fluorine shaped alumina of the dipping
Processing and calcination process or non-calcination process is dried in alumina supporter.The method and condition of the drying process and calcination process is equal
It is well known to those skilled in the art, for example, the temperature being dried can be 60-150 DEG C, preferably 80-120 DEG C；It is dry
The time of processing can be 1-5 hours, preferably 2-4 hours；The temperature of calcination process can be 350-550 DEG C, preferably
400-500℃；The time of calcination process can be 1-6 hours, preferably 2-4 hours.
Heavy oil hydrogenating treatment catalyst provided by the invention can be used alone, and can also make with other catalyst combinations
With hydrotreating of the catalyst particularly suitable for heavy oil particularly poor residuum, to be subsequent technique (such as catalytic cracking
Technique) qualified feedstock oil is provided.
The present invention also provides a kind of heavy oil hydrogenation treatment method, this method includes：Under heavy-oil hydrogenation treatment conditions, by weight
It is oily to be contacted with heavy oil hydrogenating treatment catalyst provided by the invention and carry out heavy-oil hydrogenation processing.
In the present invention, the heavy oil can be the various heavy oil feedstocks for needing to carry out hydrotreating, preferably various needs
Carry out the heavier hydrocarbon feeds of hydrodesulfurization, denitrogenation and the processing of de- carbon residue.Specifically, the heavy oil can be selected from crude oil, often
Press at least one of residual oil, decompression residuum, deep drawing wax oil, frivolous coal tar and wax tailings.At the heavy-oil hydrogenation of the present invention
Reason method is by the way that heavy oil is contacted with catalyst provided by the invention, carries out hydrotreating to heavy oil with higher efficiency, right
It is not particularly limited in remaining condition of hydrotreating, can be according to the property of pending heavy oil, the routine according to this field
Knowledge makes appropriate choice.For example, the heavy-oil hydrogenation treatment conditions can be：Reaction temperature is 300-550 DEG C, hydrogen partial pressure
For 4-20 megapascal, liquid hourly space velocity (LHSV) is 0.1-3 hours-1, hydrogen to oil volume ratio 200-2500；The heavy-oil hydrogenation treatment conditions are preferred
For：Reaction temperature is 350-450 DEG C, and hydrogen partial pressure is 8-16 megapascal, and liquid hourly space velocity (LHSV) is 0.15-2 hours-1, hydrogen to oil volume ratio is
400-2000。
Heavy-oil hydrogenation processing can it is any be enough to make the heavy oil under heavy-oil hydrogenation treatment conditions with it is described heavy
Oil hydrogenating treatment catalyst is contacted and carried out in the reactor of heavy-oil hydrogenation processing, for example, can fixed bed reactors,
It is carried out in moving-burden bed reactor or fluidized bed reactor.
Heavy oil hydrogenation treatment method according to the present invention, the catalyst before the use, can be in the routines of this field
Under the conditions of first carry out presulfurization.The condition of presulfurization can be：In presence of hydrogen, with sulphur, sulphur at a temperature of 140-370 DEG C
Change hydrogen or presulfurization is carried out to catalyst containing sulfur feedstock, the presulfurization can carry out outside the reactor also can be described anti-
It answers In-situ sulphiding in device.
The present invention will be further detailed by embodiment below, but it is not thereby limiting the invention.
Agents useful for same in following embodiment and comparative example is chemically pure reagent except as expressly described.
In following embodiment and comparative example, the radial direction that carrier is measured using method specified in RIPP 25-90 is crushed by force
Degree；Using method specified in RIPP 151-90 measure the total surface area of carrier, the Kong Rong of carrier and carrier can several Kong Zhi
Diameter；Using the content of the molybdenum of x ray fluorescence spectrometry (i.e. XRF) the measure catalyst in RIPP133-90, nickel and cobalt；Using
The silicon of Coupled Plasma-Atomic Emission Spectrometric Determination catalyst or the content of fluorine in RIPP128-90；Herein and RIPP mentioned below
Standard method for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, nineteen ninety version.
