CN103801313A

CN103801313A - Distillate hydrotreating catalyst and preparation method thereof

Info

Publication number: CN103801313A
Application number: CN201310527896.4A
Authority: CN
Inventors: 杨占林; 唐兆吉; 姜虹; 王继锋; 温德荣; 魏登凌
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2012-11-08
Filing date: 2013-10-31
Publication date: 2014-05-21
Anticipated expiration: 2033-10-31
Also published as: CN103801313B

Abstract

The invention discloses a hydrotreating catalyst and a preparation method thereof. The hydrotreating catalyst adopts an alumina-base support, and the active metal components are Mo, Co and Ni. The active metal components are distributed in the catalyst granules as follows: Co0/Co1<Co1/2/Co1<1, Mo0/Mo1<Mo1/2/Mo1<1, and the Ni concentration is basically distributed uniformly. The preparation method comprises the following steps: impregnating the alumina-base support with a wetting liquid containing an adsorbent by an unsaturated impregnation process, impregnating with the supported active metal components Mo and Co, and introducing the Ni into the hydrotreating catalyst by a conventional process. The hydrotreating catalyst is especially suitable to be used as a deep hydrodesulfurization catalyst for diesel.

Description

A kind of catalyst for hydrogenation of fraction oil and preparation method thereof

Technical field

The present invention relates to a kind of preparation method of hydrotreating catalyst, particularly a kind of preparation method who is suitable for catalyst for hydro-processing heavy distillate.

Background technology

Along with the requirement that society cleans heavy distillate (particularly diesel oil) is more and more higher, the deep hydrodesulfurizationof technology of heavy distillate just seems more and more important.Sulfur-containing compound in heavy distillate mainly contains analiphatic sulphur compound, thioether, dibenzothiophenes, alkylbenzene bithiophene and methyldibenzothiophene etc., it is wherein more difficult that what remove is the thiophenes such as dibenzothiophenes, alkylbenzene bithiophene and methyldibenzothiophene, especially with 4,6-dimethyl Dibenzothiophene (4,6-BMDBT) with 2,4,6-trimethyl dibenzothiophenes (2,4,6-BMDBT) the most difficult the removing of sulfur-containing compound of the complicated and steric effect of having living space of class formation.Reach the degree of depth and ultra-deep desulfurization, just need to remove these complex structures and sterically hindered large sulfur-containing compound, and these sulfur-containing compounds also more difficult removing under the operating condition of the harshnesses such as HTHP conventionally.Therefore, the heavy distillate degree of depth and ultra-deep desulfurization have significant difference with conventional hydrodesulfurization in reaction mechanism, and this just requires there is specific (special) requirements in the design of deep hydrodesulfurizationof catalyst.

Hydrotreating catalyst normally adopts alumina-based supports, and take group vib and group VIII metal as hydrogenation active metals component, wherein active metal component is generally equally distributed in catalyst.CN99103007.9 discloses a kind of light-end products hydrotreating catalyst containing molybdenum and/or tungsten.This catalyst contains the tungsten oxide and/or molybdenum oxide, nickel oxide and the cobalt oxide that load on alumina support, the content of described tungsten oxide and/or molybdenum oxide is that 4 heavy % are to being less than 10 heavy %, the content of nickel oxide is 1～5%, the content of cobalt oxide is 0.01～1 heavy %, and nickel and cobalt total atom number are 0.3～0.9 with the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum.Compared with prior art, this catalyst has lower tenor and but has higher low temperature active.This catalyst is specially adapted 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, take aluminium oxide or silicon-containing alumina as carrier, take W, Mo, Ni as active component, adds phosphate builder.By adopting segmentation total immersion technology, make the Metal Distribution on catalyst more even, the activity of catalyst, particularly hydrodenitrogenationactivity activity is greatly improved.

The hydrotreating catalyst of these prior aries all belongs to conventional Hydrobon catalyst, can not effectively be applicable to the hydrodesulfurization of heavy distillate (especially diesel oil).Therefore, prior art still needs a kind of hydrotreating catalyst, is particularly useful 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.

Hydrotreating catalyst of the present invention, adopts alumina-based supports, and active metal component is Mo, Co and Ni, and wherein the CONCENTRATION DISTRIBUTION of active metal component on the cross section of each catalyst granules is as follows: Co ₀/ Co ₁< Co _1/2/ Co ₁< 1, Mo ₀/ Mo ₁< Mo _1/2/ Mo ₁< 1, the concentration of Ni is essentially and is uniformly distributed.

In the present invention, the CONCENTRATION DISTRIBUTION of active metal component on the cross section of each catalyst granules formula A _m/ B _nrepresent, be the ratio of the concentration of m place elements A and the concentration of n place element B on the cross section of each catalyst granules (in the present invention, unit is mol ratio), wherein A represents active metal elements Mo, Co or Ni, B represents active metal elements Mo, Co or Ni, wherein A and B can be identical, also can be different, being outer most edge point take any point of catalyst granules cross section outer most edge is designated as 0 as starting point, be designated as 1 take the central point of catalyst granules cross section as terminal, connect starting point and terminal and obtain straight line line segment, m and n are illustrated respectively in the location point of choosing on above-mentioned straight line line segment, the value representation of m and n accounts for the ratio of the length of above-mentioned straight line line segment from starting point to the distance of the location point of choosing, the value of m and n is 0 ~ 1, wherein m(or n) value be 0, 1/4, 1/2, 3/4, within 1 o'clock, represent respectively to account for from starting point to the distance of the location point of choosing above-mentioned straight line

line segment length

0, 1/4, 1/2, 3/4, the position (see figure 3) at 1 o'clock selected point place, above-mentioned location point is selected (or appearance millet cake) also referred to as outer most edge, 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 adopt active metal elements Mo, Co or Ni to replace, and m and n are directly with definite location point on 0～1 the above-mentioned straight line line segment of digitized representation, represent on above-mentioned straight line line segment location point arbitrarily with x1 or x2, such as, Co ₀/ Co ₁represent that A and B are Co, m=0, n=1 represents the ratio of the concentration of the catalyst granules cross section outer most edge point Elements C o of place and the concentration of central spot Elements C o, Ni _1/2/ Ni ₁represent that A and B are Ni, m=1/2, n=1 is illustrated on the described straight line line segment on catalyst granules cross section, makes the ratio of the concentration of the 1/2 o'clock selected point position element Ni that accounts for above-mentioned straight line line segment length from outer most edge point to the distance of selected point and the concentration of central spot element Ni.Co ₀/ Mo ₀expression A is Co, and B is Mo, m=0, and n=0, represents the ratio of the concentration of the catalyst granules cross section outer most edge point Elements C o of place and the concentration of this elements Mo.X1 in the present invention and x2 are being connected the location point (but not comprising outer most edge point and central point) of choosing arbitrarily on the straight line line segment that above-mentioned outer most edge point and central point obtain respectively, and put from outer most edge the distance that x1 orders and be less than the i.e. 0 < x1 < x2 < 1 of distance of ordering to x2 from outer most edge point.

