CN107345152B

CN107345152B - A kind of heavy oil hydrogenation treatment method

Info

Publication number: CN107345152B
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: 2019-05-21
Anticipated expiration: 2036-05-05
Also published as: CN107345152A

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 of layer distributed in the carrier, and it is gradually increased from the modified support particle surface to center acidity.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.

The present inventor passes through the study found that if can be by the acidity in the catalyst carrier of heavy-oil hydrogenation catalyst Auxiliary agent is prepared into bilayer or multilayer distribution, as internally diffusion comes into contact with acid to reactant molecule outside catalyst granules Property stronger acid additive, being beneficial to metal deposit and carbon deposit being uniformly distributed along catalyst is radial, so as to improve The activity and stability of residual oil hydrocatalyst.

For this purpose, the present invention provides a kind of heavy oil hydrogenation treatment methods, this method comprises: under hydrogenation conditions, it will Heavy oil feedstock successively with protective agent, metal remover and desulfurization agent, the protective agent, the metal remover and the desulfurizing agent Respectively containing catalyst carrier and the active metal component that is carried in the catalyst carrier, wherein the protective agent, described de- The catalyst carrier of at least one of metal agent and the desulfurizing agent is modified support, and the modified support contains in the carrier The acid additive of layer distributed, and gradually increased from the modified support particle surface to center acidity.

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 the acid additive in modified catalyst carrier (i.e. modified support) is in layering Be distributed and gradually increased from modified support particle surface to center acidity, such reactant molecule outside catalyst granules to Inside diffusion can come into contact with acid stronger acid additive, be beneficial to metal deposit and carbon deposit along catalyst radial direction Be uniformly distributed, enable the heavy oil hydrogenation treatment method effectively to play all kinds of catalyst actions, be used for heavy distillate There is better demetalization, desulfurization, de- carbon residue activity and stability with residual hydrogenation, can effectively control the temperature of catalyst bed It rises, slows down the deactivation rate of catalyst, extend 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 of cloth, and gradually increased from the modified support particle surface to center acidity.

In the modified support, " layer distributed " of the acid additive refers to that acid additive unevenly divides in the carrier Cloth, the distribution of the type and/or concentration of acid additive is different in the different radii regional scope of modified support particle.For example, Layer distributed can refer to that concentration distribution of the same acid additive in the different radii regional scope of carrier granular is different, Can refer to and be distributed different types of acid additive in the different radii regional scope of carrier granular, be possibly even this two The combination of person.

In the modified support, " gradually increasing from the modified support particle surface to center acidity " refers to from carrier The surface of grain is in enhancing trend to center acidity, and there is no particular limitation for the trend of this enhancing, can be linear, specific It is functional relation or gradient, it is also possible to random enhancing trend.When containing a kind of acid additive in the modified support, Described acidity refers to the various concentration distribution of acid additive, and concentration is higher then acid stronger, and concentration is lower then acid weaker；When When containing two or more acid additives in the modified support, described acidity refers to the difference of the acid additive of different acidity Distribution, acid strong acidic assistant concentration is significantly higher then acid stronger, the concentration of acid strong acid additive obviously it is weaker then It is acid weaker.