In following embodiment and comparative example, the distribution of active metal component in catalyst is measured by x-ray powder diffraction instrument
State is confirmed whether have molybdenum trioxide to form aggregation, and instrument uses Philips XPERT Series X-ray powder diffractometers, test
Condition is：Cu K alpha rays (λ=0.154nm), Ni wave filters, voltage 40kV, electric current 30mA, scanning range are 5~70 °.
Embodiment 1-2 provides the siliceous or fluorine shaped alumina alumina supporter of the present invention.
Embodiment 1
The boehmite dry glue powder RPB90 and 30 grams of sesbania powder that 1 kilogram of Chang Ling catalyst plant is produced are uniformly mixed,
At room temperature by the Ludox of the aqueous solution of nitric acid and the % containing the weight of silica 30 of the mixture and 1.1 liters of a concentration of 1 weight %
120 grams are uniformly mixed, and continue kneading on double screw banded extruder after plastic, to be extruded into the trilobal item of 1.1 millimeters of ф, wet bar
After 120 DEG C 3 hours dry, siliceous shaped alumina alumina supporter Z1 is obtained within 3 hours in 600 DEG C of roastings.Measure the materialization result of Z1
It is shown in Table 1.
Embodiment 2
The boehmite dry glue powder RPB100 and 30 grams of sesbania powders that 1 kilogram of Chang Ling catalyst plant is produced are uniformly mixed,
The mixture is mixed with 1.2 liters of the aqueous solution of 90g containing ammonium fluoride, nitric acid 25 milliliters (mass fraction 65%) at room temperature
It is even, continue kneading on double screw banded extruder after plastic, to be extruded into the butterfly item of 1.1 millimeters of ф, wet bar is through 110 DEG C dry 2
After hour, fluorine-containing shaped alumina alumina supporter Z2 is obtained within 3 hours in 700 DEG C of roastings.The materialization for measuring Z2 the results are shown in Table 1.
Embodiment 3-6 provides the heavy oil hydrogenating treatment catalyst of the present invention.
Embodiment 3
Weigh Z1 carriers 150g be placed in hydration kettle in, add in 450g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, control heating rate are 10 DEG C of min-1, treatment temperature is 80 DEG C, and the time is 12 hours.After the completion of hydro-thermal
Aluminium oxide is filtered, it is then 3 hours dry with 120 DEG C, obtain the alumina support of hydrothermal treatment.
Z1100 grams of carrier after water intaking heat treatment contains MoO with 220 milliliters3170 g/l, 10 g/l of NiO, CoO24 grams/
Ammonium molybdate, nickel nitrate, the cobalt nitrate mixed solution risen impregnates 1 hour, filters and is dried after 120 DEG C 2 hours, 410 DEG C of roastings 4 are small
When, obtain catalyst C1.It is counted by oxide and on the basis of unit carrier surface load capacity, is surveyed using Xray fluorescence spectrometer
Determine the content of molybdenum oxide in catalyst C1, nickel oxide and cobalt oxide, being measured in catalyst C1 using x-ray powder diffraction instrument is
No to have molybdenum trioxide to form aggregation, measurement result is as shown in table 2, and the XRD spectra of catalyst C1 is as shown in Figure 1.
Embodiment 4
Weigh Z1 carriers 150g be placed in hydration kettle in, add in 150g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, control heating rate are 10 DEG C of min-1, treatment temperature is 100 DEG C, and the time is 8 hours.After the completion of hydro-thermal
Aluminium oxide is filtered, it is then 3 hours dry with 120 DEG C, obtain the alumina support of hydrothermal treatment.
Z1100 grams of carrier after water intaking heat treatment contains MoO with 110 milliliters3260 g/l, 18 g/l of NiO, CoO 42
G/l molybdenum oxide, basic nickel carbonate, basic cobaltous carbonate mixed solution impregnate 0.5 hour, in 120 DEG C dry 2 hours, 450
DEG C roasting 2 hours, obtain catalyst C2.It is counted by oxide and on the basis of unit carrier surface load capacity, using x-ray fluorescence
The content of molybdenum oxide, nickel oxide and cobalt oxide in spectrometer measure catalyst C2, is measured using x-ray powder diffraction instrument and is catalyzed
Whether there is molybdenum trioxide to form aggregation in agent, measurement result is as shown in table 2.
