CN105772006B - 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, and the catalyst is included containing alkaline earth or alkali metal shaped alumina alumina supporter, metal component molybdenum and metal component cobalt or nickel；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 content of the metal component cobalt or nickel is 1.5 μm of ol/m2‑4.0μmol/m2；When the catalyst is characterized using XRD, there is no MoO in θ=26 ° ± 2 ° of the angle of diffraction 23Characteristic peak occurs.Compared with existing heavy oil hydrogenating treatment catalyst, there is more preferable hydrodesulfurization, denitrogenation and de- carbon residue effect when carrying out heavy-oil hydrogenation processing using the heavy oil hydrogenating treatment catalyst of the present invention.
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, deep processing particularly is carried out to residual oil, not only contribute to improve the utilization rate of crude oil, 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, and these impurity are to follow-up process and production
Moral character matter has serious adverse effect, thus must be removed.Because 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 it is directly related with calculation in catalyst surface active, surface with compared with
More activated centres is beneficial to the lifting 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 to cause accumulation of metal, reduce the utilization rate of active metal on the contrary.Therefore the dispersity of active metal is improved,
The aggregation of active metal is avoided, improves the utilization rate of active metal, is to develop high-performance heavy oil desulfurization, the pass of de- carbon residue catalyst
Key.
Patent ZL201110187353.3 discloses a kind of Hydrobon catalyst, and the catalyst is modified oxygen to be supported on titanium
Change molybdenum, cobalt, the component catalyst of nickel three on alumina supporter, wherein, by weight, oxidation molybdenum content is 4~18%, nickel oxide content
For 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
Dried after carrier and calcination for activation is made.
Nickel molybdenum or cobaltmolybdate catalyst disclosed in prior art, it is not easy that there is higher activity due to the aggregation between metal
Tenor, the especially content of active oxidation molybdenum can not improve, which results in the activated centre quantity of catalyst surface is limited,
It has impact on the raising of catalyst reaction activity.
The content of the invention
The technical problem to be solved in the present invention is, for the heavy oil hydrogenating treatment catalyst that prior art provides with compared with
The aggregation of active metal can not be avoided during high metal content, so as to cause catalyst surface active center reduce the drawbacks of, there is provided
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, and the catalyst includes containing alkaline earth
Or alkali metal shaped alumina alumina supporter, metal component molybdenum and metal component cobalt or nickel；Contain alkaline earth in terms of oxide and with described
Or on the basis of the gross weight of alkali metal shaped alumina alumina supporter, it is described containing alkaline earth in alkaline earth or alkali metal shaped alumina alumina supporter or
The content of alkali metal is 0.5-5 weights %；Counted by oxide and on the basis of unit carrier surface load capacity, institute in the catalyst
The content for stating metal component molybdenum is 4.8 μm of ol/m2-9.0μmol/m2, the content of the metal component cobalt or nickel is 1.5 μm of ol/
m2-4.0μmol/m2；When the catalyst is characterized using XRD, there is no MoO in θ=26 ° ± 2 ° of the angle of diffraction 23Characteristic peak occurs.
Preferably, wherein, 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 content of the metal component cobalt or nickel is 1.8 μm of ol/m2-3.6
μmol/m2。
Preferably, wherein, 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 content of the metal component cobalt or nickel is 2.0 μm of ol/m2-3.1
μmol/m2。
Preferably, wherein, it is described containing alkaline earth or alkali metal shaped alumina alumina supporter load the metal component molybdenum and
Before the metal component cobalt or 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 hydro-thermal process reclaimed water is containing alkaline earth or the 100-300 of alkali metal formed alumina vehicle weight weights %.
