CN107345158B

CN107345158B - A kind of heavy oil hydrogenation treatment method

Info

Publication number: CN107345158B
Application number: CN201610292669.1A
Authority: CN
Inventors: 贾燕子; 杨清河; 李大东; 刘学芬; 邓中活; 刘涛
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-05-05
Filing date: 2016-05-05
Publication date: 2019-07-23
Anticipated expiration: 2036-05-05
Also published as: CN107345158A

Abstract

The present invention relates to petrochemical industries, disclose a kind of heavy oil hydrogenation treatment method, this method comprises: under hydrogenation conditions, by heavy oil feedstock successively with protective agent, metal remover and desulfurization agent, the protective agent, the metal remover and the desulfurizing agent are respectively containing catalyst carrier and the active metal component being carried in the catalyst carrier, wherein, the protective agent, the catalyst carrier of at least one of the metal remover and the desulfurizing agent is modified support, the modified support contains the acid additive and metal promoter of layer distributed in the carrier, the acid additive is distributed in stratum nucleare, the metal promoter is distributed in shell.The Heavy oil hydrogenation method provided by the invention can not only obtain higher metal, sulphur and carbon residue removal effect, more praiseworthy is catalyst stability height, the duration of runs is long, so that the heavy oil hydrogenation treatment method provided by the invention has preferable prospects for commercial application.

Description

A kind of heavy oil hydrogenation treatment method

Technical field

The present invention relates to petrochemical industries, and in particular, to a kind of heavy oil hydrogenation treatment method.

Background technique

The utilization rate that deep processing not only contributes to improve heavy oil is carried out to the heavy oil including residual oil, alleviates the energy and supplies The nervous trend answered, while can also reduce environmental pollution, reach the clean utilization of the energy.Since residual oil has, density is big, miscellaneous original The high feature of sub- content, a kind of catalyst is difficult to meet a variety of hetero atom requirements of removing and easy in inactivation, therefore residual hydrogenation is urged Agent generallys use gradation system, is gradually reduced along reactor stream direction catalyst aperture and partial size, and catalyst hydrogenation Activity but gradually increases.Carbon deposit and metal deposit are the principal elements for causing residual oil hydrocatalyst to inactivate, and research shows that Since carbon deposit and metal deposit are intended to deposit in residual oil hydrocatalyst aperture, this is also to cause residual oil hydrocatalyst One of the main reason for activity is mutually unable to get effective use.

In order to solve the above-mentioned technical problem, CN101928592B discloses a kind of grading composition method of hydrogenation catalyst, Reactor loads Hydrodemetalation catalyst and desulfurizing agent respectively from top to bottom；The activity of Hydrodemetalation catalyst and desulfurizing agent Metal component and acidic assistant concentration distribution are in uneven distribution, from catalyst particle surface to center, hydrodemetallisation catalyst The active metal component and acidic assistant concentration gradient of agent increase, the active metal component and acidic assistant concentration gradient of desulfurizing agent It reduces.However, method for preparing catalyst is complicated in the grading composition, energy consumption is high and the repeatability and controllability of the preparation method It is poor.

Summary of the invention

The purpose of the invention is to overcome all kinds of catalyst actions in existing heavy oil hydrogenation treatment method cannot be effective The shortcomings that performance, providing one kind can be realized comprehensive demetalization, desulfurization, de- carbon residue effect and is not easy to form carbon deposit, has height steady Qualitative heavy oil hydrogenation treatment method.

To achieve the goals above, the present invention provides a kind of heavy oil hydrogenation treatment methods, this method comprises: adding hydrogen anti- Under the conditions of answering, by heavy oil feedstock successively with protective agent, metal remover and desulfurization agent, the protective agent, the metal remover With the desulfurizing agent respectively containing catalyst carrier and the active metal component being carried in the catalyst carrier, wherein described The catalyst carrier of at least one of protective agent, the metal remover and the desulfurizing agent is modified support, the modified load Body contains the acid additive and metal promoter of layer distributed in the carrier, and the acid additive is distributed in stratum nucleare, the metal promoted Agent is distributed in shell, and the acid additive is selected from least one of F (fluorine) component, P (phosphorus) component and B (boron) component, described Metal promoter is group ia metal component and/or group iia metal component, and the active metal component is at least one Section VI B The combination of race's metal component and at least one group VIII metal component.

In heavy oil hydrogenation treatment method provided by the invention, by protective agent, metal remover and desulfurizing agent extremely A kind of few catalyst carrier is modified, so that acid additive and metal in modified catalyst carrier (i.e. modified support) Auxiliary agent is in layer distributed and acid additive is made to be distributed in stratum nucleare, and metal promoter is distributed in shell, in this way on reactant molecule edge During internally spreading outside catalyst granules, be conducive to metal deposit and carbon deposit along the radially uniform distribution of catalyst, Enable the heavy oil hydrogenation treatment method effectively to play all kinds of catalyst actions, has for heavy distillate and residual hydrogenation There are better demetalization, desulfurization, de- carbon residue activity and stability, can effectively control the temperature rise of catalyst bed, slow down catalysis The deactivation rate of agent extends the operation cycle of catalyst.

Moreover, the preparation method of catalyst carrier used in the present invention is relatively easy to implement, energy consumption is smaller, and The repeatability and controllability of the preparation method are preferable.

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 endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

The present invention provides a kind of heavy oil hydrogenation treatment methods, this method comprises: under hydrogenation conditions, by heavy oil original For material successively with protective agent, metal remover and desulfurization agent, the protective agent, the metal remover and the desulfurizing agent are each self-contained The active metal component for having catalyst carrier and being carried in the catalyst carrier, wherein the protective agent, the metal remover Catalyst carrier at least one of the desulfurizing agent is modified support, and the modified support contains layering point in the carrier The acid additive and metal promoter of cloth, the acid additive are distributed in stratum nucleare, and the metal promoter is distributed in shell, the acidity Auxiliary agent is selected from least one of F (fluorine) component, P (phosphorus) component and B (boron) component, and the metal promoter is group ia metal group Point and/or group iia metal component, the active metal component be at least one vib metals component and at least one the The combination of group VIII metal component.

In the modified support, the concept of " shell " and " stratum nucleare " is introduced, but is not to illustrate the modified load There are two separable layers each other for body tool, but there are two different acid additives and gold in order to illustrate tool in the modified support Belong to the integrated distribution region of auxiliary agent, and the two distributed areas are in stratiform, one is located at the central area of the modified support, It is known as stratum nucleare, another is located at the surface region of the modified support, i.e. referred to as shell.

In the modified support, the layer distributed of acid additive and metal promoter refers to that acid additive and metal promoter exist It is uneven distribution in entire modified support, metal promoter is distributed mainly on shell, can also have and be distributed in stratum nucleare on a small quantity；And Acid additive is distributed mainly on stratum nucleare, can also have and be distributed in shell on a small quantity.SEM-EDX (Scanning is used in the present invention Electron Microscope-Energy Dispersive Spectrometry) method analyzes acidity in the modified support and helps Agent and metal promoter and indicate acid additive and metal promoter along modified support along the distribution of particle radial direction with distribution factor σ The regularity of distribution of particle radial direction.The distribution factor σ is the ratio of auxiliary agent concentration on a certain position of carrier granular and at center Value (R is particle radius, using at modified hydrogen at-ing catalyst carrier granular center as starting point).Wherein, auxiliary agent carrier granular certain Concentration on one position refers to (position deviation≤20nm) 20 numerical point numerations nearby in the position in SEM-EDX characterization result Average value, concentration of the auxiliary agent at the center of carrier granular refers to that (position is inclined near central point in SEM-EDX characterization result Difference≤20nm) 20 numerical point numerations average value.If σ > 1, show that the content of auxiliary agent at that point is higher than modified support The content of corresponding additive at grain center；If σ=1, show the content of auxiliary agent at that point and phase at modified support granular center Answer the content of auxiliary agent identical；If σ < 1, show the content of auxiliary agent at that point lower than corresponding additive at modified support granular center Content.Wherein, in the modified support, the distribution factor σ > 1 of the metal promoter of carrier granular outer layer (shell), and carry The distribution factor σ < 1 of the acid additive of body particle outer layer (shell).For example, in σ_FIn (1/3R), R is particle radius, with modification It is starting point at carrier granular center, F refers to the F component in terms of F element, specifically, σ_F(1/3R) refers to from modified support center The ratio between the F constituent content at the center of the F constituent content and the modified support at 1/3R is located.