Embodiment 5
Weigh Z2 carriers 150g be placed in hydration kettle in, add in 225g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, control heating rate are 10 DEG C of min-1, treatment temperature is 120 DEG C, and the time is 6 hours.After the completion of hydro-thermal
Aluminium oxide is filtered, it is then 3 hours dry with 110 DEG C, obtain the alumina support of hydrothermal treatment.
Z2100 grams of carrier after water intaking heat treatment contains MoO with 120 milliliters3290 g/l, 20 g/l of NiO, CoO 45
G/l molybdenum oxide, basic nickel carbonate and basic cobaltous carbonate mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, 480
DEG C roasting 4 hours, obtain catalyst C3.It is counted by oxide and on the basis of unit carrier surface load capacity, using x-ray fluorescence
The content of molybdenum oxide, nickel oxide and cobalt oxide in spectrometer measure catalyst C3, is measured using x-ray powder diffraction instrument and is catalyzed
Whether there is molybdenum trioxide to form aggregation in agent, measurement result is as shown in table 2.
Embodiment 6
Weigh Z2 carriers 150g be placed in hydration kettle in, add in 375g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, control heating rate are 10 DEG C of min-1, treatment temperature is 150 DEG C, and the time is 4 hours.After the completion of hydro-thermal
Aluminium oxide is filtered, it is then 3 hours dry with 110 DEG C, obtain the alumina support of hydrothermal treatment.
Z2100 grams of carrier after water intaking heat treatment contains MoO with 220 milliliters3260 g/l, NiO18 g/l, CoO 41
G/l molybdenum oxide, basic nickel carbonate, basic cobaltous carbonate mixed solution impregnate 1 hour, filter after 110 DEG C dry 3 hours,
450 DEG C roast 2 hours, obtain catalyst C4.It is counted by oxide and on the basis of unit carrier surface load capacity, using X ray
The content of molybdenum oxide, nickel oxide and cobalt oxide in Fluorescence Spectrometer measure catalyst C4, is measured using x-ray powder diffraction instrument
Whether there is molybdenum trioxide to form aggregation in catalyst, measurement result is as shown in table 2.
Comparative example 1-3 provides the heavy oil hydrogenating treatment catalyst prepared using existing method.
Comparative example 1
The use of the aluminium oxide Z1 of not hydrothermal treatment is carrier, ginseng is made using the active component carrying method of embodiment 3
Than catalyst DC1.It is counted by oxide and on the basis of unit carrier surface load capacity, is urged using Xray fluorescence spectrometer measure
The content of molybdenum oxide, nickel oxide and cobalt oxide in agent DC1, using x-ray powder diffraction instrument measure in catalyst DC1 whether
There is molybdenum trioxide to form aggregation, measurement result is as shown in table 2, and the XRD spectra of catalyst DC1 is as shown in Figure 2.
Comparative example 2
The use of the aluminium oxide Z2 of not hydrothermal treatment is carrier, ginseng is made using the active component carrying method of embodiment 6
Than catalyst DC2.It is counted by oxide and on the basis of unit carrier surface load capacity, is urged using Xray fluorescence spectrometer measure
Whether the content of molybdenum oxide, nickel oxide and cobalt oxide in agent DC2, being measured in catalyst using x-ray powder diffraction instrument is had
Molybdenum trioxide forms aggregation, and measurement result is as shown in table 2.
Comparative example 3
It weighs Z1 carriers 100g to be placed in tube furnace, the air blast into stove with the air quantity of 100ml/ minutes, while with 120ml/
Hour rate is pumped into deionized water into stove, and 500 DEG C are warming up to 2 DEG C/min of rates, in 500 DEG C of constant temperature 3 hours, by carrier
Steam treatment is carried out, obtains alumina support DZ1.