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 modified support, the type of the acid additive can be the conventional selection of this field, in preferable case Under, the acid additive is selected from least one of F (fluorine) component, P (phosphorus) component and B (boron) component.Under normal conditions, in F Between component, P component and B component three, the acidity of F component is most strong, and the acidity of P component is taken second place, and the acidity of B component is most weak.? In the present invention, the F component, the P component and the B component can exist in various conventional forms, such as can be with list The form of matter exists, and can also exist in the form of compound.Compound containing F for example can be ammonium fluoride, ammonium acid fluoride, hydrogen One of fluoric acid, sodium fluoride and calcirm-fluoride are a variety of.Compound containing P for example can be phosphoric acid, Diammonium phosphate (DAP), biphosphate One of sodium and potassium dihydrogen phosphate are a variety of.Compound containing B can be for example one in boric acid, metaborate and borate Kind 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, in the modified support, the acid additive is selected from F component, P At least two in component and B component, and when the modified support contains F component as acid additive, from the modified support Particle surface is gradually incremented by concentration of the center F component in terms of F element, it is highly preferred that the distribution factor σ of F component_F(R) it is 0.25 or less (preferably 0.22 hereinafter, more preferably 0.10-0.22, most preferably 0.12-0.20), σ_F(2/3R) is 0.28- 0.5 (preferably 0.30-0.45, more preferably 0.32-0.42), σ_F(1/3R) be 0.55-0.85 (preferably 0.60-0.85, more Preferably 0.75-0.85)；When the modified support contains P component as acid additive and without the timesharing of F group, from modification load Body particle surface is gradually incremented by concentration of the center P component in terms of P element, it is highly preferred that the distribution factor σ of P component_P(R) it is 0.25 or less (preferably 0.22 hereinafter, more preferably 0.10-0.22, most preferably 0.12-0.20), σ_P(2/3R) is 0.28- 0.5 (preferably 0.30-0.45, more preferably 0.32-0.42), σ_P(1/3R) be 0.55-0.85 (preferably 0.60-0.85, more Preferably 0.75-0.85).According to the preferred embodiment, acid stronger acid additive is made more to be distributed in close urge The central area of agent carrier, so as to more advantageously improve the effect of demetalization, desulfurization and de- carbon residue.Above-mentioned preferred In embodiment, " being gradually incremented by " refers to from the surface of carrier granular to the content of the corresponding acid additive element in center in increase Trend, there is no particular limitation for the trend of this increase, can be it is linear, specific function relationship or gradient, can also To be random increase tendency.

In the present invention, the distribution factor σ of acid additive is for indicating that acid additive along the regularity of distribution of carrier radial direction, is used σ indicate acid additive acid additive element at the content of acid additive element and center at a certain position of particle content it Than showing that this acid additive constituent content is higher than at modified support granular center if σ > 1；If σ=1, show point acid Property auxiliary element content is identical as at modified support granular center；If σ < 1, shows that this acid additive constituent content is less than and change At property carrier granular center.For example, in σ_FIn (1/3R), R is particle radius, using, as starting point, F is at modified support granular center Refer to the F component in terms of F element, specifically, σ_F(1/3R) refer to F constituent content from modified support center at 1/3R with should The ratio between F constituent content at the center of modified support.The content distribution of acid additive element uses in the particle of modified support SEM-EDX (Scanning Electron Microscope-Energy Dispersive Spectrometry) method is divided Analysis.

A preferred embodiment of the invention, the modified support are made by method comprising the following steps: Carrier Jing Guo hydro-thermal process is repeatedly successively impregnated and dried, and the desciccate obtained for the last time is roasted It burns, wherein maceration extract used in each dipping process contains the compound for being provided with identical or different acid additive, duplicate Frequency n >=2, and as n >=3, during from (n-1)th dipping is impregnated into the 2nd time, dry temperature after impregnating each time Than after adjacent preceding single-steeping, dry temperature is 20-150 DEG C high, preferably 30-120 DEG C, more preferably 30-80 DEG C；It is each The dry time is 1-10 hours longer than the time of drying after adjacent preceding single-steeping after secondary dipping, and preferably 1-9 hours, more preferably 2-5 hours.

In the preparation method of above-mentioned modified support, carrier after hydro-thermal process since density of surface hydroxyl increases and Negatively charged, after being immersed in maceration extract, the compound of the offer acid additive in maceration extract is easily enriched in the table of carrier Face, and after the carrier drying after first time is impregnated, density of surface hydroxyl reduces, the position of hydroxy density maximum value on carrier It is migrated along the radial direction of carrier toward carrier center, after being immersed in another maceration extract, in another maceration extract The compound of offer acid additive be easy to be enriched in be located at and carry intracorporal hydroxy density maximum, as dipping time n >=3, During from (n-1)th dipping is impregnated into the 2nd time, by dry temperature after control dipping and dry time with leaching Stain number gradually increases, and enables to the position for carrying intracorporal hydroxy density maximum value gradually to migrate toward carrier center, and in turn It is adsorbed on the compound that the offer acid additive in the maceration extract used is provided every time on the different location of carrier, finally passes through The modified support that acid additive is in layer distributed is obtained after roasting.

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, 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, need that the carrier of hydro-thermal process is repeatedly successively impregnated and done It is dry, wherein the type for the compound for providing acid additive in maceration extract used in each dipping process can be identical, can also not Together, preferably different, the advantages of modified hydrogen at-ing catalyst carrier enabled in this way can converge a variety of different acid additives, In particular, acid stronger acid additive (such as F component) can be made relatively centrally to be distributed in the centre of modified support.

