CN104588114B - Catalyst for hydrogenating hydrocarbon oil and preparation method thereof - Google Patents
Catalyst for hydrogenating hydrocarbon oil and preparation method thereof Download PDFInfo
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- CN104588114B CN104588114B CN201310527466.2A CN201310527466A CN104588114B CN 104588114 B CN104588114 B CN 104588114B CN 201310527466 A CN201310527466 A CN 201310527466A CN 104588114 B CN104588114 B CN 104588114B
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Abstract
The invention discloses a kind of catalyst for hydrogenating hydrocarbon oil and preparation method thereof.This hydrotreating catalyst, uses alumina-based supports, and active metal component is Mo, W, Co and Ni, and wherein active metal component concentration distribution on each catalyst granules cross section is as follows: Ni0/Ni1＞ Ni1/2/Ni1＞ 1, W0/W1＞ W1/2/W1＞ 1, Mo and Co is substantially uniformly distributed, containing polyhydric alcohol in described catalyst.The method first prepares the alumina-based supports containing Co and Mo, then saturated dipping or the excess infusion process solution impregnation alumina-based supports containing adsorbent are used, again by the solution impregnation containing active metal component Ni, W, through dried, obtain hydrotreating catalyst.The hydrotreating catalyst of the present invention is particularly suitable as deep hydrodesulfurizationof of diesel oil catalyst, has higher deep desulfuration activity.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, be particularly suitable as heavy distillate (especially
It is diesel oil) deep hydrodesulfurizationof catalyst.
Background technology
The requirement cleaned heavy distillate (particularly diesel oil) along with society is more and more higher, heavy distillate
Deep hydrodesulfurizationof technology just seems more and more important.Sulfur-containing compound in heavy distillate mainly have aliphatic sulfides,
Thioether, dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene etc., the most difficult removing is dibenzothiophenes, alkane
The thiophenes such as base benzothiophene and methyldibenzothiophene, especially with 4,6-dimethyl Dibenzothiophene (4,6-
And 2,4,6-trimethyl dibenzothiophenes (2,4,6-BMDBT) class formation is complicated and have the sulfur-bearing of space steric effect BMDBT)
Compound is most difficult to removing.The degree of depth to be reached and ultra-deep desulfurization, it is necessary to remove that these structures are complicated and sterically hindered big containing
Sulphur compound, and the generally the most difficult removing under the harsh operating conditions such as High Temperature High Pressure of these sulfur-containing compounds.Therefore, heavy
Distillate oil deep and ultra-deep desulfurization have significant difference with conventional hydrodesulfurization in reaction mechanism, and this just requires in the degree of depth
Particular/special requirement is had in the design of Hydrobon catalyst.
Hydrotreating catalyst is typically with alumina-based supports, lives with vib and group VIII metal for hydrogenation
Property metal component, wherein active metal component is the most equally distributed.CN99103007.9 discloses one
Light-end products hydrotreating catalyst containing molybdenum and/or tungsten.This catalyst contain load tungsten oxide on the alumina support and/
Or molybdenum oxide, nickel oxide and cobalt oxide, the content of described tungsten oxide and/or molybdenum oxide is that 4 weight % are to less than 10 weight %, nickel oxide
Content be 1～5%, the content of cobalt oxide is 0.01～1 weight %, and nickel and cobalt total atom number are the most former with nickel, cobalt, tungsten and/or molybdenum
The ratio of subnumber is 0.3～0.9.Compared with prior art, this catalyst has relatively low tenor and but has higher low temperature
Activity.This catalyst is particularly well-suited to the hydro-sweetening process of light-end products.
CN99113281.5 discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof.This catalyst is with oxidation
Aluminum or silicon-containing alumina are carrier, with W, Mo, Ni as active component, add phosphate builder.By using segmentation total immersion technology so that
Metal Distribution on catalyst is more uniform, and the activity of catalyst, particularly hydrodenitrogenationactivity activity are greatly improved.
The hydrotreating catalyst of these prior aries belongs to the Hydrobon catalyst of routine, can not effectively fit
Hydrodesulfurization for heavy distillate (especially diesel oil).Therefore, prior art is still required for a kind of hydrotreating catalyst,
It is particularly suited for the hydrodesulfurization (especially deep hydrodesulfurizationof) of heavy distillate (especially diesel oil).
Summary of the invention
For problems of the prior art, the invention provides a kind of hydrotreating catalyst and preparation method thereof.
This catalyst has higher hydrodesulfurization activity.
The hydrotreating catalyst of the present invention, uses alumina-based supports, and active metal component is Mo, W, Co and Ni, its
The concentration distribution on the cross section of each catalyst granules of the middle active metal component is as follows: Ni0/Ni1＞ Ni1/2/Ni1＞ 1,
W0/W1＞ W1/2/W1The concentration of ＞ 1, Mo and Co is substantially uniformly distributed, the most polynary containing Organic substance A in described catalyst
Alcohol, the number-average molecular weight of polyhydric alcohol is 400～10000, and polyhydric alcohol is the 0.05% ~ 10.0% of alumina-based supports weight, preferably
It is 0.1% ~ 9.0%.
