CN104667956B - A catalyst for hydrogenation modification of hydrocarbon oil and a preparing method thereof - Google Patents
A catalyst for hydrogenation modification of hydrocarbon oil and a preparing method thereof Download PDFInfo
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- CN104667956B CN104667956B CN201310604986.9A CN201310604986A CN104667956B CN 104667956 B CN104667956 B CN 104667956B CN 201310604986 A CN201310604986 A CN 201310604986A CN 104667956 B CN104667956 B CN 104667956B
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Abstract
A catalyst for hydrogenation modification and a preparing method thereof are disclosed. In the catalyst, a carrier comprises aluminum oxide and a molecular sieve, active metal components are Mo, Co and Ni, and distribution situations of concentrations of the active metal components in the cross section of each catalyst particle are that Co0/Co1<Co<1/2>/Co1<1, Ni0/Ni1>Ni<1/2>/Ni1>1 and the Mo is evenly distributed. In the preparing method, the MO is introduced into the catalyst by a conventional method; and the Co and the Ni are introduced by dipping the carrier with a wetting solution containing an absorbent I by adopting an unsaturated dipping method, loading the active metal Co by dipping, dipping with a solution containing an absorbent II by saturated dipping or excessive dipping, and loading the active metal Ni by dipping. The catalyst is used in a diesel oil hydrogenation modification process, has deep hydrodesulfurization activity, and can improve comprehensive properties such as the cetane number under the circumstance that a high diesel oil yield is maintained.
Description
Technical field
The present invention relates to a kind of catalyst for hydro-upgrading and preparation method thereof, particularly a kind of hydrogenation being suitable to diesel modifying
Modifying catalyst and preparation method thereof.
Background technology
For cleaning diesel production, prior art mainly includes the technology such as hydrofinishing and MHUG.Hydrogenation essence
System can reduce the sulfur content of modification diesel oil, but limited with reduction T95 temperature capability to improving Cetane number.MHUG is
Using containing molecular sieve（Y type molecular sieve or beta-molecular sieve）Catalyst for hydro-upgrading, aromatic hydrocarbons in diesel oil etc. is suitably cracked,
While reducing sulfur nitrogen impurity content in diesel oil, improve the combination properties such as diesel cetane-number.But using current hydro-upgrading
Catalyst, to improve the combination property of diesel oil（Sulfur nitrogen impurity content, Cetane number, T95 temperature, arene content etc.）, generally
Need higher cracking degree, diesel yield so can be made relatively low, and the yield of diesel oil to be kept, the combination property of diesel oil is again
Improve less than good.
Sulfur-containing compound in diesel oil distillate and aromatic hydrocarbons, are generally existed with complicated structure, such as dibenzothiophenes, alkyl
Benzothiophene and methyldibenzothiophene etc., be wherein hydrogenated with more difficult removing is dibenzothiophenes, alkyl benzothiophenes and alkyl
The thiophenes such as dibenzothiophenes, especially with 4,6- dimethyl Dibenzothiophene（4,6- BMDBT）With 2,4,6- front three
Base dibenzothiophenes（2,4,6- BMDBT）Class formation is complicated and sulfur-containing compound that have space steric effect is most difficult to remove.Reach
To depth and ultra-deep desulfurization it is necessary to remove these complex structures and sterically hindered big sulfur-containing compound, and these sulfur-bearings
Compound generally more difficult removing under the harsh hydrofinishing operating condition such as High Temperature High Pressure, and pass through to be hydrocracked, can reduce
Diesel yield.Therefore, in the case of keeping diesel yield higher, how to remove the impurity in diesel oil, bavin can be improved simultaneously again
The combination property of oil, this is the important topic being currently needed for studying.
Catalyst for hydro-upgrading is typically with the alumina support containing molecular sieve, with vib and group VIII metal
For hydrogenation active metals component, wherein active metal component is usually equally distributed in the catalyst.CN1184843A is open
A kind of catalyst for hydrocracking diesel oil, this catalyst consist of aluminium oxide 40～80wt%, amorphous silica-alumina 0～20wt%, Y
Type molecular sieve 5～30wt%.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, main
If adopting predecessor and Y type molecular sieve mixing, molding and the roasting of silica-alumina, aluminium oxide and/or aluminium oxide, afterwards
Introduce the hydrogenation metal of effective dose in molding species.Above-mentioned catalyst has higher desulfurization and denitrification activity, but diesel product
The amplitude that yield is low, diesel-fuel cetane number improves little, the shortcomings of condensation point is high and density is big.
CN201110350790.2 discloses a kind of diesel oil hydrogenation modification catalyst and preparation method thereof.This catalyst comprises
The carrier being made up of modified beta molecular sieve and aluminium oxide and hydrogenation active metals component, wherein active metal component are in the catalyst
It is equally distributed.It is used for during diesel oil hydrogenation modification although the condensation point of diesel oil distillate can be reduced using this catalyst, raising changes
Matter diesel-fuel cetane number, but diesel yield is below 97%, still relatively low.
Content of the invention
For problems of the prior art, the invention provides a kind of catalyst for hydro-upgrading and preparation method thereof.
During this catalyst is used for diesel oil hydrogenation modification, there is deep hydrodesulfurizationof activity, and diesel yield can kept higher
In the case of improve the combination properties such as Cetane number.
The catalyst for hydro-upgrading of the present invention, carrier includes aluminium oxide and molecular sieve, active metal component be Mo, Co and
Ni, the wherein active metal component concentration distribution on the cross section of each catalyst granules is as follows：Co0/Co1＜ Co1/2/Co1
＜ 1, Ni0/Ni1＞ Ni1/2/Ni1＞ 1, Mo is essentially uniformly distributed.
In the present invention, concentration distribution formula A on the cross section of each catalyst granules for the active metal componentm/BnTable
Show, that is, at m on the cross section of each catalyst granules at the concentration of elements A and n the concentration of element B ratio（In the present invention,
Unit is mol ratio）, wherein A represents active metallic element Mo, Co or Ni, and B represents active metallic element Mo, Co or Ni, wherein A
With B can identical it is also possible to different；Any point with catalyst granules cross section outer most edge is that outer most edge point is remembered for starting point
For 0, it is designated as 1 with the central point of catalyst granules cross section for terminal, connect starting point and terminal obtains straight-line segment, m and n divides
The location point chosen is not represented on above-mentioned straight-line segment, the value of m and n represents that the distance from starting point to the location point of selection accounts for
The ratio of the length of above-mentioned straight-line segment, the value of m and n is 0 ~ 1, wherein m（Or n）Value was 0,1/4,1/2,3/4,1 time-division
Choose when not representing account for the length of above-mentioned straight-line segment to the distance of the location point chosen from starting point 0,1/4,1/2,3/4,1
The position that point is located（See Fig. 3）, above-mentioned location point also referred to as outer most edge point（Or appearance cake）, 1/4 location point, 1/2 location point,
3/4 location point, central point.In the present invention, in the present invention, in order to express easily, A and B directly adopts active metallic element Mo, Co
Or Ni replaces, m and n is directly with defined location point on 0～1 above-mentioned straight-line segment of digitized representation, with x1 or x2 representative
State arbitrary location point on straight-line segment, such as, Co0/Co1Represent that A and B is Co, m=0, n=1 represent that catalyst granules is horizontal
The ratio of the concentration of the concentration of Elements C o and central spot Elements C o, Ni at the outer most edge point of section1/2/Ni1Represent that A and B is
Ni, m=1/2, n=1 represent on the described straight-line segment on catalyst granules cross section, make from outer most edge point to selected point
At selected point position when distance accounts for the 1/2 of above-mentioned straight-line segment length, the concentration of element Ni and central spot element Ni's is dense
The ratio of degree.X1 and x2 in the present invention arbitrarily selects respectively on the straight-line segment that the above-mentioned outer most edge point of connection and central point obtain
The location point taking（But do not include outer most edge point and central point）, and from outer most edge point to the distance of x1 point be less than from outer most edge point to
The distance of x2 point is 0 ＜ x1 ＜ x2 ＜ 1.