In the present invention, relate to and use formula A _m/ B _nit is specific as follows that form represents: Co ₀/ Co ₁(A and B are Co, m=0, n=1), Co _1/4/ Co ₁(A and B are Co, m=1/4, n=1), Co _1/2/ Co ₁(A and B are Co, m=1/2, n=1), Co _3/4/ Co ₁(A and B are Co, m=3/4, n=1), Co _x1/ Co ₁(A and B are Co, m=x1, n=1), Co _x2/ Co ₁(A and B are Co, m=x2, n=1), Ni ₀/ Ni ₁(A and B are Ni, m=0, n=1), Ni _1/4/ Ni ₁(A and B are Ni, m=1/4, n=1), Ni _1/2/ Ni ₁(A and B are Ni, m=1/2, n=1), Ni _3/4/ Ni ₁(A and B are Ni, m=3/4, n=1), Mo ₀/ Mo ₁(A and B are Mo, m=0, n=1), Mo _1/4/ Mo ₁(A and B are Mo, m=1/4, n=1), Mo _1/2/ Mo ₁(A and B are Mo, m=1/2, n=1), Mo _3/4/ Mo ₁(A and B are Mo, m=3/4, n=1), Mo _x1/ Mo ₁(A and B are Mo, m=x1, n=1), Mo _x2/ Mo ₁(A and B are Mo, m=x2, n=1), Co ₀/ Mo ₀(A is Co, and B is Mo, m=0, n=0).。

In hydrotreating catalyst of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Co ₀/ Co ₁with Co _1/2/ Co ₁ratio be 0.2 ~ 0.8, be preferably 0.2 ~ 0.7; Mo ₀/ Mo ₁with Mo _1/2/ Mo ₁ratio be 0.2 ~ 0.8, be preferably 0.2 ~ 0.7.

In hydrotreating catalyst of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Co ₀/ Mo ₀ratio be 0.07 ~ 2.0, be preferably 0.08 ~ 1.2.

In hydrotreating catalyst of the present invention, the distribution of active metal component on catalyst granules cross section is preferably as follows: Co ₀/ Co ₁< Co _1/4/ Co ₁< Co _1/2/ Co ₁.

In hydrotreating catalyst of the present invention, the distribution of active metal component on catalyst granules cross section is preferably as follows: Co _1/2/ Co ₁< Co _3/4/ Co ₁< 1.

In hydrotreating catalyst of the present invention, the distribution of active metal component on catalyst granules cross section is preferably as follows: Mo ₀/ Mo ₁< Mo _1/4/ Mo ₁< Mo _1/2/ Mo ₁.

In hydrotreating catalyst of the present invention, the distribution of active metal component on catalyst granules cross section is preferably as follows: Mo _1/2/ Mo ₁< Mo _3/4/ Mo ₁< 1.

In hydrotreating catalyst of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Co ₀/ Co ₁with Co _1/4/ Co ₁ratio be 0.30 ~ 0.90, be preferably 0.30 ~ 0.85; Co _1/4/ Co ₁with Co _1/2/ Co ₁ratio be 0.4 ~ 0.9, be preferably 0.4 ~ 0.87; Mo ₀/ Mo ₁with Mo _1/4/ Mo ₁ratio be 0.30 ~ 0.90, be preferably 0.30 ~ 0.85; Mo _1/4/ Mo ₁with Mo _1/2/ Mo ₁ratio be 0.4 ~ 0.9, be preferably 0.4 ~ 0.87.

In hydrotreating catalyst of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Co ₀/ Co ₁< Co _x1/ Co ₁< Co _x2/ Co ₁< 1, wherein 0 < x1 < x2 < 1.

In hydrotreating catalyst of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Mo ₀/ Mo ₁< Mo _x1/ Mo ₁< Mo _x2/ Mo ₁< 1, wherein 0 < x1 < x2 < 1.

In hydrotreating catalyst of the present invention, on catalyst granules cross section, put central point along described straight line line segment from outer most edge, active metal component concentration distributes as follows: the concentration of Co increases substantially gradually, the concentration of Mo increases substantially gradually, and the concentration of Ni is essentially and is uniformly distributed.

In the present invention, the CONCENTRATION DISTRIBUTION that described " substantially increasing gradually along described straight line line segment " refers to described active metal element presents generally the trend increasing gradually in the whole interval from outer most edge point to central point along described straight line line segment, but allows to exist between one or more partial zones; In this partial zones, the CONCENTRATION DISTRIBUTION of described active metal element presents different trend (such as remaining constant and/or reducing gradually and/or disordered state) along described straight line line segment.Prerequisite is, existence between this class partial zones is can tolerate or negligible to those skilled in the art, or for the state-of-art of this area, be inevitably, and existence between these partial zones does not affect those skilled in the art, and by described active metal element, the CONCENTRATION DISTRIBUTION in described whole interval is still judged to be " presenting generally the trend increasing gradually ".In addition, the existence between this partial zones does not affect the present invention and expects the realization of object, is acceptable, and within being also contained in protection scope of the present invention.

In the present invention, described " concentration of Ni is essentially and is uniformly distributed " refers to the CONCENTRATION DISTRIBUTION of Ni on the whole cross section of each described catalyst granules is uniformity, maybe can ignore or inevitable CONCENTRATION DISTRIBUTION fluctuation (deviation) for the state-of-art of this area but allow existence can tolerate to those skilled in the art.For example, such as, now Ni ₀/ Ni ₁in 1 ± 5% scope and Ni _m/ Ni ₁in 1 ± 5% scope, preferably Ni ₀/ Ni ₁in 1 ± 2% scope and Ni _m/ Ni ₁in 1 ± 2% scope.The fluctuation of this CONCENTRATION DISTRIBUTION does not affect the present invention and expects the realization of object, is acceptable, and within being also contained in protection scope of the present invention.

In the present invention, described hydrotreating catalyst is that (solid) is granular, rather than the amorphous state such as powder.As the shape of described particle, can enumerate the conventional various shapes that use of this area hydrotreating catalyst,, column spherical such as can further enumerating etc., wherein preferred spherical or column.As described spherical, such as enumerating spheroidal and elliposoidal etc.; As described column,, flat column cylindric such as enumerating and profiled-cross-section (such as clover, bunge bedstraw herb etc.) column etc.The granularity of described hydrotreating catalyst is 3 ~ 8mm, is preferably 3 ~ 5mm.

In the present invention, described " cross section of catalyst granules " refers to along the minimum dimension direction of a catalyst granules and cuts the rear whole surface exposing by the geometric center of its shape.Such as, at described catalyst granules while being spherical, described cross section refers to the whole surface (such as referring to Fig. 1) exposing after by its centre of sphere cutting along the radius of this ball or short-axis direction.Or, in the time that described catalyst granules is column, the whole surface (such as referring to Fig. 2) that described cross section exposes after referring to and cutting by the central point of this length dimension perpendicular to the length dimension direction of this post.In the present invention, the periphery of described exposed surface is called to the outer most edge of this cross section, described geometric center (such as the central point of the aforesaid centre of sphere or length dimension) is called to the central point on this cross section.

Hydrotreating catalyst provided by the invention, take the weight of catalyst as benchmark, the content of alumina-based supports is 46wt% ~ 87wt%, is preferably surplus, Mo is with MoO ₃the content of meter is 10wt%～40wt%, and Co is take the content of CoO as 0.5 wt%～6wt%, and Ni is take the content of NiO as 1wt%～8wt%.

In described hydrotreating catalyst, the concentration of Mo at outer most edge point place and the concentration ratio (mol ratio) of the Mo of particle central spot that are positioned at catalyst granules cross section are Mo ₀/ Mo ₁be 0.20～0.90, the concentration of Co and the concentration ratio (mol ratio) of central spot Co that are positioned at the outer most edge point place of catalyst granules cross section are Co ₀/ Co ₁be 0.08～0.80.

In hydrotreating catalyst of the present invention, can also contain adjuvant component, such as one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, take element, the weight content in catalyst, as below 15%, is preferably 1% ~ 10% to adjuvant component.In hydrotreating catalyst of the present invention, preferably contain phosphorus, with P ₂o ₅the weight content of meter in catalyst is 1% ~ 6%.

In hydrotreating catalyst of the present invention, described alumina-based supports refers to take aluminium oxide as key component, can not contain adjuvant component, also can contain adjuvant component, wherein adjuvant component can be one or more in silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component in element the content in alumina-based supports below 30wt%, preferably below 20wt%.Described alumina-based supports can adopt conventional method preparation.The character of described alumina-based supports is preferably as follows: specific area is 100～500 m ²/ g, is preferably 150 ~ 400 m ²/ g, pore volume is 0.25～1.0mL/g, is preferably 0.3 ~ 0.9 mL/g.

