CN110404552A

CN110404552A - A kind of hydrodenitrogenation catalyst and its application

Info

Publication number: CN110404552A
Application number: CN201810408926.2A
Authority: CN
Inventors: 贾燕子; 杨清河; 刘学芬; 曾双亲; 邵志才; 刘涛
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 2018-04-27
Filing date: 2018-04-27
Publication date: 2019-11-05
Anticipated expiration: 2038-04-27
Also published as: CN110404552B

Abstract

The present invention relates to a kind of hydrodenitrogenation catalyst and its application, the hydrodenitrogenation catalyst includes modified aluminium oxide supports and the hydrodenitrogenationactivity activity metal component that is carried in the modified aluminium oxide supports；The modified aluminium oxide supports are for graininess and as hydrated alumina composition successively through prepared by forming processes and modification；Wherein, the hydrated alumina composition contains hydrated alumina and the compound at least two proton acceptor sites, the composition

Description

A kind of hydrodenitrogenation catalyst and its application

Technical field

The present invention relates to a kind of hydrodenitrogenation catalyst and its applications.

Background technique

Fixed bed residual oil hydrocatalyst uses gradation system, mainly includes protective agent, metal remover, desulfurizing agent, denitrogenation Agent, de- carbon residue agent etc..With building successively for the residual hydrogenation equipments such as the riverine refinery of Sinopec and China Petroleum North China branch company If processing raw material will turn to mainly using the triumph low-sulfur high-nitrogens such as piped oil or North China crude oil residual oil as raw material.With Middle East height The characteristics of sulfur resid compares, such residual oil raw material: sulfur content is lower (0.2%~2.5%), nitrogen content height (0.3%~ 0.7%), gum level is high, and asphalt content is low, and nickel content is high, content of vanadium is low.Compared with the low nitrogen residual oil of Middle East high-sulfur, low-sulfur Nitrogenous compound in high nitrogen residual oil is difficult to hydro-conversion, while causing lower carbon residue conversion ratio, fills to downstream catalytic cracking It sets and has an adverse effect, the nitride in hydrogenated residue not only makes the reduction of catalytic cracking catalyst activity, but also makes product distribution It is deteriorated, catalytically cracked material nitrogen content 150 μ g/g of every increase, conversion ratio decline 1% or so.Existing residual oil hydrocatalyst is to state The reducing effect of sulphur and carbon residue is significant in the low nitrogen class residual oil of outer high-sulfur.But for low-sulfur high-nitrogen class residual oil, since sulphur contains Measure lower, the removing of sulphur is for the removing of nitrogen, for adding the reduction contribution of oil product carbon residue before and after hydrogen smaller.

Chinese patent CN101928592A discloses a kind of grading composition method of hydrogenation catalyst, in this method, reaction Device loads Hydrodemetalation catalyst and desulfurizing agent respectively from top to bottom；The active metal of Hydrodemetalation catalyst and desulfurizing agent Component and acidic assistant concentration distribution are in uneven distribution, from catalyst particle surface to center, Hydrodemetalation catalyst Active metal component and acidic assistant concentration gradient increase, and the active metal component and acidic assistant concentration gradient of desulfurizing agent subtract It is few.However, method for preparing catalyst is complicated in the grading composition, energy consumption is high and the repeatability of the preparation method and controllability compared with Difference.

In conventional methods where, aluminium oxide, particularly gama-alumina, because it is with preferable pore structure, specific surface and heat-resisting steady It is qualitative, it is used frequently as the carrier of adsorbent or loaded catalyst.This aluminium oxide usually by the hydrated alumina after drying, Such as boehmite formed, dried after, high-temperature roasting obtains again.

Based on above-mentioned cognition, it is typically starting point by the boehmite powder after drying, chemical peptizing agent (nothing is added Machine acid or organic acid) and extrusion aid, it forms after kneading and peptization, and make after drying and roasting as adsorbent or carrier With.This customary preparation methods dust pollution is big, and energy consumption is high.

Chinese patent CN103769118A discloses a kind of heavy-oil hydrogenation catalyst and preparation method thereof, and there is disclosed with dry Base content is 50% method that boehmite below forms, dry and roasting prepares carrier, catalyst.It is wanted according to its right The claim 4 in book is sought it is found that its water content for reducing preparation process boehmite or improving boehmite butt Method is the method by conventional drying, this is that common people can expect but be difficult the method carried out, and main cause is four aspects: First is that the boehmite viscosity not being completely dried is stronger, transfer is difficult, will cause secondary dust pollution.Second is that all because of drying It is since surface, since what is taken is not to be completely dried, it to be exactly part boehmite surface that there are sandwich biscuits phenomenons Dry (being substantially free of Free water) and it is internal wet (Free water maintains the state before drying substantially), surface-dry place will form hard Particle, the explanation based on the patent, not special method eliminate this phenomenon, and this boehmite not parched completely adds When entering peptizing agent, binder etc. and forming after mediating, the blocking of extrusion process, shadow will cause in the grit that drying process is formed Ring production efficiency.Third is that due to being limited by conventional boehmite preparation process and drying condition, the butt of boehmite It is difficult control to stablize, butt is unstable to cause very big interference to molding, keep forming process highly unstable, cause unqualified Product increases, and production efficiency is low.Fourth is that since the butt of boehmite is low (30%-50%), far below conventional 70% The contents on dry basis of left and right, i.e. water content are high, and molding formula is conventional formula, since water content is too high, in forming process base Extrusion pressure is not generated in sheet, therefore the carrier that the strip squeezed out obtains after drying and roasting is substantially no mechanical strength, Arbitrarily apply some external force, will dusting, do not have a possibility that industrial application, this is the greatest problem of the technology.

Summary of the invention

The object of the present invention is to provide a kind of hydrodenitrogenation catalyst and its application, hydrodenitrogeneration catalysis provided by the invention Agent has good hydrodenitrogeneration effect.

To achieve the goals above, the present invention provides a kind of hydrodenitrogenation catalyst, and the hydrodenitrogenation catalyst includes Modified aluminium oxide supports and the hydrodenitrogenationactivity activity metal component being carried in the modified aluminium oxide supports；It is described modified oxidized Alumina supporter is for graininess and as hydrated alumina composition successively through prepared by forming processes and modification；Wherein, the water It closes alumina composition and contains hydrated alumina and the compound at least two proton acceptor sites, the composition Value is for 5 hereinafter, describedValue is measured using following methods: by 10 grams of compositions at 120 DEG C dry 240 in air atmosphere Minute, the quality of dried composition is denoted as w₁Gram, it is calculated using Formulas IValue,

The modification makes modified aluminium oxide supports particle have one of following two kinds of states:

(i), with the acid additive of a variety of layer distributeds in modified aluminium oxide supports particle, and according to alumina support The direction at surface to the center of grain, is better than the acidity positioned at outer layer acid additive positioned at the acidity of internal layer acid additive；

(ii) with the acid additive and metal promoter of layer distributed in modified aluminium oxide supports particle, and the acidity helps Agent is distributed in the first stratum nucleare, and the metal promoter is distributed in the first shell；

Wherein, the acid additive be selected from least one of F, P and B, the metal promoter be group ia metal and/ Or group iia metal, preferably at least one of Li, Na, K, Mg and Ca；

When modified aluminium oxide supports particle has state (i), the hydrodenitrogenationactivity activity metal component is modified oxidized It is in layer distributed in alumina supporter particle, the active metal component for being distributed in stratum nucleare is Ni and W, the active metal being distributed in shell Group is divided into Mo and is selected from the combination of Ni and/or Co；

When modified aluminium oxide supports particle has state (ii), the hydrodenitrogenationactivity activity metal component is modified oxidized It is in layer distributed in alumina supporter particle, the active metal component for being distributed in the second stratum nucleare is Ni and W, is distributed in the second shell Active metal component is Mo and the combination for being selected from Ni and/or Co.

Optionally, describedValue is for 4 hereinafter, preferably 3.5 hereinafter, more preferably 3.2 or less；It is highly preferred that describedValue It is 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more；It is further preferred that describedValue is 1.2-5, preferably 1.2-4, more preferably 1.3-3.5, further preferably 1.4-3.2.

Optionally, relative to hydrated alumina described in 100 parts by weight, the change at least two proton acceptor sites The content for closing object is 1-25 parts by weight, preferably 1.2-20 parts by weight, more preferably 1.5-18 parts by weight, further preferably 3- 17 parts by weight；

In the compound for having at least two proton acceptor sites, proton acceptor site is that can form hydrogen bond with water F, at least one of O and N；Preferably, the compound at least two proton acceptor sites is to contain in molecular structure There is the compound of hydroxyl；It is highly preferred that the compound at least two proton acceptor sites is polyhydroxy organic compound Object；It is further preferred that the compound at least two proton acceptor sites is the etherate of polysaccharide and/or polysaccharide； It is further preferred that the compound at least two proton acceptor sites is that galactan, mannosan, gala are sweet Reveal at least one of glycan and cellulose ether, the cellulose ether is preferably methylcellulose, hydroxyethyl cellulose and hydroxypropyl At least one of base cellulose；It is particularly preferred that the compound at least two proton acceptor sites is that gala is sweet Reveal glycan and cellulose ether, it is preferable that on the basis of the total amount of the compound at least two proton acceptor sites, institute The content for stating galactomannans is 10-70 weight %, preferably 15-68 weight %, more preferably 20-65 weight %；It is described The content of cellulose ether is 30-90 weight %, preferably 32-85 weight %, more preferably 35-80 weight %.

Optionally, the hydrated alumina contains boehmite, preferably boehmite；

The hydrated alumina be hydrated alumina wet gel or be hydrated alumina wet gel washed product；Wherein, The i value of the hydrated alumina wet gel or its washed product is not less than 60%, preferably not less than 62%, it is preferable that the water The i value for closing aluminium oxide wet gel or its washed product is not higher than 82%, preferably no greater than 80%, more preferably no higher than 78.5%, The i value is measured using following methods: by 10 grams of hydrated alumina wet gels or its washed product at 120 DEG C in air atmosphere It is 240 minutes dry, the quality of dried sample is denoted as w₂Gram, i value is calculated using Formula II,

Optionally, it is measured by mercury injection method, the hydrated alumina composition is through aluminium oxide formed body obtained by forming processes Pore-size distribution be in bimodal distribution, most probable pore size be respectively 4-20nm and be greater than 20nm；Or it is measured by mercury injection method, the hydration Aperture of the alumina composition through aluminium oxide formed body obtained by forming processes is in Unimodal Distribution, most probable pore size 4-20nm；

The radial crushing strength of the aluminium oxide formed body be 10N/mm or more, preferably 10-55N/mm, more preferably 12N/mm or more, further preferred 12-35N/mm.

Optionally, in state (i), on the basis of the total weight of the modified aluminium oxide supports, acidity based on the element The content of auxiliary agent be 0.1-15 weight %, preferably 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably 1-5 weight % is still more preferably 2-4 weight %；

In state (ii), on the basis of the total weight of the modified aluminium oxide supports, acid additive based on the element Content is 0.1-15 weight %, preferably 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably 1-5 weight % is measured, is still more preferably 2-4 weight %；On the basis of the total weight of the modified aluminium oxide supports, in terms of oxide The content of the metal promoter is 0.1-15 weight %, preferably 0.2-12 weight %, more preferably 0.3-8 weight %, into one Step is preferably 1-3 weight %.

Optionally, the step of making modified aluminium oxide supports particle have the modification of state (i) includes: by the hydration Alumina composition carries out hydro-thermal process through aluminium oxide formed body obtained by forming processes, then by the carrier of gained hydro-thermal process according to It is secondary to be impregnated and dried, and last time gained desciccate is roasted, wherein it is soaked used in each dipping process Stain liquid, which contains, is provided with the compound of identical or different acid additive, duplicate frequency n >=2, preferably 2-3 times, and as n >=3, During from (n-1)th dipping is impregnated into the 2nd time, after dry temperature is than adjacent preceding single-steeping after impregnating each time Dry temperature is 20-150 DEG C high, and the dry time is 1- longer than the time of drying after adjacent preceding single-steeping after impregnating each time 10 hours；It is in acidity that first n-1 times, which impregnates used maceration extract, and pH value is preferably 2-6；Maceration extract used by n-th impregnates In alkalinity, pH value is preferably 8-11；

The step of making modified aluminium oxide supports particle have the modification of state (ii) includes: (1), by the hydration oxygen Change aluminium composition and carry out hydro-thermal process through aluminium oxide formed body obtained by forming processes, is then provided with the metal in containing for alkalinity It is impregnated in first solution of the metal promoter compound of auxiliary agent, is then dried, obtain the load that load has the metal promoter Body；(2), there is the carrier of the metal promoter acid containing the acid additive for being provided with the acid additive load It closes and is impregnated in the second solution of object, be then dried and roast；The pH value of first solution is 7.5-11, described the The pH value of two solution is 2-6.5；In step (1), the condition of hydro-thermal process includes: that temperature is 50-200 DEG C, and the time is that 5-30 is small When；Preferably, the immersion condition of step (1) and (2) is identical or different, and the condition of dipping includes: that temperature is 20-300 DEG C, preferably It is 40-100 DEG C；Time is 1-20 hours, preferably 1-6 hours；Preferably, in step (1), dry condition includes: temperature It is 30-300 DEG C, the time is 1-20 hours；Preferably, in step (2), dry condition includes: that temperature is 80-200 DEG C, the time It is 1-10 hours；Preferably, in step (2), the condition of roasting includes: that temperature is 300-900 DEG C, and the time is 1-10 hours.

Optionally, it is counted by metal oxide and on the basis of the total weight of the catalyst, the hydrodenitrogenation catalyst The content of middle Mo is 2-30 weight %, preferably 5-25 weight %, more preferably 5-20 weight %, most preferably 8-16 weight Measure %；The total content of Ni is 0.5-15 weight %, preferably 1-10 weight %, more preferably 2-9 weight %, most preferably 3-6 Weight %；The content of Co is 0-15 weight %, preferably 1-10 weight %, more preferably 2-9 weight %, most preferably 3-5 weight Measure %；The content of W is 2-40 weight %, preferably 5-35 weight %, more preferably 8-30 weight %, most preferably 15-30 weight Measure %.

Optionally, the preparation step of the hydrodenitrogenation catalyst includes:

(a), the modified aluminium oxide supports are subjected to hydro-thermal process, then by the modified aluminium oxide supports after hydro-thermal process Acid containing being impregnated in molybdenum compound and the combined third solution of nickel compound and/or cobalt compound, then into Row drying；The pH value of the third solution is 2-6.5；

(b), the carrier by step (a) after dry in the 4th solution containing nickel compound and tungsten compound of alkalinity into Row dipping, is then dried and roasts；The pH value of 4th solution is 7.5-11；

Nickel compound described in step (a) and step (b) is each independently selected from nickel oxide, nickel nitrate, nickel acetate, alkali formula One of nickelous carbonate and nickel chloride are a variety of；The molybdenum compound is selected from molybdenum oxide, molybdate, paramolybdate, ammonium dimolybdate With one of ammonium tetramolybdate or a variety of；The tungsten compound is selected from tungsten oxide, ammonium tungstate, ammonium metatungstate, ammonium paratungstate and second One of base ammonium metatungstate is a variety of；The cobalt compound is selected from cobalt carbonate, cobalt nitrate, cobalt acetate, basic cobaltous carbonate and chlorine Change one of cobalt or a variety of；

In step (a), the condition of hydro-thermal process includes: that temperature is 50-200 DEG C, and the time is 5-30 hours；Preferably, it walks Suddenly the immersion condition of (a) and (b) is identical or different, and the condition of dipping includes: that temperature is 50-300 DEG C, preferably 50-100 DEG C； Time is 1-20 hours, preferably 1-6 hours；Preferably, in step (a), dry condition includes: that temperature is 30-300 DEG C, Time is 1-20 hours；Preferably, in step (b), dry condition includes: that temperature is 80-200 DEG C, and the time is 1-10 hours； Preferably, in step (b), the condition of roasting includes: that temperature is 300-900 DEG C, and the time is 1-10 hours.

The present invention also provides a kind of methods of heavy-oil hydrogenation processing, this method comprises: under hydrogenation conditions, by heavy oil Raw material is successively contacted and is reacted with hydrogenation protecting agent, Hydrodemetalation catalyst and hydrodenitrogenation catalyst, wherein described At least one of hydrogenation protecting agent, Hydrodemetalation catalyst and hydrodenitrogenation catalyst meet the following conditions:

The hydrodenitrogenation catalyst is hydrodenitrogenation catalyst provided by the present invention；

The hydrogenation protecting agent includes modified aluminium oxide supports provided by the present invention and is carried on the modified aluminas Hydrogenation protecting active component in carrier, the hydrogenation protecting active component is at least one group VIII metal component and at least A kind of vib metals component, is counted by metal oxide and on the basis of the total weight of hydrogenation protecting agent, the group VIII metal The content of component is greater than 0 weight % and is less than or equal to 1 weight %, and the content of the vib metals component is greater than 0 weight % and small In equal to 6 weight %；

The Hydrodemetalation catalyst includes modified aluminium oxide supports provided by the present invention and is carried on the modification Hydrodemetallization active component in alumina support, the hydrodemetallization active component are at least one group VIII metal Component and at least one vib metals component, are counted using metal oxide and using the total weight of Hydrodemetalation catalyst as base Standard, the content of the group VIII metal component are 1-3 weight %, and the content of the vib metals component is 6-13 weight %.

The present invention has the advantage that

(1), modified aluminium oxide supports used in hydrodenitrogenation catalyst of the present invention are by hydrated alumina composition through forming Prepared by processing and modification, it can be improved prepared hydrodenitrogenation catalyst and optional hydrogenation protecting agent and add hydrogen de- The intensity and hydrotreating effect of metallic catalyst.On the one hand, containing at least two protons in hydrated alumina composition The compound of acceptor site can interact to form hydrogen bond with the Free water in hydrated alumina composition, absorption hydration oxygen Change the Free water in aluminium, at the same have the compound at least two proton acceptor sites also can in hydrated alumina molecular structure Hydroxyl interaction of hydrogen bond occurs, play the role of physics peptization so that hydrated alumina can not only form, Er Qieneng So that the formed body finally prepared intensity with higher, meets the needs of industrial application.On the other hand, modification to change Property alumina carrier particle there is state (i) and (ii), the modified aluminium oxide supports particle that state (i) enables converges more The advantages of kind of different acid additives, the modified aluminium oxide supports particle that state (ii) enables converge simultaneously acid additive and The advantages of metal promoter.