In hydrotreating catalyst of the present invention, the Organic substance A i.e. number-average molecular weight of polyhydric alcohol is 400～10000, is preferably
1000～8000, 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), 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), 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 equal
For W, m=x2, n=1).
In hydrotreating catalyst of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Ni0/
Ni1With Ni1/2/Ni1Ratio 1.5 ~ 2.6, preferably 1.7 ~ 2.5, W0/W1With W1/2/W1Ratio 1.5 ~ 2.6, preferably 1.7 ~
2.5。
In hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst of the present invention, active metal component is in catalyst granules, and preferred version is as follows: 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,
It is 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 and Mo is substantially uniformly distributed, the concentration of Ni substantially by
The fewest, the concentration of W substantially gradually decreases.
In the present invention, described " substantially gradually decreasing along described straight-line segment " refers to described active metallic element
Concentration distribution presents generally in the whole interval from outer most edge point to central point along described straight-line segment and to gradually decrease
Trend, but it is interval to allow to there is one or more local；In this local is interval, the concentration distribution edge of described active metallic element
Described straight-line segment and present different trend (such as remain constant and/or be gradually increased and/or disordered state).Premise
It is that the existence in interval, this kind of local is can to tolerate or negligible to those skilled in the art, or for this
It is inevitable for the state-of-art in field, and the existence in these intervals, local has no effect on people in the art
The concentration distribution in the described whole interval of the described active metallic element is still judged to " present generally and gradually decrease by member
Trend ".It addition, the interval existence in this local has no effect on the present invention expects the realization of purpose, it is acceptable, and also wraps
Within being contained in protection scope of the present invention.
In the present invention, described " Co and Mo is substantially uniformly distributed " refers to Co or Mo at each described catalyst granules
On whole cross section concentration distribution be uniformity, but allow exist can tolerate to those skilled in the art or
Can ignore or inevitable concentration distribution fluctuation (deviation) for the state-of-art of this area.Citing and
Speech, such as, now Mo0/Mo1In the range of being in 1 ± 5% and Mom/Mo1In the range of being in 1 ± 5%, preferably Mo0/Mo1It is in 1 ± 2%
In the range of and Mom/Mo1In the range of being in 1 ± 2%.Now Co0/Co1In the range of being in 1 ± 5% and Com/Co1It is in 1 ± 5% scope
In, preferably Co0/Co1In the range of being in 1 ± 2% and Com/Co1In the range of being in 1 ± 2%.The distribution fluctuation of this concentration has no effect on this
The realization of invention expection purpose, is acceptable, and within being also contained in protection scope of the present invention.
In the present invention, described hydrotreating catalyst is that (solid) granular rather than the amorphous state such as powder.Make
For the shape of described granule, this area hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst of the present invention, on the basis of the weight of catalyst, the content of alumina-based supports is
45wt% ~ 84wt%, preferably surplus, Mo is with MoO3The content of meter is 6wt%～26wt%, and Co content in terms of CoO is
1wt%～8wt%, W are with WO3The content of meter is 6wt%～28wt%, and the content that Ni counts with NiO is as 1wt%～8wt%.
In the hydrotreating catalyst 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 the hydrotreating catalyst of the present invention, be positioned on catalyst granules cross section the concentration of W at outer most edge point with
Concentration ratio (mol ratio) the i.e. W of W at grain center points0/W1It is 1.2～7.0, is positioned at outer most edge point on catalyst granules cross section
The concentration of the Ni at place and concentration ratio (mol ratio) the i.e. Ni of central spot Ni0/Ni1It is 1.2～7.0.
Hydrotreating catalyst 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 processes in catalyst and preferably comprises phosphorus, with P2O5Meter weight content in the catalyst is 1% ~ 6%.
In the hydrotreating catalyst of the present invention, described alumina-based supports refers to aluminium oxide as key component, can
With without adjuvant component, it is also possible to containing adjuvant component, wherein adjuvant component can be the one in fluorine, silicon, phosphorus, titanium, zirconium, boron etc.
Or multiple, adjuvant component in terms of element the content in alumina-based supports at below 30wt%, preferably below 20wt%.Described
Alumina-based supports can use conventional method to prepare.The character of described alumina-based supports is preferably as follows: specific surface area is 100
～500 m2/ g, preferably 150 ~ 400 m2/ g, pore volume is 0.25～1.0mL/g, preferably 0.3 ~ 0.9 mL/g.
The character of the hydrotreating catalyst 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 described hydrotreating catalyst, it is also possible to containing Organic substance B, described Organic substance B be carbon number be 2 ~
One or more in organic compounds containing nitrogen, organic compounds containing sulfur and the oxygen-containing organic compound of 20.
The Organic substance (i.e. Organic substance A or Organic substance A and Organic substance B) contained in the hydrotreating catalyst of the present invention, with
Mo and W atomic molar is than for 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 TGA, mercaptopropionic acid, dimercaptopropanol, BAL etc..Except above-mentioned
Outside sulfur-containing compound, sulfone and sulfoxide compound can be comprised, such as one or more in dimethyl sulfoxide, dimethyl sulfone etc..