In the preparation method of above-mentioned modified support, the compound for providing acid additive can be to provide the chemical combination of F component At least one of object, the compound that P component is provided or compound that B component is provided.

Wherein, the compound for providing F component for example can be ammonium fluoride, ammonium acid fluoride, hydrofluoric acid, sodium fluoride and calcirm-fluoride One of or it is a variety of.

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

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

In the preparation method of above-mentioned modified support, the type of solvent in the maceration extract is not particularly limited, it can With for the existing various inertia liquids that can dissolve the compound for providing acid additive, for example, water, alcohol can be selected from At least one of (such as methanol, ethyl alcohol etc.), ether (such as ether), aldehyde (such as formaldehyde) and ketone (such as acetone).In addition, every The content that the compound of acid additive is provided in maceration extract used in secondary dipping may be the same or different, and respectively independent Ground is 1-100 grams per liter, preferably 5-50 grams per liter, more preferably 5-15 grams per liter.Further, dipping used is impregnated every time The dosage of liquid may be the same or different, and the carrier relative to 100g, every time the use of dipping maceration extract used Amount can be each independently 20-200mL, preferably 50-100mL.The content model of such compound that acid additive is provided Enclosing can make with the dosage of maceration extract in above-mentioned modified support, on the basis of the total weight of the modified support, with F, P and The content of the acid additive of tri- kinds of element meters of B be 0.1-15 weight %, more preferably 0.2-12 weight %, further it is excellent It is selected as 0.3-8 weight %.

In the preparation method of above-mentioned modified support, the acid-base property of the maceration extract is not particularly limited, for example, can Think acid, alkaline, neutral maceration extract.Preferably, maceration extract used by preceding n-1 dipping is in acid, and n-th Maceration extract used by impregnating is in alkalinity.It is highly preferred that the first n-1 times pH value for impregnating used maceration extract is 2-6.More preferably Ground, the pH value of maceration extract used by n-th impregnates are 8-11.It was found by the inventors of the present invention that working as the acid of the maceration extract The alkalinity control layer distributed of more advantageous acid additive on carrier in the above preferred range, thus the modified load made Body is prepared into after hydrogenation catalyst, and being more advantageous to improves heavy-oil hydrogenation treatment effect.

Wherein, typically basic species are added into the maceration extract in the method that the maceration extract is adjusted to alkalinity Matter, for example, at least one of ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc..And contain in F, P and B at least Maceration extract of compound a kind of itself may just present it is acid, can be with if not shown acid or acid degree is insufficient Acidic materials (for example, at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc.) is added into the maceration extract with by the leaching Stain liquid is adjusted to expected acidity.

In the preparation method of above-mentioned modified support, the number of the dipping can according to obtained modified support into Row reasonably selects, but comprehensively considers from the effect of the complexity of preparation process and the modified support obtained, it is preferable that described The number of dipping is 2-3 times, i.e. n is preferably 2-3 times.

Wherein, as dipping time n=2, as long as using by the carrier of hydro-thermal process and after guaranteeing to impregnate first time Carrier be dried and can make acid additive on carrier in layer distributed；As dipping time n >=3, as long as using warp It crosses the carrier of hydro-thermal process and guarantees that condition dry after repeatedly impregnating meets above-mentioned specific condition and can make acid additive It is in layer distributed on carrier.

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

According to another preferred method of implementation of the present invention, as dipping time n=3, used leaching is impregnated for the first time The compound of offer acid additive in stain liquid is to provide the compound of F component, in maceration extract used in second of dipping The compound for providing acid additive is to provide the compound of P component, and the offer that third time impregnates in used maceration extract is acid The compound of auxiliary agent is to provide the compound of B component.

In the preparation method of above-mentioned modified support, the drying condition after each dipping is not particularly limited, it can With the condition of the carrier after the dry dipping using this field routine, as long as can satisfy above-mentioned difference, for example, different The immersion condition of impregnation steps may be the same or different, and usual can be each independently 20- including dipping temperature 300 DEG C, preferably 50-100 DEG C；Dip time can be 1-20 hours, preferably 1-6 hours.