Preferably, wherein, loaded by containing alkaline earth or alkali metal shaped alumina alumina supporter described in the hydro-thermal process
Before the metal component molybdenum and the metal component cobalt or nickel, by drying process；The temperature of the drying process is 60-
350 DEG C, the time of drying process is 1-48 hours.
Preferably, wherein, the preparation process containing alkaline earth or alkali metal shaped alumina alumina supporter includes：To aluminum oxide
Introduced in predecessor and contain alkaline earth or alkali metal compound, be then introduced into and described contained alkaline earth or alkali metal compound
Aluminum oxide precursor thing be molded, and the aluminum oxide precursor thing after shaping is calcined.
Preferably, wherein, it is described have selected from γ containing alkaline earth or alkali metal shaped alumina alumina supporter-, η-, θ-, δ-and χ-
At least one of alumina crystalline phase crystalline phase.
Preferably, wherein, it is described containing alkaline earth or alkali metal shaped alumina alumina supporter be selected from it is spherical, cylindrical, annular, three
At least one of clover shape, quatrefoil, honeycombed and butterfly shape.
Preferably, wherein, the metal component molybdenum and the metal component cobalt or nickel are contained by dip loading described in
On alkaline earth or alkali metal shaped alumina alumina supporter.
Preferably, wherein, pass through by containing alkaline earth or alkali metal shaped alumina alumina supporter described in the dipping at dry
Reason 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 small for 1-5
When；The temperature of the calcination process 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, and 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, according to the present invention heavy oil hydrogenation treatment method, 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, according to the heavy oil hydrogenation treatment method of the present invention, wherein, the heavy-oil hydrogenation treatment conditions include：Instead
It is 300-550 DEG C to answer temperature, and hydrogen dividing potential drop is 4-20 MPas, 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 is carried out using the heavy oil hydrogenating treatment catalyst of the present invention and added
There is more preferable 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.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is heavy oil hydrogenating treatment catalyst C1 provided by the invention (catalyst i.e. prepared by embodiment 3) XRD spectrums
Figure；
Fig. 2 is the heavy oil hydrogenating treatment catalyst DC1 (catalyst i.e. prepared by comparative example 1) prepared using prior art
XRD spectra.
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of heavy oil hydrogenating treatment catalyst, and the catalyst includes containing alkaline earth or alkali metal formed alumina
Carrier, metal component molybdenum and metal component cobalt or nickel；Contain alkaline earth or alkali metal formed alumina in terms of oxide and with described
On the basis of the gross weight of carrier, described containing the content of alkaline earth or alkali metal in alkaline earth or alkali metal shaped alumina alumina supporter is 0.5-
5 heavy %；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, preferably 5.4 μm of ol/m2-8.0μmol/m2, more preferably 5.9 μm of ol/m2-7.5μ
mol/m2, the content of the metal component cobalt or nickel is 1.5 μm of ol/m2-4.0μmol/m2, preferably 1.8 μm of ol/m2-3.6μ
mol/m2, more preferably 2.0 μm of ol/m2-3.1μmol/m2；The catalyst using XRD characterize when, the θ of the angle of diffraction 2=
26 ° ± 2 ° do not have MoO3Characteristic peak occurs.Wherein, the unit carrier surface load capacity refers to negative on unit carrier surface area
The ratio between the load capacity of metal component and carrier total surface area in carrying capacity, i.e. catalyst, carrier described herein refers to carried metal
Contain alkaline earth or alkali metal shaped alumina alumina supporter before component, if described carrier loaded containing alkaline earth or alkali metal formed alumina
Pass through hydro-thermal process before metal component, then the carrier refer to before hydro-thermal process containing alkaline earth or alkali metal formed alumina load
Body.The size of the 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 into XRD signs,
θ=26 ° ± 2 ° of the angle of diffraction 2 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 has higher reactivity.