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 hydrotreating catalyst of the present invention, active metal component Co and Mo introduced before step (1) and urges
In agent, specifically include:
(1) contain the alumina-based supports of Co and Mo by the solution impregnation containing adsorbent, drying, described adsorbent is
Number-average molecular weight is the polyhydric alcohol of 400～10000, and the consumption of adsorbent accounts for the 0.1% ~ 1.0% of alumina-based supports weight, described
Dipping use saturated dipping or excess dipping；
(2) by solution impregnation step (1) gains containing active metal component W, Ni, drying, obtain containing polyhydric alcohol
Hydrotreating catalyst.
In the inventive method, adsorbent be number-average molecular weight be the polyhydric alcohol of 400～10000, preferably number-average molecular weight
Being the polyhydric alcohol of 1000～8000, described polyhydric alcohol can be, preferably Polyethylene Glycol.
In the inventive method step (1), adsorbent amount makes its content in the final catalyst account for alumina-based supports
The 0.05% ~ 10.0% of weight, preferably 0.1% ~ 9.0%.
The described solution containing adsorbent can also comprise alcohol, the one or many during wherein alcohol is the alcohol of below C5
Kind, can be one or more in monohydric alcohol, polyhydric alcohol, concrete alcohol comprised such as ethylene glycol, propylene glycol, glycerol, season penta
One or more in tetrol, xylitol etc..The addition of described alcohol accounts for the 0.1% ~ 10% of alumina-based supports weight.
The inventive method, by the solution impregnation alumina-based supports containing adsorbent, 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, after impregnating with the dipping solution containing W, 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.Drying condition is as follows: baking temperature is 60 DEG C～250 DEG C, is preferably
100～200 DEG C, drying time 0.5h～20h, preferably 1h～6h.Drying condition to be controlled makes final hydrotreating catalyst
In containing adsorbent.
Those skilled in the art are according to the character of adsorbent selected species, it is possible to select suitable drying condition, so that
Containing adsorbent in final hydrotreating catalyst.
In hydrotreating catalyst preparation method of the present invention, active metal W, Ni be load to catalyst by infusion process before
On body, generally use incipient impregnation.Dipping method is known to technical staff.It is catalyzed by the solution impregnation containing active metal
After agent precursor, need through being dried.Active metal solution manufacturing method is known to technical staff, and its solution concentration can be passed through
The consumption of each compound regulates, thus prepares the catalyst of specified activity constituent content.The raw material of required active component is general
For the compound of the types such as salt, oxide or acid, if nickel source is from nickel nitrate, nickelous carbonate, basic nickel carbonate, Nickel dichloride., grass
One or more in acid nickel, tungsten source is generally from ammonium metatungstate.In described dipping solution, in addition to active metal component,
Phosphorus-containing compound can also be contained, as the one in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate etc. or
Several.The hydrotreating catalyst of the present invention preferably comprises phosphorus, with P2O5Meter weight 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.
Introducing Organic substance B in hydrotreating catalyst, its Adding Way is: molten in the dipping containing Ni and W of step (2)
After liquid adds Organic substance B, or step (2), impregnate with Organic substance B；The consumption of described Organic substance B, makes hydrorefining catalyst
Organic substance in agent is 0.002:1～2:1, preferably 0.02:1 ~ 1.5:1 with the mol ratio of Mo and W atom, more preferably
0.02:1 ~ 1.0:1.In the inventive method, can make in final catalyst by controlling drying condition according to organic difference
Containing required Organic substance.Organic substance A be number-average molecular weight be the polyhydric alcohol of 400 ~ 10000, Organic substance B is selected generally from nitrogenous to be had
One or more in machine compound, organic compounds containing sulfur and oxygen-containing organic compound.
Hydrotreating catalyst of the present invention is at hydrodesulfurization (the especially deep hydrogenation of heavy distillate (especially diesel oil)
Desulfurization) in as the application of Hydrobon 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%.
Use hydrotreating catalyst of the present invention as Hydrobon catalyst, can be by the total sulfur of described heavy distillate
Content is reduced to 0.05wt% or lower, is preferably decreased to 0.005wt% or lower, especially can remove more than 80wt% (preferably
More than 90wt%) described difficulty take off sulfur-containing compound.
The present invention, in described application or described hydrodesulfurizationprocess process, can only use the hydrorefining catalyst of the present invention
Agent, it is also possible to by the hydrotreating catalyst of the present invention and other hydrotreating catalysts (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 hydrodesulfurization 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。
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 hydrotreating catalyst containing adsorbent II polyhydric alcohol, polyhydric alcohol be alumina-based supports weight 0.05% ~
10.0%, preferably 0.1% ~ 9.0%.
Hydrotreating catalyst Co and Mo of the present invention is substantially uniformly distributed in catalyst, W and Ni is from catalyst particles
Grain outer surface to center in the trend gradually decreased, and containing polyhydric alcohol.This catalyst is particularly well-suited in hydrodesulfurization,
Improve the activity and selectivity of hydrodesulfurization, especially removing and there is the thiophene sulfocompounds of sterically hindered difficult removing.