The character of hydrotreating catalyst of the present invention is as follows: specific area is 100～260 m ²/ g, is preferably 120 ~ 220 m ²/ g, pore volume is 0.20～0.60mL/g, is preferably 0.2 ~ 0.5 mL/g.

In described hydrotreating catalyst, contain organic matter, described organic matter is that carbon number is one or more in 2 ~ 20 organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound.

In hydrotreating catalyst of the present invention, organic matter, with Mo atomic molar than for 0.002:1～2.0:1, is preferably 0.02:1 ~ 1.5:1, more preferably 0.02:1 ~ 1.0:1.

Described organic compounds containing nitrogen is the organic matter that at least comprises a covalent bond nitrogen-atoms, in organic compounds containing nitrogen, carbon number is 2 ~ 20, specifically as one or more in ethylenediamine, hexamethylene diamine etc., be preferably except the nitrogen-atoms that comprises at least one covalent bond, also at least comprise the organic compound of a hydroxyl or carboxy moiety, as: monoethanolamine, diethanol amine, triethanolamine, one or more in ethylenediamine tetra-acetic acid (EDTA), nitrilotriacetic acid (NTA) and ring ethylenediamine tetra-acetic acid etc.

Described organic compounds containing sulfur is the organic matter that at least comprises a covalent bond sulphur atom, and in organic compounds containing sulfur, carbon number is generally 2 ~ 20.As sulphonic acids (general formula R-SO ₃h) R is wherein the alkyl containing 2 ~ 20 carbon atoms, as one or more in benzene sulfonic acid, DBSA, p-methyl benzenesulfonic acid etc.The group that can contain one or more carboxyls, carbonyl, ester, ether, hydroxyl, sulfydryl in organic compounds containing sulfur replaces, as TGA, mercaptopropionic acid, dimercaprol dimercaptopropanol etc.Except above-mentioned sulfur-containing compound, can comprise sulfone and sulfoxide compound, as one or more in dimethyl sulfoxide (DMSO), dimethyl sulfone etc.

Described oxygen-containing organic compound is the organic matter that at least contains a carbon atom and an oxygen atom.The organic compound that preferably comprises at least two oxygen atoms and two carbon atoms, oxygen-containing organic compound carbon number is preferably 2 ~ 20.Can be carboxyl, carbonyl, hydroxylic moiety or their combination containing oxygen part.These materials can be one or more in acids, alcohols, ethers, carbohydrate, ketone, phenols, aldehydes and lipid.Further be preferably as follows: one or more in acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid etc., TGA, mercaptopropionic acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ring ethylenediamine tetra-acetic acid, ethylene glycol, propane diols, butanediol, glycerine, diethylene glycol (DEG), DPG, triethylene glycol, three butanediols, tetraethylene glycol, polyethylene glycol, glucose, fructose, lactose, maltose, sucrose etc.

The preparation method of hydrotreating catalyst provided by the invention, wherein active metal component Ni step (1) before and/or step (2) introduce afterwards in catalyst, active metal component Mo introduces the mode in catalyst: or all Mo and Co together introduce in catalyst, or part Mo together introduces in catalyst with Co, and remainder Mo and Ni together introduce in catalyst; The process that active metal Co and all or part of Mo introduce in catalyst comprises:

(1) adopt the fountain solution impregnated alumina base carrier that contains adsorbent for unsaturated infusion process, the consumption of adsorbent accounts for 0.1% ~ 10% of alumina-based supports weight, and adsorbent is that carbon number is one or more in 2～15 organic carboxyl acid and its esters;

(2) dip loading active metal component Mo, Co on step (1) gains.

In the inventive method, part Mo together introduces in catalyst with Co, and remainder Mo and Ni together introduce in catalyst; Wherein the former to introduce Mo amount be 0.4 ~ 2.5 with the mol ratio that the latter introduces Mo amount.

In the inventive method, part Mo introduces in catalyst in step (1) before with Ni, solution impregnation step (1) gains that contain active metal component Mo, Co for step (2), and drying or dry and roasting, obtain hydrotreating catalyst.

In the inventive method, part Mo introduces in catalyst in step (2) afterwards with Ni, specific as follows:

(1) adopt the fountain solution impregnated alumina base carrier that contains adsorbent for unsaturated infusion process, the consumption of wherein said adsorbent accounts for 0.1% ~ 10.0% of alumina-based supports weight, and adsorbent is that carbon number is one or more in 2～15 organic carboxyl acid and its esters;

(2) with solution impregnation step (1) gains containing active metal component Mo, Co, drying and roasting,

(3) dip loading active metal Mo, Ni on step (2) gains, after drying or dry and roasting, obtains hydrotreating catalyst.

Described adsorbent is one or more in organic carboxyl acid and its esters, and its carbon number is not more than 15, is generally 2～15.Described organic acid comprises one or more in acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid etc., TGA, mercaptopropionic acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ring ethylenediamine tetra-acetic acid etc.One or more in the ammonium salt of the preferred above-mentioned organic carboxyl acid of organic carboxylate.

The inventive method, containing in the fountain solution of adsorbent, adopting water and/or ethanol is solvent.

In the described fountain solution that contains adsorbent, can also comprise alcohol, wherein alcohol is one or more in the alcohol below C5, can be one or more in monohydric alcohol, polyalcohol, concrete alcohol comprises as one or more in ethylene glycol, propane diols, glycerine, pentaerythrite, xylitol etc.The addition of described alcohol accounts for 0.1% ~ 10% of alumina-based supports weight.

In the present invention, the fountain solution that dipping contains adsorbent, adopts unsaturated dipping, preferably adopts unsaturated spraying, and wherein unsaturated dipping immersion liquid amount used and the volume ratio of alumina-based supports saturated absorption amount of solution are 0.02 ~ 0.4.After the fountain solution that dipping contains adsorbent, can drying, the solution that also can direct impregnation contains active metal Mo, Co, wherein baking temperature is generally 60 ℃～250 ℃, is preferably 100～200 ℃, and drying time, 0.5h～20h, was preferably 1h～6h.While spraying the fountain solution that contains adsorbent, should select the shower nozzle that atomizing effect is good, solution is evenly spread in alumina-based supports.After the fountain solution dipping that dipping contains adsorbent finishes, can directly enter next step, also can carry out next step through health again, conditioned time is 0.5～8h.

The inventive method, in step (2), with after the dipping solution dipping that contains Mo, Co, can pass through health, also can be without health, as need health, conditioned time is 0.5～8.0h, then is dried.Described drying condition is as follows: baking temperature is 60 ℃～250 ℃, is preferably 70 ~ 200 ℃, is preferably 100～200 ℃, and drying time, 0.5h～20h, was preferably 1h～6h.After dry, can carry out roasting, described roasting condition is as follows: burning temperature is 300 ℃～750 ℃, is preferably 400 ℃～650 ℃, and roasting time is 0.5h～20h, is preferably 1h～6h.

The inventive method, the drying condition described in step (3) is as follows: baking temperature is 60 ℃～250 ℃, is preferably 70 ~ 200 ℃, is preferably 100～200 ℃, and drying time, 0.5h～20h, was preferably 1h～6h.After dry, can carry out roasting, described roasting condition is as follows: burning temperature is 300 ℃～750 ℃, is preferably 400 ℃～650 ℃, and roasting time is 0.5h～20h, is preferably 1h～6h.