Under preferable case, after impregnating for the first time dry condition include: temperature be 30-300 DEG C (preferably 50-300 DEG C, More preferably 100-250 DEG C, most preferably 100-150 DEG C), the time is 1-20 hours (preferably 2-18 hours, more preferably 3- 10 hours, most preferably 3-8 hours).The drying can be vacuum drying.

Under preferable case, it is 30-300 DEG C of (preferably 50-300 that last time condition dry after impregnating, which includes: temperature, DEG C, more preferably 100-200 DEG C, most preferably 120-180 DEG C), the time be 1-20 hours (preferably 2-18 hours, more preferably It is 3-10 hours, most preferably 3-5 hours).The drying can be vacuum drying.

In the preparation method of above-mentioned modified support, the condition of roasting is not particularly limited, for example, the roasting Condition may include: that temperature is 300-900 DEG C (preferably 300-800 DEG C, more preferably 350-500 DEG C), and the time is that 1-10 is small When (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.

In a preferred embodiment, in order to further increase demetallization per, desulfurization degree and de- carbon yield, described de- In sulphur agent, the active metal component is in layer distributed, the active metal of stratum nucleare along the radial direction of the catalyst carrier Group is divided into 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. In the preferred embodiment, by making Ni component and being distributed in selected from the active metal component of Mo component and/or W component de- The shell of sulphur agent, and Co component and Mo component is made to be distributed in the stratum nucleare of desulfurizing agent so that in heavy oil more difficult reaction condensed-nuclei aromatics The higher Ni component of hydrogenation activity and Mo component and/or W component are first touched during the reaction, and hydrogen is added to be saturated open loop, so that It is various that the substance removed is needed to expose in succession, it is further spread to catalytic inner, it is higher to touch hydrodesulfurization activity Co component and Mo component, using the reaction characteristics of different activities metal component, optimum organization, to obtain higher activity.

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 in 70 DEG C of hydro-thermal process 24 hours, then by the carrier after hydrothermal treatment with 165 milliliters of temperature be 50 DEG C contain 15 grams per liter H₃BO₃Aqueous solution (pH value It is 6) saturation dipping 1 hour, it is 3 hours dry in 100 DEG C later, obtain the carrier that load has B component；

(1-2) by obtained in step (1-1) load have the carrier of B component 140 milliliters of temperature be 50 DEG C containing 15 grams/ Rise NH₄Dipping 1 hour in the aqueous solution (pH value 11) of F, it is then 3 hours dry in 120 DEG C, it is roasted 3 hours then at 400 DEG C, 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 150 DEG C of hydro-thermals Reason 10 hours, then by 155 milliliters of temperature of the carrier after hydrothermal treatment be 80 DEG C containing 6 grams per liter H₃BO₃Aqueous solution (pH value It is 2) saturation dipping 1 hour, it is 6 hours dry in 120 DEG C later, obtain the carrier that load has B component；

(1-2) by obtained in step (1-1) load have the carrier of B component 135 milliliters of temperature be 80 DEG C containing 8 grams/ Rise H₃PO₄Aqueous solution (pH value 2) in dipping 1 hour, 8 hours dry in 180 DEG C later, obtaining load has B component and P group The carrier divided；

The load that (1-3) obtains step (1-2) has the carrier of B component and P component to be 80 DEG C in 125 milliliters of temperature to contain 10 grams per liter NH₄Dipping 1 hour in the aqueous solution (pH value 10) of F, it is then 3 hours dry in 120 DEG C, then at 400 DEG C of roastings 3 Hour, 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

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 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:

It takes 200 grams of carrier Z1, Z2 and Z3 prepared by preparation example 1 respectively, is 40 DEG C with 160 milliliters of temperature respectively and contains 28 grams per liter H₃BO₃Aqueous solution (pH 7) impregnate 1 hour, then at 120 DEG C dry 4 hours, then 400 DEG C roast 3 hours, Reference modified support DS1-1, DS2-1 and DS3-1 are respectively obtained, and these modified supports are mutually applied to subsequent step respectively In.

Comparative example 3

200 grams of carrier Z1, Z2 and Z3 prepared by preparation example 1 are taken respectively, at a temperature of 90 °C are contained with 155 milliliters respectively 25 grams per liter NH₄The solution (pH 7) of F impregnates 1 hour, dries 4 hours then at 120 DEG C, then roasts 3 hours, obtain at 400 DEG C Mutually it is applied in subsequent step respectively to reference modified support DS1-2, DS2-2 and DS3-2, and by these modified supports.

