CN104588029B - Hydrotreatment catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a hydrotreatment catalyst and a preparation method thereof. The hydrotreatment catalyst comprises an alumina-based carrier and active metal ingredients of Mo, Co and Ni. The distribution of the active metal ingredients in the catalyst particles is characterized by comprising Co0/Co1<Co1/2/Co1<1, Ni0/Ni1>Ni1/2/Ni1>1 and uniform distribution of Mo. The hydrotreatment catalyst contains polyhydric alcohol. The preparation method utilizes a conventional method to introduce Mo into the catalyst and the process of introducing Co and Ni comprises the following steps of immersing the alumina-based carrier in an adsorbent I-containing solution by a unsaturated impregnation method, carrying out immersion in a solution containing active metal Co, carrying out drying and roasting, carrying out saturated or excess immersion in an adsorbent II-containing solution, carrying out immersion loading with active metal Ni and carrying out drying to obtain the hydrotreatment catalyst. The hydrotreatment catalyst is especially suitable as a diesel oil deep hydrodesulfurization catalyst and has good deep-hydrodesulfurization activity.

Description

A kind of hydrogenation catalyst and preparation method thereof

Technical field

The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly one kind are suitable to heavy distillate hydrogenation Process catalyst and preparation method thereof.

Background technology

With today's society to heavy distillate（Particularly diesel oil）The requirement more and more higher cleaning, 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., wherein more difficult removing is dibenzothiophenes, alkane The thiophenes such as base benzothiophene and methyldibenzothiophene, especially with 4,6- dimethyl Dibenzothiophene（4,6- BMDBT）With 2,4,6- trimethyl dibenzothiophenes（2,4,6- BMDBT）Class formation is complicated and sulfur-bearing that have space steric effect Compound is most difficult to remove.Depth to be reached and ultra-deep desulfurization are it is necessary to remove these complex structures and sterically hindered big containing Sulphur compound, and the generally also more difficult removing under the harsh operating condition such as HTHP 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 requires in depth There is particular/special requirement in the design of Hydrobon catalyst.

Hydrotreating catalyst is typically with alumina-based supports, is lived with vib and group VIII metal for hydrogenation Property metal component, wherein active metal component is usually equally distributed in the catalyst.CN99103007.9 discloses one kind 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 4 weight % 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 always 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 to aoxidize Aluminium 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 arts belongs to the Hydrobon catalyst of routine, can not effectively fit For heavy distillate（Especially diesel oil）Hydrodesulfurization.Therefore, prior art is still required for a kind of hydrotreating catalyst, It is particularly suited for heavy distillate（Especially diesel oil）Hydrodesulfurization（Especially deep hydrodesulfurizationof）.

Content 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, using alumina-based supports, active metal component is Mo, Co and Ni, wherein Concentration distribution on each catalyst granules cross section for the active metal component is as follows：Co₀/Co₁＜ Co_1/2/Co₁＜ 1, Ni₀/Ni₁ ＞ Ni_1/2/Ni₁The concentration of ＞ 1, Mo is substantially uniformly distributed；In described hydrotreating catalyst, it is many containing organic matter A First alcohol, the polyalcohol that described polyalcohol is 400～10000 for number-average molecular weight；Polyalcohol weight content in the catalyst For 0.05% ~ 10.0%, preferably 0.1% ~ 9.0%.

In the present invention, concentration distribution formula A on the cross section of each catalyst granules for the active metal component_m/B_nTable Show, that is, at m on the cross section of each catalyst granules at the concentration of elements A and n the concentration of element B ratio（In the present invention, Unit is mol ratio）, wherein A represents active metallic element Mo, Co or Ni, and B represents active metallic element Mo, Co or Ni, wherein A With B can identical it is also possible to different；Any point with catalyst granules cross section outer most edge is that outer most edge point is remembered for starting point For 0, it is designated as 1 with the central point of catalyst granules cross section for terminal, connect starting point and terminal obtains straight-line segment, m and n divides The location point chosen is not represented on above-mentioned straight-line segment, the value of m and n represents that the distance from starting point to the location point of selection accounts for The ratio of the length of above-mentioned straight-line segment, the value of m and n is 0 ~ 1, wherein m（Or n）Value was 0,1/4,1/2,3/4,1 time-division Choose when not representing account for the length of above-mentioned straight-line segment to the distance of the location point chosen from starting point 0,1/4,1/2,3/4,1 The position that point is located（See Fig. 3）, above-mentioned location point also referred to as outer most edge point（Or appearance millet cake）, 1/4 location point, 1/2 location point, 3/4 location point, central point.In the present invention, in the present invention, in order to express easily, A and B directly adopts active metallic element Mo, Co Or Ni replaces, m and n is directly with defined location point on 0～1 above-mentioned straight-line segment of digitized representation, with x1 or x2 representative State arbitrary location point on straight-line segment, such as, Co₀/Co₁Represent that A and B is Co, m=0, n=1 represent that catalyst granules is horizontal The ratio of the concentration of the concentration of Elements C o and central spot Elements C o, Ni at the outer most edge point of section_1/2/Ni₁Represent that A and B is Ni, m=1/2, n=1 represent on the described straight-line segment on catalyst granules cross section, make from outer most edge point to selected point At selected point position when distance accounts for the 1/2 of above-mentioned straight-line segment length, the concentration of element Ni and central spot element Ni's is dense The ratio of degree.X1 and x2 in the present invention arbitrarily selects respectively on the straight-line segment that the above-mentioned outer most edge point of connection and central point obtain The location point taking（But do not include outer most edge point and central point）, and from outer most edge point to the distance of x1 point be less than from outer most edge point to The distance of x2 point is 0 ＜ x1 ＜ x2 ＜ 1.

In the present invention, it is related to use formula A_m/B_nIt is specific as follows that form represents：Co₀/Co₁（A and B is Co, m=0, n= 1）、Co_1/4/Co₁（A and B is Co, m=1/4, n=1）、Co_1/2/Co₁（A and B is Co, m=1/2, n=1）、Co_3/4/Co₁（A and B It is Co, m=3/4, n=1）、Co_x1/Co₁（A and B is Co, m=x1, n=1）、Co_x2/Co₁（A and B is Co, m=x2, n=1）、 Ni₀/Ni₁（A and B is Ni, m=0, n=1）、Ni_1/4/Ni₁（A and B is Ni, m=1/4, n=1）、Ni_1/2/Ni₁（A and B is Ni, m=1/2, n=1）、Ni_3/4/Ni₁（A and B is Ni, m=3/4, n=1）、Ni_x1/Ni₁（A and B is Ni, m=x1, n=1）、 Ni_x2/Ni₁（A and B is Ni, m=x2, n=1）、Mo₀/Mo₁（A and B is Mo, m=0, n=1）、Mo_1/4/Mo₁（A and B is Mo, m =1/4, n=1）、Mo_1/2/Mo₁（A and B is Mo, m=1/2, n=1）、Mo_3/4/Mo₁（A and B is Mo, m=3/4, n=1）.