In the modified support, the thickness for being distributed the shell of metal promoter and the stratum nucleare of distribution acid additive is not special Ground limits, for example, the thickness of the shell can be 0.1-5mm, preferably 0.1-4mm, more preferably 0.1-2.5mm；It is described The thickness of stratum nucleare can be 0.1-5mm, preferably 0.1-4mm, more preferably 0.15-3.5mm.Wherein, the thickness of the shell Refer to the thickness of the part distribution factor σ >=2 of the metal promoter, and the stratum nucleare thickness refers to the distribution factor of acid additive The thickness of 1 part 0.5≤σ <.In the present invention, the thickness of the shell and stratum nucleare is measured using SEM-EDX method, specifically, It randomly selects 30 modified supports and measures its cross section and partial size with SEM, it is radial along each modified support respectively with EDX later Scanning obtains the radial distribution of metal promoter component and obtains the thickness of the part σ >=2, takes the arithmetic mean of instantaneous value of above-mentioned thickness to be The thickness of shell of the present invention；And the diameter of acid additive component is obtained along each modified support radial scan respectively with EDX To being distributed and obtaining the thickness of 1 part 0.5≤σ <, taking the arithmetic mean of instantaneous value of above-mentioned thickness is stratum nucleare of the present invention Thickness.

In the present invention, as long as the catalysis of at least one of the protective agent, the metal remover and described desulfurizing agent Agent carrier is that goal of the invention of the invention can be realized in modified support, to realize comprehensive demetalization, desulfurization, the effect for taking off carbon residue, Under preferable case, in order to further improve the effect of demetalization, desulfurization and de- carbon residue, the catalyst carrier of the desulfurizing agent is institute State modified support, that is to say, that the catalyst carrier of at least described desulfurizing agent is the modified support, the protective agent and described The catalyst carrier of metal remover can be optionally the modified support.

It is the protective agent, described it is further preferred that in order to further improve the effect of demetalization, desulfurization and de- carbon residue The catalyst carrier of metal remover and the desulfurizing agent is the modified support.

In the present invention, the F component, the P component and the B component can exist in various conventional forms, example Can such as exist in the form of simple substance, can also exist in the form of compound.Compound containing F for example can for ammonium fluoride, One of ammonium acid fluoride, hydrofluoric acid, sodium fluoride and calcirm-fluoride are a variety of.Compound containing P for example can be phosphoric acid, di(2-ethylhexyl)phosphate One of ammonium, sodium dihydrogen phosphate and potassium dihydrogen phosphate are a variety of.Compound containing B for example can for boric acid, metaborate and One of borate is a variety of.

Institute in the modified support, on the basis of the total weight of the modified support, in terms of tri- kinds of elements of F, P and B State acid additive content can for 0.1-15 weight %, such as can for 0.2 weight %, 0.3 weight %, 0.5 weight %, 0.6 weight %%, 0.8 weight %, 1.0 weight %, 1.2 weight %, 1.4 weight %, 1.5 weight %, 1.8 weight %, 2.0 weights Measure %, 2.2 weight %, 2.5 weight %, 2.7 weight %, 2.9 weight %, 3.0 weight %, 3.5 weight %, 4 weight %, 4.5 Weight %, 5 weight %, 5.5 weight %, 6 weight %, 6.5 weight %, 7 weight %, 7.5 weight %, 8 weight %, 8.5 weights Measure %, 9 weight %, 9.5 weight %, 10 weight %, 10.5 weight %, 11 weight %, 11.5 weight %, 12 weight %, 12.5 Weight %, 13 weight %, 13.5 weight %, 14 weight %, 14.5 weight %, 15 weight % or aforementioned any two numerical value it Between value.In the preferred case, in the modified support, on the basis of the total weight of the modified support, with F, P and B tri- The content of the acid additive of kind element meter is 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably 1- 5 weight % are still more preferably 2-4 weight %.In the present invention, " the acid additive in terms of tri- kinds of elements of F, P and B Content " refer to that the weight of the acid additive is measured using the total weight of tri- kinds of elements of F, P and B as representative, wherein when When the acid additive does not include one of tri- kinds of elements of F, P and B or two kinds, " described in terms of tri- kinds of elements of F, P and B The content of acid additive " also includes such case, and only removing naturally not includes that usually the First Astronautic Research Institute for Measurement and Test states acidity to that member The content of auxiliary agent.

A preferred embodiment of the invention, the modified support are made by method comprising the following steps:

(1) carrier Jing Guo hydro-thermal process is provided with the metal promoter compound of the metal promoter in alkaline containing It is impregnated in solution A, is then dried；

(2) carrier that step (1) obtains is provided with the acid additive compound of the acid additive in acid containing It is impregnated in solution B, is then dried and roasts.

In the preparation method of above-mentioned modified support, the present inventor is contained by further investigation discovery in dipping Before the solution A of the metal promoter compound, the carrier is first subjected to hydro-thermal process, and control the maceration extract impregnated twice Acid-base property enable to metal promoter to be mainly distributed on the shell of carrier, and acid additive is mainly distributed on the stratum nucleare of carrier, To realize that layer distributed of the auxiliary agent on carrier, preparation process controllability and repeatability are very good.Speculate its reason, it may Be due to: when preparing modified support using infusion process, absorption of the different carriers to same active component solute in dipping process Ability is different, and same carrier is also different to the adsorption capacity of different activities component solute.Carrier composed mainly of oxide Following three parameters: isoelectric point, maceration extract pH value and the metal network of oxide are depended mainly on to the absorption of metel complex ion The property of ion.After carrier after hydro-thermal process is immersed in maceration extract several times, by being done after controlling repeatedly dipping Dry condition can guarantee the position of hydroxy density maximum value on carrier as the progress of dipping process is constantly moved to carrier center It moves.At this point, when the isoelectric point of the pH value > carrier of maceration extract, on carrier the position of hydroxy density maximum value be easy to adsorb just from Son；When the isoelectric point of the pH value < carrier of maceration extract, the position of hydroxy density maximum value is easy to adsorb anion on carrier.Oxygen Change alumina supporter isoelectric point be usually 7.0-9.0 or so, and the active principle in the alkaline assistant compound be usually positive from Son, the active principle in acid additive compound is usually anion.Therefore, dry after control hydro-thermal process severity, dipping Degree and maceration extract pH value, the active principle that can be realized in maceration extract are layered suction along the radial direction of carrier from outside to inside It is attached on carrier.

In the preparation method of above-mentioned modified support, the carrier needs first to carry out hydro-thermal process, and the present invention is to the water The condition of heat treatment is not particularly limited, for example, it is 50-200 DEG C (excellent that the condition of the hydro-thermal process, which may include: temperature, It is selected as 60-180 DEG C, more preferably 70-150 DEG C), the time is that (preferably 8-28 hours, more preferably 10-24 was small in 5-30 hours When).

In the preparation method of above-mentioned modified support, the metal promoter compound will provide the metal promoter, and institute It states metal promoter and refers to metallic element in group ia and/or group iia, wherein group ia metal is preferably Li, Na and K One of or it is a variety of, group iia metal is preferably Mg and/or Ca.Therefore, metal promoter of the present invention is preferably Li group Point, one of Na component, K component, Mg component and Ca component or a variety of, more preferably in K component, Mg component and Ca component It is one or more.

Wherein, the metal promoter compound for providing Li for example can be lithium nitrate and/or lithium sulfate.

Wherein, the metal promoter compound for providing Na for example can be sodium nitrate and/or sodium sulphate.

Wherein, the metal promoter compound for providing K for example can be potassium nitrate and/or potassium sulfate.

