CN104667961B - Catalyst for hydro-upgrading and preparation method thereof - Google Patents
Catalyst for hydro-upgrading and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of catalyst for hydro-upgrading and preparation method thereof.In this catalyst for hydro-upgrading, carrier includes aluminium oxide and molecular sieve, and active metal component is Mo, W, Co and Ni, and wherein active metal component concentration distribution situation on each catalyst granules cross section is as follows: Co0/Co1＜ Co1/2/Co1＜ 1, Mo0/Mo1＜ Mo1/2/Mo1＜ 1, Ni0/Ni1＞ Ni1/2/Ni1＞ 1, W0/W1＞ W1/2/W1＞ 1, containing polyhydric alcohol in described catalyst.Its preparation method is as follows: carrier is impregnated by the unsaturated infusion process fountain solution containing adsorbent I, the dipping solution containing active metal Mo, Co again, drying and roasting, then by saturated dipping or excess infusion process with containing the adsorbent II i.e. solution impregnation of polyhydric alcohol, impregnate W, Ni active metal solution again, obtain after drying.This catalyst, during diesel oil hydrogenation modification, has deep hydrodesulfurizationof activity, and can improve the combination properties such as Cetane number in the case of keeping diesel yield higher.
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, W, 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, Mo0/Mo1＜ Mo1/2/Mo1＜ 1, Ni0/Ni1＞ Ni1/2/Ni1＞ 1, W0/W1＞ W1/2/W1＞ 1；Described catalyst contains
Organic substance A i.e. polyhydric alcohol, the number-average molecular weight of polyhydric alcohol is 400～10000, and polyhydric alcohol is the 0.05% ~ 10.0% of vehicle weight,
It is preferably 1.0% ~ 10.0%.
In catalyst for hydro-upgrading of the present invention, polyhydric alcohol be number-average molecular weight be the polyhydric alcohol of 400～10000, be preferably
Number-average molecular weight is the polyhydric alcohol of 1000～8000, and described polyhydric alcohol can be PTMEG, preferably Polyethylene Glycol.
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, Ni or W, and B represents active metallic element Mo, Co, Ni or W,
Wherein A with B can be identical, it is also possible to different；With any point i.e. outer most edge point of catalyst granules cross section outer most edge for rising
Initial 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 segment,
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 location point chosen
Distance accounts for the ratio of the length of above-mentioned straight-line segment, and the value of m and n is 0 ~ 1, wherein m(or n) value be 0,1/4,1/2,3/4,
Represent respectively when 1 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
Time selected 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 metal unit
Element Mo, Co, Ni or W replace, m and n is directly with defined location point on the above-mentioned straight-line segment of digitized representation of 0～1, uses x1
Or x2 represents arbitrary location point on above-mentioned straight-line segment, such as, Co0/Co1Representing that A and B is Co, m=0, n=1 i.e. represent and urge
The ratio of the concentration of the concentration of Elements C o and central spot Elements C o, Ni at catalyst particles cross section outer most edge point1/2/Ni1Represent
A and B is Ni, and 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
When the distance of selected point accounts for the 1/2 of above-mentioned straight-line segment length, at selected point position, the concentration of element Ni is first with central spot
The ratio of the concentration of element Ni.The straight-line segment that x1 and x2 in the present invention obtains at the above-mentioned outer most edge point of connection and central point respectively
On the location point (but not including outer most edge point and central point) arbitrarily chosen, and from outer most edge point to x1 the distance of point less than from
Outer rim point is to the distance that is 0 ＜ x1 ＜ x2 ＜ 1 of x2 point.
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), 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), Mox1/
Mo1(A and B is Mo, m=x1, n=1), Mox2/Mo1(A and B is Mo, m=x2, n=1), W0/W1(A and B is W, m=0, n=
1), W1/4/W1(A and B is W, m=1/4, n=1), W1/2/W1(A and B is W, m=1/2, n=1), W3/4/W1(A and B is W, m=
3/4, n=1), Wx1/W1(A and B is W, m=x1, n=1), Wx2/W1(A and B is W, m=x2, n=1).
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；Mo0/Mo1With Mo1/2/Mo1Ratio be 0.2 ~ 0.8, preferably 0.2 ~ 0.7, W0/W1With W1/2/W1Ratio 1.5 ~
2.6, preferably 1.7 ~ 2.5.