In hydrotreating catalyst of the present invention, in catalyst granules, preferred version is as follows for active metal component：Co₀/Co₁ With Co_1/2/Co₁Ratio be 0.2 ~ 0.8, preferably 0.2 ~ 0.7, Ni₀/Ni₁With Ni_1/2/Ni₁Ratio 1.5 ~ 2.6, preferably 1.7~2.5.

In hydrotreating catalyst of the present invention, distribution on catalyst granules cross section for the active metal component is preferably such as Under：Co₀/ Co₁＜ Co_1/4/ Co₁＜ Co_1/2/ Co₁.

In hydrotreating catalyst of the present invention, distribution on catalyst granules cross section for the active metal component is preferably such as Under：Co_1/2/ Co₁＜ Co_3/4/ Co₁＜ 1.

In hydrotreating catalyst of the present invention, distribution on catalyst granules cross section for the active metal component is preferably such as Under：Ni₀/Ni₁＞ Ni_1/4/Ni₁＞ Ni_1/2/Ni₁.

In hydrotreating catalyst of the present invention, distribution on catalyst granules cross section for the active metal component is preferably such as Under：Ni_1/2/Ni₁＞ Ni_3/4/Ni₁＞ 1.

In hydrotreating catalyst of the present invention, in catalyst granules, preferred version is as follows for active metal component：Co₀/Co₁ With Co_1/4/Co₁Ratio be 0.30 ~ 0.90, preferably 0.30 ~ 0.85, Co_1/4/Co₁With Co_1/2/Co₁Ratio be 0.4 ~ 0.9, It is preferably 0.4 ~ 0.87；Ni₀/Ni₁With Ni_1/4/Ni₁Ratio be 1.2 ~ 1.8, preferably 1.3 ~ 1.7, Ni_1/4/Ni₁With Ni_1/2/ Ni₁Ratio be 1.1 ~ 1.7, preferably 1.2 ~ 1.6.

In hydrotreating catalyst of the present invention, concentration distribution on catalyst granules cross section for the active metal component is preferred As follows：Co₀/Co₁＜ Co_x1/Co₁＜ Co_x2/Co₁＜ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1.

In hydrotreating catalyst of the present invention, concentration distribution on catalyst granules cross section for the active metal component is preferred As follows：Ni₀/Ni₁＞ Ni_x1/Ni₁＞ Ni_x2/Ni₁＞ 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 is distributed as follows：The concentration of Co is substantially gradually increased, and the concentration of Ni substantially gradually subtracts Few, the concentration of Mo is substantially uniformly distributed.

In the present invention, described " substantially gradually decrease along described straight-line segment（Or be gradually increased）" refer to described work Property metallic element concentration distribution along described straight-line segment from outer most edge point to central point entirely interval in be in generally Now gradually decrease（Or be gradually increased）Trend, but it is interval to allow to exist one or more local；In this local interval, described The concentration distribution of active metallic element presents different trend along described straight-line segment（Such as remain constant and/or gradually Increase（Or gradually decrease）And/or disordered state）.Premise is that the interval presence in this kind of local is for those skilled in the art Speech is can to tolerate or negligible, or is inevitable for the state-of-art of this area, and this The interval presence in a little local has no effect on those skilled in the art, and described active metallic element is dense in described whole interval Degree distribution is still judged to " generally present and gradually decrease（Or be gradually increased）Trend ".In addition, the interval presence in this local Have no effect on the realization of expected purpose of the present invention, be acceptable, and be also contained within protection scope of the present invention.

In the present invention, described " concentration of Mo is substantially uniformly distributed " refers to Mo in each described catalyst granules Concentration distribution on whole cross section is uniformity, but allow to exist can tolerate to those skilled in the art or Can ignore or inevitable concentration distribution fluctuation for the state-of-art of this area（Deviation）.Citing and Speech, such as, now Mo₀/Mo₁It is in the range of 1 ± 5% and Mo_m/Mo₁It is in the range of 1 ± 5%, preferably Mo₀/Mo₁It is in 1 ± 2% In the range of and Mo_m/Mo₁It is in the range of 1 ± 2%.The fluctuation of this concentration distribution has no effect on the realization of expected purpose of the present invention, is can With accept, and it is also contained within protection scope of the present invention.

In the present invention, described hydrotreating catalyst is（Solid）Granular, rather than the amorphous state such as powder.Make For the shape of described particle, it is conventional use of variously-shaped to enumerate this area hydrotreating catalyst, such as can enter one Step enumerates spherical, column etc., wherein preferably spherical or column.As described spherical, spheroidal and elliposoidal such as can be enumerated Deng；As described column, cylindric, flat column and profiled-cross-section such as can be enumerated（Such as clover, bunge bedstraw herb etc.）Column 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 To the whole surface being exposed after the geometric center cutting of its shape.Such as, when described catalyst granules is spherical, described Cross section refers to the whole surface exposing after the cutting of its centre of sphere along radius or the short-axis direction of this ball（Such as referring to figure 1）.Or, when described catalyst granules is column, described cross section refers to pass through perpendicular to the length dimension direction of this post The whole surface exposing after the central point cutting of this length dimension（Such as referring to Fig. 2）.In the present invention, by described exposed surface Periphery is referred to as the outer most edge of this cross section, by described geometric center（Central point than the centre of sphere as the aforementioned or length dimension）Referred to as Central point on this cross section.

The hydrotreating catalyst of the present invention, on the basis of the weight of catalyst, the content of alumina-based supports is The content that 46wt% ~ 87wt%, Ni are counted with NiO as 1wt%～8wt%, Mo is with MoO₃The content of meter is 10wt%～40wt%, The content that Co is counted with CoO as 0.5wt%～6wt%.

In the hydrotreating catalyst of the present invention, positioned at the Co at the outer most edge point of catalyst granules cross section concentration with The concentration ratio of Co at heart point（Mol ratio）I.e. Co₀/Co₁For 0.08～0.80, the Ni's at catalyst granules outer most edge point is dense Degree and the concentration ratio of central spot Ni（Mol ratio）I.e. Ni₀/Ni₁For 1.2～7.0.

Can also contain adjuvant component in hydrotreating catalyst of the present invention, such as fluorine, silicon, phosphorus, titanium, zirconium, in boron one Kind or multiple, adjuvant component counts weight content in the catalyst for less than 15% with element, 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 refer to aluminum oxide as key component, can With without adjuvant component it is also possible to contain adjuvant component, wherein adjuvant component can be one of fluorine, silicon, phosphorus, titanium, zirconium, boron etc. Or multiple, adjuvant component in terms of element the content in alumina-based supports in below 30wt%, preferably below 20wt%.Described Alumina-based supports can be using conventional method preparation.The property 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 property 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 the hydrotreating catalyst of the present invention, it is polyalcohol containing organic matter A, described polyalcohol is number-average molecular weight Polyalcohol for 400～10000, preferably number-average molecular weight are 1000～8000 polyalcohol, and described polyalcohol can be PTMEG, preferably polyethylene glycol.Polyalcohol weight content in the catalyst is 0.05% ~ 10.0%, preferably 0.1% ~ 9.0%.

