CN107345152A

CN107345152A - A kind of heavy oil hydrogenation treatment method

Info

Publication number: CN107345152A
Application number: CN201610291341.8A
Authority: CN
Inventors: 贾燕子; 杨清河; 李大东; 赵新强; 邵志才
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: 2017-11-14
Anticipated expiration: 2036-05-05
Also published as: CN107345152B

Abstract

The present invention relates to petrochemical industry, discloses a kind of heavy oil hydrogenation treatment method, and this method includes：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 each containing catalyst carrier and the active metal component being carried in the catalyst carrier; wherein; the catalyst carrier of at least one of the protective agent, the metal remover and the desulfurizing agent is modified support; the modified support contains the acid additive of layer distributed in the carrier, and the acid gradually enhancing from the modified support particle surface to center.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 grown, so as to which 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 industry, in particular it relates to a kind of heavy oil hydrogenation treatment method.

Background technology

The utilization rate that deep processing not only contributes to improve heavy oil is carried out to the heavy oil including residual oil, is delayed The nervous trend of energy supply is solved, while can also be reduced environmental pollution, reaches the clean utilization of the energy.By There is the characteristics of density is big, content of heteroatoms is high in residual oil, a kind of catalyst is difficult to meet that removing is a variety of miscellaneous Atom requirement and easy in inactivation, therefore residual oil hydrocatalyst generally use grading system, along reaction implements Stream direction catalyst aperture and particle diameter are gradually reduced, and catalyst hydrogenation activity gradually increases.Carbon deposit With metal deposit be cause residual oil hydrocatalyst inactivate principal element, and study show due to carbon deposit It is intended to deposit in residual oil hydrocatalyst aperture with metal deposit, this is also to cause residual hydrogenation to urge One of the main reason for agent activity can not mutually be utilized effectively.

In order to solve the above-mentioned technical problem, CN101928592B discloses a kind of grading of hydrogenation catalyst Combined method, reactor load Hydrodemetalation catalyst and desulfurizing agent respectively from top to bottom；The de- gold of hydrogenation The distribution of the active metal component and acidic assistant concentration of metal catalyst and desulfurizing agent is in uneven distribution, from urging Catalyst particles surface to center, active metal component and the acidic assistant concentration ladder of Hydrodemetalation catalyst Degree increase, the active metal component and acidic assistant concentration gradient of desulfurizing agent are reduced.However, this grade of combo Method for preparing catalyst is complicated in conjunction, energy consumption is big and the repeatability and controllability of the preparation method are poor.

The content of the invention

The invention aims to overcome all kinds of catalyst actions in existing heavy oil hydrogenation treatment method The shortcomings that can not effectively playing, there is provided one kind can realize comprehensive demetalization, desulfurization, de- carbon residue effect and It is not easy to form carbon deposit, there is the heavy oil hydrogenation treatment method of high stability.

The present inventor is had found by studying, if can be by the catalyst carrier of heavy-oil hydrogenation catalyst On acid additive be prepared into double-deck or Multi-layers distributing, with reactant molecule along outside catalyst granules to Diffusion inside comes into contact with acid stronger acid additive, is beneficial to metal deposit and carbon deposit edge is urged Agent radial direction is uniformly distributed, so as to improve the activity of residual oil hydrocatalyst and stability.

Therefore, the invention provides a kind of heavy oil hydrogenation treatment method, this method includes：In hydrogenation reaction Under the conditions of, by heavy oil feedstock successively with protective agent, metal remover and desulfurization agent, the protective agent, The metal remover and the desulfurizing agent each containing catalyst carrier and are carried in the catalyst carrier Active metal component, wherein, in the protective agent, the metal remover and the desulfurizing agent at least The catalyst carrier of one is modified support, and the modified support contains the acidity of layer distributed in the carrier Auxiliary agent, and the acid gradually enhancing from the modified support particle surface to center.

In heavy oil hydrogenation treatment method provided by the invention, by protective agent, metal remover and desulfurization The catalyst carrier of at least one of agent is modified so that modified catalyst carrier is (i.e. modified to carry Body) in acid additive acid from modified support particle surface to center increase in layer distributed and gradually By force, such reactant molecule along outside catalyst granules internally diffusion can come into contact with it is acid stronger Acid additive, be beneficial to metal deposit and carbon deposit being uniformly distributed along catalyst radial direction so that institute All kinds of catalyst actions can effectively be played by stating heavy oil hydrogenation treatment method, for heavy distillate and residual oil Hydrogenation can effectively control catalyst with more preferable demetalization, desulfurization, de- carbon residue activity and stability The temperature rise of bed, slow down the deactivation rate of catalyst, extend the service cycle of catalyst.

Moreover, the preparation method of the catalyst carrier used in the present invention is relatively easily implemented, energy consumption It is smaller, and the repeatability and controllability of the preparation method are preferable.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Embodiment

The embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The end points of disclosed scope and any value are not limited to the accurate scope or value herein, this A little scopes or value should be understood to comprising the value close to these scopes or value.For number range, respectively Between the endpoint value of individual scope, between the endpoint value of each scope and single point value, and single point Can be combined with each other between value and obtain one or more new number ranges, these number ranges should by regarding For specific disclosure herein.

The invention provides a kind of heavy oil hydrogenation treatment method, this method includes：Under hydrogenation conditions, By heavy oil feedstock successively with protective agent, metal remover and desulfurization agent, the protective agent, the de- gold Category agent and the desulfurizing agent are each containing catalyst carrier and the activity gold being carried in the catalyst carrier Belong to component, wherein, at least one of the protective agent, the metal remover and described desulfurizing agent are urged Agent carrier is modified support, and the modified support contains the acid additive of layer distributed in the carrier, and The acid gradually enhancing from the modified support particle surface to center.

In the modified support, " layer distributed " of the acid additive refers to acid additive in carrier Middle uneven distribution, in the different radii regional extent of modified support particle the species of acid additive and/ Or the distribution of concentration is different.For example, layer distributed can refer to same acid additive in carrier granular Concentration distribution in different radii regional extent is different or refers in the different radii area of carrier granular Different types of acid additive is distributed in the range of domain, is possibly even the combination of both.

In the modified support, " the acid gradually enhancing from the modified support particle surface to center " is From the surface of carrier granular to center, acidity is in enhancing trend to finger, and the trend of this enhancing does not limit particularly It is fixed, can be linear, specific function relation or gradient or random enhancing trend. When containing a kind of acid additive in the modified support, described acidity refers to the different dense of acid additive Degree distribution, concentration is higher then acid stronger, and concentration is relatively low then acid weaker；Contain when in the modified support When having two or more acid additives, described acidity refers to the difference point of different acid acid additives Cloth, acid strong acidic assistant concentration is significantly higher then acid stronger, the concentration of acid strong acid additive It is obvious weaker then acid weaker.

In the present invention, if in the protective agent, the metal remover and the desulfurizing agent at least one The catalyst carrier of person is that modified support is the goal of the invention that the present invention can be achieved, to realize de- gold comprehensively Category, desulfurization, the effect of de- carbon residue, under preferable case, in order to further improve demetalization, desulfurization and de- The effect of carbon residue, the catalyst carrier of the desulfurizing agent is the modified support, that is to say, that at least institute The catalyst carrier for stating desulfurizing agent is the modified support, the catalysis of the protective agent and the metal remover Agent carrier can be optionally the modified support.

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

In the modified support, the species of the acid additive can be the conventional selection of this area, Under preferable case, the acid additive is selected from F (fluorine) component, P (phosphorus) components and B (boron) component At least one of.Under normal circumstances, between F components, P components and B component three, F components Acidity it is most strong, the acidity of P components is taken second place, B component acidity it is most weak.In the present invention, the F Component, the P components and the B component can by it is various it is conventional in the form of exist, such as can be with list The form of matter is present, and can also exist in the form of compound.Compound containing F for example can be fluorination One or more in ammonium, ammonium acid fluoride, hydrofluoric acid, sodium fluoride and calcirm-fluoride.Compound example containing P Such as can be the one or more in phosphoric acid, Diammonium phosphate (DAP), sodium dihydrogen phosphate and potassium dihydrogen phosphate.Containing B Compound for example can be boric acid, metaborate and borate in one or more.

