CN105754638B - A kind of heavy oil hydrogenation treatment method - Google Patents
A kind of heavy oil hydrogenation treatment method Download PDFInfo
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- CN105754638B CN105754638B CN201410788218.8A CN201410788218A CN105754638B CN 105754638 B CN105754638 B CN 105754638B CN 201410788218 A CN201410788218 A CN 201410788218A CN 105754638 B CN105754638 B CN 105754638B
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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 to carry
Body I is shaped alumina alumina supporter, and the pore volume of the carrier I is 0.8 ml/g -1.2 mls/g, is 90 meters than surface2/
Grams -230 meters2/ gram, most probable bore dia is 20 nanometers -30 nanometers, and average pore diameter is 25 nanometers -35 nanometers, and bore dia is 10
The pore volume in the hole of -60 nanometers of nanometer accounts for the 95%-99.8% of total pore volume；The hydrogenation active metal component I includes being selected from
At least one metal component of group vib and at least one metal component selected from VIII, add in terms of oxide and with heavy oil
On the basis of hydrogen processing catalyst I gross weight, the content of group vib metal component is big in the heavy oil hydrogenating treatment catalyst I
In 0 weight % to 15 heavy % are less than or equal to, the content of group VIII metal component is to less than or equal to 5 heavy % more than 0 weight %；It is described heavy
Oil hydrogenating treatment catalyst II includes carrier II and hydrogenation active metal component II；The carrier II is siliceous or fluorine shaped alumina
Alumina supporter, is counted by element and on the basis of the gross weight of the carrier II, in described siliceous or fluorine shaped alumina alumina supporter, silicon or
The content of fluorine is 0.5-10 weights %；The hydrogenation active metal component II includes metal component molybdenum and metal component cobalt or nickel,
Counted by oxide and on the basis of unit carrier II area load amount, metal described in the heavy oil hydrogenating treatment catalyst II
The content of component molybdenum is 4.8 μm of ol/m2-9.0μmol/m2, metal component cobalt described in the heavy oil hydrogenating treatment catalyst II or
The content of nickel is 1.5 μm of ol/m2-4.0μmol/m2, when the heavy oil hydrogenating treatment catalyst II is characterized using XRD, in the angle of diffraction
2 θ=26 ° ± 2 ° are without MoO3Characteristic peak occurs.
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 metal component molybdenum described in catalyst II2-8.0μmol/m2, the heavy oil hydrogenating treatment catalyst
The content of metal component cobalt described in II or nickel is 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 metal component molybdenum described in catalyst II2-7.5μmol/m2, the heavy oil hydrogenating treatment catalyst
The content of metal component cobalt described in II or nickel is 2.0 μm of ol/m2-3.1μmol/m2。
Preferably, wherein, counted by oxide and on the basis of heavy oil hydrogenating treatment catalyst I gross weight, the heavy oil
The content of group vib metal component described in hydrotreating catalyst I is 0.5-10 weight %, the content of the group VIII metal component
For 0.1-3 weights %.
Preferably, wherein, group vib metal component described in the heavy oil hydrogenating treatment catalyst I be molybdenum and/or tungsten, institute
Group VIII metal component is stated for nickel and/or cobalt.
Preferably, wherein, siliceous described in the heavy oil hydrogenating treatment catalyst II or fluorine shaped alumina alumina supporter is negative
Before carrying the metal component molybdenum and metal component cobalt or nickel, by hydro-thermal process in confined conditions.
Preferably, wherein, the temperature of the hydro-thermal process is 60-180 DEG C, and the time is 1-24 hours；By weight, it is described
The consumption of hydro-thermal process reclaimed water is siliceous or fluorine formed alumina vehicle weight described in the heavy oil hydrogenating treatment catalyst II
100-300 weight %.
Preferably, wherein, the described siliceous or fluorine in the heavy oil hydrogenating treatment catalyst II Jing Guo the hydro-thermal process
Shaped alumina alumina supporter is before the metal component molybdenum and metal component cobalt or nickel is loaded, by drying process；The drying
The temperature of processing is 60-350 DEG C, and the time of drying process is 1-48 hours.
Preferably, wherein, siliceous described in the heavy oil hydrogenating treatment catalyst II or fluorine shaped alumina alumina supporter system
Standby step includes：Siliceous or fluorine element compound is introduced into the predecessor of aluminum oxide, described siliceous or fluorine has then been introduced into
The aluminum oxide precursor thing of element compound is molded, and the aluminum oxide precursor thing after shaping is calcined.
Preferably, wherein, siliceous described in the heavy oil hydrogenating treatment catalyst II or fluorine shaped alumina alumina supporter has
Selected from γ-, η-, θ-, at least one of δ-and χ-alumina crystalline phase crystalline phase.
Preferably, wherein, siliceous described in the heavy oil hydrogenating treatment catalyst II or fluorine shaped alumina alumina supporter for choosing
From at least one of spherical, cylindrical, annular, cloverleaf pattern, quatrefoil, honeycombed and butterfly shape.