In described hydrotreating catalyst, organic matter B can also be contained, described organic matter B for carbon number be 2 ~ One or more of 20 organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound.The hydrogenation of the present invention Process the organic matter containing in catalyst（I.e. organic matter A or organic matter A and organic matter B）, with Mo atomic molar 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 matter including at least a covalent bond nitrogen-atoms, in organic compounds containing nitrogen Carbon number is 2 ~ 20, concrete such as one or more of ethylenediamine, hexamethylene diamine etc., preferably removes and comprises at least one covalent bond Nitrogen-atoms outside, also include at least the organic compound of a hydroxyl or carboxy moiety, such as：Monoethanolamine, diethanol amine, three ethanol Amine, ethylenediamine tetra-acetic acid（EDTA）, nitrilotriacetic acid（NTA）One or more of with ring ethylenediamine tetra-acetic acid etc..

Described organic compounds containing sulfur is the organic matter including at least a covalent bond sulphur atom, in organic compounds containing sulfur Carbon number generally 2 ~ 20.As sulphonic acids（General formula R-SO₃H）R therein is the alkyl containing 2 ~ 20 carbon atoms, such as benzene sulphur One or more of acid, DBSA, p-methyl benzenesulfonic acid etc..One or many can be contained in organic compounds containing sulfur Individual carboxyl, carbonyl, ester, ether, hydroxyl, the substituent group of sulfydryl, such as TGA, mercaptopropionic acid, dimercaprol dimercaptopropanol etc..Except above-mentioned Outside sulfur-containing compound, sulfone and sulfoxide compound can be comprised, such as one or more of dimethyl sulfoxide (DMSO), dimethyl sulfone etc..

Described oxygen-containing organic compound is the organic matter at least containing a carbon atom and 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 Divide to be carboxyl, carbonyl, hydroxylic moiety or combinations thereof.These materials can be acids, alcohols, ethers, carbohydrate, ketone, phenol One or more of class, aldehydes and lipid.Further preferably as follows：Acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, lemon Lemon acid, ethylene glycol, propane diols, butanediol, glycerine, diethylene glycol (DEG), DPG, triethylene glycol, three butanediols, tetraethylene glycol, poly- second two One or more of alcohol, glucose, fructose, lactose, maltose, sucrose etc..

The preparation method of the hydrotreating catalyst that the present invention provides, wherein active metal Mo is in step（1）Before, step （2）Afterwards and in step（3）It is introduced in hydrotreating catalyst in arbitrary step in before, specifically include：

（1）Using unsaturated infusion process, with the fountain solution oxide impregnation alumina-based support containing adsorbent I, the use of adsorbent I Amount accounts for the 0.1% ~ 10.0% of alumina-based supports weight, wherein said adsorbent I for carbon number be 2～15 organic carboxyl acid and One or more of its esters；

（2）In step（1）Solution containing active metal component Co is impregnated on gains, after drying, roasting, obtains Catalyst intermediate；

（3）With the solution impregnation catalyst intermediate containing adsorbent II, drying, obtain the catalyst containing adsorbent II Intermediate, described adsorbent II（I.e. organic matter A）Consumption account for the 0.1% ~ 10.0% of alumina-based supports weight, adsorbent II It is 400～10000 for number-average molecular weight, preferably 400 ~ 8000 polyalcohol, described dipping adopts saturation dipping or excessive Dipping；

（4）With the dipping solution impregnation steps containing Ni（3）Gains, through drying, obtain hydrotreating catalyst.

In the inventive method, active metal component Mo is introduced into the method in hydrotreating catalyst, can be in step（1）It Front introduce it is also possible in step（2）Afterwards and in step（3）Introduce before.Active metal component Mo is in step（1）Introduce before When, can be using following at least one methods：Carrier component dry glue powder preparation process adds and then reshaping is made containing Mo's Alumina-based supports, add in carrier component kneading and compacting make alumina-based supports containing Mo and carrier component shaping after adopt Add the alumina-based supports made containing Mo with infusion process.Active metal component Mo is in step（1）In step（2）Afterwards and in step Suddenly（3）When introducing, can be introduced using infusion process before.Active metal component Mo is in step（1）When introducing, with aluminum oxide before Illustrate as a example carrier component：

First, add in the preparation process of aluminum oxide dry glue powder, such as to be co-precipitated, fractional precipitation mode introduces, Ran Houcheng Type, is obtained the alumina support containing Mo after drying, roasting；

2nd, added with kneading form when carrier is molded：Aluminum oxide dry glue powder and the chemical combination containing active metal component Mo Thing mixes, and then through kneading and compacting, is dried, the alumina support being obtained containing Mo is made in roasting；

3rd, by aluminum oxide dry glue powder kneading and compacting, then it is dried, alumina support is made in roasting, afterwards with containing work The solution impregnation of alumina carrier of property metal component Mo, drying, roasting make the alumina support containing Mo.

The shaping assistant of routine in above-mentioned forming process, can be added, in such as extrusion aid, adhesive, peptizing agent etc. One or more, addition can according to prepare catalyst property by ability domain knowledge determine.Wherein adhesive typically adopts Little porous aluminum oxide, the boehmite producing selected from aluminium chloride-Ammonia Process, carbonizatin method or aluminum sulfate method and Zlegler synthesis SB alumina powder of byproduct of reaction etc..

In hydrotreating catalyst preparation method of the present invention, the drying in alumina-based supports preparation process containing Mo and roasting Burn the prior art condition that adopts, such as baking temperature is 40 DEG C～250 DEG C, and drying time is 0.5h～20h；Sintering temperature is 350 DEG C～750 DEG C, roasting time is 0.5h～20h.

The inventive method step（1）Described adsorbent I is one or more of organic carboxyl acid and its esters.Described Organic acid include acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, sulfydryl One or more of acetic acid, mercaptopropionic acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ring ethylenediamine tetra-acetic acid etc..Organic carboxyl acid Salt is preferably one or more of ammonium salt of above-mentioned organic carboxyl acid.

In the inventive method, in the fountain solution and the solution containing adsorbent II containing adsorbent I, using water and/or ethanol For solvent.

Step of the present invention（1）In, impregnate the fountain solution containing adsorbent I, using unsaturated dipping, preferably with unsaturation Spray, the volume ratio of wherein unsaturated dipping dip amount used and catalyst precarsor saturated absorption amount of solution is 0.02 ~ 0.4. After the fountain solution containing adsorbent for the dipping, can be dried it is also possible to direct impregnation under the decomposition temperature less than selected adsorbent Generally 60 DEG C～250 DEG C of solution containing active metal Co, wherein baking temperature, preferably 100～200 DEG C, drying time 0.5h～20h, preferably 1h～6h.When spraying the fountain solution containing adsorbent, the good shower nozzle of atomizing effect should be selected, make solution Evenly spread on catalyst precarsor.After the dipping dipping of the fountain solution containing adsorbent terminates, directly can carry out next step, Next step can be carried out through health again, conditioned time is 0.5～8h.