The use of the aluminium oxide DZ1 of steam treatment is carrier, reference is made using the active component carrying method of embodiment 3
Catalyst DC3.It is counted by oxide and on the basis of carrier surface load capacity of the unit without steam treatment, it is glimmering using X ray
The content of molybdenum oxide, nickel oxide and cobalt oxide in photothermal spectroscopic analyzer measure catalyst DC3, is measured using x-ray powder diffraction instrument
Whether there is molybdenum trioxide to form aggregation in catalyst, measurement result is as shown in table 2.
Embodiment 7-10 is provided at the heavy oil hydrogenation treatment method and explanation heavy-oil hydrogenation provided by the invention of the present invention
Manage the heavy-oil hydrogenation process performance of catalyst.
Using nickel content as 13ppm, content of vanadium 21ppm, sulfur content 3.3%, carbon residue 10%, nitrogen content 0.3%
Reduced crude is raw material, and catalyst is evaluated on 100 milliliters of small fixed reactors.
Catalyst C1, C2, C3 and C4 are broken into the particle of 0.8-1.2 millimeters of diameter respectively, catalyst loading amount is 100 millis
It rises.Reaction condition is：Reaction temperature is 380 DEG C, hydrogen partial pressure is 14 megapascal, liquid hourly space velocity (LHSV) is 0.6 hour-1, hydrogen to oil volume ratio is
1000, reaction 200 hours after sample, using inductive coupling plasma emission spectrograph (ICP-AES) measure treated oil
The content of middle nickel and vanadium.(instrument is U.S.'s PE companies PE-5300 type plasma quantometers, and specific method is shown in oil
Work analysis method RIPP124-90).
The content of sulphur is measured using coulometry (specific method is shown in Petrochemical Engineering Analysis method RIPP62-90).
The content of nitrogen is measured using coulometry (specific method is shown in Petrochemical Engineering Analysis method RIPP63-90).
It uses microdetermination carbon residue content (specific method is shown in Petrochemical Engineering Analysis method RIPP148-90).
Calculate the removal efficiency of sulphur, carbon residue, nitrogen and metal respectively according to the following formula：
Comparative example 4-6
According to every impurity removal performance of method evaluation catalyst DC1, DC2 and DC3 of embodiment 7-10, the results are shown in Table
3。
Can see by 3 result of table, when catalyst provided by the present invention carries out heavy-oil hydrogenation processing reaction, heavy oil it is whole
Body impurity removal activity is obviously improved than the prior art, is especially promoted more significantly in terms of desulfurization, de- carbon residue and denitrogenation.
Table 1
| Embodiment is numbered | Embodiment 1 | Embodiment 2 |
| Bearer number | Z1 | Z2 |
| Specific surface (rice2/ gram) | 254 | 268 |
| Kong Rong (ml/g) | 0.65 | 0.70 |
| It can several bore dias (nm) | 8 | 9 |
| Silicon (%) | 2.6 | |
| Fluorine (%) | 4.0 | |
| Intensity (Newton/millimeter) | 18 | 17 |
Table 2
Table 3
Claims (12)
1. a kind of heavy oil hydrogenating treatment catalyst, the catalyst include siliceous or fluorine shaped alumina alumina supporter, metal component molybdenum with
And metal component cobalt and nickel；Wherein, the atomic ratio of the cobalt and the nickel is 2-4；Based on the element and with described siliceous or fluorine into
On the basis of the total weight of type alumina support, the content of silicon or fluorine is 0.5-10 in described siliceous or fluorine shaped alumina alumina supporter
Weight %；It is counted by oxide and on the basis of unit carrier surface load capacity, the content of metal component molybdenum described in the catalyst
For 4.8 μm of ol/m2-9.0μmol/m2, the total content of the metal component cobalt and nickel is 1.5 μm of ol/m2-4.0μmol/m2；It is described
When catalyst uses XRD characterization, there is no MoO in 2 θ=26 ° ± 2 ° of the angle of diffraction3Characteristic peak occurs；
Described siliceous or fluorine shaped alumina alumina supporter before the metal component molybdenum and the metal component cobalt and nickel is loaded,
By hydro-thermal process in confined conditions；
Described siliceous or fluorine shaped alumina alumina supporter by the hydro-thermal process is loading the metal component molybdenum and described
Before metal component cobalt and nickel, by being dried, without calcination process；The temperature of the drying process is 60-350 DEG C, is done
The time of dry processing is 1-48 hours.