It is described to be loaded containing alkaline earth or alkali metal shaped alumina alumina supporter according to the heavy oil hydrogenating treatment catalyst of the present invention
Before the metal component molybdenum and the metal component cobalt or nickel, hydro-thermal process in confined conditions can be passed through.It is described
Hydro-thermal process contains alkaline earth or alkali metal formed alumina unlike the catalyst high-temperature vapor processing of routine in the present invention
The hydro-thermal process of carrier refers to be put into the closed containers such as reactor containing alkaline earth or alkali metal shaped alumina alumina supporter and water,
Certain temperature is heated under confined conditions, and hydro-thermal process is then carried out at a temperature of the hydro-thermal process.Contain alkali after hydro-thermal process
Soil or alkali metal shaped alumina alumina supporter can make the metal component of load that more preferable dispersity be presented, and improve prepared be catalyzed
The number of active center and catalytic activity of agent.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 1-24 hours, preferably 4-12 hours；By weight, the use of the hydro-thermal process reclaimed water
Amount can be described containing alkaline earth or the 100-300 of alkali metal formed alumina vehicle weight weight %, be preferably it is described containing alkaline earth or
The 150-250 weights % of alkali metal formed alumina vehicle weight.In the present invention, the pressure of hydro-thermal process under confined conditions from
Raw pressure, when the hydro-thermal process is carried out at a constant temperature, hydro-thermal process temperature is the thermostat temperature, the hydro-thermal process when
Between be the timing since when the closed container reaches the hydro-thermal process temperature；The heating of temperature-rise period before hydro-thermal process
Speed has no particular limits, preferably 5-15 DEG C/min, more preferably 8-12 DEG C/min.
According to the heavy oil hydrogenating treatment catalyst of the present invention, by contain described in the hydro-thermal process alkaline earth or alkali metal into
Type alumina support may also pass through dry place before the metal component molybdenum and the metal component cobalt or nickel is loaded
Reason, to remove the moisture in oxidation aluminium surface and duct.The condition of the drying process is not particularly limited, and can be this area
Conventional selection, by can remove oxidation aluminium surface and duct in moisture be defined.Usually, the drying process can be
Carried out at a temperature of 60-350 DEG C, carry out preferably at a temperature of 80-200 DEG C, more preferably enter at a temperature of 100-150 DEG C
OK.The time of the drying process can carry out appropriate selection according to the temperature of drying process, be not particularly limited.Typically
Ground, the time of the drying process can be 1-48 hours, preferably 1-24 hours, more preferably 1-8 hours.
According to the heavy oil hydrogenating treatment catalyst of the present invention, wherein, it is described to contain alkaline earth or alkali metal shaped alumina alumina supporter
Preparation process can include：Introduced into the predecessor of aluminum oxide and contain alkaline earth or alkali metal compound, be then introduced into
The aluminum oxide precursor thing containing alkaline earth or alkali metal compound is molded, and by the aluminum oxide precursor thing after shaping
It is calcined.Described containing alkaline earth or alkali metal compound can be selected from the arbitrarily oxidation containing alkaline earth or alkali metal
At least one of thing, acid, alkali and salt.It is contained in alkaline earth or alkali metal shaped alumina alumina supporter due to containing described in the present invention
Alkaline earth or alkali metal are less, therefore described typically also maintains pure alumina containing alkaline earth or alkali metal shaped alumina alumina supporter
Crystalline phase.The alumina crystalline phase is well-known to those skilled in the art, for example, described contain alkaline earth or alkali metal shaped alumina
Alumina supporter can have γ-, η-, θ-, δ-and χ-etc. at least one of alumina crystalline phase crystalline phase.
, can be according to the specifically used requirement of catalyst, using extrusion according to the heavy oil hydrogenating treatment catalyst of the present invention
The shaping jigs such as machine are molded to introducing the aluminum oxide precursor thing containing alkaline earth or alkali metal compound, and this is to add
Commonly used in hydrogen processing catalyst preparation process, such as：The alkaline earth or alkali metal shaped alumina alumina supporter of containing can be choosing
From at least one of spherical, cylindrical, annular, cloverleaf pattern, quatrefoil, honeycombed and butterfly etc. shape.