(2), hydrodenitrogenation catalyst provided by the invention is by control active metal component along hydrodenitrogenation catalyst diameter To layer distributed, using the reaction characteristics of different activities metal component, optimum organization, to obtain higher activity.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

The present invention provides a kind of hydrodenitrogenation catalyst, and the hydrodenitrogenation catalyst includes modified aluminium oxide supports and bears The hydrodenitrogenationactivity activity metal component being loaded in the modified aluminium oxide supports；The modified aluminium oxide supports be graininess and by Hydrated alumina composition is successively through prepared by forming processes and modification；Wherein, the hydrated alumina composition contains Hydrated alumina and compound at least two proton acceptor sites, the compositionValue is for 5 hereinafter, describedValue It is measured using following methods: by 10 grams of compositions 120 DEG C of drying 240 minutes in air atmosphere, by dried group The quality for closing object is denoted as w₁Gram, it is calculated using Formulas IValue,

Modified aluminium oxide supports according to the present invention, the hydrated alumina compositionValue for 5 hereinafter, preferably 4 with Under, more preferably 3.5 hereinafter, further preferably 3.2 or less.Value can be 1.2 or more (such as 1.2-5 or 1.2-4), excellent It is selected as 1.3 or more (such as 1.3-3.5), more preferably 1.4 or more (such as 1.4-3.2).In one embodiment, the hydration oxygen Change aluminium compositionValue is not less than 1.8, such as can be 1.8-5, and preferably not lower than 1.85, such as can be 1.85- 3.5, more preferably it is not less than 1.9, such as can be 1.9-3.2.It can be with according to the hydrated alumina composition of the embodiment Prepare the modified aluminium oxide supports that aperture is in bimodal distribution.In another embodiment, the hydrated alumina composition Value is less than 1.8, such as can be 1.2 to less than 1.8, preferably not higher than 1.7, such as can be 1.3-1.7.According to the reality The hydrated alumina composition for applying mode can prepare the modified aluminium oxide supports that aperture is in Unimodal Distribution.

Modified aluminium oxide supports according to the present invention, the content of the compound at least two proton acceptor sites The composition can be madeValue meets subject to above-mentioned requirements.Preferably, described relative to hydrated alumina described in 100 parts by weight The content of compound at least two proton acceptor sites can be 1-25 parts by weight, preferably 1.2-20 parts by weight, more Preferably 1.5-18 parts by weight, further preferably 3-17 parts by weight.

Modified aluminium oxide supports according to the present invention, in the compound at least two proton acceptor sites, matter Sub- acceptor site refers to the position that can form hydrogen bond in the molecular structure of the compound with water and hydroxyl, such as proton acceptor position Point is at least one of fluorine (F), oxygen (O) and the nitrogen (N) that hydrogen bond can be formed with water；It is described that there are at least two proton acceptor positions The specific example of the compound of point can include but is not limited in molecular structure containing selected from hydroxyl, carboxyl, amino, ehter bond, aldehyde The compound of the group of one or more of base, carbonyl, amide groups and fluorine atom, preferably hydroxyl and/or ehter bond, more Preferably hydroxyl, further preferably polyhydroxy.

Modified aluminium oxide supports according to the present invention, the compound at least two proton acceptor sites can be Organic compound, or inorganic compound can also be the combination of organic compound and inorganic compound.Using with extremely The organic compound in few two proton acceptor sites, the organic compound can be removed by roasting process.Using at least The inorganic compound in two proton acceptor sites, the Partial Elements in the inorganic compound can be retained in the molding finally prepared In body, it is possible thereby to introduce auxiliary element in formed body by the inorganic compound.

Modified aluminium oxide supports according to the present invention, it is in a preferred embodiment of the invention, described to have extremely The compound in few two proton acceptor sites is the polymerization in molecular structure with multiple (such as three or more) proton acceptor sites Object.According to the preferred embodiment, physically better peptization can be obtained, to further increase the modification finally prepared The intensity of alumina support can be further improved the modification oxygen finally prepared especially when being formed using extrusion process Change the intensity of alumina supporter.Preferably, the polymer is organic polymer.It is described to have extremely according to the preferred embodiment The specific example of the compound in few two proton acceptor sites can include but is not limited to polyol, polyethers and acrylic acid One or more of type polymer.

Modified aluminium oxide supports according to the present invention, the polyol can enumerate but be not limited to polysaccharide, more The etherate and polyalcohol of sugar, the preferably etherate of polysaccharide and/or polysaccharide.The polysaccharide can be homopolysaccharide, or Heteroglycan can also be the combination of homopolysaccharide and heteroglycan.The polysaccharide and its etherate specific examples thereof include but be not limited to Glucan, galactan, mannosan, galactomannans, cellulose ether, starch, chitin, glycosaminoglycan and amino are more At least one of sugar, preferably galactan, mannosan, galactomannans and cellulose ether.The cellulose ether is Refer to the ether system derivative formed after the hydrogen atom in the part of hydroxyl in cellulosic molecule is replaced by alkyl, wherein multiple described Alkyl can be identical, or different.The alkyl is selected from the alkyl and unsubstituted alkyl replaced.It is described unsubstituted Alkyl is preferably alkyl (such as: the alkyl of C1-C5).In the present invention, the specific example of the alkyl of C1-C5 includes the straight of C1-C5 The branched alkyl of alkyl group and C3-C5 can be but be not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Tert-butyl, n-pentyl, isopentyl and tertiary pentyl.The substituted alkyl for example can be for by hydroxyl, carboxyl, cyano or aryl Substituted alkyl (such as: the alkyl being optionally substituted by a hydroxyl group of C1-C5, C1-C5 the alkyl replaced by carboxyl, be substituted with aryl The alkyl of C1-C5), the aryl can be phenyl or naphthalene.The specific example of the substituted alkyl may include but not It is limited to: cyano, benzyl, phenethyl, methylol, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl.Institute State cellulose ether specific example can include but is not limited to methylcellulose, hydroxyethylmethylcellulose, carboxymethyl cellulose, Ethyl cellulose, benzylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl fiber Element, benzyl cyanethyl cellulose, carboxymethyl hydroxyethyl cellulose and benzyl cellulose, preferably methylcellulose, ethoxy are fine At least one of dimension element and hydroxypropyl cellulose.The polysaccharide and its etherate can provide in a variety of manners, such as: gala Mannosan can derive from sesbania powder.

Modified aluminium oxide supports according to the present invention, the polyalcohol specific examples thereof include but be not limited to polyvinyl alcohol, Part acetalation polyvinyl alcohol (acetalizing degree can be 95% hereinafter, preferably 80% hereinafter, more preferably 70% hereinafter, into One step is preferably 50% or less), one or more of the pure and mild polyester polyol of polyether polyols.Polyethers can specifically be enumerated Out but it is not limited to polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer and polytetrahydrofuran.Acrylic type Polymer refers to that the polymer containing acrylic monomer unit, the acrylic monomer unit are specifically as follows but are not limited to Acrylic monomer units and acrylate monomer units (preferably C₁-C₅Acrylate monomer units, more preferably first Base acrylic monomer units).Specific examples thereof include polyacrylic acid, polymethylacrylic acid, propylene for the acrylic acid polymer Acid-methyl acrylate copolymer, acryl acid-methyl methacrylate copolymer, methacrylic acid-acrylic acid methyl terpolymer and EUDRAGIT L100.

Modified aluminium oxide supports according to the present invention, it is described that there are at least two protons in the preferred embodiment The etherate of the compound of acceptor site further preferably polysaccharide and/or polysaccharide, the further preferably ether of polysaccharide and/or polysaccharide Compound.In a kind of more preferably embodiment of the invention, the compound at least two proton acceptor sites Contain galactomannans and cellulose ether.According to the more preferably embodiment, formed by composition according to the present invention Formed body have higher intensity.It is further preferred that the compound at least two proton acceptor sites is preferred For galactomannans and cellulose ether.In this more preferably embodiment, there are at least two proton acceptors with described On the basis of the total amount of the compound in site, the content of the galactomannans can be 10-70 weight %, preferably 15-68 Weight %, more preferably 20-65 weight %；The content of the cellulose ether can be 30-90 weight %, preferably 32-85 weight Measure %, more preferably 35-80 weight %.

Modified aluminium oxide supports according to the present invention, the hydrated alumina can be for selected from gibbsites and a water oxygen Change one or more of aluminium.The hydrated alumina preferably comprises a water aluminium oxide, more preferably a water aluminium oxide.Institute State hydrated alumina specific example can include but is not limited to boehmite, gibbsite, unformed hydrated alumina and Boehmite.When selecting boehmite or boehmite, the hydrated alumina composition is through aluminium oxide obtained by forming processes It forms body opening to hold between 0.3-1.5ml/g, specific surface area is in 50-450m²Between/g, hole holds between preferred 0.4-1.2ml/g, The preferred 70-400m of specific surface area²Between/g, when selecting gibbsite, the hydrated alumina composition is through obtained by forming processes Aluminium oxide, which forms body opening, to be held between 0.01-0.4ml/g, and specific surface area is in 5-200m²Between/g, hole holds preferred 0.05- Between 0.2ml/g, the preferred 6-100m of specific surface area²Between/g.

Modified aluminium oxide supports according to the present invention, in a preferred embodiment of the invention, the hydration oxygen Change aluminium and contains boehmite, more preferably boehmite.According to the hydrated alumina composition of the preferred embodiment Particularly suitable for preparing the formed body for being used as catalyst carrier.

Modified aluminium oxide supports according to the present invention, the hydrated alumina be directed to hydrated alumina wet gel or For the washed product of hydrated alumina wet gel, it is not originating from hydrated alumina dry glue powder.

Modified aluminium oxide supports according to the present invention, the hydrated alumina wet gel or hydrated alumina wet gel are washed Product is washed to obtain and do not live through that its i value is reduced to the de- of 60% or less (62% or less preferably) preferably by synthetic reaction The aqueous alumina hydrate gel of water process.Preferably, the i value of the hydrated alumina wet gel or its washed product is not high In 82%, preferably no greater than 80%, more preferably no higher than 78.5%, for example, i value can be 60-82%, preferably 60-80%, More preferably 62-78.5%, the i value are measured using following methods: by 10 grams of hydrated alumina wet gels or its washed product 120 DEG C of drying 240 minutes in air atmosphere, the quality of dried sample is denoted as w₂Gram, i value is calculated using Formula II,

Modified aluminium oxide supports according to the present invention, the synthetic reaction refer to the reaction for preparing gel aluminum hydroxide, can Think alumina hydrate gel synthetic reaction commonly used in the art, specific examples thereof include the precipitation method (including acid system and alkali Method), Hydrolyze method, kind point-score and rapid dehydration method.The alumina hydrate gel of synthesis can be for without the hydration for going through aging Alumina gel, or live through the alumina hydrate gel of aging.The precipitation method, Hydrolyze method, kind point-score and fast The concrete operation method and condition of fast evaporation can be conventional selection.The hydrated alumina wet gel can be by that will synthesize After the alumina hydrate gel that reaction obtains optionally carries out aging, is washed and be separated by solid-liquid separation and collected solid phase and obtain. The precipitation method include acid system and alkaline process.The acid system is that aluminium salt is carried out precipitation reaction with alkali compounds.The alkaline process is Aluminate is subjected to precipitation reaction with acid compound.In the precipitation method, the mixture that precipitation reaction obtains optionally is carried out always After changing (preferably progress aging), it is separated by solid-liquid separation, the solid phase isolated is washed, it is wet to obtain the hydrated alumina Gel.The aluminium salt and the type of the aluminate can be conventional selection.The specific example of the aluminium salt may include but not It is limited to one or more of aluminum sulfate, aluminium chloride and aluminum nitrate.The specific example of the aluminate may include but not It is limited to one or more of sodium metaaluminate, potassium metaaluminate and meta-aluminic acid magnesium.The alkali compounds and the acidification Closing object can be conventional selection.The alkali compounds can be the common various compounds that can make water in alkalinity, Ke Yixuan From ammonium hydroxide, hydroxide and basic salt.The hydroxide can be common water soluble hydroxide, such as alkali metal hydroxide Object.The basic salt can be decomposed in water for common so that water is in alkaline salt, such as meta-aluminate, carbonate and bicarbonate Salt.The specific example of the alkali compounds can include but is not limited to ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium metaaluminate, partially One or more of potassium aluminate, ammonium hydrogen carbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, saleratus and potassium carbonate.Institute Stating acid compound can be the common various compounds that can make water in acidity, can be inorganic acid and/or organic acid.It is described The specific example of acid compound can include but is not limited to sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid One or more of with oxalic acid.The carbonic acid can be generated in situ by introducing carbon dioxide.The precipitation reaction It can carry out under normal conditions, this is not particularly limited in the present invention.Generally, the alkali compounds or the acidity The dosage of compound makes the pH of the aluminum salt solution or the aluminate solution be 6-10, preferably 7-9.The precipitating is anti- Should can 30-90 DEG C, preferably 40-80 DEG C at a temperature of carry out.The method that hydrated alumina wet gel is prepared using Hydrolyze method May include: that reaction is hydrolyzed in aluminum contained compound, the mixture that hydrolysis is obtained optionally carry out aging (preferably into Row aging) after, it is separated by solid-liquid separation, the solid phase isolated is washed, to obtain the hydrated alumina wet gel.Institute Aluminum contained compound usually used in alumina hydrate gel technique can be prepared for Hydrolyze method by stating aluminum contained compound.It is described to contain aluminium Compound is preferably the organo-aluminum compound that hydrolysis can occur, more preferably aluminium alcoholates.The aluminum contained compound it is specific Example can include but is not limited in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and isooctanol aluminium It is one or more kinds of.The actual conditions of hydrolysis are not particularly limited in the present invention, can carry out under normal conditions. Generally, the hydrolysis can carry out under conditions of pH is 3-11, is preferably 6-10.The hydrolysis can be It is carried out at a temperature of 30-90 DEG C, preferably 40-80 DEG C.In the precipitation method and Hydrolyze method, the condition of the aging is not limited especially It is fixed, it can carry out under normal conditions.Generally, the aging can 35-98 DEG C, preferably 40-80 DEG C at a temperature of carry out. The duration of the aging can be 0.2-6 hours.It can wrap using the method that kind of point-score prepares hydrated alumina wet gel It includes: adding crystal seed into supersaturated aluminate solution, decompose and generate aluminium hydroxide, obtained mixture will be decomposed and carry out solid-liquid point From the solid phase isolated being washed, to obtain the hydrated alumina wet gel.The specific example of the aluminate can To include but is not limited to one or more of sodium metaaluminate, potassium metaaluminate and meta-aluminic acid magnesium.Using fast dewatering legal system The method of standby hydrated alumina wet gel may include: the temperature by hydrated alumina at 600-950 DEG C, preferably 650-800 DEG C Under roasted, product of roasting carry out hydro-thermal process, the mixture that hydro-thermal process is obtained is separated by solid-liquid separation, to obtain water Close aluminium oxide wet gel.The duration of the roasting can be 1-6 hours, preferably 2-4 hours.The hydro-thermal process can be with 120-200 DEG C, preferably 140-160 DEG C at a temperature of carry out.The hydro-thermal process is usually in closed container, in self-generated pressure Lower progress.In the precipitation method, Hydrolyze method, kind point-score and rapid dehydration method, the separation of solid and liquid can be carried out using conventional method, It is specifically as follows the combination of filtering, centrifugation or both.

Modified aluminium oxide supports according to the present invention, can be by containing alumina hydrate gel solution to what is be prepared Separation of solid and liquid condition when being separated by solid-liquid separation is controlled, thus obtain i value meet above-mentioned requirements hydrated alumina it is wet solidifying Glue.In one embodiment of the invention, be separated by solid-liquid separation as more than once or twice, at least last time be separated by solid-liquid separation for plus Press filtration and/or vacuum filter.In this embodiment, by adjusting the pressure of application and/or the size of vacuum degree, to acquisition Hydrated alumina wet gel i value is controlled.The specific example for the device that the pressure filtration uses can enumerate but unlimited In the combination of plate and frame type filter-press, band filter or both.In order to control acquisition hydrated alumina wet gel i value, Isolated solid phase can also be purged using natural wind or wind with pressure, to improve the efficiency of moisture abjection.Institute The pressure for stating wind with pressure can be conventional selection, generally can be 0.1-12MPa, preferably 0.5-10MPa.

Modified aluminium oxide supports according to the present invention, it is different from from the hydrated alumina of dry glue powder, it is directed to The hydrated alumina of hydrated alumina wet gel during storage meet and change by the object of hydrated alumina.For example, It is placed 72 hours under environment temperature and sealing condition, the object of hydrated alumina, which is met, in the composition after placement changes. It generally can be 5-50 DEG C, such as 20-40 DEG C depending on the environment temperature is with environment is placed.The sealing condition refers to will be described Composition is placed in closed container, and the closed container can be closure container (such as tank, bucket or case), or sealing Flexible coating (such as sealed bag), the flexibility coating can be paper and/or polymer material, preferably polymer material, Such as plastics.

Modified aluminium oxide supports according to the present invention are directed to hydrated alumina wet gel in an example Hydrated alumina contains boehmite (hydrated alumina for being such as directed to alumina hydrate gel is boehmite) When, the composition is placed 72 hours under environment temperature and sealing condition, the gibbsite in composition after placement Content is higher than the gibbsite content in the composition before placing.In this example, with three water in the composition before placement On the basis of the total amount of the content of aluminium oxide, gibbsite content in the composition after placement generally at least improves 0.5%, excellent Choosing at least improves 1%, preferably improves 1.1% to 2%.

Modified aluminium oxide supports according to the present invention, without using dry glue powder as starting material, can be used to molding (especially It is extrusion molding), and the reason of obtained modified aluminium oxide supports intensity with higher, may is that described there is at least two Interaction of hydrogen bond occurs for the compound in a proton acceptor site and the Free water in hydrated alumina wet gel, so that absorption is certainly It interacts by water, while with the hydroxyl in hydrated alumina molecular structure, plays the role of peptization.

Modified aluminium oxide supports according to the present invention, composition can contain peptizing agent, can also not contain peptizing agent.Institute State the reagent with gelatification that peptizing agent can be usually used for aluminium oxide formed body preparation technical field, specific example It can include but is not limited to Aluminum sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid.For example, Relative to 100 parts by weight hydrated aluminas, the content of the peptizing agent is 5 parts by weight hereinafter, below preferably 3 parts by weight.

Modified aluminium oxide supports according to the present invention, the compound at least two proton acceptor sites, especially It is in the compound at least two proton acceptor sites for containing the polymerization at least two proton acceptor sites When object, the compound at least two proton acceptor sites can play physics peptization, so as to reduce glue The dosage of solvent, it might even be possible to not use peptizing agent.

Modified aluminium oxide supports according to the present invention by hydrated alumina wet gel and can be had extremely using conventional method The compound mixing in few two proton acceptor sites.It can be under shear action by hydrated alumina wet gel and at least two The compound in a proton acceptor site mixes.In one embodiment, the mixed mode is stirring.It can will be hydrated oxygen Change aluminium wet gel and the compound at least two proton acceptor sites in the container with agitating device, it will by stirring The two is uniformly mixed, to obtain hydrated alumina composition according to the present invention.The stirring can be with agitating device Container in carry out, can also be carried out in beater.In another embodiment, the mixed mode is to mediate.It can Hydrated alumina wet gel and the compound at least two proton acceptor sites to be mediated in kneader, thus Obtain hydrated alumina composition according to the present invention.The type of the kneader is not particularly limited.A kind of embodiment, can Will stir and kneading is applied in combination, by hydrated alumina wet gel with the compound at least two proton acceptor sites Mixing.At this point, it is preferred that be first stirred, then mediated, the time stirred or mediated is no less than 1min.