In catalyst for hydro-upgrading of the present invention, active metal component distribution on catalyst granules cross section is the most such as
Under: Co0/ Co1＜ Co1/4/ Co1＜ Co1/2/ Co1。
In catalyst for hydro-upgrading of the present invention, active metal component distribution on catalyst granules cross section is the most such as
Under: Co1/2/ Co1＜ Co3/4/Co1＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component distribution on catalyst granules cross section is the most such as
Under: Mo0/Mo1＜ Mo1/4/Mo1＜ Mo1/2/Mo1。
In catalyst for hydro-upgrading of the present invention, active metal component distribution on catalyst granules cross section is the most such as
Under: Mo1/2/Mo1＜ Mo3/4/Mo1＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component distribution on catalyst granules cross section is the most such as
Under: Ni0/Ni1＞ Ni1/4/Ni1＞ Ni1/2/Ni1。
In catalyst for hydro-upgrading of the present invention, active metal component distribution on catalyst granules cross section is the most such as
Under: Ni1/2/Ni1＞ Ni3/4/Ni1＞ 1.
In catalyst for hydro-upgrading of the present invention, active metal component distribution on catalyst granules cross section is the most such as
Under: W0/W1＞ W1/4/W1＞ W1/2/W1。
In catalyst for hydro-upgrading of the present invention, active metal component distribution on catalyst granules cross section is the most such as
Under: W1/2/W1＞ W3/4/W1＞ 1.
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；Mo0/Mo1With Mo1/4/Mo1Ratio be 0.30 ~ 0.90, preferably 0.30 ~ 0.85；Mo1/4/Mo1With
Mo1/2/Mo1Ratio be 0.4 ~ 0.9, preferably 0.4 ~ 0.87；Ni0/Ni1With Ni1/4/Ni1Ratio be 1.2 ~ 1.8, be preferably
1.3~1.7；Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.1 ~ 1.7, preferably 1.2 ~ 1.6；W0/W1With W1/4/W1Ratio be
1.2 ~ 1.8, preferably 1.3 ~ 1.7；W1/4/W1With W1/2/W1Ratio be 1.1 ~ 1.7, preferably 1.2 ~ 1.6.
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: Mo0/Mo1＜ Mox1/Mo1＜ Mox2/Mo1＜ 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: W0/W1＞ Wx1/W1＞ Wx2/W1＞ 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 distribution is as follows: the concentration of Co is substantially gradually increased, and the concentration of Mo the most gradually increases
Adding, the concentration of Ni substantially gradually decreases, and the concentration of W substantially gradually decreases.
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 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 45wt% ~
84wt%, preferably 45% ~ 80%, more preferably surplus, Mo is with MoO3The content of meter is 6wt%～26wt%, and Co is with CoO
The content of meter is 1wt%～8wt%, and W is with WO3The content of meter is 6wt%～28wt%, the content that Ni counts with NiO as 1wt%～
8wt%；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%.
In the catalyst for hydro-upgrading of the present invention, Ni/W atomic ratio is 0.11 ~ 4.1, preferably 0.13 ~ 3.9, and Co/Mo is former
Son ratio is 0.07 ~ 2.5, preferably 0.08 ~ 2.3.
In catalyst for hydro-upgrading of the present invention, it is positioned at the concentration of Mo at the outer most edge point of catalyst granules cross section
The concentration i.e. Mo of ratio with central spot Mo0/Mo1It is 0.08～0.80, is positioned at Co at the outer most edge point of catalyst granules cross section
The concentration i.e. Co of ratio of concentration and central spot Co0/Co1It is 0.08～0.80.
In the catalyst for hydro-upgrading of the present invention, be positioned at the outer most edge point of catalyst granules cross section the concentration of W with in
The concentration i.e. W of ratio of W at heart point0/W1Be 1.2～7.0, be positioned at the outer most edge point of catalyst granules cross section the concentration of Ni with in
The concentration i.e. Ni of ratio of Ni at heart point0/Ni1It is 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
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.
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, 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.
In the catalyst for hydro-upgrading of the present invention, containing Organic substance B, described Organic substance B be carbon number be 2 ~ 20
One or more in organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound.
The Organic substance contained in the catalyst for hydro-upgrading of the present invention i.e. Organic substance A and/or Organic substance B, rubs with Mo atom
That ratio is 0.002:1～2.0:1, preferably 0.02:1 ~ 1.5:1, more preferably 0.02:1 ~ 1.0:1.
Described organic compounds containing nitrogen is the Organic substance including at least a covalent bond nitrogen-atoms, in organic compounds containing nitrogen
Carbon number is 2 ~ 20, specifically such as one or more in ethylenediamine, hexamethylene diamine etc., is preferably except comprising at least one covalent bond
Nitrogen-atoms outside, also including at least a hydroxyl or the organic compound of carboxy moiety, such as: ethanolamine, diethanolamine, three ethanol
Amine, one or more in ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and ring ethylenediaminetetraacetic acid etc..
Described organic compounds containing sulfur is the Organic substance including at least a covalent bond sulphur atom, in organic compounds containing sulfur
Carbon number is generally 2 ~ 20.Such as sulphonic acids (general formula R-SO3H) R therein is the alkyl containing 2 ~ 20 carbon atoms, such as benzene sulphur
One or more in acid, DBSA, p-methyl benzenesulfonic acid etc..Can be containing one or many in organic compounds containing sulfur
Individual carboxyl, carbonyl, ester, ether, hydroxyl, the group of sulfydryl replace, such as in TGA, mercaptopropionic acid, dimercaptopropanol, BAL etc.