It is art technology in the method for supported on carriers metal component according to the heavy oil hydrogenating treatment catalyst of the present invention
Known to personnel, for example, can be by dipping by the metal component molybdenum and the metal component cobalt or Ni to institute
State and contain on alkaline earth or alkali metal shaped alumina alumina supporter, i.e., using the compound of the component containing molybdenum and containing cobalt or nickeliferous metal
The solution dipping of component composition contains alkaline earth or alkali metal shaped alumina alumina supporter.Wherein, the component composition containing molybdenum
Can selected from the one or more in its soluble compound, such as the one or more in molybdenum oxide, molybdate and paramolybdate,
The one or more preferably being selected from molybdenum oxide therein, ammonium molybdate and ammonium paramolybdate；The change containing cobalt or nickeliferous metal component
Compound can be selected from the one or more in their soluble compound, such as cobalt nitrate, cobalt acetate, basic cobaltous carbonate, chlorination
Cobalt, the soluble complexes of cobalt, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel soluble complexes in one kind
Or several, the one or more preferably being selected from cobalt nitrate, basic cobaltous carbonate, nickel nitrate and basic nickel carbonate.The dipping is this
It can be equivalent impregnation or excessive dipping known to art personnel, can be that co-impregnation can also be substep
Dipping, such as the solution containing single various metal component compounds can be used to impregnate respectively containing alkaline earth or alkali metal shaping oxygen
Change alumina supporter, the mixed solution dipping of the component composition containing various metals can also be used to contain alkaline earth or alkali metal formed alumina
Carrier.By the concentration of dipping solution and the dosage of dipping solution for adjusting metallic components compound described in dipping process,
Those skilled in the art can be controlled to the content for the metal component being introduced into catalyst, repeat no more here.
According to the heavy oil hydrogenating treatment catalyst of the present invention, can also by by the dipping containing alkaline earth or alkali metal into
Processing and calcination process or non-calcination process is dried in type alumina support.The method of the drying process and calcination process and
Condition is well known to the skilled person, for example, the temperature of drying process can be 60-150 DEG C, preferably 80-120
℃；The time of drying process can be 1-5 hours, preferably 2-4 hours；The temperature of calcination process can be 350-550 DEG C, excellent
Elect 400-500 DEG C as；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, and 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, and hydrotreating is carried out 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 area
Knowledge carries out appropriate selection.For example, the heavy-oil hydrogenation treatment conditions can be：Reaction temperature is 300-550 DEG C, hydrogen dividing potential drop
For 4-20 MPas, 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 dividing potential drop is 8-16 MPas, 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,
Carried out in moving-burden bed reactor or fluidized bed reactor.
According to the heavy oil hydrogenation treatment method of the present invention, the catalyst before the use, can be in the routine of this area
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 be carried out outside the reactor also can be described anti-
Answer 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 examples and comparative example, it is chemically pure reagent except as expressly described.
In following examples and comparative example, the radial direction that carrier is determined using method specified in RIPP 25-90 is crushed by force
Degree；Using the method measure total surface area of carrier specified in RIPP 151-90, the pore volume of carrier and carrier can several Kong Zhi
Footpath；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 alkaline earth of Coupled Plasma-Atomic Emission Spectrometric Determination catalyst and the content of alkali metal in RIPP128-90；Herein and it is mentioned below
RIPP standard methods for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, nineteen ninety version.
In following examples and comparative example, the distribution of active metal component in catalyst is determined by x-ray powder diffraction instrument
State, it is confirmed whether have molybdenum trioxide to form aggregation, instrument uses Philips XPERT Series X-ray powder diffractometers, tests
Condition is：Cu K alpha rays (λ=0.154nm), Ni wave filters, voltage 40kV, electric current 30mA, scanning range are 5~70 °.
The embodiment 1-2 offer present invention's contains alkaline earth or alkali metal shaped alumina alumina supporter.