In the modified support, on the basis of the gross weight of the modified support, with F, P and B tri- The content of the acid additive of kind element meter can be 0.1-15 weight %, such as can be 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 weight %, 2.2 weight %, 2.5 weight %, 2.7 weight %, 2.9 weight %, 3.0 weight %, 3.5 weight %, 4 weight %, 4.5 weight %, 5 weights Measure %, 5.5 weight %, 6 weight %, 6.5 weight %, 7 weight %, 7.5 weight %, 8 weight %, 8.5 weight %, 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 Value between weight %, 15 weight % or foregoing any two numerical value.In the preferred case, described In modified support, on the basis of the gross weight of the modified support, in terms of tri- kinds of elements of F, P and B The content of the acid additive is 0.2-12 weight %, more preferably 0.3-8 weight %, further preferably It is still more preferably 2-4 weight % for 1-5 weight %.In the present invention, " with F, P and B tri- The content of the acid additive of kind element meter " refers to the weight of the acid additive with F, P and B tri- The gross weight of kind of element is measured for representative, wherein, when the acid additive does not include F, P With one kind in tri- kinds of elements of B, or at two kinds, " acidity in terms of tri- kinds of elements of F, P and B The content of auxiliary agent " also includes such case, simply remove naturally do not include that member usually measure The content of the acid additive.

A preferred embodiment of the invention, in the modified support, the acid additive choosing At least two from F components, P components and B component, and make when the modified support contains F components For acid additive when, it is gradual from concentration of the modified support particle surface to center F components in terms of F elements It is incremented by, it is highly preferred that the distribution factor σ of F components_F(R) for less than 0.25 (be preferably less than 0.22, More preferably 0.10-0.22, most preferably 0.12-0.20), σ_F(2/3R) is that 0.28-0.5 (is preferably 0.30-0.45, more preferably 0.32-0.42), σ_F(1/3R) is that 0.55-0.85 (is preferably 0.60-0.85, more Preferably 0.75-0.85)；When the modified support contains P components as acid additive and is free of F components When, the concentration from the modified support particle surface to center P components in terms of P element is gradually incremented by, more excellent Selection of land, the distribution factor σ of P components_P(R) (it is preferably less than 0.22, more preferably for less than 0.25 0.10-0.22, most preferably 0.12-0.20), σ_P(2/3R) is that 0.28-0.5 (is preferably 0.30-0.45, more Preferably 0.32-0.42), σ_P(1/3R) is that 0.55-0.85 (is preferably 0.60-0.85, more preferably 0.75-0.85).According to the preferred embodiment, acid stronger acid additive is set more to be distributed in Close to the central area of catalyst carrier, so as to more advantageously improve demetalization, desulfurization and de- carbon residue Effect.In above-mentioned preferred embodiment, " gradually be incremented by " refer to from the surface of carrier granular to The content of the corresponding acid additive element in center is in increase tendency, and the trend of this increase does not limit particularly It is fixed, can be linear, specific function relation or gradient or random increase tendency.

In the present invention, the distribution factor σ of acid additive is used to represent point of the acid additive along carrier radial direction Cloth rule, represent acid additive at the content of a certain opening position acid additive element of particle and center with σ The ratio between content of acid additive element, if σ>1, then show this acid additive constituent content higher than modification At carrier granular center；If σ=1, show in this acid additive constituent content and modified support particle It is identical at the heart；If σ<1, then show that this acid additive constituent content is less than at modified support granular center. For example, in σ_FIn (1/3R), R is particle radius, so that, as starting point, F is at modified support granular center Refer to the F components in terms of F elements, specifically, σ_F(1/3R) refers to from modified support center at 1/3R F constituent contents and the modified support center at the ratio between F constituent contents.In the particle of modified support The content distribution of acid additive element uses SEM-EDX (Scanning Electron Microscope-Energy Dispersive Spectrometry) method analyzed.

A preferred embodiment of the invention, the modified support are the sides by comprising the following steps Method is made：Carrier Jing Guo hydro-thermal process is repeatedly impregnated and dried successively, and will last time Obtained desciccate is calcined, wherein, maceration extract used, which contains, in each dipping process is provided with phase With or different acid additive compound, frequency n >=2 repeated, and as n >=3, from the 2nd It is secondary be impregnated into (n-1)th dipping during, the temperature dried after impregnating each time than before adjacent once The temperature dried after dipping is high 20-150 DEG C, preferably 30-120 DEG C, more preferably 30-80 DEG C；It is each After secondary dipping dry time than after adjacent preceding single-steeping dry time long 1-10 hours, preferably 1-9 hours, more preferably 2-5 hours.

In the preparation method of above-mentioned modified support, carrier after hydro-thermal process is close due to surface hydroxyl Degree increase and it is negatively charged, after being immersed in maceration extract, in maceration extract offer acid additive change Compound is easily enriched in the surface of carrier, and after the carrier drying after first time is impregnated, surface hydroxyl is close Degree is reduced, and the position of hydroxy density maximum is moved along the radial direction of carrier toward carrier center on carrier Move, after being immersed in another maceration extract, the change of the offer acid additive in another maceration extract Compound is easy to be enriched in the hydroxy density maximum in carrier, as dipping time n >=3, from During being impregnated into (n-1)th dipping for 2nd time, by control impregnate after the temperature dried and dry Time gradually increases with dipping time, enables to the position of hydroxy density maximum in carrier gradual Toward carrier center migrate, and and then make every time dipping use maceration extract in offer acid additive chemical combination Thing is adsorbed on the diverse location of carrier, and acid additive is finally obtained after roasting in layer distributed Modified support.

In the preparation method of above-mentioned modified support, the species of the carrier can be the conventional choosing of this area Select, for example, can be aluminum oxide, or in aluminum oxide and silica, titanium oxide and zirconium oxide extremely A kind of few mixture.Wherein, the aluminum oxide for example can be gama-alumina, η-aluminum oxide, θ-oxygen Change at least one of aluminium, δ-aluminum oxide and χ-aluminum oxide.Above-mentioned carrier can be commercially available, It can be prepared according to well known to a person skilled in the art various methods.For example, alumina support can be with By the way that aluminum oxide precursor is calcined, make its be converted into gama-alumina, η-aluminum oxide, θ-aluminum oxide, δ- At least one of aluminum oxide and χ-aluminum oxide and be prepared.Optionally, before firing and/or it Afterwards, first aluminum oxide precursor can be molded, to prepare shape (such as ball required for suitable practical operation Shape, sheet, bar shaped etc.).The shaping can be carried out according to the conventional method in this area, as rolling ball method, Pressed disc method and extrusion method etc..In forming process, such as during extruded moulding, in order to ensure to be molded Be smoothed out, water, extrusion aid and/or peptizing agent can be added into the aluminum oxide precursor, and appoint Choosing adds expanding agent, then extrusion molding, is dried and is calcined afterwards.The extrusion aid, peptizing agent It is known to the skilled person with the species and dosage of expanding agent, for example, common extrusion aid can select From at least one of sesbania powder, methylcellulose, starch, polyvinyl alcohol and PVOH, the peptization Agent can be organic acid and/or organic acid, and the expanding agent can be starch, synthetic cellulose, polymeric alcohol At least one of with surfactant.Wherein, the synthetic cellulose be preferably hydroxymethyl cellulose, At least one of methylcellulose, ethyl cellulose and hydroxyl fiber fat alcohol polyethylene ether.It is described poly- It is preferably at least one of polyethylene glycol, poly- propyl alcohol and polyvinyl alcohol to close alcohol.The surfactant is excellent Elect fat alcohol polyethylene ether, fatty alkanol amide and its derivative as, the propylene that molecular weight is 200-10000 At least one of alcohol copolymer and maleic acid copolymer.The condition for extruding bar drying is generally included： Drying temperature can be 40-350 DEG C, preferably 100-200 DEG C；Drying time can be 1-24 hours, Preferably 2-12 hours.The condition of dried extrusion bar roasting is generally included：Sintering temperature can be with For 350-1000 DEG C, preferably 600-950 DEG C；Roasting time can be 1-10 hours, preferably 2-6 Hour.In addition, the aluminum oxide precursor can be selected from hibbsite, monohydrate alumina, nothing Shape at least one of aluminium hydroxide etc..The carrier can be cloverleaf pattern, butterfly, cylinder, Hollow cylindrical, quatrefoil, five shapes such as leaf, spherical.

In the preparation method of above-mentioned modified support, the carrier needs advanced water-filling heat treatment, the present invention The condition of the hydro-thermal process is not particularly limited, for example, the condition of the hydro-thermal process can wrap Include：Temperature is 50-200 DEG C (be preferably 60-180 DEG C, more preferably 70-150 DEG C), time 5-30 Hour (being preferably 8-28 hours, more preferably 10-24 hours).