Hydrotreating catalyst prepared by the present invention, Mo and Co used conventional method to introduce before step (1) and makes
It is uniformly distributed in catalyst, the solution containing adsorbent by saturated dipping or excess dipping, then impregnates W, Ni activity gold
Belong to after solution, slow down W, Ni diffusion velocity to catalyst granules center, so that dense in each catalyst granules of W, Ni
Degree in the trend gradually decreased, is so being catalyzed by control Mo, Co and W, the combination of Ni different metal from marginal position to center
Distribution in variable concentrations in agent so that it is cooperate, give full play to both advantages, thus improve activity and the choosing of catalyst
Selecting property, especially removing have the thiophene sulfocompounds of sterically hindered difficult removing.Additionally, the present invention is hydrogenated with by control
Process the preparation condition of catalyst, make Organic substance be present in final hydrotreating catalyst, after active metal sulfuration, it is possible to
Form more lamination number, make the hydrogenation activity of catalyst be further enhanced.
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 is active metal component Ni and Co concentration profile on this cross section in embodiment 4 gained catalyst C6.
Wherein abscissa is each position point on this cross section, and vertical coordinate is the concentration at a certain location point and central point on this cross section
The ratio of the concentration at place.
Detailed description of the invention
According to the preparation method of the hydrotreating catalyst that the present invention provides, by active metal component before step (1)
Mo and Co introduces in catalyst, at least uses one of following method: add in carrier component dry glue powder preparation process the most again
Molding is made the alumina-based supports containing Mo and Co, is added when carrier component kneading and compacting and make the alumina base containing Mo and Co
Use infusion process to add after carrier and carrier component molding and make the alumina-based supports containing Mo and Co.Using aluminium oxide as carrier
Illustrate as a example by component:
One, add in the preparation process of aluminum oxide dry glue powder, as introduced with co-precipitation, fractional precipitation mode, then become
Type, prepares the alumina support containing Mo and Co after drying, roasting；
Two, add with kneading form when carrier molding: aluminum oxide dry glue powder and containing Mo and Co active metal component
Compound mix homogeneously, then through kneading and compacting, the alumina support containing Mo and Co is made in dry, roasting；
Three, by aluminum oxide dry glue powder kneading and compacting, then it is dried, carrier is made in roasting, lives with containing Mo and Co afterwards
The solution impregnation of alumina carrier of property metal component, drying, roasting make the alumina support containing Mo and Co.
In above-mentioned forming process, the shaping assistant of routine can be added, in such as extrusion aid, binding agent, peptizer etc.
One or more, addition can be determined by this area knowledge according to preparing catalyst property.Wherein binding agent typically uses
Little porous aluminum oxide, the boehmite produced selected from aluminum chloride-Ammonia Process, carbonizatin method or aluminum sulfate method and Zlegler synthesis
The SB alumina powder etc. of byproduct of reaction.
In hydrotreating catalyst preparation method of the present invention, being dried in the alumina-based supports preparation process containing Mo and Co
Using prior art condition with roasting, if baking temperature is 40 DEG C～250 DEG C, drying time is 0.5h～20h；Sintering temperature is
350 DEG C～750 DEG C, roasting time is 0.5h～20h.
The preparation method of hydrotreating catalyst provided according to the present invention, specific as follows:
I, the preparation alumina-based supports containing Mo and Co containing Mo and Co active metal component,
II, required adsorbent is added in metering water, prepare solution, the alumina-based supports containing Mo and Co sprays
Solution containing adsorbent, obtains sample and carries out next step preferably through health preserving again, and conditioned time is 1～12h；
III, step II gained sample is preferably through carrying out next step more after drying, and baking temperature is generally 60 DEG C～250
DEG C, 0.5h～20h, controlled drying condition and made adsorbent be present in catalyst drying time；
IV, use equi-volume impregnating, with the active metal solution impregnation step III gained sample containing W, Ni, at 70 DEG C～
It is dried 0.5h～20h at a temperature of 300 DEG C, controls drying condition and make adsorbent be present in catalyst, obtain adding containing adsorbent
Hydrogen processes catalyst.
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 (m of catalyst2/ 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 pass through division calculation, it is thus achieved that each dense
The ratio (being mol ratio in the present invention) of angle value.
Fig. 4 be embodiment 4 gained catalyst C6 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) catalyst is the most desulphurizing activated
The most desulphurizing activated=100 × [(1/S1)0.65-(1/S0)0.65]/ [(1/Sc1)0.65-(1/S0)0.65], S in formula1
And Sc1Represent the sulfur content used in catalyst of the present invention or reference agent gained hydrogenation products, S respectively0Represent and use the present invention to urge
Sulfur content in agent or the raw materials used oil of reference agent.Wherein sulfur content is in terms of S, and unit is g/g.
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.
Column type carrier used in embodiment, wherein carrier lengths is about 3 ~ 5mm.
Embodiment 1
The present embodiment introduces the preparation method of catalyst precarsor.Siliceous, the aluminum oxide dry glue powder specific surface 350m of boron2/ g,
Pore volume is 0.90ml/g.
Weigh siliceous, the aluminum oxide dry glue powder 400g of boron, add citric acid and each 6g of sesbania powder, after being mixed evenly, add
Acid solution 345g, HNO in acid solution3Weight concentration be 1.74%, remaining is distilled water.After rolling 20min, use diameter
The circular orifice extrusion of 1.7mm.500 DEG C of roasting 3h after 120 DEG C of dry 4h.The carrier strip prepared is designated as S1.Molten with containing W, Ni
Carrier strip S1 obtained by immersion stain, 500 DEG C of roasting 2h after 130 DEG C of dry 4h, the prepared alumina-based supports containing Mo and Co
It is designated as Z1.