In the present invention, it is related to use formula Am/BnIt is specific as follows that form represents：Co0/Co1（A and B is Co, m=0, n=
1）、Co1/4/Co1（A and B is Co, m=1/4, n=1）、Co1/2/Co1（A and B is Co, m=1/2, n=1）、Co3/4/Co1（A and B
It is Co, m=3/4, n=1）、Cox1/Co1（A and B is Co, m=x1, n=1）、Cox2/Co1（A and B is Co, m=x2, n=1）、
Ni0/Ni1（A and B is Ni, m=0, n=1）、Ni1/4/Ni1（A and B is Ni, m=1/4, n=1）、Ni1/2/Ni1（A and B is
Ni, m=1/2, n=1）、Ni3/4/Ni1（A and B is Ni, m=3/4, n=1）、Nix1/Ni1（A and B is Ni, m=x1, n=1）、
Nix2/Ni1（A and B is Ni, m=x2, n=1）、Mo0/Mo1（A and B is Mo, m=0, n=1）、Mo1/4/Mo1（A and B is Mo, m
=1/4, n=1）、Mo1/2/Mo1（A and B is Mo, m=1/2, n=1）、Mo3/4/Mo1（A and B is Mo, m=3/4, n=1）.
In catalyst for hydro-upgrading of the present invention, in catalyst granules, preferred version is as follows for active metal component：Co0/Co1
With Co1/2/Co1Ratio be 0.2 ~ 0.8, preferably 0.2 ~ 0.7, Ni0/Ni1With Ni1/2/Ni1Ratio 1.5 ~ 2.6, preferably
1.7~2.5.
In catalyst for hydro-upgrading of the present invention, distribution on catalyst granules cross section for the active metal component is preferably such as
Under：Co0/Co1＜ Co1/4/Co1＜ Co1/2/Co1.
In catalyst for hydro-upgrading of the present invention, distribution on catalyst granules cross section for the active metal component is preferably such as
Under：Co1/2/Co1＜ Co3/4/Co1＜ 1.
In catalyst for hydro-upgrading of the present invention, distribution on catalyst granules cross section for the active metal component is preferably such as
Under：Ni0/Ni1＞ Ni1/4/Ni1＞ Ni1/2/Ni1.
In catalyst for hydro-upgrading of the present invention, distribution on catalyst granules cross section for the active metal component is preferably such as
Under：Ni1/2/Ni1＞ Ni3/4/Ni1＞ 1.
In catalyst for hydro-upgrading of the present invention, in catalyst granules, preferred version is as follows for active metal component：Co0/Co1
With Co1/4/Co1Ratio be 0.30 ~ 0.90, preferably 0.30 ~ 0.85, Co1/4/Co1With Co1/2/Co1Ratio be 0.4 ~ 0.9,
It is preferably 0.4 ~ 0.87；Ni0/Ni1With Ni1/4/Ni1Ratio be 1.2 ~ 1.8, preferably 1.3 ~ 1.7, Ni1/4/Ni1With Ni1/2/
Ni1Ratio be 1.1 ~ 1.7, preferably 1.2 ~ 1.6.
In catalyst for hydro-upgrading of the present invention, concentration distribution on catalyst granules cross section for the active metal component is preferred
As follows：Co0/Co1＜ Cox1/Co1＜ Cox2/Co1＜ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
In catalyst for hydro-upgrading of the present invention, concentration distribution on catalyst granules cross section for the active metal component is preferred
As follows：Ni0/Ni1＞ Nix1/Ni1＞ Nix2/Ni1＞ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
In catalyst for hydro-upgrading of the present invention, on catalyst granules cross section, along described straight-line segment from outer most edge point
To central point, active metal component concentration is distributed as follows：The concentration of Co is substantially gradually increased, and the concentration of Ni substantially gradually subtracts
Few, the concentration of Mo is substantially uniformly distributed.
In the present invention, described " substantially gradually decrease along described straight-line segment（Or be gradually increased）" refer to described work
Property metallic element concentration distribution along described straight-line segment from outer most edge point to central point entirely interval in be in generally
Now gradually decrease（Or be gradually increased）Trend, but it is interval to allow to exist one or more local；In this local interval, described
The concentration distribution of active metallic element presents different trend along described straight-line segment（Such as remain constant and/or gradually
Increase（Or gradually decrease）And/or disordered state）.Premise is that the interval presence in this kind of local is for those skilled in the art
Speech is can to tolerate or negligible, or is inevitable for the state-of-art of this area, and this
The interval presence in a little local has no effect on those skilled in the art, and described active metallic element is dense in described whole interval
Degree distribution is still judged to " generally present and gradually decrease（Or be gradually increased）Trend ".In addition, the interval presence in this local
Have no effect on the realization of expected purpose of the present invention, be acceptable, and be also contained within protection scope of the present invention.
In the present invention, described " concentration of Mo is substantially uniformly distributed " refers to Mo in each described catalyst granules
Concentration distribution on whole cross section is uniformity, but allow to exist can tolerate to those skilled in the art or
Can ignore or inevitable concentration distribution fluctuation for the state-of-art of this area（Deviation）.Citing and
Speech, such as, now Mo0/Mo1It is in the range of 1 ± 5% and Mom/Mo1It is in the range of 1 ± 5%, preferably Mo0/Mo1It is in 1 ± 2%
In the range of and Mom/Mo1It is in the range of 1 ± 2%.The fluctuation of this concentration distribution has no effect on the realization of expected purpose of the present invention, is can
With accept, and it is also contained within protection scope of the present invention.
In the present invention, described catalyst for hydro-upgrading is（Solid）Granular, rather than the amorphous state such as powder.Make
For the shape of described granule, it is conventional use of variously-shaped to enumerate this area catalyst for hydro-upgrading, such as can enter one
Step enumerates spherical, column etc., wherein preferably spherical or column.As described spherical, spheroidal and elliposoidal such as can be enumerated
Deng；As described column, cylindric, flat column and profiled-cross-section such as can be enumerated（Such as Herba Trifolii Pratentis, Herba Galii Bungei etc.）Column
Deng.The granularity of described catalyst for hydro-upgrading is 3 ~ 8mm, preferably 3 ~ 5mm.
In the present invention, described " cross section of catalyst granules " refers to the minimum dimension side along a catalyst granules
To the whole surface being exposed after the geometric center cutting of its shape.Such as, when described catalyst granules is spherical, described
Cross section refers to the whole surface exposing after the cutting of its centre of sphere along radius or the short-axis direction of this ball（Such as referring to figure
1）.Or, when described catalyst granules is column, described cross section refers to pass through perpendicular to the length dimension direction of this post
The whole surface exposing after the central point cutting of this length dimension（Such as referring to Fig. 2）.In the present invention, by described exposed surface
Periphery is referred to as the outer most edge of this cross section, by described geometric center（Central point than the centre of sphere as the aforementioned or length dimension）Referred to as
Central point on this cross section.
The catalyst for hydro-upgrading of the present invention, on the basis of the weight of catalyst, the content of carrier be 46wt% ~
87wt%, preferably 46% ~ 80%, more preferably surplus, the content that Ni is counted with NiO as 1wt%～8wt%, Mo with
MoO3The content of meter is 10wt%～40wt%, the content that Co is counted with CoO as 0.5wt%～6wt%；Weight with catalyst carrier
On the basis of amount, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.
In the catalyst for hydro-upgrading of the present invention, positioned at the Co at the outer most edge point of catalyst granules cross section concentration with
The concentration ratio of Co at heart point（Mol ratio）I.e. Co0/Co1For 0.08～0.80, the Ni's at catalyst granules outer most edge point is dense
Degree and the concentration ratio of central spot Ni（Mol ratio）I.e. Ni0/Ni1For 1.2～7.0.
In the catalyst for hydro-upgrading of the present invention, described molecular sieve is Y type molecular sieve and/or beta-molecular sieve.With catalyst
On the basis of the weight of carrier, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.Wherein said molecular sieve
For hydrogen type molecular sieve.Wherein beta-molecular sieve preferred property is as follows：Specific surface area 450m2/ g～750m2/ g, total pore volume 0.30ml/g～
0.45ml/g, SiO2/Al2O3Mol ratio 40～100, meleic acid amount 0.1～0.5mmol/g, framework aluminum non-framework aluminum mole
For 5～20, B-acid/L acid is 0.30～0.50, Na to ratio2O≤0.15wt%.Beta-molecular sieve of the present invention can be using existing method preparation.