Plant or multiple.In addition to above-mentioned sulfur-containing compound, sulfone and sulfoxide compound can be comprised, such as dimethyl sulfoxide, dimethyl sulfone etc.
In one or more.
Described oxygen-containing organic compound is at least to contain a carbon atom and the Organic substance of an oxygen atom.Preferably comprise to
Few two oxygen atoms and the organic compound of two carbon atoms, oxygen-containing organic compound carbon number is preferably 2 ~ 20.Oxygen-containing portion
Dividing can be carboxyl, carbonyl, hydroxylic moiety or combinations thereof.These materials can be acids, alcohols, ethers, saccharide, ketone, phenol
One or more in class, aldehydes and lipid.As follows: acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, lemon
Lemon acid, ethylene glycol, propylene glycol, butanediol, glycerol, diethylene glycol, dipropylene glycol, 2,2'-ethylenedioxybis(ethanol)., three butanediols, tetraethylene glycol (TEG), poly-second two
One or more in alcohol, glucose, fructose, lactose, maltose, sucrose etc..
The preparation method of the catalyst for hydro-upgrading of the present invention, including:
A, with containing adsorbent I fountain solution impregnate carrier, obtain the carrier containing adsorbent I, the use of described adsorbent I
Amount is the 0.1% ~ 10.0% of vehicle weight, and described adsorbent I is one or more in organic carboxyl acid and its esters, described
Dipping uses unsaturation dipping；
B, with the dipping solution impregnation steps A gains containing Co, Mo, through being dried and roasting, obtain in the middle of catalyst
Body；
C, with the solution impregnation catalyst intermediate containing adsorbent II, after drying, obtain the catalysis containing adsorbent II
Agent intermediate, wherein adsorbent II consumption is the 0.1% ~ 10.0% of vehicle weight；Described adsorbent II is that number-average molecular weight is
The polyhydric alcohol of 400～10000, described dipping uses saturated dipping or excess dipping；
D, with the dipping solution impregnation steps C gains containing W, Ni, through being dried, 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.
In the inventive method, described adsorbent I is one or more in organic carboxyl acid and its esters, its carbon atom
Number is not more than 15, generally 2～15.Described organic acid includes acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, lemon
Lemon acid, trichloroacetic acid, chloroacetic acid etc., TGA, mercaptopropionic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ring ethylenediamine tetraacetic
One or more in acetic acid etc..One or more in the ammonium salt of the preferred above-mentioned organic carboxyl acid of organic carboxylate.
In the inventive method, adsorbent II be number-average molecular weight be the polyhydric alcohol of 400～10000, be preferably number equal molecules
Amount is the polyhydric alcohol of 1000～8000, and described polyhydric alcohol can be PTMEG, preferably Polyethylene Glycol.
The inventive method, solution containing adsorbent II and containing in the fountain solution of adsorbent I, use water and/or the ethanol to be
Solvent.
The inventive method, impregnates carrier with the fountain solution containing adsorbent I in step A, and dipping therein is preferably with insatiable hunger
With spray, the time of spraying is generally 1min～40min, preferably 2min～20min.The body of the fountain solution containing adsorbent I used
The ratio of long-pending imbibition volume saturated with carrier is 0.02 ~ 0.4.When spraying the fountain solution containing adsorbent I, atomizing effect should be selected good
Shower nozzle, make solution evenly spread on carrier.After fountain solution dipping carrier containing adsorbent I, can be through drying steps, also
Step B can be directly entered without drying steps.Drying condition is as follows: temperature is generally 60 DEG C～250 DEG C, and preferably 100
～200 DEG C, time 0.5h～20h, preferably 1h～6h.
The inventive method, when step B is with dipping solution containing Mo, Co, can be through health preserving, it is possible to without health preserving, as
Needing health preserving, conditioned time is 0.5～4.0h, then is dried.Described drying condition is as follows: baking temperature is 70 DEG C～300
DEG C, preferably 70 DEG C～200 DEG C, more preferably 100 DEG C～160 DEG C, drying time 0.5h～20h, preferably 1h～6h.
Described roasting condition is as follows: sintering temperature is 300 DEG C～750 DEG C, preferably 400 DEG C～650 DEG C, roasting time be 0.5h～
20h, preferably 1h～6h.