The inventive method step（2）After the dipping of the dipping solution containing Co, through health or without health, then enter Row is dried and roasting.As needed health, conditioned time is 0.5～6.0h.Described drying condition is as follows：Baking temperature be 70 DEG C～ 200 DEG C, preferably 100 DEG C～160 DEG C, drying time is 0.5h～20h, preferably 1h～6h；Described roasting condition：Roasting temperature Spend for 300 DEG C～750 DEG C, preferably 400 DEG C～650 DEG C, roasting time is 0.5h～20h, preferably 1h～6h.

The inventive method step（3）In, the polyalcohol that adsorbent II is 400～10000 for number-average molecular weight, preferably several Average molecular weight is 1000～8000 polyalcohol, and described polyalcohol can be PTMEG, preferably polyethylene glycol.

The inventive method step（3）In, the consumption of adsorbent II makes its content in the final catalyst account for alumina base The 0.05% ~ 10.0% of vehicle weight, preferably 0.1% ~ 10.0%.

Step（3）With the solution impregnation containing adsorbent II, using incipient impregnation or excessive dipping, impregnate after terminating, Sample is through health or without health, then is dried.If needing health, conditioned time is 1～12h.Described drying condition As follows：Temperature is 60 DEG C～250 DEG C, drying time 0.5h～20h.

Step（4）After solution impregnation with active metal component Ni, through health or without health, then done Dry.As needed health, conditioned time is 0.5～6.0h.Described drying condition is as follows：Described drying condition is as follows：Temperature is dried Spend for 70 DEG C～300 DEG C, preferably 100 DEG C～160 DEG C, drying time is 0.5h～20h, preferably 1h～6h.

In hydrotreating catalyst preparation method of the present invention, active metal component Co or Ni loads to catalysis by infusion process When in agent, generally adopt equi-volume impregnating.Dipping method is known to technical staff.Active metal solution manufacturing method is Known to technical staff, its solution concentration can be adjusted by the consumption of each compound, thus prepare specified activity component containing The catalyst of amount.The raw material of required active component is generally the compound of the types such as salt, oxide or acid, comes as molybdenum source One or more of autoxidation molybdenum, ammonium molybdate, ammonium paramolybdate, cobalt source is derived from cobalt nitrate, cobalt carbonate, basic cobaltous carbonate, chlorination One or more of cobalt, cobalt oxalate.Nickel source be derived from nickel nitrate, nickelous carbonate, basic nickel carbonate, nickel chloride, in nickel oxalate one Plant or several.In described dipping solution, in addition to active metal component, phosphorus-containing compound can also be contained, such as phosphoric acid, Asia One or more of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate etc..

In the inventive method, one or more of adjuvant component fluorine, silicon, phosphorus, titanium, zirconium and boron, are drawn using conventional method Enter in catalyst, such as can be introduced into when prepared by carrier in catalyst it is also possible to introduce catalyst after carrier preparation.Carrying Is introduced in catalyst after body preparation, can be introduced in catalyst using the method individually impregnating it is also possible to and active metal component Together dipping is introduced in catalyst.

Introduce organic matter B in hydrotreating catalyst, its Adding Way is：In step（4）The dipping solution containing Ni Middle addition organic matter B, or step（4）Afterwards, impregnated with organic matter B；The consumption of described organic matter B, makes hydrotreating catalyst In the mol ratio of organic matter and Mo atom be 0.002：1～2：1, preferably 0.02：1~1.5：1, more preferably 0.02： 1~1.0：1.In the inventive method, can make to contain in final catalyst by controlling drying condition according to the difference of organic matter The organic matter needing.Organic matter A is 400 ~ 10000 polyalcohol for number-average molecular weight, and organic matter B is selected generally from nitrogenous organic compound One or more of thing, organic compounds containing sulfur and oxygen-containing organic compound.

Hydrotreating catalyst of the present invention is in heavy distillate（Especially diesel oil）Hydrodesulfurization（Especially deep hydrogenation Desulfurization）The middle application as 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 For meter）The sulfur content contributed is about more than 0.01wt%, usually 0.01 wt% ~ 0.05wt%.

Using 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 difficult de- sulfur-containing compound.

The present invention, in described application or described hydrodesulfurizationprocess process, can be only using the hydrorefining catalyst of the present invention Agent is 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） Use cooperatively according to any ratio needing, such as joined using different catalysts bed level or be used in mixed way.

According to the present invention, there is no any special restriction to the operating condition of described hydrodesulfurization, ability can be adopted The conventional use of operating condition in domain, such as 260 ~ 400 DEG C of reaction temperature, react stagnation pressure 3 ~ 13MPa, preferably by preferably 310 ~ 370 DEG C 5 ~ 9MPa, volume space velocity 0.5 ~ 4h during liquid^-1, preferably 1 ~ 2h^-1, hydrogen to oil volume ratio 200：1~2000：1, preferably 400：1~1000： 1.

Those skilled in the art, according to the property of adsorbent II selected species, can select suitable drying condition, thus Make in final hydrotreating catalyst contain adsorbent II polyalcohol, polyalcohol be alumina-based supports weight 0.05% ~ 10.0%, preferably 0.1% ~ 9.0%.

In hydrotreating catalyst of the present invention, active metal component Mo is evenly distributed substantially, active metal component Co from Catalyst granules outer surface is in substantially the trend being gradually increased to center, and Ni is from catalyst granules outer surface to center substantially In the trend gradually decreasing, in catalyst, contain polyalcohol.This catalyst is particularly well-suited in hydrodesulfurization, improves hydrogenation The activity and selectivity of desulfurization, especially removing have the thiophene sulfocompounds of sterically hindered difficult removing.

The hydrotreating catalyst of present invention preparation, Mo is introduced into using conventional method makes it be uniformly distributed in catalyst, By the fountain solution containing adsorbent I for the unsaturated dipping, make the part absorption on catalyst granules outer surface and marginal position surface The adsorbed agent I in position occupies, and when dipping contains the solution of active metal Co, decreases the absorption in carrier edge position for the Co, makes activity The concentration of metal Co is in the trend that is gradually increased from outer surface to center, make further the amount of Mo-Co activity phase from outer surface to Center is in the trend being incremented by；The concentration of the Ni then soaking is in the trend gradually decreasing from catalyst external surface to center, further The amount making Mo-Ni activity phase is in the trend gradually decreasing from outer surface to center, so passes through to control Mo, Co different with Mo, Ni Distribution in variable concentrations, so as to cooperate, gives full play to both advantages in the catalyst for metallic combination, thus improve urging The activity and selectivity of agent, especially removing have the thiophene sulfocompounds of sterically hindered difficult removing.Additionally, this The bright preparation condition by controlling hydrotreating catalyst, makes organic matter be present in final hydrotreating catalyst, activity After metal sulfuration, more lamination numbers can be formed, so that the hydrogenation activity of catalyst is further enhanced.

Brief description

Fig. 1 is the schematic diagram of spherical catalyst particles cutting mode；

Fig. 2 is the schematic diagram of cylindrical catalyst particle cutting mode；

Fig. 3 is the selected each position point on catalyst granules gained cross section and this cross section after the cutting, Wherein 0 any point representing in outer most edge on this cross section is outer most edge point, and 1/4 represents 1/4 location point, and 1/2 represents 1/2 Put a little, 3/4 represents 3/4 location point, and 1 represents central point.