Wherein, the metal promoter compound for providing Mg for example can be magnesium nitrate and/or magnesium chloride.

Wherein, provide the metal promoter compound of Ca for example can for one of calcium nitrate, calcium chloride and calcium acetate or It is a variety of.

In the present invention, the acid additive is derived from the acid additive compound, and the acid additive refers to selecting From at least one of F component, P component and B component.

Wherein, the acid additive compound for providing F component for example can be ammonium fluoride, ammonium acid fluoride, hydrofluoric acid, sodium fluoride With one of calcirm-fluoride or a variety of.

Wherein, the acid additive compound for providing P component for example can be phosphoric acid, Diammonium phosphate (DAP), sodium dihydrogen phosphate and phosphorus One of acid dihydride potassium is a variety of.

Wherein, the acid additive compound for providing B component can be for example one of boric acid, metaborate and borate Or it is a variety of.

In the preparation method of above-mentioned modified support, the solution A be it is alkaline, can use this field routine alkalinity Substance makes the solution A in alkalinity, such as can be using in ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc. It is one or more, come so that the solution A for alkalinity.Under preferable case, the pH value of the solution A is 7.5-11, more preferably For 8-11.

In the preparation method of above-mentioned modified support, the solution B is acid, the usual acid additive compound energy Enough so that the solution B is in acidity, but when the solution B does not show as acidity, the acid of this field routine can be used Property substance make the solution B in acidity, such as can be using one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid or a variety of.It is preferred that In the case of, the pH value of the solution B is 2-6.5, more preferably 4-6.

In the preparation method of above-mentioned modified support, the present invention does not limit the type of solvent in the solution A particularly It is fixed, it can be the existing various inertia liquids that can dissolve the metal promoter compound under alkaline condition, for example, can Selected from one of water, alcohol (such as methanol, ethyl alcohol etc.), ether (such as ether), aldehyde (such as formaldehyde) and ketone (such as acetone) Or it is a variety of.In addition, metal promoter compounds content can be 10-20 grams per liter in the solution A.

In the preparation method of above-mentioned modified support, the present invention does not limit the type of solvent in the solution B particularly It is fixed, it can be the existing various inertia liquids that can dissolve the acid additive compound in acid condition, for example, can Selected from one of water, alcohol (such as methanol, ethyl alcohol etc.), ether (such as ether), aldehyde (such as formaldehyde) and ketone (such as acetone) Or it is a variety of.In addition, acid additive compounds content can be 10-20 grams per liter in the solution B.

In the preparation method of above-mentioned modified support, the dosage of the carrier and the solution A and the solution B makes to obtain Modified support in, on the basis of the total weight of the modified support, the content of the metal promoter in terms of metal oxide Preferably 0.1-15 weight %, further preferably 0.2-12 weight %, more preferably 0.3-8 weight %, most preferably 1-3 weight Measure %；The content of the acid additive in terms of tri- kinds of elements of F, P and B is preferably 0.1-15 weight %, further preferably 0.2-12 weight %, more preferably 0.3-8 weight %, most preferably 1-2 weight %.

In the preparation method of above-mentioned modified support, the type of the carrier can be the conventional selection of this field, for example, It can be aluminium oxide, or the mixture of at least one of aluminium oxide and silica, titanium oxide and zirconium oxide.Wherein, institute Stating aluminium oxide for example can be at least one of gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide. Above-mentioned carrier can be commercially available, can also be according to well known to a person skilled in the art various methods to be prepared.For example, Alumina support can make it be converted into gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-by roasting aluminium oxide precursor At least one of aluminium oxide and χ-aluminium oxide and be prepared.It optionally, before firing and/or later, can be first by oxygen Change the molding of aluminium precursor, to prepare shape (such as spherical shape, sheet, bar shaped) required for being suitble to practical operation.The molding can To be carried out according to the method for this field routine, such as rolling ball method, pressed disc method and extrusion method.In forming process, such as in extrusion In forming process, in order to guarantee it is molding go on smoothly, can be added into the aluminium oxide precursor water, extrusion aid and/or Peptizing agent, and it is optionally added expanding agent, then extrusion molding is dried later and roasts.The extrusion aid, peptizing agent and expansion The type and dosage of hole agent are known to the skilled person, for example, common extrusion aid can be selected from sesbania powder, Methyl cellulose At least one of element, starch, polyvinyl alcohol and polyethanol, the peptizing agent can be organic acid and/or organic acid, the expansion Hole agent can be at least one of starch, synthetic cellulose, polymeric alcohol and surfactant.Wherein, the synthetic cellulose Preferably at least one of hydroxymethyl cellulose, methylcellulose, ethyl cellulose and hydroxyl fiber fat alcohol polyethylene ether. The polymeric alcohol is preferably at least one of polyethylene glycol, poly- propyl alcohol and polyvinyl alcohol.The surfactant is preferably rouge Fat alcohol polyvinylether, fatty alkanol amide and its derivative, the propylene alcohol copolymer that molecular weight is 200-10000 and maleic acid are total At least one of polymers.The dry condition of item will be squeezed out to generally include: drying temperature can be 40-350 DEG C, preferably 100- 200℃；Drying time can be 1-24 hours, preferably 2-12 hours.The condition of extrusion item roasting after drying is usually wrapped Include: maturing temperature can be 350-1000 DEG C, preferably 600-950 DEG C；Calcining time can be 1-10 hours, preferably 2-6 Hour.In addition, the aluminium oxide precursor can be selected from hibbsite, monohydrate alumina, amorphous hydroted alumina etc. At least one of.The carrier can be cloverleaf pattern, butterfly, cylinder, hollow cylindrical, quatrefoil, five leaf, spherical Etc. shapes.

In the preparation method of above-mentioned modified support, to the no spy of the condition of dipping described in step (1) and step (2) It does not limit, the immersion condition of two steps can be identical or different, as long as metal promoter and acid additive is enabled to be supported on institute It states 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 carried out using the dipping method of this field routine, such as can be excessive liquid infusion process or saturation Infusion process.

In the preparation method of above-mentioned modified support, drying described in step (1) and step (2) can be vacuum drying. The condition of the drying all can be this field conventional selection, for example, dry condition may include: temperature in step (1) For 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, more Preferably 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).

In the preparation method of above-mentioned modified support, the present invention does not limit the condition of the roasting in step (2) particularly It is fixed, for example, the condition of roasting includes: that temperature is 300-900 DEG C of (preferably 300-800 DEG C, more preferably 400- in step (2) 600 DEG C), the time is 1-10 hours (preferably 2-8 hours, more preferably 2-6 hours).

In the present invention, the protective agent can be the hydrogenation protecting agent of this field routine.The protective agent is containing active Metal component and catalyst carrier (preferably above-mentioned modified support), wherein the active metal component is at least one the Group VIII metal component and at least one vib metals component.In the preferred case, in terms of metal oxide and with the guarantor It protects on the basis of the total weight of agent, the content of the group VIII metal component is greater than 0 weight % and is less than or equal to 1 weight % (example Such as, 0.1-0.9 weight %), the content of the vib metals component be greater than 0 weight % and be less than or equal to 6 weight % (for example, 0.1-5 weight %).

In the present invention, the metal remover can be the hydrodemetallization agent of this field routine.The metal remover contains Active metal component and catalyst carrier (preferably above-mentioned modified support), wherein the active metal component is at least one Kind group VIII metal component and at least one vib metals component.In the preferred case, in terms of metal oxide and with institute On the basis of the total weight for stating metal remover, the content of the group VIII metal component is 1-3 weight % (preferably 1.1-2.9 Weight %), the content of the vib metals component is 6-13 weight % (preferably 6.1-12.8 weight %).

In the present invention, the desulfurizing agent can be the hydrogen desulfurization agent of this field routine.The desulfurizing agent is containing active Metal component and catalyst carrier (preferably above-mentioned modified support), wherein the active metal component is at least one the Group VIII metal component and at least one vib metals component.In the preferred case, in terms of metal oxide and with described de- On the basis of the total weight of sulphur agent, the content of the group VIII metal component is 3-15 weight % (preferably 3.1-10 weight Measure %), the content of the vib metals component is 13-30 weight % (preferably 13.1-28 weight %).