The inventive method, step C, with containing adsorbent II solution impregnation catalyst intermediate, uses incipient impregnation or mistake
Amount 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, preferably 100～200
DEG C, drying 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 W, Ni, it is possible to
Without health preserving, as needed health preserving, conditioned time is 0.5～6.0h, then is dried, and drying condition is as follows: baking temperature is 70
DEG C～300 DEG C, preferably 70 DEG C～200 DEG C, more preferably 100 DEG C～160 DEG C of drying times are 0.5h～20h, preferably
For 1h～6h.The drying condition wanting rate-determining steps (4) makes in final catalyst for hydro-upgrading containing adsorbent II.
Those skilled in the art are according to the character of adsorbent II selected species, it is possible to select suitable drying condition, thus
Make in final catalyst for hydro-upgrading containing adsorbent II.
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.After active metal component solution impregnating carrier, need through being dried.Live
Property metallic solution preparation method is known to technical staff, and its solution concentration can be regulated by the consumption of each compound, from
And prepare the catalyst of specified activity constituent content.The raw material of required active component is generally the types such as salt, oxide or acid
Compound, as molybdenum source is generally from one or more in molybdenum oxide, ammonium molybdate, ammonium paramolybdate, nickel source is from nickel nitrate, carbon
Acid nickel, basic nickel carbonate, Nickel dichloride., nickel oxalate in one or more, cobalt source from cobalt nitrate, cobalt carbonate, basic cobaltous carbonate,
One or more in cobaltous chloride, cobalt oxalate, tungsten source is generally from ammonium metatungstate.In described dipping solution, except activity gold
Belong to outside component, it is also possible to containing phosphorus-containing compound, as in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate etc.
One or more.The catalyst for hydro-upgrading of the present invention preferably comprises phosphorus, with P2O5Meter mass content in the catalyst 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.
In the inventive method, Organic substance B introduces catalyst and introduces after step D and/or step D in catalyst, permissible
Infusion process is individually used to introduce, it is also possible to introduce with active metal component total immersion, such as Organic substance B is added containing of step D
The dipping solution of Mo, Ni introduces with active metal component total immersion, or impregnates in the step D dipping solution containing Mo, Ni
After, then impregnate Organic substance B introducing.After introducing Organic substance B, typically through drying steps, described drying condition is as follows: dry
Dry temperature is 60 DEG C～250 DEG C, preferably 70 ~ 200 DEG C, preferably 100～200 DEG C, and drying time, 0.5h～20h, was preferably
1h～6h.
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 and Mo from catalyst granules outer surface to center in by
The cumulative trend added, Ni and W is from catalyst granules outer surface to center in the trend gradually decreased, and the activity of uneven distribution is golden
Belong to component to match with acidic components molecular sieve in carrier, and containing polyhydric alcohol, this catalyst is particularly well-suited to the hydrogenation of diesel oil
In upgrading processes, while diesel deep desulfurization, in the case of keeping diesel yield higher, improve diesel-fuel cetane number
Etc. combination property.
Catalyst for hydro-upgrading prepared by the present invention, by the unsaturation dipping fountain solution containing adsorbent I, makes carrier granular
A part of adsorption potential on marginal position surface is adsorbed agent and occupies, when dipping is containing the solution of active metal Mo, Co, decrease Mo,
Co in the absorption of carrier edge position, makes the concentration of active metal Mo, Co in the trend being gradually increased from marginal position to center,
The fountain solution containing adsorbent II by saturated dipping or excess dipping, after then impregnating W, Ni active metal solution, slows down W, Ni
To the diffusion velocity at catalyst granules center, so that the concentration that W, Ni of rear leaching are in each catalyst granules is from marginal position
To center in the trend gradually decreased, make active metal component and the acidic components molecular sieve phase in carrier of this uneven distribution
Coordinate, improve the performances such as the deep hydrodesulfurizationof performance of catalyst, and suitable open loop, isomery, cracking, adding for diesel oil
In hydrogen upgrading processes, while diesel deep desulfurization, diesel oil 16 can be improved in the case of keeping diesel yield higher
The combination properties such as alkane value.Additionally, the present invention is by controlling the preparation condition of catalyst for hydro-upgrading, polyhydric alcohol is made to be present in finally
Catalyst for hydro-upgrading in, active metal sulfuration after, it is possible to form more lamination number, make the hydrogenation activity of catalyst obtain
Improve further.
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 3 gained catalyst C5 in active metal component Ni and Co on this cross section concentration distribution
Figure.Wherein abscissa is each position point on this cross section, vertical coordinate be concentration at a certain location point with this cross section in
The ratio of the concentration at heart point.
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: W is 53 °, and Mo is 38 °, and Ni is 24 °, and Co is 26 °,
Correction method: ZAF correction method, the standard specimen of use: pure metal oxides standard specimen (respectively NiO, CoO, MoO3And WO3), precision:
Less than 1%, secondary electron image resolution: 3nm(LaB6), linear system: Ni and Co uses KαLinear system, Mo uses LαLinear system, W uses Mα
Linear 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 3 gained catalyst C5 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, Co, P impregnation liquid used is MoO3, Co predecessor is basic cobaltous carbonate, P
Predecessor is phosphoric acid, and in W, Ni impregnation liquid used, W predecessor is ammonium metatungstate, and Ni predecessor is nickel nitrate.