Fig. 4 is concentration profile on this cross section for active metal component Ni and Co in embodiment 2 gained catalyst C1. Wherein abscissa is each position point on this cross section, and ordinate is the concentration at a certain location point and central point on this cross section The ratio of the concentration at place.

Specific embodiment

The technical scheme that the invention is further illustrated by the following examples, but it is real to invention should not be deemed limited to this Apply in example.In the present invention, wt% is mass fraction.

Analysis method of the present invention is as follows：

（1）Active metal component and the content of adjuvant component（wt%）Measured using x ray fluorescence spectrometry.

（2）The specific surface area of catalyst（m²/g）And pore volume（ml/g）Measured using BET method.

（3）Concentration distribution in catalyst granules for each active metal component

In below example and comparative example, employ the carrier of cylinder（But present invention is obviously not limited to this, Can be using other grain shapes）, the catalyst granules thus being obtained is also cylindrical.From each embodiment and contrast A catalyst granules is randomly selected as measurement sample in the catalyst that example is obtained.Exist to measure each active metal component Concentration distribution in this catalyst granules, perpendicular to the length dimension direction of this cylindrical particle, by this length dimension Heart point is cut, and obtains two exposed surfaces.Take one of exposed surface as measurement cross section.

This measurement uses EPMA method, with reference to GB/T15074-2008（Electron probe quantitative analysis method general rule）Carry out, Electron probe microanalyzer（JXA-8230 type, Jeol Ltd.'s manufacture）On carry out.Measuring condition is：Accelerating potential 15kV, beam intensity 5 × 10^-8A, beam spot diameter, 1 m, X-ray detects angle：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（It is respectively NiO, CoO, MoO₃And WO₃）, precision： Less than 1%, secondary electron image resolution ratio：3nm（LaB₆）, linear system：Ni and Co adopts K_αLinear system, Mo adopts L_αLinear system, W adopts M_α Linear system.

Measuring method is：One location point is arbitrarily chosen on the outer most edge of this cross section as 0, with this cross section Central point is as 1,0 straight-line segment connecting described location point 0 and described location point 1（It is substantially the radius of this cross section, because This is also referred to as radially）, at the point of measurement assigned position, the concentration value of targeted activity metal, then passes through division calculation, obtains each dense The ratio of angle value（It is mol ratio in the present invention）.

Fig. 4 is the concentration profile of active metal in the catalyst C1 of embodiment 2 gained, is by this straight-line segment Uniformly choose 21 location points（Including location point 0 and location point 1）, with these location points as abscissa, to survey at each position point The targeted activity metal of amount（Taking Ni and Co as a example）Concentration value and location point 1 at（I.e. central point）The corresponding active metal of measurement Concentration value ratio（Use Ni respectively_m/Ni₁And Co_m/Co₁Represent）For ordinate, so draw and obtain.

（4）Catalyst relatively desulphurizing activated

Relatively desulphurizing activated=100 × [(1/S₁)^0.65-(1/S₀)^0.65]/ [(1/Sc₁)^0.65-(1/S₀)^0.65], S in formula₁ And Sc₁Represent respectively using the sulfur content in catalyst of the present invention or reference agent gained hydrogenation products, S₀Represent and urged using the present invention Sulfur content in agent or the raw materials used oil of reference agent.In terms of S, unit is g/g to wherein sulfur content.

Total sulfur content in raw material and hydrogenation products is to be measured using ultraviolet fluorescence method（ASTM D5453-1993）, 4,6- BMDBT content is to adopt GC-AED（Gas-chromatography-atom luminescence spectroscopy）Measure.

（5）Number-average molecular weight Mn adopts GPC method to measure.

Column type carrier used in embodiment, wherein carrier lengths are about 3 ~ 5mm.

Embodiment 1

The present embodiment introduces the preparation method of catalyst precarsor.Siliceous, boron aluminum oxide dry glue powder specific surface 350m²/ g, Pore volume is 0.90ml/g.

Weigh siliceous, boron aluminum oxide dry glue powder 400g, add citric acid and each 6g of sesbania powder, after mixing, add Acid solution 345g, HNO in acid solution₃Weight concentration be 1.74%, remaining be distilled water.After rolling 20min, use diameter The circular orifice extrusion of 1.7mm.After 120 DEG C are dried 4h, 500 DEG C of roasting 3h.Prepared carrier strip is designated as S1.With the solution containing Mo Obtained carrier strip S1 of dipping, after 130 DEG C are dried 4h, 500 DEG C of roasting 2h, the prepared alumina-based supports containing molybdenum are designated as S1.

Weigh siliceous, boron aluminum oxide dry glue powder 400g, add citric acid and each 6g of sesbania powder, add acid solution 345g, HNO in acid solution₃Weight concentration be 2.6%, Mo with MoO₃The weight content of meter is 27.8%, and remaining is distillation Water.After rolling 20min, with the circular orifice extrusion of diameter 1.7mm.120 DEG C are dried 500 DEG C of roasting 3h after 4h, are obtained containing molybdenum Alumina-based supports are designated as S2.

Prepare siliceous, molybdenum aluminum oxide dry glue powder.Add 1L deionized water in container, be warming up to 58 DEG C, be simultaneously introduced 3L contains Al₂O₃Aluminum nitrate solution for 4g/100mL and contain NH₃Ammonia spirit for 10g/100mL, control ph is 7.8, charging Time is 120min.After stopping charging, system aging 50min under said temperature and pH value condition, add SiO₂Content is The solution of sodium metasilicate through 100mL of 5.0g, continues aging 60min, is washed out 4 times, to Cl^-/Al₂O₃<Till 0.5%.Preparation contains The aqueous solution 1L of molybdenum, wherein MoO₃Concentration 4.3g/100mL, adds in filter cake, stirs into pasty state, after 120 DEG C are dried 8h, by it It is crushed to granularity and accounts for more than 95% less than 180 purposes, obtain required dry glue powder.The aluminum oxide dry glue powder of the siliceous and molybdenum of gained Property as follows：Specific surface area is 340m²/ g, pore volume is 0.88ml/g.

Weigh siliceous and molybdenum aluminum oxide dry glue powder 400g, add citric acid and each 6g of sesbania powder, after mixing, add Acid solution 345g, HNO in acid solution₃Weight concentration be 1.74%, remaining be distilled water.After rolling 20min, use diameter The circular orifice extrusion of 1.7mm.120 DEG C are dried 500 DEG C of roasting 3h after 4h.Prepared carrier strip is designated as S3.

