CN105754640B - A kind of heavy oil hydrogenation treatment method - Google Patents
A kind of heavy oil hydrogenation treatment method Download PDFInfo
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- CN105754640B CN105754640B CN201410788159.4A CN201410788159A CN105754640B CN 105754640 B CN105754640 B CN 105754640B CN 201410788159 A CN201410788159 A CN 201410788159A CN 105754640 B CN105754640 B CN 105754640B
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Abstract
The present invention provides a kind of heavy oil hydrogenation treatment method, and this method includes：Under heavy-oil hydrogenation treatment conditions, heavy oil is contacted with the catalyst combination including heavy oil hydrogenating treatment catalyst I and heavy oil hydrogenating treatment catalyst II and heavy-oil hydrogenation processing is carried out；Wherein, the heavy oil is first contacted with the heavy oil hydrogenating treatment catalyst I, then contacted again with the heavy oil hydrogenating treatment catalyst II；By volume and on the basis of the cumulative volume of the catalyst combination, the content that heavy oil hydrogenating treatment catalyst I content described in the catalyst combination is 20 60 body %, the heavy oil hydrogenating treatment catalyst II is 40 80 body %.Compared with existing heavy oil hydrogenation treatment method, there is more preferable hydrodesulfurization, demetalization and de- carbon residue effect when carrying out heavy-oil hydrogenation processing using the heavy oil hydrogenation treatment method of the present invention.
Description
Technical field
The present invention relates to a kind of heavy oil hydrogenation treatment method.
Background technology
It is continuously increased with the continuous in short supply of crude resources and to high-quality oil product demand, it is petroleum chemical enterprise's counterweight, bad
The process throughput of matter oil product increases year by year.It is miscellaneous containing metals such as substantial amounts of Ni-V-Fe and calcium in heavy oil compared with distillate
Matter, therefore above metal impurities must effectively be removed in hydroprocessing processes and accommodate deposition, otherwise it is easily caused catalysis
Agent is inactivated, and bed pressure drop rises, and shortens the catalyst runs cycle.At the same time, weight, in low grade oilses also containing substantial amounts of sulphur and
The harmful substances such as carbon residue, influence product distribution and the product property of the secondary processing process such as catalytic cracking, it is necessary to be effectively subject to
Removing.Solve problem above effective way be exactly develop impurity removal function admirable hydrotreating catalyst series and by its
Carry out effective and reasonable level to match somebody with somebody, so as to lift the residual hydrogenation economic benefit overall with catalytic cracking combination technique.
The content of the invention
The technical problem to be solved in the present invention is that the technology for being directed to current heavy raw oil desulfurization, demetalization and de- carbon residue is needed
Ask there is provided it is a kind of it is new, the heavy oil hydrogenation treatment method of heavy-oil hydrogenation product property can be effectively improved.
To achieve these goals, the present invention provides a kind of heavy oil hydrogenation treatment method, and this method includes：In heavy-oil hydrogenation
Under treatment conditions, by heavy oil with including heavy oil hydrogenating treatment catalyst I and heavy oil hydrogenating treatment catalyst II catalyst combination
Contact and carry out heavy-oil hydrogenation processing；Wherein, the heavy oil is first contacted with the heavy oil hydrogenating treatment catalyst I, Ran Houzai
Contacted with the heavy oil hydrogenating treatment catalyst II；It is described by volume and on the basis of the cumulative volume of the catalyst combination
The content of heavy oil hydrogenating treatment catalyst I described in catalyst combination is 20-60 bodies %, the heavy oil hydrogenating treatment catalyst II
Content be 40-80 bodies %；The heavy oil hydrogenating treatment catalyst I includes carrier I and hydrogenation active metal component I；It is described heavy
Oil hydrogenating treatment catalyst II, which includes carrier II and hydrogenation active metal component II, the hydrogenation active metal component II, includes choosing
From at least one metal component of group vib and at least one metal component selected from VIII, carried in terms of oxide and with unit
On the basis of body II area load amount, the content of group vib metal component is 4.8 μ in the heavy oil hydrogenating treatment catalyst II
mol/m2-9.0μmol/m2, the content of group VIII metal component is 1.5 μm of ol/m in the heavy oil hydrogenating treatment catalyst II2-
4.0μmol/m2。
Preferably, wherein, counted by oxide and on the basis of unit carrier II area load amount, at the heavy-oil hydrogenation
It is 5.4 μm of ol/m to manage the content of group vib metal component described in catalyst II2-8.0μmol/m2, the group VIII metal component
Content be 1.8 μm of ol/m2-3.6μmol/m2。
Preferably, wherein, counted by oxide and on the basis of unit carrier II area load amount, at the heavy-oil hydrogenation
It is 5.9 μm of ol/m to manage the content of group vib metal component described in catalyst II2-7.5μmol/m2, the group VIII metal component
Content be 2.0 μm of ol/m2-3.1μmol/m2。
Preferably, wherein, carrier I described in the heavy oil hydrogenating treatment catalyst I be selected from aluminum oxide, silica, oxygen
Change at least one of titanium, magnesia and zirconium oxide, the hydrogenation active metal component I include molybdenum and/or tungsten and cobalt and/or
Nickel.
Preferably, wherein, counted by oxide and on the basis of the gross weight of the heavy oil hydrogenating treatment catalyst I, it is described
The content of molybdenum and/or tungsten described in heavy oil hydrogenating treatment catalyst I is 0.5-15 weight %, and the content of the cobalt and/or nickel is
0.2-8 weights %.