Embodiment 1
Weigh tartaric acid 10g, stirring and dissolving in 30g water, prepare fountain solution I.Take S1 carrier 200g, 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
The above-mentioned carrier of impregnation liquid incipient impregnation, gained sample average is divided into three parts, wherein first part of sample not health preserving, through 120 DEG C
Be dried 3h, after 480 DEG C of roasting 2h, it is thus achieved that sample be designated as B1；Second sample health preserving 1h, through 120 DEG C of dry 3h, 480 DEG C of roastings
After burning 2h, the sample prepared is designated as B2.
Weigh 6g Macrogol 2000 (i.e. molecular weight is the Polyethylene Glycol of 2000, lower same), stir in the water measured
Dissolve, obtained solution II.With this solution II incipient impregnation sample B1 and B2 respectively, then carry out the health preserving of 10h, through 120
After DEG C dry 3h, the sample prepared is designated as Z1 and Z2 respectively.
Spray above-mentioned Z1 and Z2 sample with the impregnation liquid equal-volume containing W, Ni respectively, directly enter without health preserving after spraying end
120 DEG C of dry 3h of row, it is thus achieved that catalyst be designated as C1 and C2 respectively.
Embodiment 2
Weigh malic acid 2g, stirring and dissolving in 16g ethanol, prepare fountain solution I.Take S2 carrier 200g, by equal for fountain solution I
Even spraying in carrier S 2, the time of spraying is 5min.With the above-mentioned carrier of impregnation liquid incipient impregnation containing Mo, Co, P, dipping knot
Health preserving 1h after bundle, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that sample be designated as B3.
Weigh 16g cetomacrogol 1000, stirring and dissolving in the water measured, obtained solution II.With this solution II body such as grade
Long-pending impregnated sample B3, then carries out the health preserving of 5h, and after 120 DEG C of dry 3h, the sample prepared is designated as Z3.
Spray Z3 sample with the impregnation liquid equal-volume containing W, Ni, after spraying end, sample average is divided into two parts, Qi Zhong
The a direct 120 DEG C of dry 3h of sample, it is thus achieved that catalyst be designated as C3；Second sample health preserving 1h, 120 DEG C of dry 3h, prepare
Catalyst be designated as C4.
Embodiment 3
Weigh citric acid and each 7g of malonic acid, stirring and dissolving in 40g water, prepare fountain solution I.Take S3 carrier 200g, will
Fountain solution I uniformly sprays in carrier S 3, and the time of spraying is 25min.With containing Mo, Co, P above-mentioned load of impregnation liquid incipient impregnation
Body, dipping terminates rear health preserving 1h, and after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, the sample obtained is designated as B4.
Weigh 4g PEG 8000, stirring and dissolving in the aqueous solution measured, obtained solution II.With this solution II etc.
Volume 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 the impregnation liquid equal-volume containing W, Ni, directly through 120 DEG C of dry 3h, it is thus achieved that catalyst be designated as
C5。
Preparing glycerinated aqueous solution, equal-volume sprays part C5 sample, the glycerol of introducing and the rubbing of Mo and W on catalyst
You than be 0.03:1, after spraying end, through 120 DEG C of dry 3h, it is thus achieved that catalyst be designated as C6.
Comparative example 1
Take S1 carrier 100g, after the above-mentioned carrier of impregnation liquid incipient impregnation containing Mo, Co, P, through 120 DEG C of dry 3h,
After 480 DEG C of roasting 2h, it is thus achieved that sample be designated as B5.With the impregnation liquid incipient impregnation B5 containing W, Ni, 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 2
Take S4 carrier 100g, use the preparation method identical with C5 catalyst to prepare, it is thus achieved that sample be designated as C8.
Table 2 embodiment forms with comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| Catalyst forms | ||||||||
| Mo(is with MoO3Meter), wt% | 19.2 | 19.4 | 19.4 | 19.3 | 19.4 | 19.5 | 19.3 | 19.5 |
| Co(is in terms of CoO), wt% | 13.1 | 13.2 | 13.3 | 13.6 | 13.3 | 13.3 | 13.2 | 13.4 |
| Ni(is in terms of NiO), wt% | 2.4 | 2.3 | 2.4 | 2.3 | 2.4 | 2.4 | 2.3 | 2.2 |
| P(is with P2O5Meter), wt% | 2.7 | 2.7 | 2.6 | 2.5 | 2.6 | 2.6 | 2.6 | 2.7 |
| Mo(is with MoO3Meter), wt% | 1.45 | 1.48 | 1.46 | 1.47 | 1.47 | 1.46 | 1.45 | 1.48 |
| Carrier * | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Character | ||||||||
| Specific surface area, m2/g | 165 | 165 | 168 | 169 | 165 | 165 | 166 | 163 |
| Pore volume, mL/g | 0.34 | 0.34 | 0.33 | 0.33 | 0.33 | 0.33 | 0.34 | 0.34 |
In table 2, the aluminium oxide in carrier * i.e. C1, C2 and C7 and beta-molecular sieve, the aluminium oxide in C3 and C4 and Y molecular sieve,
Aluminium oxide and β and Y molecular sieve, the aluminium oxide in C8 in C5 and C6.