In the present invention, the group VIII metal can be selected from Ni, Co and Fe, preferably Ni and/or Co.Described Group vib metal can be selected from Cr, Mo and W, preferably Mo and/or W.

In the heavy oil hydrogenation treatment method provided by the invention, along logistics direction, the protective agent, the demetalization The catalytic activity of agent and the desulfurizing agent is gradually increased.In one embodiment, the active metal in the protective agent The active metal component content in active metal component content and the desulfurizing agent in constituent content, the metal remover is It is gradually increased.

A preferred embodiment of the invention, in order to further increase demetallization per, desulfurization degree and de- carbon yield, In the desulfurizing agent, the active metal component is in layer distributed along the radial direction of the catalyst carrier, stratum nucleare Active metal component is Co component and Mo component, and the active metal component of shell for Ni component and is selected from Mo component and/or W component Combination.In the preferred embodiment, by making Ni component and the active metal component selected from Mo component and/or W component It is distributed in the shell of desulfurizing agent, and Co component and Mo component is made to be distributed in the stratum nucleare of desulfurizing agent, so that more difficult reaction in heavy oil Condensed-nuclei aromatics first touches the higher Ni component of hydrogenation activity and Mo component and/or W component during the reaction, and hydrogen saturation is added to open Ring further spreads to catalytic inner so that various need the substance removed to expose in succession, touches hydrodesulfurization activity Higher Co component and Mo component, using the reaction characteristics of different activities metal component, optimum organization, to obtain higher work Property.

It here, introduce the concept of " shell " and " stratum nucleare ", but is not to illustrate the desulfurizing agent tool there are two each other Separable layer, but there are two the distributed areas of different active metal components in order to illustrate tool in the desulfurizing agent, and The two distributed areas are in stratiform, and one is located at the central area of the sorbent particle, i.e. referred to as stratum nucleare, another is located at institute The surface region of sorbent particle is stated, i.e. referred to as shell.

It should be noted that " active metal component of stratum nucleare is Co component and Mo component, and the active metal component of shell is Ni component and the combination selected from Mo component and/or W component " refers to the radial direction along modified support, is carried in modified support Active metal component is in layer distributed, forms the structure of similar stratum nucleare and shell, wherein the active metal component of stratum nucleare is main For Co component and Mo component, a small amount of other active metal components such as Ni component and/or W component can also be distributed with；The work of shell Property metal component be mainly Ni component and the combination selected from Mo component and/or W component, other a small amount of activity gold can also be distributed with Belong to component such as Co component.SEM-EDX (Scanning Electron Microscope-Energy is used in the present invention Dispersive Spectrometry) method analyzes active metal component in the desulfurizing agent and is used in combination along the distribution of particle radial direction Distribution factor σ indicates active metal component element along the regularity of distribution of sorbent particle radial direction.The distribution factor σ is activity gold Belong to content at content of the component at a certain position of catalyst granules and center the ratio between, if σ=1, show point activity Metallic constituent element content is identical as at center；If σ < 1, show this active metal component constituent content lower than at center. Wherein, in the desulfurizing agent, the distribution factor σ > 1 of the Ni component of sorbent particle outer layer (i.e. shell), and sorbent particle The distribution factor σ < 1 of the Co component of outer layer (i.e. shell).

In the desulfurizing agent, the thickness of the shell and stratum nucleare is not particularly limited, for example, the thickness of the shell It can be 0.1-5mm, preferably 0.1-4mm, more preferably 0.1-2.5mm；The thickness of the stratum nucleare can be 0.1-5mm, excellent It is selected as 0.1-4mm, more preferably 0.15-3.5.Wherein, the thickness of the shell refer to the distribution factor σ of the Ni component >= The thickness of 2.0 parts, and the stratum nucleare thickness refers to the thickness of 1 part 0.5≤σ of distribution factor < of Co component.In the present invention In, the thickness of the shell and stratum nucleare is measured using SEM-EDX method, specifically, is randomly selected 30 desulfurizing agents and is measured with SEM Its cross section and partial size, obtain the radial distribution of Ni component along each desulfurizing agent radial scan respectively with EDX later and obtain σ >= The thickness of 2.0 parts, take above-mentioned thickness arithmetic mean of instantaneous value be shell of the present invention thickness；And with the edge respectively EDX Each desulfurizing agent radial scan obtains the radial distribution of Co component and obtains the thickness of 1 part 0.5≤σ <, takes above-mentioned thickness Arithmetic mean of instantaneous value is the thickness of stratum nucleare of the present invention.

It in the desulfurizing agent, is counted by metal oxide and on the basis of the total weight of the catalyst, Co component contains Amount can be 0.5-15 weight %, further preferably 2-8 weight %, more preferably 3-7 weight %, most preferably 3-5 weight Measure %.

It in the desulfurizing agent, is counted by metal oxide and on the basis of the total weight of the catalyst, Mo component contains Amount can be 5-25 weight %, further preferably 8-20 weight %, more preferably 10-20 weight %, most preferably 15-20 weight Measure %.

It in the desulfurizing agent, is counted by metal oxide and on the basis of the total weight of the catalyst, Ni component contains Amount can be 0.5-15 weight %, further preferably 2-8 weight %, more preferably 3-7 weight %, most preferably 3-5 weight Measure %.

It in the desulfurizing agent, is counted by metal oxide and on the basis of the total weight of the catalyst, the content of W component It can be 0-35 weight %, further preferably 5-30 weight %, more preferably 10-30 weight %, most preferably 15-25 weight Measure %.

It is highly preferred that the weight ratio of the Mo component of the Mo component and shell of the stratum nucleare is when shell contains Mo group timesharing 1:0.5-1.

In the present invention, due to the desulfurizing agent be usually modified support load after upper active metal component by roasting and Obtained, therefore, above-mentioned active metal component exists usually in the form of metal oxide in the desulfurizing agent, this certain hair Bright to be also not limited to this, the active metal component is also possible to the offer active metal group in addition to an oxide The form of the compound divided exists.

It wherein, can be CoO as the metal oxide form of Co, the metal oxide form as Ni can be NiO, Metal oxide form as Mo can be MoO₃, the metal oxide form as W can be WO₃。

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, the compound of the 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 more Kind.Providing the nickel compound of Ni is preferably nickel oxide (NiO), 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.

Wherein, in addition to MoO₃The compound of offer Mo in addition for example can be ammonium molybdate ((NH₄)₂MoO₄), ammonium paramolybdate ((NH₄)₆Mo₇O₂₄), ammonium dimolybdate ((NH₄)₂Mo₂O₇), ammonium heptamolybdate ((NH₄)₆Mo₇O₂₄) and ammonium tetramolybdate ((NH₄)₂Mo₄O₁₃) One of or it is a variety of.Providing the molybdenum compound of Mo is preferably molybdenum oxide (MoO₃), ammonium molybdate ((NH₄)₂MoO₄), para-molybdic acid Ammonium ((NH₄)₆Mo₇O₂₄), ammonium dimolybdate ((NH₄)₂Mo₂O₇), ammonium heptamolybdate ((NH₄)₆Mo₇O₂₄) and ammonium tetramolybdate ((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.Providing the tungsten compound of W is preferably oxygen Change tungsten (WO₃), ammonium tungstate ((NH₄)₁₀W₁₂O₄₁), ammonium metatungstate ((NH₄)₆H₂W₁₂O₄₀), in ammonium paratungstate and ethyl ammonium metatungstate It is one or more.

In the present invention, the desulfurizing agent can also contain the adjuvant component of other this fields routine, such as Si.

A preferred embodiment of the invention, the desulfurizing agent are made by method comprising the following steps:

(a) catalyst carrier (modified support preferably as described above) is subjected to hydro-thermal process, then by hydro-thermal First solution of the catalyst carrier that treated in the combination containing nickel compound and molybdenum compound and/or tungsten compound of alkalinity In impregnated, be then dried；

(b) carrier by step (a) after dry in acid the second solution containing cobalt compound and molybdenum compound into Row dipping, is then dried and roasts.