Weigh siliceous, the aluminum oxide dry glue powder 400g of boron, add citric acid and each 6g of sesbania powder, add acid solution
345g, HNO in acid solution3Weight concentration be 2.6%, Mo is with MoO3The content of meter is 14.9wt%, Co containing in terms of CoO
Amount is 2.9wt%, and remaining is distilled water.After rolling 20min, by the circular orifice extrusion of diameter 1.7mm.After 120 DEG C of dry 4h
500 DEG C of roasting 3h, the prepared alumina-based supports containing Mo and Co is designated as Z2.
Prepare the aluminum oxide dry glue powder of siliceous, molybdenum and cobalt.In container, add 1L deionized water, be warming up to 58 DEG C, simultaneously
Add 3L containing Al2O3For the aluminum nitrate solution of 4g/100mL with containing NH3For the ammonia spirit of 10g/100mL, control ph is 7.8,
Feed time is 120min.After stopping charging, system is aging 50min under said temperature and pH value condition, adds SiO2Content
For the solution of sodium metasilicate through 100mL of 5.0g, continue aging 60min, be washed out 4 times, to Cl-/Al2O3< till 0.5%.Preparation
Aqueous solution 1L containing molybdenum and cobalt, wherein MoO3Concentration 2.7g/100mL, CoO concentration 0.5g/100mL, add in filter cake, stir into
Pasty state, after 120 DEG C of dry 8h, is crushed to granularity and is accounted for more than 95% less than 180 purposes, obtained required dry glue powder.
Gained is siliceous, molybdenum and the aluminum oxide dry glue powder specific surface 310m of cobalt2/ g, pore volume is 0.78ml/g.
Weigh the aluminum oxide dry glue powder 400g of siliceous, molybdenum and cobalt, add citric acid and each 6g of sesbania powder, after being mixed evenly,
Add acid solution 345g, HNO in acid solution3Weight concentration be 1.74%, remaining is distilled water.After rolling 20min, use
The circular orifice extrusion of diameter 1.7mm.500 DEG C of roasting 3h after 120 DEG C of dry 4h.Prepare the alumina-based supports note containing Mo and Co
For Z3.
The composition of the table 1 alumina-based supports containing Mo and Co and character
| Catalyst precarsor | Z1 | Z2 | Z3 |
| Si, wt% | 1.25 | 1.23 | 1.37 |
| B, wt % | 1.47 | 1.45 | - |
| CoO, wt % | 3.15 | 3.10 | 2.99 |
| MoO3, wt % | 15.5 | 15.8 | 15.7 |
| Specific surface area, m2/g | 202 | 201 | 205 |
| Pore volume, mL/g | 0.48 | 0.47 | 0.47 |
| Saturated liquid absorption, mL/100g | 59 | 58 | 58 |
Embodiment 2
Stirring and dissolving cetomacrogol 1000 (i.e. molecular weight is the Polyethylene Glycol of 1000, lower same), system in the water measured
Obtaining adsorbent solution, the consumption of Polyethylene Glycol accounts for the 8% of alumina-based supports weight.Take Z1 300g, adsorbent solution is uniform
Being sprayed on Z1, spraying time is 10min.Then carrying out the health preserving of 5h, after 100 DEG C of dry 3h, the sample prepared is designated as
B1.B1 is sprayed with the impregnation liquid equal-volume containing W, Ni, P and citric acid, on the citric acid of introducing and catalyst total mole of Mo Yu W
Than be 0.05:1, gained sample aliquot after dipping is become three parts, first part of direct 120 DEG C of dry 3h of sample, it is thus achieved that finished product remember
For C1；Second sample health preserving 1h, through 120 DEG C of dry 3h, prepared finished product is designated as C2；Triplicate sample health preserving 3h, through 120 DEG C
Being dried 3h, prepared finished product is designated as C3.
Embodiment 3
Stirring and dissolving PEG 8000 in the water measured, prepares adsorbent solution, and the consumption of Polyethylene Glycol accounts for oxygen
Change the 2% of alumina-based support weight.Take Z2 100g, adsorbent solution is uniformly sprayed on Z2, then carry out the health preserving of 5h, pass through
After 100 DEG C of dry 3h, the sample prepared is designated as B2.Spray B2 sample with the impregnation liquid equal-volume containing W, Ni, P and benzenesulfonic acid, draw
On the benzenesulfonic acid entered and catalyst, total mol ratio of Mo Yu W is 0.2:1, directly through 120 DEG C of dry 3h, it is thus achieved that finished product be designated as
C4。
Embodiment 4
Stirring and dissolving Macrogol 2000 in the water measured, prepares adsorbent solution, and the consumption of Polyethylene Glycol accounts for oxygen
Change the 6% of alumina-based support weight.Take Z3 200g, adsorbent solution is uniformly sprayed on Z3, then carry out the health preserving of 5h, pass through
After 100 DEG C of dry 3h, the sample prepared is designated as B3.B3 sample is sprayed, directly through 120 DEG C with the impregnation liquid equal-volume containing W, Ni, P
Be dried 3h, it is thus achieved that finished product be designated as C5.
