CN104667963B - A catalyst for hydrogenation modification and a preparing method thereof - Google Patents
A catalyst for hydrogenation modification and a preparing method thereof Download PDFInfo
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- CN104667963B CN104667963B CN201310604990.5A CN201310604990A CN104667963B CN 104667963 B CN104667963 B CN 104667963B CN 201310604990 A CN201310604990 A CN 201310604990A CN 104667963 B CN104667963 B CN 104667963B
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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, Ni0/Mo0>Ni<1/2>/Mo<1/2>>Ni1/Mo1 and Co0/Mo0<Co<1/2>/Mo<1/2><Co1/Mo1. The preparing method includes dipping with a wetting solution containing an absorbent I by adopting an unsaturated dipping method, loading the active metal Mo and 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 Mo and 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, 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
Use the catalyst for hydro-upgrading containing molecular sieve (Y type molecular sieve or beta-molecular sieve), the aromatic hydrocarbons in diesel oil etc. is suitably cracked,
In reduction diesel oil while sulfur nitrogen impurity content, improve the combination properties such as diesel cetane-number.But use current hydro-upgrading
Catalyst, to improve the combination property (sulfur nitrogen impurity content, Cetane number, T95 temperature, arene content etc.) of diesel oil, 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
Less than well improving.
Sulfur-containing compound in diesel oil distillate and aromatic hydrocarbons, generally exist 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) and 2,4,6-front threes
Base dibenzothiophenes (2,4,6-BMDBT) class formation is complicated and has the sulfur-containing compound of space steric effect to be most difficult to removing.Reach
To the degree of depth and ultra-deep desulfurization, it is necessary to remove that these structures are complicated and sterically hindered big sulfur-containing compound, and these sulfur-bearings
Compound generally more difficult removing under the harsh hydrofinishing operating conditions such as High Temperature High Pressure, by being 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 again simultaneously
The combination property of oil, this is the important topic being currently needed for research.
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 the most equally distributed.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 using silica-alumina, aluminium oxide and/or the predecessor of aluminium oxide and Y type molecular sieve mixing, molding and roasting, afterwards
The hydrogenation metal of effective dose is introduced at molding species.Above-mentioned catalyst has higher desulfurization and a denitrification activity, but diesel product
The amplitude that yield is low, diesel-fuel cetane number improves is little, the shortcoming such as 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 is in the catalyst
It is equally distributed.Using this catalyst when diesel oil hydrogenation modification, although can reduce the condensation point of diesel oil distillate, raising changes
Matter diesel-fuel cetane number, but diesel yield is below 97%, the most relatively low.
Summary of the invention
For problems of the prior art, the invention provides a kind of catalyst for hydro-upgrading and preparation method thereof.
This catalyst, during diesel oil hydrogenation modification, has 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, 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, Ni0/Mo0＞ Ni1/2/Mo1/2＞ Ni1/Mo1, Co0/Mo0＜ Co1/2/Mo1/2＜ Co1/Mo1。
In the present invention, active metal component concentration distribution formula A on the cross section of each catalyst granulesm/BnTable
Showing, on the cross section of the most each catalyst granules, at m, at the concentration of elements A and n, the ratio of the concentration of element B is (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
Can be identical with B, it is also possible to different；Remember with any point i.e. outer most edge point of catalyst granules cross section outer most edge for starting point
Being 0, be 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
Not representing the location point chosen on above-mentioned straight-line segment, the value of m and n represents and accounts for from starting point to the distance of the location point chosen
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 be 0,1/4,1/2,3/4,1 time-division
Choose when not representing and account for the 0 of length of above-mentioned straight-line segment, 1/4,1/2,3/4,1 from starting point to the distance of the location point chosen
Point place position (see figure 3), above-mentioned location point be also referred to as outer most edge select (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 uses active metallic element Mo, Co
Or Ni replaces, m and n is directly with defined location point on the above-mentioned straight-line segment of digitized representation of 0～1, with in x1 or x2 representative
State arbitrary location point on straight-line segment, such as, Co0/Co1Representing that A and B is Co, m=0, n=1 i.e. 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 cross section1/2/Ni1Represent that A and B is
Ni, m=1/2, n=1 i.e. represent on the described straight-line segment on catalyst granules cross section, make from outer most edge point to selected point
The concentration of element Ni and central spot element Ni dense at selected point position when distance accounts for the 1/2 of above-mentioned straight-line segment length
The ratio of degree, Ni0/Mo0Expression A be Ni, B be Mo, m=0, n=0, i.e. represent element Ni at catalyst granules cross section outer most edge point
The ratio of concentration of concentration and this elements Mo.X1 and x2 in the present invention is connecting above-mentioned outer most edge point and central point respectively
The location point (but not including outer most edge point and central point) arbitrarily chosen on the straight-line segment obtained, and from outer most edge point to x1 point
Distance less than from outer most edge point to x2 point distance that is 0 ＜ x1 ＜ x2 ＜ 1.
In the present invention, relate to using 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
Be 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), Ni0/Mo0(A be Ni, B be Mo, m=0, n=0), Ni1/4/Mo1/4(A is that Ni, B are
Mo, m=1/4, n=1/4), Ni1/2/Mo1/2(A be Ni, B be Mo, m=1/2, n=1/2), Ni3/4/Mo3/4(A be Ni, B be Mo, m=3/
4, n=3/4), Ni1/Mo1(A be Ni, B be Mo, m=1, n=1), Nix1/Mox1(A be Ni, B be Mo, m=x1, n=x1), Nix2/Mox2
(A be Ni, B be Mo, m=x2, n=x2), Co0/Mo0(A be Co, B be Mo, m=0, n=0), Co1/4/Mo1/4(A be Co, B be Mo, m=
1/4, n=1/4), Co1/2/Mo1/2(A be Co, B be Mo, m=1/2, n=1/2), Co3/4/Mo3/4(A be Co, B be Mo, m=3/4, n=
3/4), Co1/Mo1(A be Co, B be Mo, m=1, n=1), Cox1/Mox1(A be Co, B be Mo, m=x1, n=x1), Cox2/Mox2(A is
Co, B are Mo, m=x2, n=x2).