In the above-mentioned method for preparing the desulfurizing agent, although as long as before supported active metals component, it first will be described Modified support carries out hydro-thermal process, and is alkaline and control the second solution institute can be realized for acidity by the control of the first solution Active metal component is stated along the radial direction of the modified support in layer distributed (for example, double-deck be distributed), but in order into one Step improves the controllability and repeatability of preparation process, it is preferable that in step (a), the condition of hydro-thermal process includes: that temperature is 50- 200 DEG C (further preferably 60-180 DEG C, more preferably 70-150 DEG C), the time is 5-30 hours (further preferably 8-28 Hour, more preferably 10-24 hours).

Wherein, the nickel compound, molybdenum compound, tungsten compound, cobalt compound respectively can be the oxidation of respective metal The compound of object and the corresponding metal component of offer as hereinbefore defined, details are not described herein.And step (a) and step (b) molybdenum compound used by is selected each independently, can be identical or different.

Wherein, first solution is alkaline, can be made using the alkaline matter of this field routine described first molten Liquid is in alkalinity, such as can use one of ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc. or a variety of, comes So that first solution is alkalinity.Under preferable case, the pH value of first solution is 7.5-11, more preferably 8-11.

Wherein, second solution is acid, can be made using the acidic materials of this field routine described second molten Liquid is in acidity, such as can use one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc. or a variety of, comes so that second solution is in It is acid.Under preferable case, it is still more preferably 4-6 that the pH value of second solution, which is 2-6.5, more preferably 2-6,.

The present invention is not particularly limited the type of solvent in first solution, can for it is existing it is various can be in alkali Property under the conditions of dissolve the inertia liquid of the nickel compound, molybdenum compound and/or tungsten compound, for example, can selected from water, At least one of alcohol (such as methanol, ethyl alcohol etc.), ether (such as ether), aldehyde (such as formaldehyde) and ketone (such as acetone).In addition, The total content of nickel compound, molybdenum compound and tungsten compound can be 10-20 grams per liter in first solution.

The present invention is not particularly limited the type of solvent in second solution, can for it is existing it is various can be in acid Property under the conditions of dissolve the inertia liquid of the cobalt compound and molybdenum compound, for example, can selected from water, alcohol (such as methanol, Ethyl alcohol etc.), ether (such as ether), at least one of aldehyde (such as formaldehyde) and ketone (such as acetone).In addition, second solution The total content of middle cobalt compound and molybdenum compound can be 10-20 grams per liter.

According to the present invention, in step (a) and (b), the dosage of the modified support and the first solution and the second solution can be with It in the desulfurizing agent made, is counted by metal oxide and on the basis of the total weight of the desulfurizing agent, the content of Co component is 0.5-15 weight %, preferably 2-8 weight %, more preferably 3-7 weight %, most preferably 3-5 weight %；The content of Mo component For 5-25 weight %, preferably 8-20 weight %, more preferably 10-20 weight %, most preferably 15-20 weight %；Ni component Content be 0.5-15 weight %, preferably 2-8 weight %, more preferably 3-7 weight %, most preferably 3-5 weight %；W group The content divided is 0-35 weight %, preferably 5-30 weight %, more preferably 10-30 weight %, most preferably 15-25 weight Measure %.

According to the present invention, the present invention is not particularly limited the condition of the dipping in step (a) and step (b), can With identical or different, as long as active metal component is enabled to be supported on modified support, for example, the condition of dipping can be with Include: temperature be 50-300 DEG C, preferably 50-100 DEG C；Time is 1-20 hours, preferably 1-6 hours.

In addition, drying described in step (a) and step (b) can be vacuum drying.The condition of the drying all can be The conventional selection of this field, for example, dry condition may include: that temperature is 30-300 DEG C of (preferably 50- in step (a) 300 DEG C, more preferably 100-250 DEG C), the time is 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).

According to the present invention, to the roasting in step (b), there is no particular limitation, can use the desulfurizing agent of this field routine Roasting condition, for example, in step (b), the condition of roasting may include: temperature be 300-900 DEG C (preferably 300-800 DEG C, More preferably 400-600 DEG C), the time is 1-10 hours (preferably 2-8 hours, more preferably 2-6 hours).

According to the present invention, above-mentioned preparation method can also include that desulfurizing agent is loaded to the auxiliary agent group of upper other this fields routine Point, such as Si.Such adjuvant component can be introduced into the desulfurizing agent in the method for this field routine, such as can prepared It introduces, can be introduced in supported active metals group timesharing when modified support, alternatively, before supported active metals component, individually Solution containing the compound for being provided with adjuvant component and modified hydrogen at-ing catalyst carrier are subjected to immersive contact, and drying and roasting Mode (dipping, dry and roasting condition can be carried out using the condition that above any one place records), simultaneously to this present invention It is limited without special.

In the heavy oil hydrogenation treatment method provided by the invention, along logistics direction, the protective agent, the demetalization The catalytic activity of agent and the desulfurizing agent is gradually increased, and aperture is gradually reduced, and granularity is gradually reduced.Protectant carrier Kong Rongke is with for 0.85-1.0mL/g, specific surface area can be 0-=-100m²/ g, granularity can be 3-10mm.The demetalization The Kong Rongke of agent is with for 0.75-0.85mL/g, specific surface area can be 120-160m²/ g, granularity can be 1-5mm.It is described de- The Kong Rongke of sulphur agent is with for 0.3-0.75mL/g, specific surface area can be 160-300m²/ g, granularity can be 1-2mm.In this hair In bright, granularity refers to the particle size of catalyst granules, and when catalyst granules is sphere, then the diameter of granularity sphere is indicated, When catalyst granules is cube, then the side length of granularity cube is indicated, then when catalyst granules is irregular shape Granularity is indicated with the mesh size for the sieve that can screen out the catalyst granules just.

In the heavy oil hydrogenation treatment method provided by the invention, do not have to the reaction condition of heavy-oil hydrogenation processing Especially limitation, in a preferred embodiment, the reaction condition of the hydrotreating include: that temperature is 300-550 DEG C, further Preferably 330-480 DEG C, hydrogen partial pressure 4-20MPa, further preferably 6-18MPa, volume space velocity 0.1-3.0h^-1, into one Step is preferably 0.15-2h^-1, hydrogen to oil volume ratio 200-2500, further preferably 300-2000.In the present invention, described Pressure refers to gauge pressure.

In the heavy oil hydrogenation treatment method provided by the invention, the reaction unit of the hydrotreating can be any It is enough to contact the heavy oil with the catalyst (i.e. protective agent, metal remover and desulfurizing agent) at hydrotreating reaction conditions It is carried out in the reactor of reaction, for example, being carried out in the fixed bed reactors, moving-burden bed reactor or fluidized bed reactor.

It in the heavy oil hydrogenation treatment method provided by the invention, in catalyst grading composition, calculates by volume, institute It states protective agent and accounts for 1-20%, preferably 5-15%；The metal remover accounts for 15-60%, preferably 20-50%；The desulfurizing agent Account for 20-85%, preferably 50-75%.

The catalyst before the use, usually can in presence of hydrogen, with sulphur, vulcanization at a temperature of 140-370 DEG C Hydrogen carries out presulfurization containing sulfur feedstock, and this presulfurization can carry out also In-situ sulphiding in device outside device, it is loaded Active metal component is converted into metal sulfide component.

The heavy oil hydrogenation treatment method provided by the invention add at hydrogen suitable for heavy oil especially poor residuum Reason, to provide qualified feedstock oil for subsequent technique (such as catalytic cracking process).

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

The present invention will be described in detail by way of examples below.

Heavy oil used in following embodiment and comparative example is Ni constituent content 34ppm, V element content 98ppm, density 1.041,19.6 weight %, S content of carbon residue, 4.8 weight %, 0.63 weight % of N content Zhenghai Iran subtract slag.