Table 1 contains the composition of alumina-based supports and the property of molybdenum

Bearer number	S1	S2	S3
				Si, wt%	1.39	1.36	1.41
B, wt%	1.68	1.73	-
				MO3, wt%	25.8	25.7	25.5
Specific surface area, m2/g	184	182	185
				Pore volume, mL/g	0.39	0.41	0.40
Saturation liquid absorption, mL/100g	48	50	49

Embodiment 2

Weigh tartaric acid 12g, stirring and dissolving in 30g water, prepared fountain solution I.Take S1 200g, fountain solution I is uniformly sprayed It is immersed on S1, the time that sprays is 15min.After fountain solution I sprays end, 2h is dried through 100 DEG C, with bodies such as the maceration extracts containing Co, P The above-mentioned carrier of long-pending dipping, the sample average obtaining is divided into two parts, and wherein first part sample not health is dried 3h through 120 DEG C, and 480 DEG C roasting 2h, the sample of acquisition is designated as B1；Second sample health 1h, is dried 3h through 120 DEG C, 480 DEG C of roasting 2h, prepared sample Product are designated as B2.

Stirring and dissolving polyethylene glycol 2000 in the water measuring（I.e. molecular weight is 2000 polyethylene glycol, similarly hereinafter）, system Obtain solution II.The consumption of polyethylene glycol accounts for the 6% of alumina-based supports weight, with this solution II incipient impregnation sample B1, then Carry out the health of 10h, after 120 DEG C are dried 3h, prepared sample is designated as Z1.Take B2 sample, through processing step with B1 identical Suddenly, prepared sample is designated as Z2..

Spray above-mentioned Z1 and Z2 sample, the citric acid of introducing and catalyst with the maceration extract equal-volume containing Ni, P and citric acid The mol ratio of upper Mo is 0.05：1, directly carry out 120 DEG C without health after spraying end and 3h is dried, the catalyst of acquisition is remembered respectively For C1 and C2.

Embodiment 3

Weigh malic acid 4g, stirring and dissolving in 16g ethanol, prepared fountain solution I.Take S2 200g, will be uniform for fountain solution I Spray on S2, the time that sprays is 5min.With the above-mentioned carrier of maceration extract incipient impregnation containing Co, P, impregnate and terminate rear health 1h, is dried 3h through 120 DEG C, 480 DEG C of roasting 2h, and the sample of acquisition is designated as B3.

Stirring and dissolving cetomacrogol 1000 in the water measuring, obtained solution II.The consumption of polyethylene glycol accounts for aluminum oxide The 8% of base load body weight, with this solution II incipient impregnation sample B3, then carries out the health of 5h, after 120 DEG C are dried 3h, Prepared sample is designated as Z3.

Spray Z3 sample with the maceration extract equal-volume containing Ni, P and glucose, the glucose of introducing and the rubbing of Mo on catalyst That ratio is 0.04：1, spray the sample average after end and be divided into two parts, direct 120 DEG C of wherein first part sample is dried 3h, obtain Catalyst be designated as C3；Second sample health 1h, 120 DEG C are dried 3h, and prepared catalyst is designated as C4.

Embodiment 4

Weigh citric acid and each 7g of malonic acid, stirring and dissolving in 40g water, prepared fountain solution I.Take S3 200g, will soak Liquid I uniformly sprays on S3, and the time that sprays is 25min.With the above-mentioned carrier of the maceration extract incipient impregnation containing Co, P, impregnate after terminating Health 1h, is dried 3h through 120 DEG C, 480 DEG C of roasting 2h, and the sample of acquisition is designated as B4.

Stirring and dissolving PEG 8000 in the aqueous solution measuring, obtained solution II.The consumption of polyethylene glycol accounts for oxygen Change the 3.5% of alumina-based support weight, with this solution II incipient impregnation sample B4, then carry out the health of 5h, dry through 120 DEG C After dry 3h, prepared sample is designated as Z4.

Spray Z4 sample with the maceration extract equal-volume containing Ni, P, directly 3h is dried through 120 DEG C, the catalyst of acquisition is designated as C5.

Prepare aqueous acid containing lemon, equal-volume sprays part C5 sample, the citric acid of introducing and Mo on catalyst Mol ratio is 0.08：1, after spraying end, 3h is dried through 120 DEG C, the catalyst of acquisition is designated as C6.

Embodiment 5

Weigh tartaric acid 5g, stirring and dissolving in 12g water, prepared fountain solution I.Take S1 100g, fountain solution I is uniformly sprayed It is immersed on S1, the time that sprays is 10min.After fountain solution I sprays end, 2h is dried through 100 DEG C, with bodies such as the maceration extracts containing Co, P The above-mentioned carrier of long-pending dipping, the sample not health obtaining, 3h is dried through 120 DEG C, 480 DEG C of roasting 2h, the sample of acquisition is designated as B5.

Stirring and dissolving Macrogol 3000 in the water measuring, obtained solution II.The consumption of polyethylene glycol accounts for aluminum oxide The 5% of base load body weight, with this solution II incipient impregnation sample B5, then carries out the health of 10h, 3h is dried through 120 DEG C Afterwards, prepared sample is designated as Z5.

Spray above-mentioned Z5 sample with the maceration extract equal-volume containing Ni, P, after spraying end, directly carry out 120 DEG C without health 3h is dried, the catalyst of acquisition is designated as C7 respectively.

Comparative example 1

Take S3 100g, prepare the maceration extract containing Ni, Co, P and citric acid and each 3.5g of malonic acid, incipient impregnation is above-mentioned After carrier, 3h is dried through 120 DEG C, the sample of acquisition is designated as C8.

Table 2 embodiment is formed with comparative example catalyst activity metal

Catalyst is numbered	C1	C2	C3	C4	C5	C6	C7	C8
									Mo（With MoO3Meter）, wt%	24.0	24.1	23.9	24.0	23.9	24.0	24.1	24.0
Co（In terms of CoO）, wt%	2.3	2.4	2.3	2.4	2.3	2.3	2.4	2.4
									Ni（In terms of NiO）, wt%	1.9	2.1	2.0	2.1	2.0	2.1	2.1	2.0
P（With P2O5Meter）, wt%	2.8	2.7	2.7	2.8	2.7	2.8	2.8	2.7

Table 3 embodiment and concentration distribution in catalyst granules for the elements Mo in comparative example gained catalyst

Catalyst is numbered	C1	C2	C3	C4	C5	C6	C7	C8
									Mo0/Mo1	1.0	1.01	1.01	0.99	1.0	1.0	1.01	1.0
Mo1/4/Mo1	1.01	0.98	1.02	1.02	1.01	1.01	0.98	1.01
									Mo1/2/Mo1	0.99	0.99	0.98	0.98	1.0	0.99	1.0	0.98
Mo3/4/Mo1	0.99	1.01	0.99	1.00	0.99	0.99	0.99	0.99

Table 4 embodiment and concentration distribution in catalyst granules for Elements C o in comparative example catalyst

Catalyst is numbered	C1	C2	C3	C4	C5	C6	C7	C8
									Co0/Co1	0.13	0.27	0.31	0.32	0.30	0.34	0.17	0.96
Co1/4/Co1	0.29	0.45	0.79	0.78	0.43	0.45	0.32	0.97
									Co1/2/Co1	0.60	0.81	0.97	0.96	0.80	0.81	0.61	1.00
Co3/4/Co1	0.91	0.94	0.99	0.99	0.95	0.95	0.91	0.99