Modified aluminium oxide supports according to the present invention can supplement addition water in mixed process, can not also supplement and add Add water, as long as can make in the hydrated alumina composition of preparationValue meets above-mentioned requirements.Generally, mixed from improving The angle of the uniformity of conjunction is set out, and addition water can be supplemented in mixed process.Generally, it supplements the water of addition and has at least The weight ratio of the compound in two proton acceptor sites can be 5-15:1, preferably 8-12:1, more preferably 9-10:1.

The forming processes of modified aluminium oxide supports according to the present invention, hydrated alumina composition can be normal using this field The molding mode of rule forms, and is then dried and (is preferably dried and roasts) with optional roasting, dry gained formed body Referred to as hydrated alumina formed body, dry and roasting gained formed body are known as aluminium oxide formed body.Molding mode can be with are as follows: squeezes Item, spraying, round as a ball, tabletting or their combination.In a preferred embodiment of the invention, by way of extrusion come Molding.According to the difference of molding mode and specifically used requirement, the modified aluminium oxide supports can have various shape, such as: Spherical shape, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.Dry condition can be the conventional selection of this field, described dry Dry temperature can be for 60 DEG C or more and not higher than 350 DEG C, preferably 80-300 DEG C, more preferably 110-260 DEG C.The drying Time can be made appropriate choice according to dry temperature, for example, the duration of the drying can be 1-48 hours, Preferably 2-24 hours, more preferably 2-12 hours, further preferably 2-4 hours.The drying can oxygen-containing atmosphere (such as Air atmosphere) in carry out, can also be carried out in inert atmosphere (atmosphere that such as nitrogen and/or zero group gas are formed), preferably It is carried out in oxygen-containing atmosphere.The condition of roasting can be the conventional selection of this field, and the temperature of the roasting can be 450- 1500℃.Furthermore it is also possible to be optimized according to temperature of the type of hydrated alumina to roasting.In one embodiment, The hydrated alumina is boehmite, and the temperature of the roasting is preferably 450-1100 DEG C, more preferably 460-1000 DEG C, Further preferably 500-950 DEG C.In another embodiment, the hydrated alumina is gibbsite, the roasting Temperature is preferably 800-1500 DEG C, and more preferably 900-1400 DEG C.The duration of the roasting can be 1-8 hours.It is described Roasting can carry out in oxygen-containing atmosphere (such as air atmosphere), can also be in inert atmosphere (such as nitrogen and/or zero group gas shape At atmosphere) in carry out, carried out preferably in oxygen-containing atmosphere.

Modified aluminium oxide supports according to the present invention, the hydrated alumina composition through aluminium oxide obtained by forming processes at Type body has pore structure abundant, and pore-size distribution is adjustable, for example, being measured by mercury injection method, the hydrated alumina composition Pore-size distribution through aluminium oxide formed body obtained by forming processes is in bimodal distribution.Most probable pore size be respectively 4-20nm (preferably 7-18nm) and it is greater than 20nm (such as 20.1-40nm, preferably 20.2-35nm).In another embodiment, it is surveyed by mercury injection method Fixed, aperture of the hydrated alumina composition through aluminium oxide formed body obtained by forming processes is in Unimodal Distribution.Most probable pore size For 4-20nm, preferably 8-20nm.

Modified aluminium oxide supports according to the present invention, the hydrated alumina composition through aluminium oxide obtained by forming processes at Type body intensity with higher.Generally, the radial crushing strength of aluminium oxide formed body according to the present invention is 10N/mm or more (such as can be 10-55N/mm), preferably 12N/mm or more, such as 12-35N/mm.The measurement of radial crushing strength is according to RIPP 25-90 is carried out.

The forming processes of modified aluminium oxide supports according to the present invention, a kind of embodiment, hydrated alumina composition can With the following steps are included:

(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains Monohydrate alumina wet gel；

Optionally (2) are handled the first hydrated alumina wet gel using (2-1) or (2-2),

The first hydrated alumina wet gel and aqueous mixtures are formed slurries by (2-1), and the slurries are carried out solid-liquid Separation, obtains the second hydrated alumina wet gel；

The first hydrated alumina wet gel is separated by solid-liquid separation by (2-2), obtains the second hydrated alumina wet gel；

(3) hydrated alumina wet gel and the compound at least two proton acceptor sites are mixed using preceding method It closes, obtains hydrated alumina composition, the hydrated alumina wet gel is the first hydrated alumina wet gel or institute State the second hydrated alumina wet gel；

(4) the hydrated alumina composition is formed, obtains hydrated alumina forming matter；

(5) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；

(6) at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body.

According to the embodiment that hydrated alumina composition molding is handled, in step (1), the alumina hydrate gel is molten Liquid refer to it is that alumina hydrate gel synthetic reaction obtains, by or without aging containing the molten of alumina hydrate gel Liquid.The alumina hydrate gel solution, which can be, to be prepared in situ, and is also possible to transport from other production scenes Alumina hydrate gel solution.Preferably, the alumina hydrate gel solution is the hydrated alumina being prepared in situ Gel solution.Detailed description has been carried out above for the synthetic method and condition of alumina hydrate gel, no longer superfluous herein It states.

According to the embodiment that hydrated alumina composition molding is handled, since the hydrated alumina that synthetic reaction obtains is solidifying Sol solution has acid-base property, and step washs hydrated alumina wet gel in (1), to remove acidic materials and alkali therein Property substance, the adverse effect for avoiding the presence of acidic materials and alkaline matter from generating alumina hydrate gel, while improving water Close the solid content of alumina gel solution.Washing described in step (1) can carry out under normal conditions, as long as oxygen can will be hydrated The amount for changing acidic materials and alkaline matter in alumina gel solution is reduced to satisfaction to usually require that.

According to the embodiment that hydrated alumina composition molding is handled, also it is related in step (1), in washing process solid Liquid separation, washing water is squeezed out, the first hydrated alumina wet gel is obtained.The i value of the first hydrated alumina wet gel It can be the i value for meeting the aforementioned hydrated alumina wet gel mixed with the compound at least two proton acceptor sites, Or it is higher than the i of the aforementioned hydrated alumina wet gel mixed with the compound at least two proton acceptor sites Value.

According to the embodiment that hydrated alumina composition molding is handled, in one embodiment, first hydration The i value content of aluminium oxide wet gel meets the aforementioned aqua oxidation mixed with the compound at least two proton acceptor sites The i value of aluminium wet gel, i.e., the i value of the described first hydrated alumina wet gel are not less than 60% preferably not lower than 62%.In In the embodiment, the i value of the first hydrated alumina wet gel is preferably not higher than 82%, more preferably not above 80%, further preferably it is not higher than 78.5%.

According to the embodiment that hydrated alumina composition molding is handled, the first hydrated alumina wet gel can directly be sent Enter in step (3), is mixed with the compound at least two proton acceptor sites.This is claimed below especially suitable for meeting Occasion: the solid-liquid separating equipment in (A) wash mill has preferable separating capacity, it is sufficient to by the first hydrated alumina wet gel The control of i value to meet the above range；(B) wash mill compact can be arranged with mixing arrangement, so that the discharging of wash mill Mixing arrangement can be directly entered.

According to the embodiment that hydrated alumina composition molding is handled, the first hydrated alumina wet gel can also be sent into In step (2), handled using (2-1).This is especially suitable for meeting occasion claimed below: consolidating in (A) wash mill Liquid separation equipment has preferable separating capacity, it is sufficient to control the i value of the first hydrated alumina wet gel to meet above-mentioned model It encloses；(B) wash mill compact can not be arranged with mixing arrangement, so that the discharging of wash mill can not be directly entered mixing arrangement.

According to the embodiment that hydrated alumina composition molding is handled, in another embodiment, the first hydration oxygen Change aluminium wet gel i value be higher than 82%, be unable to satisfy it is aforementioned with have at least two proton acceptor sites compound mix Requirement.According to the embodiment, the first hydrated alumina wet gel is sent into step (2), using (2-1) or (2-2) is handled.

According to the embodiment that hydrated alumina composition molding is handled, the embodiment is especially suitable in wash mill Solid-liquid separating equipment separating capacity or operating condition be not enough to the control of the i value of the first hydrated alumina wet gel be full The occasion and wash mill of sufficient aforementioned claim and mixing arrangement can not compact setting occasion.

According to the embodiment that hydrated alumina composition molding is handled, in step (2), using (2-1) or (2-2) First hydrated alumina wet gel is handled, the second hydrated alumina wet gel is obtained.

It is in (2-1), the first hydrated alumina is wet solidifying according to the embodiment that hydrated alumina composition molding is handled Glue is mixed with water, forms slurries, can improve hydrated alumina wet gel in this way transports performance.

According to the embodiment that hydrated alumina composition molding is handled, in (2-1), slurries of the additive amount of water to be formed It is able to satisfy and transports subject to requirement, can be selected according to specific conveying equipment.

According to the embodiment that hydrated alumina composition molding is handled, second aqua oxidation that step (2) obtains The i value of aluminium wet gel meets the aforementioned hydrated alumina wet gel mixed with the compound at least two proton acceptor sites I value, i.e., the i value of the described hydrated alumina wet gel is not less than 60% preferably not lower than 62%.The second hydration oxygen The i value for changing aluminium wet gel is preferably not higher than 82%, more preferably not above 80%, is further preferably not higher than 78.5%.

According to the embodiment that hydrated alumina composition molding is handled, solid-liquid described in rate-determining steps (2) can be passed through Isolated condition obtains the second hydrated alumina wet gel that i value meets above-mentioned requirements.By selection solid-liquid separating method and Detailed description has been carried out above come the method for adjusting the i value of hydrated alumina wet gel for its condition, herein no longer in detail It states.

According to the embodiment that hydrated alumina composition molding is handled, in step (3), using preceding method by the first water Aluminium oxide wet gel or the second hydrated alumina wet gel is closed to mix with the compound at least two proton acceptor sites, To obtain hydrated alumina composition.The first hydrated alumina wet gel and the second hydrated alumina for being sent into step (3) are wet The i value of gel meets the i of the aforementioned hydrated alumina wet gel mixed with the compound at least two proton acceptor sites Value.

It can be according to expected hydration oxygen in step (3) according to the embodiment that hydrated alumina composition molding is handled The pore-size distribution for changing aluminium formed body or aluminium oxide formed body, determines hydrated alumina compositionValue, this is in preceding method It is illustrated, and will not be described here in detail.

According to the embodiment that hydrated alumina composition molding is handled, in step (4), hydration that step (3) is obtained Alumina composition is formed, and hydrated alumina forming matter is obtained.The shape of the molding method and molding can be with Referring to hereinbefore about molding associated description, details are not described herein again.

According to the embodiment that hydrated alumina composition molding is handled, in step (5), hydration that step (3) is obtained Aluminium oxide molding is dried, and obtains hydrated alumina formed body.Hydrated alumina forming matter is dried and is hydrated Detailed description has been carried out in the drying condition of aluminium oxide formed body in preceding method, and details are not described herein again.

According to the embodiment that hydrated alumina composition molding is handled, according to the type of expected formed body, Ke Yijin Row step (6), can also be without step (6).It, can be by whole aqua oxidations of step (5) acquisition when carrying out step (6) Aluminium formed body is sent into step (6), is roasted；The partially hydrated aluminium oxide formed body that step (5) can also be obtained is sent into In step (6), hydrated alumina formed body and aluminium oxide formed body can be prepared simultaneously in this way.The condition of the roasting is aforementioned Detailed description has been carried out in aluminium oxide formed body, details are not described herein again.

With the existing process phase for preparing modified aluminium oxide supports using boehmite dry glue powder as starting material Than the present invention has following directly using the hydrated alumina wet gel that synthetic reaction is prepared as molding starting material Advantage:

(1) it is omitted in prior art for the step of drying hydrated alumina wet gel, and is preparing shaping raw material When, boehmite dry glue powder is modulated into plastic material without additionally introducing water, simplifies overall craft process, is reduced Overall operation energy consumption；

(2) dust pollution due to causing using boehmite dry glue powder as raw material is avoided, is greatly improved Operating environment.

With carrier is directly prepared using hydrated alumina wet gel as starting material prior art, such as US4613585 It is compared with CN103769118A, technical process of the invention is more succinct, and operability is stronger, and can effectively improve final The intensity of the formed body of preparation, while the pore-size distribution of the formed body finally prepared can be adjusted meets and a variety of uses field The requirement of conjunction.The reason of present invention can have the formed body of higher-strength as starting material preparation using hydrated alumina wet gel can It can be: the Free water interaction shape in compound and hydrated alumina wet gel at least two proton acceptor sites At hydrogen bond, the Free water in hydrated alumina wet gel is adsorbed, while there is the compound at least two proton acceptor sites Interaction of hydrogen bond can occur with the hydroxyl in hydrated alumina molecular structure, play the role of physics peptization, so that water Closing aluminium oxide wet gel can not only form, and can make the formed body finally prepared intensity with higher.Also, by changing The content for the compound for becoming at least two proton acceptor sites can be adjusted the aperture of the formed body of preparation, respectively obtain The formed body of bimodal distribution or Unimodal Distribution.

Modified aluminium oxide supports according to the present invention, in state (i), the total weight with the modified aluminium oxide supports is Benchmark, the content of acid additive based on the element can be 0.1-15 weight %, preferably 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably 1-5 weight % are still more preferably 2-4 weight %；In state (ii), with described On the basis of the total weight of modified aluminium oxide supports, the content of acid additive based on the element can be 0.1-15 weight %, preferably It is still more preferably 2-4 weight for 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably 1-5 weight % Measure %；On the basis of the total weight of the modified aluminium oxide supports, the content of the metal promoter in terms of oxide can be 0.1-15 weight %, preferably 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably 1-3 weight %.

Modified aluminium oxide supports according to the present invention make modified aluminium oxide supports particle have the modification of state (i) The step of (hereinafter referred to as the first modification) may include: by the hydrated alumina composition through aoxidizing obtained by forming processes Aluminium formed body carries out hydro-thermal process, and then the carrier of gained hydro-thermal process is successively impregnated and dried, and will last time Gained desciccate is roasted, wherein maceration extract used in each dipping process is helped containing being provided with identical or different acidity The compound of agent, duplicate frequency n >=2, preferably 2-3 times, and as n >=3, (n-1)th dipping is being impregnated into from the 2nd time In the process, the dry temperature temperature drier than after adjacent preceding single-steeping is 20-150 DEG C high after impregnating each time, each time The dry time is 1-10 hours longer than the time of drying after adjacent preceding single-steeping after dipping.

First modification according to the present invention, carrier after hydro-thermal process due to density of surface hydroxyl increases and band Negative electricity, after being immersed in maceration extract, the acid additive compound in maceration extract is easily enriched in the table of aluminium oxide formed body Face, and after the carrier drying after first time is impregnated, density of surface hydroxyl reduces, and hydroxy density is maximum on aluminium oxide formed body The position of value is migrated along the radial direction of aluminium oxide formed body toward carrier center, is immersed in it in another maceration extract Afterwards, the acid additive compound in another maceration extract, which is easy to be enriched in be located at, carries intracorporal hydroxy density maximum, works as dipping When frequency n >=3, during from (n-1)th dipping is impregnated into the 2nd time, pass through temperature and drying dry after control dipping Time gradually increase with dipping time, the position for enabling to aluminium oxide to form intracorporal hydroxy density maximum value is gradually past Aluminium oxide formed body Center shift, and the acid additive compound impregnated in the maceration extract used every time is made to be adsorbed on oxidation in turn On the different location of aluminium formed body, the modified aluminium oxide supports that acid additive is in layer distributed are finally obtained after roasting.

First modification according to the present invention, the modified aluminium oxide supports contain the acidity of layer distributed in the carrier Auxiliary agent, and the acid additive of different layers is gradually increased from the modified aluminium oxide supports particle surface to center acidity, using this kind Modified aluminium oxide supports preparation catalyst be used for hydrotreating reaction when, reactant molecule outside catalyst granules internally Diffusion can come into contact with acid stronger acid additive (acid intensity F > P > B), be beneficial to metal deposit and product Charcoal is uniformly distributed along catalyst radial direction, improves the effect of hydrotreating.

First modification according to the present invention, the modified aluminium oxide supports need first to carry out hydro-thermal process, the present invention The condition of the hydro-thermal process is not particularly limited, for example, it is 50- that the condition of the hydro-thermal process, which may include: temperature, 200 DEG C (preferably 60-180 DEG C, more preferably 70-150 DEG C), the time be 5-30 hours (preferably 8-28 hours, more preferably 10-24 hours).

First modification according to the present invention needs that the formed body of hydro-thermal process is repeatedly successively impregnated and done It is dry, wherein the type of acid additive compound may be the same or different in maceration extract used in each dipping process, excellent The advantages of choosing is different, and the modified aluminium oxide supports enabled in this way can converge a variety of different acid additives.

First modification according to the present invention, the type of the acid additive can be the conventional selection of this field, special It You Xuanwei not at least one of F, P and B component.Although existing by F in the modified aluminium oxide supports with simple substance form, P component and B component are usually to exist in the form of its oxide, but the present invention is not limited thereto, F, P as acid additive It can also be to exist in the form of the acid additive compound for providing acid additive component with B.Wherein, the acid additive of F is provided Closing object for example can be one of ammonium fluoride, ammonium acid fluoride, hydrofluoric acid, sodium fluoride and calcirm-fluoride or a variety of.Wherein, P is provided Acid additive compound can be for example one of phosphoric acid, Diammonium phosphate (DAP), sodium dihydrogen phosphate and potassium dihydrogen phosphate or a variety of. Wherein, the acid additive compound for providing B for example can be one of boric acid, metaborate and borate or a variety of.It is preferred that In the case of, in the modified aluminium oxide supports, on the basis of the total weight of the modified aluminium oxide supports, with tri- kinds of members of F, P and B Element meter the acid additive content be 0.1-15 weight %, more preferably 0.2-12 weight %, still more preferably for 0.3-8 weight %.Wherein, " content of the acid additive in terms of tri- kinds of elements of F, P and B " refers to the weight of the acid additive Amount is measured using the total weight of tri- kinds of elements of F, P and B as representative, wherein when the acid additive does not include F, P and B One of three kinds of elements or at two kinds, " content of the acid additive in terms of tri- kinds of elements of F, P and B " also includes this Kind of situation, only removing naturally not includes that usually First Astronautic Research Institute for Measurement and Test states the content of acid additive to that member.Therefore, the present invention is preferred The dosage of used acid additive compound makes the content of the acid additive in modified aluminium oxide supports meet above-mentioned requirements.