Preparation example 1

The preparation example is used to illustrate the preparation process of alumina support used in the present invention.

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), 30 grams of sesbania powder (Henan Lankao Sesbania gum factory product) and 30g hydroxymethyl cellulose and be uniformly mixed, the aqueous solution of 1200 milliliters of nitric acid containing 28g is added later, The Rasching ring item that outer diameter is 2.5mm, internal diameter is 1mm is extruded on plunger type bar extruder.Then by Rasching ring wet bar in 120 It is 4 hours dry at DEG C, it is roasted 3 hours at 960 DEG C, obtains protection agent carrier Z1.It is obtained using BET method measurement, protective agent The Kong Rongwei 0.95mL/g of carrier Z1, 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), 80 grams of sesbania powder (Henan Lankao Sesbania gum factory product), 60g hydroxymethyl cellulose and 36g carbon black and be uniformly mixed, 2400 milliliters of nitric acid containing 32g are added later Aqueous solution is extruded into the butterfly wet bar that outer diameter is 1.8mm on plunger type bar extruder.Then by butterfly wet bar dry 4 at 120 DEG C Hour, it is roasted 3 hours at 900 DEG C, obtains metal remover carrier Z2.It is obtained using mercury injection method measurement, metal remover carrier The Kong Rongwei 0.78mL/g of Z2, specific surface area 142m²Bimodal shape distribution is presented in/g, pore structure, and wherein the hole 5nm-20nm Zhan is total The hole 55%, 100nm-300nm of Kong Rong 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), 60 grams of sesbania powder (Henan Lankao Sesbania gum factory product), 60g hydroxymethyl cellulose and 15g carbon black and be uniformly mixed, 1800 milliliters of nitric acid containing 32g are added later Aqueous solution is extruded into the butterfly wet bar that outer diameter is 1.4mm on plunger type bar extruder.Then by butterfly wet bar dry 4 at 120 DEG C Hour, it is roasted 3 hours at 600 DEG C, obtains desulfurization agent carrier Z3.It is obtained using mercury injection method measurement, the hole of desulfurization agent carrier Z Hold is 0.7mL/g, specific surface area 231m²/g。

Embodiment 1

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

(1) modified support is prepared

(1-1) takes 200 grams of carrier Z1, Z2 and Z3 prepared by preparation example 1 respectively, first by carrier at 135 DEG C of hydro-thermals Reason 12 hours, then by 165 milliliters of temperature of the carrier after hydrothermal treatment be 40 DEG C containing 15 grams per liter Mg (NO₃)₂Aqueous solution It is (pH value 11) saturation dipping 1 hour, 8 hours dry in 200 DEG C later, obtain the carrier that load has metal promoter；

(1-2) will load obtained in step (1) to have the carrier of metal promoter in 145 milliliters of temperature be 40 DEG C containing 10 Grams per liter H₃BO₃Aqueous solution (pH value 6) in 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 modified support S1-1, S2-1, S3-1.

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

(2-1) takes 200 grams of modified support S1-1, with 210 milliliters of molybdenum oxides and basic cobaltous 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) in room It impregnates 1 hour, is dried in 120 DEG C 2 hours under warm (about 25 DEG C), 420 DEG C roast 3 hours, obtain protective agent CS1-1.

(2-2) takes 200 grams of modified support S2-1, with 190 milliliters of molybdenum oxides and basic cobaltous 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) 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 metal remover CS2-1.

(2-3) takes 200 grams of modified support S3-1, first by the modified support in 135 DEG C hydro-thermal process 12 hours, then will be through The mixed solution containing ammonium heptamolybdate and nickel nitrate that carrier after hydro-thermal process is 50 DEG C with 160 milliliters of temperature and pH value is 11 (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 liters, and solvent is Water) saturation dipping 1 hour, it is 8 hours dry in 100 DEG C later.Then, with 140 milliliters of temperature be 50 DEG C and pH value is 6 containing seven The mixed solution of ammonium molybdate and cobalt nitrate is (wherein, with MoO₃80 grams per liter of concentration of the Mo element of meter, Co element in terms of CoO Concentration is 50 grams per liters, and 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, Obtain desulfurizing agent CS3-1.

(3) catalyst grade is matched and hydrotreating

The protective agent CS1-1 is broken into the particle that diameter is 2 millimeters, it is 1 that metal remover CS2-1, which is broken into diameter, Desulfurizing agent CS3-1 is broken into the particle that diameter is 0.6 millimeter, is then charged into heavy-oil hydrogenation fixed bed reaction by the particle of millimeter Device.Assembling scheme is matched using catalyst grade, along reactor stream direction, first reactor loads protective agent and metal remover, the Two reactors load metal remover and desulfurizing agent.Entire reaction unit loads ratio, is by volume that protective agent accounts for 10%, Metal remover accounts for 40%, and desulfurizing agent accounts for 50%.Reaction condition are as follows: 380 DEG C of temperature, hydrogen partial pressure 14MPa, volume space velocity 0.5h^-1, Hydrogen to oil volume ratio is 500.

Embodiment 2

(1) modified support is prepared

(1-1) takes 200 grams of carrier Z1, Z2 and Z3 prepared by preparation example 1 respectively, first by carrier at 120 DEG C of hydro-thermals Reason 20 hours, then by 155 milliliters of temperature of the carrier after hydrothermal treatment be 50 DEG C containing 12 grams per liter KNO₃Aqueous solution (pH Value is 10) saturation dipping 1 hour, 6 hours dry in 100 DEG C later, obtains the carrier that load has metal promoter；

(1-2) will load obtained in step (1) to have the carrier of metal promoter in 135 milliliters of temperature be 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 small then at 400 DEG C of roastings 3 When, obtain modified support S1-2, S2-2, S3-2.

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

(2-1) takes 200 grams of modified support S1-2, with 210 milliliters of molybdenum oxides and basic cobaltous 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) in room It impregnates 1 hour, is dried in 120 DEG C 2 hours under warm (about 25 DEG C), 420 DEG C roast 3 hours, obtain protective agent CS1-2.

(2-2) takes 200 grams of modified support S2-2, with 190 milliliters of molybdenum oxides and basic cobaltous 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) 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 metal remover CS2-2.

(2-3) takes 200 grams of modified support S3-2, first by the modified support in 120 DEG C hydro-thermal process 20 hours, then will be through Carrier after hydro-thermal process is 60 DEG C with 155 milliliters of temperature and pH value is 10 containing ammonium metatungstate and nickel nitrate mixed solution (its In, with WO₃The concentration of the W element of meter is 100 grams per liters, and the concentration of the Ni element in terms of NiO is 60 grams per liters, and solvent is water) it is full With dipping 2 hours, it is 6 hours dry in 100 DEG C later.Then, with 132 milliliters of temperature be 60 DEG C and pH value is 2 containing seven molybdic acids The mixed solution of ammonium and cobalt nitrate is (wherein, with MoO₃40 grams per liter of concentration of the Mo element of meter, the concentration of the Co element in terms of CoO For 60 grams per liters, solvent is water) saturation dipping 2 hours, it is then 3 hours dry in 120 DEG C, it roasts 3 hours, obtains then at 400 DEG C Desulfurizing agent CS3-2.

(3) catalyst grade is matched and hydrotreating

The protective agent CS1-2 is broken into the particle that diameter is 2 millimeters, it is 1 that metal remover CS2-2, which is broken into diameter, Desulfurizing agent CS3-2 is broken into the particle that diameter is 0.6 millimeter, is then charged into heavy-oil hydrogenation fixed bed reaction by the particle of millimeter Device.Assembling scheme is matched using catalyst grade, along reactor stream direction, first reactor loads protective agent and metal remover, the Two reactors load metal remover and desulfurizing agent.Entire reaction unit loads ratio, is by volume that protective agent accounts for 10%, Metal remover accounts for 40%, and desulfurizing agent accounts for 50%.Reaction condition are as follows: 380 DEG C of temperature, hydrogen partial pressure 14MPa, volume space velocity 0.5h^-1, Hydrogen to oil volume ratio is 500.