In the present invention, SiO2/Al2O3Mol ratio adopts chemical determination, and meleic acid amount, B-acid and L acid adopt Pyridine adsorption IR spectra
Method measures, and wherein meleic acid amount is B-acid and the sum of L acid acid amount.Sodium oxide content adopts ion emission spectroscopy method to measure.Framework aluminum
And non-framework aluminum content adopts NMR method to measure.
In the catalyst for hydro-upgrading of the present invention, can be without adjuvant component it is also possible to contain adjuvant component, wherein in carrier
Adjuvant component can be one or more of fluorine, silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component containing in the carrier in terms of element
Amount is in below 30wt%, preferably below 20wt%.Described carrier can be using conventional method preparation, such as kneading method etc..
The property of the catalyst for hydro-upgrading of the present invention is as follows：Specific surface area is 100～260 m2/ g, preferably 120 ~
220 m2/ g, pore volume is 0.20～0.60mL/g, preferably 0.2 ~ 0.5 mL/g.
The preparation method of the catalyst for hydro-upgrading that the present invention provides, at least adopts one of with the following method, first method
Including：
（1）With the solution impregnating carrier containing adsorbent I, drying, obtain the carrier containing adsorbent I, the use of adsorbent I
Amount accounts for the 0.1% ~ 10.0% of vehicle weight, and the polyhydric alcohol that described adsorbent I is 400～10000 for number-average molecular weight is described
Dipping is using saturation dipping or excessive dipping；
（2）With the dipping solution impregnation steps containing Ni（1）Gains, through dry and roasting, obtain in the middle of catalyst
Body；
（3）Using unsaturated infusion process, with the fountain solution impregnation steps containing adsorbent II（2）In the middle of prepared catalyst
Body, the consumption of adsorbent II accounts for the 0.1% ~ 10.0% of vehicle weight, and wherein said adsorbent II is organic carboxyl acid and its salt
One or more of class；
（4）With the dipping solution impregnation steps containing Co（3）Gains, through dry and roasting,
Wherein active metal Mo is in step（1）Before, step（2）Afterwards and in step（3）Before, step（4）In afterwards
At least one step be introduced in catalyst for hydro-upgrading；
Second method includes：
A, using unsaturated infusion process, with the fountain solution impregnated carrier containing adsorbent II, the consumption of adsorbent II accounts for load
The 0.1% ~ 10.0% of body weight, wherein said adsorbent II is one or more of organic carboxyl acid and its esters；
B, with the dipping solution impregnation steps A gains containing Co, through being dried and roasting, obtain catalyst intermediate,
C, with the solution impregnation catalyst intermediate containing adsorbent I, drying, obtain in the catalyst containing adsorbent I
Mesosome, the consumption of adsorbent I accounts for the 0.1% ~ 10.0% of vehicle weight, described adsorbent I for number-average molecular weight be 400～
10000 polyhydric alcohol, described dipping adopts saturation dipping or excessive dipping；
D, with the dipping solution impregnation steps C gains containing Ni, through being dried and roasting；
During wherein active metal Mo is before step A, after step B and before step C, after step D at least one
Step is introduced in catalyst for hydro-upgrading.
In the inventive method, carrier can be drawn using conventional method preparation, molecular sieve in aluminium oxide kneading process
Enter it is also possible to introduce in aluminium oxide preparation process.
The polyhydric alcohol that described adsorbent I is 400～10000 for number-average molecular weight, preferably number-average molecular weight are 1000
～8000 polyhydric alcohol, described polyhydric alcohol can be PTMEG, preferably Polyethylene Glycol.The addition of polyhydric alcohol accounts for carrier
The 0.05% ~ 10.0% of weight, preferably 0.1% ~ 9.0%.
Described adsorbent II is one or more of organic carboxyl acid and its esters.Described organic acid includes vinegar
Acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, TGA, mercaptopropionic acid,
One or more of ethylenediaminetetraacetic acid, nitrilotriacetic acid, ring ethylenediaminetetraacetic acid etc..Organic carboxylate is preferably above-mentioned to be had
One or more of ammonium salt of machine carboxylic acid.
In the inventive method, in the fountain solution and the solution containing adsorbent I containing adsorbent II, using water and/or ethanol
For solvent.
In first method, preferred condition is as follows：
Step（1）With the solution impregnating carrier containing adsorbent I, using incipient impregnation or excessive dipping, dipping terminates
Afterwards, sample is through health preserving or without health preserving, then is dried, if needing health preserving, conditioned time is 1～12h；Described dried strip
Part is as follows：Temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h.
Step（2）After the dipping of the dipping solution containing Ni, through health preserving or without health preserving, then it is dried and roasts
Burn.As needed health preserving, conditioned time is 0.5～6.0h.Described drying condition is as follows：Baking temperature is 70 DEG C～200 DEG C, preferably
For 100 DEG C～160 DEG C, drying time is 0.5h～20h, preferably 1h～6h；Described roasting condition：Sintering temperature is 300 DEG C
～750 DEG C, preferably 400 DEG C～650 DEG C, roasting time is 0.5h～20h, preferably 1h～6h.
In the present invention, step（3）With the dipping of the fountain solution containing adsorbent II, using unsaturated dipping, preferably with not
Saturation sprays, and the volume ratio of wherein unsaturated dipping dip amount used and catalyst intermediate saturated absorption amount of solution is 0.02
~0.4.After the fountain solution containing adsorbent for the dipping, generally 60 DEG C～250 DEG C of baking temperature, preferably 100～200 DEG C, it is dried
Time 0.5h～20h, preferably 1h～6h.When spraying the fountain solution containing adsorbent, the good shower nozzle of atomizing effect should be selected, make
Solution evenly spreads in catalyst intermediate.After the dipping dipping of the fountain solution containing adsorbent terminates, can directly carry out next
Step, may also pass through health preserving and carries out next step again, and conditioned time is 0.5～8h.
Step（4）Loaded to by infusion process with the dipping solution containing Co and incipient impregnation is adopted on catalyst intermediate
Method, through health preserving or without health preserving after dipping, then is dried.As needed health preserving, conditioned time is 0.5～6.0h.Described
Drying condition as follows：Baking temperature is 60 DEG C～300 DEG C, preferably 100 DEG C～160 DEG C, and drying time is 0.5h～20h,
It is preferably 1h～6h.Described roasting condition：Sintering temperature is 300 DEG C～750 DEG C, preferably 400 DEG C～650 DEG C, during roasting
Between be 0.5h～20h, preferably 1h～6h.
In second method, preferred condition is as follows：
In the present invention, step A is impregnated with the fountain solution containing adsorbent II, using unsaturated dipping, preferably with insatiable hunger
With spray, the volume ratio of wherein unsaturated dipping dip amount used and carrier saturated absorption amount of solution is 0.02 ~ 0.4.Dipping
After fountain solution containing adsorbent, generally 60 DEG C～250 DEG C of baking temperature, preferably 100～200 DEG C, drying time 0.5h
～20h, preferably 1h～6h.When spraying the fountain solution containing adsorbent, the good shower nozzle of atomizing effect should be selected, make solution uniform
It is distributed on carrier.After the dipping dipping of the fountain solution containing adsorbent terminates, directly can carry out next step, may also pass through health preserving
Carry out next step again, conditioned time is 0.5～8h.
Step B is loaded to by infusion process with the dipping solution containing Co and adopts equi-volume impregnating on carrier, warp after dipping
Cross health preserving or without health preserving, then be dried.As needed health preserving, conditioned time is 0.5～6.0h.Described drying condition is such as
Under：Baking temperature is 60 DEG C～300 DEG C, preferably 100 DEG C～160 DEG C, and drying time is 0.5h～20h, preferably 1h～6h.
Described roasting condition：Sintering temperature is 300 DEG C～750 DEG C, preferably 400 DEG C～650 DEG C, and roasting time is 0.5h～20h,
It is preferably 1h～6h.