First modification according to the present invention is not particularly limited the type of solvent in the maceration extract, can be with For the existing various inertia liquids that can dissolve the acid additive compound, for example, can be selected from water, alcohol (such as first Alcohol, ethyl alcohol etc.), ether (such as ether), at least one of aldehyde (such as formaldehyde) and ketone (such as acetone).In addition, impregnating every time The content of acid additive compound may be the same or different in maceration extract used, and be each independently 1-100 grams/ It rises, preferably 5-50 grams per liter, more preferably 5-15 grams per liter.Further, the dosage of dipping maceration extract used can be with every time It is identical, it can also be different, and the carrier relative to 100g, the dosage of dipping maceration extract used can respectively solely every time It is on the spot 20-200mL, preferably 50-100mL.The content range of such acid additive compound and the dosage of maceration extract can So that in above-mentioned modified aluminium oxide supports, on the basis of the total weight of the modified aluminium oxide supports, with tri- kinds of F, P and B The content of the acid additive of element meter be 0.1-15 weight %, more preferably 0.2-12 weight %, still more preferably for 0.3-8 weight %.

First modification according to the present invention, in the preparation method of the modified aluminium oxide supports, to the dipping The acid-base property of liquid is not particularly limited, for example, maceration extract that can be acid, alkaline, neutral.Preferably, preceding n-1 leaching Maceration extract used by stain is in acidity, and n-th impregnates used maceration extract in alkalinity.It is highly preferred that preceding n-1 dipping institute The pH value of the maceration extract used is 2-6.It is highly preferred that the pH value that n-th impregnates used maceration extract is 8-11.Of the invention Inventors have found that when by the control of the acid-base property of the maceration extract in the above preferred range more advantageous acid additive on carrier Layer distributed be more advantageous to raising catalyst so that the modified aluminium oxide supports made are prepared into after hydrogenation catalyst Demetallization per and asphaltene removal.Wherein, the maceration extract is adjusted to the method for alkalinity typically toward the leaching Alkaline matter is added in stain liquid, for example, at least one of ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc..And Acidity may be just presented in maceration extract of compound containing at least one of F, P and B itself, if not shown acid or acid Degree is insufficient, then acidic materials can be added into the maceration extract (for example, in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc. at least It is a kind of) the maceration extract is adjusted to expected acidity.

The number of first modification according to the present invention, the dipping can be carried according to obtained modified aluminas Body is reasonably selected, but is comprehensively considered from the effect of the complexity of preparation process and the modified aluminium oxide supports obtained, Preferably, the number of the dipping is 2-3 times, i.e. n is preferably 2-3 times.Wherein, as dipping time n=2, as long as using warp It crosses the carrier of hydro-thermal process and guaranteeing that the carrier after impregnating first time is dried can make the acid additive be on carrier Layer distributed；As dipping time n >=3, as long as using item dry by the carrier of hydro-thermal process and after guaranteeing repeatedly dipping Part, which meets above-mentioned specific condition, can make acid additive on carrier in layer distributed.However, usually, drying temperature It is too high, it is unfavorable for the control of production process, too low, the carrier after cannot making dipping is able to abundant drying；And when drying Between it is too long, be unfavorable for the raising of yield, it is too short, cannot make dipping after carrier sufficiently dried, therefore, from every side Combined factors consider, it is preferable that as n >=3, during from (n-1)th dipping is impregnated into the 2nd time, impregnate each time The dry temperature temperature drier than after adjacent preceding single-steeping is 30-120 DEG C high afterwards, more preferably 30-80 DEG C high；It soaks each time The dry time is 1-9 hours longer than the time of drying after adjacent preceding single-steeping after stain, more preferably 2-5 hours long.

First modification according to the present invention is not particularly limited the drying condition after each dipping, can be with Using the condition of the carrier after the conventional dry dipping in this field, as long as can satisfy above-mentioned difference, for example, different leachings The immersion condition of stain step may be the same or different, and usual can be each independently 20- including dipping temperature 300 DEG C, preferably 50-100 DEG C；Dip time can be 1-20 hours, preferably 1-6 hours.Under preferable case, soak for the first time After stain dry condition include: temperature be 30-300 DEG C (preferably 50-300 DEG C, more preferably 100-250 DEG C, most preferably 100-150 DEG C), the time is 1-20 hours (preferably 2-18 hours, more preferably 3-10 hours, most preferably 3-8 hours).It is excellent In the case of choosing, last time condition dry after impregnating include: temperature be 30-300 DEG C (preferably 50-300 DEG C, more preferably 100-200 DEG C, most preferably 120-180 DEG C), the time be 1-20 hours (preferably 2-18 hours, more preferably 3-10 hours, Most preferably 3-5 hours).In addition, in the present invention, the drying all can be dried in vacuo.

First modification according to the present invention, in the preparation method of the modified aluminium oxide supports, to the item of roasting Part is not particularly limited, for example, the condition of the roasting include: temperature be 300-900 DEG C (preferably 300-800 DEG C, it is more excellent It is selected as 350-500 DEG C), the time is 1-10 hours (preferably 2-8 hours, more preferably 2-6 hours).

Modified aluminium oxide supports according to the present invention make modified aluminium oxide supports particle have the modification of state (ii) The step of (hereinafter referred to as the second modification) may include: (1), by the hydrated alumina composition through obtained by forming processes Aluminium oxide formed body carries out hydro-thermal process, then in the containing the metal promoter compound for being provided with the metal promoter of alkalinity It is impregnated in one solution, is then dried, obtain the carrier that load has the metal promoter；(2), the load there is into the gold The carrier for belonging to auxiliary agent is impregnated in acid the second solution containing the acid additive compound for being provided with the acid additive, Then it is dried and roasts.

Second modification according to the present invention, metal promoter compound will provide the metal promoter, and the metal Auxiliary agent refers to the metallic element in group ia and/or group iia, wherein group ia metal is preferably one in Li, Na and K Kind or it is a variety of, group iia metal be preferably Mg and/Ca, thus, metal promoter of the invention is preferably in Li, Na, K, Mg and Ca It is one or more.Wherein, the metal promoter compound for providing Li for example can be lithium nitrate and/or lithium sulfate.Wherein, it provides The metal promoter compound of Na for example can be sodium nitrate and/or sodium sulphate.Wherein, the metal promoter compound of K is provided for example It can be potassium nitrate and/or potassium sulfate.Wherein, the metal promoter compound for providing Mg for example can be magnesium nitrate and/or chlorination Magnesium.Wherein, the metal promoter compound for providing Ca for example can be one of calcium nitrate, calcium chloride and calcium acetate or a variety of.

Second modification according to the present invention, the acid additive are derived from the acid additive compound, the acid Property auxiliary agent refer to selected from least one of F, P and B element.Wherein, the acid additive compound for providing F for example can be fluorine Change one of ammonium, ammonium acid fluoride, hydrofluoric acid, sodium fluoride and calcirm-fluoride or a variety of.Wherein, the acid additive compound of P is provided It such as can be one of phosphoric acid, Diammonium phosphate (DAP), sodium dihydrogen phosphate and potassium dihydrogen phosphate or a variety of.Wherein, the acidity of B is provided Auxiliary compound for example can be one of boric acid, metaborate and borate or a variety of.

Second modification according to the present invention, it should be noted that " acid additive is distributed in the first stratum nucleare, institute State metal promoter and be distributed in the first shell " refer to radial direction along the modified aluminium oxide supports, it is carried in the modified aluminas Metal promoter and acid additive are in layer distributed on body, wherein metal promoter is mainly distributed on the first shell, can there is a small amount of point Cloth is in the first stratum nucleare；And acid additive is mainly distributed on the first stratum nucleare, can also have and be distributed in the first shell on a small quantity.Due to SEM- Change in EDX (Scanning Electron Microscope-Energy Dispersive Spectrometry) characterization result The numerical value for the every bit constituent content that property alumina carrier particle radially measures is corresponded to each other with the point element content, although the number The size of value may not represent the real content of the point element, but be able to reflect the point element content height.In order to indicate gold The regularity of distribution for belonging to auxiliary agent and acid additive along carrier radial direction introduces distribution factor σ.The distribution factor σ is auxiliary agent in carrier (R is particle radius, to be at modified aluminium oxide supports granular center with the ratio of concentration at center on a certain position of grain Point).Wherein, concentration of the auxiliary agent on a certain position of carrier granular refers in SEM-EDX characterization result in the position (position nearby Set deviation≤20nm) average value of 20 numerical point numerations, concentration of the auxiliary agent at the center of carrier granular refers to SEM-EDX table Levy the average value that (position deviation≤20nm) 20 numerical points count near central point in result.If σ > 1, show that auxiliary agent exists Content on the aspect is higher than the content of corresponding additive at modified aluminium oxide supports granular center；If σ=1, show auxiliary agent at this Content on point is identical as the content of corresponding additive at modified aluminium oxide supports granular center；If σ < 1, show auxiliary agent in the point On content lower than corresponding additive at modified aluminium oxide supports granular center content.Wherein, in the modified aluminium oxide supports In, the distribution factor σ > 1 of the metal promoter of carrier granular outer layer (the first shell), and carrier granular outer layer (the first shell) The distribution factor σ < 1 of acid additive.

Second modification according to the present invention, the present invention be not special to the thickness of first shell and the first stratum nucleare Ground limits, for example, the thickness of first shell can be 0.1-5mm, preferably 0.1-4mm, more preferably 0.1-2.5mm； The thickness of first stratum nucleare can be 0.1-5mm, preferably 0.1-4mm, more preferably 0.15-3.5mm.Wherein, described The thickness of one shell refers to the thickness of the part distribution factor σ >=2 of the metal promoter, and the first stratum nucleare thickness refers to acid The thickness of 1 part 0.5≤σ of distribution factor < of property auxiliary agent.In the present invention, the thickness of first shell and the first stratum nucleare is adopted It is measured with SEM-EDX method, specifically, randomly selects 30 modified aluminium oxide supports and measure its cross section and partial size with SEM, it The radial distribution of metal promoter component is obtained along each modified aluminium oxide supports radial scan respectively with EDX afterwards and obtains σ >=2 Point thickness, take above-mentioned thickness arithmetic mean of instantaneous value be the first shell of the present invention thickness；And with EDX respectively along every A modified aluminium oxide supports radial scan obtains the radial distribution of acid additive component and obtains the thickness of 1 part 0.5≤σ <, Take above-mentioned thickness arithmetic mean of instantaneous value be the first stratum nucleare of the present invention thickness.

Second modification according to the present invention, the present invention be not special to the content of the metal promoter and acid additive Ground limits, but in order to enable the hydrodenitrogenation catalyst made of the modified aluminium oxide supports is shown more in hydrogenation reaction Good catalytic activity, it is preferable that the content of the metal promoter in terms of metal oxide is 0.1-15 weight %, further excellent It is selected as 0.2-12 weight %, more preferably 0.3-8 weight %, most preferably 1-3 weight %.Preferably, with tri- kinds of members of F, P and B The content of the acid additive of element meter is 0.1-15 weight %, further preferably 0.2-12 weight %, more preferably 0.3-8 Weight %, most preferably 1-2 weight %.Wherein, " content of the acid additive in terms of tri- kinds of elements of F, P and B " refers to institute The weight for stating acid additive is measured using the total weight of tri- kinds of elements of F, P and B as representative, wherein when the acid additive When not including one or both of tri- kinds of elements of F, P and B, " acid additive in terms of tri- kinds of elements of F, P and B contains Amount " also includes such case, and only removing naturally not includes that usually First Astronautic Research Institute for Measurement and Test states the content of acid additive to that member.

Second modification according to the present invention, in step (1), although as long as first will before carried metal auxiliary agent The aluminium oxide formed body carries out hydro-thermal process (aluminium oxide formed body is added to the water and heats), and will contain The solution control for having metal promoter compound be alkaline and control the solution containing acid additive compound can be real for acidity Existing metal promoter and acid additive are in layer distributed along the radial direction of the aluminium oxide formed body, preparation process controllability and Repeatability is very good.In order to further increase the controllability and repeatability of preparation process, it is preferable that the condition packet of hydro-thermal process Include: temperature is 50-200 DEG C (further preferably 60-180 DEG C, more preferably 70-150 DEG C), and the time is 5-30 hours (into one Step preferably 8-28 hours, more preferably 10-24 hours).

Second modification according to the present invention, first solution be it is alkaline, can use this field routine alkali Property substance makes first solution alkaline, such as can use ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate Deng one of or it is a variety of, come so that first solution for alkalinity.Under preferable case, the pH value of first solution is 7.5- 11, more preferably 8-11.Second solution be it is acid, the usual acid additive compound enables to described second molten Liquid can be made in acidity, but when second solution does not show as acidity using the acidic materials of this field routine Second solution is in acidity, such as can use one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc. or a variety of.Preferable case Under, the pH value of second solution is 2-6.5, more preferably 4-6.The present invention does not have the type of solvent in first solution It particularly limits, can be the existing various inertia liquid objects that can dissolve the metal promoter compound under alkaline condition Matter, for example, can be selected from water, alcohol (such as methanol, ethyl alcohol etc.), ether (such as ether), aldehyde (such as formaldehyde) and ketone (such as third Ketone) one of or it is a variety of.In addition, the first GOLD FROM PLATING SOLUTION category auxiliary compound content can be 10-20 grams per liter.This hair The bright type to solvent in second solution is not particularly limited, and various can be dissolved in acid condition to be existing The inertia liquid of the acid additive compound, for example, can selected from water, alcohol (such as methanol, ethyl alcohol etc.), ether (such as Ether), one of aldehyde (such as formaldehyde) and ketone (such as acetone) or a variety of.In addition, described contain acid additive in the second solution Compounds content can be 10-20 grams per liter.

Second modification according to the present invention, it is no special to the condition of dipping described in step (1) and step (2) Ground limits, and the immersion condition of two steps can be identical or different, as long as it is described to enable to metal promoter and acid additive to be supported on On carrier, for example, it is 20-300 DEG C of (preferably 40-100 DEG C, more preferably 40-80 that the condition of dipping, which includes: temperature, DEG C), the time is 1-20 hours (preferably 1-6 hours, more preferably 1-3 hours).The above dipping can be conventional using this field Dipping method carry out, such as can be excessive liquid dipping, hole saturation infusion process.

Drying described in second modification according to the present invention, step (1) and step (2) can be vacuum drying.Institute State dry condition all can be this field conventional selection, for example, dry condition may include: that temperature is in step (1) 30-300 DEG C (preferably 50-300 DEG C, more preferably 100-250 DEG C), the time be 1-20 hours (preferably 2-18 hours, it is more excellent It is selected as 3-10 hours).For example, dry condition may include: that temperature is 80-200 DEG C of (preferably 80-180 in step (2) DEG C, more preferably 80-150 DEG C), the time is 1-10 hours (preferably 2-8 hours, more preferably 2-6 hours).

Second modification according to the present invention, the present invention are not particularly limited the condition of the roasting in step (2), For example, it is 300-900 DEG C (preferably 300-800 DEG C, more preferably 400-600 DEG C) that the condition of the roasting, which includes: temperature, when Between be 1-10 hours (preferably 2-8 hours, more preferably 2-6 hours).

Hydrodenitrogenation catalyst according to the present invention, when modified aluminium oxide supports particle has state (i), described plus hydrogen Denitrification activity metal component is in layer distributed in modified aluminium oxide supports particle, and the active metal component for being distributed in stratum nucleare is Ni And W, for Mo, (hydrodenitrogenation catalyst is denoted as the active metal component being distributed in shell with the combination selected from Ni and/or Co First hydrodenitrogenation catalyst)；

When modified aluminium oxide supports particle has state (ii), the hydrodenitrogenationactivity activity metal component is modified oxidized It is in layer distributed in alumina supporter particle, the active metal component for being distributed in the second stratum nucleare is Ni and W, is distributed in the second shell For Mo, (hydrodenitrogenation catalyst is denoted as the second hydrodenitrogeneration catalysis to active metal component with the combination selected from Ni and/or Co Agent).

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, the present invention are de- to described plus hydrogen The content of each active metal component is not particularly limited in nitrogen catalyst, but in order to enable the hydrodenitrogenation catalyst is adding Better catalytic activity is shown in hydrogen reaction, it is preferable that is counted using metal oxide and using the total weight of the catalyst as base Standard, the content of Mo are 2-30 weight %, further preferably 5-25 weight %, more preferably 5-20 weight %, most preferably 8- 16 weight %.Preferably, the total content of Ni is 0.5-15 weight %, further preferably 1-10 weight %, more preferably 2-9 weight Measure %, most preferably 3-6 weight %.Preferably, the content of Co be 0-15 weight %, further preferably 1-10 weight %, more Preferably 2-9 weight %, most preferably 3-5 weight %.Preferably, the content of W is 2-40 weight %, further preferably 5-35 Weight %, more preferably 8-30 weight %, most preferably 15-30 weight %.It is highly preferred that when shell contains Ni, the core The weight ratio of the Ni of the Ni and shell of layer is 1:0.5-1.

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, since the hydrodenitrogeneration is urged Agent is usually that modified aluminium oxide supports load after upper active metal component by prepared by roasting, therefore, above-mentioned activity gold Belong to component to exist usually in the form of metal oxide in the hydrodenitrogenation catalyst, the present invention is also not limited to certainly This, the active metal component is also possible to the shape of the compound of the offer active metal component in addition to an oxide Formula exists.Wherein, the compound of the offer Co other than CoO for example can be cobalt carbonate (CoCO₃), cobalt nitrate (CoNO₃)、 Cobalt acetate (Co (AcO)₃), basic cobaltous carbonate (2CoCO₃·3Co(OH)₂·H₂) and cobalt chloride (CoCl O₂) one of or it is more Kind.Providing the cobalt compound of Co is preferably cobalt oxide (CoO), cobalt carbonate (CoCO₃), cobalt nitrate (CoNO₃), cobalt acetate (Co (AcO)₃), basic cobaltous carbonate (2CoCO₃·3Co(OH)₂·H₂) and cobalt chloride (CoCl O₂) one of or it is a variety of.Wherein, it removes The compound of offer Ni other than NiO for example can be nickelous carbonate (NiCO₃), nickel nitrate (NiNO₃), nickel acetate (Ni (AcO)₃), basic nickel carbonate (NiCO₃·2Ni(OH)₂·4H₂) and nickel chloride (NiCl O₂) one of or it is a variety of.Ni is provided Nickel compound be preferably nickel oxide (NiO), nickelous carbonate (NiCO₃), nickel nitrate (NiNO₃), nickel acetate (Ni (AcO)₃), alkali formula Nickelous carbonate (NiCO₃·2Ni(OH)₂·4H₂) and nickel chloride (NiCl O₂) one of or it is a variety of.Wherein, in addition to MoO₃In addition The compound for providing Mo for example can be ammonium molybdate ((NH₄)₂MoO₄), ammonium paramolybdate ((NH₄)₆Mo₇O₂₄), ammonium dimolybdate ((NH₄)₂Mo₂O₇) and ammonium tetramolybdate ((NH₄)₂Mo₄O₁₃) one of or it is a variety of.The molybdenum compound for providing Mo preferably aoxidizes Molybdenum (MoO₃), ammonium molybdate ((NH₄)₂MoO₄), ammonium paramolybdate ((NH₄)₆Mo₇O₂₄), ammonium dimolybdate ((NH₄)₂Mo₂O₇) and four molybdic acids Ammonium ((NH₄)₂Mo₄O₁₃) one of or it is a variety of.Wherein, in addition to WO₃The compound of offer W in addition for example can be ammonium tungstate ((NH₄)₁₀W₁₂O₄₁), ammonium metatungstate ((NH₄)₆H₂W₁₂O₄₀), one of ammonium paratungstate and ethyl ammonium metatungstate or a variety of.Mention Tungsten compound for W is preferably tungsten oxide (WO₃), ammonium tungstate ((NH₄)₁₀W₁₂O₄₁), ammonium metatungstate ((NH₄)₆H₂W₁₂O₄₀), secondary tungsten One of sour ammonium and ethyl ammonium metatungstate are a variety of.