Preferably, wherein, metal component molybdenum and metal component cobalt described in the heavy oil hydrogenating treatment catalyst II or
Nickel passes through on dip loading to 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 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 used in the heavy oil hydrogenation treatment method of the present invention
Catalyst prepared by 12) 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 be 20-60 body %, preferably 25-50 bodies %, the heavy oil hydrogenating treatment catalyst II's
Content is 40-80 body %, preferably 50-70 bodies %；The heavy oil hydrogenating treatment catalyst I includes carrier I and hydrogenation activity gold
Belong to component I；The carrier I is shaped alumina alumina supporter, and the pore volume of the carrier I is 0.8 ml/g -1.2 mls/g, than
Surface is 90 meters2/ grams -230 meters2/ gram, most probable bore dia is 20 nanometers -30 nanometers, and average pore diameter is 25 nanometer -35 and received
Rice, bore dia accounts for the 95%-99.8% of total pore volume for the pore volume in 10 nanometers -60 nanometers of hole；The hydrogenation active metals
Component I 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 heavy oil hydrogenating treatment catalyst I gross weight, group vib metal group in the heavy oil hydrogenating treatment catalyst I
The content divided is that the content of group VIII metal component is big to 15 heavy %, preferably 0.5-10 weight % is less than or equal to more than 0 weight %
In 0 weight % to less than or equal to 5 heavy %, preferably 0.1-3 weights %；The heavy oil hydrogenating treatment catalyst II includes carrier II and added
Hydrogen activity metal component II；The carrier II is siliceous or fluorine shaped alumina alumina supporter, in terms of element and with the carrier II's
On the basis of gross weight, in described siliceous or fluorine shaped alumina alumina supporter, the content of silicon or fluorine is 0.5-10 weights %；The hydrogenation is lived
Property metal component II include metal component molybdenum and metal component cobalt or nickel, it is in terms of oxide and negative with unit carrier II surface
On the basis of carrying capacity, the content of metal component molybdenum described in the heavy oil hydrogenating treatment catalyst II is 4.8 μm of ol/m2-9.0μ
mol/m2, preferably 5.4 μm ol/m2-8.0μmol/m2, more preferably 5.9 μm ol/m2-7.5μmol/m2, the heavy oil adds
The content of metal component cobalt or nickel is 1.5 μm of ol/m described in hydrogen processing catalyst II2-4.0μmol/m2, preferably 1.8 μm ol/
m2-3.6μmol/m2, more preferably 2.0 μm ol/m2-3.1μmol/m2, the heavy oil hydrogenating treatment catalyst II uses
When XRD is characterized, in θ=26 ° ± 2 ° of the angle of diffraction 2 without MoO3Characteristic peak occurs.Wherein, the area load of the unit carrier II
Amount refers to the load capacity and load of metal component in the load capacity in carrier II per surface areas, i.e. heavy oil hydrogenating treatment catalyst II
The ratio between body II total surface area.The carrier II refers to the heavy-oil hydrogenation before carried metal component molybdenum and metal component cobalt or nickel
The siliceous or fluorine shaped alumina alumina supporter in catalyst II is handled, if described siliceous in the heavy oil hydrogenating treatment catalyst II
It is or fluorine shaped alumina alumina supporter passes through hydro-thermal process before carried metal component molybdenum and metal component cobalt or nickel, then described herein
Carrier II refer to described siliceous or fluorine shaped alumina alumina supporter in the heavy oil hydrogenating treatment catalyst II before hydro-thermal process.Institute
The size for stating carrier II total surface areas 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.
According to the present invention, the group vib metal component and VIII employed in the heavy oil hydrogenating treatment catalyst I
Metal component is well-known to those skilled in the art, and the present invention is repeated no more, for example, the group vib metal component can be
Molybdenum and/or tungsten, the group VIII metal component can be nickel and/or cobalt.
The present invention will further provide the reference preparation method of the heavy oil hydrogenating treatment catalyst I, so that this area skill
The present invention can be better achieved in art personnel, but the present invention is not therefore subject to any restriction.The heavy-oil hydrogenation of the present invention
The reference preparation method for handling catalyst I is as follows：
, should present invention firstly provides the reference preparation method of carrier I described in heavy oil hydrogenating treatment catalyst I a kind of
Method can include：
(1), aging, washing will be carried out after the aqueous solution and the acid solution reaction of sodium metaaluminate and/or sodium aluminate and dried
Large aperture, the boehmite of high pore volume are made afterwards；The condition of the reaction includes：PH value in reaction is 4.5-9, is preferably
5.5-8.5, reaction temperature is 15-75 DEG C, preferably 20-60 DEG C；The aging condition includes：Add aging agent, aging temperature
For 15-75 DEG C, preferably 20-60 DEG C, ageing time is 0.5-8 hours, and preferably 2-6 hours, the aging agent was selected from carbon
At least one of sour ammonium, ammonium hydrogen carbonate, ammonium carbonate solution and ammonium bicarbonate aqueous solution, preferably ammonium carbonate solution；Institute
It is conventional method to state washing, its object is to remove other acid ions and cation, is required so that reaction product is met；
The drying is also conventional method, including the drying mode such as oven drying, expansion drying, spray drying.