Preparation aqueous acid in Fructus Citri Limoniae, equal-volume sprays part C5 sample, on the citric acid of introducing and catalyst W and
The mol ratio of Mo is 0.07:1, after spraying end, through 120 DEG C of dry 3h, it is thus achieved that catalyst be designated as C6.
Embodiment 5
Stirring and dissolving Macrogol 4000 in the water measured, prepares adsorbent solution, and the consumption of Polyethylene Glycol accounts for oxygen
Change the 4% of alumina-based support weight.Take Z3 100g, adsorbent solution is uniformly sprayed on Z3, then carry out the health preserving of 5h, pass through
After 100 DEG C of dry 3h, the sample prepared is designated as B4.B4 sample is sprayed, directly through 120 DEG C with the impregnation liquid equal-volume containing W, Ni, P
Be dried 3h, it is thus achieved that finished product be designated as C7.
Comparative example 1
Take Z1 precursor 100g, after the above-mentioned carrier of impregnation liquid incipient impregnation containing W, Ni, P, through 120 DEG C of dry 3h, etc.
Volume sprays containing Macrogol 2000 and Fructus Citri Limoniae aqueous acid, and the consumption of Polyethylene Glycol accounts for the 6% of alumina-based supports weight,
The citric acid amount introduced is 0.07:1 with the mol ratio of Mo and W on catalyst, after spraying end, and health preserving 3h, 120 DEG C of dry 3h,
After 480 DEG C of roasting 2h, it is thus achieved that catalyst be designated as C8.
Table 2 embodiment forms with comparative example catalyst activity metal
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| W is with WO3Meter, wt% | 19.4 | 19.4 | 19.6 | 19.5 | 19.5 | 19.4 | 19.5 | 19.7 |
| Mo is with MoO3Meter, wt% | 13.1 | 13.2 | 13.3 | 13.2 | 13.6 | 13.5 | 13.3 | 13.3 |
| Co in terms of CoO, wt% | 2.4 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.4 |
| Ni in terms of NiO, wt% | 2.6 | 2.7 | 2.6 | 2.6 | 2.6 | 2.6 | 2.7 | 2.5 |
| P is with P2O5Meter, wt% | 1.35 | 1.38 | 1.35 | 1.37 | 1.35 | 1.36 | 1.35 | 1.35 |
Table 3 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 | 2.83 | 2.48 | 2.02 | 2.50 | 2.88 | 2.82 | 2.78 | 0.99 |
| W1/4/ W1 | 1.79 | 1.67 | 1.52 | 1.71 | 1.89 | 1.85 | 1.80 | 1.02 |
| W1/2/ W1 | 1.30 | 1.20 | 1.17 | 1.22 | 1.28 | 1.26 | 1.25 | 0.98 |
| W3/4/W1 | 1.07 | 1.07 | 1.05 | 1.06 | 1.11 | 1.10 | 1.09 | 1.00 |
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 |
| Ni0/ Ni1 | 2.89 | 2.49 | 2.09 | 2.52 | 3.00 | 2.93 | 2.81 | 1.01 |
| Ni/4/ Ni1 | 1.86 | 1.69 | 1.51 | 1.72 | 1.93 | 1.89 | 1.85 | 0.99 |
| Ni1/2/ Ni1 | 1.27 | 1.22 | 1.18 | 1.21 | 1.30 | 1.27 | 1.26 | 1.00 |
| Ni3/4/ Ni1 | 1.11 | 1.08 | 1.05 | 1.06 | 1.11 | 1.09 | 1.08 | 0.98 |
The concentration distribution in catalyst granules of table 5 embodiment and elements Mo in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| Mo0/Mo1 | 1.00 | 1.01 | 0.99 | 1.01 | 0.99 | 1.00 | 1.00 | 1.01 |
| Mo1/4/Mo1 | 1.02 | 0.98 | 0.98 | 1.02 | 1.02 | 1.02 | 1.02 | 1.02 |
| Mo1/2/Mo1 | 0.99 | 0.99 | 1.01 | 0.98 | 0.98 | 0.99 | 0.99 | 1.00 |
| Mo3/4/Mo1 | 1.02 | 1.01 | 1.00 | 0.99 | 1.00 | 1.00 | 1.02 | 1.01 |
The concentration distribution in catalyst granules of table 6 embodiment and Elements C o in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| Co0/ Co1 | 0.98 | 0.99 | 1.02 | 0.98 | 1.01 | 1.01 | 0.98 | 1.01 |
| Co1/4/ Co1 | 0.99 | 1.00 | 1.01 | 1.02 | 0.99 | 0.99 | 1.02 | 0.98 |
| Co1/2/ Co1 | 0.99 | 1.02 | 1.00 | 1.01 | 0.99 | 0.99 | 0.99 | 1.02 |
| Co3/4/ Co1 | 1.00 | 0.99 | 1.00 | 1.00 | 0.98 | 1.00 | 1.00 | 0.99 |
From table 3 and table 4, using catalyst C1～C7 prepared by the present invention, active metal W, Ni are along catalyst granules
Radially it is gradually reduced from outer surface to centre concentration, and comparative example catalyst C8 active metal W, Ni are at radial direction on each position
Concentration essentially identical, be obvious Gradient distribution unlike the present invention prepares catalyst.Found by C1, C2 and C3, by control
Conditioned time processed, can adjust active metal at catalyst granules distributed density radially；Find out from C1, C4 and C5, pass through
The content of adsorbent and the change of molecular weight also can adjust active metal W, Ni at catalyst granules distributed density radially.Therefore
The preparation method of catalyst of the present invention is compared with comparative example catalyst, in that context it may be convenient to adjust active metal at catalyst particles particle diameter
Distributed density upwards, thus improve the deep desulfuration performance of catalyst.