Preferably, wherein, carrier II described in the heavy oil hydrogenating treatment catalyst II be shaped alumina alumina supporter.
Preferably, wherein, the shaped alumina alumina supporter load the group vib metal component and the VIII gold
Before category component, 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 consumption of hydro-thermal process reclaimed water is the 100-300 weights % of formed alumina vehicle weight.
Preferably, wherein, the shaped alumina alumina supporter by the hydro-thermal process is loading the group vib metal group
Point and the group VIII metal component before, by drying process；The temperature of the drying process is 60-350 DEG C, drying process
Time be 1-48 hours.
Preferably, wherein, the shaped alumina alumina supporter has selected from γ-, η-, θ-, in δ-and χ-alumina crystalline phase
At least one crystalline phase.
Preferably, wherein, the shaped alumina alumina supporter be selected from spherical, cylindrical, annular, cloverleaf pattern, quatrefoil,
At least one of honeycombed and butterfly shape.
Preferably, wherein, the metal component of the metal component of the group vib and the VIII is arrived by dip loading
On the carrier II.
Preferably, wherein, by the dipping carrier II dryings processing and calcination process or do not roast
Burning processing；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, the time of calcination process is 1-6 hours.
Preferably, wherein, the group vib metal component be molybdenum and/or tungsten, the group VIII metal component be cobalt and/or
Nickel.
Preferably, wherein, the group vib metal component be molybdenum, the group VIII metal component be cobalt and/or nickel, it is described
When heavy oil hydrogenating treatment catalyst II is characterized using XRD, in θ=26 ° ± 2 ° of the angle of diffraction 2 without MoO3Characteristic peak occurs.
Preferably, wherein, the heavy oil be selected from crude oil, reduced crude, decompression residuum, deep drawing wax oil, frivolous coal tar
At least one of with wax tailings.
Preferably, wherein, the heavy-oil hydrogenation treatment conditions include：Reaction temperature is 300-450 DEG C, and hydrogen dividing potential drop is 6-20
MPa, liquid hourly space velocity (LHSV) is 0.1-1 hours-1, hydrogen to oil volume ratio is 600-1500.
Compared with existing heavy oil hydrogenation treatment method, carried out using the heavy oil hydrogenation treatment method of the present invention at heavy-oil hydrogenation
There is more preferable hydrodesulfurization, demetalization and de- carbon residue effect during reason.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, 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 CII1 (i.e. embodiments 3 used in the heavy oil hydrogenation treatment method of the present invention
Prepared catalyst) XRD spectra；
Fig. 2 is that heavy oil hydrogenating treatment catalyst DCII1 (is contrasted used in the heavy oil hydrogenation treatment method of prior art
Catalyst prepared by example 1) 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 hydrogenation treatment method, and this method includes：Under heavy-oil hydrogenation treatment conditions, by heavy oil
Contacted with the catalyst combination including heavy oil hydrogenating treatment catalyst I and heavy oil hydrogenating treatment catalyst II and carry out heavy-oil hydrogenation
Processing；Wherein, the heavy oil is first contacted with the heavy oil hydrogenating treatment catalyst I, then handled again with the heavy-oil hydrogenation
Catalyst II is contacted；By volume and on the basis of the cumulative volume of the catalyst combination, weight described in the catalyst combination
Oil hydrogenating treatment catalyst I content is that 20-60 bodies %, the heavy oil hydrogenating treatment catalyst II content are 40-80 body %,
Heavy oil hydrogenating treatment catalyst I content described in the catalyst combination is preferably 25-50 bodies %, the heavy-oil hydrogenation processing
Catalyst II content is preferably 50-75 bodies %；The heavy oil hydrogenating treatment catalyst I includes carrier I and hydrogenation active metals
Component I；The heavy oil hydrogenating treatment catalyst II includes carrier II and hydrogenation active metal component II, the hydrogenation active metals
Component II includes at least one metal component selected from group vib and at least one metal component selected from VIII, with oxide
Count and on the basis of unit carrier II area load amount, group vib metal component in the heavy oil hydrogenating treatment catalyst II
Content is 4.8 μm of ol/m2-9.0μmol/m2, preferably 5.4 μm ol/m2-8.0μmol/m2, more preferably 5.9 μm ol/m2-
7.5μmol/m2, the content of group VIII metal component is 1.5 μm of ol/m in the heavy oil hydrogenating treatment catalyst II2-4.0μmol/
m2, preferably 1.8 μm ol/m2-3.6μmol/m2, more preferably 2.0 μm ol/m2-3.1μmol/m2.Wherein, the unit
Carrier II area load amount refers to the load capacity of metal component in the load capacity in carrier II per surface areas, i.e. catalyst II
The ratio between with carrier II total surface area.The carrier II refers to the carrier II before carried metal component, if the carrier II is negative
Carry and pass through hydro-thermal process before metal component, then carrier II described herein refers to the carrier II before hydro-thermal process.The carrier II
The size of total surface area is measured according to RIPP151-90 standard methods using BET method.
According to the present invention, the effect of the heavy oil hydrogenating treatment catalyst I is the weight by carrying out on the catalyst
The metal impurities such as Ni-V-Fe and calcium in oily hydrotreating reaction, main removing raw material, and have to the metal impurities removed
Effect deposition is accommodated, it is to avoid the rising of bed pressure drop.