The concentration distribution in catalyst granules of table 3 embodiment and elements Mo in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| Mo0/Mo1 | 0.11 | 0.28 | 0.35 | 0.33 | 0.27 | 0.29 | 0.98 | 0.29 |
| Mo1/4/Mo1 | 0.30 | 0.40 | 0.68 | 0.70 | 0.38 | 0.39 | 1.0 | 0.41 |
| Mo1/2/Mo1 | 0.64 | 0.77 | 0.87 | 0.89 | 0.79 | 0.80 | 0.99 | 0.79 |
| Mo3/4/Mo1 | 0.89 | 0.93 | 0.97 | 0.98 | 0.94 | 0.95 | 0.98 | 0.94 |
The concentration distribution in catalyst granules of table 4 embodiment and Elements C o in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| Co0/ Co1 | 0.12 | 0.25 | 0.32 | 0.32 | 0.28 | 0.30 | 0.99 | 0.30 |
| Co1/4/ Co1 | 0.30 | 0.44 | 0.72 | 0.74 | 0.43 | 0.44 | 1.01 | 0.45 |
| Co1/2/ Co1 | 0.65 | 0.79 | 0.88 | 0.90 | 0.81 | 0.80 | 0.98 | 0.82 |
| Co3/4/ Co1 | 0.92 | 0.94 | 0.98 | 1.00 | 0.95 | 0.95 | 1.00 | 0.95 |
Table 5 embodiment and element W in the comparative example catalyst concentration distribution in catalyst granules
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| W0/W1 | 2.78 | 2.76 | 2.82 | 2.48 | 2.55 | 2.48 | 1.0 | 2.53 |
| W1/4/W1 | 1.79 | 1.81 | 1.84 | 1.65 | 1.70 | 1.66 | 1.02 | 1.69 |
| W1/2/W1 | 1.24 | 1.25 | 1.31 | 1.20 | 1.23 | 1.20 | 0.99 | 1.22 |
| W3/4/W1 | 1.08 | 1.07 | 1.09 | 1.07 | 1.09 | 1.08 | 1.01 | 1.09 |
Table 6 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 |
| Ni0/ Ni1 | 2.83 | 2.81 | 2.99 | 2.57 | 2.61 | 2.53 | 0.98 | 2.59 |
| Ni/4/ Ni1 | 1.89 | 1.87 | 1.97 | 1.72 | 1.77 | 1.73 | 1.0 | 1.76 |
| Ni1/2/ Ni1 | 1.26 | 1.25 | 1.34 | 1.25 | 1.23 | 1.22 | 0.99 | 1.23 |
| Ni3/4/ Ni1 | 1.08 | 1.10 | 1.12 | 1.09 | 1.07 | 1.07 | 0.98 | 1.07 |
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 |
| Diesel oil | ||||
| Yield, wt% | 98.1 | 98.0 | 98.2 | 97.5 |
| Density (20 DEG C)/g.cm-3 | 0.8392 | 0.8396 | 0.8388 | 0.8390 |
| T95, DEG C | 349 | 350 | 348 | 349 |
| Condensation point, DEG C | -21 | -20 | -22 | -21 |
| Cetane number | 47.1 | 46.8 | 48.0 | 47.9 |
| Sulfur, g/g | 8 | 9 | 7 | 9 |
Table 8 continues
| Catalyst | C5 | C6 | C7 | C8 |
| Diesel oil | ||||
| Yield, wt% | 97.5 | 97.6 | 97.5 | 99.5 |
| Density (20 DEG C)/g.cm-3 | 0.8387 | 0.8385 | 0.8415 | 0.8572 |
| T95, DEG C | 348 | 347 | 350 | 355 |
| Condensation point, DEG C | -21 | -22 | -19 | 4 |
| Cetane number | 47.8 | 48.1 | 45.0 | 34.5 |
| Sulfur, g/g | 7 | 6 | 12 | 8 |
Claims (33)
1. a catalyst for hydro-upgrading, carrier includes aluminium oxide and molecular sieve, and active metal component is Co, Mo, Ni, W, wherein
Active metal component concentration distribution on each catalyst granules cross section is as follows: Co0/Co1＜ Co1/2/Co1＜ 1, Mo0/
Mo1＜ Mo1/2/Mo1＜ 1, Ni0/Ni1＞ Ni1/2/Ni1＞ 1, W0/W1＞ W1/2/W1＞ 1；Containing Organic substance A in described catalyst
I.e. polyhydric alcohol, polyhydric alcohol be number-average molecular weight be the polyhydric alcohol of 400～10000, the content of polyhydric alcohol is the 0.05% of vehicle weight
～10.0%；
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, Ni or W, B represents active metallic element Mo, Co, Ni or W；Any one with catalyst granules cross section outer most edge
Point is designated as 0 for starting point, is designated as 1 with the central point of catalyst granules cross section for terminal, connects starting point and terminal obtains directly
Line line segment, m and n be illustrated respectively on above-mentioned straight-line segment the location point chosen, and the value of m and n represents from starting point to choosing
The distance of location 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 is direct
Using active metallic element Mo, Co, Ni or W to replace, m and n is directly with determining on the above-mentioned straight-line segment of digitized representation of 0～1
Location point,
Wherein, described catalyst for hydro-upgrading, on the basis of the weight of catalyst, the content of carrier be 45wt%～
84wt%, Mo are with MoO3The content of meter is 6wt%～26wt%, and the content that Co counts with CoO is as 1wt%～8wt%, and W is with WO3Meter
Content be 6wt%～28wt%, the content that Ni counts with NiO is as 1wt%～8wt%；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%.
2. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, the content of polyhydric alcohol
For vehicle weight 0.1%～9.0%.
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 0.2～0.8；
(2) Mo0/Mo1With Mo1/2/Mo1Ratio be 0.2～0.8；
(3) Ni0/Ni1With Ni1/2/Ni1Ratio 1.5～2.6；
(4) W0/W1With W1/2/W1Ratio be 1.5～2.6.
4. 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) Mo0/Mo1With Mo1/2/Mo1Ratio be 0.2～0.7；
(3) Ni0/Ni1With Ni1/2/Ni1Ratio 1.7～2.5；
(4) W0/W1With W1/2/W1Ratio be 1.7～2.5.
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＜ 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) W0/W1＞ W1/4/W1＞ W1/2/W1；
(6) W1/2/W1＞ W3/4/W1＞ 1；
(7) Mo0/Mo1＜ Mo1/4/Mo1＜ Mo1/2/Mo1；
(8) Mo1/2/Mo1＜ Mo3/4/Mo1＜ 1.
6. 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) Mo0/Mo1＜ Mox1/Mo1＜ Mox2/Mo1＜ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
(3) Ni0/Ni1＞ Nix1/Ni1＞ Nix2/Ni1＞ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
(4) W0/W1＞ Wx1/W1＞ Wx2/W1＞ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
7. according to the catalyst described in claim 5 or 6, 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) Mo0/Mo1With Mo1/4/Mo1Ratio be 0.3～0.9；
(4) Mo1/4/Mo1With Mo1/2/Mo1Ratio be 0.4～0.9；
(5) Ni0/Ni1With Ni1/4/Ni1Ratio be 1.2～1.8；
(6) Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.1～1.7；
(7) W0/W1With W1/4/W1Ratio be 1.2～1.8；
(8) W1/4/W1With W1/2/W1Ratio be 1.1～1.7.
8. according to the catalyst described in claim 5 or 6, 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) Mo0/Mo1With Mo1/4/Mo1Ratio be 0.3～0.85；
(4) Mo1/4/Mo1With Mo1/2/Mo1Ratio be 0.4～0.87；
(5) Ni0/Ni1With Ni1/4/Ni1Ratio be 1.3～1.7；
(6) Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.2～1.6；
(7) W0/W1With W1/4/W1Ratio be 1.3～1.7；
(8) W1/4/W1With W1/2/W1Ratio be 1.2～1.6.
9. 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 Co
Being gradually increased on Ben, the concentration of Mo is substantially gradually increased, and the concentration of Ni substantially gradually decreases, and the concentration of W is the most gradually
Reduce.
10. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, Ni/W atomic ratio
Being 0.11～4.1, Co/Mo atomic ratio is 0.07～2.5.
11. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, be positioned at catalyst
The concentration i.e. Mo of ratio of the concentration of Mo and central spot Mo at the outer most edge point of particle cross section0/Mo1It is 0.08～0.80, is positioned at and urges
The concentration i.e. Co of ratio of the concentration of Co and central spot Co at the outer most edge point of catalyst particles cross section0/Co1It is 0.08～0.80.
12. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, be positioned at catalyst
The concentration i.e. W of ratio of the concentration of W and central spot W at the outer most edge point of particle cross section0/W1It is 1.2～7.0, is positioned at catalyst particles
The concentration i.e. Ni of ratio of concentration and central spot Ni of Ni at the outer most edge point of grain cross section0/Ni1It is 1.2～7.0.