Embodiment 6
The present embodiment is activity rating of catalyst experiment.
Catalyst activity evaluation experimental is carried out on 100mL small hydrogenation device, carries out pre-to catalyst before activity rating
Sulfuration.Evaluating catalyst condition is at reaction stagnation pressure 6.0MPa, volume space velocity 2.0 h during liquid-1, hydrogen-oil ratio 500:1, reaction temperature
It it is 340 DEG C.Active appraisal experiment raw oil character is shown in Table 7, and Activity evaluation is shown in Table 8, and table 9 provides typical case in hydrogenation products
The content of difficult de-sulfur-containing compound, from data in table, with the desulfurization work of hydrotreating catalyst prepared by the inventive method
Property is apparently higher than comparative example catalyst.
Table 7 raw oil character
| Raw oil | Atmosphere 3rd side cut diesel oil |
| Density (20 DEG C), g/cm3 | 0.8533 |
| Boiling range, DEG C | |
| IBP | 217 |
| EBP | 375 |
| S, wt% | 1.78 |
| N, g/g | 140 |
Table 8 catalyst activity evaluation result
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 |
| The most desulphurizing activated, % | 140 | 137 | 136 | 138 | 133 | 142 | 132 | 100 |
The content of the difficult de-sulfur-containing compound of typical case in table 9 raw material and hydrogenation products
| Raw material/hydrogenation products | Raw material | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products |
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | |
| 4,6-BMDBT, g/g | 215 | 12.7 | 13.0 | 13.2 | 12.9 | 13.6 | 12.4 | 13.8 | 24.0 |
Claims (27)
1. a hydrotreating catalyst, uses alumina-based supports, and active metal component is Co, Mo, Ni, W, wherein activity gold
Belong to component concentration distribution on each catalyst granules cross section as follows: Ni0/Ni1＞ Ni1/2/Ni1＞ 1, W0/W1＞ W1/2/W1
The concentration of ＞ 1, Co and Mo is substantially uniformly distributed；Containing Organic substance A, described Organic substance A for counting in described catalyst
Average molecular weight is the polyhydric alcohol of 400～10000；Described Organic substance A weight content in the catalyst is 0.05% ~ 10.0%；Institute
The hydrotreating catalyst stated, on the basis of the weight of catalyst, the content of alumina-based supports is 45wt% ~ 84wt%, Mo
With MoO3The content of meter is 6wt%～26wt%, and the content that Co counts with CoO is as 1wt%～8wt%, and W is with WO3The content of meter is
The content that 6wt%～28wt%, Ni count with NiO is as 1wt%～8wt%；
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.
2. according to the catalyst described in claim 1, it is characterised in that described Organic substance A weight content in the catalyst is
0.1%~9.0%。
3. according to the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, active metal component
In catalyst granules, at least include following a kind of scheme:
(1) Ni0/Ni1With Ni1/2/Ni1Ratio 1.5 ~ 2.6；
(2) 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 hydrotreating catalyst, active metal component
In catalyst granules, at least include following a kind of scheme:
(1) Ni0/Ni1With Ni1/2/Ni1Ratio 1.7 ~ 2.5；
(2) 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 hydrotreating catalyst, active metal component
Concentration on catalyst granules cross section is distributed and at least includes following a kind of scheme:
(1) Ni0/Ni1＞ Ni1/4/Ni1＞ Ni1/2/Ni1；
(2) Ni1/2/Ni1＞ Ni3/4/Ni1＞ 1；
(3) W0/W1＞ W1/4/W1＞ W1/2/W1；
(4) W1/2/W1＞ W3/4/W1＞ 1.
6. according to the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, active metal component
Concentration on catalyst granules cross section is distributed and at least includes following a kind of scheme:
(5) Ni0/Ni1＞ Nix1/Ni1＞ Nix2/Ni1＞ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
(6) 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 hydrotreating catalyst, active metal
Component, in catalyst granules, at least includes following a kind of scheme:
(1) Ni0/Ni1With Ni1/4/Ni1Ratio be 1.2 ~ 1.8；
(2) Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.1 ~ 1.7；
(3) W0/W1With W1/4/W1Ratio be 1.2 ~ 1.8；
(4) 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 hydrotreating catalyst, active metal
Component, in catalyst granules, at least includes following a kind of scheme:
(1) Ni0/Ni1With Ni1/4/Ni1Ratio be 1.3 ~ 1.7；
(2) Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.2 ~ 1.6；
(3) W0/W1With W1/4/W1Ratio be 1.3 ~ 1.7；
(4) 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 hydrotreating catalyst, 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: Co's and Mo is dense
Degree is substantially uniformly distributed, and the concentration of Ni substantially gradually decreases, and the concentration of W substantially gradually decreases.