In hydrotreating catalyst preparation method of the present invention, active metal Mo, Co load in alumina-based supports by infusion process, conventionally adopt incipient impregnation.Dipping method is that technical staff is known.With containing after the solution impregnation alumina-based supports of active metal, need to be through super-dry.Active metal solution manufacturing method is that technical staff is known, and its solution concentration can regulate by the consumption of each compound, thereby prepares the catalyst of specified activity constituent content.The raw material of required active component is generally the compound of the types such as salt, oxide or acid, as molybdenum source, from one or more in molybdenum oxide, ammonium molybdate, ammonium paramolybdate, cobalt source is from one or more in cobalt nitrate, cobalt carbonate, basic cobaltous carbonate, cobalt chloride, cobalt oxalate.Tungsten source is ammonium metatungstate.Nickel source is from one or more in nickel nitrate, nickelous carbonate, basic nickel carbonate, nickel chloride, nickel oxalate.Containing in the solution of active metal Mo, Ni of the solution that contains active metal component Mo, Co in step (2) and/or step (3), contain phosphorus, phosphorus source is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate, and the introduction volume of phosphorus is with P ₂o ₅meter accounts for 1% ~ 6% of final hydrotreating catalyst weight.

In the inventive method, one or more in adjuvant component fluorine, silicon, phosphorus, titanium, zirconium and boron, adopt conventional method to introduce in catalyst, such as introducing in catalyst time prepared by carrier, also can after carrier preparation, introduce catalyst.After carrier preparation, introduce in catalyst, can adopt the method for independent dipping to introduce in catalyst, also can together flood and introduce in catalyst with active metal component.

In described hydrotreating catalyst, can contain organic matter, one or more in organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound that it is 2 ~ 20 that organic matter is selected from as carbon number.

In hydrotreating catalyst of the present invention, organic matter is 0.002:1～2.0:1 with Mo and W atomic molar ratio, is preferably 0.02:1 ~ 1.5:1, more preferably 0.02:1 ~ 1.0:1.

The mode that described organic matter is introduced in catalyst can adopt usual manner to introduce, and can flood separately introducing, also can introduce with active metal solution total immersion, and after introducing organic matter, general drying processing can obtain containing organic hydrotreating catalyst.

Hydrotreating catalyst of the present invention in the hydrodesulfurization (especially deep hydrodesulfurizationof) of heavy distillate (especially diesel oil) as the application of Hydrobon catalyst.

Described heavy distillate can be diesel oil, wax oil, wherein preferred diesel oil.The total sulfur content of described heavy distillate is generally 0.3wt% ~ 3.0wt%, preferably 0.3wt% ~ 2.5wt%, the sulfur content that wherein difficult de-sulfur-containing compound (with 4,6-dimethyl Dibenzothiophene for counting) is contributed is approximately more than 0.01wt%, is generally 0.01wt% ~ 0.05wt%.

Adopt hydrotreating catalyst of the present invention as Hydrobon catalyst, the total sulfur content of described heavy distillate can be reduced to 0.05wt% or lower, preferably be reduced to 0.005wt% or lower, especially can remove the de-sulfur-containing compound of described difficulty of 80wt% above (preferably more than 90wt%).

The present invention, in described application or described hydrodesulfurizationprocess process, can only use hydrotreating catalyst of the present invention, also hydrotreating catalyst of the present invention and other hydrotreating catalysts (than as be known in the art those) can be used in conjunction with according to the ratio of any needs, use such as adopting different catalysts bed grating or mixing.

According to the present invention, without any special restriction, can adopt the conventional operating condition using in this area to the operating condition of described hydrodesulfurization, such as enumerating 260 ~ 400 ℃ of reaction temperatures, preferably 310 ~ 370 ℃, reaction stagnation pressure 3 ~ 13MPa, preferably 5 ~ 9MPa, volume space velocity 0.5 ~ 4h when liquid ^-1, preferably 1 ~ 2h ^-1, hydrogen to oil volume ratio 200:1 ~ 2000:1, preferably 400:1 ~ 1000:1.

In hydrotreating catalyst of the present invention, active metal component Co and Mo are the trend increasing gradually from catalyst granules outer surface to center, and Ni is essentially and is uniformly distributed, and preferably contains organic matter.This catalyst is specially adapted in hydrodesulfurization, improves the activity and selectivity of hydrodesulfurization, especially removes and has the thiophene sulfocompounds that sterically hindered difficulty removes.

Hydrotreating catalyst prepared by the present invention, fountain solution by unsaturated dipping containing adsorbent, making a part of adsorption potential on carrier granular outer surface and marginal position surface be adsorbed agent occupies, dipping is containing active metal Mo, when the solution of Co, reduce Mo, Co is in the absorption of carrier edge position, make the active metal Mo of rear dipping, the concentration of Co is the trend increasing gradually from outer surface to center, further make the amount of the active phase of Mo-Co from outer surface to center, be the trend increasing gradually, Ni is uniformly distributed in each catalyst granules, particularly jointly introduce in catalyst with part Mo, like this by controlling Mo, Co, the CONCENTRATION DISTRIBUTION of Ni different metal, it is cooperatively interacted, thereby improve the activity and selectivity of catalyst, especially remove and there is the thiophene sulfocompounds that sterically hindered difficulty removes.In addition, the present invention, by controlling the preparation condition of hydrotreating catalyst, is present in final hydrotreating catalyst organic matter, after active metal sulfuration, can form more lamination number, and the hydrogenation activity of catalyst is further enhanced.

Accompanying drawing explanation

fig. 1 is the schematic diagram of spheric catalyst particle cutting mode;

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

Fig. 3 is that catalyst granules is by cutting the selected each location point on rear gained cross section and this cross section, wherein 0 represent that on this cross section, any point in outer most edge is outer most edge point, 1/4 represents 1/4 location point, 1/2 represents 1/2 location point, 3/4 represents 3/4 location point, and 1 represents central point.

Fig. 4 is active metal component Ni and the concentration profile of Co on this cross section in embodiment 3 gained catalyst C4.Wherein abscissa is the each location point on this cross section, and ordinate is the ratio of the concentration of central spot on the concentration at a certain location point place and this cross section.

The specific embodiment

In the inventive method, introduce before the method for active metal Ni and part Mo in step (1), can adopt following at least one method: in carrier component dry glue powder preparation process, add and then moulding is made to add containing the alumina-based supports of Ni and Mo, when the carrier component kneading and compacting to make containing adopting infusion process to add after the alumina-based supports of Ni and Mo and carrier component moulding and made the alumina-based supports containing Ni and Mo.Take aluminium oxide as carrier component as example describes:

One, in the preparation process of aluminum oxide dry glue powder, add, as introduced with co-precipitation, fractional precipitation mode, then moulding, makes the alumina support containing Ni and Mo after drying, roasting;

Two, in the time of carrier moulding, add with kneading form: aluminum oxide dry glue powder, with even containing Mo and Ni active metal component compound, then through kneading and compacting, the alumina support containing Ni and Mo is made in dry, roasting;

Three, by aluminum oxide dry glue powder kneading and compacting, be then dried, roasting makes carrier, with the solution impregnation of alumina carrier containing Mo and Ni active metal component, the alumina support containing Ni and Mo is made in drying, roasting afterwards.

In above-mentioned forming process, can add conventional shaping assistant, such as one or more in extrusion aid, adhesive, peptizing agent etc., addition can be determined by this area knowledge according to Kaolinite Preparation of Catalyst character.Wherein the little porous aluminum oxide of the general employing of adhesive, is selected from boehmite and the SB alumina powder of Zlegler synthetic reaction accessory substance etc. that aluminium chloride-Ammonia Process, carbonizatin method or aluminum sulfate method are produced.

In hydrotreating catalyst preparation method of the present invention, adopt prior art condition containing the dry and roasting in the alumina support preparation process of Ni and Mo, if baking temperature is 40 ℃～250 ℃, be 0.5h～20h drying time; Sintering temperature is 350 ℃～750 ℃, and roasting time is 0.5h～20h.

According to the preparation method of hydrotreating catalyst provided by the invention, its concrete steps are as follows:

I, preparation contain the alumina-based supports of Mo and Ni;

II, required adsorbent is added to the water, selectively adds alcohol, preparation fountain solution, the volume of described fountain solution accounts for 2%～40% of the saturated liquid absorption of catalyst precarsor;

III, in alumina-based supports, spray fountain solution with the good shower nozzle of atomizing effect, according to the volume of fountain solution, the time of spraying is 1min～40min;

IV, step III gained sample preferably carry out next step again through health, and conditioned time is 0.5～8h.