(2), the boehmite obtained by step (1) is molded, is dried and is calcined, large aperture, high hole body is made
Product alumina support；Wherein, the shaping and dry method are method customary in the art and conventional, the temperature of the roasting
It can be 850-1100 DEG C, preferably 900-1000 DEG C, the time of the roasting can be 1.5-6 hours, and preferably 2-4.5 is small
When.
Carrier I according to the present invention reference preparation method, acid solution described in step (1) refers to can be by partially
The pH value that the aqueous solution of sodium aluminate and/or sodium aluminate is precipitated is less than 7 solution, can be selected from inorganic acid aqueous solution, organic
One or more in the aqueous solution of aqueous acid and non acid compounds, are preferably selected from aluminum sulfate aqueous solution, aluminium chloride water-soluble
One or more in liquid and aluminum nitrate aqueous solution.
Prepared boehmite tool in carrier I according to the present invention reference preparation method, step (1)
There are the crystal phase structures different from common boehmite, containing a small amount of aluminum carbonate basic ammonium, by weight and with prepared
On the basis of the gross weight of boehmite, the content of aluminum carbonate basic ammonium is 3.0-14.0 weight %, preferably 5.0-10.0 weights %.
The boehmite determines related physical ginseng after 400 DEG C of -650 DEG C of roastings using the method for testing in RIPP 151-90
Number, pore volume is preferably 1.35 mls/g -1.6 mls/g, specific surface area be preferably -320 square metres of 280 meters squared per gram/
Gram, most probable bore dia is preferably 23 nanometers -28 nanometers, and average pore diameter is preferably 19 nanometers -22 nanometers, and bore dia 10 is received
The pore volume in the hole of -60 nanometers of rice accounts for total pore volume ratio preferably 83%-95%.
Carrier I according to the present invention reference preparation method, forming method described in step (2) includes tabletting, rolling
The method such as ball and extrusion.To ensure being smoothed out for shaping, auxiliary agent can be introduced into the boehmite, be adopted for example, working as
When using extruded moulding, appropriate extrusion aid, peptizing agent and water, afterwards extrusion molding can be introduced into the boehmite.Institute
The species and consumption for stating extrusion aid may each be this area routine, for example, can be selected from sesbania powder, methylcellulose, shallow lake
One or more in powder, polyvinyl alcohol and PVOH.The species and consumption of the peptizing agent may each be this area routine,
Can be for example the one or more in nitric acid, acetic acid, citric acid and oxalic acid.
The heavy oil hydrogenating treatment catalyst I of present invention reference preparation method also includes introducing on prepared carrier I
The step of hydrogenation active metal component I, to the carrier I on to introduce hydrogenation active metal component I method be art technology
Known to personnel, for example, the carrier can be impregnated by using the solution of the compound containing the hydrogenation active metal component I
I, the step of being dried, be calcined or be not calcined afterwards.The compound containing the hydrogenation active metal component I can include
The compound of the metal component containing group vib, is preferably the compound containing molybdenum and/or tungstenic, is selected from their soluble chemical combination
One or more in thing；The compound containing molybdenum can in molybdenum oxide, molybdate and paramolybdate one kind or
It is several, it is preferably selected from the one or more in molybdenum oxide, ammonium molybdate and ammonium paramolybdate；The compound of the tungstenic can be choosing
One or more from tungstates, metatungstate and ethyl metatungstate, preferably ammonium metatungstate and/or ethyl metatungstic acid
Ammonium.The compound containing the hydrogenation active metal component I can also include the compound of the component containing group VIII metal, preferably
For compound nickeliferous and/or containing cobalt, the one or more in their soluble compound are selected from；The change containing cobalt
Compound can be one or more in cobalt nitrate, cobalt acetate, basic cobaltous carbonate and cobalt chloride, preferably cobalt nitrate and/
Or basic cobaltous carbonate；The nickeliferous compound can be one in nickel nitrate, nickel acetate, basic nickel carbonate and nickel chloride
Plant or several, preferably nickel nitrate and/or basic nickel carbonate.The present invention can be prepared using various solvents commonly used in the art
The solution of the compound containing the hydrogenation active metal component I, as long as the compound can be dissolved in the solvent, shape
Into the solution of stable homogeneous.For example：The alcohol that the solvent can be water and/or carbon number is 1-5 is (such as：Ethanol), it is excellent
Elect water and/or ethanol, more preferably water as.The method of the dipping can be various dipping methods commonly used in the art, for example
It can be hole saturation infusion process.The present invention is not particularly limited for the time of the dipping and the number of times of dipping, as long as can
Ensure that the content of the hydrogenation activity composition I with catalytic action on the catalyst I finally given meets specific use requirement
；Usually, the time of the dipping can be 0.5-12 hours.The method and condition of the drying are not also limited especially
It is fixed.Usually, the temperature of the drying can be 60-150 DEG C, preferably 80-120 DEG C；The time of the drying can be 1-
12 hours, preferably 2-8 hours.The method and condition of the roasting are not particularly limited, and can be the conventional method of this area
And condition.Usually, the temperature of the roasting can be 350-550 DEG C, preferably 400-500 DEG C；The time of the roasting can
Think 1-6 hours, preferably 2-4 hours.The roasting can be carried out in oxygen-containing atmosphere, can also be entered in an inert atmosphere
OK.