10. according to the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, 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 hydrotreating catalyst, be positioned at catalyst
The concentration i.e. W of ratio of W at the concentration of the W at granule outer most edge point and grain center points0/W1It is 1.2～7.0, is positioned at catalyst granules
The concentration i.e. Ni of ratio of the concentration of the Ni at cross section outer rim point and central spot Ni0/Ni1It is 1.2～7.0.
12. according to the catalyst described in claim 1, it is characterised in that the character of described hydrotreating catalyst 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 described polyhydric alcohol is Polyethylene Glycol.
14. according to the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, containing Organic substance A
For the polyhydric alcohol that number-average molecular weight is 1000～8000.
15. according to the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, 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；During wherein oxygen-containing organic compound is acids, ethers, saccharide, ketone, phenols, aldehydes and lipid
One or more.
16. according to claim 1-6, the arbitrary described catalyst of 9-15, it is characterised in that in described hydrotreating catalyst
The Organic substance contained and Mo and W atomic molar are than for 0.002:1～2.0:1.
17. as according to the catalyst described in claim 16, it is characterised in that contain in described hydrotreating catalyst has
Machine thing and Mo and W atomic molar are than for 0.02:1 ~ 1.0:1.
18. according to the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, aluminium oxide base load
Body is with aluminium oxide as key component, without adjuvant component or containing adjuvant component, wherein adjuvant component be fluorine, silicon, phosphorus, titanium,
One or more in zirconium, boron, adjuvant component in terms of element the content in alumina-based supports at below 30wt%.
19. according to the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, 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%.
20. according to the catalyst described in claim 1, it is characterised in that containing phosphorus in described hydrotreating catalyst, with P2O5
Meter weight content in the catalyst is 1% ~ 6%.
The preparation method of the arbitrary described catalyst of 21. claim 1 ~ 13, wherein active metal Mo and Co is before step (1)
Introduce in hydrotreating catalyst, including:
(1) use saturated infusion process or excess infusion process, impregnate containing Mo's and Co with the fountain solution containing the i.e. Organic substance A of adsorbent
Alumina-based supports, adsorbent amount accounts for the 0.1% ~ 10.0% of alumina-based supports weight, and wherein said adsorbent is molecule
Amount is 400～10000 polyhydric alcohol；
(2) by solution impregnation step (1) gains containing active metal component Ni, W, drying, adding containing Organic substance A is obtained
Hydrogen processes catalyst.
22. in accordance with the method for claim 21, it is characterised in that: the step (1) solution impregnation containing adsorbent aoxidizes
Alumina-based support, uses incipient impregnation or excess dipping, and after dipping terminates, sample is through health preserving or without health preserving, then carries out
Being 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.
23. in accordance with the method for claim 21, it is characterised in that: after step (2) impregnates with the dipping solution containing W, Ni,
Through health preserving or without health preserving, then being dried, as needed health preserving, conditioned time is 0.5～6.0h；Described drying condition
As follows: baking temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h.
24. in accordance with the method for claim 21, it is characterised in that: in the dipping solution described in step (2), except active metal
Outside component, possibly together with phosphorus, phosphorus source one or several in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate
Kind, the introduction volume of phosphorus is with P2O5Meter accounts for the 1% ~ 6% of final hydrotreating catalyst weight.
25. in accordance with the method for claim 21, it is characterised in that: introducing Organic substance B in hydrotreating catalyst, it adds
Entering method is: after adding Organic substance B, or step (2) in the dipping solution containing Ni and W of step (2), soaks with Organic substance B
Stain；The consumption of described Organic substance B, make the mol ratio of Organic substance in hydrotreating catalyst and Mo and W atom be 0.002:1～
2:1；One or more in organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound of Organic substance B.
The method of 26. 1 kinds of heavy distillate hydrodesulfurizations, it is characterised in that use the arbitrary described hydrogenation of claim 1 ~ 20
Process catalyst.
27. in accordance with the method for claim 26, it is characterised in that: described heavy distillate is diesel oil.
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| CN105251494A (en) * | 2015-11-13 | 2016-01-20 | 无锡普爱德环保科技有限公司 | Preparing method for hydrogenation catalyst |
| CN105289618A (en) * | 2015-11-13 | 2016-02-03 | 无锡普爱德环保科技有限公司 | Hydrogenation catalyst, and applications thereof |
| RU2620089C1 (en) * | 2016-04-08 | 2017-05-23 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Catalyst for hydrofining diesel fractions and method of preparing thereof |
| RU2640210C1 (en) * | 2016-10-06 | 2017-12-27 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Oil faction hydroprocessing catalyst (versions) |
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| US4382854A (en) * | 1978-02-03 | 1983-05-10 | Kaiser Aluminum & Chemical Corporation | Ni/Co Mo P on titania-alumina hydrodesulfurizing catalyst and process of hydrodesulfurizing using the same |
| 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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| US4382854A (en) * | 1978-02-03 | 1983-05-10 | Kaiser Aluminum & Chemical Corporation | Ni/Co Mo P on titania-alumina hydrodesulfurizing catalyst and process of hydrodesulfurizing using the same |
| 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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