When step C is with the solution impregnation containing adsorbent I, using incipient impregnation or excessive dipping, after dipping terminates, sample
Product are through health preserving or without health preserving, then are dried, if needing health preserving, conditioned time is 1～12h；Described drying condition is such as
Under：Temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h.
Step D is with, after the dipping of the dipping solution containing Ni, through health preserving or without health preserving, then being dried and roasting
Burn.As needed health preserving, conditioned time is 0.5～6.0h.Described drying condition is as follows：Baking temperature is 70 DEG C～200 DEG C, preferably
For 100 DEG C～160 DEG C, drying time is 0.5h～20h, preferably 1h～6h；Described roasting condition：Sintering temperature is 300 DEG C
～750 DEG C, preferably 400 DEG C～650 DEG C, roasting time is 0.5h～20h, preferably 1h～6h.
In catalyst for hydro-upgrading preparation method of the present invention, active metal is loaded by infusion process, generally adopts equal-volume
Infusion process.Dipping method is known to technical staff.Active metal solution manufacturing method is known to technical staff, and it is molten
Liquid concentration can be adjusted by the consumption of each compound, thus preparing the catalyst of specified activity constituent content.Required activearm
The raw material dividing is generally the compound of the types such as salt, oxide or acid, and such as cobalt source is derived from cobalt nitrate, cobalt carbonate, basic carbonate
One or more of cobalt, cobaltous chloride, cobalt oxalate.Nickel source is derived from nickel nitrate, nickelous carbonate, basic nickel carbonate, Nickel dichloride., nickel oxalate
One or more of.In described dipping solution, in addition to active metal component, phosphorus-containing compound can also be contained, be such as
One or more of phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate etc..
In the inventive method, one or more of adjuvant component fluorine, silicon, phosphorus, titanium, zirconium and boron, are drawn using conventional method
Enter in catalyst, such as can be introduced into when prepared by carrier in catalyst it is also possible to introduce catalyst after carrier preparation.Carrying
Is introduced in catalyst after body preparation, can be introduced in catalyst using the method individually impregnating it is also possible to and active metal component
Together dipping is introduced in catalyst.
Catalyst for hydro-upgrading of the present invention is in heavy distillate（Especially diesel oil）Hydro-upgrading in as hydro-upgrading
The application of catalyst.
Described heavy distillate can be diesel oil, wax oil, wherein preferred diesel oil.The total sulfur content one of described heavy distillate
As be 0.3wt% ~ 3.0wt%, preferably 0.3wt% ~ 2.5wt%, wherein difficult de- sulfur-containing compound（With 4,6- dimethyl Dibenzothiophene
For meter）The sulfur content contributed is about more than 0.01wt%, usually 0.01 wt% ~ 0.05wt%.
The present invention, in described application or described hydrogenation modification method, can be only catalyzed using the hydro-upgrading of the present invention
Agent is it is also possible to by the catalyst for hydro-upgrading of the present invention and other catalyst for hydro-upgrading（Than as be known in the art those）
Use cooperatively according to any ratio needing, such as joined using different catalysts bed level or be used in mixed way.
According to the present invention, there is no any special restriction to the operating condition of described hydro-upgrading, ability can be adopted
The conventional use of operating condition in domain, such as 260 ~ 400 DEG C of reaction temperature, react stagnation pressure 3 ~ 13MPa, preferably by preferably 310 ~ 370 DEG C
5 ~ 9MPa, volume space velocity 0.5 ~ 4h during liquid-1, preferably 1 ~ 2h-1, hydrogen to oil volume ratio 200：1~2000：1, preferably 400：1~1000：
1.
In catalyst for hydro-upgrading of the present invention, active metal component Mo is evenly distributed substantially, active metal component Co from
Catalyst granules outer surface is in substantially the trend being gradually increased to center, and Ni is from catalyst granules outer surface to center substantially
In the trend gradually decreasing, the active metal component of uneven distribution is matched with acidic components molecular sieve in carrier, this catalysis
During agent is particularly well-suited to the hydro-upgrading of diesel oil, while diesel deep desulfurization, keeping the higher feelings of diesel yield
Improve the combination properties such as diesel-fuel cetane number under condition.
The catalyst for hydro-upgrading of present invention preparation, Mo is introduced into using conventional method makes it be uniformly distributed in catalyst,
Impregnated by saturation or the solution containing adsorbent I for the excessive dipping, then impregnate Ni, make the concentration of Ni from catalyst external surface to
The trend that the heart tapers off, the amount making Mo-Ni activity phase further is in the trend gradually decreasing from outer surface to center, by insatiable hunger
With the fountain solution containing adsorbent II for the dipping, catalyst granules outer surface and a part of adsorption potential on marginal position surface is made to be adsorbed
Agent occupies, and during the solution containing active metal Co for the dipping, decreases the absorption in carrier edge position for the Co, makes that active metal Co's is dense
Degree is in the trend being gradually increased from outer surface to center, and the amount making Mo-Co activity phase further is in be incremented by from outer surface to center
Trend, so that the active metal component of this uneven distribution is matched with acidic components molecular sieve in carrier, improve catalyst
Deep hydrodesulfurizationof performance, and the performance such as suitable open loop, isomery, cracking, during the hydro-upgrading of diesel oil, energy
While diesel deep desulfurization, keeping improving the combination properties such as diesel-fuel cetane number in the case that diesel yield is higher.
Brief description
Fig. 1 is the schematic diagram of spherical catalyst particles cutting mode；
Fig. 2 is the schematic diagram of cylindrical catalyst granule cutting mode；
Fig. 3 is the selected each position point on catalyst granules gained cross section and this cross section after the cutting,
Wherein 0 any point representing in outer most edge on this cross section is outer most edge point, and 1/4 represents 1/4 location point, and 1/2 represents 1/2
Put a little, 3/4 represents 3/4 location point, and 1 represents central point.
Fig. 4 is concentration profile on this cross section for active metal component Ni and Co in embodiment 2 gained catalyst C3.
Wherein abscissa is each position point on this cross section, and vertical coordinate is the concentration at a certain location point and central point on this cross section
The ratio of the concentration at place.
Specific embodiment
The technical scheme that the invention is further illustrated by the following examples, but it is real to invention should not be deemed limited to this
Apply in example.In the present invention, wt% is mass fraction.
In the inventive method, active metal component Mo is introduced into the method in catalyst for hydro-upgrading, with first method is
Example illustrates, such as can be in step（1）Introduce it is also possible in step before（2）Afterwards and in step（3）Introduce before,
Can also be in step（4）Introduce afterwards.Active metal component Mo is in step（1）When introducing, following at least one can be adopted before
Method：Carrier component dry glue powder preparation process adds and then reshaping is made carrier containing Mo, become in carrier component kneading
After adding, during type, carrier and the carrier component molding made containing Mo, the carrier made containing Mo is added using infusion process.Active metal group
Divide Mo in step（2）Afterwards and in step（3）When introducing, can be introduced using infusion process before.Active metal component Mo is in step
Suddenly（4）When introducing afterwards, it would however also be possible to employ infusion process introduces.Active metal component Mo is in step（1）When introducing, can adopt before
One of with the following method：
First, add in the preparation process of aluminum oxide dry glue powder, such as to be co-precipitated, fractional precipitation mode introduces, Ran Houyu
Molecular sieve kneading and compacting, is obtained the carrier containing Mo after drying, roasting；
2nd, added with kneading form in carrier molding：Aluminum oxide dry glue powder, molecular sieve and Mo containing active metal component
Compound mix homogeneously, then through kneading and compacting, be dried, roasting make be obtained containing Mo carrier；
3rd, by aluminum oxide dry glue powder, molecular sieve kneading and compacting, then it is dried, carrier is made in roasting, afterwards with containing work
The solution impregnating carrier of property metal component Mo, drying, roasting make the carrier containing Mo.
The shaping assistant of routine in above-mentioned forming process, can be added, in such as extrusion aid, binding agent, peptizer etc.