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, siliceous described in the heavy oil hydrogenating treatment catalyst II or fluorine shaped alumina alumina supporter is in load
, can be by hydro-thermal process in confined conditions before the metal component molybdenum and metal component cobalt or nickel.The hydro-thermal
Handle unlike being handled from conventional catalyst high-temperature vapor, siliceous or fluorine shaped alumina alumina supporter hydro-thermal in the present invention
Processing refers to siliceous or fluorine shaped alumina alumina supporter and water being put into the closed containers such as reactor, is heated in confined conditions
Certain temperature, then carries out hydro-thermal process at a temperature of the hydro-thermal process.Siliceous or fluorine formed alumina after hydro-thermal process is carried
Body can make the metal component of load that more preferable dispersity is presented, and improve prepared catalyst II number of active center and urge
Change activity.Wherein, the hydro-thermal process temperature can be 60-180 DEG C, preferably 90-150 DEG C；The time of the hydro-thermal process
It can be 1-24 hours, preferably 4-12 hours；By weight, the consumption of the hydro-thermal process reclaimed water can add for the heavy oil
Siliceous or fluorine formed alumina vehicle weight 100-300 weights % described in hydrogen processing catalyst II, it is preferably described siliceous or
The 150-250 weights % of fluorine formed alumina vehicle weight.In the present invention, the pressure of hydro-thermal process is spontaneous pressure under confined conditions
Power, when the hydro-thermal process is carried out at a constant temperature, hydro-thermal process temperature is the thermostat temperature, and the time of the hydro-thermal process is
Timing when the closed container reaches the hydro-thermal process temperature；The heating rate of temperature-rise period before hydro-thermal process
Have no particular limits, preferably 5-15 DEG C/min, more preferably 8-12 DEG C/min.
According to the present invention, described siliceous or fluorine in the heavy oil hydrogenating treatment catalyst II Jing Guo the hydro-thermal process into
Type alumina support may also pass through drying process before the metal component molybdenum and metal component cobalt or nickel is loaded, with
Remove the moisture in oxidation aluminium surface and duct.The condition of the drying process is not particularly limited, and can be the normal of this area
Rule selection, is defined by that can remove the moisture in oxidation aluminium surface and duct.Usually, the temperature of the drying process can be
60-350 DEG C, more preferably preferably 80-200 DEG C, 100-150 DEG C.The time of the drying process can be according to dry temperature
Degree carries out appropriate selection, is not particularly limited.Usually, the time of the drying process can be 1-48 hours, be preferably
1-24 hours, more preferably 1-8 hours.
According to the present invention, siliceous described in the heavy oil hydrogenating treatment catalyst II or fluorine shaped alumina alumina supporter preparation
Step can include：Siliceous or fluorine element compound is introduced into the predecessor of aluminum 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 calcined.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 typically 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
Plant crystalline phase.
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：At the heavy-oil hydrogenation
It can be selected from spherical, cylindrical, annular, cloverleaf pattern, four to manage siliceous or fluorine shaped alumina alumina supporter described in catalyst II
At least one of leaf, honeycombed and butterfly etc. shape.
It is well-known to those skilled in the art in the method for supported on carriers metal component, for example, can according to the present invention
With by impregnating the metal component molybdenum and the metal component cobalt or Ni to the heavy oil hydrogenating treatment catalyst
On siliceous or fluorine shaped alumina alumina supporter in II, i.e., using the compound of the component containing molybdenum and containing cobalt or nickeliferous metal group
The solution for breaking up compound impregnates siliceous or fluorine shaped alumina alumina supporter.Wherein, the component composition containing molybdenum can be selected from
One or more in one or more in its soluble compound, such as molybdenum oxide, molybdate and paramolybdate, preferably are selected from it
In molybdenum oxide, ammonium molybdate and ammonium paramolybdate in one or more；The compound of the metal component containing cobalt can be selected from it
Soluble compound in one or more, the soluble network of such as cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt
One or more in compound, preferably are selected from one or both of cobalt nitrate and basic cobaltous carbonate.The nickeliferous metal component
Compound can also be selected from the one or more in its soluble compound, such as nickel nitrate, nickel acetate, basic nickel carbonate, chlorine
Change the one or more in the soluble complexes of nickel and nickel, preferably be selected from one or both of nickel nitrate and basic nickel carbonate.