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: 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, be preferably
1.7~2.5。
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Ni0/Mo0
With Ni1/2/Mo1/2Ratio be 1.4 ~ 2.3, preferably 1.5 ~ 2.2；Co0/Mo0With Co1/2/Mo1/2Ratio be 0.10 ~ 0.70,
It is preferably 0.12 ~ 0.65.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Co0/Co1＜ Co1/4/Co1＜ Co1/2/Co1。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Co1/2/Co1＜ Co3/4/Co1＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Ni0/Ni1＞ Ni1/4/Ni1＞ Ni1/2/Ni1。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Ni1/2/Ni1＞ Ni3/4/Ni1＞ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Ni0/Mo0＞ Ni1/4/Mo1/4＞ Ni1/2/Mo1/2。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Ni1/2/Mo1/2＞ Ni3/4/Mo3/4＞ Ni1/Mo1。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Co0/Mo0＜ Co1/4/Mo1/4＜ Co1/2/Mo1/2。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Co1/2/Mo1/2＜ Co3/4/Mo3/4＜ Co1/Mo1。
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: 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, active metal component is in catalyst granules, and preferred version is as follows: Ni0/Mo0
With Ni1/4/Mo1/4Ratio be 1.1 ~ 1.8, preferably 1.15 ~ 1.7；Ni1/4/Mo1/4With Ni1/2/Mo1/2Ratio be 1.1 ~
1.8, preferably 1.15 ~ 1.7；Co0/Mo0With Co1/4/Mo1/4Ratio be 0.25 ~ 0.85, preferably 0.3 ~ 0.8；Co1/4/Mo1/4
With Co1/2/Mo1/2Ratio be 0.25 ~ 0.85, preferably 0.3 ~ 0.8.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Co0/Co1＜ Cox1/Co1＜ Cox2/Co1＜ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Ni0/Ni1＞ Nix1/Ni1＞ Nix2/Ni1＞ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Ni0/Mo0＞ Nix1/Mox1＞ Nix2/Mox2＞ Ni1/Mo1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably
As follows: Co0/Mo0＜ Cox1/Mox1＜ Cox2/Mox2＜ Co1/Mo1, 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 distribution is as follows: the concentration of Ni substantially gradually decreases, and the concentration of Co the most gradually increases
Adding, the concentration mol ratio of Ni/Mo substantially gradually decreases, and the concentration mol ratio of Co/Mo is substantially gradually increased.
In the present invention, described " substantially gradually decreasing (or being gradually increased) along described straight-line segment " refers to described work
Property metallic element concentration distribution along described straight-line segment in the whole interval from outer most edge point to central point generally in
Now gradually decrease the trend of (or being gradually increased), but it is interval to allow to there is one or more local；In this local is interval, described
The concentration distribution of active metallic element presents different trend along described straight-line segment and (such as remains constant and/or gradually
Increase (or gradually decreasing) and/or disordered state).Premise is, the existence in interval, 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 existence in a little local have no effect on those skilled in the art by dense in described whole interval of described active metallic element
Degree distribution is still judged to " presenting the trend gradually decreasing (or being gradually increased) generally ".It addition, the existence that this local is interval
Have no effect on the present invention and expect the realization of purpose, be acceptable, and within being also contained in protection scope of the present invention.
In the present invention, described catalyst for hydro-upgrading is that (solid) granular rather than the amorphous state such as powder.Make
For the shape of described granule, this area catalyst for hydro-upgrading can be enumerated conventional use of variously-shaped, such as can enter one
Step enumerates spherical, column etc., the most 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 Herba Trifolii Pratentis, Herba Galii Bungei etc.) column such as can be enumerated
Deng.The granularity of described catalyst for hydro-upgrading is generally 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
The whole surface exposed after being cut by the geometric center of its shape.Such as, when described catalyst granules is spherical, described
Cross section refers to (such as see figure along radius or the short-axis direction of this ball by the whole surface exposed after the cutting of its centre of sphere
1).Or, when described catalyst granules is column, described cross section refers to be perpendicular to the length dimension direction of this post to be passed through
The whole surface (such as seeing Fig. 2) exposed after the central point cutting of this length dimension.In the present invention, by described exposed surface
Periphery is referred to as the outer most edge of this cross section, described geometric center (than the centre of sphere as the aforementioned or the central point of length dimension) is 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 55wt% ~
88wt%, preferably 55wt% ~ 85wt%, more preferably surplus, the content that Ni counts with NiO is as 1wt%～8wt%, Mo
With MoO3The content of meter is 8wt%～32wt%, and the content that Co counts with CoO is as 1wt%～8wt%；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%.
Catalyst for hydro-upgrading of the present invention can also contain in adjuvant component, such as fluorine, silicon, phosphorus, titanium, zirconium, boron
Kind or multiple, adjuvant component weight content in the catalyst in terms of element is less than 15%, preferably 1% ~ 10%.The present invention adds
Hydrogen modifying catalyst preferably comprises phosphorus, with P2O5Meter weight content in the catalyst is 1% ~ 6%.
In the catalyst for hydro-upgrading of the present invention, be positioned at catalyst granules cross section outer most edge point the concentration of element Ni with
The ratio i.e. Ni of the concentration of central spot element Ni0/Ni1It is 1.2～7.0, preferably 1.5 ~ 5.0, it is positioned at catalyst granules transversal
The ratio i.e. Co of the concentration of the concentration of Elements C o and central spot Co at the outer most edge point of face0/Co1It is 0.1～0.8, preferably 0.2 ~
0.7。
In the catalyst for hydro-upgrading of the present invention, be positioned at catalyst granules cross section outer most edge point the concentration of element Ni with
Ratio (mol ratio) the i.e. Ni of the concentration of elements Mo0/Mo0It is 0.22～0.80, is positioned at unit at catalyst granules cross-section center point
The concentration of element Co and ratio (mol ratio) the i.e. Co of the concentration of elements Mo1/Mo1It is 0.20～0.78.
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
Ratio is 5～20, and B-acid/L acid is 0.30～0.50, Na2O≤0.15wt%.Beta-molecular sieve of the present invention can use existing method to prepare.
In the present invention, SiO2/Al2O3Mol ratio uses chemical determination, meleic acid amount, B-acid and L acid to use 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 uses ion emission spectroscopy method to measure.Framework aluminum
And non-framework aluminum content uses NMR method to measure.
In the catalyst for hydro-upgrading of the present invention, carrier can not contain adjuvant component, it is also possible to containing adjuvant component, wherein
Adjuvant component can be one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component containing in the carrier in terms of element
Measure at below 30wt%, preferably below 20wt%.Described carrier can use conventional method to prepare, such as kneading method etc..