, it is necessary to which the carrier of hydro-thermal process is repeatedly carried out successively in the preparation method of above-mentioned modified support Impregnate and dry, wherein, the compound of acid additive is provided in the maceration extract used in each dipping process Species can be with identical, can also be different, preferably different, the modified hydrogen at-ing catalyst so enabled to Carrier can converge the advantages of a variety of different acid additives, particularly, can help acid stronger acidity Agent (such as F components) is relatively centrally distributed in the centre of modified support.

In the preparation method of above-mentioned modified support, there is provided the compound of acid additive can be to provide F groups At least one of compound of compound, the compound of offer P components or offer B component divided.

Wherein, there is provided the compound of F components for example can be ammonium fluoride, ammonium acid fluoride, hydrofluoric acid, fluorine Change the one or more in sodium and calcirm-fluoride.

Wherein, there is provided the compound of P components for example can be phosphoric acid, Diammonium phosphate (DAP), sodium dihydrogen phosphate and One or more in potassium dihydrogen phosphate.

Wherein, there is provided the compound of B component for example can be one in boric acid, metaborate and borate Kind is a variety of.

It is no especially to the species of solvent in the maceration extract in the preparation method of above-mentioned modified support Limit, can be the inertia liquid object of the existing various compounds that the offer acid additive can be provided Matter, for example, water, alcohol (such as methanol, ethanol 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, every time in dipping maceration extract used The content for providing the compound of acid additive can be with identical, can also be different, and is each independently 1-100 G/l, preferably 5-50 g/l, more preferably 5-15 g/l.Further, every time used in dipping The dosage of maceration extract can be with identical, can also be different, and relative to the 100g carrier, often The dosage of maceration extract used in secondary dipping can be each independently 20-200mL, preferably 50-100mL. Such content range of compound for providing acid additive and the dosage of maceration extract can cause above-mentioned In modified support, on the basis of the gross weight of the modified support, in terms of tri- kinds of elements of F, P and B The content of the acid additive is 0.1-15 weight %, more preferably 0.2-12 weight %, further excellent Elect 0.3-8 weight % as.

In the preparation method of above-mentioned modified support, the acid-base property of the maceration extract is not limited especially It is fixed, for example, can be acid, alkaline, neutral maceration extract.Preferably, preceding n-1 dipping Used maceration extract is in acidity, and maceration extract is in alkalescence used by n-th dipping.It is highly preferred that The pH value of maceration extract is 2-6 used by preceding n-1 dipping.It is highly preferred that n-th dipping is used The pH value of maceration extract be 8-11.It was found by the inventors of the present invention that work as the acid-base property of the maceration extract The control layer distributed of more favourable acid additive on carrier in preferable scope more than, so as to make to obtain Modified support be prepared into after hydrogenation catalyst, be more beneficial for improve heavy-oil hydrogenation treatment effect.

Wherein, the maceration extract is adjusted into the method to alkalescence typically toward adding in the maceration extract Alkaline matter, for example, in ammoniacal liquor, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc. at least It is a kind of.And acidity may be just presented in the maceration extract of the compound containing at least one of F, P and B in itself, , can be toward adding acidic materials in the maceration extract if acid or acid degree deficiency is not presented (for example, at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc.) with by the maceration extract adjust to Expected acidity.

In the preparation method of above-mentioned modified support, the number of the dipping can change according to what is obtained Property carrier carry out reasonable selection, but from the complexity of preparation process and the effect of the modified support obtained Consider, it is preferable that 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 the carrier Jing Guo hydro-thermal process and ensureing first Carrier after secondary dipping, which is dried, can just make acid additive be in layer distributed on carrier；When dipping During number n >=3, as long as the condition dried using the carrier by hydro-thermal process and after ensureing repeatedly dipping is expired The above-mentioned specific condition of foot can just make acid additive be in layer distributed on carrier.

A preferred embodiment of the invention, as dipping time n=2, dipping is made for the first time The compound of offer acid additive in maceration extract is to provide the compound of F components, second of dipping The compound of offer acid additive in used maceration extract is to provide the compound of P components and/or carry For the compound of B component.

According to another preferred embodiment of the present invention, as dipping time n=3, institute is impregnated for the first time The compound of offer acid additive in the maceration extract used is soaked for the second time to provide the compound of F components The compound of offer acid additive in maceration extract used in stain is to provide the compound of P components, the 3rd The compound of offer acid additive in maceration extract used in secondary dipping is to provide the compound of B component.

It is not special to the drying condition after dipping every time in the preparation method of above-mentioned modified support Limit, the condition for drying the carrier after impregnating that this area is conventional can be used, as long as it disclosure satisfy that Difference is stated, for example, the immersion condition of different impregnation steps can be with identical, can also be different, and It can be 20-300 DEG C, preferably 50-100 DEG C generally to include dipping temperature independently of one another；Dip time It can be 1-20 hours, preferably 1-6 hours.

Under preferable case, the condition dried after impregnating for the first time includes：Temperature is 30-300 DEG C 50-300 DEG C, more preferably 100-250 DEG C, most preferably 100-150 DEG C), the time is that 1-20 hours are (excellent Elect 2-18 hours, more preferably 3-10 hours, most preferably 3-8 hours as).The drying can be Vacuum drying.

Under preferable case, the condition that last time is dried after impregnating includes：Temperature be 30-300 DEG C (preferably For 50-300 DEG C, more preferably 100-200 DEG C, most preferably 120-180 DEG C), the time is 1-20 hours (being preferably 2-18 hours, more preferably 3-10 hours, most preferably 3-5 hours).The drying can Think vacuum drying.

In the preparation method of above-mentioned modified support, the condition of roasting is not particularly limited, for example, The condition of the roasting can include：It (is preferably 300-800 DEG C, more preferably that temperature, which is 300-900 DEG C, 350-500 DEG C), the time is 1-10 hours (being preferably 2-8 hours, more preferably 2-6 hours).

In the present invention, the protective agent can be the conventional hydrogenation protecting agent in this area.The protective agent Containing active metal component and catalyst carrier (being preferably above-mentioned modified support), wherein, the activity Metal component is at least one group VIII metal component and at least one vib metals component. Under preferable case, counted by metal oxide and on the basis of protectant gross weight, the VIII The content of race's metal component is more than 0 weight % and is less than or equal to 1 weight % (for example, 0.1-0.9 weight %), The content of the vib metals component is more than 0 weight % and less than or equal to 6 weight % (for example, 0.1-5 Weight %).

In the present invention, the metal remover can be the conventional HDM agent in this area.It is described de- Metal agent contains active metal component and catalyst carrier (being preferably above-mentioned modified support), wherein, institute It is at least one group VIII metal component and at least one vib metals group to state active metal component Point.In the preferred case, counted and on the basis of the gross weight of the metal remover by metal oxide, institute The content of group VIII metal component is stated as 1-3 weight % (being preferably 1.1-2.9 weight %), described the The content of group vib metal component is 6-13 weight % (being preferably 6.1-12.8 weight %).

In the present invention, the desulfurizing agent can be the conventional hydrogen desulfurization agent in this area.The desulfurizing agent Containing active metal component and catalyst carrier (being preferably above-mentioned modified support), wherein, the activity Metal component is at least one group VIII metal component and at least one vib metals component. Under preferable case, counted by metal oxide and on the basis of the gross weight of the desulfurizing agent, the VIII The content of race's metal component is 3-15 weight % (being preferably 3.1-10 weight %), and the vib is golden The content for belonging to component is 13-30 weight % (being 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.The vib metals 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 catalytic activity of the metal remover and the desulfurizing agent gradually increases.In one embodiment, The active metal component content in active metal component content, the metal remover in the protective agent with And the active metal component content in the desulfurizing agent gradually increases.

In a preferred embodiment, in order to further improve demetallization per, desulfurization degree and de- carbon yield, In the desulfurizing agent, radial direction of the active metal component along the catalyst carrier is in layering Distribution, the active metal component of stratum nucleare is Co components and Mo components, and the active metal component of shell is Ni components and the combination selected from Mo components and/or W components.In the preferred embodiment, by making Ni components and active metal component selected from Mo components and/or W components are distributed in the shell of desulfurizing agent, And Co components and Mo components is set to be distributed in the stratum nucleare of desulfurizing agent so that the condensed ring of more difficult reaction in heavy oil Aromatic hydrocarbons first touches the higher Ni components of hydrogenation activity and Mo components and/or W groups during the course of the reaction Point, it is hydrogenated with saturation open loop so that the various materials for needing to remove expose in succession, further to catalyst Diffusion inside, hydrodesulfurization activity higher Co components and Mo components are touched, utilizes different activities The reaction characteristicses of metal component, optimum organization, so as to obtain higher activity.