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, the hydrodenitrogenation catalyst Preparation step include: (a), by the modified aluminium oxide supports carry out hydro-thermal process, then by the modification oxygen after hydro-thermal process Change alumina supporter acid containing being soaked in molybdenum compound and the combined third solution of nickel compound and/or cobalt compound Then stain is dried；The pH value of the third solution is 2-6.5；(b), the carrier by step (a) after dry containing in alkaline It is impregnated in the 4th solution for having nickel compound and tungsten compound, is then dried and roasts；The pH of 4th solution Value is 7.5-11.

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, although as long as in supported active Before metal component, the modified aluminium oxide supports are first subjected to hydro-thermal process, and are acid and will by the control of the first solution The control of second solution can be realized the active metal component for alkalinity and add the radial direction of hydrogen carrier to be in point along the modification Layer distribution (for example, double-deck distribution), but in order to further increase the controllability of preparation process and repeatability, it is preferable that at hydro-thermal The condition of reason includes: that temperature is 50-200 DEG C (further preferably 60-180 DEG C, more preferably 70-150 DEG C), time 5-30 Hour (further preferably 8-28 hours, more preferably 10-24 hours).Wherein, the nickel compound, molybdenum compound, tungsten It is as hereinbefore defined to close object, cobalt compound, details are not described herein.And nickel compound used by step (a) and step (b) Selected each independently, can with it is identical can be different.

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, the third solution are acidity , can using this field routine acidic materials make the third solution in acidity, such as can use hydrochloric acid, sulfuric acid, One of nitric acid, phosphoric acid etc. are a variety of.Under preferable case, the pH value of the third solution is 2-6.5, more preferably 2-6, more Further preferably 4-6.4th solution be it is alkaline, the described 4th can be made using the alkaline matter of this field routine Solution alkaline, such as one of ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc. or a variety of can be used, Come so that the 4th solution is alkalinity.Under preferable case, the pH value of the 4th solution is 7.5-11, more preferably 8-11.

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, the present invention are molten to the third The type of solvent is not particularly limited in liquid, can for it is existing it is various can dissolve under alkaline condition the molybdenum compound, The inertia liquid of nickel compound and/or cobalt compound, for example, water, alcohol (such as methanol, ethyl alcohol etc.), ether (example can be selected from Such as ether), at least one of aldehyde (such as formaldehyde) and ketone (such as acetone).In addition, the third in terms of metal oxide The total content of Molybdenum in Solution compound, nickel compound and cobalt compound can be 10-20 grams per liter.The present invention is molten to the described 4th The type of solvent is not particularly limited in liquid, can for it is existing it is various can dissolve in acid condition the nickel compound and The inertia liquid of tungsten compound, for example, water, alcohol (such as methanol, ethyl alcohol etc.), ether (such as ether), aldehyde (example can be selected from At least one of such as formaldehyde) and ketone (such as acetone).In addition, nickel compound in the 4th solution in terms of metal oxide Total content with tungsten compound can be 10-20 grams per liter.

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, in step (a) and (b), institute It states in the hydrodenitrogenation catalyst that the dosage of modified aluminium oxide supports and third solution and the 4th solution can make, with metal Oxide meter and on the basis of the total weight of the catalyst, the content of Mo are 2-30 weight %, preferably 5-25 weight %, more Preferably 5-20 weight %, most preferably 8-16 weight %；The total content of Ni is 0.5-15 weight %, preferably 1-10 weight Measure %, more preferably 2-9 weight %, most preferably 3-6 weight %；The content of Co is 0-15 weight %, preferably 1-10 weight Measure %, more preferably 2-9 weight %, most preferably 3-5 weight %；The content of W is 2-40 weight %, preferably 5-35 weight Measure %, more preferably 8-30 weight %, most preferably 15-30 weight %.

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, the present invention to step (a) and The condition of dipping in step (b) is not particularly limited, can be identical or different, as long as enabling to active metal component It is supported on carrier, for example, it is 50-300 DEG C, preferably 50-100 DEG C that the condition of dipping, which may include: temperature,；Time is 1-20 hours, preferably 1-6 hours.In addition, drying described in step (a) and step (b) can be vacuum drying.The drying Condition all can be this field conventional selection, for example, in step (a), dry condition may include: that temperature is 30-300 DEG C (preferably 50-300 DEG C, more preferably 100-250 DEG C), time are 1-20 hours (preferably 2-18 hours, more preferably 3- 10 hours).For example, in step (b), dry condition may include: temperature be 80-200 DEG C (preferably 80-180 DEG C, it is more excellent It is selected as 80-150 DEG C), the time is 1-10 hours (preferably 2-8 hours, more preferably 2-6 hours).

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, to the roasting in step (b) There is no particular limitation, can be using the roasting condition of the hydrodenitrogenation catalyst of this field routine, for example, roasting in step (b) The condition of burning may include: that temperature is 300-900 DEG C (preferably 300-800 DEG C, more preferably 400-600 DEG C), time 1- 10 hours (preferably 2-8 hours, more preferably 2-6 hours).

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, above-mentioned preparation method can be with Adjuvant component including hydrodenitrogenation catalyst to be loaded to upper other this fields routine, such as Si.Such adjuvant component can be with The method of this field routine is introduced into the hydrodenitrogenation catalyst, such as can be drawn when preparing modified aluminium oxide supports Enter, can be introduced in supported active metals group timesharing, alternatively, individually will contain to be provided with and help before supported active metals component The solution of the compound of agent component and modified aluminium oxide supports carry out immersive contact, and drying and roasting mode (dipping, it is dry and The condition of roasting can be carried out using the condition that above any one place records), to this present invention, there is no particular limitation.

First hydrodenitrogenation catalyst and the second hydrodenitrogenation catalyst according to the present invention, hydrodenitrogeneration of the invention are urged Agent has both preferable denitrification effect and carbon residue removal effect, and one of reason is: hydrodenitrogenation catalyst of the invention Active metal catalyst component be in the form of layer distributed exist, shell using Mo be selected from Ni and/or Co group cooperation For active metal component, stratum nucleare uses Ni and W as active metal component, with special using the reaction of different activities metal component Point, the denitrification activity and carbon residue removal activity of Lai Youhua hydrodenitrogenation catalyst.

First hydrodenitrogenation catalyst according to the present invention, it should be noted that " be distributed in the active metal component of stratum nucleare For Ni and W, the active metal component being distributed in shell is Mo and the combination for being selected from Ni and/or Co " refer to that the activity of stratum nucleare is golden Belonging to component is mainly Ni and W, and a small amount of other components such as Mo and/or Co can also be distributed with；The active metal component of shell is main For Mo and the combination for being selected from Ni and/or Co, a small amount of other components such as W can also be distributed with.Due to SEM-EDX (Scanning Electron Microscope-Energy Dispersive Spectrometry) in characterization result along Hydrogenation catalyst granule The numerical value of the every bit constituent content radially measured is corresponded to each other with the point element content, although the size of the numerical value may be not The real content of the point element is represented, but is able to reflect the point element content height.In order to indicate above-mentioned active metal component member Element introduces distribution factor σ along the regularity of distribution of carrier radial direction.The distribution factor σ be active metal component carrier granular certain On one position with the ratio of concentration at center (R is particle radius, using at Hydrogenation catalyst granule center as starting point).Wherein, living Property concentration of the metal component on a certain position of catalyst granules refer in SEM-EDX characterization result in the position (position nearby Set deviation≤20nm) average value of 20 numerical point numerations, concentration of the active metal component at the center of catalyst granules is Refer to the average value that neighbouring (position deviation≤20nm) 20 numerical points of heart point count in the catalyst in SEM-EDX characterization result. If σ > 1, show that this active metal component constituent content is higher than at catalyst granules center；If σ=1, show that the point is lived Property metallic constituent element content is identical as at catalyst granules center；If σ < 1, show this active metal component constituent content At catalyst granules center.Wherein, in the hydrogenation catalyst, the MoO of catalyst granules outer layer (shell)₃And CoO The distribution factor σ > 1 of active metal component, and the WO of catalyst granules outer layer (shell)₃The distribution factor σ of active metal component < 1.

First hydrodenitrogenation catalyst according to the present invention, the present invention is to the thickness of the shell and stratum nucleare without particularly It limits, for example, the thickness of the shell can be 0.1-5mm, preferably 0.1-4mm, more preferably 0.1-2.5mm；The core The thickness of layer can be 0.1-5mm, preferably 0.1-4mm, more preferably 0.15-3.5mm.Wherein, the thickness of the shell is Refer to the thickness of the part distribution factor σ >=2.0 of the Mo active metal component, and the stratum nucleare thickness refers to W active metal group The thickness for 1 part 0.5≤σ of distribution factor < divided.In the present invention, the thickness of the shell and stratum nucleare uses SEM-EDX method It measures, specifically, randomly selects 30 hydrodenitrogenation catalysts and measure its cross section and partial size with SEM, distinguished later with EDX The radial distribution of Mo active metal component is obtained along each hydrodenitrogenation catalyst radial scan and obtains the thickness of the part σ >=2.0 Degree, take above-mentioned thickness arithmetic mean of instantaneous value be shell of the present invention thickness；And with EDX respectively along each hydrodenitrogeneration Catalyst radial scan obtains the radial distribution of W active metal component and obtains the thickness of 1 part 0.5≤σ <, takes above-mentioned thickness Arithmetic mean of instantaneous value be stratum nucleare of the present invention thickness.

Second hydrodenitrogenation catalyst according to the present invention, it will be apparent to a skilled person that in the present invention " the first stratum nucleare " and " the second stratum nucleare " is merely to distinguish acid additive and the formd stratum nucleare of active metal component, wherein the One stratum nucleare be partial to the layer on carrier (the aluminium oxide formed body of addition) surface for modified aluminium oxide supports, and Second stratum nucleare is to be partial to the layer on modified aluminium oxide supports surface for hydrodenitrogenation catalyst, similarly can also be with " the first shell " and " the second shell " are understood, it may be said that be that hydrodenitrogenation catalyst provided by the invention is from the inside to the outside It should be carrier (the aluminium oxide formed body of addition), acid additive layer, (this three forms modified aluminas load to metal promoted oxidant layer Body) and subsequent Ni and W layers and Mo and the combination layer selected from Ni and/or Co.

Second hydrodenitrogenation catalyst according to the present invention, it should be noted that " be distributed in the active metal of the second stratum nucleare Group is divided into Ni and W, and the active metal component being distributed in the second shell is Mo and the combination for being selected from Ni and/or Co " refer to stratum nucleare Active metal component be mainly Ni and W, a small amount of other components such as Mo and/or Co can also be distributed with；The active metal of shell Component is mainly Mo with selected from the combination of Ni and/or Co, and a small amount of other components such as W can also be distributed with.Due to SEM-EDX Edge plus hydrogen in (Scanning Electron Microscope-Energy Dispersive Spectrometry) characterization result The numerical value for the every bit constituent content that catalyst granules radially measures is corresponded to each other with the point element content, although the numerical value is big It is small not represent the real content of the point element, but it is able to reflect the point element content height.In order to indicate above-mentioned activity Metallic constituent element introduces distribution factor σ along the regularity of distribution of carrier radial direction.The distribution factor σ is that active metal component is carrying (R is particle radius, to be at Hydrogenation catalyst granule center with the ratio of concentration at center on a certain position of body particle Point).Wherein, concentration of the active metal component on a certain position of catalyst granules refers in SEM-EDX characterization result at this The average value of position (position deviation≤20nm) 20 numerical points numeration nearby, active metal component is at the center of catalyst granules The concentration at place refers to heart point (position deviation≤20nm) 20 numerical point numerations nearby in the catalyst in SEM-EDX characterization result Average value.If σ > 1, show that this active metal component constituent content is higher than at catalyst granules center；If σ=1, table Bright this active metal component constituent content is identical as at catalyst granules center；If σ < 1, show this active metal component Constituent content is lower than at catalyst granules center.Wherein, in the hydrogenation catalyst, catalyst granules outer layer (the second shell) MoO₃With the distribution factor σ > 1 of CoO active metal component, and the WO of catalyst granules outer layer (the second shell)₃Active metal The distribution factor σ < 1 of component.

Second hydrodenitrogenation catalyst according to the present invention, the present invention do not have the thickness of second shell and the second stratum nucleare Have and particularly limit, for example, the thickness of second shell can be 0.1-5mm, preferably 0.1-4mm, more preferably 0.1- 2.5mm；The thickness of second stratum nucleare can be 0.1-5mm, preferably 0.1-4mm, more preferably 0.15-3.5mm.Wherein, The thickness of second shell refers to the thickness of the part distribution factor σ >=2.0 of the Mo active metal component, and described second Stratum nucleare thickness refers to the thickness of 1 part 0.5≤σ of distribution factor < of W active metal component.In the present invention, the second shell The thickness of layer and the second stratum nucleare is measured using SEM-EDX method, specifically, is randomly selected 30 hydrodenitrogenation catalysts and is used SEM Its cross section and partial size are measured, obtains Mo active metal group along each hydrodenitrogenation catalyst radial scan respectively with EDX later Point radial distribution and obtain the thickness of the part σ >=2.0, taking the arithmetic mean of instantaneous value of above-mentioned thickness is of the present invention second The thickness of shell；And the radial distribution of W active metal component is obtained along each hydrodenitrogenation catalyst radial scan respectively with EDX And obtain the thickness of 1 part 0.5≤σ <, take above-mentioned thickness arithmetic mean of instantaneous value be the second stratum nucleare of the present invention thickness Degree.

According to the method for the present invention, if modified aluminium oxide supports have state (i), the modified aluminium oxide supports contain The acid additive of layer distributed in carrier, and the acid additive of different layers is felt sad from the modified aluminium oxide supports particle surface in Property gradually increase, using this kind of modified aluminium oxide supports prepare hydrogenation protecting agent, Hydrodemetalation catalyst and hydrodenitrogeneration When at least one of catalyst is used for hydrotreating reaction, internally diffusion can outside catalyst granules for reactant molecule Come into contact with acid stronger acid additive (the acid intensity F > P > B of acid additive), be beneficial to metal deposit and Carbon deposit is uniformly distributed along catalyst radial direction, improves the effect of hydrotreating.

According to the method for the present invention, if modified aluminium oxide supports have state (ii), by the hydrogenation protecting agent, plus The catalyst carrier of at least one of hydrogen catalyst for demetalation and hydrodenitrogenation catalyst is modified, and can be made modified Acid additive and metal promoter in catalyst carrier (i.e. modified aluminium oxide supports) in layer distributed and make acid additive point It is distributed in stratum nucleare, metal promoter is distributed in shell, the process internally spread outside catalyst granules in reactant molecule in this way In, be conducive to metal deposit and carbon deposit along the radially uniform distribution of catalyst, the heavy oil hydrogenation treatment method is had Effect plays all kinds of catalyst actions, has better demetalization, denitrogenation, de- carbon residue activity for heavy distillate and residual hydrogenation And stability, the temperature rise of catalyst bed can be effectively controlled, the deactivation rate of catalyst is slowed down, extends the operating week of catalyst Phase.Moreover, the preparation method of catalyst carrier used in the present invention is relatively easy to implement, energy consumption is smaller, and the system The repeatability and controllability of Preparation Method are preferable.

According to the method for the present invention, the hydrogenation protecting agent can be the hydrogenation protecting agent of this field routine.Described plus hydrogen Protective agent contains active metal component and catalyst carrier (preferably above-mentioned modified aluminium oxide supports), wherein the activity gold Category group is divided at least one group VIII metal component and at least one vib metals component.In the preferred case, with metal The content of oxide meter and on the basis of the total weight of the hydrogenation protecting agent, the group VIII metal component is greater than 0 weight It measures % and is less than or equal to 1 weight % (for example, 0.1-0.9 weight %), the content of the vib metals component is greater than 0 weight It measures % and is less than or equal to 6 weight % (for example, 0.1-5 weight %).

According to the method for the present invention, the Hydrodemetalation catalyst can be the hydrodemetallisation catalyst of this field routine Agent.The Hydrodemetalation catalyst contains active metal component and catalyst carrier (preferably above-mentioned modified aluminas load Body), wherein the active metal component is at least one group VIII metal component and at least one vib metals component. In the preferred case, it is counted by metal oxide and on the basis of the total weight of the Hydrodemetalation catalyst, the Section VIII The content of race's metal component is 1-3 weight % (preferably 1.1-2.9 weight %), and the content of the vib metals component is 6-13 weight % (preferably 6.1-12.8 weight %).

According to the method for the present invention, the denitrogenation denitrification catalyst can be the hydrodenitrogeneration agent of this field routine.It is described Denitrogenation denitrification catalyst contains active metal component and catalyst carrier (preferably above-mentioned modified aluminium oxide supports), wherein institute Active metal component is stated as at least one group VIII metal component and at least one vib metals component.In preferable case Under, it is counted by metal oxide and on the basis of the total weight of the denitrifier, the content of the group VIII metal component is 3- 15 weight % (preferably 3.1-10 weight %), the content of the vib metals component be 13-50 weight % (preferably 13.1-30 weight %).

According to the method for the present invention, the group VIII metal can be selected from Ni, Co and Fe, preferably Ni and/or Co.Institute Cr, Mo and W, preferably Mo and/or W can be selected from by stating vib metals.

According to the method for the present invention, along logistics direction, the hydrogenation protecting agent, the Hydrodemetalation catalyst and described The catalytic activity of hydrodenitrogenation catalyst is gradually increased.In one embodiment, the activity in the hydrogenation protecting agent In active metal component content and the hydrodenitrogenation catalyst in metal component content, the Hydrodemetalation catalyst Active metal component content be gradually increased.