The character 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 of the present invention, including:
(1) impregnate carrier with the fountain solution containing adsorbent I, obtain the carrier containing adsorbent I, wherein adsorbent I
Consumption accounts for the 0.1% ~ 10.0% of vehicle weight；Described adsorbent I is one or more in organic carboxyl acid and its esters, institute
The dipping stated uses unsaturation dipping；
(2) with dipping solution impregnation steps (1) gains containing Mo, Co, through being dried and roasting, obtain in catalyst
Mesosome；
(3) by the solution impregnation catalyst intermediate containing adsorbent II, drying, the catalyst containing adsorbent II is obtained
Intermediate, wherein the consumption of adsorbent II accounts for the 0.1% ~ 10.0% of vehicle weight, and described adsorbent II for number-average molecular weight is
The polyhydric alcohol of 400～10000, described dipping uses saturated dipping or excess dipping；
(4) with dipping solution impregnation steps (3) gains containing Mo, Ni, through being dried and roasting, hydro-upgrading is obtained
Catalyst；
Second method includes:
A, by the solution impregnating carrier containing adsorbent II, drying, obtain the carrier containing adsorbent II, wherein adsorbent
The consumption of II accounts for the 0.1% ~ 10.0% of vehicle weight, and described adsorbent II is 400～10000 for molecular weight, preferably 1000 ~
The polyhydric alcohol of 8000, described dipping uses saturated dipping or excess dipping；
B, with the dipping solution impregnation steps A gains containing Mo, Ni, through being dried and roasting, obtain in the middle of catalyst
Body；
C, with the fountain solution impregnated catalyst intermediate containing adsorbent I, obtain the catalyst intermediate containing adsorbent I,
Wherein the consumption of adsorbent I is the 0.1% ~ 10.0% of vehicle weight；Described adsorbent I is in organic carboxyl acid and its esters
One or more, described dipping uses unsaturation dipping；
D, with the dipping solution impregnation steps C gains containing Mo, Co, through being dried and roasting, obtain catalyst.
In the inventive method, carrier can use conventional method to prepare, and molecular sieve can draw in aluminium oxide kneading process
Enter, it is also possible to introduce in aluminium oxide preparation process.
Described adsorbent I is one or more in organic carboxyl acid and its esters, and its carbon number is not more than 15, one
As be 2～15.Described organic acid includes acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, three chloroethenes
In acid, chloroacetic acid etc., TGA, mercaptopropionic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ring ethylenediaminetetraacetic acid etc.
One or more.One or more in the ammonium salt of the preferred above-mentioned organic carboxyl acid of organic carboxylate.
Described adsorbent II is 1000 for the polyhydric alcohol that number-average molecular weight is 400～10000, preferably number-average molecular weight
～the polyhydric alcohol of 8000, described polyhydric alcohol can be PTMEG, preferably Polyethylene Glycol.
The inventive method, fountain solution containing adsorbent I and containing in the solution of adsorbent II, use water and/or the ethanol to be
Solvent.
In the inventive method, the condition of first method is preferably as follows:
The inventive method, impregnates carrier with the fountain solution containing adsorbent I in step (1), and dipping therein is not preferably with
Saturated spraying, the time of spraying is generally 1min～40min, preferably 2min～20min.Fountain solution containing adsorbent I used
The ratio of volume imbibition saturated with carrier volume is 0.02 ~ 0.40.When spraying the fountain solution containing adsorbent I, atomization effect should be selected
The best shower nozzle, makes solution evenly spread on carrier.After fountain solution dipping carrier containing adsorbent I, can be through being dried step
Suddenly, it is also possible to be directly entered step (2) without drying steps.Drying condition is as follows: temperature is generally 60 DEG C～250 DEG C, excellent
Elect 100～200 DEG C as, time 0.5h～20h, preferably 1h～6h.
The inventive method, step (2), with after dipping solution impregnation steps (1) gains containing Mo, Co, can be passed through and support
Raw, it is possible to without health preserving, as needed health preserving, conditioned time is 0.5～4.0h, then is dried, and baking temperature is 70 DEG C～300
DEG C, preferably 70 ~ 200 DEG C, more preferably 100 DEG C～160 DEG C, drying time is 0.5h～20h, preferably 1h～6h.
After drying can be through roasting, roasting condition is as follows: sintering temperature is 300 DEG C～750 DEG C, preferably 400 DEG C～650 DEG C, roasting
The burning time is 0.5h～20h, preferably 1h～6h.
The inventive method, the step (3) the fountain solution impregnated catalyst intermediate containing adsorbent II, use equal-volume leaching
Stain or excess dipping.Dipping terminate after, sample can through health preserving or without health preserving, if through the general conditioned time of health preserving be 1
～12h.After health preserving terminates, drying step.Described drying condition is as follows: temperature is 60 DEG C～250 DEG C, is preferably
100～200 DEG C, drying time 0.5h～20h, preferably 1h～6h.
The inventive method, in step (4), after impregnating with the dipping solution containing Mo, Ni, can be through health preserving, it is possible to without
Crossing health preserving, as needed health preserving, conditioned time is 0.5～6.0h, then is dried.Described drying condition is as follows: baking temperature is
60 DEG C～250 DEG C, preferably 70 ~ 200 DEG C, preferably 100～200 DEG C, drying time 0.5h～20h, preferably 1h～6h.Institute
The roasting condition stated is as follows: burning 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.
In the inventive method, active metal component Mo is introduced by step (2) and step (4) two step, wherein step (2) and
The mol ratio 0.4～2.5 of Mo added by step (4).
In the inventive method, the condition of second method is preferably as follows:
The inventive method, the step A fountain solution containing adsorbent II impregnates carrier, uses incipient impregnation or excess leaching
Stain.Dipping terminate after, sample can through health preserving or without health preserving, if through the general conditioned time of health preserving be 1～12h.Health preserving
After end, drying step.Described drying condition is as follows: temperature is 60 DEG C～250 DEG C, preferably 100～200 DEG C,
Drying time 0.5h～20h, preferably 1h～6h.
The inventive method, in step B, after impregnating with the dipping solution containing Mo, Ni, can be through health preserving, it is possible to without
Health preserving, as needed health preserving, conditioned time is 0.5～6.0h, then is dried.Described drying condition is as follows: baking temperature is 60
DEG C～250 DEG C, preferably 70 ~ 200 DEG C, preferably 100～200 DEG C, drying time 0.5h～20h, preferably 1h～6h.Described
Roasting condition as follows: burn temperature be 300 DEG C～750 DEG C, preferably 400 DEG C～650 DEG C, roasting time is 0.5h～20h, excellent
Elect 1h～6h as.
The inventive method, with the fountain solution impregnated catalyst intermediate containing adsorbent I in step C, dipping therein is best
Employing unsaturation sprays, and the time of spraying is generally 1min～40min, preferably 2min～20min.Profit containing adsorbent I used
The ratio of the volume of wet liquid imbibition saturated with catalyst intermediate volume is 0.02 ~ 0.40.Spray the fountain solution containing adsorbent I
Time, the shower nozzle that atomizing effect is good should be selected, make solution evenly spread on carrier.Fountain solution dipping carrier containing adsorbent I
After, can be through drying steps, it is also possible to be directly entered step D without drying steps.Drying condition is as follows: temperature is generally 60
DEG C～250 DEG C, preferably 100～200 DEG C, time 0.5h～20h, preferably 1h～6h.