Here, introducing the concept of " shell " and " stratum nucleare ", but the explanation desulfurizing agent is not it With two separable layers each other, but in order to illustrate there are two different activity in the desulfurizing agent The distributed areas of metal component, and the two distributed areas are in stratiform, and one is located at the desulfurizing agent The central area of grain, i.e. referred to as stratum nucleare, another is located at the surface region of the sorbent particle, that is, claimed For shell.

It should be noted that " active metal component of stratum nucleare is Co components and Mo components, the work of shell Property metal component be Ni components and the combination selected from Mo components and/or W components " refer to carry along modified The radial direction of body, the active metal component being carried in modified support is in layer distributed, forms similar stratum nucleare With the structure of shell, wherein, the active metal component of stratum nucleare is mainly Co components and Mo components, A small amount of other active metal components such as Ni components and/or W components can be distributed with；The active metal of shell Component is mainly Ni components and the combination selected from Mo components and/or W components, can also be distributed with a small amount of Other active metal components such as Co components.SEM-EDX (Scanning Electron are used in the present invention Microscope-Energy Dispersive Spectrometry) method analyzes active metal group in the desulfurizing agent Divide the distribution along particle radial direction, and represent active metal component element along desulfurizing agent with distribution factor σ Particle diameter to the regularity of distribution.The distribution factor σ is active metal component in a certain position of catalyst granules Put the content at place with center content the ratio between, if σ=1, show that this active metal component element contains Amount is identical with center；If σ<1, then show this active metal component constituent content less than at center. Wherein, in the desulfurizing agent, the distribution factor σ of the Ni components of sorbent particle outer layer (i.e. shell) ＞ 1, and the distribution factor σ ＜ 1 of the Co components of sorbent particle outer layer (i.e. shell).

In the desulfurizing agent, the thickness of the shell and stratum nucleare is not particularly limited, for example, described The thickness of 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 0.15-3.5.Wherein, The thickness of the shell refers to the thickness of the part of the distribution factor σ of the Ni components >=2.0, and the core Thickness degree refers to the thickness of the parts of 0.5≤σ of distribution factor ＜ 1 of Co components.In the present invention, it is described The thickness of shell and stratum nucleare is measured using SEM-EDX methods, specifically, randomly selects 30 desulfurizing agents And its cross section and particle diameter are measured with SEM, obtained respectively along each desulfurizing agent radial scan with EDX afterwards To Ni components radial distribution and obtain the thickness of the part of σ >=2.0, take the arithmetic mean of instantaneous value of above-mentioned thickness The thickness of shell as of the present invention；And obtained respectively along each desulfurizing agent radial scan with EDX The radial distribution of Co components and the thickness for obtaining the parts of 0.5≤σ ＜ 1, take the arithmetic mean of instantaneous value of above-mentioned thickness The thickness of stratum nucleare as of the present invention.

In the desulfurizing agent, counted by metal oxide and on the basis of the gross weight of the catalyst, Co The content of component can be 0.5-15 weight %, more preferably 2-8 weight %, more preferably 3-7 Weight %, most preferably 3-5 weight %.

In the desulfurizing agent, counted by metal oxide and on the basis of the gross weight of the catalyst, The content of Mo components can be 5-25 weight %, more preferably 8-20 weight %, be more preferably 10-20 weight %, most preferably 15-20 weight %.

In the desulfurizing agent, counted by metal oxide and on the basis of the gross weight of the catalyst, Ni The content of component can be 0.5-15 weight %, more preferably 2-8 weight %, more preferably 3-7 Weight %, most preferably 3-5 weight %.

In the desulfurizing agent, counted by metal oxide and on the basis of the gross weight of the catalyst, W The content of component can be 0-35 weight %, more preferably 5-30 weight %, more preferably 10-30 Weight %, most preferably 15-25 weight %.

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

In the present invention, because the desulfurizing agent is typically to be passed through after modified support loads upper active metal component Prepared by crossing roasting, therefore, above-mentioned active metal component are generally aoxidized in the desulfurizing agent with metal The form of thing is present, and the present invention is also not limited to this certainly, the active metal component can also be with The form of the compound of the offer active metal component in addition to an oxide is present.

Wherein, the metal oxide form as Co can be CoO, the metal oxide as Ni Form can be NiO, and the metal oxide form as Mo can be MoO₃, the metal as W Oxide form can be WO₃。

Wherein, the compound of the offer Co in addition to CoO for example can be cobalt carbonate (CoCO₃)、 Cobalt nitrate (CoNO₃), cobalt acetate (Co (AcO)₃), basic cobaltous carbonate (2CoCO₃·3Co(OH)₂·H₂O) With cobalt chloride (CoCl₂) in one or more.The cobalt compound for providing Co is preferably cobalt oxide (CoO), cobalt carbonate (CoCO₃), cobalt nitrate (CoNO₃), cobalt acetate (Co (AcO)₃), alkali formula Cobalt carbonate (2CoCO₃·3Co(OH)₂·H₂) and cobalt chloride (CoCl O₂) in one or more.

Wherein, the compound of the offer Ni in addition to NiO for example can be nickelous carbonate (NiCO₃)、 Nickel nitrate (NiNO₃), nickel acetate (Ni (AcO)₃), basic nickel carbonate (NiCO₃·2Ni(OH)₂·4H₂O) With nickel chloride (NiCl₂) in one or more.The nickel compound for providing Ni is preferably nickel oxide (NiO), nickelous carbonate (NiCO₃), nickel nitrate (NiNO₃), nickel acetate (Ni (AcO)₃), alkali formula carbon Sour nickel (NiCO₃·2Ni(OH)₂·4H₂) and nickel chloride (NiCl O₂) in one or more.

Wherein, except MoO₃The compound of offer Mo in addition for example can be ammonium molybdate ((NH₄)₂MoO₄), ammonium paramolybdate ((NH₄)₆Mo₇O₂₄), ammonium dimolybdate ((NH₄)₂Mo₂O₇), seven Ammonium molybdate ((NH₄)₆Mo₇O₂₄) and ammonium tetramolybdate ((NH₄)₂Mo₄O₁₃) in one or more.I.e. The molybdenum compound for providing Mo is preferably molybdenum oxide (MoO₃), ammonium molybdate ((NH₄)₂MoO₄), secondary molybdenum Sour ammonium ((NH₄)₆Mo₇O₂₄), ammonium dimolybdate ((NH₄)₂Mo₂O₇), ammonium heptamolybdate ((NH₄)₆Mo₇O₂₄) With ammonium tetramolybdate ((NH₄)₂Mo₄O₁₃) in one or more.

Wherein, except WO₃The compound of offer W in addition for example can be ammonium tungstate ((NH₄)₁₀W₁₂O₄₁), ammonium metatungstate ((NH₄)₆H₂W₁₂O₄₀), ammonium paratungstate and ethyl ammonium metatungstate In one or more.The tungsten compound for providing W is preferably tungsten oxide (WO₃), ammonium tungstate ((NH₄)₁₀W₁₂O₄₁), ammonium metatungstate ((NH₄)₆H₂W₁₂O₄₀), ammonium paratungstate and ethyl ammonium metatungstate In one or more.

In the present invention, the desulfurizing agent can also contain the conventional adjuvant component in other this areas, example Such as Si.

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

(a) catalyst carrier (being preferably modified support as described above) is subjected to hydro-thermal process, Then the catalyst carrier after hydro-thermal process is contained into nickel compound and molybdenum compound and/or tungsten in alkalescence Impregnated in first solution of the combination of compound, be then dried；

(b) by the dried carrier of step (a) in the of acidity containing cobalt compound and molybdenum compound Impregnated in two solution, be then dried and be calcined.

In the above-mentioned method for preparing the desulfurizing agent, although as long as before supported active metals component, The modified support is first subjected to hydro-thermal process, and by the control of the first solution for alkalescence and by the second solution It is in point to control as acid radial direction of the active metal component along the modified support that can be achieved Layer distribution (being, for example, double-deck distribution), but in order to further improve the controllability of preparation process and repeatability, Preferably, in step (a), the condition of hydro-thermal process includes：Temperature is 50-200 DEG C (further excellent Elect 60-180 DEG C, more preferably 70-150 DEG C as), the time is 5-30 hours (more preferably 8-28 Hour, more preferably 10-24 hours).