One or more, addition can according to prepare catalyst property by ability domain knowledge determine.Wherein binding agent typically adopts
Little porous aluminum oxide, the boehmite producing selected from aluminum chloride-Ammonia Process, carbonizatin method or aluminum sulfate method and Zlegler synthesis
SB alumina powder of byproduct of reaction etc..
In catalyst for hydro-upgrading preparation method of the present invention, the drying in carrier preparation process containing Mo and roasting adopt now
There are technical conditions, such as baking temperature is 40 DEG C～250 DEG C, drying time is 0.5h～20h；Sintering temperature is 350 DEG C～750
DEG C, roasting time is 0.5h～20h.
Analysis method of the present invention is as follows：
（1）Active metal component and the content of adjuvant component（wt%）Measured using X-ray fluorescence spectroscopy.
（2）Specific surface area（m2/g）And pore volume（ml/g）Measured using BET method.
（3）Concentration distribution in catalyst granules for each active metal component
In below example and comparative example, employ the carrier of cylinder（But present invention is obviously not limited to this,
Can be using other grain shapes）, the catalyst granules thus being obtained is also cylindrical.From each embodiment and contrast
A catalyst granules is randomly selected as measuring samples in the catalyst that example is obtained.Exist to measure each active metal component
Concentration distribution in this catalyst granules, perpendicular to the length dimension direction of this cylindrical particle, by this length dimension
Heart point is cut, and obtains two exposed surfaces.Take one of exposed surface as measurement cross section.
This measurement uses EPMA method, with reference to GB/T15074-2008（Electron probe quantitative analysis method general rule）Carry out,
Electron probe microanalyzer（JXA-8230 type, Jeol Ltd.'s manufacture）On carry out.Measuring condition is：Accelerating potential
15kV, beam intensity 5 × 10-8A, beam spot diameter, 1 m, X-ray detects angle：Mo is 38 °, and Ni is 24 °, and Co is 26 °, more square
Method：ZAF correction method, the standard specimen of use：Pure metal oxides standard specimen（It is respectively NiO, CoO and MoO3）, precision：Less than 1%, two
Secondary charge pattern resolution：3nm（LaB6）, linear system：Ni and Co adopts KαLinear system, Mo adopts LαLinear system.
Measuring method is：One location point is arbitrarily chosen on the outer most edge of this cross section as 0, with this cross section
Central point, as 1, connects the straight-line segment of described location point 0 and described location point 1（It is substantially the radius of this cross section, because
This is also referred to as radially）, at the point of measurement assigned position, the concentration value of targeted activity metal, then passes through division calculation, obtains each dense
The ratio of angle value（It is mol ratio in the present invention）.
Fig. 4 is the concentration profile of active metal in the catalyst C3 of embodiment 2 gained, is by this straight-line segment
Uniformly choose 21 location points（Including location point 0 and location point 1）, with these location points as abscissa, to survey at each position point
The targeted activity metal of amount（Taking Ni and Co as a example）Concentration value and location point 1 at（I.e. central point）The corresponding active metal of measurement
Concentration value ratio（Use Ni respectivelym/Ni1And Com/Co1Represent）For vertical coordinate, so draw and obtain.
（4）Total sulfur content in raw material and hydrogenation products is to be measured using ultraviolet fluorescence method（ASTM D5453-1993）, 4,
6-BMDBT content is to adopt GC-AED（Gas chromatogram-atom luminescence spectroscopy）Measure.
（5）Number-average molecular weight Mn adopts GPC method to measure.
Cylindrical vector used in embodiment, wherein carrier lengths are about 3 ~ 5mm.
Embodiment 1
The present embodiment introduces the preparation method of catalyst precarsor.Siliceous, boron aluminum oxide dry glue powder specific surface 350m2/ g,
Pore volume is 0.90ml/g.
Weigh siliceous, boron aluminum oxide dry glue powder 380g, add citric acid and each 6g of sesbania powder, beta-molecular sieve 18g, mixing
After uniformly, add acid solution 340g, HNO in acid solution3Weight concentration be 1.74%, remaining be distilled water.Roll
After 20min, with the circular orifice extrusion of diameter 1.7mm.After 120 DEG C are dried 4h, 500 DEG C of roasting 3h.Prepared carrier strip is designated as
S1.With carrier strip S1 obtained by the solution impregnation containing Mo, after 130 DEG C are dried 4h, 500 DEG C of roasting 2h, before prepared catalyst
Body is designated as S1.
Weigh siliceous, boron aluminum oxide dry glue powder 360g, add citric acid and each 6g of sesbania powder, Y molecular sieve 30g, add
Acid solution 335g, HNO in acid solution3Weight concentration be 2.6%, Mo with MoO3The weight content of meter is 27.8%, remaining
For distilled water.After rolling 20min, with the circular orifice extrusion of diameter 1.7mm.120 DEG C are dried 500 DEG C of roasting 3h after 4h, are obtained
Catalyst precarsor be designated as S2.
Prepare siliceous, molybdenum aluminum oxide dry glue powder.Add 1L deionized water in container, be warming up to 58 DEG C, be simultaneously introduced
3L contains Al2O3Aluminum nitrate solution for 4g/100mL and contain NH3Ammonia spirit for 10g/100mL, control ph is 7.8, charging
Time is 120min.After stopping charging, system aging 50min under said temperature and pH value condition, add SiO2Content is
The solution of sodium metasilicate through 100mL of 5.0g, continues aging 60min, is washed out 4 times, to Cl-/Al2O3<Till 0.5%.Preparation contains
The aqueous solution 1L of molybdenum, wherein MO3Concentration 4.3g/100mL, adds in filter cake, stirs into pasty state, after 120 DEG C are dried 8h, by its powder
It is broken to granularity and accounts for more than 95% less than 180 purposes, obtain required dry glue powder.
The property of the aluminum oxide dry glue powder of siliceous and molybdenum of gained is as follows：Specific surface 340m2/ g, pore volume is 0.88ml/g.
Weigh siliceous and molybdenum aluminum oxide dry glue powder 360g, add citric acid and each 6g of sesbania powder, Y molecular sieve 18g, β divide
Son sieve 9g, after mix homogeneously, add acid solution 345g, HNO in acid solution3Weight concentration be 1.74%, remaining be steam
Distilled water.After rolling 20min, with the circular orifice extrusion of diameter 1.7mm.120 DEG C are dried 500 DEG C of roasting 3h after 4h.Prepared load
Body bar is designated as S3.
Identical with S3 carrier preparation process, simply it is added without molecular sieve, the carrier made is designated as S4.
The physico-chemical property of used carrier in table 1 embodiment
In Ni, P and Co used in the present embodiment, P impregnation liquid, Ni predecessor is nickel nitrate, and Co predecessor is cobalt nitrate, before P
Drive thing is phosphoric acid.
Embodiment 2
Weigh tartaric acid 18g, stirring and dissolving in 45g water, prepared fountain solution I.Take S1 carrier 30 as one kind 0g, will be equal for fountain solution I
Even spray on S1, spray the time be 15min.After fountain solution I sprays end, 2h is dried through 100 DEG C, with the impregnation liquid containing Co, P
The above-mentioned carrier of incipient impregnation, gained sample average is divided into three parts, wherein first part sample not health preserving, 3h is dried through 120 DEG C,
480 DEG C of roasting 2h, the sample of acquisition is designated as B1；Second sample health preserving 1h, is dried 3h through 120 DEG C, 480 DEG C of roasting 2h, is obtained
Sample be designated as B2；Triplicate sample health preserving 3h, is dried 3h through 120 DEG C, 480 DEG C of roasting 2h, and prepared sample is designated as B3.
Weigh 6g Macrogol 2000（I.e. molecular weight is 2000 Polyethylene Glycol, similarly hereinafter）, stir in the water measuring
Dissolving, obtained solution II.With this solution II incipient impregnation sample B1, B2 and B3 respectively, then carry out the health preserving of 10h, pass through
After 120 DEG C are dried 3h, prepared sample is designated as Z1, Z2 and Z3 respectively.
Spray above-mentioned Z1, Z2 and Z3 sample with the impregnation liquid equal-volume containing Ni, P respectively, spray straight without health preserving after end
Tap into 120 DEG C of row and 3h is dried, 480 DEG C of roasting 2h, the catalyst of acquisition is designated as C1, C2 and C3 respectively.