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 well mixed,
The mixture is mixed with 30g containing magnesium nitrate, nitric acid 20 milliliters (mass fraction 65%) 1.1 liters of the aqueous solution at room temperature
It is even, continue kneading on double screw banded extruder after plastic, to be extruded into 1.1 millimeters of ф trilobal bar, wet bar is through 120 DEG C of dryings
After 3 hours, the alumina supporter of shaped alumina containing magnesium Z1 is obtained within 3 hours in 600 DEG C of roastings.Measure Z1 materialization the results are 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 well mixed,
The mixture is mixed with 30g containing potassium nitrate, nitric acid 25 milliliters (mass fraction 65%) 1.2 liters of the aqueous solution at room temperature
It is even, continue kneading on double screw banded extruder after plastic, to be extruded into 1.1 millimeters of ф butterfly bar, wet bar dries 2 through 110 DEG C
After hour, the alumina supporter of shaped alumina containing potassium Z2 is obtained within 3 hours in 700 DEG C of roastings.Measure Z2 materialization 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 450g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, it is 10 DEG C of min to control programming rate-1, treatment temperature is 80 DEG C, and the time is 12 hours.After the completion of hydro-thermal
Aluminum oxide is filtered, is then dried 3 hours with 120 DEG C, obtains the alumina support of hydrothermal treatment.
Z1100 grams of carrier after water intaking heat treatment, contains MoO with 220 milliliters3170 g/l, the ammonium molybdate that 30 g/l of NiO,
Nickel nitrate mixed solution impregnates 1 hour, filters and is dried after 120 DEG C 2 hours, 410 DEG C are calcined 4 hours, obtain catalyst C1.With
Oxide meter and on the basis of unit carrier surface load capacity, the oxidation in catalyst C1 is determined using Xray fluorescence spectrometer
Whether the content of molybdenum, nickel oxide, being determined using x-ray powder diffraction instrument in catalyst C1 has molybdenum trioxide to form aggregation, measure
As a result as shown in table 2, catalyst C1 XRD spectra is as shown in Figure 1.
Embodiment 4
Weigh Z1 carriers 150g be placed in hydration kettle in, add 150g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, it is 10 DEG C of min to control programming rate-1, treatment temperature is 100 DEG C, and the time is 8 hours.After the completion of hydro-thermal
Aluminum oxide is filtered, is then dried 3 hours with 120 DEG C, obtains the alumina support of hydrothermal treatment.
Z1100 grams of carrier after water intaking heat treatment, contains MoO with 110 milliliters3260 g/l, CoO58 g/l of oxidation
Molybdenum, the mixed solution of basic cobaltous carbonate impregnate 0.5 hour, are dried in 120 DEG C 2 hours, 450 DEG C are calcined 2 hours, obtain catalyst
C2.Counted by oxide and on the basis of unit carrier surface load capacity, determined using Xray fluorescence spectrometer in catalyst C2
The content of molybdenum oxide, cobalt oxide, whether have molybdenum trioxide form aggregation, survey if being determined using x-ray powder diffraction instrument in catalyst
It is as shown in table 2 to determine result.
Embodiment 5
Weigh Z2 carriers 150g be placed in hydration kettle in, add 225g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, it is 10 DEG C of min to control programming rate-1, treatment temperature is 120 DEG C, and the time is 6 hours.After the completion of hydro-thermal
Aluminum oxide is filtered, is then dried 3 hours with 110 DEG C, obtains the alumina support of hydrothermal treatment.
Z2100 grams of carrier after water intaking heat treatment, contains MoO with 120 milliliters3290 g/l, the oxidation that 63 g/l of NiO
Molybdenum, the mixed solution of basic nickel carbonate impregnate 1 hour, are dried in 120 DEG C 2 hours, 480 DEG C are calcined 4 hours, obtain catalyst
C3.Counted by oxide and on the basis of unit carrier surface load capacity, determined using Xray fluorescence spectrometer in catalyst C3
The content of molybdenum oxide, nickel oxide, whether have molybdenum trioxide form aggregation, survey if being determined using x-ray powder diffraction instrument in catalyst
It is as shown in table 2 to determine result.
