CN105772007B - 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
- Publication number
- CN105772007B CN105772007B CN201410788461.XA CN201410788461A CN105772007B CN 105772007 B CN105772007 B CN 105772007B CN 201410788461 A CN201410788461 A CN 201410788461A CN 105772007 B CN105772007 B CN 105772007B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- catalyst
- metal component
- alumina
- siliceous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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 or nickel；Based on the element and on the basis of described siliceous or fluorine shaped alumina alumina supporter gross weight, the content of silicon or fluorine is 0.5 10 heavy % in described siliceous or fluorine shaped alumina alumina supporter；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 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 more preferable 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 carry out deep processing to residual oil, not only contributes to improve the utilization rate of crude oil, alleviates 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 follow-up 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 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, 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
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
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,
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 prior art provide heavy oil hydrogenating treatment catalyst with compared with
The aggregation of active metal can not be avoided during high metal content, so that the drawbacks of causing catalyst surface active center to be reduced, 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, the catalyst include it is siliceous or
Fluorine shaped alumina alumina supporter, metal component molybdenum and metal component cobalt or nickel；Based on the element and with described siliceous or fluorine shaping oxygen
On the basis of the gross weight for changing alumina supporter, the content of silicon or fluorine is 0.5-10 weights % in described siliceous or fluorine shaped alumina alumina supporter；
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 μ
mol/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 is adopted
During with XRD characterization, there is no MoO in 2 θ=26 ° ± 2 ° of the angle of diffraction3Characteristic 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, described siliceous or fluorine shaped alumina alumina supporter is loading the metal component molybdenum and the gold
Before belonging to 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, when the time is 1-24 small；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 or nickel, by drying process；The temperature of the drying process is 60-350 DEG C, is done
When the time of dry processing is 1-48 small.
Preferably, wherein, described siliceous or fluorine shaped alumina alumina supporter preparation process includes：To the predecessor of aluminium oxide
The siliceous or fluorine element compound of middle introducing, has then been introduced into described siliceous or fluorine element compound aluminum oxide precursor thing and has carried out
Shaping, and the aluminum oxide precursor thing after shaping 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 or nickel are contained by dip loading described in
On silicon or fluorine shaped alumina alumina supporter.
Preferably, wherein, by the described siliceous or fluorine shaped alumina alumina supporter of the dipping by drying process and
Calcination process or non-calcination process；The temperature of the drying process is 60-150 DEG C, when the time of drying process is 1-5 small；The roasting
The temperature for burning processing is 350-550 DEG C, when the time of calcination process is 1-6 small.
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 dividing potential drop is 4-20 megapascal, when liquid hourly space velocity (LHSV) is 0.1-3 small-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 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
Attached 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 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) prepared using the prior art
XRD spectra.
Embodiment
The embodiment of the present invention is described in detail below in conjunction with attached 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, the catalyst include siliceous or fluorine shaped alumina alumina supporter,
Metal component molybdenum and metal component cobalt or nickel；Based on the element and using described siliceous or fluorine shaped alumina alumina supporter gross weight as
Benchmark, the content of silicon or fluorine is 0.5-10 weights % in described siliceous or fluorine shaped alumina alumina supporter；In terms of oxide and with unit
On the basis of carrier surface load capacity, the content of metal component molybdenum described in the catalyst is 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/m2-7.5μmol/m2, the metal component cobalt or
The content of nickel is 1.5 μm of ol/m2-4.0μmol/m2, it is preferably 1.8 μm of ol/m2-3.6μmol/m2, more preferably 2.0 μ
mol/m2-3.1μmol/m2；When the catalyst uses XRD characterization, there is no MoO in 2 θ=26 ° ± 2 ° of the angle of diffraction3Characteristic peak goes out
It is existing.Wherein, the unit carrier surface load capacity refers to the load capacity on unit carrier surface area, i.e. metal component in catalyst
Load capacity and the ratio between carrier total surface area, carrier described herein refer to carried metal component before siliceous or fluorine shaping oxygen
Change alumina supporter, if passing through hydro-thermal process, the carrier before described siliceous or fluorine formed alumina carrier to load metal component
Refer to the siliceous or fluorine shaped alumina alumina supporter before hydro-thermal process.The size of the carrier total surface area is marked according to RIPP151-90
Quasi- method is measured 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 that nothing
Method detects MoO3Characteristic peak, and such catalyst has 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 or nickel, hydro-thermal process in confined conditions can be passed through.At the hydro-thermal
Manage unlike conventional catalyst high-temperature vapor processing, 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
Constant temperature degree, then 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 more preferable 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, be preferably 90-150 DEG C；The time of the hydro-thermal process can be with
For 1-24 it is small when, be preferably 4-12 it is small when；By weight, in the hydro-thermal process water dosage can be described siliceous or fluorine into
The 100-300 weight % of type carrying alumina body weight, are preferably described siliceous or fluorine formed alumina vehicle weight 150-250
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 to reach from the closed container at the hydro-thermal
Start timing when managing temperature；The heating rate of temperature-rise period before hydro-thermal process has no particular limits, 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 before the metal component molybdenum and the metal component cobalt or nickel is loaded, with except
Moisture in deoxidation aluminium surface and duct.The condition of the drying process is not particularly limited, and can be the routine of this area
Selection, so as to removing is aoxidized subject to the moisture in aluminium surface and duct.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
When the time of processing can be 1-48 small, when being preferably 1-24 small, when more preferably 1-8 is small.