Heavy oil hydrogenating treatment catalyst I of the present invention can be selected from can arbitrarily realize this function in the prior art
It is prepared by one or more of or commercially available commodity or any existing method of use in catalyst.For example, the heavy oil adds
Carrier I is at least one in aluminum oxide, silica, titanium oxide, magnesia and zirconium oxide described in hydrogen processing catalyst I
Plant, preferably aluminum oxide, more preferably selected from macropore alumina supporter, double-hole alumina support, Bimodal-pore alumina support
At least one of with small specific surface alumina support.Wherein, the macropore alumina supporter can several diameters can be 14-20
Nanometer, pore volume can be 0.6-1.2 mls/g, and specific surface area can be 150-250 meters2/ gram；The double-hole carrying alumina
Body can have following pore-size distribution：Bore dia is that 10-20 nanometers of pore volume accounts for the 35-80% of total pore volume, and bore dia is
500-1200 nanometers of pore volume accounts for the 15-60% of total pore volume, bore dia<10 nanometers,>20-<500 nanometers and>1200 nanometers
Pore volume sum accounts for the 5-40% of total pore volume；The pore volume of the Bimodal-pore alumina support can be 0.8-1.6 mls/g, compare table
Area can be 150-350 meters2/ gram, aperture can account for the 40-90% of total pore volume in 10-30 nanometers of pore volume, and aperture is in 100-
2000 nanometers of pore volume can account for the 10-60% of total pore volume；The specific surface area of the small specific surface alumina support can be 2-
50 meters2/ gram, pore volume can be 0.4-1.2 mls/g.The hydrogenation active metal component I can include molybdenum and/or tungsten and
Cobalt and/or nickel, are counted and on the basis of the gross weight of the heavy oil hydrogenating treatment catalyst I by oxide, at the heavy-oil hydrogenation
The content for managing molybdenum and/or tungsten described in catalyst I can be 0.5-15 weight %, and the content of the cobalt and/or nickel can be 0.2-8
Weight %.In addition, the heavy oil hydrogenating treatment catalyst I can also contain halogens, in terms of element and with catalyst I total matter
On the basis of amount, the content of the halogen can be 0.5-10 weights %.
According to the present invention, the effect of the heavy oil hydrogenating treatment catalyst II is the weight by carrying out on the catalyst
Harmful structural materials, one-step removal metal impurities of going forward side by side such as sulphur and carbon residue in oily hydrotreating reaction, main removing raw material.
According to the present invention, carrier II described in the heavy oil hydrogenating treatment catalyst II can also be selected from aluminum oxide, oxygen
At least one of SiClx, titanium oxide, magnesia and zirconium oxide, preferably aluminum oxide, more preferably shaped alumina alumina supporter.
According to the present invention, the shaped alumina alumina supporter in the heavy oil hydrogenating treatment catalyst II is described in load
, can be by hydro-thermal process in confined conditions before group vib metal component and group VIII metal component.At the hydro-thermal
Reason with unlike conventional catalyst high-temperature vapor processing, it is of the invention in shaped alumina alumina supporter hydro-thermal process refer to by
Shaped alumina alumina supporter and water are put into the closed containers such as reactor, certain temperature are heated in confined conditions, then at this
Hydro-thermal process is carried out at a temperature of hydro-thermal process.Shaped alumina alumina supporter after hydro-thermal process can present the metal component of load
More preferable dispersity, improves prepared catalyst II number of active center and catalytic activity.Wherein, the hydro-thermal process temperature
Degree can be 60-180 DEG C, preferably 90-150 DEG C；The time of the hydro-thermal process can be 1-24 hours, and preferably 4-12 is small
When；By weight, the consumption of the hydro-thermal process reclaimed water can be the 100-300 weight % of the formed alumina vehicle weight,
The 150-250 weights % of preferably described formed alumina vehicle weight.In the present invention, the pressure of hydro-thermal process is under confined conditions
Self-generated pressure, when the hydro-thermal process is carried out at a constant temperature, hydro-thermal process temperature be the thermostat temperature, the hydro-thermal process
Time be when the closed container reaches the hydro-thermal process temperature timing；Temperature-rise period before hydro-thermal process
Heating rate has no particular limits, preferably 5-15 DEG C/min, more preferably 8-12 DEG C/min.
According to the present invention, the shaped alumina alumina supporter by the hydro-thermal process is loading the group vib metal group
Point and the group VIII metal component before, may also pass through drying process, with remove oxidation aluminium surface and duct in water
Point.The condition of the drying process is not particularly limited, and can be the conventional selection of this area, can remove oxidation aluminium surface
It is defined with the moisture in duct.Usually, the temperature of the drying process can be 60-350 DEG C, preferably 80-200 DEG C, more
Preferably 100-150 DEG C.The time of the drying process can carry out appropriate selection according to dry temperature, not limit especially
It is fixed.Usually, the time of the drying process can be 1-48 hours, preferably 1-24 hours, more preferably 1-8 hours.
According to the present invention, the shaped alumina alumina supporter can have various crystalline phases well-known to those skilled in the art
Aluminum oxide, for example, can have γ-, η-, θ-, δ-and χ-etc. at least one of alumina crystalline phase crystalline phase., can in the present invention
With by by the predecessor of aluminum oxide, such as boehmite be molded and then being calcined and obtain the formed alumina and carry
Body, can also directly buy after the aluminum oxide including above-mentioned alumina crystalline phase is molded and obtain shaped alumina alumina supporter.
According to the present invention it is possible to according to catalyst II specifically used requirement, using shaping jigs such as banded extruders to oxidation
Aluminium or its predecessor are molded, and this is commonly used in hydrotreating catalyst preparation process, for example：The formed alumina
Carrier can be selected from least one of spherical, cylindrical, annular, cloverleaf pattern, quatrefoil, honeycombed and butterfly etc. shape
Shape.