The dipping is well-known to those skilled in the art, can be equivalent impregnation or excessive dipping, can be co-impregnation
It can also be step impregnation, for example, the solution containing single various metal component compounds can be used to impregnate siliceous or fluorine respectively
Shaped alumina alumina supporter, it would however also be possible to employ the mixed solution of the component composition containing various metals impregnates siliceous or fluorine formed alumina
Carrier.By the concentration and the consumption of dipping solution of the dipping solution that adjusts metallic components compound described in dipping process,
Those skilled in the art can be controlled to the content for the metal component being introduced into catalyst II, repeat 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.
It was found by the inventors of the present invention that the heavy oil hydrogenating treatment catalyst II using XRD characterize when, the θ of the angle of diffraction 2=
26 ° ± 2 ° without MoO3Characteristic peak occurs, and this illustrates that heavy oil hydrogenating treatment catalyst II and existing high molybdenum content heavy oil add
Unlike hydrogen processing catalyst, molybdenum trioxide in catalyst II of the invention is in the well dispersed of catalyst surface, not
A large amount of aggregations, so that MoO can not be detected3Characteristic peak, and with such feature catalyst II have higher reaction
Activity.
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, when heavy oil feedstock contact heavy oil hydrogenating treatment catalyst I and heavy oil hydrogenating treatment catalyst II,
Before and after any time in, can contact any other catalyst for helping to improve the catalyst combination performance or
Filler.For example, contact such as porcelain ball, active supporter can be filled out before heavy oil contacts the heavy oil hydrogenating treatment catalyst I
Material, 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 silicon and the content of fluorine of the Coupled Plasma-Atomic Emission Spectrometric Determination catalyst in RIPP128-90；Carry herein and hereafter
And RIPP standard methods for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, nineteen ninety version.
The predecessor that embodiment 1-3 provides carrier I in heavy oil hydrogenating treatment catalyst I of the invention (intends thin water aluminium
Stone).
Embodiment 1
Weigh 483 grams of aluminium chloride (Beijing Chemical Plant's product), plus deionized water dissolving into molar concentration be the molten of 1mol/L
Liquid a1；Weigh 210 grams of sodium metaaluminate (Tianjin Jin Ke fine chemistry industries research institute product), plus deionized water dissolving is into molar concentration
For 3.0mol/L solution b1；Weigh 230 grams of ammonium carbonate (Beijing chemical reagents corporation product), plus deionized water dissolving into mole
Concentration is 0.5mol/L solution c1.Solution a1 and solution b1 are added to one 10 liters of plastic cans simultaneously in manner of cocurrent flow
Middle reaction, control solution a1 and solution b1 inflow velocities, the pH value for making course of reaction are 8.5, and gelling temperature is 60 DEG C, has been reacted
Cheng Hou, adds solution c1, aging 2.5 hours at 60 DEG C are filtered, filter cake is washed with 10 liters 60 DEG C of deionized water, in drying
150 DEG C of dryings 2 hours in case, obtain boehmite A, after 600 DEG C of roastings, the ginseng such as its pore volume, specific surface area and bore dia
Number is listed in Table 1 below.By weight and on the basis of boehmite A gross weight, aluminum carbonate basic ammonium contains in boehmite A
Measure as 7.3 heavy %.
Embodiment 2
Weigh 666 grams of aluminum sulfate (Beijing Chemical Plant's product), plus deionized water dissolving into molar concentration be 0.5mol/L's
Solution a2；Weigh 210 grams of sodium metaaluminate (Tianjin Jin Ke fine chemistry industries research institute product), plus deionized water dissolving is into mole dense
Spend the solution b2 for 2.0mol/L；Weigh 370 grams of ammonium hydrogen carbonate (Beijing chemical reagents corporation product), plus deionized water dissolving into
Molar concentration is 1.0mol/L solution c2.Solution a2 and solution b2 are added to simultaneously in manner of cocurrent flow one 10 liters into
Reacted in glue tank, control solution a2 and solution b2 inflow velocities, the pH value for making course of reaction are 6.0, gelling temperature is 40 DEG C, instead
After the completion of answering, solution c2 is added, aging 6 hours at 40 DEG C, filtering, filter cake is washed with 15 liters 40 DEG C of deionized water, Yu Gan
100 DEG C of dryings 6 hours in dry case, obtain boehmite B, after 600 DEG C of roastings, its pore volume, specific surface area and bore dia etc.
Parameter is listed in Table 1 below.By weight and on the basis of boehmite B gross weight, aluminum carbonate basic ammonium in boehmite B
Content is 5.5 heavy %.
Embodiment 3
Weigh 750 grams of aluminum nitrate (Beijing Chemical Plant's product), plus deionized water dissolving into molar concentration be 1.5mol/L's
Solution a3；Weigh 210 grams of sodium metaaluminate (Tianjin Jin Ke fine chemistry industries research institute product), plus deionized water dissolving is into mole dense
Spend the solution b3 for 4.5mol/L；Weigh 300 grams of ammonium carbonate (Beijing chemical reagents corporation product), plus deionized water dissolving is into rubbing
The solution c3 that your concentration is 1.5mol/L.Solution a3 and solution b3 are added to one 10 liters of plastic simultaneously in manner of cocurrent flow
Reacted in tank, control solution a3 and solution b3 inflow velocities, it is 7.0 to make pH value in course of reaction, and plastic cans temperature is 25 DEG C, instead
After the completion of answering, solution c3 is added, aging 4 hours at 25 DEG C, filtering, filter cake is washed with 25 liters 25 DEG C of deionized water, Yu Gan
120 DEG C of dryings 4 hours in dry case, obtain boehmite C, after 600 DEG C of roastings, its pore volume, specific surface area and bore dia etc.