Wherein, the nickel compound, molybdenum compound, tungsten compound, cobalt compound can be each corresponding The compound of the oxide of metal and the corresponding metal component of offer as hereinbefore defined, herein not Repeat again.And molybdenum compound is selected independently of one another used by step (a) and step (b), Can be with identical or different.

Wherein, first solution is alkaline that the alkaline matter that this area can be used conventional causes institute The first solution alkaline is stated, such as ammoniacal liquor, sodium hydroxide, potassium hydroxide, sodium carbonate, carbon can be used One or more in sour potassium etc., to cause first solution for alkalescence.Under preferable case, described The pH value of one solution is 7.5-11, more preferably 8-11.

Wherein, second solution is acid that the acidic materials that this area can be used conventional cause institute The second solution is stated in acidity, such as one kind or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc. can be used Kind, to cause second solution in acidity.Under preferable case, the pH value of second solution is 2-6.5, More preferably 2-6, it is still more preferably 4-6.

The present invention is not particularly limited to the species of solvent in first solution, can be existing various The inertia liquid object of the nickel compound, molybdenum compound and/or tungsten compound can be dissolved in the basic conditions Matter, for example, water, alcohol (such as methanol, ethanol 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 first solution, The total content of molybdenum compound and tungsten compound can be 10-20 g/l.

The present invention is not particularly limited to the species of solvent in second solution, can be existing various The inertia liquid of the cobalt compound and molybdenum compound can be dissolved in acid condition, for example, can With selected from water, alcohol (such as methanol, ethanol etc.), ether (such as ether), aldehyde (such as formaldehyde) and ketone At least one of (such as acetone).In addition, cobalt compound and molybdenum compound in second solution Total content can be 10-20 g/l.

According to the present invention, in step (a) and (b), the modified support and the first solution and second are molten The dosage of liquid can make in obtained desulfurizing agent, in terms of metal oxide and with the gross weight of the desulfurizing agent On the basis of, the content of Co components is 0.5-15 weight %, preferably 2-8 weight %, more preferably 3-7 Weight %, most preferably 3-5 weight %；The content of Mo components is 5-25 weight %, preferably 8-20 Weight %, more preferably 10-20 weight %, most preferably 15-20 weight %；The content of Ni components is 0.5-15 weight %, preferably 2-8 weight %, more preferably 3-7 weight %, most preferably 3-5 weight %；The content of W components is 0-35 weight %, more preferably preferably 5-30 weight %, 10-30 weight %, most preferably 15-25 weight %.

According to the present invention, the present invention is to the condition of the dipping in step (a) and step (b) without spy Do not limit, can be with identical or different, as long as enabling to active metal component to be supported on modified support , for example, the condition of dipping can include：Temperature is 50-300 DEG C, preferably 50-100 DEG C；When Between be 1-20 hours, preferably 1-6 hours.

In addition, step (a) and the drying described in step (b) can be vacuum drying.The drying Condition can be the conventional selection of this area, for example, in step (a), dry condition can wrap Include：Temperature is 30-300 DEG C (be preferably 50-300 DEG C, more preferably 100-250 DEG C), time 1-20 Hour (being preferably 2-18 hours, more preferably 3-10 hours).

For example, in step (b), dry condition can include：Temperature is 80-200 DEG C 80-180 DEG C, more preferably 80-150 DEG C), the time be 1-10 hours (be preferably 2-8 hours, it is more excellent Elect 2-6 hours as).

According to the present invention, to the roasting in step (b), there is no particular limitation, can use this area The roasting condition of conventional desulfurizing agent, for example, in step (b), the condition of roasting can include：Temperature It is that 1-10 is small to spend for 300-900 DEG C (be preferably 300-800 DEG C, more preferably 400-600 DEG C), time When (be preferably 2-8 hours, more preferably 2-6 hours).

According to the present invention, above-mentioned preparation method can also include desulfurizing agent loading upper other this areas routine Adjuvant component, such as Si.Such adjuvant component can be incorporated into described de- in the conventional method in this area It in sulphur agent, such as can introduce, can be introduced in supported active metals component when preparing modified support, Or before supported active metals component, individually by the solution containing the compound for being provided with adjuvant component Immersive contact is carried out with modified hydrogen at-ing catalyst carrier, and the mode of drying and roasting (dipping, is dried and roasted The condition of burning can use the condition that above any one place records to carry out), this present invention is had no especially Restriction.

In the heavy oil hydrogenation treatment method provided by the invention, along logistics direction, the protective agent, The catalytic activity of the metal remover and the desulfurizing agent gradually increases, and aperture is gradually reduced, and granularity is gradual Reduce.The pore volume of protectant carrier can be 0.85-1.0mL/g, and specific surface area can be 0-=-100m²/ g, granularity can be 3-10mm.The pore volume of the metal remover can be 0.75-0.85mL/g, specific surface area can be 120-160m²/ g, granularity can be 1-5mm.It is described de- The pore volume of sulphur agent can be 0.3-0.75mL/g, and specific surface area can be 160-300m²/ g, granularity can be 1-2mm.In the present invention, granularity refers to the particle size of catalyst granules, when catalyst granules is ball Then granularity is represented with the diameter of spheroid during body, the then granularity cube when catalyst granules is cube The length of side represent, when catalyst granules is irregular shape then granularity with this can be screened out just The mesh size of the screen cloth of catalyst granules represents.

In the heavy oil hydrogenation treatment method provided by the invention, the reaction to heavy-oil hydrogenation processing Condition is not particularly limited, and in a preferred embodiment, the reaction condition of the hydrotreating includes： Temperature is 300-550 DEG C, more preferably 330-480 DEG C, hydrogen dividing potential drop 4-20MPa, further excellent Elect 6-18MPa, volume space velocity 0.1-3.0h as^-1, more preferably 0.15-2h^-1, hydrogen oil volume Than for 200-2500, more 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 With it is any be enough to make the heavy oil at hydrotreating reaction conditions with the catalyst (i.e. protective agent, Metal remover and desulfurizing agent) carry out in catalytic reactor, for example, the fixed bed reactors, Carried out in moving-burden bed reactor or fluidized bed reactor.

In the heavy oil hydrogenation treatment method provided by the invention, in catalyst grading composition, by body Product calculates, and the protective agent accounts for 1-20%, preferably 5-15%；The metal remover accounts for 15-60%, excellent Elect 20-50% as；The desulfurizing agent accounts for 20-85%, preferably 50-75%.

The catalyst before the use, generally can in presence of hydrogen, at a temperature of 140-370 DEG C Presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock, this presulfurization can be carried out also in device outside device In-situ sulphiding, the active metal component that it is loaded is converted into metal sulfide component.

The heavy oil hydrogenation treatment method provided by the invention, which is suitable for heavy oil particularly poor residuum, to be carried out Hydrotreating, to provide qualified feedstock oil for subsequent technique (such as catalytic cracking process).

The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality The detail in mode is applied, can be to the technical side of the present invention in the range of the technology design of the present invention Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.

It is further to note that each particular technique described in above-mentioned embodiment is special Sign, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not The repetition wanted, the present invention no longer separately illustrate to various combinations of possible ways.

In addition, various embodiments of the present invention can be combined randomly, as long as its Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.

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

The heavy oil used in following examples and comparative example is Ni constituent contents 34ppm, V element content 98ppm, density 1.041, the weight % of 19.6 weight %, S content of carbon residue 4.8, the weight of N content 0.63 % Zhenghai Iran subtracts slag.

Preparation example 1

The preparation example is used for the preparation process for illustrating alumina support used in the present invention.