Embodiment 3

(1) modified support is prepared

(1-1) takes 200 grams of carrier Z1, Z2 and Z3 prepared by preparation example 1 respectively, first by carrier in 70 DEG C of hydro-thermal process 24 hours, then by the carrier after hydrothermal treatment with 165 milliliters of temperature be 80 DEG C contain 15 grams per liter Ca (NO₃)₂Aqueous solution (pH Value is 8) saturation dipping 1 hour, 8 hours dry in 200 DEG C later, obtains the carrier that load has metal promoter；

(1-2) will load obtained in step (1) to have the carrier of metal promoter in 145 milliliters of temperature be 80 DEG C containing 10 Dipping 1 hour in the aqueous solution (pH value 4) of grams per liter hydrofluoric acid, it is then 3 hours dry in 120 DEG C, it is small then at 400 DEG C of roastings 3 When, obtain modified support S1-3, S2-3, S3-3.

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

(2-1) takes 200 grams of carrier S 1-3, with 210 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO₃ The 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 (about 25 DEG C) under impregnate 1 hour, in 120 DEG C dry 2 hours, 420 DEG C roast 3 hours, obtain protective agent CS1-3.

(2-2) takes 200 grams of carrier S 2-3, with 190 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO₃ The 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 (about 25 DEG C) under impregnate 1 hour, in 120 DEG C dry 2 hours, 420 DEG C roast 3 hours, obtain catalyst CS2-3.

(2-3) takes 200 grams of carrier S 3-3, first by the modified support in 70 DEG C hydro-thermal process 24 hours, then will be through hydro-thermal Carrier is 80 DEG C with 160 milliliters of temperature and pH value is 8 the mixing containing ammonium heptamolybdate, nickel nitrate and ammonium metatungstate that treated is molten Liquid is (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, with WO₃ The concentration of the W element of meter is 150 grams per liters, and solvent is water) saturation dipping 1 hour, it is 8 hours dry in 100 DEG C later；Then, it uses The mixed solution containing ammonium heptamolybdate and cobalt nitrate that 140 milliliters of temperature are 80 DEG C and pH value is 4 is (wherein, with MoO₃The Mo member of meter 80 grams per liter of concentration of element, the concentration of the Co element in terms of CoO are 70 grams per liters, and solvent is water) saturation dipping 1 hour, then in 120 DEG C drying 3 hours, then at 400 DEG C roast 3 hours, obtain desulfurizing agent CS3-3.

(3) catalyst grade is matched and hydrotreating

The protective agent CS1-3 is broken into the particle that diameter is 2 millimeters, it is 1 that metal remover CS2-3, which is broken into diameter, Desulfurizing agent CS3-3 is broken into the particle that diameter is 0.6 millimeter, is then charged into heavy-oil hydrogenation fixed bed reaction by the particle of millimeter Device.Assembling scheme is matched using catalyst grade, along reactor stream direction, first reactor loads protective agent and metal remover, the Two reactors load metal remover and desulfurizing agent.Entire reaction unit loads ratio, is by volume that protective agent accounts for 10%, Metal remover accounts for 40%, and desulfurizing agent accounts for 50%.Reaction condition are as follows: 380 DEG C of temperature, hydrogen partial pressure 14MPa, volume space velocity 0.5h^-1, Hydrogen to oil volume ratio is 500.

Embodiment 4

According to the method implementation steps (1) to (3) of embodiment 2, the difference is that preparing the process of desulfurizing agent are as follows:

The modified support S3-2 for taking 200 grams, it is mixed containing ammonium metatungstate, nickel nitrate, ammonium heptamolybdate and cobalt nitrate with 200 milliliters Solution is closed (wherein, with WO₃The concentration of the W element of meter is 100 grams per liters, and the concentration of the Ni element in terms of NiO is 60 grams per liters, with MoO₃40 grams per liter of concentration of the Mo element of meter, the concentration of the Co element in terms of CoO are 60 grams per liters, and solvent is water) in room temperature (about 25 DEG C) under impregnate 2 hours, it is 6 hours dry in 120 DEG C later, roasted 3 hours then at 400 DEG C, obtain desulfurizing agent CS3-4.

Embodiment 5

According to the method implementation steps (1) to (3) of embodiment 2, the difference is that in step (1) not to carrier Z1 and Z2 is modified, and is directly respectively used to carrier Z1 and Z2 to prepare protective agent and demetalization in step (2-1) and step (2-2) Agent.

Comparative example 1

According to the method implementation steps (1) to (3) of embodiment 2, the difference is that not to carrier Z1, Z2 in step (1) It is modified with Z3, carrier Z1, Z2 and Z3 is directly respectively used to preparation in step (2-1), step (2-2) and step (2-3) Protective agent, metal remover and desulfurizing agent.

Comparative example 2

According to the method implementation steps (1) to (3) of embodiment 2, the difference is that step (1) prepares modified support Process are as follows:

Take 200 grams of carrier Z1, Z2 and Z3 prepared by preparation example 1 respectively, by they respectively 135 milliliters of temperature be 50 DEG C contain 12 grams per liter H₃PO₄Aqueous solution (pH value 2) in dipping 1 hour, it is then 3 hours dry in 120 DEG C, then at 400 DEG C Roasting 3 hours, respectively obtains reference modified support DS1-1, DS2-1 and DS3-1, and these modified supports are mutually applied to respectively In subsequent step.

Comparative example 3

It takes 200 grams of carrier Z1, Z2 and Z3 prepared by preparation example 1 respectively, is 50 DEG C with 155 milliliters of temperature respectively and contains 12 grams per liter KNO₃Aqueous solution (pH value 10) saturation dipping 1 hour, it is 6 hours dry in 100 DEG C later, it is modified to obtain reference Carrier DS1-2, DS2-2 and DS3-2, and these modified supports are mutually applied in subsequent step respectively.

Comparative example 4

According to the method implementation steps (1) to (3) of embodiment 2, the difference is that preparing modified support in step (1) During, the KNO in step (1-1)₃Aqueous solution be in neutrality (pH value 7), respectively obtain reference modified support DS1-3, DS2-3 and DS3-3, and these modified supports are mutually applied in subsequent step respectively.

Test case 1

Using SEM-EDX method to the thickness of Elemental redistribution and shell and stratum nucleare in modified hydrogen at-ing catalyst carrier granular It is analyzed.Since the counting rate in SEM-EDX characterization result along carrier radial direction every bit is corresponded to each other with the point element content, Although the size of counting rate may not represent the real content of the point element, the size of counting rate reflects the point element content Just.Therefore, in order to indicate each element along carrier radial direction the regularity of distribution introduce distribution factor σ.Indicate auxiliary agent in particle with σ On one position with the ratio between concentration at center (R is particle radius, using at modified hydrogen at-ing catalyst carrier granular center as starting point).Certain Concentration is certain average value for putting (position deviation≤20nm) 20 numerical point counting rates nearby on one position；During concentration is at center The average value of (position deviation≤20nm) 20 numerical point counting rates near heart point.If σ > 1, show that the point element content is higher than At modified hydrogen at-ing catalyst carrier granular center；If σ=1, show the point element content and modified hydrogen at-ing catalyst carrier It is identical at grain center；If σ < 1, show that the point element content is less than at modified hydrogen at-ing catalyst carrier granular center.Table 1 is to change The relevant parameter of property catalyst carrier for hydrgenating, wherein the content of auxiliary agent is calculated according to inventory.Table 2 is that modified support exists Distribution factor at different location.For being distributed the thickness of the shell of metal promoter and the stratum nucleare of distribution acid additive, shell is thick Degree refers to that the thickness of the part distribution factor σ >=2 of metal promoter, stratum nucleare thickness refer to 0.5≤σ of distribution factor < of acid additive The thickness of 1 part.

Table 1

Table 2

By upper table 1 and 2 as can be seen that modified support provided by the invention includes carrier and loads on the carrier Metal promoter and acid additive, the metal promoter and acid additive are in layer distributed on the carrier, and shell is metal Auxiliary agent, stratum nucleare are acid additive.