Parameter is listed in Table 1 below.By weight and on the basis of boehmite C gross weight, aluminum carbonate basic ammonium in boehmite C
Content is 9.6 heavy %.
Embodiment 4-6 provides the carrier I in the heavy oil hydrogenating treatment catalyst I of the present invention.
Embodiment 4
100 grams and 4 grams polyvinyl alcohols of boehmite A are added containing the water that 2.5 grams of concentration are 65 heavy % nitric acid
130 milliliters of solution, in being extruded into the trilobal bar that equivalent diameter is 1.2 millimeters on screw rod banded extruder, is dried 2 hours in 120 DEG C,
900 DEG C are calcined 4.5 hours, obtain carrier ZI1, the parameter such as its pore volume, specific surface area and bore dia is listed in Table 2 below.
Embodiment 5
By boehmite B, 100 grams mix with 4 grams of sesbania powders, 120 milliliters of the aqueous solution containing 3 grams of acetic acid are added, in spiral shell
The trilobal bar that equivalent diameter is 1.2 millimeters is extruded on bar banded extruder, is dried in 120 DEG C 2 hours, 950 DEG C are calcined 3 hours, obtain
To carrier ZI2, the parameter such as its pore volume, specific surface area and bore dia is listed in Table 2 below.
Embodiment 6
By boehmite C, 100 grams mix with 1.5 grams of methylcellulose, 2 grams of sesbania powders, add containing 4 grams of citric acids
135 milliliters of the aqueous solution, in being extruded into the trilobal bar that equivalent diameter is 1.2 millimeters on screw rod banded extruder, is dried 2 hours in 120 DEG C,
1000 DEG C are calcined 2 hours, obtain carrier ZI3, the parameter such as its pore volume, specific surface area and bore dia is listed in Table 2 below.
Embodiment 7-9 provides the heavy oil hydrogenating treatment catalyst I of the present invention.
Embodiment 7
ZI190 grams of carrier prepared by Example 4, contains 64 g/l of molybdenum oxide, the molybdenum that 14 g/l of nickel oxide with 120 milliliters
Sour ammonium and nickel nitrate mixed solution impregnates 1 hour, is dried in 120 DEG C 2 hours, 500 DEG C are calcined 4 hours, obtain catalyst CI1.
Catalyst CI1 composition is listed in Table 3 below.
Embodiment 8
ZI2200 grams of carrier prepared by Example 5, contains MoO with 500 milliliters350 g/l, NiO8 g/l of ammonium molybdate
Impregnated 1 hour with nickel nitrate mixed solution, filtering is dried 2 hours after 120 DEG C, and 480 DEG C are calcined 4 hours, obtain catalyst
CI2.Catalyst CI2 composition is listed in Table 3 below.
Embodiment 9
ZI3200 grams of carrier prepared by Example 6, contains MoO with 500 milliliters3100 g/l, NiO20 g/l of molybdic acid
Ammonium and nickel nitrate solution are impregnated 1 hour, and filtering is dried 2 hours after 120 DEG C, and 500 DEG C are calcined 4 hours, obtain catalyst CI3.
Catalyst CI3 composition is listed in Table 3 below.
Embodiment 10-11 provides the carrier II in the heavy oil hydrogenating treatment catalyst II of the present invention.
Embodiment 10
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,
It is at room temperature 1 weight % aqueous solution of nitric acid and the Ludox of the % containing the weight of silica 30 by the mixture and 1.1 liters of concentration
120 grams are well mixed, and continue kneading on double screw banded extruder after plastic, to be extruded into 1.1 millimeters of ф trilobal bar, wet bar
After being dried 3 hours through 120 DEG C, carrier ZII1 is obtained within 3 hours in 600 DEG C of roastings.The materialization for determining ZII1 the results are shown in Table 4.
Embodiment 11
The boehmite dry glue powder RPB100 and 30 grams of sesbania powders that 1 kilogram of Chang Ling catalyst plant is produced are well mixed,
The mixture is well mixed with 90g containing ammonium fluoride, 25 milliliters of nitric acid (65 heavy %) 1.2 liters of the aqueous solution at room temperature, double
Continue kneading on screw rod banded extruder after plastic, to be extruded into 1.1 millimeters of ф butterfly bar, after wet bar is dried 2 hours through 110 DEG C,
Carrier ZII2 is obtained in 700 DEG C of roastings within 3 hours.The materialization for determining ZII2 the results are shown in Table 4.
Embodiment 12-15 provides the heavy oil hydrogenating treatment catalyst II of the present invention.