Embodiment 3
Weigh 24g Macrogol 1000, stirring and dissolving in the water measuring, obtained solution II.With this solution II grade body
The sample S2 of long-pending dipping 300g, then carries out the health preserving of 5h, after 120 DEG C are dried 3h, prepared sample is designated as B4.
Spray B4 sample with the impregnation liquid equal-volume containing Ni, P, after spraying end, gained sample average is divided into three parts, wherein
Direct 120 DEG C of first part of sample is dried 3h, 480 DEG C of roasting 2h, and the sample of acquisition is designated as Z4；Second sample health preserving 1h, 120 DEG C
3h is dried, 480 DEG C of roasting 2h, prepared sample is designated as Z5；Triplicate sample health preserving 3h, 120 DEG C are dried 3h, 480 DEG C of roasting 2h,
Prepared sample is designated as Z6.
Weigh malic acid 2g, stirring and dissolving in 8g ethanol, prepared fountain solution I.Fountain solution I is uniformly sprayed on Z4,
The time that sprays is 5min.With the above-mentioned carrier of impregnation liquid incipient impregnation containing Co, P, dipping terminates rear health preserving 1h, dry through 120 DEG C
Dry 3h, 480 DEG C of roasting 2h, the catalyst of acquisition is designated as C4.With processing Z5 and Z6 respectively with process Z4 identical method, obtain
Catalyst is designated as C5 and C6.
Embodiment 4
Weigh citric acid and each 3.5g of malonic acid, stirring and dissolving in 20g water, prepared fountain solution I.Take S3 carrier 100g,
Fountain solution I is uniformly sprayed on S3, the time that sprays is 25min.With the above-mentioned carrier of the impregnation liquid incipient impregnation containing Co, P, impregnate
Health preserving 1h after end, is dried 3h through 120 DEG C, 480 DEG C of roasting 2h, and the sample of acquisition is designated as B5.
Weigh 2g Macrogol 8000, stirring and dissolving in the aqueous solution measuring, obtained solution II.With this solution II etc.
Volume impregnation sample B5, then carries out the health preserving of 5h, and after 120 DEG C are dried 3h, prepared sample is designated as Z7.
Spray Z5 sample with the impregnation liquid equal-volume containing Ni, P, directly 3h is dried through 120 DEG C, 480 DEG C of roasting 2h, acquisition
Catalyst is designated as C7.
Comparative example 1
Take S1 carrier 100g, prepare the impregnation liquid containing Ni, Co, P and citric acid and each 3.5g of malonic acid, on incipient impregnation
After stating carrier, 3h is dried through 120 DEG C, 480 DEG C of roasting 2h, the sample of acquisition is designated as C8.
Comparative example 2
Take S4 carrier 100g, prepare using with C7 catalyst identical preparation method, the catalyst of acquisition is designated as C9.
Table 2 embodiment is formed with comparative example catalyst activity metal
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Composition | |||||||||
| MoO3, wt% | 24.0 | 24.1 | 23.8 | 23.9 | 24.0 | 24.1 | 23.9 | 24.0 | 24.1 |
| CoO, wt% | 2.3 | 2.4 | 2.3 | 2.3 | 2.4 | 2.4 | 2.3 | 2.4 | 2.4 |
| NiO, wt% | 1.9 | 2.1 | 1.9 | 2.0 | 2.1 | 2.1 | 2.0 | 2.0 | 2.0 |
| P2O5, wt% | 2.8 | 2.7 | 2.8 | 2.7 | 2.8 | 2.7 | 2.7 | 2.7 | 2.7 |
| Carrier * | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
In table 2, carrier * is aluminium oxide and beta-molecular sieve and auxiliary agents of silicon and the boron of C1, C2, C3 and C8, in C4, C5 and C6
Aluminium oxide and Y molecular sieve and auxiliary agents of silicon and boron, aluminium oxide, β and Y molecular sieve and auxiliary agents of silicon in C7, the aluminium oxide in C9 and
Auxiliary agents of silicon.
Table 3 embodiment and concentration distribution in catalyst granules for the elements Mo in comparative example gained catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Mo0/Mo1 | 1.01 | 1.00 | 1.00 | 1.01 | 0.99 | 1.00 | 1.02 | 1.0 | 0.99 |
| Mo1/4/Mo1 | 1.01 | 0.98 | 0.98 | 1.00 | 1.00 | 1.02 | 1.01 | 1.01 | 1.02 |
| Mo1/2/Mo1 | 1.00 | 0.99 | 1.01 | 0.98 | 0.98 | 0.99 | 1.0 | 0.98 | 1.0 |
| Mo3/4/Mo1 | 0.99 | 1.01 | 1.00 | 0.99 | 1.00 | 1.01 | 0.99 | 0.99 | 0.99 |
Table 4 embodiment and concentration distribution in catalyst granules for Elements C o in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Co0/Co1 | 0.13 | 0.27 | 0.56 | 0.31 | 0.32 | 0.32 | 0.30 | 0.96 | 0.29 |
| Co1/4/Co1 | 0.29 | 0.45 | 0.64 | 0.79 | 0.78 | 0.80 | 0.43 | 0.97 | 0.41 |
| Co1/2/Co1 | 0.60 | 0.81 | 0.91 | 0.97 | 0.96 | 0.96 | 0.80 | 1.00 | 0.81 |
| Co3/4/Co1 | 0.91 | 0.94 | 0.98 | 0.99 | 0.99 | 1.00 | 0.95 | 0.99 | 0.94 |
Table 5 embodiment and concentration distribution in catalyst granules for the element Ni in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Ni0/Ni1 | 2.82 | 2.83 | 2.82 | 3.03 | 2.50 | 2.08 | 2.51 | 0.95 | 2.53 |
| Ni1/4/ Ni1 | 1.90 | 1.88 | 1.89 | 1.94 | 1.72 | 1.50 | 1.70 | 0.97 | 1.72 |
| Ni1/2/ Ni1 | 1.27 | 1.28 | 1.27 | 1.31 | 1.22 | 1.18 | 1.20 | 0.99 | 1.21 |
| Ni3/4/ Ni1 | 1.10 | 1.11 | 1.10 | 1.11 | 1.08 | 1.05 | 1.06 | 1.00 | 1.06 |
Embodiment 5
The present embodiment is the henchnmrk test of catalyst.
Catalyst performance evaluation experiment is carried out on 100mL small hydrogenation device, before performance evaluation, catalyst is carried out pre-
Sulfuration.Evaluating catalyst condition is in reaction stagnation pressure 10.0MPa, volume space velocity 1.5 h during liquid-1, hydrogen-oil ratio 800：1, reaction temperature
Spend for 365 DEG C.Henchnmrk test raw material oil nature is shown in Table 6, and Evaluation results are shown in Table 7, from data in table, with this
Catalyst for hydro-upgrading is prepared in invention, catalyst desulphurizing activated apparently higher than comparative example catalyst, keeping diesel yield not
Under conditions of less than 97%, diesel-fuel cetane number is improved more than 10 units, product quality has obtained good improvement.