Weighing the dry glue powder of 1000 grams of Chang Ling catalyst plants production, (butt is 71 weight %, wherein intending thin Diaspore content is 68 weight %, and hibbsite content is 5 weight %, and surplus is amorphous Aluminium), 30 grams of sesbania powders (Henan Lankao sesbania gum factory product) and 30g hydroxymethyl celluloses and mix equal It is even, the aqueous solution of 1200 milliliters of nitric acid containing 28g is added afterwards, and external diameter is extruded on plunger type bar extruder The Rasching ring bar for being 1mm for 2.5mm, internal diameter.Then by the wet bar of Rasching ring bar at 120 DEG C Dry 4 hours, be calcined 3 hours at 960 DEG C, obtain protecting agent carrier Z1.Using BET method Measurement obtains, and protection agent carrier Z1 pore volume is 0.95mL/g, specific surface area 90m²/g。

Weighing the dry glue powder of 2000 grams of Chang Ling catalyst plants production, (butt is 73 weight %, wherein intending thin Diaspore content is 68 weight %, and hibbsite content is 5 weight %, and surplus is amorphous Aluminium), 80 grams of sesbania powders (Henan Lankao sesbania gum factory product), 60g hydroxymethyl celluloses and 36g carbon blacks And be well mixed, the aqueous solution of 2400 milliliters of nitric acid containing 32g is added afterwards, on plunger type bar extruder It is extruded into the wet bar of butterfly that external diameter is 1.8mm.Then the wet bar of butterfly is dried 4 hours at 120 DEG C, then It is calcined 3 hours at 900 DEG C, obtains metal remover carrier Z2.Obtained using mercury injection method measurement, take off gold The pore volume for belonging to agent carrier Z2 is 0.78mL/g, specific surface area 142m²Bimodal shape is presented in/g, pore structure 55%, the 100nm-300nm holes that distribution, wherein 5nm-20nm holes account for total pore volume account for the 30% of total pore volume.

Weighing the dry glue powder of 2000 grams of Chang Ling catalyst plants production, (butt is 73 weight %, wherein intending thin Diaspore content is 68 weight %, and hibbsite content is 5 weight %, and surplus is amorphous Aluminium), 60 grams of sesbania powders (Henan Lankao sesbania gum factory product), 60g hydroxymethyl celluloses and 15g carbon blacks And be well mixed, the aqueous solution of 1800 milliliters of nitric acid containing 32g is added afterwards, on plunger type bar extruder It is extruded into the wet bar of butterfly that external diameter is 1.4mm.Then the wet bar of butterfly is dried 4 hours at 120 DEG C, then It is calcined 3 hours at 600 DEG C, obtains desulfurization agent carrier Z3.Obtained using mercury injection method measurement, desulfurizing agent Carrier Z pore volume is 0.7mL/g, specific surface area 231m²/g。

Embodiment 1

The present embodiment is used to illustrate 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, will first carry Body with 165 milliliters of temperature is 50 in 70 DEG C of hydro-thermal process 24 hours, then by the carrier after hydrothermal treatment DEG C contain 15 g/l of H₃BO₃The aqueous solution (pH value 6) saturation impregnate 1 hour, after 100 DEG C dry 3 hours, obtain being loaded with the carrier of B component；

The carrier for being loaded with B component obtained in step (1-1) is by (1-2) in 140 milliliters of temperature 50 DEG C contain 15 g/l of NH₄Dipping 1 hour in the F aqueous solution (pH value 11), then in 120 DEG C dry 3 hours, then at 400 DEG C be calcined 3 hours, 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, is mixed with 210 milliliters of molybdenum oxides and basic cobaltous carbonate Solution is (wherein, with MoO₃The concentration of the Mo elements of meter is 50 g/l, the Ni elements in terms of NiO Concentration be 10.3 g/l, solvent is water) impregnated 1 hour under room temperature (about 25 DEG C), in 120 DEG C drying 2 hours, 420 DEG C be calcined 3 hours, obtain protective agent CS1-1.

(2-2) takes 200 grams of modified support S2-1, is mixed with 190 milliliters of molybdenum oxides and basic cobaltous carbonate Solution is (wherein, with MoO₃The concentration of the Mo elements of meter is 64 g/l, the Ni elements in terms of NiO Concentration be 13 g/l, solvent is water) impregnated 1 hour under room temperature (about 25 DEG C), in 120 DEG C Drying 2 hours, 420 DEG C are calcined 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 of hydro-thermal process 12 hours, then be 50 DEG C with 160 milliliters of temperature by the carrier after hydrothermal treatment and pH value is 11 Mixed solution containing ammonium heptamolybdate and nickel nitrate is (wherein, with MoO₃The concentration of the Mo elements of meter is 80 G/l, using the concentration of the NiO Ni elements counted as 50 g/l, solvent is water) saturation impregnate 1 hour, After 100 DEG C dry 8 hours.Then, with 140 milliliters of temperature be 50 DEG C and pH value is 6 to contain The mixed solution of ammonium heptamolybdate and cobalt nitrate is (wherein, with MoO₃80 grams of the concentration of the Mo elements of meter/ Rise, using the concentration of the CoO Co elements counted as 50 g/l, solvent is water) saturation dipping 1 hour, Then dried 3 hours in 120 DEG C, be calcined 3 hours then at 400 DEG C, obtain desulfurizing agent CS3-1.

(3) catalyst grade is matched somebody with somebody and hydrotreating

The protective agent CS1-1 is broken into a diameter of 2 millimeters of particle, metal remover CS2-1 is broken A diameter of 1 millimeter of particle is broken into, desulfurizing agent CS3-1 is broken into a diameter of 0.6 millimeter of particle, It is then charged into heavy-oil hydrogenation fixed bed reactors.Assembling scheme is matched somebody with somebody using catalyst grade, along reactor stream Direction, first reactor filling protective agent and metal remover, second reactor filling metal remover and desulfurization Agent.Whole reaction unit filling ratio, is that protective agent accounts for 10%, and metal remover accounts for by volume 40%, desulfurizing agent accounts for 50%.Reaction condition is：380 DEG C of temperature, hydrogen dividing potential drop 14MPa, volume space velocity For 0.5h^-1, hydrogen to oil volume ratio 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, will first carry Body is with 155 milliliters of temperature in 150 DEG C of hydro-thermal process 10 hours, then by the carrier after hydrothermal treatment 80 DEG C contain 6 g/l of H₃BO₃The aqueous solution (pH value 2) saturation impregnate 1 hour, after 120 DEG C dry 6 hours, obtain being loaded with the carrier of B component；

The carrier for being loaded with B component obtained in step (1-1) is by (1-2) in 135 milliliters of temperature 80 DEG C contain 8 g/l of H₃PO₄The aqueous solution (pH value 2) in dipping 1 hour, after 180 DEG C dry 8 hours, obtain being loaded with the carrier of B component and P components；

The carrier for being loaded with B component and P components that (1-3) obtains step (1-2) is at 125 milliliters Temperature is 80 DEG C and contains 10 g/l of NH₄Dipping 1 hour in the F aqueous solution (pH value 10), so After 120 DEG C dry 3 hours, then at 400 DEG C be calcined 3 hours, 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, is mixed with 210 milliliters of molybdenum oxides and basic cobaltous carbonate Solution is (wherein, with MoO₃The concentration of the Mo elements of meter is 50 g/l, the Ni elements in terms of NiO Concentration be 10.3 g/l, solvent is water) impregnated 1 hour under room temperature (about 25 DEG C), in 120 DEG C drying 2 hours, 420 DEG C be calcined 3 hours, obtain protective agent CS1-2.

(2-2) takes 200 grams of modified support S2-2, is mixed with 190 milliliters of molybdenum oxides and basic cobaltous carbonate Solution is (wherein, with MoO₃The concentration of the Mo elements of meter is 64 g/l, the Ni elements in terms of NiO Concentration be 13 g/l, solvent is water) impregnated 1 hour under room temperature (about 25 DEG C), in 120 DEG C Drying 2 hours, 420 DEG C are calcined 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 of hydro-thermal process 20 hours, then be 60 DEG C with 155 milliliters of temperature by the carrier after hydrothermal treatment and pH value is 10 Containing ammonium metatungstate and nickel nitrate mixed solution (wherein, with WO₃The concentration of the W elements of meter is 100 grams / liter, using the concentration of the NiO Ni elements counted as 60 g/l, solvent is water) saturation impregnate 2 hours, After 100 DEG C dry 6 hours.Then, with 132 milliliters of temperature be 60 DEG C and pH value is 2 to contain The mixed solution of ammonium heptamolybdate and cobalt nitrate is (wherein, with MoO₃40 grams of the concentration of the Mo elements of meter/ Rise, using the concentration of the CoO Co elements counted as 60 g/l, solvent is water) saturation dipping 2 hours, Then dried 3 hours in 120 DEG C, be calcined 3 hours then at 400 DEG C, obtain desulfurizing agent CS3-2.