The inventive method, step D, can be through health preserving with after the dipping solution impregnation steps C gains containing Mo, Co, also
Can be without health preserving, as needed health preserving, conditioned time is 0.5～4.0h, then is dried, and baking temperature is 70 DEG C～300 DEG C, excellent
Electing 70 ~ 200 DEG C as, more preferably 100 DEG C～160 DEG C, drying time is 0.5h～20h, preferably 1h～6h.Drying
After can be through roasting, roasting condition is as follows: sintering temperature is 300 DEG C～750 DEG C, preferably 400 DEG C～650 DEG C, roasting time
For 0.5h～20h, preferably 1h～6h.
In the inventive method, active metal component Mo is introduced by step B and step D two step, wherein step B and step D
The mol ratio 0.4～2.5 of added Mo.
In catalyst for hydro-upgrading preparation method of the present invention, active metal component is to support on carrier by infusion process,
Generally using incipient impregnation, spray preferably with saturated, the time of spraying is generally 5min～40min, preferably 10min～
20min.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 regulated by the consumption of each compound, thus prepares the catalyst of specified activity constituent content.Required activity group
The raw material divided is generally the compound of the types such as salt, oxide or acid, as molybdenum source is generally from molybdenum oxide, ammonium molybdate, secondary molybdenum
One or more in acid ammonium, nickel source is from the one in nickel nitrate, nickelous carbonate, basic nickel carbonate, Nickel dichloride., nickel oxalate or several
Kind, cobalt source is from one or more in cobalt nitrate, cobalt carbonate, basic cobaltous carbonate, cobaltous chloride, cobalt oxalate.At described dipping
In solution, in addition to active metal component, it is also possible to containing phosphorus-containing compound, as phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, di(2-ethylhexyl)phosphate
One or more in hydrogen ammonium and ammonium phosphate etc..The catalyst for hydro-upgrading of the present invention preferably comprises phosphorus, with P2O5Count in catalysis
Weight content in agent is 1% ~ 6%.
In the inventive method, one or more in adjuvant component fluorine, silicon, phosphorus, titanium, zirconium and boron, use conventional method to draw
Enter in catalyst, such as can introduce when prepared by carrier in catalyst, it is also possible to after prepared by carrier, introduce catalyst.Carrying
Introduce in catalyst after body preparation, the method for individually dipping can be used to introduce in catalyst, it is also possible to active metal component
During together dipping introduces catalyst.
Catalyst for hydro-upgrading of the present invention in the hydro-upgrading of heavy distillate (especially diesel oil) 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
By meter) 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 only use the hydro-upgrading of the present invention to be catalyzed
Agent, 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)
According to the ratio arbitrarily needed with the use of, such as use different catalysts bed grating or be used in mixed way.
According to the present invention, the operating condition of described hydro-upgrading is not had any special restriction, ability can be used
The conventional use of operating condition in territory, such as reaction temperature 260 ~ 400 DEG C, 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 Co is incremental from catalyst granules outer surface to center
Trend, the trend that Ni tapers off from catalyst granules outer surface to center, Co/Mo atomic ratio from catalyst granules outer surface to
The heart is incremental trend, the trend that Ni/Mo atomic ratio tapers off from catalyst granules outer surface to center, this uneven distribution
Active metal component match with acidic components molecular sieve in carrier, this catalyst is particularly well-suited to the hydro-upgrading mistake of diesel oil
Cheng Zhong, while diesel deep desulfurization, in the case of keeping diesel yield higher, raising diesel-fuel cetane number etc. are comprehensive
Performance.
The present invention prepares in the method for catalyst for hydro-upgrading, by the unsaturation dipping fountain solution containing adsorbent I, makes load
A part of adsorption potential of body grain edges surface of position is adsorbed agent and occupies, and when dipping contains the solution of active metal Mo, Co, reduces
Mo, Co absorption in carrier edge position, makes the concentration of active metal Mo, Co in being gradually increased from marginal position to center
Trend, and the fountain solution of adsorbent II is contained by saturated dipping or excess dipping, after then impregnating Mo, Ni active metal solution,
Slow down Mo, Ni diffusion velocity to catalyst granules center, make active metal component and the acid in carrier of this uneven distribution
Property component molecular sieve match, improve the property such as the deep hydrodesulfurizationof performance of catalyst, and suitable open loop, isomery, cracking
Can, during the hydro-upgrading of diesel oil, can be while diesel deep desulfurization, in the case of keeping diesel yield higher
Improve the combination properties such as diesel-fuel cetane number.
Accompanying drawing explanation
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 catalyst granules by each position point selected by gained cross section after cutting and this cross section,
Wherein 0 any point represented on this cross section in outer most edge i.e. outer most edge point, 1/4 represents 1/4 location point, and 1/2 represents 1/2
Putting a little, 3/4 represents 3/4 location point, and 1 represents central point.
Fig. 4 be embodiment 1 gained catalyst C1 granule in active metal component Ni and Co concentration on this cross section
Scattergram.Wherein abscissa is each position point on this cross section, and vertical coordinate is the concentration at a certain location point and this cross section
The ratio of the concentration of upper central spot.
Detailed description of the invention
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
Execute in example.In the present invention, wt% is mass fraction.
Analysis method of the present invention is as follows:
(1) content (wt%) of active metal component and adjuvant component uses X-ray fluorescence spectroscopy to measure.
(2) specific surface area (m2/ g) and pore volume (ml/g) use BET method measure.
(3) each active metal component concentration distribution in catalyst granules
In below example and comparative example, the carrier employing cylinder (but present invention is obviously not limited to this, also
Other grain shape can be used), the catalyst granules thus obtained is also round cylindricality.From each embodiment and contrast
The catalyst that example is obtained randomly selects a catalyst granules as measuring samples.Exist to measure each active metal component
Concentration distribution in this catalyst granules, is perpendicular to the length dimension direction of this cylindrical particle, by this length dimension
Heart point cuts, it is thus achieved that two exposed surfaces.Take one of them 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,
Carry out on electron probe microanalyzer (JXA-8230 type, Jeol Ltd. manufactures).Measuring condition is: accelerating potential
15kV, beam intensity 5 × 10-8A, beam spot diameter, 1 m, X-ray detection 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 (respectively NiO, CoO and MoO3), precision: less than 1%, two
Secondary charge pattern resolution: 3nm(LaB6), linear system: Ni and Co uses KαLinear system, Mo uses LαLinear system.