2. catalyst according to claim 1, wherein, it is counted by oxide and on the basis of unit carrier surface load capacity, it is described
The content of metal component molybdenum described in catalyst is 5.4 μm of ol/m2-8.0μmol/m2, the total content of the metal component cobalt and nickel
For 1.8 μm of ol/m2-3.6μmol/m2。
3. catalyst according to claim 1, wherein, it is counted by oxide and on the basis of unit carrier surface load capacity, it is described
The content of metal component molybdenum described in catalyst is 5.9 μm of ol/m2-7.5μmol/m2, the total content of the metal component cobalt and nickel
For 2.0 μm of ol/m2-3.1μmol/m2。
4. catalyst according to claim 1, wherein, the temperature of the hydro-thermal process is 60-180 DEG C, and the time is 1-24 hours；
By weight, the dosage of water is siliceous or fluorine formed alumina vehicle weight 100-300 weights % in the hydro-thermal process.
5. catalyst according to claim 1, wherein, described siliceous or fluorine shaped alumina alumina supporter preparation process includes：To
Siliceous or fluorine element compound is introduced in the predecessor of aluminium oxide, then will introduce described siliceous or fluorine element compound oxygen
Change aluminium predecessor to be molded, and aluminum oxide precursor object after molding is roasted.
6. catalyst according to claim 1, wherein, described siliceous or fluorine shaped alumina alumina supporter has selected from γ-, η-, θ-,
At least one of δ-and χ-alumina crystalline phase crystalline phase.
7. catalyst according to claim 1, wherein, described siliceous or fluorine shaped alumina alumina supporter be selected from it is spherical, cylindrical,
At least one of annular, cloverleaf pattern, quatrefoil, honeycombed and butterfly shape.
8. catalyst according to claim 1, wherein, the metal component molybdenum and the metal component cobalt and nickel pass through dipping
It loads on described siliceous or fluorine shaped alumina alumina supporter.
9. catalyst according to claim 8, wherein, pass through by the described siliceous or fluorine shaped alumina alumina supporter of the dipping
Drying process and calcination process or non-calcination process；The temperature of the drying process is 60-150 DEG C, and the time of drying process is
1-5 hours；The temperature of the calcination process is 350-550 DEG C, and the time of calcination process is 1-6 hours.
10. a kind of heavy oil hydrogenation treatment method, this method include：Under heavy-oil hydrogenation treatment conditions, by heavy oil and claim
Heavy oil hydrogenating treatment catalyst in 1-9 described in any one contacts and carries out heavy-oil hydrogenation processing.
11. method according to claim 10, wherein, the heavy oil is selected from crude oil, reduced crude, decompression residuum, deep drawing wax
At least one of oily, frivolous coal tar and wax tailings.
12. method according to claim 10, wherein, the heavy-oil hydrogenation treatment conditions include：Reaction temperature is 300-550
DEG C, hydrogen partial pressure is 4-20 megapascal, and liquid hourly space velocity (LHSV) is 0.1-3 hours-1, hydrogen to oil volume ratio 200-2500.
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| CN101618326A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Heavy oil hydrogenation processing catalyst and method for preparing same |
| CN101745400A (en) * | 2008-12-17 | 2010-06-23 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
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| CN101745400A (en) * | 2008-12-17 | 2010-06-23 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
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| Title |
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| 氧化铝载体的水热改性研究;刘百军等;《工业催化》;20061130;第14卷(第11期);第56-59页 * |
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