(3) catalyst grade is matched somebody with somebody and hydrotreating

The protective agent CS1-2 is broken into a diameter of 2 millimeters of particle, metal remover CS2-2 is broken A diameter of 1 millimeter of particle is broken into, desulfurizing agent CS3-2 is broken into a diameter of 0.6 millimeter of particle, It is then charged into heavy-oil hydrogenation fixed bed reactors.Assembling scheme is matched somebody with somebody using catalyst grade, along reactor stream Direction, first reactor filling protective agent and metal remover, second reactor filling metal remover and desulfurization Agent.Whole reaction unit filling ratio, is that protective agent accounts for 10%, and metal remover accounts for by volume 40%, desulfurizing agent accounts for 50%.Reaction condition is：380 DEG C of temperature, hydrogen dividing potential drop 14MPa, volume space velocity For 0.5h^-1, hydrogen to oil volume ratio 500.

Embodiment 3

(1) modified support is prepared

Modified support S1-3, S2-3, S3-3 are prepared according to the method for embodiment 2.

(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 MoO₃The concentration of the Mo elements of meter is 12 g/l, the Co elements in terms of CoO Concentration is 3.5 g/l, and solvent is water) impregnated 1 hour under room temperature (about 25 DEG C), in 120 DEG C of bakings Dry 2 hours, 420 DEG C are calcined 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 MoO₃The concentration of the Mo elements of meter is 95 g/l, the Co elements in terms of CoO Concentration is 18 g/l, and solvent is water) impregnated 1 hour under room temperature (about 25 DEG C), in 120 DEG C of bakings Dry 2 hours, 420 DEG C are calcined 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 of hydro-thermal process 24 hours, By the carrier after hydrothermal treatment with 160 milliliters of temperature be again 80 DEG C and pH value be 8 containing ammonium heptamolybdate, The mixed solution of nickel nitrate and ammonium metatungstate is (wherein, with MoO₃The concentration of the Mo elements of meter is 100 G/l, using the concentration of the NiO Ni elements counted as 70 g/l, with WO₃The concentration of the W elements of meter For 150 g/l, solvent is water) saturation impregnate 1 hour, after 100 DEG C dry 8 hours；Then, Mixed solution (its containing ammonium heptamolybdate and cobalt nitrate that with 140 milliliters of temperature be 80 DEG C and pH value is 4 In, with MoO₃80 g/l of the concentration of the Mo elements of meter, the concentration of the Co elements in terms of CoO are 70 g/l, solvent is water) saturation impregnate 1 hour, then in 120 DEG C dry 3 hours, then at 400 DEG C roasting 3 hours, obtain desulfurizing agent CS3-3.

(3) catalyst grade is matched somebody with somebody and hydrotreating

The protective agent CS1-3 is broken into a diameter of 2 millimeters of particle, metal remover CS2-3 is broken A diameter of 1 millimeter of particle is broken into, desulfurizing agent CS3-3 is broken into a diameter of 0.6 millimeter of particle, It is then charged into heavy-oil hydrogenation fixed bed reactors.Assembling scheme is matched somebody with somebody using catalyst grade, along reactor stream Direction, first reactor filling protective agent and metal remover, second reactor filling metal remover and desulfurization Agent.Whole reaction unit filling ratio, is that protective agent accounts for 10%, and metal remover accounts for by volume 40%, desulfurizing agent accounts for 50%.Reaction condition is：380 DEG C of temperature, hydrogen dividing potential drop 14MPa, volume space velocity For 0.5h^-1, hydrogen to oil volume ratio 500.

Embodiment 4

According to the method implementation steps (1) of embodiment 2 to (3), except that, prepare desulfurizing agent Process be：

200 grams of modified support S3-2 is taken, with 200 milliliters containing ammonium metatungstate, nickel nitrate, ammonium heptamolybdate Mixed solution with cobalt nitrate is (wherein, with WO₃The concentration of the W elements of meter is 100 g/l, with The concentration of the Ni elements of NiO meters is 60 g/l, with MoO₃40 g/l of the concentration of the Mo elements of meter, Using the concentration of the CoO Co elements counted as 60 g/l, solvent is water) soaked under room temperature (about 25 DEG C) Stain 2 hours, after 120 DEG C dry 6 hours, then at 400 DEG C be calcined 3 hours, obtain desulfurizing agent CS3-4。

Embodiment 5

According to the method implementation steps (1) of embodiment 2 to (3), except that, in step (1) In carrier Z1 and Z2 are not modified, carrier Z1 and Z2 are directly respectively used to step (2-1) Protective agent and metal remover are prepared with step (2-2).

Comparative example 1

According to the method implementation steps (1) of embodiment 2 to (3), except that, in step (1) In carrier Z1, Z2 and Z3 are not modified, directly carrier Z1, Z2 and Z3 are respectively used to walk Suddenly protective agent, metal remover and desulfurizing agent are prepared in (2-1), step (2-2) and step (2-3).

Comparative example 2

According to the method implementation steps (1) of embodiment 2 to (3), except that, step (1) The process for preparing modified support is：

200 grams of carrier Z1, Z2 and Z3 prepared by preparation example 1 are taken respectively, respectively with 160 milliliters Temperature is 40 DEG C and contains 28 g/l of H₃BO₃The aqueous solution (pH 7) impregnate 1 hour, then at 120 DEG C drying 4 hours, then 400 DEG C be calcined 3 hours, respectively obtain reference modified support DS1-1, DS2-1 and DS3-1, and these modified supports are mutually applied in subsequent step respectively.

Comparative example 3

200 grams of carrier Z1, Z2 and Z3 prepared by preparation example 1 are taken respectively, respectively with 155 milliliters Temperature is 90 DEG C and contains 25 g/l of NH₄F solution (pH 7) impregnates 1 hour, then at 120 DEG C Drying 4 hours, then it is calcined 3 hours at 400 DEG C, obtains reference modified support 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) of embodiment 2 to (3), except that, in step (1) Prepare modified support during, the drying temperature in step (1-1) and step (1-2) is 120 DEG C, and contain H₃BO₃The aqueous solution, containing H₃PO₄The aqueous solution and containing NH₄The pH of the F aqueous solution It is 7, respectively obtains reference modified support DS1-3, DS2-3 and DS3-3, and these modifications are carried Body is mutually applied in subsequent step respectively.

Test case 1

Using SEM-EDX (Scanning Electron Microscope-Energy Dispersive Spectrometry) method is analyzed the Elemental redistribution in modified support particle.Due to SEM-EDX It is mutually corresponding with the constituent content along the numerical value of carrier radial direction every bit constituent content in characterization result, though The size of the right numerical value may not represent the real content of the element, but can reflect that the element contains Amount height.Therefore, in order to represent that the regularity of distribution of the acid additive along carrier radial direction introduces distribution factor σ. With σ represent acid additive on a certain position of particle with the ratio between concentration at center (R is particle radius, with It is starting point at modified support granular center).Acid additive concentration on a certain position refers to The position (position deviation≤20nm) 20 numerical point numerations nearby is flat in SEM-EDX characterization results Average；The acid additive puts (position deviation≤20nm) 20 numbers nearby centered on concentration at center The average value of value point counting rate.If σ>1, then show that this acid additive constituent content is higher than modified support At granular center；If σ=1, show at this acid additive constituent content and modified support granular center It is identical；If σ<1, then show that this acid additive constituent content is less than at modified support granular center.Table 1 is the relevant parameter of modified support, wherein, the content (being calculated with element) of acid additive is according to feeding intake Amount is calculated.Table 2 is distribution factor of the different acid additives at diverse location on modified support.

Table 1

Table 2

Numbering	S3-1	S3-2	S3-3	DS3-1	DS3-2	DS3-3
							σ_B(R)	2.67	2.58	2.58	1.05	-	1.12
σ_B(2/3R)	2.00	1.97	1.97	0.98	-	1.35
							σ_B(1/3R)	1.05	1.34	1.34	1.01	-	0.98
σ_P(R)	-	1.54	1.54	-	-	1.36
							σ_P(2/3R)	-	2.36	2.36	-	-	1.45
σ_P(1/3R)	-	1.56	1.56	-	-	1.21
							σ_F(R)	0.18	0.19	0.19	-	0.98	1.39
σ_F(2/3R)	0.32	0.42	0.42	-	0.96	0.96
							σ_F(1/3R)	0.78	0.81	0.81	-	0.95	1.56

Test case 2

According to the method described in test case 1, unlike, measure be embodiment 1-3 desulfurizing agent Active metal component is distributed and the thickness of stratum nucleare and shell, wherein, the thickness of shell refers to Ni point The thickness of the part of cloth factor sigma >=2.0, the thickness of stratum nucleare refer to the Co parts of 0.5≤σ of distribution factor ＜ 1 Thickness.Table 3 below is the relevant parameter of desulfurizing agent, wherein, active metal component content is according to inventory It is calculated.Table 4 is distribution factor of the desulfurizing agent at diverse location.