V, step IV gained sample preferably carry out next step after super-dry again, and baking temperature is generally 60 ℃～250 ℃, and 0.5h～20h, controlled drying condition adsorbent was present in catalyst drying time;

VI, employing equi-volume impregnating, with the active metal solution impregnation step V gained sample containing Mo, Co, dry 0.5h～20h at 70 ℃～300 ℃ temperature, controls drying condition adsorbent is present in catalyst, obtains hydrotreating catalyst.

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

Analytical method of the present invention is as follows:

(1) content of active metal component and adjuvant component (wt%) adopts x ray fluorescence spectrometry to measure.

(2) specific area (m of catalyst ²/ g) and pore volume (ml/g) adopt BET method to measure.

(3) CONCENTRATION DISTRIBUTION of each active metal component in catalyst granules

In following embodiment and comparative example, use columniform carrier (but the present invention is obviously not limited to this, also can use other grain shape), the catalyst granules that obtained is thus also columniform.From the catalyst that each embodiment and comparative example obtain, choose at random a catalyst granules as measuring sample.In order to measure the CONCENTRATION DISTRIBUTION of each active metal component in this catalyst granules, perpendicular to the length dimension direction of this cylindrical particle, cut by the central point of this length dimension, obtain two exposed surfaces.Get one of them exposed surface as measurement cross section.

This measurement is used EPMA method, with reference to GB/T15074-2008(Electron probe quantitative analysis method general rule) carry out, on electron probe microanalyzer (JXA-8230 type, Jeol Ltd. manufactures), carry out.Measuring condition is: accelerating potential 15kV, beam intensity 5 × 10 ^-8a, beam spot diameter, 1 μ 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 (is respectively NiO, CoO, MoO ₃and WO ₃), precision: be less than 1%, secondary electron image resolution ratio: 3nm(LaB ₆), linear system: Ni and Co adopt K _αlinear system, Mo adopts L _αlinear system, W adopts M _αlinear system.

Measuring method is: in the outer most edge of this cross section, choose arbitrarily a location point as 0, using the central point on this cross section as 1, connecting described location point 0 (is in fact the radius of this cross section with the straight line line segment of described location point 1, therefore also referred to as radially), the concentration value of measuring gage allocation point place targeted activity metal, then by division calculation, obtain the ratio (being mol ratio in the present invention) of each concentration value.

Fig. 4 is the concentration profile of active metal in the catalyst C4 of embodiment 3 gained, by evenly choose 21 location points (comprising location point 0 and location point 1) on this straight line line segment, take these location points as abscissa, the concentration value of the targeted activity metal (take Ni and Co as example) of measuring with each location point place (is used respectively Ni with the ratio of the concentration value of the corresponding active metal of location point 1 place (being central point) measurement _m/ Ni ₁and Co _m/ Co ₁represent) be ordinate, so draw and obtain.

(4) catalyst is relatively desulphurizing activated

Relatively desulphurizing activated=100 × [(1/S ₁) ^0.65-(1/S ₀) ^0.65]/[(1/Sc ₁) ^0.65-(1/S ₀) ^0.65], S in formula ₁and Sc ₁represent respectively to adopt the sulfur content in catalyst of the present invention or reference agent gained hydrogenation products, S ₀represent to adopt the sulfur content in catalyst of the present invention or the raw materials used oil of reference agent.Wherein sulfur content is in S, and unit is μ g/g.

Total sulfur content in raw material and hydrogenation products is to adopt ultraviolet fluorescence method to measure (ASTM D5453-1993), and 4,6-BMDBT content is to adopt GC-AED(gas-chromatography-atom luminescent spectrum method) measure.

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

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

Embodiment 1

The present embodiment is introduced the preparation method of catalyst precarsor.The aluminum oxide dry glue powder specific surface 350m of siliceous, boron ²/ g, pore volume is 0.90ml/g.

Take aluminum oxide dry glue powder 400g siliceous, boron, add citric acid and the each 6g of sesbania powder, after mixing, add acid solution 345g, HNO in acid solution ₃weight concentration be 1.74%, all the other are distilled water.Roll after 20min, by the circular orifice extrusion of diameter 1.7mm.After 120 ℃ of dry 4h, 500 ℃ of roasting 3h.The carrier strip making is designated as S1.With the prepared carrier strip S1 of solution impregnation containing Mo, Ni, after 130 ℃ of dry 4h, 500 ℃ of roasting 2h, the alumina-based supports containing Mo and Ni making is designated as Z1.

Take aluminum oxide dry glue powder 400g siliceous, boron, add citric acid and the each 6g of sesbania powder, add acid solution 345g, HNO in acid solution ₃weight concentration be that 2.6%, Mo is with MoO ₃the weight content of meter is 12.9%, Ni take the weight content of NiO as 2.9%, and all the other are distilled water.Roll after 20min, by the circular orifice extrusion of diameter 1.7mm.500 ℃ of roasting 3h after 120 ℃ of dry 4h, the alumina-based supports containing Mo and Ni making is designated as Z2.

Prepare the aluminum oxide dry glue powder of siliceous, molybdenum and nickel.In container, add 1L deionized water, be warming up to 58 ℃, add 3L to contain Al simultaneously ₂o ₃for the aluminum nitrate solution of 4g/100mL with containing NH ₃for the ammonia spirit of 10g/100mL, controlling pH value is 7.8, and feed time is 120min.After stopping feeding in raw material, system is aging 50min under said temperature and pH value condition, adds SiO ₂content is the solution of sodium metasilicate through 100mL of 4.2g, continues aging 60min, then washs 4 times, to Cl ^-/ Al ₂o ₃till <0.5%.Preparation is containing the aqueous solution 1L of molybdenum and nickel, wherein MO ₃concentration 1.8g/100mL, NiO concentration 0.4g/100mL, adds in filter cake, stirs into pasty state, after 120 ℃ of dry 8h, is crushed to granularity and is less than 180 objects and accounts for more than 95%, obtains required dry glue powder.

The character of siliceous, the molybdenum of gained and the aluminum oxide dry glue powder of nickel is as follows: specific surface 330m ²/ g, pore volume is 0.85ml/g.

The aluminum oxide dry glue powder 400g that takes siliceous, molybdenum and nickel, adds citric acid and the each 6g of sesbania powder, after mixing, adds acid solution 345g, HNO in acid solution ₃weight concentration be 1.74%, all the other are distilled water.Roll after 20min, by the circular orifice extrusion of diameter 1.7mm.500 ℃ of roasting 3h after 120 ℃ of dry 4h.The alumina-based supports containing Mo and Ni making is designated as Z3.

Table 1 is containing composition and the character of the alumina-based supports of Mo and Ni

Catalyst precarsor	Z1	Z2	Z3
				Si，wt%	1.33	1.34	1.36
B，wt%	1.66	1.63	－
				NiO，wt%	2.87	2.95	2.78
MO ₃，wt%	12.5	12.9	12.2
				Specific area, m ²/g	218	221	225
Pore volume, mL/g	0.52	0.53	0.53
				Saturated liquid absorption, mL/100g	60	61	61

Embodiment 2

Take citric acid 5.0g, stirring and dissolving in 45g water, makes fountain solution.Get Z1 300g, fountain solution is evenly sprayed to Z1 upper, spraying time is 10min.After fountain solution sprays and finishes, sample average is divided into three parts, the wherein direct 100 ℃ of dry 2h of the first duplicate samples, with the above-mentioned sample of maceration extract (the first maceration extract) incipient impregnation containing Mo, Co, P and mercaptopropionic acid, the mercaptopropionic acid of introducing and the mol ratio of Mo are 0.02:1, after 120 ℃ of dry 3h, the finished product of acquisition is designated as C1; The second duplicate samples health 1h, through the post-processing step identical with C1, through 120 ℃ of dry 3h, the finished product making is designated as C2; Triplicate sample health 5h, through the post-processing step identical with C1, through 120 ℃ of dry 3h, the finished product making is designated as C3.