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 drying temperature in step (1-1) and step (1-2) is 120 DEG C, and contains H₃BO₃Aqueous solution, contain H₃PO₄'s Aqueous solution and contain NH₄The pH of the aqueous solution of F is 7, respectively obtains reference modified support DS1-3, DS2-3 and DS3-3, and will These modified supports are mutually applied in subsequent step respectively.

Test case 1

Using SEM-EDX (Scanning Electron Microscope-Energy Dispersive Spectrometry) method analyzes the Elemental redistribution in modified support particle.Due in SEM-EDX characterization result along carrier The numerical value of radial every bit constituent content is corresponded to each other with the point element content, although the size of the numerical value may not represent this The real content of point element, but it is able to reflect the point element content height.Therefore, in order to indicate that acid additive is along carrier radial The regularity of distribution introduces distribution factor σ.Indicate that (R is particle to acid additive with the ratio between concentration at center on a certain position of particle with σ Radius, using at modified support granular center as starting point).Acid additive concentration on a certain position refers to that SEM-EDX is characterized As a result the average value of the position (position deviation≤20nm) 20 numerical points numeration nearby in；The acid additive is dense at center The average value of (position deviation≤20nm) 20 numerical point counting rates nearby is put centered on degree.If σ > 1, show that the point acidity helps Agent constituent content is higher than at modified support granular center；If σ=1 shows this acid additive constituent content and modified support It is identical at granular center；If σ < 1, show that this acid additive constituent content is less than at modified support granular center.Table 1 is to change Property carrier relevant parameter, wherein the content (based on the element calculate) of acid additive is calculated according to inventory.Table 2 is to be modified The distribution factor of different acid additives at different locations on carrier.

Table 1

Table 2

Number	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 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	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, 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 invention 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 gradually increased from the modified support particle surface to center acidity；

Wherein, the catalyst carrier of the desulfurizing agent is modified support.

2. 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.

3. method according to claim 1 or 2, wherein the acid additive is in F component, P component and B component It is at least one.

4. according to the method described in claim 3, wherein, in the modified support, using the total weight of the modified support as base Standard, the content of the acid additive in terms of tri- kinds of elements of F, P and B are 0.1-15 weight %.

5. according to the method described in claim 4, wherein, the acid additive in F component, P component and B component at least Two kinds, and when the modified support contains F component as acid additive, from the modified support particle surface to center F component Concentration in terms of F element is gradually incremented by.

6. according to the method described in claim 5, wherein, the distribution factor σ of F component_F(R) for 0.25 hereinafter, σ_F(2/3R) is 0.28-0.5, σ_F(1/3R) is 0.55-0.85, wherein R is particle radius, and σ is that acid additive is acid at a certain position of particle The ratio between the content of acid additive element at the content of auxiliary element and center, F are the F component in terms of F element, σ_F(R) for from changing Property carrier center at play the ratio between F constituent content at the F constituent content at the place R and the center of the modified support, σ_F(2/3R) be from The ratio between the F constituent content at the center of the F constituent content and the modified support at 2/3R, σ are played at modified support center_F(1/3R) For the ratio between the F constituent content at the center of F constituent content and the modified support from modified support center at 1/3R.

7. according to the method described in claim 4, wherein, when the modified support contains P component as acid additive and without F Group timesharing, is gradually incremented by from the modified support particle surface to concentration of the center P component in terms of P element.

8. according to the method described in claim 7, wherein, the distribution factor σ of P component_P(R) for 0.25 hereinafter, σ_P(2/3R) is 0.28-0.5, σ_P(1/3R) is 0.55-0.85, wherein R is particle radius, and σ is that acid additive is acid at a certain position of particle The ratio between the content of acid additive element at the content of auxiliary element and center, P are the P component in terms of P element, σ_P(R) for from changing Property carrier center at play the ratio between P element content at the P element content at the place R and the center of the modified support, σ_P(2/3R) be from The ratio between the P element content at the center of the P element content and the modified support at 2/3R, σ are played at modified support center_P(1/3R) For the ratio between the P element content at the center of P element content and the modified support from modified support center at 1/3R.