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, be then introduced into it is described siliceous or
The aluminum oxide precursor thing of fluorine element compound is molded, and the aluminum oxide precursor thing after shaping 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 phase 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 thing, 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 or nickel load to institute
State on siliceous or fluorine shaped alumina alumina supporter, i.e., using the compound of the component containing molybdenum and containing cobalt or nickeliferous metal component
The solution of compound impregnates siliceous or fluorine shaped alumina alumina supporter.Wherein, the component composition containing molybdenum can selected from it
One or more in soluble compound, such as the one or more in molybdenum oxide, molybdate and paramolybdate, preferably are selected from therein
One or more in molybdenum oxide, ammonium molybdate and ammonium paramolybdate；The compound containing cobalt or nickeliferous metal component can be selected from
One or more in their soluble compound, as cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride, cobalt solubility
Complex compound, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel soluble complexes in one or more, preferably be selected from
One or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate and basic nickel carbonate.The dipping is those skilled in the art institute
It is well known, it can be equivalent impregnation or excessive dipping, can be that co-impregnation can also be step impregnation, such as can be with
Siliceous or fluorine shaped alumina alumina supporter is impregnated using the solution containing single various metal component compounds respectively, can also be used
The mixed solution of the component composition containing various metals impregnates siliceous or fluorine shaped alumina alumina supporter.By adjusting institute in dipping process
The concentration of the dipping solution of metallic components compound and the dosage of dipping solution are stated, those skilled in the art can urge introducing
The content of metal component in agent is controlled, and which is not described herein again.
Heavy oil hydrogenating treatment catalyst according to the present invention, can also be by by 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 are equal
It is well known to those skilled in the art, for example, the temperature of drying process can be 60-150 DEG C, it is preferably 80-120 DEG C；It is dry
When the time of processing can be 1-5 small, when being preferably 2-4 small；The temperature of calcination process can be 350-550 DEG C, be preferably
400-500℃；When the time of calcination process can be 1-6 small, when being preferably 2-4 small.
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, be 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 the efficiency of higher, 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 makes appropriate choice.For example, the heavy-oil hydrogenation treatment conditions can be：Reaction temperature is 300-550 DEG C, hydrogen dividing potential drop
For 4-20 megapascal, liquid hourly space velocity (LHSV) for 0.1-3 it is small when-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 megapascal, when liquid hourly space velocity (LHSV) is 0.15-2 small-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.
Heavy oil hydrogenation treatment method according to the present invention, the catalyst before the use, can be in the routines 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 carry 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 embodiments and comparative example, is chemically pure reagent except as expressly described.