Table 5 embodiment and Ni element in comparative example catalyst are along the concentration distribution in catalyst granules

Catalyst is numbered	C1	C2	C3	C4	C5	C6	C7	C8
									Ni0/Ni1	2.82	2.83	3.03	2.50	2.51	2.47	2.70	0.95
Ni1/4/ Ni1	1.90	1.88	1.94	1.72	1.70	1.67	1.81	0.97
									Ni1/2/ Ni1	1.27	1.28	1.31	1.22	1.20	1.20	1.23	0.99
Ni3/4/ Ni1	1.10	1.11	1.11	1.08	1.06	1.05	1.09	1.00

From table 4 and table 5, using the catalyst C1～C7 of present invention preparation, active metal Co is along catalyst particles particle diameter It is gradually increased to from edge to centre concentration, active metal Ni gradually subtracts from edge to centre concentration along catalyst granules radial direction Little, and the concentration on comparative example catalyst C8 active metal Co, Ni each position at radial direction is essentially identical, unlike system of the present invention Standby catalyst is in obvious uneven distribution.Found by C1 and C2, conditioned time after controlling fountain solution I to spray end, Active metal Co distributed density in catalyst granules radially can be adjusted；Find out from C2, C4 and C5, by fountain solution I Changes of contents also can adjust active metal Co distributed density in catalyst granules radially；Find out from C3, C4 and C5, by profit The content of wet liquid II and the conditioned time spraying Ni, P rear catalyst, can adjust active metal Ni in catalyst granules radially Distributed density.Therefore, the inventive method can easily adjust active metal distributed density in catalyst granules radially, Thus improving the deep desulfuration performance of catalyst.

Embodiment 6

The present embodiment is the active appraisal experiment of catalyst.

Catalyst activity evaluation experimental is carried out on 100ml small hydrogenation device, before activity rating, catalyst is carried out pre- Sulfuration.Evaluating catalyst condition is in reaction stagnation pressure 5.5MPa, volume space velocity 2.0 h during liquid^-1, hydrogen-oil ratio 500：1, reaction temperature For 340 DEG C.Active appraisal experiment raw material oil nature is shown in Table 6, and Activity evaluation is shown in Table 7, and table 8 provides typical case in hydrogenation products The content of difficult de- sulfur-containing compound, from data in table, prepares hydrotreating catalyst with the present invention, the desulfurization of catalyst is lived Property is apparently higher than comparative example catalyst.

Table 6 raw material oil nature

Feedstock 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 7 catalyst activity evaluation result

Catalyst	C1	C2	C3	C4	C5	C6	C7	C8
									Relatively desulphurizing activated, %	130	128	124	120	127	131	129	100

The content of the difficult de- sulfur-containing compound of typical case in table 8 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

14.1

14.5

15.1

15.9

14.7

13.9

14.2

23.2

Claims (32)

1. a kind of hydrotreating catalyst, using alumina-based supports, active metal component is Co, Mo, Ni, wherein active metal Concentration distribution on each catalyst granules cross section for the component is as follows：Co₀/Co₁＜ Co_1/2/Co₁＜ 1, Ni₀/Ni₁＞ Ni_1/2/ Ni₁The concentration of ＞ 1, Mo is substantially uniformly distributed；Organic matter A is contained, described is organic in described hydrotreating catalyst The polyalcohol that thing A is 400～10000 for number-average molecular weight；Organic matter A weight content in the catalyst is 0.05% ~ 10.0%； Described hydrotreating catalyst, on the basis of the weight of catalyst, the content of alumina-based supports is 46wt% ~ 87wt%, The content that Ni is counted with NiO as 1wt%～8wt%, Mo is with MoO₃The content of meter is 10wt%～40wt%, Co containing in terms of CoO Measure as 0.5wt%～6wt%；

Wherein, concentration distribution formula A on the cross section of each catalyst granules for the active metal component_m/B_nRepresent, that is, often The ratio of the concentration of element B at the concentration of elements A and n at m on the cross section of individual catalyst granules, wherein A represents active metal Elements Mo, Co or Ni, B represents active metallic element Mo, Co or Ni；Any point with catalyst granules cross section outer most edge is Starting point is designated as 0, is designated as 1 with the central point of catalyst granules cross section for terminal, connects starting point and terminal obtains straight line line Section, m and n is illustrated respectively in the location point choose on above-mentioned straight-line segment, and the value of m and n represents from starting point to the position chosen The distance of point accounts for the ratio of the length of above-mentioned straight-line segment, and the value of m and n is 0 ~ 1, and in order to express easily, A and B directly adopts Active metallic element Mo, Co or Ni replace, m and n is directly with defined location on 0～1 above-mentioned straight-line segment of digitized representation Point.

2. according to the catalyst described in claim 1 it is characterised in that described organic matter 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 a kind of following scheme：

（1）Co₀/Co₁With Co_1/2/Co₁Ratio be 0.2 ~ 0.8；

（2）Ni₀/Ni₁With Ni_1/2/Ni₁Ratio 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 a kind of following scheme：

（1）Co₀/Co₁With Co_1/2/Co₁Ratio be 0.2 ~ 0.7；

（2）Ni₀/Ni₁With Ni_1/2/Ni₁Ratio 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 distribution on catalyst granules cross section at least includes a kind of following scheme：

（1）Co₀/Co₁＜ Co_1/4/Co₁＜ Co_1/2/Co₁；

（2）Co_1/2/Co₁＜ Co_3/4/Co₁＜ 1；

（3）Ni₀/Ni₁＞ Ni_1/4/Ni₁＞ Ni_1/2/Ni₁；

（4）Ni_1/2/Ni₁＞ Ni_3/4/Ni₁＞ 1.

6. according to the catalyst described in claim 1 it is characterised in that in described hydrotreating catalyst, active metal component Concentration distribution on catalyst granules cross section at least includes a kind of following scheme：

（5）Co₀/Co₁＜ Co_x1/Co₁＜ Co_x2/Co₁＜ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1；

（6）Ni₀/Ni₁＞ Ni_x1/Ni₁＞ Ni_x2/Ni₁＞ 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 a kind of following scheme：

（1）Co₀/Co₁With Co_1/4/Co₁Ratio be 0.3 ~ 0.9；

（2）Co_1/4/Co₁With Co_1/2/Co₁Ratio be 0.4 ~ 0.9；

（3）Ni₀/Ni₁With Ni_1/4/Ni₁Ratio be 1.2 ~ 1.8；

（4）Ni_1/4/Ni₁With Ni_1/2/Ni₁Ratio 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 a kind of following scheme：

（1）Co₀/Co₁With Co_1/4/Co₁Ratio be 0.3 ~ 0.85；

（2）Co_1/4/Co₁With Co_1/2/Co₁Ratio be 0.4 ~ 0.87；

（3）Ni₀/Ni₁With Ni_1/4/Ni₁Ratio be 1.3 ~ 1.7；

（4）Ni_1/4/Ni₁With Ni_1/2/Ni₁Ratio be 1.2 ~ 1.6.