It is well-known to those skilled in the art in the method for supported on carriers metal component according to the present invention, for example, institute
State group vib metal component and the group VIII metal component can be by dip loading to the carrier II, that is, using and containing
The solution impregnating carrier II of the compound of the group vib metal component and compound containing the group VIII metal component.It is described
The compound of the metal component containing group vib can be the compound containing molybdenum and/or tungstenic metal component, can be selected from its solubilityization
One or more in compound, such as one in molybdenum oxide, tungsten oxide, molybdate, tungstates, metatungstate and paramolybdate
Plant or several, preferably be selected from the one or more in molybdenum oxide therein, ammonium molybdate, ammonium paramolybdate and metatungstate；It is described to contain VIB
The compound of the more preferably self-contained molybdenum component of the compound of race's metal component, is selected from molybdenum oxide, molybdate and para-molybdic acid
One or more in salt.The compound of the component containing group VIII metal can be the change of the nickeliferous and/or metal component containing cobalt
Compound, can be the one or more in the soluble compound selected from them, such as be selected from cobalt nitrate, cobalt acetate, basic carbonate
Cobalt, cobalt chloride, the soluble complexes of cobalt, nickel nitrate, nickel acetate, basic nickel carbonate, the soluble complexes of nickel chloride and nickel
In one or more, preferably be selected from the one or more in cobalt nitrate, basic cobaltous carbonate, 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, for example, the solution difference impregnated carrier II containing single various metal component compounds can be used, also may be used
With using the mixed solution impregnated carrier II of the component composition containing various metals.By adjusting group containing metal described in dipping process
Break up the concentration and the consumption of dipping solution of the dipping solution of compound, those skilled in the art can be to being introduced into catalyst II
The content of metal component is controlled, and is repeated no more here.
According to the present invention, it can be handled and be calcined or be not calcined place with drying by the carrier II of the dipping
Reason.The method and condition of the drying process and calcination process are well known to the skilled person, for example, the temperature of drying process
Degree can be 60-150 DEG C, preferably 80-120 DEG C；The time of drying process can be 1-5 hours, preferably 2-4 hours；Roasting
The temperature for burning processing can be 350-550 DEG C, preferably 400-500 DEG C；The time of calcination process can be 1-6 hours, preferably
For 2-4 hours.
According to the present invention, the hydrogenation active metal component II in the heavy oil hydrogenating treatment catalyst II can conduct
Hydrogenation sites, this is well-known to those skilled in the art, can mainly include VIB and group VIII metal component.It is described
Group vib metal component can be molybdenum and/or tungsten, and the group VIII metal component can be nickel and/or cobalt；Preferably, the VIB
Race's metal component can be molybdenum, and the group VIII metal component can be nickel and/or cobalt.It was found by the inventors of the present invention that working as institute
Group vib metal component is stated for molybdenum, when the group VIII metal component is cobalt and/or nickel, the heavy oil hydrogenating treatment catalyst II
When being characterized using XRD, in θ=26 ° ± 2 ° of the angle of diffraction 2 without MoO3Characteristic peak occurs, and this illustrates heavy-oil hydrogenation processing catalysis
Agent II from unlike the heavy oil hydrogenating treatment catalyst of existing high molybdenum content, the molybdenum trioxide in catalyst II of the invention exists
Well dispersed, not a large amount of aggregations, so that MoO can not be detected of catalyst surface3Characteristic peak, and with such feature
Catalyst II have higher reactivity.
In the present invention, the heavy oil can be the various heavy oil feedstocks for needing to carry out hydrotreating, preferably various to need
Carry out the heavier hydrocarbon feeds of hydrodesulfurization, demetalization and the processing of de- carbon residue.Specifically, the heavy oil can be selected from crude oil,
At least one of reduced crude, decompression residuum, deep drawing wax oil, frivolous coal tar and wax tailings.The heavy-oil hydrogenation of the present invention
Processing method be by the way that heavy oil is contacted with the catalyst that provides of the present invention, hydrotreating is carried out to heavy oil with higher efficiency,
Remaining condition for hydrotreating is not particularly limited, can be according to the property of pending heavy oil, according to the normal of this area
Advise knowledge and carry out appropriate selection.For example, the heavy-oil hydrogenation treatment conditions can be：Hydrogen dividing potential drop is 6-20MPa, reaction temperature
For 300-450 DEG C, liquid hourly space velocity (LHSV) is 0.1-1.0h-1, hydrogen to oil volume ratio is 600-1500；The heavy-oil hydrogenation treatment conditions are preferred
For：Hydrogen dividing potential drop is 10-18MPa, and reaction temperature is 350-420 DEG C, and liquid hourly space velocity (LHSV) is 0.2-0.6h-1, hydrogen to oil volume ratio is 800-
1100。
According to the present invention, the heavy-oil hydrogenation processing can be enough to make the heavy oil in heavy-oil hydrogenation treatment conditions any
It is lower to contact and carried out in the reactor of hydrotreating with the heavy oil hydrogenating treatment catalyst, for example, can be in fixed bed
Carry out, carried out preferably in fixed bed reactors in reactor, moving-burden bed reactor or fluidized bed reactor.When the heavy oil adds
When hydrogen processing is carried out in fixed bed reactors, the heavy oil hydrogenating treatment catalyst I and heavy oil hydrogenating treatment catalyst II can
Used with being layered to be loaded in same reactor or be loaded in the reactor of several series connection successively successively, to this
The present invention is not particularly limited.