In following embodiments and comparative example, crushed using the radial direction of method measure carrier specified in RIPP 25-90 strong
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 silicon of Coupled Plasma-Atomic Emission Spectrometric Determination catalyst and 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 embodiments 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, tests
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,
The aqueous solution of nitric acid and the Ludox of the % containing the weight of silica 30 that are at room temperature 1 weight % by the mixture and 1.1 liters of concentration
120 grams are uniformly mixed, and continue kneading on double screw banded extruder after plastic, to be extruded into the trilobal bar of 1.1 millimeters of ф, wet bar
After when 120 DEG C of dryings 3 are small, siliceous shaped alumina alumina supporter Z1 is obtained when 600 DEG C of roastings 3 are small.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 bar 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 when 700 DEG C of roastings 3 are small.The materialization of measure 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 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, when the time is 12 small.After the completion of hydro-thermal
Filter aluminium oxide, then with 120 DEG C it is dry 3 it is small when, obtain 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,
When nickel nitrate mixed solution dipping 1 is small, filters when 120 DEG C of drying 2 are small, when 410 DEG C of roastings 4 are small, obtain catalyst C1.With
Oxide meter and on the basis of unit carrier surface load capacity, using the oxidation in Xray fluorescence spectrometer measure catalyst C1
Whether the content of molybdenum, nickel oxide, using having molybdenum trioxide to form aggregation in x-ray powder diffraction instrument measure catalyst C1, measure
The results are 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 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, when the time is 8 small.After the completion of hydro-thermal
Filter aluminium oxide, then with 120 DEG C it is dry 3 it is small when, obtain 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 molybdenum oxide,
When the mixed solution dipping 0.5 of basic cobaltous carbonate is small, when 120 DEG C of drying 2 are small, when 450 DEG C of roastings 2 are small, catalyst C2 is obtained.
Counted by oxide and on the basis of unit carrier surface load capacity, using the oxygen in Xray fluorescence spectrometer measure catalyst C2
Change molybdenum, the content of cobalt oxide, whether measured using x-ray powder diffraction instrument in catalyst has molybdenum trioxide to form aggregation, measure
The results are shown in Table 2.
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, when the time is 6 small.After the completion of hydro-thermal
Filter aluminium oxide, then with 110 DEG C it is dry 3 it is small when, obtain 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
When molybdenum, the mixed solution dipping 1 of basic nickel carbonate are small, when 120 DEG C of drying 2 are small, when 480 DEG C of roastings 4 are small, catalyst is obtained
C3.Counted by oxide and on the basis of unit carrier surface load capacity, using in Xray fluorescence spectrometer measure catalyst C3
The content of molybdenum oxide, nickel oxide, whether have molybdenum trioxide form aggregation, survey if being measured using x-ray powder diffraction instrument in catalyst
It is fixed that the results are shown in Table 2.
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, when the time is 4 small.After the completion of hydro-thermal
Filter aluminium oxide, then with 110 DEG C it is dry 3 it is small when, obtain 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
When molybdenum, basic cobaltous carbonate mixed solution dipping 1 are small, filter when 110 DEG C of drying 3 are small, when 450 DEG C of roastings 2 are small, be catalyzed
Agent C4.Counted by oxide and on the basis of unit carrier surface load capacity, using in Xray fluorescence spectrometer measure catalyst C4
Molybdenum oxide, the content of cobalt oxide, using x-ray powder diffraction instrument measure 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
Aluminium 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, measures in catalyst DC1 whether have three oxidations using x-ray powder diffraction instrument
Molybdenum forms aggregation, and measurement result is as shown in table 2, and the XRD spectra of catalyst DC1 is as shown in Figure 2.
Comparative example 2
Aluminium 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, measures 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, 500 DEG C is warming up to 2 DEG C/min of speed, when 500 DEG C of constant temperature 3 are small, by carrier
Steam treatment is carried out, obtains alumina support DZ1.
Aluminium 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 measured 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 0.8-1.2 millimeters of diameter respectively, catalyst loading amount is 100 millis
Rise.Reaction condition is：When reaction temperature is 380 DEG C, hydrogen dividing potential drop is 14 megapascal, liquid hourly space velocity (LHSV) is 0.6 small-1, hydrogen to oil volume ratio is
1000, reaction 200 it is small when after sample, using inductive coupling plasma emission spectrograph (ICP-AES) measure handle after 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).