9. according to the catalyst described in claim 1 it is characterised in that in described hydrotreating catalyst, in catalyst granules On cross section, along described straight-line segment from outer most edge point to central point, active metal component concentration distribution is as follows：The concentration base of Co It is gradually increased on this, the concentration of Ni substantially gradually decreases, and the concentration of Mo is substantially uniformly distributed.

10. according to the catalyst described in claim 1 it is characterised in that in described hydrotreating catalyst, positioned at catalyst The concentration of Co at particle cross section outer most edge point and the concentration ratio of central spot Co are Co₀/Co₁For 0.08～0.90, positioned at urging The concentration of Ni at the outer most edge point of catalyst particles cross section and the concentration ratio of central spot Ni are Ni₀/Ni₁For 1.2～7.0.

11. according to the catalyst described in claim 1 it is characterised in that the property of described hydrotreating catalyst is as follows：Than Surface area is 120～220 m²/ g, pore volume is 0.20～0.60mL/g.

12. according to the catalyst described in claim 1 it is characterised in that described polyalcohol be polyethylene glycol.

13. according to the catalyst described in claim 1 it is characterised in that in described hydrotreating catalyst, containing organic matter A The polyalcohol being 1000～8000 for number-average molecular weight.

14. according to the catalyst described in claim 1 it is characterised in that in described hydrotreating catalyst, containing organic matter B, organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic that described organic matter B is 2 ~ 20 for carbon number close One or more of thing；Wherein oxygen-containing organic compound is in acids, ethers, carbohydrate, ketone, phenols, aldehydes and lipid One or more.

15. according to the arbitrary described catalyst of claim 1-6,9-14 it is characterised in that in described hydrotreating catalyst The organic matter containing and Mo atomic molar are than for 0.002：1～2.0：1.

16. according to the catalyst described in claim 15 it is characterised in that contain in described hydrotreating catalyst is organic Thing and Mo atomic molar are than for 0.02：1~1.0：1.

17. according to the catalyst described in claim 1 it is characterised in that in described hydrotreating catalyst, aluminum oxide base load Body is with aluminum oxide as key component, without adjuvant component or contain adjuvant component, wherein adjuvant component be fluorine, silicon, phosphorus, titanium, One or more of zirconium, boron, adjuvant component in terms of element the content in alumina-based supports in below 30wt%.

18. according to the catalyst described in claim 1 it is characterised in that in described hydrotreating catalyst, containing auxiliary agent group Point, wherein adjuvant component is one or more of fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in terms of element in the catalyst Weight content is in below 15wt%.

19. 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 hydrotreating catalyst of 20. claims 1 ~ 12, wherein active metal Mo is in step（1） Before, step（2）Afterwards and in step（3）It is introduced in hydrotreating catalyst in arbitrary step in before, including：

（1）With the fountain solution oxide impregnation alumina-based support containing adsorbent I, the consumption of adsorbent I is alumina-based supports weight 0.1% ~ 10.0%；Described adsorbent I is one or more of organic carboxyl acid and its esters, and described dipping is not using Saturation impregnates；

（2）With the dipping solution impregnation steps containing Co（1）Gains, through dry and roasting, obtain catalyst intermediate,

（3）With the solution impregnation catalyst intermediate containing adsorbent II, drying, obtain in the middle of the catalyst containing adsorbent II Body, the consumption of wherein adsorbent II accounts for the 0.1% ~ 10.0% of alumina-based supports weight, and described adsorbent II is that organic matter A is Number-average molecular weight is 400～10000 polyalcohol, and described dipping adopts saturation dipping or excessive dipping；

（4）With the dipping solution impregnation steps containing Ni（3）Gains, through drying, obtain hydrotreating catalyst.

21. in accordance with the method for claim 20 it is characterised in that described adsorbent I is in organic carboxyl acid and its esters One or more, its carbon number be 2～15.

22. in accordance with the method for claim 20 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, ethylenediamine tetra-acetic acid, nitrogen One or more of river triacetic acid, ring ethylenediamine tetra-acetic acid；Organic carboxylate is one of ammonium salt of above-mentioned organic carboxyl acid Or it is multiple.

23. in accordance with the method for claim 20 it is characterised in that：Fountain solution containing adsorbent I and containing adsorbent II In solution, it is solvent using water and/or ethanol.

24. in accordance with the method for claim 20 it is characterised in that：Step（1）The middle fountain solution containing adsorbent I impregnates oxygen Change alumina-based support, dipping therein is sprayed using unsaturation, the time that sprays is 1min～40min；Profit containing adsorbent I used The volume of wet liquid is 0.02 ~ 0.4 with the ratio of carrier saturation imbibition volume.

25. in accordance with the method for claim 20 it is characterised in that：Step（1）The middle fountain solution containing adsorbent I impregnates After alumina-based supports, through drying steps or without drying steps, then carry out step（2）, described drying condition is such as Under：Temperature is 60 DEG C～250 DEG C, time 0.5h～20h.

26. in accordance with the method for claim 20 it is characterised in that：Step（2）With the dipping solution impregnation steps containing Co （1）After gains, through health or without health, then be dried and roasting, such as need health, conditioned time be 0.5～ 4.0h；Described baking temperature is 70 DEG C～300 DEG C, and drying time is 0.5h～20h；Described roasting condition is as follows：Roasting Temperature is 300 DEG C～750 DEG C, and roasting time is 0.5h～20h.

27. in accordance with the method for claim 20 it is characterised in that：Step（3）Urged with the solution impregnation containing adsorbent II Agent intermediate, using incipient impregnation or excessive dipping, after dipping terminates, sample is through health or without health, then enters Row drying, if needing health, conditioned time is 1～12h；Described drying condition is as follows：Temperature is 60 DEG C～250 DEG C, when being dried Between 0.5h～20h.

28. in accordance with the method for claim 20 it is characterised in that：Step（4）In, with the dipping of the dipping solution containing Ni After solution impregnation, through health or without health, such as need health, conditioned time is 0.5～6.0h, then is dried, institute The drying condition stated is as follows：Baking temperature is 70 DEG C～300 DEG C, drying time 0.5h～20h.

29. in accordance with the method for claim 20 it is characterised in that：Step（2）And/or step（4）Described dipping solution In, in addition to active metal component, also contain phosphorus, phosphorus source is selected from phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate One or more of, the introduction volume of phosphorus is with P₂O₅Meter accounts for the 1% ~ 6% of final hydrotreating catalyst weight.

30. in accordance with the method for claim 20 it is characterised in that：Introduce organic matter B in hydrotreating catalyst, it adds Entering method is：In step（4）The dipping solution containing Ni in add organic matter B, or step（4）Afterwards, impregnated with organic matter B； The consumption of described organic matter B, makes the organic matter in hydrotreating catalyst be 0.002 with the mol ratio of Mo atom：1～2：1；Have Machine thing B is selected from one or more of organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound.

A kind of 31. methods of heavy distillate hydrodesulfurization are it is characterised in that adopt the arbitrary described hydrogenation of claim 1 ~ 19 Process catalyst.

32. according to the method described in claim 31 it is characterised in that：Described heavy distillate is diesel oil.