According to the method for the present invention, as long as the hydrogenation protecting agent, the Hydrodemetalation catalyst and described plus hydrogen are de- The catalyst carrier of at least one of nitrogen catalyst is that goal of the invention of the invention can be realized in modified aluminium oxide supports, with reality Now comprehensive demetalization, denitrogenation, de- carbon residue effect, under preferable case, in order to further improve demetalization, denitrogenation and de- carbon residue Effect, the catalyst carrier of the hydrodenitrogenation catalyst are the modified aluminium oxide supports, that is to say, that at least described plus hydrogen The catalyst carrier of denitrification catalyst is the modified aluminium oxide supports, the hydrogenation protecting agent and the hydrodemetallisation catalyst The catalyst carrier of agent can be optionally the modified aluminium oxide supports.It is further preferred that in order to further improve de- gold Belong to, the effect of denitrogenation and de- carbon residue, the hydrogenation protecting agent, the Hydrodemetalation catalyst and the hydrodenitrogenation catalyst Catalyst carrier be the modified aluminium oxide supports.

According to the method for the present invention, the reaction condition of heavy-oil hydrogenation processing is not particularly limited, preferred real Apply in mode, the reaction condition of the hydrotreating include: temperature be 300-550 DEG C, further preferably 330-480 DEG C, hydrogen Partial pressure is 4-20MPa, further preferably 6-18MPa, volume space velocity 0.1-3.0h^-1, further preferably 0.15-2h^-1, Hydrogen to oil volume ratio is 200-2500, further preferably 300-2000.In the present invention, the pressure refers to gauge pressure.

According to the method for the present invention, the method provided by the present invention is suitable for heavy oil feedstock especially high nitrogen inferior heavy oil (such as High nitrogen poor residuum) hydrotreating is carried out, to provide qualified feedstock oil for subsequent technique (such as catalytic cracking process).At this In invention, the heavy oil feedstock can be the high nitrogen inferior heavy that nitrogen content is 0.1-1 weight % (preferably 0.5-0.9 weight %) Oil.

Below will by embodiment, the present invention will be described in detail, but be not used in limitation the present invention.In following embodiment, Hydrogenation protecting agent is referred to as protective agent, and Hydrodemetalation catalyst is referred to as metal remover, and hydrodenitrogenation catalyst is referred to as de- Nitrogen agent.

Carrier water absorption rate of the present invention measures with the following method: first 120 DEG C of sample to be tested dried 4 hours, takes out sample, It is placed in drier and is cooled to room temperature, sieved with 40 mesh standard sieves, weigh oversize 20g sample to be tested, 50g deionization is added Water impregnates 30min, filtering, and solid phase drains 5min, weighs w grams of solid phase weight.Water absorption rate=(w-20)/20 × 100%.

Preparation example 1

Take the wet filter of boehmite of catalyst Chang Ling branch company sodium aluminate-aluminum sulfate method production band filter washing Cake (wet cake number SLB-1), after measured, the i value of the wet cake are 78.2%.

The wet cake SLB-1 of 200g is taken, 5g methylcellulose and 3 grams of sesbania powders containing 80% galactomannans is added, 10min is stirred, 30min is stood, obtains hydrated alumina composition JF-1,Value is 3.03.

By hydrated alumina composition JF-1 in laboratory F-26 type double screw banded extruder (South China Science & Engineering University's science and technology industry Head factory manufacture, it is the same below) on utilize Φ 1.4mm butterfly orifice plate extruded moulding.Wet bar is 3 hours dry at 120 DEG C, at 980 DEG C The radial crushing strength of lower roasting 3h, obtained aluminium oxide formed body Z-1 are 11.2N/mm, water absorption rate 1.19, Mercury injection Its bimodal hole pore size distribution can several bore dias be respectively 17.8nm and 30nm, BET method measures Kong Rongwei 0.71ml/g, specific surface area For 133m²/g。

Preparation example 2

The wet cake SLB-1 about 5Kg in preparation example 1 is taken, about 500g water is added and is beaten 1min, slurries are then pressed into plate The pressure of sheet frame is adjusted to 0.7Mpa and squeezes moisture, kept 15min, obtain filter cake 2.6Kg (filter cake number LB-1), passed through by frame Measurement, the i value of the filter cake are 62%.

Take 300g filter cake LB-1 that 4.5g hydroxyethylmethylcellulose and 1.5g sesbania powder (85% galactomannans) is added, Hydrated alumina composition JT-2 is obtained after mixing, through analyzing,Value is 1.60.

By hydrated alumina composition JT-2 on the F-26 double screw banded extruder of laboratory using Φ 1.4mm circular orifice at Type, extrusion is smooth, obtains the cylindrical strip of Glabrous thorn, 2 hours dry at 150 DEG C, and it is small that 3 are roasted at 700 DEG C When, obtain aluminium oxide formed body Z-2, its unimodal hole pore size distribution of Mercury injection can several bore dias be 15nm, BET method measures Kong Rong For 0.76ml/g, specific surface area 299m²/g。

Preparation example 3

300g filter cake LB-1 in preparation example 2 is taken, 2.6g hydroxypropyl methyl cellulose and 3.5g sesbania powder (85% gala is added Mannosan), hydrated alumina composition JT-3 is obtained after mixing, through analyzing itValue is 1.59.

By hydrated alumina composition JT-3, in laboratory SK132S/4 single-screw extruder, (BONNOT company, the U.S. is raw Produce) on squeeze out outer diameter be Φ 1.4mm wet bar.Wet bar is cut into the particle of 5mm or so length, it is 2 hours and 110 dry at 60 DEG C DEG C dry 2 hours, roasted 3 hours at 600 DEG C, obtain aluminium oxide formed body Z-3, its unimodal hole pore size distribution of Mercury injection can Several bore dias are 10nm, and BET method measures Kong Rongwei 0.60ml/g, specific surface area 260m²/g。

Preparation example 4

The preparation example is used to illustrate the preparation process of conventional oxidation alumina supporter.

Weighing the dry glue powder that 1000 grams of Chang Ling catalyst plants produce, (butt is 71 weight %, wherein boehmite content For 68 weight %, hibbsite content is 5 weight %, and surplus is amorphous alumina, i value be 20%), 30 grams of sesbania powders (Henan Lankao sesbania gum factory product) and 30g hydroxymethyl cellulose are simultaneously uniformly mixed, and 1200 milliliters of nitric acid containing 28g are added later Aqueous solution, the mixture determiningValue is 1.1, and the wet bar that outer diameter is 1.4mm is extruded on plunger type bar extruder.Then by wet bar It is 4 hours dry at 120 DEG C, it is roasted 3 hours at 960 DEG C, obtains aluminium oxide formed body DZ1, its unimodal hole of Mercury injection Pore size distribution can several bore dias be 17nm, using BET measure Kong Rongwei 0.95mL/g, specific surface area 90m²/g。

Weighing the dry glue powder that 2000 grams of Chang Ling catalyst plants produce, (butt is 73 weight %, wherein boehmite content For 68 weight %, hibbsite content is 5 weight %, and surplus is amorphous alumina, i value be 29%), 80 grams of sesbania powders (Henan Lankao sesbania gum factory product), 60g hydroxymethyl cellulose and 36g carbon black are simultaneously uniformly mixed, and are added 2400 milliliters later and are contained The aqueous solution of 32g nitric acid, the mixture determiningValue is 0.5, and it is wet that the butterfly that outer diameter is 1.4mm is extruded on plunger type bar extruder Item.Then butterfly wet bar is 4 hours dry at 120 DEG C, it is roasted 3 hours at 900 DEG C, obtains aluminium oxide formed body DZ2. It is obtained using mercury injection method measurement, the Kong Rongwei 0.78mL/g of aluminium oxide formed body DZ2, specific surface area 142m²/ g, pore structure are in Existing bimodal shape distribution, the hole 55%, 100nm-300nm that wherein hole 5nm-20nm accounts for total pore volume accounts for the 30% of total pore volume.

Weighing the dry glue powder that 2000 grams of Chang Ling catalyst plants produce, (butt is 73 weight %, wherein boehmite content For 68 weight %, hibbsite content is 5 weight %, and surplus is amorphous alumina, i value be 22%), 60 grams of sesbania powders (Henan Lankao sesbania gum factory product), 60g hydroxymethyl cellulose and 15g carbon black are simultaneously uniformly mixed, and are added 1800 milliliters later and are contained The aqueous solution of 32g nitric acid, the mixture determiningValue is 0.9, and it is wet that the butterfly that outer diameter is 1.4mm is extruded on plunger type bar extruder Item.Then butterfly wet bar is 4 hours dry at 120 DEG C, it is roasted 3 hours at 600 DEG C, obtains aluminium oxide formed body DZ3. Its unimodal hole pore size distribution of Mercury injection can several bore dias be 13nm, obtained using mercury injection method measurement, aluminium oxide formed body DZ3's Kong Rongwei 0.7mL/g, specific surface area 231m²/g。

Embodiment 1-1

The present embodiment is used to illustrate the hydrotreating method of the high nitrogen inferior heavy oil provided by the invention.

(1) modified aluminium oxide supports are prepared

(1-1) takes 200 grams of aluminium oxide formed body Z-1, Z-2 and Z-3 prepared by preparation example 1~3 respectively, first by formed body Respectively at 70 DEG C hydro-thermal process 24 hours, then by the formed body after hydrothermal treatment with 165 milliliters of temperature be 50 DEG C containing 15 grams/ Rise H₃BO₃Aqueous solution (pH value 6) saturation dipping 1 hour, it is 3 hours dry in 100 DEG C later, obtain the oxygen that load has B component Change aluminium formed body Z-1, Z-2 and Z-3；

Load obtained in step (1-1) is had aluminium oxide formed body Z-1, Z-2 and Z-3 of B component to exist respectively by (1-2) 140 milliliters of temperature are 50 DEG C containing 15 grams per liter NH₄Dipping 1 hour in the aqueous solution (pH value 11) of F, then in 120 DEG C of dryings It 3 hours, is roasted 3 hours then at 400 DEG C, obtains modified aluminium oxide supports S1-1-1, S2-1-1, S3-1-1.

(2) protective agent, metal remover and denitrifier are prepared

(2-1) takes 200 grams of modified aluminium oxide supports S1-1-1, with 210 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 50 grams per liters, and the concentration of the Ni element in terms of NiO is 10.3 grams per liters, and solvent is Water) it is impregnated 1 hour under room temperature (about 25 DEG C), it is dried in 120 DEG C 2 hours, 420 DEG C roast 3 hours, obtain protective agent CS1-1- 1。

(2-2) takes 200 grams of modified aluminium oxide supports S2-1-1, with 190 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 64 grams per liters, and the concentration of the Ni element in terms of NiO is 13 grams per liters, and solvent is Water) it is impregnated 1 hour under room temperature (about 25 DEG C), it is dried in 120 DEG C 2 hours, 420 DEG C roast 3 hours, obtain metal remover CS2- 1-1。

(2-3) takes 200 grams of modified aluminium oxide supports S3-1-1, first by the modified aluminium oxide supports at 135 DEG C of hydro-thermals Reason 12 hours, then by the carrier after hydrothermal treatment with 160 milliliters of temperature be 50 DEG C and pH value is 6 to contain ammonium heptamolybdate and nitric acid The mixed solution of nickel is (wherein, with MoO₃The concentration of the Mo element of meter is 80 grams per liters, and the concentration of the Ni element in terms of NiO is 50 Grams per liter, solvent are water) saturation dipping 1 hour, it is 8 hours dry in 200 DEG C later.Then, with 140 milliliters of temperature be 50 DEG C and The mixed solution containing ammonium metatungstate and nickel nitrate that pH value is 11 is (wherein, with WO₃80 grams per liter of concentration of the W element of meter, with NiO The concentration of the Ni element of meter is 30 grams per liters, and solvent is water) saturation dipping 2 hours, it is then 3 hours dry in 120 DEG C, then at 400 DEG C roasting 3 hours, obtain denitrifier CS3-1-1.

(3) catalyst grade is matched and hydrotreating

The protective agent CS1-1-1 is broken into the particle that diameter is 2 millimeters, metal remover CS2-1-1 is broken into directly Denitrifier CS3-1-1 is broken into the particle that diameter is 0.6 millimeter, is then charged into heavy-oil hydrogenation and fixes by the particle that diameter is 1 millimeter Bed reactor.Assembling scheme is matched using catalyst grade, along reactor stream direction, first reactor loads protective agent and demetalization Agent, second reactor load metal remover and denitrifier.Entire reaction unit loads ratio, is by volume that protective agent accounts for 6%, metal remover accounts for 40%, and denitrifier accounts for 54%.Reaction condition are as follows: 380 DEG C of temperature, hydrogen partial pressure 14MPa, volume space velocity is 0.5h^-1, hydrogen to oil volume ratio 500.The heavy oil feedstock used is Ni constituent content 65.1ppm, V element content 207ppm, density 1.01cm³/ g, 18 weight %, S content of carbon residue, 3.5 weight %, 0.74 weight % of N content Iran subtract slag.

Embodiment 1-2

The present embodiment is for illustrating the heavy oil hydrogenation treatment method provided by the invention.

(1) modified aluminium oxide supports are prepared

(1-1) takes 200 grams of modified aluminas formed body Z1, Z2 and Z3 prepared by preparation example 1~3 respectively, first will molding Body respectively at 150 DEG C hydro-thermal process 10 hours, then by the formed body after hydrothermal treatment with 155 milliliters of temperature be 80 DEG C contain 6 Grams per liter H₃BO₃Aqueous solution (pH value 2) saturation dipping 1 hour, 6 hours dry in 120 DEG C later, obtaining load has B component Modified aluminas formed body Z1, Z2 and Z3；

Load obtained in step (1-1) is had modified aluminas formed body Z1, Z2 and Z3 of B component to exist respectively by (1-2) 135 milliliters of temperature are 80 DEG C containing 8 grams per liter H₃PO₄Aqueous solution (pH value 2) in dipping 1 hour, later in 180 DEG C dry 8 Hour, obtain modified aluminas formed body Z1, Z2 and Z3 that load has B component and P component；

The load that (1-3) obtains step (1-2) has modified aluminium oxide supports Z1, Z2 and Z3 of B component and P component difference It is 80 DEG C containing 10 grams per liter NH in 125 milliliters of temperature₄Dipping 1 hour in the aqueous solution (pH value 10) of F, it is then dry in 120 DEG C It dry 3 hours, is roasted 3 hours then at 400 DEG C, obtains modified aluminium oxide supports S1-1-2, S2-1-2, S3-1-2.

(2) protective agent, metal remover and denitrifier are prepared

(2-1) takes 200 grams of modified aluminium oxide supports S1-1-2, with 210 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 50 grams per liters, and the concentration of the Ni element in terms of NiO is 10.3 grams per liters, and solvent is Water) it is impregnated 1 hour under room temperature (about 25 DEG C), it is dried in 120 DEG C 2 hours, 420 DEG C roast 3 hours, obtain protective agent CS1-1- 2。

(2-2) takes 200 grams of modified aluminium oxide supports S2-1-2, with 190 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 64 grams per liters, and the concentration of the Ni element in terms of NiO is 13 grams per liters, and solvent is Water) it is impregnated 1 hour under room temperature (about 25 DEG C), it is dried in 120 DEG C 2 hours, 420 DEG C roast 3 hours, obtain metal remover CS2- 1-2。

(2-3) takes 200 grams of modified aluminium oxide supports S3-1-2, first by carrier in 120 DEG C hydro-thermal process 20 hours, then will The mixed solution containing ammonium heptamolybdate and nickel nitrate that carrier after hydrothermal treatment is 50 DEG C with 155 milliliters of temperature and pH value is 2 (wherein, with MoO₃The concentration of the Mo element of meter is 40 grams per liters, and the concentration of the Ni element in terms of NiO is 60 grams per liters, and solvent is Water) saturation dipping 2 hours, it is 6 hours dry in 100 DEG C later.Then, with 135 milliliters of temperature be 60 DEG C and pH value is 10 to contain The mixed solution of ammonium metatungstate and nickel nitrate is (wherein, with WO₃100 grams per liter of concentration of the W element of meter, the Ni element in terms of NiO Concentration be 60 grams per liters, solvent is water) saturation dipping 1 hour, it is then 3 hours dry in 120 DEG C, it is small then at 400 DEG C of roastings 3 When, obtain denitrifier CS3-1-2.

(3) catalyst grade is matched and hydrotreating

The protective agent CS1-1-2 is broken into the particle that diameter is 2 millimeters, metal remover CS2-1-2 is broken into directly Denitrifier CS3-1-2 is broken into the particle that diameter is 0.6 millimeter, is then charged into heavy-oil hydrogenation and fixes by the particle that diameter is 1 millimeter Bed reactor.Assembling scheme is matched using catalyst grade, along reactor stream direction, first reactor loads protective agent and demetalization Agent, second reactor load metal remover and denitrifier.Entire reaction unit loads ratio, is by volume that protective agent accounts for 6%, metal remover accounts for 40%, and denitrifier accounts for 54%.Reaction condition are as follows: 380 DEG C of temperature, hydrogen partial pressure 14MPa, volume space velocity is 0.5h^-1, hydrogen to oil volume ratio 500.The heavy oil feedstock used is Ni constituent content 65.1ppm, V element content 207ppm, density 1.01cm³/ g, 18 weight %, S content of carbon residue, 3.5 weight %, 0.74 weight % of N content Iran subtract slag.

Embodiment 1-3

(1) modified aluminium oxide supports are prepared

Modified aluminium oxide supports S1-1-3, S2-1-3, S3-1-3 are prepared according to the method for embodiment 1-2.

(2) protective agent, metal remover and denitrifier are prepared

(2-1) takes 200 grams of carrier S 1-1-3, with 210 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 12 grams per liters, and the concentration of the Co element in terms of CoO is 3.5 grams per liters, and solvent is water) in room temperature It impregnates 1 hour, is dried in 120 DEG C 2 hours under (about 25 DEG C), 420 DEG C roast 3 hours, obtain protective agent CS1-1-3.

(2-2) takes 200 grams of carrier S 2-1-3, with 190 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 95 grams per liters, and the concentration of the Co element in terms of CoO is 18 grams per liters, and solvent is water) in room temperature It impregnates 1 hour, is dried in 120 DEG C 2 hours under (about 25 DEG C), 420 DEG C roast 3 hours, obtain catalyst CS2-1-3.