9. according to the method described in claim 3, wherein, the modified support is made by method comprising the following steps: will Carrier by hydro-thermal process is repeatedly successively impregnated and is dried, and the desciccate obtained for the last time is roasted It burns, wherein maceration extract used in each dipping process contains the compound for being provided with identical or different acid additive, duplicate Frequency n >=2, and as n >=3, during from (n-1)th dipping is impregnated into the 2nd time, dry temperature after impregnating each time Than after adjacent preceding single-steeping, dry temperature is 20-150 DEG C high；The dry time is more primary than before adjacent after impregnating each time The dry time is 1-10 hours long after dipping.

10. according to the method described in claim 9, wherein, dry temperature is than adjacent preceding single-steeping after impregnating each time Dry temperature is 30-120 DEG C high afterwards；The dry time is longer than the time of drying after adjacent preceding single-steeping after impregnating each time 1-9 hours.

11. according to the method described in claim 10, wherein, dry temperature is than adjacent preceding single-steeping after impregnating each time Dry temperature is 30-80 DEG C high afterwards；The dry time is longer than the time of drying after adjacent preceding single-steeping after impregnating each time 2-5 hours.

12. according to the method for claim 11, wherein it is 30-300 that dry condition, which includes: temperature, after impregnating for the first time DEG C, the time is 1-20 hours；It is 30-300 DEG C that last time condition dry after impregnating, which includes: temperature, and the time is 1-20 hours.

13. according to the method described in claim 9, wherein, the condition of roasting includes: that temperature is 300-900 DEG C, time 1-10 Hour.

14. according to the method described in claim 9, wherein, in the preparation method of the modified support, preceding n-1 dipping institute The maceration extract of use is in acidity；Maceration extract used by n-th impregnates is in alkalinity.

15. according to the method for claim 14, wherein in the preparation method of the modified support, preceding n-1 dipping institute The maceration extract of use is in acidity, pH value 2-6；Maceration extract used by n-th impregnates is in alkalinity, pH value 8-11.

16. according to the method described in claim 9, wherein, in the preparation method of the modified support, the number of the dipping It is 2-3 times.

17. according to the method described in claim 9, 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.

18. 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 group VIII metal component is 0.1-0.9 weight %, and the content of vib metals component 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, group VIII gold The content for belonging to component is 1.1-2.9 weight %, and the content of 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, group VIII metal group The content divided is 3.1-10 weight %, and the content of vib metals component is 13.1-28 weight %.

19. according to the method for claim 18, wherein in the desulfurizing agent, the active metal component is along described The radial direction of catalyst carrier is in layer distributed, and the active metal component of stratum nucleare is Co component and Mo component, the activity of shell Metal component is Ni component and the combination selected from Mo component and/or W component.

20. according to the method for claim 19, wherein the shell with a thickness of 0.1-5mm, the stratum nucleare with a thickness of 0.1-5mm。

21. method described in any one of 9-20 according to claim 1, wherein the desulfurizing agent is by including the following steps Method be made:

(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.

22. according to claim 1, method described in any one of 2 and 18-20, wherein with the protective agent, the de- gold On the basis of the total amount for belonging to agent and the desulfurizing agent, the protective agent accounts for 1-20 volume %；The metal remover accounts for 15-60 volume %； The desulfurizing agent accounts for 20-85 volume %, wherein the sum of the protective agent, the metal remover and volume of the desulfurizing agent are 100%。

23. according to the method for claim 22, 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 body Product %.

24. according to the method for claim 22, wherein by heavy oil feedstock successively with protective agent, metal remover and desulfurizing agent The condition of contact includes: that temperature is 300-550 DEG C, hydrogen partial pressure 4-20MPa, and volume space velocity is 0.1-3.0 h^-1, hydrogen oil volume Than for 200-2500.

25. according to the method for claim 24, wherein by heavy oil feedstock successively with protective agent, metal remover and desulfurizing agent The condition of contact includes: that temperature is 330-480 DEG C, hydrogen partial pressure 6-18MPa, and volume space velocity is 0.15-2 h^-1, hydrogen to oil volume ratio For 300-2000.

26. according to claim 1, method described in any one of 2 and 18-20, wherein along logistics direction, the protective agent, The catalytic activity of the metal remover and the desulfurizing agent is gradually increased, and aperture is gradually reduced, and granularity is gradually reduced.