13. 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.
14. 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%。
15. according to the catalyst described in claim 1, it is characterised in that described polyhydric alcohol is Polyethylene Glycol.
16. according to the catalyst described in claim 1, it is characterised in that the number-average molecular weight of described polyhydric alcohol be 1000～
8000。
17. 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.
18. 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%.
19. 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%.
20. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, containing Organic substance
B, described Organic substance B be carbon number be the organic compounds containing nitrogen of 2～20, organic compounds containing sulfur and oxygen-containing organic close
One or more in thing.
21. according to the catalyst described in claim 20, it is characterised in that in described catalyst for hydro-upgrading, Organic substance i.e. has
Machine thing A and Organic substance B, with Mo atomic molar than for 0.002:1～2.0:1.
22. according to the catalyst described in claim 21, it is characterised in that in described catalyst for hydro-upgrading, Organic substance i.e. has
Machine thing A and Organic substance B, with Mo atomic molar than for 0.02:1～1.5:1.
23. according to the catalyst described in claim 21, it is characterised in that in described catalyst for hydro-upgrading, Organic substance i.e. has
Machine thing A and Organic substance B, with Mo atomic molar than for 0.02:1～1.0:1.
The preparation method of the arbitrary described catalyst of 24. claim 1～17, including:
A, with containing adsorbent I fountain solution impregnate carrier, obtain the carrier containing adsorbent I, the consumption of adsorbent I accounts for carrier weight
The 0.1%～10.0% of amount, described adsorbent I is one or more in organic carboxyl acid and its esters, and described dipping uses
Unsaturated dipping；
B, with the dipping solution impregnation steps A gains containing Co, Mo, through being dried and roasting, obtain catalyst intermediate；
C, with the solution impregnation catalyst intermediate containing adsorbent II, after drying, obtain the carrier containing adsorbent II, wherein inhale
Attached dose of II consumption is the 0.1%～10.0% of vehicle weight；Described adsorbent II be molecular weight be the poly-second two of 400～10000
Alcohol, described dipping uses saturated dipping or excess dipping；
D, with the dipping solution impregnation steps C gains containing W, Ni, through being dried, obtain catalyst.
25. in accordance with the method for claim 24, 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.
26. in accordance with the method for claim 24, 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 selected from the ammonium salt of above-mentioned organic carboxyl acid
Plant or multiple.
27. in accordance with the method for claim 24, it is characterised in that described adsorbent II is Polyethylene Glycol.
28. in accordance with the method for claim 24, it is characterised in that: the solution containing adsorbent II and the profit containing adsorbent I
In wet liquid, using water and/or ethanol is solvent.
29. in accordance with the method for claim 24, it is characterised in that: described method at least uses at least one side in a～e
Case:
Using unsaturation to spray when impregnating with the fountain solution containing adsorbent I in a, step A, the time of spraying is 1min～40min；Institute
The ratio of volume imbibition saturated with carrier volume of the fountain solution containing adsorbent I be 0.02～0.4；
After b, step A contain the fountain solution dipping of adsorbent I, it is directly entered step through drying steps or without drying steps
Rapid B；Described drying condition is as follows: temperature is 60 DEG C～250 DEG C, time 0.5h～20h；
When c, step B impregnate with the dipping solution containing Mo, Co, through health preserving or without health preserving, then it is dried, as needed
Health preserving, conditioned time is 0.5～4.0h；Described drying condition is as follows: baking temperature is 70 DEG C～300 DEG C, drying time
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, step C are with containing adsorbent II solution impregnation catalyst intermediate, after dipping terminates, sample through health preserving or without
Health preserving, drying step, if through health preserving, conditioned time is 1～12h；Drying condition described in step C is as follows: be dried
Temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h；
E, step D, with after the dipping solution impregnation steps C gains containing W, Ni, through health preserving or without health preserving, then are entered
Row is dried and roasting, and as needed health preserving, conditioned time is 0.5～6.0h；Described drying condition is as follows: baking temperature be 70 DEG C～
300 DEG C, drying time is 0.5h～20h.
30. in accordance with the method for claim 24, it is characterised in that: in the dipping solution described in step B and/or step D,
In addition to active metal component, possibly together with phosphorus, phosphorus source is in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate
One or more；The addition of phosphorus is with P2O5It is 1%～6% that meter makes its mass content in catalyst for hydro-upgrading.
31. in accordance with the method for claim 24, it is characterised in that: Organic substance B introduces after step D and/or step D and urges
In agent, make in the catalyst of gained containing Organic substance B.
The method of 32. 1 kinds of heavy distillate hydro-upgradings, it is characterised in that use the arbitrary described hydrogenation of claim 1～23
Modifying catalyst.
33. according to the method described in claim 32, it is characterised in that: described heavy distillate is diesel oil.
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| 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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