According to the present invention, heavy oil feedstock contact heavy oil hydrogenating treatment catalyst I and heavy oil hydrogenating treatment catalyst II it
Before, afterwards and when any time in, can contact any helps to improve other catalysis of the catalyst combination performance
Agent or filler.For example, can contact such as porcelain ball, active supporter before heavy oil contacts the heavy oil hydrogenating treatment catalyst I
Deng filler, to improve the distribution of heavy oil in the reactor etc..Use on this filler is known to those skilled in the art,
Here do not repeat.
According to the heavy oil hydrogenation treatment method of the present invention, the heavy oil hydrogenating treatment catalyst I and/or II is using it
Before, presulfurization can be first carried out under the normal condition of this area.The condition of presulfurization can be：In presence of hydrogen, in
Presulfurization is carried out to catalyst with sulphur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140-370 DEG C, the presulfurization can be described
Being carried out outside reactor also can be In-situ sulphiding in the reactor.
The present invention will be further detailed by embodiment below, but therefore the present invention does not limit.
Agents useful for same in following examples and comparative example, is chemically pure reagent except as expressly described.
In following examples and comparative example, the radial direction for determining carrier using method specified in RIPP 25-90 crushes strong
Degree；Using method specified in RIPP 151-90 determine the total surface area of carrier, the pore volume of carrier, the pore-size distribution of carrier and
Can several bore dias；Containing for the molybdenum of catalyst, nickel and cobalt is determined using the x ray fluorescence spectrometry (that is, XRF) in RIPP133-90
Amount；Using the content of the fluorine of the Coupled Plasma-Atomic Emission Spectrometric Determination catalyst in RIPP128-90；It is herein and 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, is confirmed whether there is molybdenum trioxide formation 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 °.
The heavy oil hydrogenating treatment catalyst II of the present invention is provided first below：
Embodiment 1-2 provides the 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 well mixed,
At room temperature by the aqueous solution of nitric acid that the mixture and 1.1 liters of concentration are 1 weight %, it is well mixed, on double screw banded extruder
Continue kneading after plastic, to be extruded into 1.1 millimeters of ф trilobal bar, after wet bar is dried 3 hours through 120 DEG C, in 600 DEG C of roastings
Obtain within 3 hours shaped alumina alumina supporter ZII1.The materialization for determining ZII1 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 aqueous solution of nitric acid that 1.2 liters of concentration are 1 weight % is added, is well mixed, is continued on double screw banded extruder after kneading is plastic,
It is extruded into 1.1 millimeters of ф butterfly bar, after wet bar is dried 2 hours through 110 DEG C, obtains within 3 hours formed alumina in 700 DEG C of roastings and carry
Body ZII2.The materialization for determining ZII2 the results are shown in Table 1.
Embodiment 3-6 provides the heavy oil hydrogenating treatment catalyst II of the present invention.
Embodiment 3
Weigh ZII1 carriers 150g be placed in hydration kettle in, add 150 grams of deionized waters, will be hydrated kettle it is closed after be put into baking oven
In, 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 16 hours.Hydro-thermal is completed
After filter aluminum oxide, then with 120 DEG C dry 3 hours, obtain the alumina support of hydrothermal treatment.
100 grams of carrier ZII1 after water intaking heat treatment, contains MoO with 220 milliliters3170 g/l, the molybdic acid that 30 g/l of NiO
Ammonium, nickel nitrate mixed solution are impregnated 1 hour, and filtering is dried 2 hours after 120 DEG C, and 410 DEG C are calcined 2 hours, obtain catalyst
CII1.Counted by oxide and on the basis of unit carrier II area load amounts, catalyst is determined using Xray fluorescence spectrometer
The content of molybdenum oxide, nickel oxide in CII1, determines in catalyst CII1 whether have molybdenum trioxide using x-ray powder diffraction instrument
Aggregation is formed, as shown in table 2, catalyst CII1 XRD spectra is as shown in Figure 1 for measurement result.
Embodiment 4
Weigh ZII1 carriers 150g be placed in hydration kettle in, add 225 grams of deionized waters, will be hydrated kettle it is closed after be put into baking oven
In, 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.Hydro-thermal is completed
After filter aluminum oxide, then with 120 DEG C dry 3 hours, obtain the alumina support of hydrothermal treatment.
100 grams of carrier ZII1 after water intaking heat treatment, contains MoO with 110 milliliters3260 g/l, CoO58 g/l of oxygen
Change molybdenum, the mixed solution of basic cobaltous carbonate impregnates 0.5 hour, dried in 120 DEG C 2 hours, 450 DEG C are calcined 2 hours, are catalyzed
Agent CII2.Counted by oxide and on the basis of unit carrier II area load amounts, catalyst is determined using Xray fluorescence spectrometer
Whether the content of molybdenum oxide, cobalt oxide in CII2, being determined using x-ray powder diffraction instrument in catalyst has molybdenum trioxide to be formed
Aggregation, measurement result is as shown in table 2.
Embodiment 5
Weigh ZII2 carriers 150g be placed in hydration kettle in, add 300 grams of deionized waters, will be hydrated kettle it is closed after be put into baking oven
In, 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.Hydro-thermal is completed
After filter aluminum oxide, then with 110 DEG C dry 3 hours, obtain the alumina support of hydrothermal treatment.