Measuring method is: arbitrarily choose a location point in the outer most edge of this cross section as 0, with on this cross section
Central point as 1, connect described location point 0 and described location point 1 straight-line segment (the substantially radius of this cross section, because of
This is also referred to as radially), measure the concentration value of targeted activity metal at the point of assigned position, then by calculating, it is thus achieved that each concentration value
Ratio (being mol ratio in the present invention).
Fig. 4 be embodiment 1 gained catalyst C1 in the concentration profile of active metal, be 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 corresponding active metal that the concentration value of the targeted activity metal (as a example by Ni and Co) of amount is measured to (i.e. central point) at location point 1
The ratio of concentration value (use Ni respectivelym/Ni1And Com/Co1Represent) it is vertical coordinate, so draw and obtain.
(4) total sulfur content in raw material and hydrogenation products is to use ultraviolet fluorescence method to measure (ASTM D5453-1993), 4,
6-BMDBT content is to use GC-AED(gas chromatogram-atom luminescence spectroscopy) measure.
(5) number-average molecular weight Mn uses GPC method to measure.
In embodiment, the diameter of cylindrical vector used is about 1.2mm, and length is about 3 ~ 5mm, its physico-chemical property such as table 1 institute
Show:
The physico-chemical property of used carrier in table 1 embodiment
In the present embodiment, the Mo predecessor in Mo, Ni, P and Mo, Co, P impregnation liquid used is MoO3, Ni predecessor is alkali formula
Nickelous carbonate, Co predecessor is basic cobaltous carbonate, and P predecessor is phosphoric acid.
Embodiment 1
Weigh tartaric acid 15g, stirring and dissolving in 45g water, prepare fountain solution I.Take S1 carrier 30 as one kind 0g, by equal for fountain solution I
Even spraying on S1 carrier, the time of spraying is 15min.After fountain solution I sprays end, through 100 DEG C of dry 2h, with containing Mo, Co, P
Impregnation liquid (the first impregnation liquid) the above-mentioned carrier of incipient impregnation, gained sample average is divided into three parts, and wherein first part of sample is not
Health preserving, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that sample be designated as B1；Second sample health preserving 1h, passes through and catalysis
The post-processing step that agent intermediate B 1 is identical, prepared sample is designated as B2；Triplicate sample health preserving 3h, through with catalyst in the middle of
The post-processing step that body B1 is identical, prepared sample is designated as B3.
Weigh 6g Macrogol 2000 (i.e. molecular weight is the Polyethylene Glycol of 2000, lower same), stir in the water measured
Dissolve, prepare fountain solution II.With this fountain solution II incipient impregnation sample B1, B2 and B3 respectively, then carry out the health preserving of 10h,
After 120 DEG C of dry 3h, the sample prepared is designated as Z1, Z2 and Z3 respectively.
Spray above-mentioned Z1, Z2 and Z3 sample with impregnation liquid (the second impregnation liquid) equal-volume containing Mo, Ni, P respectively, spray knot
Directly carry out 120 DEG C of dry 3h after bundle without health preserving, after 480 DEG C of roasting 2h, it is thus achieved that catalyst be designated as C1, C2 and C3 respectively.
Embodiment 2
Weigh malic acid 3.0g, stirring and dissolving in 18g ethanol, prepare fountain solution I.Take S2 carrier 30 as one kind 0g, by fountain solution I
Uniformly spraying on S2 carrier, the time of spraying is 5min.With on impregnation liquid (the first impregnation liquid) incipient impregnation containing Mo, Co, P
Stating carrier, dipping terminates rear health preserving 1h, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that sample be designated as B4.
Weigh 24g cetomacrogol 1000, stirring and dissolving in the water measured, prepare fountain solution II.With this fountain solution II
Incipient impregnation sample B4, then carries out the health preserving of 5h, and after 120 DEG C of dry 3h, the sample prepared is designated as Z4.
Spray Z4 sample with impregnation liquid (the second impregnation liquid) equal-volume containing Mo, Ni, P, spray sample average after end
Be divided into three parts, wherein first part of direct 120 DEG C of dry 3h of sample, after 480 DEG C of roasting 2h, it is thus achieved that catalyst be designated as C4；Second
Part sample health preserving 1h, through the post-processing step identical with catalyst C4, prepared catalyst is designated as C5；Triplicate sample health preserving
3h, through the post-processing step identical with catalyst C4, prepared catalyst is designated as C6.
Embodiment 3
Weigh citric acid and each 3.5g of malonic acid, stirring and dissolving in 20g water, prepare fountain solution I.Take S3 carrier 100g,
Uniformly being sprayed by fountain solution I on S3 carrier, the time of spraying is 25min.With containing bodies such as Mo, Co, P impregnation liquid (the first impregnation liquid)
Long-pending impregnating above-mentioned carrier, dipping terminates rear health preserving 1h, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that sample be designated as B7.
Weigh 2g PEG 8000, stirring and dissolving in the aqueous solution measured, prepare fountain solution II.Use this fountain solution
II incipient impregnation sample B7, then carries out the health preserving of 5h, and after 120 DEG C of dry 3h, the sample prepared is designated as Z7.
Z7 sample is sprayed with impregnation liquid (the second impregnation liquid) equal-volume containing Mo, Ni, P, directly through 120 DEG C of dry 3h, 480
After DEG C roasting 2h, it is thus achieved that catalyst be designated as C7.
Comparative example 1
Take S1 carrier 100g, after impregnation liquid (the first impregnation liquid) the above-mentioned carrier of incipient impregnation containing Mo, Co, P, warp
120 DEG C of dry 3h, after 480 DEG C of roasting 2h, it is thus achieved that sample be designated as B8.With the impregnation liquid (the first impregnation liquid) etc. containing Mo, Ni, P
Volume impregnation B8, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that catalyst be designated as C8.
Comparative example 2
Take S4 carrier 100g, use the preparation method identical with C1 catalyst to prepare, it is thus achieved that catalyst be designated as C9.
Table 2 embodiment forms with comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Composition | |||||||||
| MoO3, wt% | 23.4 | 23.1 | 23.3 | 22.9 | 23.2 | 23.5 | 23.1 | 23.5 | 23.3 |
| CoO, wt% | 2.1 | 2.1 | 2.0 | 2.0 | 2.1 | 2.2 | 2.0 | 2.1 | 2.0 |
| NiO, wt% | 2.5 | 2.7 | 2.5 | 2.4 | 2.6 | 2.5 | 2.5 | 2.6 | 2.7 |
| P2O5, wt% | 2.4 | 2.5 | 2.5 | 2.4 | 2.4 | 2.5 | 2.4 | 2.5 | 2.5 |
| Carrier * | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| First impregnation liquid/the second impregnation liquid institute Add the mol ratio of Mo | 1.0 | 1.0 | 1.0 | 0.8 | 0.8 | 0.8 | 1.2 | 1.0 | 1.0 |
| Character | |||||||||
| Specific surface area, m2/g | 180 | 180 | 181 | 187 | 189 | 188 | 181 | 174 | 175 |
| Pore volume, mL/g | 0.36 | 0.36 | 0.35 | 0.35 | 0.35 | 0.35 | 0.36 | 0.36 | 0.36 |
In table 2, the carrier * i.e. aluminium oxide of C1, C2, C3 and C8 and beta-molecular sieve, aluminium oxide and Y molecule in C4, C5 and C6
Sieve, aluminium oxide and β and Y molecular sieve, the aluminium oxide in C9 in C7.