Table 6 raw material oil nature
| Raw oil | Catalytic diesel oil |
| Density (20 DEG C), g/cm3 | 0.9433 |
| Boiling range/DEG C | |
| IBP/10% | 182/250 |
| 30%/50% | 284/310 |
| 70%/90% | 332/347 |
| 95%/EBP | 358/370 |
| Condensation point, DEG C | 5 |
| Sulfur, g/g | 8698 |
| 4,6-BMDBT contents, g/g | 103.6 |
| Nitrogen, g/g | 1225 |
| Cetane number | 28 |
| C, wt% | 87.98 |
| H, wt% | 11.12 |
Table 7 catalyst performance evaluation result
| Catalyst | C1 | C2 | C3 | C4 |
| Diesel oil | ||||
| Yield, wt% | 98.1 | 98.0 | 98.2 | 97.5 |
| Density (20 DEG C)/g.cm-3 | 0.8341 | 0.8397 | 0.8399 | 0.8387 |
| T95, DEG C | 349 | 350 | 350 | 348 |
| Condensation point, DEG C | -20 | -20 | -21 | -22 |
| Cetane number | 46.5 | 46.6 | 46.8 | 47.8 |
| Sulfur, g/g | 11 | 10 | 10 | 9 |
Table 7 continues
| Catalyst | C5 | C6 | C7 | C8 | C9 |
| Diesel oil | |||||
| Yield, wt% | 97.5 | 97.6 | 97.8 | 97.6 | 99.6 |
| Density (20 DEG C)/g.cm-3 | 0.8388 | 0.8391 | 0.8393 | 0.8401 | 0.8576 |
| T95, DEG C | 347 | 348 | 348 | 350 | 355 |
| Condensation point, DEG C | -22 | -21 | -22 | -19 | 4 |
| Cetane number | 47.7 | 47.6 | 47.7 | 44.8 | 34.9 |
| Sulfur, g/g | 9 | 8 | 7 | 19 | 13 |
Claims (26)
1. a kind of catalyst for hydro-upgrading, carrier includes aluminium oxide and molecular sieve, and active metal component is Co, Mo and Ni, wherein
Concentration distribution on each catalyst granules cross section for the active metal component is as follows：Co0/Co1＜ Co1/2/Co1＜ 1, Ni0/Ni1
＞ Ni1/2/Ni1The concentration of ＞ 1, Mo is substantially uniformly distributed；
Wherein, concentration distribution formula A on the cross section of each catalyst granules for the active metal componentm/BnRepresent, that is, often
The ratio of the concentration of element B at the concentration of elements A and n at m on the cross section of individual catalyst granules, wherein A represents active metal
Elements Mo, Co or Ni, B represents active metallic element Mo, Co or Ni；Any point with catalyst granules cross section outer most edge is
Starting point is designated as 0, is designated as 1 with the central point of catalyst granules cross section for terminal, connects starting point and terminal obtains straight line line
Section, m and n is illustrated respectively in the location point choose on above-mentioned straight-line segment, and the value of m and n represents from starting point to the position chosen
The distance of point accounts for the ratio of the length of above-mentioned straight-line segment, and the value of m and n is 0 ~ 1, and in order to express easily, A and B directly adopts
Active metallic element Mo, Co or Ni replace, m and n is directly with defined location on 0～1 above-mentioned straight-line segment of digitized representation
Point.
2. according to the catalyst described in claim 1 it is characterised in that in described catalyst for hydro-upgrading, active metal component
In catalyst granules, at least include a kind of following scheme：
（1）Co0/Co1With Co1/2/Co1Ratio be 0.2 ~ 0.8；
（2）Ni0/Ni1With Ni1/2/Ni1Ratio 1.5 ~ 2.6.
3. according to the catalyst described in claim 1 it is characterised in that in described catalyst for hydro-upgrading, active metal component
In catalyst granules, at least include a kind of following scheme：
（1）Co0/Co1With Co1/2/Co1Ratio be 0.2 ~ 0.7；
（2）Ni0/Ni1With Ni1/2/Ni1Ratio 1.7 ~ 2.5.
4. according to the catalyst described in claim 1 it is characterised in that in described catalyst for hydro-upgrading, active metal component
Concentration distribution on catalyst granules cross section at least includes a kind of following scheme：
（1）Co0/Co1＜ Co1/4/Co1＜ Co1/2/Co1；
（2）Co1/2/Co1＜ Co3/4/Co1＜ 1；
（3）Ni0/Ni1＞ Ni1/4/Ni1＞ Ni1/2/Ni1；
（4）Ni1/2/Ni1＞ Ni3/4/Ni1＞ 1.
5. according to the catalyst described in claim 1 it is characterised in that in described catalyst for hydro-upgrading, active metal component
Concentration distribution on catalyst granules cross section at least includes a kind of following scheme：
（5）Co0/Co1＜ Cox1/Co1＜ Cox2/Co1＜ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
（6）Ni0/Ni1＞ Nix1/Ni1＞ Nix2/Ni1＞ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
6. according to the catalyst described in claim 4 or 5 it is characterised in that in described catalyst for hydro-upgrading, active metal
Component, in catalyst granules, at least includes a kind of following scheme：
（1）Co0/Co1With Co1/4/Co1Ratio be 0.3 ~ 0.9；
（2）Co1/4/Co1With Co1/2/Co1Ratio be 0.4 ~ 0.9；
（3）Ni0/Ni1With Ni1/4/Ni1Ratio be 1.2 ~ 1.8；
（4）Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.1 ~ 1.7.
7. according to the catalyst described in claim 4 or 5 it is characterised in that in described catalyst for hydro-upgrading, active metal
Component, in catalyst granules, at least includes a kind of following scheme：
（1）Co0/Co1With Co1/4/Co1Ratio be 0.3 ~ 0.85；
（2）Co1/4/Co1With Co1/2/Co1Ratio be 0.4 ~ 0.87；
（3）Ni0/Ni1With Ni1/4/Ni1Ratio be 1.3 ~ 1.7；
（4）Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.2 ~ 1.6.
8. according to the catalyst described in claim 1 it is characterised in that in described catalyst for hydro-upgrading, in catalyst granules
On cross section, along described straight-line segment from outer most edge point to central point, active metal component concentration distribution is as follows：The concentration base of Co
It is gradually increased on this, the concentration of Ni substantially gradually decreases, and the concentration of Mo is substantially uniformly distributed.
9. according to the catalyst described in claim 1 it is characterised in that described catalyst for hydro-upgrading, with the weight of catalyst
On the basis of, the content of carrier is 46wt% ~ 87wt%, the content that Ni is counted with NiO as 1wt%～8wt%, Mo is with MoO3That counts contains
Measure as 10wt%～40wt%, the content that Co is counted with CoO as 0.5wt%～6wt%；On the basis of the weight of catalyst carrier,
The content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.
10. according to the catalyst described in claim 1 it is characterised in that in described catalyst for hydro-upgrading, positioned at catalyst
The concentration of Co at particle cross section outer most edge point and the concentration ratio of central spot Co are Co0/Co1For 0.08～0.90, positioned at urging
The concentration of Ni at the outer most edge point of catalyst particles cross section and the concentration ratio of central spot Ni are Ni0/Ni1For 1.2～7.0.
11. according to the catalyst described in claim 1 it is characterised in that described molecular sieve be Y type molecular sieve and/or beta molecule
Sieve.
12. according to the catalyst described in claim 1 it is characterised in that described molecular sieve be beta-molecular sieve；Wherein beta-molecular sieve
Property is as follows：Specific surface area 450m2/ g～750m2/ g, total pore volume 0.30ml/g～0.45ml/g, SiO2/Al2O3Mol ratio 40～
100, meleic acid amount 0.1～0.5mmol/g, the mol ratio of framework aluminum non-framework aluminum is 5～20, B-acid/L acid is 0.30～
0.50, Na2O≤0.15wt%.
13. according to the catalyst described in claim 1 it is characterised in that the property of described catalyst for hydro-upgrading is as follows：Than
Surface area is 120～220 m2/ g, pore volume is 0.20～0.60mL/g.
14. according to the catalyst described in claim 1 it is characterised in that in described catalyst for hydro-upgrading, containing auxiliary agent group
Point, wherein adjuvant component is one or more of fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in terms of element in the catalyst
Weight content is in below 15wt%.
15. according to the catalyst described in claim 1 it is characterised in that containing phosphorus in described catalyst for hydro-upgrading, with P2O5
Meter weight content in the catalyst is 1% ~ 6%.