100 grams of carrier ZII2 after water intaking heat treatment, contains MoO with 120 milliliters3290 g/l, the oxygen that 63 g/l of NiO
Change molybdenum, the mixed solution of basic nickel carbonate impregnates 1 hour, dried in 120 DEG C 2 hours, 480 DEG C are calcined 4 hours, obtain catalyst
CII3.Counted by oxide and on the basis of unit carrier II area load amounts, catalyst is determined using Xray fluorescence spectrometer
Whether the content of molybdenum oxide, nickel oxide in CII3, being determined using x-ray powder diffraction instrument in catalyst has molybdenum trioxide to be formed
Aggregation, measurement result is as shown in table 2.
Embodiment 6
Weigh ZII2 carriers 150g be placed in hydration kettle in, add 450 grams of deionized waters, will be hydrated kettle it is closed after be put into baking oven
In, 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.Hydro-thermal is completed
After filter aluminum oxide, then with 110 DEG C dry 3 hours, obtain the alumina support of hydrothermal treatment.
100 grams of carrier ZII2 after water intaking heat treatment, contains MoO with 220 milliliters3260 g/l, CoO41 g/l of oxygen
Change molybdenum, basic cobaltous carbonate mixed solution to impregnate 1 hour, filtering is dried 3 hours after 110 DEG C, and 450 DEG C are calcined 2 hours, are urged
Agent CII4.Counted by oxide and on the basis of unit carrier II area load amounts, determined and be catalyzed using Xray fluorescence spectrometer
The content of molybdenum oxide, cobalt oxide in agent CII4, determines in catalyst whether have molybdenum trioxide shape using x-ray powder diffraction instrument
Into aggregation, measurement result is as shown in table 2.
Comparative example 1
The use of the aluminum oxide ZII1 of not hydrothermal treatment is carrier, is made using the active component carrying method of embodiment 3
Reference catalyst DCII1.Counted by oxide and on the basis of unit carrier II area load amounts, using Xray fluorescence spectrometer
Molybdenum oxide, the content of nickel oxide in measure catalyst DCII1, being determined using x-ray powder diffraction instrument in catalyst DCII1 is
No to have molybdenum trioxide formation aggregation, as shown in table 2, catalyst DCII1 XRD spectra is as shown in Figure 2 for measurement result.
Comparative example 2
The use of the aluminum oxide ZII2 of not hydrothermal treatment is carrier, is made using the active component carrying method of embodiment 6
Reference catalyst DCII2.Counted by oxide and on the basis of unit carrier II area load amounts, using Xray fluorescence spectrometer
Whether molybdenum oxide, the content of cobalt oxide in measure catalyst DCII2, determined using x-ray powder diffraction instrument is had in catalyst
Molybdenum trioxide formation aggregation, measurement result is as shown in table 2.
Comparative example 3
Weigh ZII1 carriers 100g to be placed in tube furnace, the air blast into stove with the air quantity of 100ml/ minutes, while with
Speed was pumped into deionized water into stove within 120ml/ hours, and 500 DEG C are warming up to 2 DEG C/min of speed, in 500 DEG C of constant temperature 3 hours,
Carrier is subjected to steam treatment, alumina support DZII3 is obtained.
The use of the aluminum oxide DZII3 of steam treatment is carrier, ginseng is made using the active component carrying method of embodiment 3
Than catalyst DCII3.Counted and on the basis of carrier II of the unit without steam treatment area load amount, used by oxide
Xray fluorescence spectrometer determines the content of the molybdenum oxide and nickel oxide in catalyst DCII3, is surveyed using x-ray powder diffraction instrument
Determine whether have molybdenum trioxide formation aggregation in catalyst, measurement result is as shown in table 2.
Embodiment 7-9 provides the heavy oil hydrogenating treatment catalyst I of the present invention.
Embodiment 7
Weighing the dry glue powder of Chang Ling oil plant catalyst plant production, (butt is 73 heavy %, and wherein boehmite content is
68 heavy %, gibbsite content is 5 heavy %, and remaining is amorphous alumina) 300 grams with 12 grams of polyvinyl alcohol (Chang Ling catalyst
Factory) mixing, 360 milliliters of the solution of 18 grams of hydrofluoric acid containing (Beijing Chemical Plant's product) is added afterwards, is squeezed on double screw banded extruder
It it is 3.5 millimeters into external diameter, internal diameter is 1.0 millimeters of Rasching ring, wet bar is dried 2 hours small after 780 DEG C of roastings 2 through 150 DEG C
When, obtain macropore alumina supporter, the macropore alumina supporter can be several a diameter of 16 nanometers, pore volume be 0.81 ml/g, than
Surface area is 156 meters2/ gram, the content of fluorine element is 2.6 heavy %.By 200 grams of macropore alumina supporters with 220 milliliters of MoO3 60
G/l, the ammonium molybdate and nickel nitrate mixed solution that 12 g/l of NiO impregnate 2 hours, and filtering dries 2 hours, 550 after 120 DEG C
DEG C roasting 2 hours, obtains catalyst CI1, catalyst CI1 oxidation molybdenum content is 7.9 heavy %, and the content of nickel oxide is 1.8
Weight %.