Embodiment 3

Take oxalic acid 0.8g, stirring and dissolving in 4g ethanol, makes fountain solution.Get Z2 100g, fountain solution is evenly sprayed on precursor, spraying time is 4min.Fountain solution sprays and finishes rear health 0.5h.Sample is through 110 ℃ of dry 2h, and with containing after the above-mentioned sample of maceration extract (the first maceration extract) incipient impregnation of Mo, Co, P and ethylene glycol, the ethylene glycol of introducing and the mol ratio of Mo are 0.2:1, and after 120 ℃ of dry 3h, the finished product of acquisition is designated as C4.

Embodiment 4

Take malonic acid 6g, stirring and dissolving in 20g water, makes fountain solution.Get Z3 100g, fountain solution is evenly sprayed to Z3 upper, spraying time is 25min.Fountain solution sprays and finishes rear health 1h, sample is through 100 ℃ of dry 2h, and with the above-mentioned sample of maceration extract (the first maceration extract) incipient impregnation containing Mo, Co, P and dimethyl sulfone, the dimethyl sulfone of introducing and the mol ratio of Mo are 0.3:1, after 120 ℃ of dry 3h, the finished product of acquisition is designated as C5.

Comparative example 1

Get Z1 100g, with the above-mentioned carrier of maceration extract incipient impregnation containing Mo, Co, P, oxalic acid and ethylene glycol, its mesoxalic acid 0.8g, the ethylene glycol of introducing and the mol ratio of Mo are 0.2:1, after the above-mentioned carrier of incipient impregnation, through 120 ℃ of dry 3h, the catalyst of acquisition is designated as C6.

Table 2 embodiment and comparative example catalyst activity metal composition

Catalyst numbering	C1	C2	C3	C4	C5	C6
							Mo(is with MoO ₃Meter), wt%	24.3	24.3	24.4	24.6	24.5	24.3
Co(is in CoO), wt%	2.4	2.3	2.3	2.4	2.3	2.3
							Ni(is in NiO), wt%	2.1	1.9	2.0	2.1	1.9	2.0
P(is with P ₂O ₅Meter), wt%	2.7	2.8	2.7	2.7	2.8	2.8
							In the Mo introducing in carrier and the first maceration extract, introduce the mol ratio of Mo	0.75	0.75	0.75	0.75	0.75	0.75

The CONCENTRATION DISTRIBUTION of elements Mo in catalyst granules in table 3 embodiment and comparative example gained catalyst

Catalyst numbering	C1	C2	C3	C4	C5	C6
							Mo ₀/Mo ₁	0.55	0.66	0.78	0.71	0.63	1.0
Mo _1/4/Mo ₁	0.64	0.73	0.82	0.77	0.69	1.01
							Mo _1/2/Mo ₁	0.82	0.90	0.93	0.94	0.89	0.98
Mo _3/4/Mo ₁	0.95	0.97	0.98	0.99	0.98	0.99

The CONCENTRATION DISTRIBUTION of Elements C o in catalyst granules in table 4 embodiment and comparative example catalyst

Catalyst numbering	C1	C2	C3	C4	C5	C6
							Co ₀/ Co ₁	0.15	0.27	0.49	0.32	0.24	1.0
Co _1/4/ Co ₁	0.31	0.43	0.60	0.80	0.41	0.99
							Co _1/2/ Co ₁	0.64	0.79	0.86	0.95	0.72	1.01
Co _3/4/ Co ₁	0.93	0.94	0.98	0.99	0.90	1.0

The CONCENTRATION DISTRIBUTION of element Ni in catalyst granules in table 5 embodiment and comparative example catalyst

Catalyst numbering	C1	C2	C3	C4	C5	C6
							Ni ₀/Ni ₁	1.01	1.0	1.01	1.01	0.99	1.02
Ni _/4/Ni ₁	1.0	1.02	0.99	1.02	0.98	1.0
							Ni _1/2/Ni ₁	0.99	1.01	1.0	1.00	1.01	0.99
Ni _3/4/Ni ₁	1.02	0.99	0.98	1.01	1.0	1.0

From table 2, table 3, table 4 and table 5, catalyst C1～the C5 that adopts the present invention to prepare, active metal Mo, Co radially increase gradually along catalyst granules from edge to centre concentration, and comparative example catalyst C6 active metal Mo, Co are radially to locate each locational concentration basic identical, are obvious gradient unlike Kaolinite Preparation of Catalyst of the present invention and distribute.Find by C1, C2 and C3, finish rear conditioned time by controlling fountain solution sprinkling, can adjust active metal at catalyst granules footpath distributed density upwards; Find out from C2, C4 and C5, also can adjust active metal Mo, Co at catalyst granules footpath distributed density upwards by the change in volume of fountain solution.Therefore the preparation method of catalyst of the present invention is compared with comparative example catalyst, can adjust easily active metal at catalyst granules footpath distributed density upwards, make Mo, Co that hydrodesulfurization activity is higher higher in particle centre concentration, make reactant molecule in the diffusion process at catalyst granules center, first after hydrogenation is saturated, in the higher Mo of direct desulfurization activity, Co active sites, react again, thus the deep desulfuration performance of raising catalyst.

Embodiment 5

The present embodiment is the active appraisal experiment of catalyst.

Catalyst activity evaluation experimental carries out on 100mL small hydrogenation device, before activity rating, catalyst is carried out to presulfurization.Evaluating catalyst condition is at reaction stagnation pressure 6.5MPa, volume space velocity 2.0 h when liquid ^-1, hydrogen-oil ratio 500:1, reaction temperature is 335 ℃.Active appraisal experiment by feedstock oil character in table 6, activity rating the results are shown in Table 7, and table 8 provides the content of the difficult de-sulfur-containing compound of typical case in hydrogenation products, from data in table, prepare hydrotreating catalyst with the present invention, catalyst desulphurizing activated apparently higher than comparative example catalyst.

Table 6 feedstock oil character

Feedstock oil	Atmosphere 3rd side cut diesel oil
		Density (20 ℃), g/cm ³	0.8533
Boiling range, ℃	?
		? IBP	217
EBP	375
		S，wt%	1.78
N，μg/g	140

Table 7 catalyst activity evaluation result

Catalyst	C1	C2	C3	C4	C5	C6
							Relatively desulphurizing activated, %	118	125	120	117	127	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

Catalyst

?

C1

C2

C3

C4

C5

C6

4，6- BMDBT，μg/g

215

14.2

12.7

13.7

14.0

12.3

21.9

Embodiment 6

In embodiment 6 and comparative example 2, used columniform alumina support, diameter is about 1.2mm, and length is about 3 ~ 5mm, and its physico-chemical property is as shown in table 9.

The physico-chemical property of alumina support used in table 9 embodiment and comparative example

Project	Alumina support
		Specific area, m ²/g	298
Pore volume, mL/g	0.64
		Bulk density, g/100ml	63
Saturated liquid absorption, ml/100g	75

Mo predecessor in the present embodiment in Mo used, Ni, P and Mo, Co, P maceration extract is MoO ₃, Ni predecessor is basic nickel carbonate, and Co predecessor is basic cobaltous carbonate, and P predecessor is phosphoric acid.