Embodiment 12
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 4 hours, obtain catalyst
CII1.Counted by oxide and on the basis of unit carrier II area load amount, catalyst is determined using Xray fluorescence spectrometer
Whether the content of molybdenum oxide, nickel oxide in CII1, being determined using x-ray powder diffraction instrument in catalyst has molybdenum trioxide to be formed
Aggregation, as shown in table 5, catalyst CII1 XRD spectra is as shown in Figure 1 for measurement result.
Embodiment 13
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 12 hours.Hydro-thermal is complete
Into rear filtering aluminum oxide, then dried 3 hours with 120 DEG C, obtain the alumina support of hydrothermal treatment.
ZII1100 grams of carrier after water intaking heat treatment, contains MoO with 110 milliliters3260 g/l, CoO58 g/l of oxidation
Molybdenum, the mixed solution of basic cobaltous carbonate impregnate 0.5 hour, are dried in 120 DEG C 2 hours, 450 DEG C are calcined 2 hours, obtain catalyst
CII2.Counted by oxide and on the basis of unit carrier II area load amount, 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 5.
Embodiment 14
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 8 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 amount, 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 5.
Embodiment 15
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 oxidation
Molybdenum, basic cobaltous carbonate mixed solution are impregnated 1 hour, and filtering is dried 3 hours after 110 DEG C, and 450 DEG C are calcined 2 hours, are catalyzed
Agent CII4.Counted by oxide and on the basis of unit carrier II area load amount, 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 5.
Comparative example 1-3 provides the heavy oil hydrogenating treatment catalyst II prepared using prior art.
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 12
Reference catalyst DCII1.Counted by oxide and on the basis of unit carrier II area load amount, using X-ray fluorescence spectra
Instrument determines molybdenum oxide in catalyst DCII1, the content of nickel oxide, using x-ray powder diffraction instrument determine in catalyst whether
There is molybdenum trioxide formation aggregation, as shown in table 5, 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 15
Reference catalyst DCII2.Counted by oxide and on the basis of unit carrier II area load amount, using X-ray fluorescence spectra
Instrument determines molybdenum oxide in catalyst DCII2, the content of cobalt oxide, using x-ray powder diffraction instrument determine in catalyst whether
There is molybdenum trioxide formation aggregation, measurement result is as shown in table 5.
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 DZII2 is obtained.
The use of the aluminum oxide DZII3 of steam treatment is carrier, is made using the active component carrying method of embodiment 12
Reference catalyst DCII3.Counted and on the basis of carrier II area load amount of the unit without steam treatment, used by oxide
The content of molybdenum oxide, cobalt oxide and nickel oxide in Xray fluorescence spectrometer measure catalyst DCII3, is spread out using x-ray powder
Penetrate instrument and determine whether have molybdenum trioxide formation aggregation in catalyst, measurement result is as shown in table 2.
Embodiment 16-19 illustrates the effect of the heavy oil hydrogenation treatment method of the present invention.
By 128ppm of Ni+V contents, sulfur content be that the mixed residue oil that 3.4%, carbon residue is 11.5% 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).
Catalyst use ratio and process conditions are listed in Table 6 below, and product property is shown in Table 7 after operating 200 hours.
Comparative example 4
Catalyst uses CI1, DCII1 combination, and when process conditions are listed in Table 6 below the volume of each catalyst amount, fortune
Sampling analysis after turning 200 hours, is as a result listed in table 7.
Comparative example 5
Catalyst uses CI1, DCII2 combination, and when process conditions are listed in Table 6 below the volume of each catalyst amount, fortune
Sampling analysis after turning 200 hours, is as a result listed in table 7.
Comparative example 6
Catalyst uses CI1, DCII3 combination, and when process conditions are listed in Table 6 below the volume of each catalyst amount, fortune
Sampling analysis after turning 200 hours, is as a result listed in table 7.