The concentration distribution in catalyst granules of table 3 embodiment and Elements C o in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Co0/Co1 | 0.14 | 0.28 | 0.53 | 0.31 | 0.34 | 0.33 | 0.30 | 0.98 | 0.14 |
| Co1/4/Co1 | 0.29 | 0.47 | 0.63 | 0.79 | 0.78 | 0.81 | 0.46 | 0.99 | 0.29 |
| Co1/2/Co1 | 0.62 | 0.82 | 0.89 | 0.96 | 0.97 | 0.95 | 0.80 | 1.00 | 0.62 |
| Co3/4/Co1 | 0.91 | 0.95 | 0.98 | 0.99 | 0.98 | 1.00 | 0.94 | 0.99 | 0.91 |
Table 4 embodiment and element Ni in the comparative example catalyst concentration distribution in catalyst granules
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Ni0/Ni1 | 2.79 | 2.81 | 2.82 | 2.99 | 2.48 | 2.08 | 2.51 | 1.00 | 2.79 |
| Ni/4/Ni1 | 1.88 | 1.85 | 1.86 | 1.92 | 1.68 | 1.51 | 1.70 | 1.01 | 1.88 |
| Ni1/2/Ni1 | 1.26 | 1.25 | 1.28 | 1.30 | 1.22 | 1.17 | 1.20 | 0.99 | 1.26 |
| Ni3/4/Ni1 | 1.09 | 1.10 | 1.11 | 1.10 | 1.07 | 1.04 | 1.06 | 0.98 | 1.09 |
Ni/Mo(mol ratio in table 5 embodiment and comparative example catalyst) concentration distribution in catalyst granules
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Ni0/Mo0 | 0.41 | 0.39 | 0.38 | 0.42 | 0.39 | 0.37 | 0.40 | 0.21 | 0.41 |
| Ni1/4/Mo1/4 | 0.28 | 0.28 | 0.29 | 0.30 | 0.29 | 0.30 | 0.28 | 0.22 | 0.28 |
| Ni1/2/Mo1/2 | 0.22 | 0.22 | 0.23 | 0.21 | 0.22 | 0.22 | 0.21 | 0.20 | 0.22 |
| Ni3/4/Mo3/4 | 0.17 | 0.18 | 0.18 | 0.15 | 0.16 | 0.17 | 0.17 | 0.21 | 0.17 |
| Ni1/Mo1 | 0.15 | 0.16 | 0.16 | 0.14 | 0.14 | 0.16 | 0.15 | 0.22 | 0.15 |
Co/Mo(mol ratio in table 6 embodiment and comparative example catalyst) concentration distribution in catalyst granules
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Co0/Mo0 | 0.05 | 0.08 | 0.11 | 0.07 | 0.06 | 0.06 | 0.07 | 0.18 | 0.05 |
| Co1/4/Mo1/4 | 0.12 | 0.15 | 0.16 | 0.16 | 0.17 | 0.18 | 0.11 | 0.18 | 0.12 |
| Co1/2/Mo1/2 | 0.28 | 0.26 | 0.22 | 0.27 | 0.28 | 0.28 | 0.23 | 0.17 | 0.28 |
| Co3/4/Mo3/4 | 0.34 | 0.31 | 0.27 | 0.29 | 0.30 | 0.30 | 0.28 | 0.17 | 0.34 |
| Co1/Mo1 | 0.38 | 0.34 | 0.29 | 0.31 | 0.32 | 0.31 | 0.33 | 0.18 | 0.38 |
Embodiment 4
The present embodiment is the henchnmrk test of catalyst.
Catalyst performance evaluation experiment is carried out on 100mL small hydrogenation device, carries out pre-to catalyst before performance evaluation
Sulfuration.Evaluating catalyst condition is at reaction stagnation pressure 10.0MPa, volume space velocity 1.5 h during liquid-1, hydrogen-oil ratio 800:1, reaction temperature
Degree is 365 DEG C.Henchnmrk test raw oil character is shown in Table 7, and Evaluation results is shown in Table 8, from data in table, with this
Catalyst for hydro-upgrading is prepared in invention, catalyst desulphurizing activated apparently higher than comparative example catalyst, is keeping diesel yield not
Less than under conditions of 97wt%, diesel-fuel cetane number being improved more than 10 units, product quality has obtained good improvement.
Table 7 raw oil character
| 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 content, g/g | 103.6 |
| Nitrogen, g/g | 1225 |
| Cetane number | 28 |
| C, wt% | 87.98 |
| H, wt% | 11.12 |
Table 8 catalyst performance evaluation result
| Catalyst | C1 | C2 | C3 | C4 | C5 |
| Diesel oil | |||||
| Yield, wt% | 98.1 | 98.0 | 98.2 | 97.5 | 97.5 |
| Density (20 DEG C)/g.cm-3 | 0.8396 | 0.8392 | 0.8395 | 0.8382 | 0.8383 |
| T95, DEG C | 349 | 350 | 350 | 348 | 347 |
| Condensation point, DEG C | -20 | -20 | -21 | -22 | -22 |
| Cetane number | 46.8 | 46.9 | 47.0 | 48.1 | 48.0 |
| Sulfur, g/g | 10 | 9 | 9 | 8 | 8 |
Table 8 continues
| Catalyst | C6 | C7 | C8 | C9 |
| Diesel oil | ||||
| Yield, wt% | 97.6 | 97.8 | 97.6 | 99.5 |
| Density (20 DEG C)/g.cm-3 | 0.8385 | 0.8388 | 0.8397 | 0.8572 |
| T95, DEG C | 348 | 348 | 350 | 355 |
| Condensation point, DEG C | -21 | -22 | -19 | 4 |
| Cetane number | 47.9 | 48.0 | 45.1 | 35.0 |
| Sulfur, g/g | 7 | 7 | 18 | 12 |
Claims (25)
1. a catalyst for hydro-upgrading, carrier includes aluminium oxide and molecular sieve, and active metal component is Mo, Co and Ni, wherein
Active metal component concentration distribution on each catalyst granules cross section is as follows: Co0/Co1＜ Co1/2/Co1＜ 1, Ni0/Ni1
＞ Ni1/2/Ni1＞ 1, Ni0/Mo0＞ Ni1/2/Mo1/2＞ Ni1/Mo1, Co0/Mo0＜ Co1/2/Mo1/2＜ Co1/Mo1；
Wherein, active metal component concentration distribution formula A on the cross section of each catalyst granulesm/BnRepresent, the most 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；With any point of catalyst granules cross section outer most edge it 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 on above-mentioned straight-line segment the location point chosen, 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 uses
Active metallic element Mo, Co or Ni replace, m and n is directly with defined location point on the above-mentioned straight-line segment of digitized representation of 0～1；
Wherein, described catalyst for hydro-upgrading, on the basis of the weight of catalyst, the content of carrier be 55wt%～
The content that 88wt%, Ni count with NiO is as 1wt%～8wt%, and Mo is with MoO3The content of meter is 8wt%～32wt%, and Co is with CoO
The content of meter is 1wt%～8wt%；On the basis of the weight of catalyst carrier, the content of molecular sieve is 3%～35%, aluminium oxide
Content be 65%～97%.