Take citric acid 1.6g, stirring and dissolving in 15g water, makes fountain solution.Get alumina support 100g, fountain solution is evenly sprayed on alumina support, spraying time is 10min, and fountain solution obtains sample after spraying and finishing.Adopt above-mentioned same method to prepare three parts, sample.After fountain solution sprays and finishes, the direct 100 ℃ of dry 2h of the first duplicate samples, with the above-mentioned carrier of maceration extract (being called the first maceration extract) incipient impregnation containing Mo, Co, P, through 120 ℃ of dry 3h, after 480 ℃ of roasting 2h, the semi-finished product of acquisition are designated as BD1; The second duplicate samples health 1h after fountain solution sprays and finishes, through the post-processing step identical with catalyst B D1, the semi-finished product that make are designated as BD2; Fountain solution sprays and finishes rear triplicate sample health 5h, and through the post-processing step identical with catalyst B D1, the semi-finished product that make are designated as BD3.

With the above-mentioned BD1 of maceration extract (being called the second maceration extract) incipient impregnation, BD2 and BD3 containing Mo, Ni, P, through 120 ℃ of dry 3h, after 480 ℃ of roasting 2h, the catalyst of acquisition is designated as respectively CD1, CD2 and CD3 respectively.

Comparative example 2

Get alumina support 100g, with after the above-mentioned carrier of maceration extract incipient impregnation containing Mo, Co, P, through 120 ℃ of dry 3h, after 480 ℃ of roasting 2h, the semi-finished product of acquisition are designated as BD4.Maceration extract incipient impregnation BD4 with 69mL containing Mo, Ni, P, through 120 ℃ of dry 3h, after 480 ℃ of roasting 2h, the catalyst of acquisition is designated as CD4.

Table 10 embodiment and comparative example catalyst activity metal component composition

Catalyst numbering	CD1	CD2	CD3	CD4
					Composition	?	?	?	?
MoO ₃，wt％	25.2	25.5	25.4	25.5
					CoO，wt％	2.4	2.3	2.4	2.3
NiO，wt％	2.6	2.5	2.6	2.5
					P ₂O ₅，wt％	2.8	2.7	2.7	2.8
Aluminium oxide	Surplus	Surplus	Surplus	Surplus
					First containing Mo maceration extract and the second mol ratio containing Mo in Mo maceration extract	1.0	1.0	1.0	1.0

The CONCENTRATION DISTRIBUTION of elements Mo in catalyst granules in table 11 embodiment and comparative example gained catalyst semi-finished product

Catalyst numbering	BD1	BD2	BD3	BD4
					Mo ₀/Mo ₁	0.13	0.28	0.55	1.01
Mo _1/4/Mo ₁	0.32	0.42	0.62	0.99
					Mo _1/2/Mo ₁	0.67	0.79	0.86	1.0
Mo _3/4/Mo ₁	0.89	0.94	0.96	1.01

The CONCENTRATION DISTRIBUTION of elements Mo in catalyst granules in table 12 embodiment and comparative example gained catalyst

Catalyst numbering	CD1	CD2	CD3	CD4
					Mo ₀/Mo ₁	0.56	0.65	0.77	0.99
Mo _1/4/Mo ₁	0.66	0.71	0.82	1.01
					Mo _1/2/Mo ₁	0.83	0.89	0.92	0.98
Mo _3/4/Mo ₁	0.95	0.97	0.98	1.00

The CONCENTRATION DISTRIBUTION of Elements C o in catalyst granules in table 13 embodiment and comparative example catalyst

Catalyst numbering	CD1	CD2	CD3	CD4
					Co ₀/ Co ₁	0.14	0.26	0.50	0.98
Co _1/4/ Co ₁	0.30	0.44	0.61	0.99
					Co _1/2/ Co ₁	0.64	0.78	0.85	1.02
Co _3/4/ Co ₁	0.92	0.94	0.98	1.01

The CONCENTRATION DISTRIBUTION of element Ni in catalyst granules in table 14 embodiment and comparative example catalyst

Catalyst numbering	CD1	CD2	CD3	CD4
					Ni ₀/Ni ₁	1.0	1.01	0.99	1.01
Ni _/4/Ni ₁	1.02	1.02	0.98	0.99
					Ni _1/2/Ni ₁	1.01	1.00	1.01	1.0
Ni _3/4/Ni ₁	0.99	1.01	1.0	0.98

Embodiment 7

The present embodiment is the active appraisal experiment of catalyst.

Catalyst activity evaluation experimental carries out on 100ml small hydrogenation device, before activity rating, catalyst is carried out to presulfurization.Evaluating catalyst condition is at reaction stagnation pressure 6.0MPa, volume space velocity 2.0 h when liquid ^-1, hydrogen-oil ratio 500:1, reaction temperature is 340 ℃.Active appraisal experiment is by feedstock oil character in table 6, and activity rating the results are shown in Table 15 and 16, from data in table, prepares hydrotreating catalyst with the present invention, catalyst desulphurizing activated apparently higher than comparative example catalyst.

Table 15 catalyst activity evaluation result

Catalyst	CD1	CD2	CD3	CD4
					Relatively desulphurizing activated, %	127	136	131	100

The content of difficult de-sulfur-containing compound in table 16 feedstock oil and hydrotreatment products

Raw material/hydrogenation products	Raw material	Hydrogenation products	Hydrogenation products	Hydrogenation products	Hydrogenation products
						Catalyst numbering	?	CD1	CD2	CD3	CD4
4,6- BMDBT，μg/g	215	15.9	14.6	15.3	23.1

Claims

1. a hydrotreating catalyst, adopts alumina-based supports, and active metal component is Co, Mo, Ni, and wherein the CONCENTRATION DISTRIBUTION of active metal component on each catalyst granules cross section is as follows: Co ₀/ Co ₁< Co _1/2/ Co ₁< 1, Mo ₀/ Mo ₁< Mo _1/2/ Mo ₁< 1, the concentration of Ni is essentially and is uniformly distributed;

Wherein, the CONCENTRATION DISTRIBUTION of active metal component on the cross section of each catalyst granules formula A _m/ B _nrepresent, i.e. the ratio of the concentration of the concentration of m place elements A and n place element B on the cross section of each catalyst granules, wherein A represents active metal elements Mo, Co or Ni, B represents active metal elements Mo, Co or Ni, be designated as 0 take any point of catalyst granules cross section outer most edge as starting point, be designated as 1 take the central point of catalyst granules cross section as terminal, connect starting point and terminal and obtain straight line line segment, m and n are illustrated respectively in the location point of choosing on above-mentioned straight line line segment, the value representation of m and n accounts for the ratio of the length of above-mentioned straight line line segment from starting point to the distance of the location point of choosing, the value of m and n is 0 ~ 1, in order to express easily, A and B directly adopt active metal elements Mo, Co or Ni replace, m and n are directly with definite location point on 0～1 the above-mentioned straight line line segment of digitized representation.

2. according to catalyst claimed in claim 1, it is characterized in that in described hydrotreating catalyst, active metal component, in catalyst granules, at least comprises following a kind of scheme:

(1) Co ₀/ Co ₁with Co _1/2/ Co ₁ratio be 0.2 ~ 0.8;

(2) Mo ₀/ Mo ₁with Mo _1/2/ Mo ₁ratio be 0.2 ~ 0.8;

(3) Co ₀/ Mo ₀ratio be 0.07 ~ 2.0.

3. according to catalyst claimed in claim 1, it is characterized in that in described hydrotreating catalyst, active metal component, in catalyst granules, at least comprises following a kind of scheme:

(1) Co ₀/ Co ₁with Co _1/2/ Co ₁ratio be 0.2 ~ 0.7;

(2) Mo ₀/ Mo ₁with Mo _1/2/ Mo ₁ratio be 0.2 ~ 0.7;

(3) Co ₀/ Mo ₀ratio be 0.08 ~ 1.2.

4. according to catalyst claimed in claim 1, it is characterized in that in described hydrotreating catalyst, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section at least comprises following a kind of scheme:

（1）Co ₀/Co ₁＜Co _1/4/Co ₁＜Co _1/2/Co ₁；

（2）Co _1/2/Co ₁＜Co _3/4/Co ₁＜1；

（3）Mo ₀/Mo ₁＜Mo _1/4/Mo ₁＜Mo _1/2/Mo ₁；

（4）Mo _1/2/Mo ₁＜Mo _3/4/Mo ₁＜1；

(5) Co ₀/ Co ₁< Co _x1/ Co ₁< Co _x2/ Co ₁< 1, wherein 0 < x1 < x2 < 1;

(6) Mo ₀/ Mo ₀< Mo _x1/ Mo ₁< Mo _x2/ Mo ₁< 1, wherein 0 < x1 < x2 < 1.