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 7,
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
Table 2
Table 3
Table 4
| Embodiment is numbered | Embodiment 10 | Embodiment 11 |
| Bearer number | ZII1 | ZII2 |
| Than surface (rice2/ gram) | 254 | 268 |
| Pore volume (ml/g) | 0.65 | 0.70 |
| Can several bore dias (nanometer) | 8 | 9 |
| Silicon (%) | 2.6 | |
| Fluorine (%) | 4.0 | |
| Intensity (Newton/millimeter) | 18 | 17 |
Table 5
Table 6
Table 7
Claims (13)
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, will
The heavy oil is first contacted with the heavy oil hydrogenating treatment catalyst I, is 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 processing catalysis of heavy-oil hydrogenation described in the catalyst combination
Agent 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 carrier I is formed alumina
Carrier, the pore volume of the carrier I is 0.8 ml/g -1.2 mls/g, is 90 meters than surface2/ grams -230 meters2/ gram, most may be used
Several bore dias are 20 nanometers -30 nanometers, and average pore diameter is 25 nanometers -35 nanometers, and bore dia is 10 nanometers -60 nanometers of hole
Pore volume accounts for the 95%-99.8% of total pore volume；The hydrogenation active metal component I includes at least one gold selected from group vib
Belong to component and at least one metal component selected from VIII, in terms of oxide and with the total of heavy oil hydrogenating treatment catalyst I
On the basis of weight, the content of group vib metal component is to being less than or equal to more than 0 weight % in the heavy oil hydrogenating treatment catalyst I
15 heavy %, the content of group VIII metal component is to less than or equal to 5 heavy % more than 0 weight %；
The heavy oil hydrogenating treatment catalyst II includes carrier II and hydrogenation active metal component II；The carrier II to be siliceous or
Fluorine shaped alumina alumina supporter, is counted and on the basis of the gross weight of the carrier II, described siliceous or fluorine formed alumina by element
In carrier, the content of silicon or fluorine is 0.5-10 weights %；The hydrogenation active metal component II includes metal component molybdenum and metal
Component cobalt or nickel, are counted and on the basis of unit carrier II area load amount, the heavy oil hydrogenating treatment catalyst by oxide
The content of metal component molybdenum described in II is 4.8 μm of ol/m2-9.0μmol/m2, described in the heavy oil hydrogenating treatment catalyst II
The content of metal component cobalt or nickel is 1.5 μm of ol/m2-4.0μmol/m2, the heavy oil hydrogenating treatment catalyst II is using XRD tables
When levying, in θ=26 ° ± 2 ° of the angle of diffraction 2 without MoO3Characteristic peak occurs；
Siliceous or fluorine shaped alumina alumina supporter described in the heavy oil hydrogenating treatment catalyst II is loading the metal component molybdenum
And before metal component cobalt or nickel, by hydro-thermal process in confined conditions；
Described siliceous or fluorine shaped alumina alumina supporter in the heavy oil hydrogenating treatment catalyst II Jing Guo the hydro-thermal process exists
Before loading the metal component molybdenum and metal component cobalt or nickel, by drying process, without calcination process；At the drying
The temperature of reason is 60-350 DEG C, and the time of drying process is 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 metal component molybdenum described in heavy oil hydrogenating treatment catalyst II2-8.0μmol/m2, the heavy oil adds
The content of metal component cobalt or nickel is 1.8 μm of ol/m described in hydrogen processing catalyst II2-3.6μmol/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 metal component molybdenum described in heavy oil hydrogenating treatment catalyst II2-7.5μmol/m2, the heavy oil adds
The content of metal component cobalt or nickel is 2.0 μm of ol/m described in hydrogen processing catalyst II2-3.1μmol/m2。
4. method according to claim 1, wherein, counted using oxide and using heavy oil hydrogenating treatment catalyst I gross weight as base
Standard, the content of group vib metal component described in the heavy oil hydrogenating treatment catalyst I is 0.5-10 weights %, the VIII gold
It is 0.1-3 weights % to belong to the content of component.
5. method according to claim 1, wherein, group vib metal component described in the heavy oil hydrogenating treatment catalyst I is molybdenum
And/or tungsten, the group VIII metal component is nickel and/or cobalt.
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 siliceous or fluorine shaped alumina described in the heavy oil hydrogenating treatment catalyst II
The 100-300 weights % of alumina supporter weight.
7. method according to claim 1, wherein, siliceous described in the heavy oil hydrogenating treatment catalyst II or fluorine shaped alumina
The preparation process of alumina supporter includes：Siliceous or fluorine element compound is introduced into the predecessor of aluminum oxide, institute has then been introduced into
State siliceous or fluorine element compound aluminum oxide precursor thing to be molded, and the aluminum oxide precursor thing after shaping is calcined.
8. method according to claim 1, wherein, siliceous described in the heavy oil hydrogenating treatment catalyst II or fluorine shaped alumina
Alumina supporter has selected from γ-, η-, θ-, at least one of δ-and χ-alumina crystalline phase crystalline phase.
9. method according to claim 1, wherein, siliceous described in the heavy oil hydrogenating treatment catalyst II or fluorine shaped alumina
Alumina supporter is selected from least one of spherical, cylindrical, annular, cloverleaf pattern, quatrefoil, honeycombed and butterfly shape.
10. method according to claim 1, wherein, metal component molybdenum described in the heavy oil hydrogenating treatment catalyst II and
Metal component cobalt or nickel pass through on dip loading to the carrier II.
11. method according to claim 10, 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.
12. 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.
13. 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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101890380A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and application thereof |
| 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 |
| CN103374387A (en) * | 2012-04-13 | 2013-10-30 | 中国石油化工股份有限公司 | Method for hydrotreating heavy oil with high nickel and vanadium contents |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN103374387A (en) * | 2012-04-13 | 2013-10-30 | 中国石油化工股份有限公司 | Method for hydrotreating heavy oil with high nickel and vanadium contents |
Non-Patent Citations (1)
| Title |
|---|
| 水热改性对氧化铝载体织构和表面性质的影响;李俊诚等;《无机化学学报》;20050309;第21卷(第2期);第212-216页 * |
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