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 following a kind of scheme:
(1) Co0/Co1With Co1/2/Co1Ratio be 0.2～0.8；
(2) Ni0/Ni1With Ni1/2/Ni1Ratio 1.5～2.6；
(3) Ni0/Mo0With Ni1/2/Mo1/2Ratio be 1.4～2.3；
(4) Co0/Mo0With Co1/2/Mo1/2Ratio be 0.10～0.70.
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 following a kind of scheme:
(1) Co0/Co1With Co1/2/Co1Ratio be 0.2～0.7；
(2) Ni0/Ni1With Ni1/2/Ni1Ratio 1.7～2.5；
(3) Ni0/Mo0With Ni1/2/Mo1/2Ratio be 1.5～2.2；
(4) Co0/Mo0With Co1/2/Mo1/2Ratio be 0.12～0.65.
4. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, active metal component
Concentration on catalyst granules cross section is distributed and at least includes following a kind of 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) Ni0/Mo0＞ Ni1/4/Mo1/4＞ Ni1/2/Mo1/2；
(6) Ni1/2/Mo1/2＞ Ni3/4/Mo3/4＞ Ni1/Mo1；
(7) Co0/Mo0＜ Co1/4/Mo1/4＜ Co1/2/Mo1/2；
(8) Co1/2/Mo1/2＜ Co3/4/Mo3/4＜ Co1/Mo1。
5. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, active metal component
Concentration on catalyst granules cross section is distributed and at least includes following a kind of scheme:
(1) Co0/Co1＜ Cox1/Co1＜ Cox2/Co1＜ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
(2) Ni0/Ni1＞ Nix1/Ni1＞ Nix2/Ni1＞ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
(3) Ni0/Mo0＞ Nix1/Mox1＞ Nix2/Mox2＞ Ni1/Mo1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
(4) Co0/Mo0＜ Cox1/Mox1＜ Cox2/Mox2＜ Co1/Mo1, 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 following a kind of 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；
(5) Ni0/Mo0With Ni1/4/Mo1/4Ratio be 1.1～1.8；
(6) Ni1/4/Mo1/4With Ni1/2/Mo1/2Ratio be 1.1～1.8；
(7) Co0/Mo0With Co1/4/Mo1/4Ratio be 0.25～0.85；
(8) Co1/4/Mo1/4With Co1/2/Mo1/2Ratio be 0.25～0.85.
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 following a kind of 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；
(5) Ni0/Mo0With Ni1/4/Mo1/4Ratio be 1.15～1.7；
(6) Ni1/4/Mo1/4With Ni1/2/Mo1/2Ratio be 1.15～1.7；
(7) Co0/Mo0With Co1/4/Mo1/4Ratio be 0.3～0.8；
(8) Co1/4/Mo1/4With Co1/2/Mo1/2Ratio be 0.3～0.8.
8. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, at 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 Ni
Gradually decreasing on Ben, the concentration of Co is substantially gradually increased, and the concentration mol ratio of Ni/Mo substantially gradually decreases, and Co/Mo's is dense
Degree mol ratio is substantially gradually increased.
9., according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, at least include as follows
A kind of scheme:
(1) being positioned at the concentration of Ni at catalyst granules cross section outer most edge point with the ratio of the concentration of the Ni of central spot is
1.2～7.0,
(2) being positioned at the concentration of Co at catalyst granules cross section outer most edge point is 0.1 with the ratio of the concentration of central spot Co
～0.8,
(3) being positioned at the concentration of Ni at catalyst granules cross section outer most edge point is 0.22～0.80 with the ratio of the concentration of Mo,
(4) ratio being positioned at the concentration of the Co at catalyst granules cross-section center point and the concentration of Mo is 0.20～0.78.
10. according to the catalyst described in claim 1, it is characterised in that described molecular sieve is Y type molecular sieve and/or beta molecule
Sieve.
11. according to the catalyst described in claim 1, it is characterised in that described molecular sieve is beta-molecular sieve；Wherein beta-molecular sieve
Character 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 be 0.30～
0.50, Na2O≤0.15wt%。
12. according to the catalyst described in claim 1, it is characterised in that the character of described catalyst for hydro-upgrading is as follows: ratio
Surface area is 120～220 m2/ g, pore volume is 0.20～0.60mL/g.
13. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, containing auxiliary agent group
Point, one or more during wherein adjuvant component is fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in terms of element in the catalyst
Weight content is at below 15wt%.
14. 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 15. claim 1～10, at least uses a kind of following method,
Wherein first method includes:
(1) impregnating carrier with the fountain solution containing adsorbent I, obtain the carrier containing adsorbent I, wherein the consumption of adsorbent I is
The 0.1%～10.0% of vehicle weight；Described adsorbent I is one or more in organic carboxyl acid and its esters, described
Dipping uses unsaturation dipping；
(2) with dipping solution impregnation steps (1) gains containing Mo, Co, through being dried and roasting, obtain in the middle of catalyst
Body；
(3) by the solution impregnation catalyst intermediate containing adsorbent II, drying, obtain in the middle of the catalyst containing adsorbent II
Body, wherein the consumption of adsorbent II accounts for the 0.1%～10.0% of vehicle weight, described adsorbent II for molecular weight be 400～
The polyhydric alcohol of 10000, described dipping uses saturated dipping or excess dipping；
(4) with dipping solution impregnation steps (3) gains containing Mo, Ni, through being dried and roasting, hydro-upgrading catalysis is obtained
Agent；
Second method includes:
A, by the solution impregnating carrier containing adsorbent II, drying, obtain the carrier containing adsorbent II, wherein adsorbent II
Consumption accounts for the 0.1%～10.0% of vehicle weight, and described adsorbent II is the polyhydric alcohol that molecular weight is 400～10000, described
Dipping uses saturated dipping or excess dipping；
B, with the dipping solution impregnation steps A gains containing Mo, Ni, through being dried and roasting, obtain catalyst intermediate；
C, with the fountain solution impregnated catalyst intermediate containing adsorbent I, obtain the catalyst intermediate containing adsorbent I, wherein
The consumption of adsorbent I is the 0.1%～10.0% of vehicle weight；Described adsorbent I is in organic carboxyl acid and its esters
Planting or multiple, described dipping uses unsaturation dipping；
D, with the dipping solution impregnation steps C gains containing Mo, Co, through being dried and roasting, obtain catalyst.