Table 3

Table 4

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

Test case 3

Using in oil before and after inductive coupling plasma emission spectrograph (ICP-AES) measure hydrotreating Ni, V and Fe content, instrument are U.S.'s PE companies PE-5300 type plasma quantometers, Specific method be RIPP124-90 (《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, Science Press, Beijing, 1990,349-351), and demetallization per, de- carbon yield and desulfurization degree are calculated according to the following formula, As a result it is as shown in table 5 below.

Table 5

	De- Ni rates %	De- V rates %	De- carbon yield %	Desulfurization degree %
					Embodiment 1	69.3	89.2	60.1	83.1
Embodiment 2	69.5	90.0	61.0	81.5
					Embodiment 3	69.0	89.3	60.9	82.6
Embodiment 4	68.1	88.3	59.1	80.2
					Embodiment 5	67.7	87.2	58.7	79.8
Comparative example 1	58.7	70.6	47.6	65.7
					Comparative example 2	60.6	80.9	51.7	71.6
Comparative example 3	62.1	77.8	53.6	70.9
					Comparative example 4	61.3	78.9	52.9	70.5

Test case 4

Embodiment 2 and comparative example 2 are subjected to long-term operation, evaluate stability, as a result as shown in table 6.

Table 6

Can be seen that the Heavy oil hydrogenation method provided by the present invention from the result of table 5 and table 6 has Preferable and comprehensive metal, sulphur and carbon residue removal activity and long-term operation stability height.As can be seen here, The Heavy oil hydrogenation method provided by the invention can not only obtain higher metal, sulphur and carbon residue removing effect Fruit, more praiseworthy is catalyst stability height, and the duration of runs is grown, so as to the heavy oil provided by the invention Hydrotreating method has preferable prospects for commercial application.

Claims

1. a kind of heavy oil hydrogenation treatment method, this method include：Under hydrogenation conditions, by heavy oil Raw material successively with protective agent, metal remover and desulfurization agent, the protective agent, the metal remover and The desulfurizing agent each containing catalyst carrier and the active metal component that is carried in the catalyst carrier, Characterized in that, the catalysis of at least one of the protective agent, the metal remover and described desulfurizing agent Agent carrier is modified support, and the modified support contains the acid additive of layer distributed in the carrier, and from The modified support particle surface gradually strengthens to center is acid.

2. according to the method for claim 1, wherein, the catalyst carrier of the desulfurizing agent is to change Property carrier；

Preferably, the catalyst carrier of the protective agent, the metal remover and the desulfurizing agent is to change Property carrier.

3. method according to claim 1 or 2, wherein, the acid additive be selected from F components, At least one of P components and B component；

Preferably, in the modified support, on the basis of the gross weight of the modified support, with F, P Content with the acid additive of tri- kinds of element meters of B is 0.1-15 weight %；

Preferably, the acid additive in F components, P components and B component at least two, and When the modified support contains F components as acid additive, from the modified support particle surface to center Concentration of the F components in terms of F elements is gradually incremented by, the preferably distribution factor σ of F components_F(R) for 0.25 with Under, σ_F(2/3R) is 0.28-0.5, σ_F(1/3R) is 0.55-0.85；When the modified support contains P components When as acid additive and being free of F components, from the modified support particle surface to center P components with P members The concentration of element meter is gradually incremented by, the preferably distribution factor σ of P components_P(R) it is less than 0.25, σ_P(2/3R) For 0.28-0.5, σ_P(1/3R) is 0.55-0.85.

4. according to the method for claim 3, wherein, the modified support is by including following step Rapid method is made：Carrier Jing Guo hydro-thermal process is repeatedly impregnated and dried successively, and will most The desciccate once obtained afterwards is calcined, wherein, maceration extract used contains in each dipping process The compound of identical or different acid additive is provided, frequency n >=2 repeated, and as n >=3, During the 2nd time is impregnated into (n-1)th dipping, the temperature dried after impregnating each time is than adjacent The temperature dried after preceding single-steeping is high 20-150 DEG C, preferably 30-120 DEG C, more preferably 30-80 DEG C； Each time impregnate after dry time than after adjacent preceding single-steeping dry time long 1-10 hours, It is preferred that 1-9 hours, more preferably 2-5 hours；

Preferably, the condition dried after impregnating for the first time includes：Temperature is 30-300 DEG C, time 1-20 Hour；The condition that last time is dried after impregnating includes：Temperature is 30-300 DEG C, and the time is that 1-20 is small When；

Preferably, the condition of roasting includes：Temperature is 300-900 DEG C, and the time is 1-10 hours.

5. the method according to claim 11, wherein, in the preparation method of the modified support, For maceration extract in acidity, pH value is preferably 2-6 used by preceding n-1 dipping；N-th dipping is used Maceration extract in alkalescence, pH value is preferably 8-11.

6. the method according to claim 11, wherein, in the preparation method of the modified support, The number of the dipping is 2-3 times.

7. the method according to claim 11, wherein, in the preparation method of the modified support, The carrier is the mixing of at least one of aluminum oxide or aluminum oxide and silica, titanium oxide and zirconium oxide Thing；The aluminum oxide is in gama-alumina, η-aluminum oxide, θ-aluminum oxide, δ-aluminum oxide and χ-aluminum oxide At least one.

8. according to the method for claim 1, wherein, in the protective agent, aoxidized with metal Thing meter and on the basis of protectant gross weight, the content of the group VIII metal component is 0.1-0.9 weight %, the content of the vib metals component is 0.1-5 weight %；

In the metal remover, counted using metal oxide and using the gross weight of the metal remover as base Standard, the content of the group VIII metal component are 1.1-2.9 weight %, the vib metals group The content divided is 6.1-12.8 weight %；

In the desulfurizing agent, counted by metal oxide and on the basis of the gross weight of the desulfurizing agent, institute The content for stating group VIII metal component is 3.1-10 weight %, and the vib metals component contains Measure as 13.1-28 weight %.

9. according to the method for claim 8, wherein, in the desulfurizing agent, the activity is golden It is in layer distributed to belong to radial direction of the component along the catalyst carrier, and the active metal component of stratum nucleare is Co components and Mo components, the active metal component of shell for Ni components and are selected from Mo components and/or W The combination of component；

Preferably, counted and on the basis of the gross weight of the desulfurizing agent by metal oxide, Co components Content is 0.5-15 weight %, more preferably preferably 2-8 weight %, 3-7 weight %, is most preferably 3-5 weight %；The content of Mo components is 5-25 weight %, preferably 8-20 weight %, is more preferably 10-20 weight %, most preferably 15-20 weight %；The content of Ni components is 0.5-15 weight %, preferably For 2-8 weight %, more preferably 3-7 weight %, most preferably 3-5 weight %；The content of W components is 0-35 weight %, preferably 5-30 weight %, more preferably 10-30 weight %, most preferably 15-25 Weight %；

Preferably, the thickness of the shell is 0.1-5mm, and the thickness of the stratum nucleare is 0.1-5mm.

10. according to the method for claim 9, wherein, the desulfurizing agent is by comprising the following steps Method be made：

(a) catalyst carrier is subjected to hydro-thermal process, then carried the catalyst after hydro-thermal process Body enters in alkalescence is containing the first solution of the nickel compound with the combination of molybdenum compound and/or tungsten compound Row dipping, is then dried；

11. according to the method described in any one in claim 1-10, wherein, with the protective agent, On the basis of the total amount of the metal remover and the desulfurizing agent, the protective agent accounts for 1-20 volume %, preferably For 5-15 volumes %；The metal remover accounts for 15-60 volume %, preferably 20-50 volumes %；It is described Desulfurizing agent accounts for 20-85 volume %, preferably 50-75 volumes %；

Preferably, condition of the heavy oil feedstock successively with protective agent, metal remover and desulfurization agent is included： Temperature be 300-550 DEG C, preferably 330-480 DEG C, preferably hydrogen dividing potential drop 4-20MPa, 6-18MPa, Volume space velocity is 0.1-3.0h^-1, preferably 0.15-2h^-1, hydrogen to oil volume ratio 200-2500, it is preferably 300-2000。

12. according to the method described in any one in claim 1-10, wherein, along logistics direction, The catalytic activity of the protective agent, the metal remover and the desulfurizing agent gradually increases, and aperture gradually subtracts Small, granularity is gradually reduced.