Embodiment 6
Weigh Z2 carriers 150g be placed in hydration kettle in, add 375g deionized waters, will be hydrated kettle it is closed after be put into baking oven,
Ramped heating schedule, it is 10 DEG C of min to control programming rate-1, treatment temperature is 150 DEG C, and the time is 4 hours.After the completion of hydro-thermal
Aluminum oxide is filtered, is then dried 3 hours with 110 DEG C, obtains the alumina support of hydrothermal treatment.
Z2100 grams of carrier after water intaking heat treatment, contains MoO with 220 milliliters3260 g/l, the oxidation that 41 g/l of CoO
Molybdenum, basic cobaltous carbonate mixed solution impregnate 1 hour, filter and are dried after 110 DEG C 3 hours, 450 DEG C are calcined 2 hours, are catalyzed
Agent C4.Counted by oxide and on the basis of unit carrier surface load capacity, determined using Xray fluorescence spectrometer in catalyst C4
Molybdenum oxide, the content of cobalt oxide, using x-ray powder diffraction instrument determine catalyst in whether have molybdenum trioxide formed aggregation,
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
Aluminum oxide Z1 using not hydrothermal treatment is carrier, and ginseng is made using the active component carrying method of embodiment 3
Than catalyst DC1.Counted by oxide and on the basis of unit carrier surface load capacity, urged using Xray fluorescence spectrometer measure
The content of molybdenum oxide, nickel oxide in agent DC1, determine in catalyst DC1 whether there are three oxidations using x-ray powder diffraction instrument
Molybdenum forms aggregation, and measurement result is as shown in table 2, and catalyst DC1 XRD spectra is as shown in Figure 2.
Comparative example 2
Aluminum oxide Z2 using not hydrothermal treatment is carrier, and ginseng is made using the active component carrying method of embodiment 6
Than catalyst DC2.Counted by oxide and on the basis of unit carrier surface load capacity, urged using Xray fluorescence spectrometer measure
The content of molybdenum oxide, cobalt oxide in agent DC2, determine in catalyst whether have molybdenum trioxide using x-ray powder diffraction instrument
Aggregation is formed, measurement result is as shown in table 2.
Comparative example 3
Weigh 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 speed is pumped into deionized water into stove, and 500 DEG C are warming up to 2 DEG C/min of speed, in 500 DEG C of constant temperature 3 hours, by carrier
Steam treatment is carried out, obtains alumina support DZ1.
Aluminum oxide DZ1 using steam treatment is carrier, and reference is made using the active component carrying method of embodiment 3
Catalyst DC3.Counted by oxide and on the basis of carrier surface load capacity of the unit without steam treatment, it is glimmering using X ray
Molybdenum oxide, the content of nickel oxide in photothermal spectroscopic analyzer measure catalyst DC3, are determined in catalyst using x-ray powder diffraction instrument
Whether there is molybdenum trioxide to form aggregation, 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 11ppm, content of vanadium 17ppm, sulfur content 3.2%, carbon residue 11%, 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 diameter 0.8-1.2 millimeters respectively, catalyst loading amount is 100 millis
Rise.Reaction condition is：Reaction temperature is 380 DEG C, hydrogen dividing potential drop is 14 MPas, liquid hourly space velocity (LHSV) is 0.6 hour-1, hydrogen to oil volume ratio is
1000, reaction samples after 200 hours, the oil after being handled using inductive coupling plasma emission spectrograph (ICP-AES) measure
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).
Use the content of coulometry measure sulphur (specific method is shown in Petrochemical Engineering Analysis method RIPP62-90).
Use the content of coulometry measure nitrogen (specific method is shown in Petrochemical Engineering Analysis method RIPP63-90).