16. in accordance with the method for claim 15, it is characterised in that: in second method, described adsorbent II is molecule
Amount is the polyhydric alcohol of 1000～8000.
17. in accordance with the method for claim 15, it is characterised in that described adsorbent I is in organic carboxyl acid and its esters
One or more, its carbon number is 2～15.
18. in accordance with the method for claim 15, it is characterised in that described adsorbent I include acetic acid, oxalic acid, lactic acid, third
Diacid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, TGA, mercaptopropionic acid, ethylenediaminetetraacetic acid, nitrogen
One or more in river triacetic acid, ring ethylenediaminetetraacetic acid；Organic carboxylate is the one in the ammonium salt of above-mentioned organic carboxyl acid
Or it is multiple.
19. in accordance with the method for claim 15, it is characterised in that described adsorbent II is Polyethylene Glycol.
20. in accordance with the method for claim 15, it is characterised in that: fountain solution containing adsorbent I and containing adsorbent II
In solution, using water and/or ethanol is solvent.
21. in accordance with the method for claim 15, it is characterised in that: in first method, at least use following condition a～f
One of:
Impregnating carrier with the fountain solution containing adsorbent I in a, step (1), dipping therein uses unsaturation to spray, and sprays the time
For 1min～40min；The ratio of volume imbibition saturated with the carrier volume of the fountain solution containing adsorbent I used is 0.02～0.4；
After b, step (1) impregnate carrier with the fountain solution containing adsorbent I, through drying steps or without dry step
Suddenly, then carrying out step (2), described drying condition is as follows: temperature is 60 DEG C～250 DEG C, time 0.5h～20h；
C, step (2) are with after dipping solution impregnation steps (1) gains containing Mo, Co, through health preserving or without health preserving,
Being dried and roasting, as needed health preserving, conditioned time is 0.5～4.0h again；Described baking temperature is 70 DEG C～300 DEG C, dry
The dry time is 0.5h～20h；Described roasting condition is as follows: sintering temperature is 300 DEG C～750 DEG C, roasting time be 0.5h～
20h；
D, the step (3) the solution impregnation catalyst intermediate containing adsorbent II, use incipient impregnation or excess dipping, leaching
After stain terminates, sample is through health preserving or without health preserving, then 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；
In e, step (4), with the dipping solution containing Mo, Ni or with containing Mo, Ni and Organic substance B dipping solution impregnate after,
Through health preserving or without health preserving, as needed health preserving, conditioned time is 0.5～6.0h, then is dried；Described drying condition
As follows: baking temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h, described roasting condition is as follows: burn temperature be 300 DEG C
～750 DEG C, roasting time is 0.5h～20h；
F, active metal component Mo are introduced by step (2) and step (4) two step, wherein Mo added by step (2) and step (4)
Mol ratio is 0.4～2.5.
22. in accordance with the method for claim 15, it is characterised in that: in second method, at least use following condition a～f
One of:
With the fountain solution impregnated catalyst intermediate containing adsorbent I in a, step C, dipping therein uses unsaturation to spray, spray
The leaching time is 1min～40min；The volume of the fountain solution containing adsorbent I used and catalyst intermediate saturated imbibition volume it
Ratio is 0.02～0.4；
With after the fountain solution impregnated catalyst intermediate containing adsorbent I in b, step C, through drying steps or without overdrying
Dry step, then carry out step D, described drying condition is as follows: temperature is 60 DEG C～250 DEG C, time 0.5h～20h；
C, step D, with after the dipping solution impregnation steps C gains containing Mo, Co, through health preserving or without health preserving, then are entered
Row is dried and roasting, and as needed health preserving, conditioned time is 0.5～4.0h；Described baking temperature is 70 DEG C～300 DEG C, when being dried
Between be 0.5h～20h；Described roasting condition is as follows: sintering temperature is 300 DEG C～750 DEG C, and roasting time is 0.5h～20h；
D, the step A solution impregnating carrier containing adsorbent II, uses incipient impregnation or excess dipping, after dipping terminates,
Sample is through health preserving or without health preserving, then is dried, if needing health preserving, conditioned time is 1～12h；Described drying condition
As follows: temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h；
In e, step B, after impregnating with the dipping solution containing Mo, Ni, through health preserving or without health preserving, as needed health preserving, support
The raw time is 0.5～6.0h, then is dried；Described drying condition is as follows: baking temperature is 60 DEG C～250 DEG C, when being dried
Between 0.5h～20h, described roasting condition is as follows: burn temperature be 300 DEG C～750 DEG C, roasting time is 0.5h～20h；
F, active metal component Mo are introduced by step B and step D two step, and wherein the mol ratio of Mo added by step B and step D is
0.4～2.5.
23. in accordance with the method for claim 15, it is characterised in that:
In first method, in the dipping solution described in step (2) and/or step (4), in addition to active metal component, possibly together with
Phosphorus, one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate of phosphorus source, the introduction volume of phosphorus with
P2O5Meter accounts for the 1%～6% of final catalyst for hydro-upgrading weight；
Or in second method, in the dipping solution described in step B and/or step D, in addition to active metal component, possibly together with phosphorus,
One or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate of phosphorus source, the introduction volume of phosphorus is with P2O5
Meter accounts for the 1%～6% of final catalyst for hydro-upgrading weight.
The method of 24. 1 kinds of heavy distillate hydro-upgradings, it is characterised in that use the arbitrary described hydrogenation of claim 1～14
Modifying catalyst.
25. in accordance with the method for claim 24, it is characterised in that: described heavy distillate is diesel oil.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229835A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工集团公司 | Light oil products hydrogenation treatment catalyst containing moly and/or tungsten, and its prepn. method |
| CN1289828A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229835A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工集团公司 | Light oil products hydrogenation treatment catalyst containing moly and/or tungsten, and its prepn. method |
| CN1289828A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
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