(2-3) takes 200 grams of carrier S 3-1-3, first by carrier in 70 DEG C hydro-thermal process 24 hours, then by hydrothermal treatment Carrier afterwards with 160 milliliters of temperature be 80 DEG C and pH value be 4 containing ammonium heptamolybdate and nickel nitrate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 100 grams per liters, and the concentration of the Ni element in terms of NiO is 70 grams per liters, and solvent is water) saturation leaching It is stain 1 hour, 8 hours dry in 100 DEG C later；Then, with the tungsten containing nitric acid and nitre that 140 milliliters of temperature are 80 DEG C and pH value is 8 The mixed solution of sour nickel is (wherein, with WO₃150 grams per liter of concentration of the W element of meter, the concentration of the Ni element in terms of NiO is 70 grams/ Rise, solvent is water) saturation dipping 1 hour, it is then 3 hours dry in 120 DEG C, it is roasted 3 hours then at 400 DEG C, obtains denitrifier CS3-1-3。

(3) catalyst grade is matched and hydrotreating

The protective agent CS1-1-3 is broken into the particle that diameter is 2 millimeters, metal remover CS2-1-3 is broken into directly Denitrifier CS3-1-3 is broken into the particle that diameter is 0.6 millimeter, is then charged into heavy-oil hydrogenation and fixes by the particle that diameter is 1 millimeter Bed reactor.Assembling scheme is matched using catalyst grade, along reactor stream direction, first reactor loads protective agent and demetalization Agent, second reactor load metal remover and denitrifier.Entire reaction unit loads ratio, is by volume that protective agent accounts for 6%, metal remover accounts for 40%, and denitrifier accounts for 54%.Reaction condition are as follows: 380 DEG C of temperature, hydrogen partial pressure 14MPa, volume space velocity is 0.5h^-1, hydrogen to oil volume ratio 500.The heavy oil feedstock used is Ni constituent content 65.1ppm, V element content 207ppm, density 1.01cm³/ g, 18 weight %, S content of carbon residue, 3.5 weight %, 0.74 weight % of N content Iran subtract slag.

Comparative example 1-1

According to the method implementation steps (1) to (3) of embodiment 1-2, the difference is that not to aluminium oxide in step (1) Formed body Z-1, Z-2 and Z-3 are modified, and aluminium oxide formed body Z-1, Z-2 and Z-3 are directly respectively used to step (2-1), step Suddenly protective agent DS1-1-1, metal remover DS2-1-1 and denitrifier DS3-1-1 are prepared in (2-2) and step (2-3).

Comparative example 1-2

Aluminium oxide formed body DZ1, the aluminium oxide formed body DZ2, aluminium oxide formed body DZ3 for taking preparation example 4 to prepare, according to reality Apply the method implementation steps (1) to (3) of a 1-2, the difference is that in step (1) not to aluminium oxide formed body DZ1, DZ2 and DZ3 is modified, does not carry out hydro-thermal process to aluminium oxide formed body in step (2-3), is directly respectively used to the aluminium oxide formed body In subsequent step, protective agent DS1-1-2, metal remover DS2-1-2 and denitrifier DS3-1-2 are prepared.

Comparative example 1-3

Aluminium oxide formed body DZ1, the aluminium oxide formed body DZ2, aluminium oxide formed body DZ3 for taking preparation example 4 to prepare, according to reality The method implementation steps (1) to (3) for applying a 1-2, prepare protective agent DS1-1-3, metal remover DS2-1-3 and denitrifier DS3-1- 3。

Embodiment 1-4

Reaction and filling condition according to embodiment 1-1, to protective agent DS1-1-3, metal remover DS2-1-3, denitrifier CS3-1-2 carries out filling and hydrotreating reaction.

Test case 1-1

Using SEM-EDX (Scanning Electron Microscope-Energy Dispersive Spectrometry) method analyzes the Elemental redistribution in modified aluminium oxide supports particle.Due in SEM-EDX characterization result Numerical value along carrier radial direction every bit constituent content is corresponded to each other with the point element content, although the size of the numerical value may be not The real content of the point element is represented, but is able to reflect the point element content height.Therefore, in order to indicate acid additive along carrier The radial regularity of distribution introduces distribution factor σ.With σ indicate acid additive on a certain position of particle with the ratio between concentration at center (R For particle radius, using at modified aluminium oxide supports granular center as starting point).Acid additive concentration on a certain position refers to The average value of the position (position deviation≤20nm) 20 numerical points numeration nearby in SEM-EDX characterization result；The acidity helps The average value of agent (position deviation≤20nm) 20 numerical point counting rates near point centered on the concentration at center.If σ > 1, table Bright this acid additive constituent content is higher than at modified aluminium oxide supports granular center；If σ=1, show this acid additive Constituent content is identical as at modified aluminium oxide supports granular center；If σ < 1, shows that this acid additive constituent content is less than and change At property alumina carrier particle center.Table 1-1 be modified aluminium oxide supports relevant parameter, wherein acid additive content (with Element calculates) it is calculated according to inventory.Table 1-2 is that different acid additives are at different locations on modified aluminium oxide supports Distribution factor.

Test case 1-2

According to method described in test case 1-1, unlike, measurement be embodiment 1-1,1-2,1-3 denitrifier The thickness of active metal component distribution and stratum nucleare and shell, wherein the thickness of shell refers to distribution factor σ >=2.0 of Mo The thickness divided, the thickness of stratum nucleare refer to the thickness of 1 part 0.5≤σ of distribution factor < of W.The following table 1-3 is the related ginseng of denitrifier Number, wherein active metal component content is calculated according to inventory.Table 1-4 be the distribution of denitrifier at different locations because Son.

Test case 1-3

Before measuring each embodiment and comparative example hydrotreating using inductive coupling plasma emission spectrograph (ICP-AES) Afterwards in oil Ni, V and Fe content, instrument is U.S. PE company PE-5300 type plasma quantometer, and specific method is RIPP124-90 (" petrochemical analysis method ", Yang Cui is surely equal to be compiled, Science Press, Beijing, 1990,349-351), and according to Following equation calculates demetallization per, de- carbon yield and denitrification percent, as a result as shown in following table 1-5.

Test case 1-4

Embodiment 1-4 and comparative example 1-3 hydrotreating are subjected to long-term operation, stability is evaluated, as a result such as table 1-6 institute Show.Table 1-1

Table 1-2

Modified aluminium oxide supports number	S3-1-1	S3-1-2	S3-1-3
				σ_B(R)	2.69	2.78	2.78
σ_B(2/3R)	2.06	1.97	1.97
				σ_B(1/3R)	1.05	1.34	1.34
σ_P(R)	-	1.64	1.64
				σ_P(2/3R)	-	2.36	2.36
σ_P(1/3R)	-	1.56	1.56
				σ_F(R)	0.12	0.15	0.15
σ_F(2/3R)	0.22	0.43	0.43
				σ_F(1/3R)	0.78	0.81	0.81

Table 1-3

Table 1-4

Number	CS3-1-1	CS3-1-2	CS3-1-3	DS3-1-1	DS3-1-2	DS3-1-3
							σNi(R)	0.98	0.98	0.98	0.98	0.97	0.99
σNi(2/3R)	0.97	0.99	0.93	0.94	1.06	0.97
							σNi(1/3R)	0.99	0.99	0.96	0.97	0.99	0.99
σMo(R)	2.6	2.9	2.6	2.7	0.97	0.96
							σMo(2/3R)	2.3	2.2	2.2	2.2	0.99	0.98
σMo(1/3R)	1.5	1.3	1.4	1.3	0.99	1.09
							σW(R)	0.2	0.3	0.1	0.2	0.97	0.97
σW(2/3R)	0.4	0.4	0.3	0.4	0.96	1.02
							σW(1/3R)	0.9	0.9	0.9	0.9	0.99	0.99

Note: R refers to the grain diameter of entire denitrifier.Table 1-5

Project	De- Ni rate %	De- V rate %	De- carbon yield %	Denitrification percent %
					Embodiment 1-1	79.3	87.2	70.1	69.1
Embodiment 1-2	79.5	87.0	70.0	68.5
					Embodiment 1-3	77.0	87.3	69.5	68.6
Comparative example 1-1	63.6	78.1	56.7	59.2
					Comparative example 1-2	60.6	79.9	59.7	50.6
Comparative example 1-3	53.6	69.9	56.7	45.6
					Embodiment 1-4	76.0	84.3	63.9	62.6

Table 1-6

Embodiment 2-1

(1) modified aluminium oxide supports are prepared

(1-1) takes 200 grams of aluminium oxide formed body Z-1, Z-2 and Z-3 prepared by preparation example 1~3 respectively, first by formed body Respectively at 135 DEG C hydro-thermal process 12 hours, then by the formed body after hydrothermal treatment with 165 milliliters of temperature be 40 DEG C contain 15 Grams per liter Mg (NO₃)₂Aqueous solution (pH value 11) saturation dipping 1 hour, 8 hours dry in 200 DEG C later, obtaining load has gold Belong to alumina catalyst support formed body Z-1, Z-2 and Z-3 of auxiliary agent；

Load obtained in step (1) is had aluminium oxide formed body Z-1, Z-2 and Z-3 of metal promoter to exist respectively by (1-2) 145 milliliters of temperature are 40 DEG C containing 10 grams per liter H₃BO₃Aqueous solution (pH value 6) in dipping 1 hour, then in 120 DEG C dry 3 Hour, it is roasted 3 hours then at 400 DEG C, obtains modified aluminium oxide supports S1-2-1, S2-2-1, S3-2-1.

(2) protective agent, metal remover and denitrifier are prepared

(2-1) takes 200 grams of modified aluminium oxide supports S1-2-1, with 210 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 50 grams per liters, and the concentration of the Ni element in terms of NiO is 10.3 grams per liters, and solvent is Water) it is impregnated 1 hour under room temperature (about 25 DEG C), it is dried in 120 DEG C 2 hours, 420 DEG C roast 3 hours, obtain protective agent CS1-2- 1。

(2-2) takes 200 grams of modified aluminium oxide supports S2-2-1, with 190 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 64 grams per liters, and the concentration of the Ni element in terms of NiO is 13 grams per liters, and solvent is Water) it is impregnated 1 hour under room temperature (about 25 DEG C), it is dried in 120 DEG C 2 hours, 420 DEG C roast 3 hours, obtain metal remover CS2- 2-1。

(2-3) takes 200 grams of modified aluminium oxide supports S3-2-1, first by the modified aluminium oxide supports at 135 DEG C of hydro-thermals Reason 12 hours, then by the carrier after hydrothermal treatment with 160 milliliters of temperature be 50 DEG C and pH value is 6 to contain ammonium heptamolybdate and nitric acid The mixed solution of nickel is (wherein, with MoO₃The concentration of the Mo element of meter is 80 grams per liters, and the concentration of the Ni element in terms of NiO is 50 Grams per liter, solvent are water) saturation dipping 1 hour, it is 8 hours dry in 200 DEG C later.Then, with 140 milliliters of temperature be 50 DEG C and The mixed solution containing ammonium metatungstate and nickel nitrate that pH value is 11 is (wherein, with WO₃80 grams per liter of concentration of the W element of meter, with NiO The concentration of the Ni element of meter is 30 grams per liters, and solvent is water) saturation dipping 2 hours, it is then 3 hours dry in 120 DEG C, then at 400 DEG C roasting 3 hours, obtain denitrifier CS3-2-1.

(3) catalyst grade is matched and hydrotreating

The protective agent CS1-2-1 is broken into the particle that diameter is 2 millimeters, metal remover CS2-2-1 is broken into directly Denitrifier CS3-2-1 is broken into the particle that diameter is 0.6 millimeter, is then charged into heavy-oil hydrogenation and fixes by the particle that diameter is 1 millimeter Bed reactor.Assembling scheme is matched using catalyst grade, along reactor stream direction, first reactor loads protective agent and demetalization Agent, second reactor load metal remover and denitrifier.Entire reaction unit loads ratio, is by volume that protective agent accounts for 6%, metal remover accounts for 40%, and denitrifier accounts for 54%.Reaction condition are as follows: 380 DEG C of temperature, hydrogen partial pressure 14MPa, volume space velocity is 0.5h^-1, hydrogen to oil volume ratio 500.The heavy oil feedstock used is Ni constituent content 65.1ppm, V element content 207ppm, density 1.01cm³/ g, 18 weight %, S content of carbon residue, 3.5 weight %, 0.74 weight % of N content Iran subtract slag.

Embodiment 2-2

(1) modified aluminium oxide supports are prepared

(1-1) takes 200 grams of aluminium oxide formed body Z-1, Z-2 and Z-3 prepared by preparation example 1~3 respectively, first by formed body In 120 DEG C hydro-thermal process 20 hours, then by the formed body after hydrothermal treatment with 155 milliliters of temperature be 50 DEG C contain 12 grams per liters KNO₃Aqueous solution (pH value 10) saturation dipping 1 hour, 6 hours dry in 100 DEG C later, obtaining load has metal promoter Aluminium oxide formed body Z-1, Z-2 and Z-3；

Load obtained in step (1) is had aluminium oxide formed body Z-1, Z-2 and Z-3 of metal promoter in 135 millis by (1-2) Rising temperature is 50 DEG C containing 12 grams per liter H₃PO₄Aqueous solution (pH value 2) in dipping 1 hour, it is then 3 hours dry in 120 DEG C, It is roasted 3 hours then at 400 DEG C, obtains modified aluminium oxide supports S1-2-2, S2-2-2, S3-2-2.

(2) protective agent, metal remover and denitrifier are prepared

(2-1) takes 200 grams of modified aluminium oxide supports S1-2-2, with 210 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 50 grams per liters, and the concentration of the Ni element in terms of NiO is 10.3 grams per liters, and solvent is Water) it is impregnated 1 hour under room temperature (about 25 DEG C), it is dried in 120 DEG C 2 hours, 420 DEG C roast 3 hours, obtain protective agent CS1-2- 2。

(2-2) takes 200 grams of modified aluminium oxide supports S2-2-2, with 190 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 64 grams per liters, and the concentration of the Ni element in terms of NiO is 13 grams per liters, and solvent is Water) it is impregnated 1 hour under room temperature (about 25 DEG C), it is dried in 120 DEG C 2 hours, 420 DEG C roast 3 hours, obtain metal remover CS2- 2-2。

(2-3) takes 200 grams of modified aluminium oxide supports S3-2-2, first by carrier in 120 DEG C hydro-thermal process 20 hours, then will The mixed solution containing ammonium heptamolybdate and nickel nitrate that carrier after hydrothermal treatment is 50 DEG C with 155 milliliters of temperature and pH value is 2 (wherein, with MoO₃The concentration of the Mo element of meter is 40 grams per liters, and the concentration of the Ni element in terms of NiO is 60 grams per liters, and solvent is Water) saturation dipping 2 hours, it is 6 hours dry in 100 DEG C later.Then, with 135 milliliters of temperature be 60 DEG C and pH value is 10 to contain The mixed solution of ammonium metatungstate and nickel nitrate is (wherein, with WO₃100 grams per liter of concentration of the W element of meter, the Ni element in terms of NiO Concentration be 60 grams per liters, solvent is water) saturation dipping 1 hour, it is then 3 hours dry in 120 DEG C, it is small then at 400 DEG C of roastings 3 When, obtain denitrifier CS3-2-2.

(3) catalyst grade is matched and hydrotreating

The protective agent CS1-2-2 is broken into the particle that diameter is 2 millimeters, metal remover CS2-2-2 is broken into directly Denitrifier CS3-2-2 is broken into the particle that diameter is 0.6 millimeter, is then charged into heavy-oil hydrogenation and fixes by the particle that diameter is 1 millimeter Bed reactor.Assembling scheme is matched using catalyst grade, along reactor stream direction, first reactor loads protective agent and demetalization Agent, second reactor load metal remover and denitrifier.Entire reaction unit loads ratio, is by volume that protective agent accounts for 6%, metal remover accounts for 40%, and denitrifier accounts for 54%.Reaction condition are as follows: 380 DEG C of temperature, hydrogen partial pressure 14MPa, volume space velocity is 0.5h^-1, hydrogen to oil volume ratio 500.The heavy oil feedstock used is Ni constituent content 65.1ppm, V element content 207ppm, density 1.01cm³/ g, 18 weight %, S content of carbon residue, 3.5 weight %, 0.74 weight % of N content Iran subtract slag.

Embodiment 2-3

(1) modified aluminium oxide supports are prepared

(1-1) takes 200 grams of aluminium oxide formed body Z-1, Z-2 and Z-3 prepared by preparation example 1~3 respectively, first by formed body In 70 DEG C hydro-thermal process 24 hours, then by the formed body after hydrothermal treatment with 165 milliliters of temperature be 80 DEG C contain 15 grams per liter Ca (NO₃)₂Aqueous solution (pH value 8) saturation dipping 1 hour, 8 hours dry in 200 DEG C later, obtaining load has metal promoter Aluminium oxide formed body Z-1, Z-2 and Z-3；

Load obtained in step (1) is had aluminium oxide formed body Z-1, Z-2 and Z-3 of metal promoter in 145 millis by (1-2) Dipping 1 hour in the aqueous solution (pH value 4) containing 10 grams per liter hydrofluoric acid that temperature is 80 DEG C is risen, it is then small in 120 DEG C of dryings 3 When, it is roasted 3 hours then at 400 DEG C, obtains modified aluminium oxide supports S1-2-3, S2-2-3, S3-2-3.

(2) protective agent, metal remover and denitrifier are prepared

(2-1) takes 200 grams of carrier S 1-2-3, with 210 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 12 grams per liters, and the concentration of the Co element in terms of CoO is 3.5 grams per liters, and solvent is water) in room temperature It impregnates 1 hour, is dried in 120 DEG C 2 hours under (about 25 DEG C), 420 DEG C roast 3 hours, obtain protective agent CS1-2-3.

(2-2) takes 200 grams of carrier S 2-2-3, with 190 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 95 grams per liters, and the concentration of the Co element in terms of CoO is 18 grams per liters, and solvent is water) in room temperature It impregnates 1 hour, is dried in 120 DEG C 2 hours under (about 25 DEG C), 420 DEG C roast 3 hours, obtain catalyst CS2-2-3.

(2-3) takes 200 grams of carrier S 3-2-3, first by carrier in 70 DEG C hydro-thermal process 24 hours, then by hydrothermal treatment Carrier afterwards with 160 milliliters of temperature be 80 DEG C and pH value be 4 containing ammonium heptamolybdate and nickel nitrate mixed solution (wherein, with MoO₃The concentration of the Mo element of meter is 100 grams per liters, and the concentration of the Ni element in terms of NiO is 70 grams per liters, and solvent is water) saturation leaching It is stain 1 hour, 8 hours dry in 100 DEG C later；Then, with the tungsten containing nitric acid and nitre that 140 milliliters of temperature are 80 DEG C and pH value is 8 The mixed solution of sour nickel is (wherein, with WO₃150 grams per liter of concentration of the W element of meter, the concentration of the Ni element in terms of NiO is 70 grams/ Rise, solvent is water) saturation dipping 1 hour, it is then 3 hours dry in 120 DEG C, it is roasted 3 hours then at 400 DEG C, obtains denitrifier CS3-2-3。

(3) catalyst grade is matched and hydrotreating

The protective agent CS1-2-3 is broken into the particle that diameter is 2 millimeters, metal remover CS2-2-3 is broken into directly Denitrifier CS3-2-3 is broken into the particle that diameter is 0.6 millimeter, is then charged into heavy-oil hydrogenation and fixes by the particle that diameter is 1 millimeter Bed reactor.Assembling scheme is matched using catalyst grade, along reactor stream direction, first reactor loads protective agent and demetalization Agent, second reactor load metal remover and denitrifier.Entire reaction unit loads ratio, is by volume that protective agent accounts for 6%, metal remover accounts for 40%, and denitrifier accounts for 54%.Reaction condition are as follows: 380 DEG C of temperature, hydrogen partial pressure 14MPa, volume space velocity is 0.5h^-1, hydrogen to oil volume ratio 500.The heavy oil feedstock used is Ni constituent content 65.1ppm, V element content 207ppm, density 1.01cm³/ g, 18 weight %, S content of carbon residue, 3.5 weight %, 0.74 weight % of N content Iran subtract slag.