Use 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 embodiment 7-10 method evaluation catalyst DC1, DC2 and DC3 every impurity removal performance, the results are shown in Table
3。
Can see by the result of table 3, 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 prior art, is especially lifted in terms of desulfurization, de- carbon residue and denitrogenation more notable.
Table 1
| Embodiment is numbered | Embodiment 1 | Embodiment 2 |
| Bearer number | Z1 | Z2 |
| Than surface (rice2/ gram) | 241 | 272 |
| Pore volume (ml/g) | 0.64 | 0.68 |
| Can several bore dias (nm) | 8 | 9 |
| Magnesia (%) | 1.3 | |
| Potassium oxide (%) | 2.2 | |
| Intensity (Newton/millimeter) | 18 | 17 |
Table 2
Table 3
Claims (12)
1. a kind of heavy oil hydrogenating treatment catalyst, the catalyst includes containing alkaline earth or alkali metal shaped alumina alumina supporter, metal group
Divide molybdenum and metal component cobalt or nickel；In terms of oxide and with the gross weight containing alkaline earth or alkali metal shaped alumina alumina supporter
On the basis of, it is described to weigh % containing the content of alkaline earth or alkali metal in alkaline earth or alkali metal shaped alumina alumina supporter for 0.5-5；With oxidation
Thing meter 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 content of the metal component cobalt or nickel is 1.5 μm of ol/m2-4.0μmol/m2；The catalyst uses
When XRD is characterized, there is no MoO in θ=26 ° ± 2 ° of the angle of diffraction 23Characteristic peak occurs；
It is described containing alkaline earth or alkali metal shaped alumina alumina supporter load the metal component molybdenum and the metal component cobalt or
Before nickel, by hydro-thermal process in confined conditions；
By contain described in the hydro-thermal process alkaline earth or alkali metal shaped alumina alumina supporter load the metal component molybdenum with
And before the metal component cobalt or nickel, by drying process, without calcination process；The temperature of the drying process is 60-350
DEG C, the time of drying process is 1-48 hours.
2. catalyst according to claim 1, wherein, 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 content of the metal component cobalt or nickel is
1.8μmol/m2-3.6μmol/m2。
3. catalyst according to claim 1, wherein, 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 content of the metal component cobalt or nickel is
2.0μmol/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 the hydro-thermal process reclaimed water is the 100-300 containing alkaline earth or alkali metal formed alumina vehicle weight
Weight %.
5. catalyst according to claim 1, wherein, the preparation process bag containing alkaline earth or alkali metal shaped alumina alumina supporter
Include：Introduced into the predecessor of aluminum oxide and contain alkaline earth or alkali metal compound, be then introduced into and described contained alkaline earth or alkali
The aluminum oxide precursor thing of metallic element compound is molded, and the aluminum oxide precursor thing after shaping is calcined.
6. catalyst according to claim 1, wherein, it is described have selected from γ containing alkaline earth or alkali metal shaped alumina alumina supporter-,
η-, θ-, at least one of δ-and χ-alumina crystalline phase crystalline phase.
7. catalyst according to claim 1, wherein, it is described containing alkaline earth or alkali metal shaped alumina alumina supporter be selected from it is spherical,
At least one of cylinder, annular, cloverleaf pattern, quatrefoil, honeycombed and butterfly shape.
8. catalyst according to claim 1, wherein, the metal component molybdenum and the metal component cobalt or nickel pass through dipping
Load to described containing on alkaline earth or alkali metal shaped alumina alumina supporter.
9. catalyst according to claim 8, wherein, carried by containing alkaline earth or alkali metal formed alumina described in the dipping
Body passes through drying process and calcination process or non-calcination process；The temperature of the drying process is 60-150 DEG C, drying process
Time 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 dividing potential drop is 4-20 MPas, and liquid hourly space velocity (LHSV) is 0.1-3 hours-1, hydrogen to oil volume ratio 200-2500.
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