Embodiment 8
Weighing the boehmite powder of Chang Ling oil plant catalyst plant production, (trade name is aluminum hydroxide solid elastomer powder, is done
Base is 65 heavy %) 300 grams, add 9 grams of sesbania powders, 120 grams of ammonium hydrogen carbonate and be well mixed, add afterwards molten containing 10 grams of ammonium fluoride
300 milliliters of liquid, kneading 15 minutes, are extruded into 1.1 millimeters of ф trilobal bar on banded extruder at room temperature, and wet bar is dry through 120 DEG C
It is calcined 2 hours after 750 DEG C within dry 4 hours, obtains double-hole alumina support, the pore volume of the double-hole alumina support is 0.9
Ml/g, specific surface area is 120 meters2/ gram, the content of fluorine element is 2.0 heavy %, and bore dia is accounted for always for 10-20 nanometers of pore volume
The 55% of pore volume, bore dia accounts for the 28% of total pore volume, bore dia for 500-1200 nanometers of pore volume<10 nanometers,>20-<500 receive
Rice and>1200 nanometers of pore volume sum accounts for the 17% of total pore volume.200 grams of double-hole alumina supports are contained with 500 milliliters
MoO380 g/l, the ammonium molybdate and nickel nitrate mixed solution that 16 g/l of NiO impregnate 1 hour, and filtering dries 2 after 120 DEG C
Hour, 500 DEG C are calcined 4 hours, obtain catalyst CI2, catalyst CI2 oxidation molybdenum content is 7.8 heavy %, the content of nickel oxide
For 1.5 heavy %.
Embodiment 9
Weigh 666 grams of aluminum sulfate (Beijing Chemical Plant's product), plus deionized water dissolving into molar concentration be 0.3mol/L's
Solution a1, weighs 1000 grams of ammonium hydrogen carbonate (Beijing Chemical Plant's product), plus deionized water dissolving into molar concentration be 2.5mol/L
Solution b1.Solution a1 and solution b1 are added in one 10 liters of plastic cans simultaneously in manner of cocurrent flow and reacted, was reacted
Control ph is 7.5 in journey, and temperature is 40 DEG C, and the white precipitate of generation is filtered after being aged 1.5 hours at 40 DEG C, and filter cake is with 10 times
The deionized water that 40 DEG C of (weight) is washed three times, and 120 DEG C of dryings 4 hours, obtain aluminium carbonate ammonium F1 in drying box.
50 grams of the boehmite powder of Chang Ling oil plant catalyst plant production is weighed, with 50 grams of aluminium carbonate ammoniums prepared above
F1 is well mixed, and is added 4 grams of sesbania powders, 95 milliliters of solution containing 6 grams of ammonium oxalate, is extruded into equivalent on screw rod banded extruder afterwards straight
Footpath is 1.2 millimeters of trilobal bar, and wet bar is dried 2 hours through 120 DEG C and is calcined 2 hours after 850 DEG C, obtains bimodal porous aluminum oxide
Carrier.The pore volume of the Bimodal-pore alumina support is 0.92 ml/g, and specific surface area is 148 meters2/ gram, intensity is 11.9 Ns
/ millimeter, bore dia is that 10-30 nanometers of pore volume accounts for the 67.0% of total pore volume, and bore dia accounts for for 100-1200 nanometers of pore volume
The 25.6% of total pore volume.200 grams of Bimodal-pore alumina supports are contained into MoO with 500 milliliters380 g/l, the molybdenum that 16 g/l of NiO
Sour ammonium and nickel nitrate mixed solution is impregnated 1 hour, and filtering is dried 2 hours after 120 DEG C, and 500 DEG C are calcined 4 hours, are catalyzed
Agent CI3.Catalyst CI3 oxidation molybdenum content is 8.2 heavy %, and the content of nickel oxide is 1.6 heavy %.
Embodiment 10-13 illustrates the effect that heavy-oil hydrogenation processing is carried out using the heavy oil hydrogenation treatment method of the present invention.
By 96ppm of Ni+V contents, sulfur content be that the mixed residue oil that 3.6%, carbon residue is 12.5% is raw material, 500 milli
Rise and evaluate catalyst on fixed bed reactors.
The content of nickel and vanadium determines (instrument used using inductive coupling plasma emission spectrograph (ICP-AES) in oil sample
Device is U.S.'s PE companies PE-5300 type plasma quantometers, and specific method is shown in Petrochemical Engineering Analysis method RIPP124-90).
Sulfur content determines (specific method is shown in Petrochemical Engineering Analysis method RIPP62-90) using coulometry in oil sample.
Carbon residue content uses microdetermination in oil sample (specific method is shown in Petrochemical Engineering Analysis method RIPP149-90).
The use ratio and process conditions of catalyst are listed in Table 3 below in catalyst combination, product property after operating 200 hours
It is listed in Table 4 below.
Comparative example 4
Catalyst uses CI1, DCII1 combination, and when process conditions are listed in Table 3 below the volume of each catalyst amount, fortune
Sampling analysis after turning 200 hours, is as a result listed in table 4.
Comparative example 5
Catalyst uses CI1, DCII2 combination, and when process conditions are listed in Table 3 below the volume of each catalyst amount, fortune
Sampling analysis after turning 200 hours, is as a result listed in table 4.
Comparative example 6
Catalyst uses CI1, DCII3 combination, and when process conditions are listed in Table 3 below the volume of each catalyst amount, fortune
Sampling analysis after turning 200 hours, is as a result listed in table 4.
When can be seen that the heavy oil hydrogenation treatment method progress heavy-oil hydrogenation processing using the present invention from the data of table 4,
After operating 200 hours, the impurity content such as metal, sulphur and carbon residue of heavy-oil hydrogenation processing product, which is significantly lower than, uses existing heavy oil
Hydrotreating method carries out the result of heavy-oil hydrogenation processing, so that improving heavy-oil hydrogenation handles product as catalytic cracking etc. two
The secondary property processed raw material.