The preparation method of the arbitrary described catalyst for hydro-upgrading of 16. claim 1 ~ 13, at least adopts one of with the following method, and first
The method of kind includes：
（1）With the solution impregnating carrier containing adsorbent I, drying, obtain the carrier containing adsorbent I, in the consumption of adsorbent I
The 0.1% ~ 10.0% of vehicle weight, the polyhydric alcohol that described adsorbent I is 400～10000 for molecular weight, described dipping adopts
Saturation dipping or excessive dipping；
（2）With the dipping solution impregnation steps containing Ni（1）Gains, through dry and roasting, obtain catalyst intermediate；
（3）Using unsaturated infusion process, with the fountain solution impregnation steps containing adsorbent II（2）Prepared catalyst intermediate,
The consumption of adsorbent II accounts for the 0.1% ~ 10.0% of vehicle weight, and wherein said adsorbent II is in organic carboxyl acid and its esters
One or more；
（4）With the dipping solution impregnation steps containing Co（3）Gains, through dry and roasting；
Wherein active metal Mo is in step（1）Before, step（2）Afterwards and in step（3）Before, step（4）In afterwards extremely
A few step is introduced in catalyst for hydro-upgrading；
Second method includes：
A, using unsaturated infusion process, with the fountain solution impregnated carrier containing adsorbent II, the consumption of adsorbent II accounts for carrier weight
The 0.1% ~ 10.0% of amount, wherein said adsorbent II is one or more of organic carboxyl acid and its esters；
B, with the dipping solution impregnation steps A gains containing Co, through being dried and roasting, obtain catalyst intermediate,
C, with the solution impregnation catalyst intermediate containing adsorbent I, drying, obtain the catalyst intermediate containing adsorbent I,
The consumption of adsorbent I accounts for the 0.1% ~ 10.0% of vehicle weight, described adsorbent I for number-average molecular weight be 400～10000 many
First alcohol, described dipping adopts saturation dipping or excessive dipping；
D, with the dipping solution impregnation steps C gains containing Ni, through being dried and roasting；
At least one step during wherein active metal Mo is before step A, after step B and before step C, after step D is drawn
Enter in catalyst for hydro-upgrading.
17. in accordance with the method for claim 16 it is characterised in that in first method, step（2）And/or step（4）'s
In dipping solution, containing phosphorus, phosphorus source is one of phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate or several
Kind；In catalyst, the introduction volume of phosphorus is with P2O5Meter accounts for the 1% ~ 6% of final catalyst for hydro-upgrading weight；In second method, step
In the dipping solution of B and/or step D, containing phosphorus, phosphorus source is phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate
One or more of；In catalyst, the introduction volume of phosphorus is with P2O5Meter accounts for the 1% ~ 6% of final catalyst for hydro-upgrading weight.
18. in accordance with the method for claim 16 it is characterised in that described adsorbent I for number-average molecular weight be 1000～
8000 polyhydric alcohol.
19. in accordance with the method for claim 16 it is characterised in that described polyhydric alcohol is Polyethylene Glycol.
20. in accordance with the method for claim 16 it is characterised in that described adsorbent II is organic carboxyl acid and its esters
One or more of, its carbon number is 2～15.
21. in accordance with the method for claim 16 it is characterised in that described organic acid include acetic acid, oxalic acid, lactic acid, the third two
Acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, TGA, mercaptopropionic acid, ethylenediaminetetraacetic acid, nitrilo
One or more of triacetic acid, ring ethylenediaminetetraacetic acid；Organic carboxylate be one of ammonium salt of above-mentioned organic carboxyl acid or
Multiple.
22. in accordance with the method for claim 16 it is characterised in that：Solution containing adsorbent I and the profit containing adsorbent II
In wet liquid, it is solvent using water and/or ethanol.
23. in accordance with the method for claim 16 it is characterised in that：First method at least adopts one of a ~ e：
A, step（1）During with the solution impregnation containing adsorbent I, using incipient impregnation or excessive dipping, after dipping terminates, sample
Product are through health preserving or without health preserving, then are dried；If needing health preserving, conditioned time is 1～12h；Described drying condition is such as
Under：Temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h；
B, step（2）During with the dipping of the dipping solution containing Ni, through health preserving or without health preserving, then it is dried and roasts
Burn；As needed health preserving, conditioned time is 0.5～6.0h；Described drying condition is as follows：Baking temperature is 70 DEG C～200 DEG C, is dried
Time 0.5h～20h；Described roasting condition：Sintering temperature is 300 DEG C～750 DEG C, and roasting time is 0.5h～20h；
C, step（3）After the dipping dipping of the fountain solution containing adsorbent II terminates, carry out next step again through health preserving, during health preserving
Between be 0.5～8h；Or step（3）After the fountain solution containing adsorbent II for the dipping, drying carries out next step again, wherein dry
Dry temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h；Or step（3）The dipping dipping of the fountain solution containing adsorbent II
After end, first through health preserving more after drying, then carry out next step, wherein conditioned time is 0.5～8h, described drying condition
As follows：Baking temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h；
D, step（3）Described unsaturated dipping is sprayed using unsaturation, wherein unsaturation dipping dip amount used and catalysis
The volume ratio of agent precursor saturated absorption amount of solution is 0.02 ~ 0.4；
E, step（4）When being loaded by infusion process with the dipping solution containing Co, using equi-volume impregnating, through health preserving after dipping
Or without health preserving, then it is dried；As needed health preserving, conditioned time is 0.5～6.0h；Described drying condition：Baking temperature
For 60 DEG C～300 DEG C, drying time is 0.5h～20h；Described roasting condition：Sintering temperature is 300 DEG C～750 DEG C, during roasting
Between be 0.5h～20h.
24. in accordance with the method for claim 16 it is characterised in that：Second method at least adopts one of a ~ e：
After a, the step A dipping dipping of the fountain solution containing adsorbent II terminate, carry out next step, conditioned time again through health preserving
For 0.5～8h；Or after the step A fountain solution containing adsorbent II for the dipping, drying carries out next step again, and temperature is wherein dried
Spend for 60 DEG C～250 DEG C, drying time 0.5h～20h；Or the step A dipping dipping of the fountain solution containing adsorbent II terminates
Afterwards, first through health preserving more after drying, then carry out next step, wherein conditioned time is 0.5～8h, and described drying condition is such as
Under：Baking temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h；
Unsaturated dipping described in b, step A is sprayed using unsaturation, and wherein unsaturated dipping dip amount used and carrier are satisfied
Volume ratio with absorbent solution amount is 0.02 ~ 0.4；
When c, step B are loaded by infusion process with the dipping solution containing Co, using equi-volume impregnating, after dipping through health preserving or
Person is without health preserving, then is dried；As needed health preserving, conditioned time is 0.5～6.0h；Described drying condition：Baking temperature is
60 DEG C～300 DEG C, drying time is 0.5h～20h；Described roasting condition：Sintering temperature is 300 DEG C～750 DEG C, roasting time
For 0.5h～20h；
When d, step C are with the solution impregnation containing adsorbent I, using incipient impregnation or excessive dipping, after dipping terminates, sample
Through health preserving or without health preserving, then it is dried；If needing health preserving, conditioned time is 1～12h；Described drying condition is as follows：
Temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h；
When e, step D are with the dipping of the dipping solution containing Ni, through health preserving or without health preserving, then it is dried and roasting；
As needed health preserving, conditioned time is 0.5～6.0h；Described drying condition is as follows：Baking temperature is 70 DEG C～200 DEG C, when being dried
Between 0.5h～20h；Described roasting condition：Sintering temperature is 300 DEG C～750 DEG C, and roasting time is 0.5h～20h.
A kind of 25. methods of heavy distillate hydro-upgrading are it is characterised in that adopt the arbitrary described hydrogenation of claim 1 ~ 15
Modifying catalyst.
26. in accordance with the method for claim 25 it is characterised in that：Described heavy distillate is diesel oil.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0204314B1 (en) * | 1985-06-05 | 1990-11-14 | Nippon Oil Co. Ltd. | Catalyst for hydrotreatment of heavy oils |
| CN102196860A (en) * | 2008-10-23 | 2011-09-21 | 第一毛织株式会社 | Supported catalyst for synthesizing carbon nanotubes, method for preparing thereof and carbon nanotube using the same |
| CN102463149A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Activation method of hydrogenation catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0204314B1 (en) * | 1985-06-05 | 1990-11-14 | Nippon Oil Co. Ltd. | Catalyst for hydrotreatment of heavy oils |
| CN102196860A (en) * | 2008-10-23 | 2011-09-21 | 第一毛织株式会社 | Supported catalyst for synthesizing carbon nanotubes, method for preparing thereof and carbon nanotube using the same |
| CN102463149A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Activation method of hydrogenation catalyst |
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