Comparative example 2-1

According to the method implementation steps (1) to (3) of embodiment 2-2, the difference is that not to aluminium oxide in step (1) Formed body Z-1, Z-2 and Z-3 are modified, and aluminium oxide formed body Z-1, Z-2 and Z-3 are directly respectively used to step (2-1), step Suddenly protective agent DS1-2-1, metal remover DS2-2-1 and denitrifier DS3-2-1 are prepared in (2-2) and step (2-3).

Comparative example 2-2

Aluminium oxide formed body DZ1, the aluminium oxide formed body DZ2, aluminium oxide formed body DZ3 for taking preparation example 4 to prepare, according to reality Apply the method implementation steps (1) to (3) of a 2-2, the difference is that in step (1) not to aluminium oxide formed body DZ1, DZ2 and DZ3 is modified, does not carry out hydro-thermal process to aluminium oxide formed body in step (2-3), is directly respectively used to the aluminium oxide formed body In subsequent step, protective agent DS1-2-2, metal remover DS2-2-2 and denitrifier DS3-2-2 are prepared.

Comparative example 2-3

Aluminium oxide formed body DZ1, the aluminium oxide formed body DZ2, aluminium oxide formed body DZ3 for taking preparation example 4 to prepare, according to reality The method implementation steps (1) to (3) for applying a 2-2, prepare protective agent DS1-2-3, metal remover DS2-2-3 and denitrifier DS3-2- 3。

Embodiment 2-4

Reaction and filling condition according to embodiment 2-1, to protective agent DS1-2-3, metal remover DS2-2-3, denitrifier CS3-2-2 carries out filling and hydrotreating reaction.

Test case 2-1

It is carried out using thickness of the SEM-EDX method to Elemental redistribution and shell and stratum nucleare in modified aluminium oxide supports particle Analysis.Table 2-1 is the relevant parameter of modified aluminium oxide supports, wherein the content of auxiliary agent is calculated according to inventory.Table 2-2 For the distribution factor of modified aluminium oxide supports at different locations.For being distributed the shell of metal promoter and being distributed acid additive The thickness of stratum nucleare, shell thickness refer to that the thickness of the part distribution factor σ >=2 of metal promoter, stratum nucleare thickness refer to acid additive 1 part 0.5≤σ of distribution factor < thickness.

It can be seen that modified aluminium oxide supports provided by the invention by upper table 2-1 and 2-2 to include carrier and be supported on institute The metal promoter and acid additive on carrier are stated, the metal promoter and acid additive are in layer distributed on the carrier, Shell is metal promoter, and stratum nucleare is acid additive.

Test case 2-2

According to method described in test case 2-1, the difference is that, measurement is embodiment 2-1,2-2, the denitrifier of 2-3 The thickness of active metal component distribution and stratum nucleare and shell, wherein the thickness of shell refers to distribution factor σ >=2.0 of Mo The thickness divided, the thickness of stratum nucleare refer to the thickness of 1 part 0.5≤σ of distribution factor < of W.The following table 2-3 is the related ginseng of denitrifier Number, wherein active metal component content is calculated according to inventory.Table 2-4 be the distribution of denitrifier at different locations because Son.

Test case 2-3

Before and after inductive coupling plasma emission spectrograph (ICP-AES) measurement embodiment and comparative example hydrotreating The content of Ni, V and Fe in oil, instrument are U.S. PE company PE-5300 type plasma quantometer, and specific method is RIPP124-90 (" petrochemical analysis method ", Yang Cui is surely equal to be compiled, Science Press, Beijing, 1990,349-351), and according to Following equation calculates demetallization per, de- carbon yield and denitrification percent, as a result as shown in following table 2-5.

Test case 2-4

Embodiment 2-2 and comparative example 2-2 hydrotreating are subjected to long-term operation, stability is evaluated, as a result such as table 2-6 institute Show.

It can be seen that Heavy oil hydrogenation method tool provided by the present invention from the result of table 1-5, table 1-6, table 2-5 and table 2-6 There are preferable and comprehensive metal, nitrogen and carbon residue removal activity and long-term operation stability is high.It can be seen that the present invention provides Hydrotreating method can not only obtain higher metal, nitrogen and carbon residue removal effect, more praiseworthy is catalyst stability Height, the duration of runs is long, so that there is the hydrotreating method of the high nitrogen inferior heavy oil provided by the invention preferable industry to answer Use prospect.Table 2-1

Table 2-2

Modified aluminium oxide supports number	S3-2-1	S3-2-2	S3-2-3
				σ_Mg(R)	2.68	-	-
σ_Mg(2/3R)	1.96	-	-
				σ_Mg(1/3R)	1.35	-	-
σ_K(R)	-	2.44	-
				σ_K(2/3R)	-	2.13	-
σ_K(1/3R)	-	1.52	-
				σ_Ca(R)	-	-	2.89
σ_Ca(2/3R)	-	-	2.30
				σ_Ca(1/3R)	-	-	1.16
σ_P(R)	-	0.13	-
				σ_P(2/3R)	-	0.40	-
σ_P(1/3R)	-	0.70	-
				σ_B(R)	0.25	-	-
σ_B(2/3R)	0.32	-	-
				σ_B(1/3R)	0.89	-	-
σ_F(R)	-	-	0.21
				σ_F(2/3R)	-	-	0.45
σ_F(1/3R)	-	-	0.81

Table 2-3

Table 2-4

Hydrodenitrogenation catalyst number	CS3-2-1	CS3-2-2	CS3-2-3	DS3-2-1	DS3-2-2
						σNi(R)	0.99	0.98	0.97	0.98	0.97
σNi(2/3R)	0.96	0.99	0.98	1.03	0.96
						σNi(1/3R)	0.99	0.97	0.96	0.97	0.99
σMo(R)	2.8	2.7	2.7	2.9	1.08
						σMo(2/3R)	2.1	2.2	2.2	2.2	0.99
σMo(1/3R)	1.3	1.3	1.4	1.3	0.97
						σW(R)	0.2	0.2	0.1	0.3	1.02
σW(2/3R)	0.4	0.4	0.3	0.4	0.99
						σW(1/3R)	0.9	0.9	0.9	0.9	0.97

Note: R refers to the grain diameter of entire denitrifier.Table 2-5

Project	De- Ni rate %	De- V rate %	De- carbon yield %	Denitrification percent %
					Embodiment 2-1	71.3	90.3	69.9	76.9
Embodiment 2-2	72.2	91.1	69.1	77.5
					Embodiment 2-3	71.1	90.5	69.3	76.6
Comparative example 2-1	64.9	80.1	56.9	50.9
					Comparative example 2-2	61.2	79.2	51.5	47.6
Comparative example 2-3	60.2	70.2	50.5	40.6
					Embodiment 2-4	69.3	90.0	65.9	70.9

Table 2-6

Claims

1. a kind of hydrodenitrogenation catalyst, the hydrodenitrogenation catalyst includes modified aluminium oxide supports and is carried on the modification Hydrodenitrogenationactivity activity metal component in alumina support；The modified aluminium oxide supports are for graininess and by hydrated alumina group Object is closed successively through prepared by forming processes and modification；Wherein, the hydrated alumina composition contain hydrated alumina and Compound at least two proton acceptor sites, the compositionValue is for 5 hereinafter, describedValue uses following methods Measurement: by 10 grams of compositions 120 DEG C of drying 240 minutes in air atmosphere, the quality of dried composition is remembered For w₁Gram, it is calculated using Formulas IValue,

(i), with the acid additive of a variety of layer distributeds in modified aluminium oxide supports particle, and according to alumina carrier particle The direction at surface to center is better than the acidity positioned at outer layer acid additive positioned at the acidity of internal layer acid additive；

(ii) with the acid additive and metal promoter of layer distributed in modified aluminium oxide supports particle, and the acid additive divides It is distributed in the first stratum nucleare, the metal promoter is distributed in the first shell；

Wherein, the acid additive is selected from least one of F, P and B, and the metal promoter is group ia metal and/or the Group IIA metal, preferably at least one of Li, Na, K, Mg and Ca；

When modified aluminium oxide supports particle has state (i), the hydrodenitrogenationactivity activity metal component is carried in modified aluminas It is in layer distributed in body particle, the active metal component for being distributed in stratum nucleare is Ni and W, the active metal component being distributed in shell For Mo and the combination for being selected from Ni and/or Co；

When modified aluminium oxide supports particle has state (ii), the hydrodenitrogenationactivity activity metal component is carried in modified aluminas It is in layer distributed in body particle, the active metal component for being distributed in the second stratum nucleare is Ni and W, the activity being distributed in the second shell Metal component is Mo and the combination for being selected from Ni and/or Co.

2. hydrodenitrogenation catalyst according to claim 1, wherein describedValue is for 4 hereinafter, preferably 3.5 hereinafter, more Preferably 3.2 or less；It is highly preferred that describedValue is 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more；Further Preferably, describedValue is 1.2-5, preferably 1.2-4, more preferably 1.3-3.5, further preferably 1.4-3.2.

3. hydrodenitrogenation catalyst according to claim 1, wherein relative to hydrated alumina described in 100 parts by weight, institute Stating has the content of the compound at least two proton acceptor sites for 1-25 parts by weight, preferably 1.2-20 parts by weight, more excellent It is selected as 1.5-18 parts by weight, further preferably 3-17 parts by weight；

In the compound for having at least two proton acceptor sites, proton acceptor site is F, O that hydrogen bond can be formed with water At least one of with N；Preferably, the compound at least two proton acceptor sites is to contain hydroxyl in molecular structure The compound of base；It is highly preferred that the compound at least two proton acceptor sites is polyhydroxy organic compound；Into Preferably, the compound at least two proton acceptor sites is the etherate of polysaccharide and/or polysaccharide to one step；More into one Preferably, the compound at least two proton acceptor sites is galactan, mannosan, galactomannans to step At least one of with cellulose ether, the cellulose ether is preferably methylcellulose, hydroxyethyl cellulose and hydroxy propyl cellulose At least one of element；It is particularly preferred that the compound at least two proton acceptor sites is galactomannans And cellulose ether, it is preferable that on the basis of the total amount of the compound at least two proton acceptor sites, the gala The content of mannosan is 10-70 weight %, preferably 15-68 weight %, more preferably 20-65 weight %；The cellulose The content of ether is 30-90 weight %, preferably 32-85 weight %, more preferably 35-80 weight %.

4. hydrodenitrogenation catalyst according to claim 1, wherein the hydrated alumina contains boehmite, excellent It is selected as boehmite；

The hydrated alumina be hydrated alumina wet gel or be hydrated alumina wet gel washed product；Wherein, described The i value of hydrated alumina wet gel or its washed product is not less than 60%, preferably not less than 62%, it is preferable that the hydration oxygen The i value for changing aluminium wet gel or its washed product is not higher than 82%, preferably no greater than 80%, more preferably no higher than 78.5%, the i Value is measured using following methods: by 10 grams of hydrated alumina wet gels or its washed product in 120 DEG C of dryings in air atmosphere 240 minutes, the quality of dried sample is denoted as w₂Gram, i value is calculated using Formula II,

5. hydrodenitrogenation catalyst according to claim 1, wherein measured by mercury injection method, the hydrated alumina combination Object is in bimodal distribution through the pore-size distribution of aluminium oxide formed body obtained by forming processes, and most probable pore size is respectively 4-20nm and is greater than 20nm；Or measured by mercury injection method, aperture of the hydrated alumina composition through aluminium oxide formed body obtained by forming processes is in Unimodal Distribution, most probable pore size 4-20nm；

The radial crushing strength of the aluminium oxide formed body is 10N/mm or more, preferably 10-55N/mm, more preferably 12N/mm More than, further preferred 12-35N/mm.

6. hydrodenitrogenation catalyst according to claim 1, in state (i), with the total of the modified aluminium oxide supports On the basis of weight, the content of acid additive based on the element is 0.1-15 weight %, preferably 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably 1-5 weight % are still more preferably 2-4 weight %；

In state (ii), on the basis of the total weight of the modified aluminium oxide supports, the content of acid additive based on the element For 0.1-15 weight %, preferably 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably 1-5 weight %, It is still more preferably 2-4 weight %；The gold on the basis of the total weight of the modified aluminium oxide supports, in terms of oxide Belong to the content of auxiliary agent for 0.1-15 weight %, preferably 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably For 1-3 weight %.

7. hydrodenitrogenation catalyst according to claim 1, wherein make modified aluminium oxide supports particle that there is state (i) Modification the step of include: that the hydrated alumina composition is subjected to hydro-thermal through aluminium oxide formed body obtained by forming processes Processing, the carrier of gained hydro-thermal process then successively impregnated and dried, and last time gained desciccate is carried out Roasting, wherein maceration extract used in each dipping process contains the compound for being provided with identical or different acid additive, duplicate Frequency n >=2, preferably 2-3 times, and as n >=3, during from (n-1)th dipping is impregnated into the 2nd time, impregnate each time The dry temperature temperature drier than after adjacent preceding single-steeping is 20-150 DEG C high afterwards, dry time ratio after impregnating each time The dry time is 1-10 hours long after adjacent preceding single-steeping；It is in acidity that first n-1 times, which impregnates used maceration extract, and pH value is excellent It is selected as 2-6；For maceration extract used by n-th impregnates in alkalinity, pH value is preferably 8-11；

The step of making modified aluminium oxide supports particle have the modification of state (ii) includes: (1), by the hydrated alumina Composition carries out hydro-thermal process through aluminium oxide formed body obtained by forming processes, is then provided with the metal promoter in containing for alkalinity Metal promoter compound the first solution in impregnated, then dry, obtaining load has the carrier of the metal promoter； (2), there is the carrier of the metal promoter acid containing the acid additive chemical combination for being provided with the acid additive load It is impregnated in second solution of object, is then dried and roasts；The pH value of first solution be 7.5-11, described second The pH value of solution is 2-6.5；In step (1), the condition of hydro-thermal process includes: that temperature is 50-200 DEG C, and the time is 5-30 hours； Preferably, the immersion condition of step (1) and (2) is identical or different, and the condition of dipping includes: that temperature is 20-300 DEG C, preferably 40-100℃；Time is 1-20 hours, preferably 1-6 hours；Preferably, in step (1), dry condition includes: that temperature is 30-300 DEG C, the time is 1-20 hours；Preferably, in step (2), dry condition includes: that temperature is 80-200 DEG C, and the time is 1-10 hours；Preferably, in step (2), the condition of roasting includes: that temperature is 300-900 DEG C, and the time is 1-10 hours.

8. hydrodenitrogenation catalyst according to claim 1, wherein in terms of metal oxide and with the total of the catalyst On the basis of weight, in the hydrodenitrogenation catalyst content of Mo be 2-30 weight %, preferably 5-25 weight %, more preferably 5-20 weight %, most preferably 8-16 weight %；The total content of Ni be 0.5-15 weight %, preferably 1-10 weight %, it is more excellent It is selected as 2-9 weight %, most preferably 3-6 weight %；The content of Co be 0-15 weight %, preferably 1-10 weight %, more preferably For 2-9 weight %, most preferably 3-5 weight %；The content of W is 2-40 weight %, preferably 5-35 weight %, more preferably 8- 30 weight %, most preferably 15-30 weight %.

9. the preparation step of hydrodenitrogenation catalyst according to claim 1, the hydrodenitrogenation catalyst includes:

(a), the modified aluminium oxide supports are subjected to hydro-thermal process, then by the modified aluminium oxide supports after hydro-thermal process in acid Property containing being impregnated in molybdenum compound and the combined third solution of nickel compound and/or cobalt compound, then done It is dry；The pH value of the third solution is 2-6.5；

(b), carrier of the step (a) after dry is soaked in the 4th solution containing nickel compound and tungsten compound of alkalinity Then stain is dried and roasts；The pH value of 4th solution is 7.5-11；

Nickel compound described in step (a) and step (b) is each independently selected from nickel oxide, nickel nitrate, nickel acetate, basic carbonate One of nickel and nickel chloride are a variety of；The molybdenum compound is selected from molybdenum oxide, molybdate, paramolybdate, ammonium dimolybdate and four One of ammonium molybdate is a variety of；It is inclined that the tungsten compound is selected from tungsten oxide, ammonium tungstate, ammonium metatungstate, ammonium paratungstate and ethyl One of ammonium tungstate is a variety of；The cobalt compound is selected from cobalt carbonate, cobalt nitrate, cobalt acetate, basic cobaltous carbonate and cobalt chloride One of or it is a variety of；

In step (a), the condition of hydro-thermal process includes: that temperature is 50-200 DEG C, and the time is 5-30 hours；Preferably, step (a) (b) immersion condition is identical or different, and the condition of dipping includes: that temperature is 50-300 DEG C, preferably 50-100 DEG C；Time is 1-20 hours, preferably 1-6 hours；Preferably, in step (a), dry condition includes: that temperature is 30-300 DEG C, and the time is 1-20 hours；Preferably, in step (b), dry condition includes: that temperature is 80-200 DEG C, and the time is 1-10 hours；It is preferred that Ground, in step (b), the condition of roasting includes: that temperature is 300-900 DEG C, and the time is 1-10 hours.

10. a kind of method of heavy-oil hydrogenation processing, this method comprises: under hydrogenation conditions, by heavy oil feedstock successively with add Hydrogen protective agent, Hydrodemetalation catalyst and hydrodenitrogenation catalyst are contacted and are reacted, wherein the hydrogenation protecting agent, At least one of Hydrodemetalation catalyst and hydrodenitrogenation catalyst meet the following conditions:

The hydrodenitrogenation catalyst is hydrodenitrogenation catalyst described in any one of claim 1-9；

The hydrogenation protecting agent includes modified aluminium oxide supports described in any one of claim 1-9 and is carried on described change Property alumina support in hydrogenation protecting active component, the hydrogenation protecting active component is at least one group VIII metal group Point and at least one vib metals component, counted by metal oxide and on the basis of the total weight of hydrogenation protecting agent, this The content of group VIII metal component is greater than 0 weight % and is less than or equal to 1 weight %, and the content of the vib metals component is greater than 0 Weight % and be less than or equal to 6 weight %；

The Hydrodemetalation catalyst includes modified aluminium oxide supports described in any one of claim 1-9 and is carried on Hydrodemetallization active component in the modified aluminium oxide supports, the hydrodemetallization active component are at least one the Group VIII metal component and at least one vib metals component, in terms of metal oxide and with Hydrodemetalation catalyst On the basis of total weight, the content of the group VIII metal component is 1-3 weight %, and the content of the vib metals component is 6- 13 weight %.