Table 1
| Embodiment is numbered | Embodiment 1 | Embodiment 2 |
| Bearer number | ZII1 | ZII2 |
| Than surface (rice2/ gram) | 248 | 270 |
| Pore volume (ml/g) | 0.66 | 0.70 |
| Can several bore dias (nanometer) | 8 | 9 |
| Intensity (Newton/millimeter) | 18 | 17 |
Table 2
Table 3
Table 4
Claims (14)
1. a kind of heavy oil hydrogenation treatment method, this method includes：Under heavy-oil hydrogenation treatment conditions, by heavy oil with adding including heavy oil
Hydrogen processing catalyst I and heavy oil hydrogenating treatment catalyst II catalyst combination contacts and carries out heavy-oil hydrogenation processing；
Wherein, the heavy oil is first contacted with the heavy oil hydrogenating treatment catalyst I, then urged again with heavy-oil hydrogenation processing
Agent II is contacted；
By volume and on the basis of the cumulative volume of the catalyst combination, the processing of heavy-oil hydrogenation described in the catalyst combination
Catalyst I content is that 20-60 bodies %, the heavy oil hydrogenating treatment catalyst II content are 40-80 bodies %；
The heavy oil hydrogenating treatment catalyst I includes carrier I and hydrogenation active metal component I；
The heavy oil hydrogenating treatment catalyst II includes carrier II and hydrogenation active metal component II, the hydrogenation active metals group
II is divided to include at least one metal component selected from group vib and at least one metal component selected from VIII, in terms of oxide
And on the basis of unit carrier II area load amount, group vib metal component contains in the heavy oil hydrogenating treatment catalyst II
Measure as 4.8 μm of ol/m2-9.0μmol/m2, the content of group VIII metal component is 1.5 μ in the heavy oil hydrogenating treatment catalyst II
mol/m2-4.0μmol/m2；
Carrier II described in the heavy oil hydrogenating treatment catalyst II is shaped alumina alumina supporter, and the shaped alumina alumina supporter exists
Load before the group vib metal component and the group VIII metal component, by hydro-thermal process in confined conditions, pass through
The shaped alumina alumina supporter for crossing the hydro-thermal process is loading the group vib metal component and the group VIII metal group
/ preceding, by drying process, without calcination process；The temperature of the drying process is 60-350 DEG C, the time of drying process
For 1-48 hours.
2. method according to claim 1, wherein, counted by oxide and on the basis of unit carrier II area load amount, institute
It is 5.4 μm of ol/m to state the content of group vib metal component described in heavy oil hydrogenating treatment catalyst II2-8.0μmol/m2, it is described
The content of group VIII metal component is 1.8 μm of ol/m2-3.6μmol/m2。
3. method according to claim 1, wherein, counted by oxide and on the basis of unit carrier II area load amount, institute
It is 5.9 μm of ol/m to state the content of group vib metal component described in heavy oil hydrogenating treatment catalyst II2-7.5μmol/m2, it is described
The content of group VIII metal component is 2.0 μm of ol/m2-3.1μmol/m2。
4. method according to claim 1, wherein, carrier I described in the heavy oil hydrogenating treatment catalyst I is selected from oxidation
At least one of aluminium, silica, titanium oxide, magnesia and zirconium oxide, the hydrogenation active metal component I include molybdenum and/or
Tungsten and cobalt and/or nickel.
5. method according to claim 4, wherein, in terms of oxide and with the gross weight of the heavy oil hydrogenating treatment catalyst I
On the basis of, the content of molybdenum and/or tungsten described in the heavy oil hydrogenating treatment catalyst I is 0.5-15 weight %, the cobalt and/or nickel
Content for 0.2-8 weight %.
6. method according to claim 1, wherein, the temperature of the hydro-thermal process is 60-180 DEG C, and the time is 1-24 hours；With
Weight meter, the consumption of the hydro-thermal process reclaimed water is the 100-300 weights % of formed alumina vehicle weight.
7. method according to claim 1, wherein, the shaped alumina alumina supporter has selected from γ-, η-, θ-, δ-and χ-oxidation
At least one of aluminium crystalline phase crystalline phase.
8. method according to claim 1, wherein, the shaped alumina alumina supporter is selected from spherical, cylindrical, annular, three leaves
At least one of careless shape, quatrefoil, honeycombed and butterfly shape.
9. method according to claim 1, wherein, the metal component of the metal component of the group vib and the VIII leads to
Dip loading is crossed to the carrier II.
10. method according to claim 9, wherein, handle and roast by the carrier II dryings of the dipping
Burn processing or not 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 of processing is 350-550 DEG C, and the time of calcination process is 1-6 hours.
11. method according to claim 1, wherein, the group vib metal component is molybdenum and/or tungsten, the group VIII metal group
It is divided into cobalt and/or nickel.
12. method according to claim 1, wherein, the group vib metal component is molybdenum, and the group VIII metal component is cobalt
And/or nickel, when the heavy oil hydrogenating treatment catalyst II is characterized using XRD, in θ=26 ° ± 2 ° of the angle of diffraction 2 without MoO3Feature
Peak occurs.
13. method according to claim 1, 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.
14. method according to claim 1, wherein, the heavy-oil hydrogenation treatment conditions include：Reaction temperature is 300-450 DEG C,
Hydrogen dividing potential drop is 6-20 MPas, and liquid hourly space velocity (LHSV) is 0.1-1 hours-1, hydrogen to oil volume ratio is 600-1500.
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| CN103357445A (en) * | 2012-03-31 | 2013-10-23 | 中国石油化工股份有限公司 | Heavy-petroleum hydrogenating deasphaltenizing catalyst and preparation and application thereof |
| CN103374391A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
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