5. according to catalyst claimed in claim 4, it is characterized in that in described hydrotreating catalyst, active metal component, in catalyst granules, at least comprises following a kind of scheme:

(1) Co ₀/ Co ₁with Co _1/4/ Co ₁ratio be 0.3 ~ 0.9;

(2) Co _1/4/ Co ₁with Co _1/2/ Co ₁ratio be 0.4 ~ 0.9;

(3) Mo ₀/ Mo ₁with Mo _1/4/ Mo ₁ratio be 0.3 ~ 0.9;

(4) Mo _1/4/ Mo ₁with Mo _1/2/ Mo ₁ratio be 0.4 ~ 0.9.

6. according to catalyst claimed in claim 4, it is characterized in that in described hydrotreating catalyst, active metal component, in catalyst granules, at least comprises following a kind of scheme:

(1) Co ₀/ Co ₁with Co _1/4/ Co ₁ratio be 0.3 ~ 0.85;

(2) Co _1/4/ Co ₁with Co _1/2/ Co ₁ratio be 0.4 ~ 0.87;

(3) Mo ₀/ Mo ₁with Mo _1/4/ Mo ₁ratio be 0.3 ~ 0.85;

(4) Mo _1/4/ Mo ₁with Mo _1/2/ Mo ₁ratio be 0.4 ~ 0.87.

7. according to catalyst claimed in claim 1, it is characterized in that in described hydrotreating catalyst, on catalyst granules cross section, put central point along described straight line line segment from outer most edge, active metal component concentration distributes as follows: the concentration of Co increases substantially gradually, the concentration of Mo increases substantially gradually, and the concentration of Ni is uniformly distributed substantially.

8. according to catalyst claimed in claim 1, it is characterized in that described hydrotreating catalyst, take the weight of catalyst as benchmark, the content of alumina-based supports is 46wt% ~ 87wt%, Mo is with MoO ₃the content of meter is 10wt%～40wt%, and Co is take the content of CoO as 0.5 wt%～6wt%, and Ni is take the content of NiO as 1wt%～8wt%.

9. according to catalyst claimed in claim 1, it is characterized in that in described hydrotreating catalyst, be positioned at the Mo of catalyst granules outer surface and the mol ratio of particle center Mo is Mo ₀/ Mo ₁be 0.08～0.90, be positioned at the Co of catalyst granules outer surface and the mol ratio of center Co is Co ₀/ Co ₁be 0.08～0.80.

10. according to catalyst claimed in claim 1, it is characterized in that the character of described hydrotreating catalyst is as follows: specific area is 120～220 m ²/ g, pore volume is 0.20～0.60mL/g.

11. according to catalyst claimed in claim 1, it is characterized in that in described hydrotreating catalyst, contain organic matter, described organic matter is that carbon number is one or more in 2 ~ 20 organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound.

12. according to the arbitrary described catalyst of claim 1 ~ 11, it is characterized in that the organic matter containing in described hydrotreating catalyst is 0.002:1～2.0:1 with Mo atomic molar ratio, is preferably 0.02:1 ~ 1.0:1.

13. according to catalyst claimed in claim 1, it is characterized in that in described hydrotreating catalyst, alumina-based supports is take aluminium oxide as key component, not containing adjuvant component or containing adjuvant component, wherein adjuvant component is one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in element the content in alumina-based supports below 30wt%.

14. according to catalyst claimed in claim 1, it is characterized in that in described hydrotreating catalyst, contain adjuvant component, wherein adjuvant component is one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in element the weight content in catalyst below 15wt%.

15. according to catalyst claimed in claim 1, it is characterized in that containing phosphorus in described hydrotreating catalyst, with P ₂o ₅the weight content of meter in catalyst is 1% ~ 6%.

The preparation method of the arbitrary described catalyst of 16. claims 1 ~ 13, wherein active metal component Ni step (1) before and/or step (2) introduce afterwards in catalyst, active metal component Mo introduces the mode in catalyst: or all Mo and Co together introduce in catalyst, or part Mo together introduces in catalyst with Co, and remainder Mo and Ni together introduce in catalyst;

The process that active metal Co and all or part of Mo introduce in catalyst comprises:

(2) dip loading active metal component Mo, Co on step (1) gains.

17. in accordance with the method for claim 16, it is characterized in that: part Mo together introduces in catalyst with Co, and remainder Mo and Ni together introduce in catalyst, wherein the former to introduce Mo amount be 0.4 ~ 2.5 with the mol ratio that the latter introduces Mo amount.

18. according to the method described in claim 16 or 17, it is characterized in that: part Mo introduces in catalyst in step (1) before with Ni, solution impregnation step (1) gains that contain active metal component Mo, Co for step (2), drying or dry and roasting, obtain hydrotreating catalyst.

19. according to the method described in claim 16 or 17, it is characterized in that: part Mo introduces in catalyst in step (2) afterwards with Ni, specific as follows:

20. in accordance with the method for claim 16, it is characterized in that described adsorbent organic acid comprises one or more in acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, TGA, mercaptopropionic acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ring ethylenediamine tetra-acetic acid etc.; Organic carboxylate is one or more in the ammonium salt of above-mentioned organic carboxyl acid.

21. in accordance with the method for claim 16, it is characterized in that comprising alcohol in the described fountain solution that contains adsorbent, wherein alcohol is one or more in ethylene glycol, propane diols, glycerine, pentaerythrite, xylitol, and the addition of described alcohol accounts for 0.1% ~ 10.0% of alumina-based supports weight.

22. in accordance with the method for claim 16, it is characterized in that the unsaturated dipping of step (1) adopts the unsaturated method that sprays, and wherein unsaturated dipping immersion liquid amount used and the volume ratio of alumina-based supports saturated absorption amount of solution are 0.02 ~ 0.4.

23. in accordance with the method for claim 16, it is characterized in that after step (1) dipping that, through health, conditioned time is 0.5～8h, or after step (1) dipping, warp is dry, described baking temperature is 60 ℃～250 ℃, and drying time, 0.5h～20h, and then carried out step (2).

24. in accordance with the method for claim 16, it is characterized in that in solution that step (2) contains active metal component Mo, Co, contain phosphorus, phosphorus source is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate, and the introduction volume of phosphorus is with P ₂o ₅meter accounts for 1% ~ 6% of final hydrotreating catalyst weight.

25. in accordance with the method for claim 19, it is characterized in that solution that step (2) contains active metal component Mo, Co and/or step (3) containing in the solution of active metal Mo, Ni, contain phosphorus, phosphorus source is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate, and the introduction volume of phosphorus is with P ₂o ₅meter accounts for 1% ~ 6% of final hydrotreating catalyst weight.

26. according to the method described in claim 16 or 19, it is characterized in that the described drying condition of step (2) or step (3) is as follows: baking temperature is 70 ℃～300 ℃, be 0.5h～20h drying time, described roasting condition: sintering temperature is 300 ℃～750 ℃, and roasting time is 0.5h～20h.

27. in accordance with the method for claim 16, it is characterized in that: in described hydrotreating catalyst, contain organic matter, making organic matter in hydrotreating catalyst and the mol ratio of Mo atom is 0.002:1～2:1; Organic matter is selected from one or more in organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound.

The method of 28. 1 kinds of heavy distillate hydrodesulfurizations, is characterized in that adopting the arbitrary described hydrotreating catalyst of claim 1 ~ 15.

29. in accordance with the method for claim 28, it is characterized in that: described heavy distillate is diesel oil.