Test case 2

According to method described in test case 1, unlike, measurement be embodiment 1-3 desulfurizing agent active metal group The thickness of distribution and stratum nucleare and shell, wherein the thickness of shell refers to the thickness of the part distribution factor σ >=2.0 of Ni, core The thickness of layer refers to the thickness of 1 part 0.5≤σ of distribution factor < of Co.The following table 3 is the relevant parameter of desulfurizing agent, wherein activity Metal component content is calculated according to inventory.Table 4 is the distribution factor of desulfurizing agent at different locations.

Table 3

Table 4

Note: R refers to the grain diameter of entire desulfurizing agent.

Test case 3

Using Ni, V and Fe in oil before and after inductive coupling plasma emission spectrograph (ICP-AES) measurement hydrotreating Content, instrument are U.S. PE company PE-5300 type plasma quantometer, and specific method is RIPP124-90 (" petroleum Work analysis method ", Yang Cui is surely equal to be compiled, Science Press, Beijing, 1990,349-351), and demetalization is calculated according to the following formula Rate, de- carbon yield and desulfurization degree, as a result as shown in table 5 below.

Table 5

	De- Ni rate %	De- V rate %	De- carbon yield %	Desulfurization degree %
					Embodiment 1	67.3	86.2	59.1	80.1
Embodiment 2	67.5	87.0	60.0	80.5
					Embodiment 3	67.0	86.3	59.9	80.6
Embodiment 4	65.5	82.6	57.5	78.9
					Embodiment 5	65.1	82.0	57.2	77.5
Comparative example 1	58.6	70.9	47.9	65.8
					Comparative example 2	61.1	73.8	50.6	70.0
Comparative example 3	62.3	72.9	51.9	69.8
					Comparative example 4	62.8	72.1	50.8	69.2

Test case 4

Embodiment 2 and comparative example 2 are subjected to long-term operation, evaluate stability, the results are shown in Table 6.

Table 6

It can be seen that the Heavy oil hydrogenation method provided by the present invention with preferable and complete from the result of table 5 and table 6 Metal, sulphur and the carbon residue removal activity and long-term operation stability in face are high.It can be seen that the heavy oil provided by the present application adds Hydrogen methods can not only obtain higher metal, sulphur and carbon residue removal effect, and more praiseworthy is catalyst stability height, when operating Between it is long, thus the heavy oil hydrogenation treatment method provided by the invention have preferable prospects for commercial application.

Claims

1. a kind of heavy oil hydrogenation treatment method, this method comprises: under hydrogenation conditions, by heavy oil feedstock successively with protection Agent, metal remover and desulfurization agent, the protective agent, the metal remover and the desulfurizing agent respectively contain catalyst carrier With the active metal component being carried in the catalyst carrier, which is characterized in that the protective agent, the metal remover and described The catalyst carrier of at least one of desulfurizing agent is modified support, and the modified support contains the acid of layer distributed in the carrier Property auxiliary agent and metal promoter, the acid additive is distributed in stratum nucleare, and the metal promoter is distributed in shell, the acid additive choosing From at least one of F component, P component and B component, the metal promoter is group ia metal component and/or group iia metal Component, the active metal component are the group of at least one vib metals component and at least one group VIII metal component It closes.

2. according to the method described in claim 1, wherein, the catalyst carrier of the desulfurizing agent is modified support.

3. according to the method described in claim 1, wherein, the catalysis of the protective agent, the metal remover and the desulfurizing agent Agent carrier is modified support.

4. method described in any one of -3 according to claim 1, wherein in the modified support, be distributed the acidity The stratum nucleare of auxiliary agent with a thickness of 0.1-5mm, be distributed the shell of the metal promoter with a thickness of 0.1-5mm；With the modified load On the basis of the total weight of body, the content of the metal promoter in terms of metal oxide is 0.1-15 weight %, with F, P and B tri- The content of the acid additive of kind element meter is 0.1-15 weight %.

5. according to the method described in claim 4, wherein, the metal promoter is selected from Li component, Na component, K component, Mg component With one of Ca component or a variety of.

6. method described in any one of -3 according to claim 1, wherein the modified support is by including the following steps Method is made:

(1) by the carrier Jing Guo hydro-thermal process in the alkaline solution containing the metal promoter compound for being provided with the metal promoter It is impregnated in A, is then dried；

(2) by carrier that step (1) obtains in the acid solution B containing the acid additive compound for being provided with the acid additive In impregnated, be then dried and roast.

7. according to the method described in claim 6, wherein, the pH value of the solution A is 7.5-11, and the pH value of the solution B is 2-6.5。

8. according to the method described in claim 7, wherein, in the preparation method of the modified support, the carrier is oxidation The mixture of at least one of aluminium or aluminium oxide and silica, titanium oxide and zirconium oxide；The aluminium oxide be gama-alumina, At least one of η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide.

9. according to the method described in claim 1, wherein, in the protective agent, in terms of metal oxide and with the protection On the basis of the total weight of agent, the content of the group VIII metal component is 0.1-0.9 weight %, the vib metals group The content divided is 0.1-5 weight %；

It in the metal remover, is counted by metal oxide and on the basis of the total weight of the metal remover, the Section VIII The content of race's metal component is 1.1-2.9 weight %, and the content of the vib metals component is 6.1-12.8 weight %；

It in the desulfurizing agent, is counted by metal oxide and on the basis of the total weight of the desulfurizing agent, the group VIII gold The content for belonging to component is 3.1-10 weight %, and the content of the vib metals component is 13.1-28 weight %.

10. according to the method described in claim 9, wherein, in the desulfurizing agent, the active metal component is urged along described The radial direction of agent carrier is in layer distributed, and the active metal component of stratum nucleare is Co component and Mo component, the activity gold of shell Category group is divided into Ni component and the combination selected from Mo component and/or W component；

Be distributed the shell of active metal component with a thickness of 0.1-5mm, be distributed the stratum nucleare of active metal component with a thickness of 0.1- 5mm。

11. according to the method described in claim 10, wherein, the desulfurizing agent is made by method comprising the following steps:

(a) catalyst carrier is subjected to hydro-thermal process, then the containing in alkalinity by the catalyst carrier after hydro-thermal process It is impregnated in nickel compound and the first solution of the combination of molybdenum compound and/or tungsten compound, is then dried；

(b) carrier of the step (a) after dry is soaked in acid the second solution containing cobalt compound and molybdenum compound Then stain is dried and roasts.

12. method described in any one of -3 according to claim 1, wherein with the protective agent, the metal remover and institute On the basis of the total amount for stating desulfurizing agent, the protective agent accounts for 1-20 volume %；The metal remover accounts for 15-60 volume %；It is described de- Sulphur agent accounts for 20-85 volume %, and the total amount of the protective agent, the metal remover and the desulfurizing agent is 100 volume %；

Successively include: with the condition of protective agent, metal remover and desulfurization agent by heavy oil feedstock temperature be 300-550 DEG C, hydrogen Partial pressure is 4-20MPa, volume space velocity 0.1-3.0h^-1, hydrogen to oil volume ratio 200-2500.

13. according to the method for claim 12, wherein with the protective agent, the metal remover and the desulfurizing agent On the basis of total amount, the protective agent accounts for 5-15 volume %；The metal remover accounts for 20-50 volume %；The desulfurizing agent accounts for 50-75 Volume %, and the total amount of the protective agent, the metal remover and the desulfurizing agent is 100 volume %；

Successively include: with the condition of protective agent, metal remover and desulfurization agent by heavy oil feedstock temperature be 330-480 DEG C, hydrogen Partial pressure is 6-18MPa, volume space velocity 0.15-2h^-1, hydrogen to oil volume ratio 300-2000.

14. according to the method for claim 13, wherein along logistics direction, the protective agent, the metal remover and described The catalytic activity of desulfurizing agent is gradually increased, and aperture is gradually reduced, and granularity is gradually reduced.