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 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 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) | 254 | 268 |
| Pore volume (ml/g) | 0.65 | 0.70 |
| 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 or nickel；It is described to contain based on the element and on the basis of described siliceous or fluorine shaped alumina alumina supporter gross weight
The content of silicon or fluorine is 0.5-10 weights % in silicon or fluorine shaped alumina alumina supporter；Loaded in terms of oxide and with unit carrier surface
On the basis of amount, the content of metal component molybdenum described in the catalyst is 4.8 μm of ol/m2-9.0μmol/m2, the metal component
The content of cobalt or nickel is 1.5 μm of ol/m2-4.0μmol/m2；When the catalyst uses XRD characterization, 2 θ=26 ° of the angle of diffraction ±
2 ° do not have MoO3Characteristic peak occurs；
Described siliceous or fluorine shaped alumina alumina supporter before the metal component molybdenum and the metal component cobalt or 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 or nickel, by drying process, without calcination process；The temperature of the drying process is 60-350 DEG C, is done
When the time of dry processing is 1-48 small.
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, when the time is 1-24 small；
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, has then been introduced into described siliceous or fluorine element compound oxygen
Change aluminium predecessor to be molded, and the aluminum oxide precursor thing after shaping 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 or nickel pass through dipping
Load 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
When 1-5 is small；The temperature of the calcination process is 350-550 DEG C, when the time of calcination process is 1-6 small.
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 megapascal, when liquid hourly space velocity (LHSV) is 0.1-3 small-1, hydrogen to oil volume ratio 200-2500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410788461.XA CN105772007B (en) | 2014-12-17 | 2014-12-17 | A kind of heavy oil hydrogenating treatment catalyst and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410788461.XA CN105772007B (en) | 2014-12-17 | 2014-12-17 | A kind of heavy oil hydrogenating treatment catalyst and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105772007A CN105772007A (en) | 2016-07-20 |
| CN105772007B true CN105772007B (en) | 2018-04-13 |
Family
ID=56373404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410788461.XA Active CN105772007B (en) | 2014-12-17 | 2014-12-17 | A kind of heavy oil hydrogenating treatment catalyst and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105772007B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111420670B (en) * | 2020-05-11 | 2023-08-04 | 太原理工大学 | Hydrogenation catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103374390A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
-
2014
- 2014-12-17 CN CN201410788461.XA patent/CN105772007B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103374390A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
Non-Patent Citations (1)
| Title |
|---|
| 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 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105772007A (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105749922B (en) | A kind of heavy oil hydrogenating treatment catalyst preparation method and thus obtained catalyst and its application | |
| CN105521792B (en) | A kind of load type double-metal hydrogenation catalyst and its preparation method and application | |
| CN106179414B (en) | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof | |
| CN106268965B (en) | A kind of hydrocracking catalyst of the molecular sieve containing Beta and its application | |
| CN105013498B (en) | A kind of hydrotreating catalyst and its application | |
| CN105749924B (en) | A kind of heavy oil hydrogenating treatment catalyst and its application | |
| CN106140316B (en) | A kind of hydrogenation catalyst and its application in hydrocarbon oil hydrogenation | |
| CN105772007B (en) | A kind of heavy oil hydrogenating treatment catalyst and its application | |
| CN105772008B (en) | A kind of heavy oil hydrogenating treatment catalyst and its application | |
| CN105754638B (en) | A kind of heavy oil hydrogenation treatment method | |
| CN105749925B (en) | A kind of heavy oil hydrogenating treatment catalyst and its application | |
| CN105749923B (en) | A kind of heavy oil hydrogenating treatment catalyst and its application | |
| CN105772006B (en) | A kind of heavy oil hydrogenating treatment catalyst and its application | |
| CN105772009B (en) | A kind of heavy oil hydrogenating treatment catalyst and its application | |
| CN105772010B (en) | A kind of heavy oil hydrogenating treatment catalyst and its application | |
| CN105754640B (en) | A kind of heavy oil hydrogenation treatment method | |
| CN105749921B (en) | A kind of heavy oil hydrogenating treatment catalyst and its application | |
| CN106268922B (en) | A kind of hydrocracking catalyst and its application | |
| CN105754642B (en) | A kind of heavy oil hydrogenation treatment method | |
| CN104449832B (en) | A kind of catalytically cracked stock weighted BMO spaces method | |
| CN106140313B (en) | A kind of hydrogenation catalyst and its application in hydrocarbon hydrogenation reaction | |
| CN102861591B (en) | Hydrogenation catalyst containing boron and preparation method thereof | |
| CN105754641B (en) | A kind of heavy oil hydrogenation treatment method | |
| CN106140309B (en) | A kind of hydrogenation catalyst and preparation method and applications | |
| CN106268724B (en) | A kind of hydrocracking catalyst and its application containing Y type molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |