CN107345151A - A kind of hydrotreating method of high nitrogen inferior heavy oil - Google Patents

A kind of hydrotreating method of high nitrogen inferior heavy oil Download PDF

Info

Publication number
CN107345151A
CN107345151A CN201610292644.1A CN201610292644A CN107345151A CN 107345151 A CN107345151 A CN 107345151A CN 201610292644 A CN201610292644 A CN 201610292644A CN 107345151 A CN107345151 A CN 107345151A
Authority
CN
China
Prior art keywords
metal
weight
denitrifier
carrier
components
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610292644.1A
Other languages
Chinese (zh)
Other versions
CN107345151B (en
Inventor
贾燕子
杨清河
李大东
刘学芬
邓中活
刘涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201610292644.1A priority Critical patent/CN107345151B/en
Publication of CN107345151A publication Critical patent/CN107345151A/en
Application granted granted Critical
Publication of CN107345151B publication Critical patent/CN107345151B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to petrochemical industry, discloses a kind of hydrotreating method of high nitrogen inferior heavy oil, and this method includes：Under hydrogenation conditions; heavy oil feedstock is contacted with protective agent, metal remover and denitrifier successively; the protective agent, the metal remover and the denitrifier are each containing catalyst carrier and the active metal component being carried in the catalyst carrier; the catalyst carrier of at least one of the protective agent, the metal remover and the denitrifier is modified support; the modified support contains the acid additive and metal promoter of layer distributed in the carrier; the acid additive is distributed in stratum nucleare, and the metal promoter is distributed in shell.The hydrotreating method of the high nitrogen inferior heavy oil provided by the invention can not only obtain higher metal, nitrogen and carbon residue removal effect, more praiseworthy is catalyst stability height, the duration of runs is grown, and has preferable prospects for commercial application so as to the hydrotreating method of the high nitrogen inferior heavy oil provided by the invention.

Description

A kind of hydrotreating method of high nitrogen inferior heavy oil
Technical field
The present invention relates to petrochemical industry, in particular it relates to a kind of hydrotreating of high nitrogen inferior heavy oil Method.
Background technology
Fixed bed residual oil hydrocatalyst uses grading system, mainly including protective agent, metal remover, de- Sulphur agent, denitrifier, de- carbon residue agent etc..With the riverine refinery of Sinopec and North China branch company of CNPC Deng the construction successively of residual hydrogenation equipment, it, which processes raw material, will turn to mainly with triumph piped oil or North China The low-sulfur high-nitrogen such as crude oil residual oil is raw material.Compared with the high-sulfur residual oil of the Middle East, the characteristics of such residual oil raw material： Sulfur content is relatively low (0.2%~2.5%), and nitrogen content height (0.3%~0.7%), gum level is high, pitch Matter content is low, and nickel content is high, content of vanadium is low.Compared with the low nitrogen residual oil of Middle East high-sulfur, low-sulfur high-nitrogen residual oil In nitrogen-containing compound be difficult to hydro-conversion, while cause relatively low carbon residue conversion ratio, downstream catalytic split Makeup, which is put, to have a negative impact, the nitride in hydrogenated residue, not only makes catalytic cracking catalyst activity drop It is low, and product distribution is deteriorated, catalytically cracked material nitrogen content often increases by 150 μ g/g, under conversion ratio Drop 1% or so.Existing residual oil hydrocatalyst is to the drop of sulphur and carbon residue in the low nitrogen class residual oil of external high-sulfur Low significant effect.But for low-sulfur high-nitrogen class residual oil, because sulfur content is relatively low, the removing of sulphur is relative For the removing of nitrogen, the reduction contribution for oil product carbon residue before and after hydrogenation is smaller.
CN101928592B discloses a kind of grading composition method of hydrogenation catalyst, reactor from upper and It is lower to load Hydrodemetalation catalyst and desulfurizing agent respectively；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, are added Active metal component and acidic assistant concentration the gradient increase of hydrogen catalyst for demetalation, the activity gold of desulfurizing agent Belong to component and acidic assistant concentration gradient is reduced.However, in the grading composition method for preparing catalyst it is complicated, Energy consumption is big and the repeatability and controllability of the preparation method are poor.
The content of the invention
The purpose of the present invention overcomes carries out hydrotreating using existing method to high nitrogen inferior heavy oil During denitrification activity and de- carbon residue activity it is relatively low the shortcomings that, there is provided one kind be applied to high nitrogen inferior heavy oil (such as high nitrogen residual oil) can realize comprehensive demetalization, denitrogenation and de- carbon residue effect and being not easy to be formed carbon deposit, Heavy oil hydrogenation treatment method with high stability.
To achieve these goals, the invention provides a kind of hydrotreating method of high nitrogen inferior heavy oil, This method includes：Under hydrogenation conditions, by heavy oil feedstock successively with protective agent, metal remover and de- Nitrogen agent contacts, the protective agent, the metal remover and the denitrifier each containing catalyst carrier and The active metal component being carried in the catalyst carrier, wherein, the protective agent, the metal remover Catalyst carrier with least one of the denitrifier is modified support, and the modified support contains The acid additive and metal promoter of layer distributed in carrier, the acid additive are distributed in stratum nucleare, the gold Category auxiliary agent is distributed in shell, the acid additive in F components, P components and B component at least one Kind, the metal promoter is group ia metal component and/or group iia metal component, and the activity is golden It is at least one vib metals component and the combination of at least one group VIII metal component to belong to component.
In the hydrotreating method of high nitrogen inferior heavy oil provided by the invention, by protective agent, de- gold The catalyst carrier for belonging at least one of agent and denitrifier is modified so that modified catalyst carrier Acid additive and metal promoter in (i.e. modified support) in layer distributed and are distributed in acid additive Stratum nucleare, metal promoter are distributed in shell, so internally expand along outside catalyst granules in reactant molecule In scattered process, be advantageous to metal deposit and carbon deposit along the radially uniform distribution of catalyst so that the side Method can effectively play all kinds of catalyst actions, have preferably de- gold for high nitrogen inferior heavy oil hydrogenation Category, denitrogenation and de- carbon residue activity and stability, can effectively control the temperature rise of beds, slow down and urge The deactivation rate of agent, 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 hydrotreating method of high nitrogen inferior heavy oil, this method includes：It is being hydrogenated with Under reaction condition, heavy oil feedstock is contacted with protective agent, metal remover and denitrifier successively, the protection Agent, the metal remover and the denitrifier each containing catalyst carrier and are carried on the catalyst carrier In active metal component, wherein, in the protective agent, the metal remover and the denitrifier extremely The catalyst carrier of few one is modified support, and the modified support contains the acid of layer distributed in the carrier Property auxiliary agent and metal promoter, the acid additive are distributed in stratum nucleare, and the metal promoter is distributed in shell, The acid additive is selected from least one of F components, P components and B component, and the metal promoter is Group ia metal component and/or group iia metal component, the active metal component are at least one the The combination of group vib metal component and at least one group VIII metal component.
In the modified support, the concept of " shell " and " stratum nucleare " is introduced, but is not to say that The bright modified support has two separable layers each other, but in order to illustrate to have in the modified support There is the integrated distribution region of two different acid additives and metal promoter, and the two distributed areas are in Stratiform, a central area for being located at the modified support, i.e. referred to as stratum nucleare, another changes positioned at described The surface region of property carrier, i.e. referred to as shell.
In the modified support, the layer distributed of acid additive and metal promoter refers to acid additive and gold It is uneven distribution in whole modified support to belong to auxiliary agent, and metal promoter is distributed mainly on shell, also may be used Stratum nucleare is distributed in have on a small quantity；And acid additive is distributed mainly on stratum nucleare, it is possibility to have be distributed in shell on a small quantity Layer.SEM-EDX (Scanning Electron Microscope-Energy Dispersive are used in the present invention Spectrometry) method analyzes in the modified support acid additive and metal promoter along particle radial direction Distribution, and represent the distribution of acid additive and metal promoter along modified support particle radial direction with distribution factor σ Rule.The distribution factor σ is ratio of the auxiliary agent on a certain position of carrier granular with concentration at center (R is particle radius, using at modified hydrogen at-ing catalyst carrier granular center as starting point).Wherein, auxiliary agent Concentration on a certain position of carrier granular refers in SEM-EDX characterization results near the position The average value of (position deviation≤20nm) 20 numerical point numerations, auxiliary agent is at the center of carrier granular Concentration refers in SEM-EDX characterization results (position deviation≤20nm) 20 numerical value near central point The average value of point numeration.If σ>1, then show that the content of auxiliary agent at that point is higher than in modified support particle The content of corresponding additive at the heart；If σ=1, show the content of auxiliary agent at that point and modified support particle The content of corresponding additive is identical at center；If σ<1, then show the content of auxiliary agent at that point less than modification The content of corresponding additive at carrier granular center.Wherein, in the modified support, carrier granular outer layer The distribution factor σ ＞ 1 of the metal promoter of (shell), and the acid additive of carrier granular outer layer (shell) Distribution factor σ ＜ 1.For example, in σFIn (1/3R), R is particle radius, with modified support particle It is starting point at the heart, F refers to the F components in terms of F elements, specifically, σF(1/3R) refers to carry from modified The ratio between F constituent contents at the center of the F constituent contents and the modified support at 1/3R are played at body center.
In the modified support, the thickness of the shell of metal promoter and the stratum nucleare of distribution acid additive is distributed It is not particularly limited, for example, the thickness of the shell 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, preferably 0.1-4mm, More preferably 0.15-3.5mm.Wherein, the thickness of the shell refers to the distribution factor of the metal promoter The thickness of the part of σ >=2, and the stratum nucleare thickness refers to the parts of 0.5≤σ of distribution factor ＜ 1 of acid additive Thickness.In the present invention, the thickness of the shell and stratum nucleare is measured using SEM-EDX methods, specifically, Randomly select 30 modified supports and measure its cross section and particle diameter with SEM, distinguished afterwards with EDX The radial distribution of metal promoter component is obtained along each modified support radial scan and obtains the part of σ >=2 Thickness, the arithmetic mean of instantaneous value for taking above-mentioned thickness are the thickness of shell of the present invention；And use EDX The radial distribution of acid additive component is obtained along each modified support radial scan and obtain 0.5≤σ ＜ respectively The thickness of 1 part, the arithmetic mean of instantaneous value for taking above-mentioned thickness are the thickness of stratum nucleare of the present invention.
In the present invention, if in the protective agent, the metal remover and the denitrifier 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, denitrogenation, the effect of de- carbon residue, under preferable case, in order to further improve demetalization, denitrogenation and de- The effect of carbon residue, the catalyst carrier of the denitrifier is the modified support, that is to say, that at least institute The catalyst carrier for stating denitrifier 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, denitrogenation and de- carbon residue, the guarantor The catalyst carrier for protecting agent, the metal remover and the denitrifier is the modified support.
In the present invention, the F components, the P components and the B component can be with various routines Form exist, such as can exist in the form of simple substance, can also exist in the form of compound.Contain F compound for example can be one in ammonium fluoride, ammonium acid fluoride, hydrofluoric acid, sodium fluoride and calcirm-fluoride Kind is a variety of.Compound containing P for example can be phosphoric acid, Diammonium phosphate (DAP), sodium dihydrogen phosphate and di(2-ethylhexyl)phosphate One or more in hydrogen potassium.Compound containing B for example can be in boric acid, metaborate and borate 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, the modified support are the sides by comprising the following steps Method is made：
(1) carrier Jing Guo hydro-thermal process is provided with to the metal promoted of the metal promoter in alkaline containing Impregnated in the solution A of immunomodulator compounds, then dried；
(2) being helped containing the acidity for being provided with the acid additive in acidity by the carrier that step (1) obtains Impregnated in the solution B of immunomodulator compounds, be then dried and be calcined.
In the preparation method of above-mentioned modified support, the present inventor is had found by furtheing investigate, Before solution A of the dipping containing the metal promoter compound, the carrier is first subjected to hydro-thermal process, And the shell for controlling the acid-base property of the maceration extract impregnated twice to enable to metal promoter to be mainly distributed on carrier Layer, and acid additive is mainly distributed on the stratum nucleare of carrier, so as to realize layer distributed of the auxiliary agent on carrier, Preparation process controllability and repeatability are very good.Speculate its reason, it may be possible to due to：Using infusion process When preparing modified support, in dipping process different carriers to the adsorption capacity of same active component solute not Together, same carrier is also different to the adsorption capacity of different activities component solute.Mainly it is made up of oxide Absorption of the carrier to metel complex ion depend mainly on following three parameters：The isoelectric point of oxide, leaching The property of stain liquid pH value and metel complex ion.Carrier after hydro-thermal process is immersed in leaching several times After in stain liquid, by controlling the condition dried after repeatedly dipping to ensure that hydroxy density is maximum on carrier The position of value constantly migrates with the progress of dipping process to carrier center.Now, as the pH of maceration extract During the isoelectric point of value ＞ carriers, the position of hydroxy density maximum is easy to adsorb cation on carrier；Work as leaching During the isoelectric point of the pH value ＜ carriers of stain liquid, it is negative to be easy to absorption for the position of hydroxy density maximum on carrier Ion.The isoelectric point of alumina support is usually 7.0-9.0 or so, and in the alkaline assistant compound Active principle be usually cation, the active principle in acid additive compound is usually anion.Cause This, degree of drying and maceration extract pH value after control hydro-thermal process severity, dipping, you can realize leaching Radial direction of the active principle along carrier in stain liquid from outside to inside layered adsorption on carrier.
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).
In the preparation method of above-mentioned modified support, the metal promoter compound will provide the metal promoted Agent, and the metal promoter refers to the metallic element in group ia and/or group iia, wherein, the IA races metal is preferably the one or more in Li, Na and K, group iia metal be preferably Mg and / or Ca.Therefore, metal promoter of the present invention be preferably Li components, Na components, K components, One or more in Mg components and Ca components, more preferably K components, Mg components and Ca components In one or more.
Wherein, there is provided Li metal promoter compound for example can be lithium nitrate and/or lithium sulfate.
Wherein, there is provided Na metal promoter compound for example can be sodium nitrate and/or sodium sulphate.
Wherein, there is provided K metal promoter compound for example can be potassium nitrate and/or potassium sulfate.
Wherein, there is provided Mg metal promoter compound for example can be magnesium nitrate and/or magnesium chloride.
Wherein, there is provided Ca metal promoter compound for example can be calcium nitrate, calcium chloride and calcium acetate In one or more.
In the present invention, the acid additive is derived from the acid additive compound, the acid additive Refer to selected from least one of F components, P components and B component.
Wherein, there is provided the acid additive compound of F components for example can be ammonium fluoride, ammonium acid fluoride, hydrogen One or more in fluoric acid, sodium fluoride and calcirm-fluoride.
Wherein, there is provided the acid additive compound of P components for example can be phosphoric acid, Diammonium phosphate (DAP), phosphoric acid One or more in sodium dihydrogen and potassium dihydrogen phosphate.
Wherein, there is provided the acid additive compound of B component for example can be boric acid, metaborate and boric acid One or more in salt.
In the preparation method of above-mentioned modified support, the solution A is alkaline, can use this area Conventional alkaline matter causes the solution A in alkalescence, such as can use ammoniacal liquor, sodium hydroxide, hydrogen One or more in potassium oxide, sodium carbonate, potassium carbonate etc., to cause the solution A for alkalescence.It is excellent In the case of choosing, the pH value of the solution A is 7.5-11, more preferably 8-11.
In the preparation method of above-mentioned modified support, the solution B is acid, and the usual acidity helps Immunomodulator compounds enable to the solution B in acidity, but when the solution B does not show as acidity When, the acidic materials that this area can be used conventional cause the solution B in acidity, such as can use One or more in hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.Under preferable case, the pH of the solution B It is worth for 2-6.5, more preferably 4-6.
In the preparation method of above-mentioned modified support, the present invention does not have to the species of solvent in the solution A Especially limit, can be that existing various can dissolve the metal promoter compound in the basic conditions Inertia liquid, for example, water, alcohol (such as methanol, ethanol etc.), ether (such as second can be selected from Ether), the one or more in aldehyde (such as formaldehyde) and ketone (such as acetone).In addition, the solution Metal promoter compounds content can be 10-20 g/l in A.
In the preparation method of above-mentioned modified support, the present invention does not have to the species of solvent in the solution B Especially limit, can be that existing various can dissolve the acid additive compound in acid condition Inertia liquid, for example, water, alcohol (such as methanol, ethanol etc.), ether (such as second can be selected from Ether), the one or more in aldehyde (such as formaldehyde) and ketone (such as acetone).In addition, the solution B Middle acid additive compounds content can be 10-20 g/l.
In the preparation method of above-mentioned modified support, the carrier and the solution A and the solution B Dosage make in obtained modified support, on the basis of the gross weight of the modified support, aoxidized with metal The content of the metal promoter of thing meter is preferably 0.1-15 weight %, more preferably 0.2-12 weight %, more preferably 0.3-8 weight %, most preferably 1-3 weight %；In terms of tri- kinds of elements of F, P and B The content of the acid additive be preferably 0.1-15 weight %, more preferably 0.2-12 weight %, More preferably 0.3-8 weight %, most preferably 1-2 weight %.
In the preparation method of above-mentioned modified support, the 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, to what is impregnated described in step (1) and step (2) Condition is not particularly limited, and the immersion condition of two steps can be with identical or different, as long as enabling to gold Belong to auxiliary agent and acid additive load on the carrier, for example, the condition of dipping includes：Temperature is 20-300 DEG C (be preferably 40-100 DEG C, more preferably 40-80 DEG C), the time be 1-20 hours (preferably For 1-6 hours, more preferably 1-3 hours).
Dipping can use the conventional dipping method in this area to carry out above, such as can be that excessive liquid impregnates Method or saturation infusion process.
In the preparation method of above-mentioned modified support, drying described in step (1) and step (2) can be with For vacuum drying.The condition of the drying can be the conventional selection of this area, for example, step (1) In, dry condition can include：It (is preferably 50-300 DEG C, more preferably that temperature, which is 30-300 DEG C, 100-250 DEG C), the time is 1-20 hours (being preferably 2-18 hours, more preferably 3-10 hours). For example, in step (2), dry condition can include：It (is preferably 80-180 that temperature, which is 80-200 DEG C, DEG C, more preferably 80-150 DEG C), the time is 1-10 hours (to be preferably 2-8 hours, be more preferably 2-6 hours).
In the preparation method of above-mentioned modified support, the present invention does not have to the condition of the roasting in step (2) Have and especially limit, for example, in step (2), the condition of roasting includes：Temperature is 300-900 DEG C (excellent Elect 300-800 DEG C, more preferably 400-600 DEG C as), the time is that 1-10 hours, (preferably 2-8 was small When, 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 denitrifier can be the conventional hydrodenitrogeneration agent in this area.The denitrifier 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 denitrifier, 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 13-50 weight % (being preferably 13.1-30 weight %).
In the present invention, the group VIII metal can be selected from Ni, Co and Fe, preferably Ni and/ Or Co, most preferably Ni.The vib metals can be selected from Cr, Mo and W, be preferably Mo and/or W.
In the hydrotreating method of the high nitrogen inferior heavy oil provided by the invention, along logistics direction, institute The catalytic activity for stating protective agent, the metal remover and the denitrifier gradually increases.A kind of real Apply in mode, the active metal in active metal component content, the metal remover in the protective agent Active metal component content in constituent content and the denitrifier gradually increases.
A preferred embodiment of the invention, in order to further improve demetallization per, denitrification percent and De- carbon yield, in the denitrifier, radial direction of the active metal component along the catalyst carrier Direction is in layer distributed, and the active metal component of stratum nucleare is Ni components and W components, and the activity of shell is golden It is Ni components and Mo components to belong to component.
Here, introducing the concept of " shell " and " stratum nucleare ", but the explanation denitrifier is not it With two separable layers each other, but in order to illustrate there are two different activity in the denitrifier The distributed areas of metal component, and the two distributed areas are in stratiform, and one is located at the denitrifier The central area of grain, i.e. referred to as stratum nucleare, another is located at the surface region of the denitrifier particle, that is, claimed For shell.
It should be noted that " active metal component of stratum nucleare is Ni components and W components, the work of shell Property metal component be Ni components and Mo components " refer to radial direction along modified support, be carried on modification Active metal component in carrier is in layer distributed, forms the structure of similar stratum nucleare and shell, wherein, The active metal component of stratum nucleare is mainly Ni components and W components, and other a small amount of activity can also be distributed with Metal component such as Mo components；The active metal component of shell is mainly Ni components and Mo components, also may be used So that a small amount of other active metal components such as W components are distributed with.SEM-EDX is used in the present invention Described in the analysis of (Scanning Electron Microscope-Energy Dispersive Spectrometry) method Distribution of the active metal component along particle radial direction in denitrifier, and represent active metal with distribution factor σ The regularity of distribution of the component element along denitrifier particle radial direction.The distribution factor σ is that active metal component exists The content of a certain opening position of catalyst granules with center content the ratio between, if σ=1, show the point Active metal component constituent content is identical with center；If σ<1, then show this active metal component member Cellulose content is less than at center.Wherein, in the denitrifier, denitrifier particle outer layer (i.e. shell) The distribution factor σ ＞ 1 of Mo components, and the distribution of the W components of denitrifier particle outer layer (i.e. shell) Factor sigma ＜ 1.
In the denitrifier, 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 Mo components >=2.0, and the core Thickness degree refers to the thickness of the parts of 0.5≤σ of distribution factor ＜ 1 of W components.In the present invention, the shell The thickness of layer and stratum nucleare is measured using SEM-EDX methods, specifically, randomly selects 30 denitrifiers simultaneously Its cross section and particle diameter are measured with SEM, is obtained respectively along each denitrifier radial scan with EDX afterwards The radial distribution of Mo components and the thickness for obtaining the part of σ >=2.0, take the arithmetic mean of instantaneous value of above-mentioned thickness i.e. For the thickness of shell of the present invention；And obtain W along each denitrifier radial scan respectively with EDX The radial distribution of component and the thickness for obtaining the parts of 0.5≤σ ＜ 1, take the arithmetic mean of instantaneous value of above-mentioned thickness i.e. For the thickness of stratum nucleare of the present invention.
In the denitrifier, counted by metal oxide and on the basis of the gross weight of the catalyst, Ni The content of component can be 3-15 weight %, preferably 3.1-10 weight %.
In the denitrifier, counted by metal oxide and on the basis of the gross weight of the catalyst, W The content of component can be 13-50 weight %, preferably 13.1-35 weight %.
In the denitrifier, counted by metal oxide and on the basis of the gross weight of the catalyst, The content of Mo components can be 13-30 weight %, preferably 13.1-28 weight %.
It is highly preferred that the weight ratio for being distributed in the Ni components of stratum nucleare and being distributed in the Ni components of shell is 1： 0.5-1。
In the present invention, because the denitrifier 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 denitrifier 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 Ni can be NiO, the metal oxide as Mo Form can be MoO3, the metal oxide form as W can be WO3。
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 denitrifier can also contain the conventional adjuvant component in other this areas, example Such as Si.
A preferred embodiment of the invention, the denitrifier 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 by the catalyst carrier after hydro-thermal process in first acid containing nickel compound and molybdenum compound Impregnated in solution, be then dried；
(b) by the dried carrier of step (a) in the of alkalescence containing nickel compound and tungsten compound Impregnated in two solution, be then dried and be calcined.
In the above-mentioned method for preparing the denitrifier, although as long as before supported active metals component, The modified support is first subjected to hydro-thermal process, and is acid and by the second solution by the control of the first solution It is in point to control and radial direction of the active metal component along the modified support can be achieved for alkalescence 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 and tungsten compound can be each the oxidation of respective metal The compound of thing and the corresponding metal component of offer as hereinbefore defined, will not be repeated here.And Nickel compound is selected independently of one another used by step (a) and step (b), can with identical or It is different.
Wherein, first solution is acid that the acidic materials that this area can be used conventional cause institute The first 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 first solution in acidity.Under preferable case, the pH value of first solution is 2-6.5, More preferably 2-6, it is still more preferably 4-6.
Wherein, second solution is alkaline that the alkaline matter that this area can be used conventional causes institute The second 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 second solution for alkalescence.Under preferable case, described The pH value of two solution is 7.5-11, more preferably 8-11.
The present invention is not particularly limited to the species of solvent in first solution, can be existing various The inertia liquid of the nickel compound and the molybdenum compound, example can be dissolved in acid condition Such as, water, alcohol (such as methanol, ethanol etc.), ether (such as ether), aldehyde (such as formaldehyde) can be selected from At least one of with ketone (such as acetone).In addition, nickel compound and molybdenum chemical combination in first solution The total content of thing 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 nickel compound and the tungsten compound, example can be dissolved in the basic conditions Such as, water, alcohol (such as methanol, ethanol etc.), ether (such as ether), aldehyde (such as formaldehyde) can be selected from At least one of with ketone (such as acetone).In addition, nickel compound and tungsten are closed in second solution The total content of thing 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 denitrifier, in terms of metal oxide and with the gross weight of the denitrifier On the basis of, the content of Ni components can be 3-15 weight %, preferably 3.1-10 weight %；W components Content can be 13-50 weight %, preferably 13.1-35 weight %；The content of Mo components can be 13-30 weight %, preferably 13.1-28 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 denitrifier, 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 denitrifier 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 nitrogen 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 hydrotreating method of the high nitrogen inferior heavy oil provided by the invention, along logistics direction, institute The catalytic activity for stating protective agent, the metal remover and the denitrifier gradually increases, and aperture is gradually reduced, Granularity is gradually reduced.The pore volume of protectant carrier can be 0.85-1.0mL/g, and specific surface area can Think 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 nitrogen 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 hydrotreating method of the high nitrogen inferior heavy oil provided by the invention, to the heavy-oil hydrogenation The reaction condition of processing is not particularly limited, in a preferred embodiment, the reaction of the hydrotreating Condition includes：Temperature be 300-550 DEG C, more preferably 330-480 DEG C, hydrogen dividing potential drop 4-20MPa, More preferably 6-18MPa, volume space velocity 0.1-3.0h-1, more preferably 0.15-2h-1, Hydrogen to oil volume ratio is 200-2500, more preferably 300-2000.In the present invention, described pressure Refer to gauge pressure.
In the hydrotreating method of the high nitrogen inferior heavy oil provided by the invention, the hydrotreating Reaction unit can it is any be enough to make the heavy oil at hydrotreating reaction conditions with the catalyst Carried out in (i.e. protective agent, metal remover and denitrifier) catalytic reactor, for example, described Carried out in fixed bed reactors, moving-burden bed reactor or fluidized bed reactor.
In the hydrotreating method of the high nitrogen inferior heavy oil provided by the invention, in catalyst grade combo In conjunction, calculate by volume, the protective agent accounts for 1-20%, preferably 5-15%；The metal remover accounts for 15-60%, preferably 20-50%；The denitrifier 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.
It is special that the hydrotreating method of the high nitrogen inferior heavy oil provided by the invention is suitable for heavy oil feedstock It is that high nitrogen inferior heavy oil (such as high nitrogen poor residuum) carries out hydrotreating, (such as to be urged for subsequent technique Change process) qualified feedstock oil is provided.In the present invention, the heavy oil feedstock can be nitrogen content For the high nitrogen inferior heavy oil of 0.1-1 weight % (being preferably 0.3-0.9 weight %).
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 feedstock used in following examples and comparative example is Ni constituent contents 65.1ppm, V element Content 207ppm, density 1.01, the weight % of 18 weight %, S content of carbon residue 3.5, N content 0.74 Weight % 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 denitrogenation agent carrier Z3.Obtained using mercury injection method measurement, denitrifier Carrier Z pore volume is 0.7mL/g, specific surface area 231m2/g。
Embodiment 1
The present embodiment is used for the hydrotreating method for illustrating the high nitrogen inferior heavy oil 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 is with 165 milliliters of temperature in 135 DEG C of hydro-thermal process 12 hours, then by the carrier after hydrothermal treatment 40 DEG C contain 15 g/l of Mg (NO3)2The aqueous solution (pH value 11) saturation impregnate 1 hour, afterwards Dried 8 hours in 200 DEG C, obtain being loaded with the carrier of metal promoter；
The carrier for being loaded with metal promoter obtained in step (1) is by (1-2) in 145 milliliters of temperature 40 DEG C contain 10 g/l of H3BO3The aqueous solution (pH value 6) in dipping 1 hour, 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 denitrifier 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 by the carrier after hydrothermal treatment with 160 milliliters of temperature be 50 DEG C and pH value is 6 to contain The mixed solution of 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 200 DEG C dry 8 hours.Then, with 140 milliliters of temperature be 50 DEG C and pH value is 11 to contain The mixed solution of ammonium metatungstate and nickel nitrate is (wherein, with WO380 g/l of the concentration of the W elements of meter, Using the concentration of the NiO Ni elements counted as 30 g/l, solvent is water) saturation impregnate 2 hours, then Dried 3 hours in 120 DEG C, be calcined 3 hours then at 400 DEG C, obtain denitrifier 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, denitrifier 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 denitrogenation Agent.Whole reaction unit filling ratio, is that protective agent accounts for 6%, and metal remover accounts for 40% by volume, Denitrifier accounts for 54%.Reaction condition is：380 DEG C of temperature, hydrogen dividing potential drop 14MPa, volume space velocity 0.5h-1, Hydrogen to oil volume ratio is 500.
Embodiment 2
The present embodiment is used for the hydrotreating method for illustrating the high nitrogen inferior heavy oil 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 is with 155 milliliters of temperature in 120 DEG C of hydro-thermal process 20 hours, then by the carrier after hydrothermal treatment 50 DEG C contain 12 g/l of KNO3The aqueous solution (pH value 10) saturation impregnate 1 hour, after 100 DEG C of dryings 6 hours, obtain being loaded with the carrier of metal promoter；
The carrier for being loaded with metal promoter obtained in step (1) is by (1-2) in 135 milliliters of temperature 50 DEG C contain 12 g/l of H3PO4The aqueous solution (pH value 2) in dipping 1 hour, then in 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 denitrifier 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 carrier in 120 DEG C of hydro-thermal process 20 hours, Again by the carrier after hydrothermal treatment with 155 milliliters of temperature it is 50 DEG C and pH value is 2 to contain ammonium heptamolybdate Mixed solution with nickel nitrate is (wherein, with MoO3The concentration of the Mo elements of meter is 40 g/l, with NiO meter Ni elements concentration be 60 g/l, solvent is water) saturation impregnate 2 hours, after 100 DEG C of dryings 6 hours.Then, with 135 milliliters of temperature be 60 DEG C and pH value is 10 to contain metatungstic acid The mixed solution of ammonium and nickel nitrate is (wherein, with WO3100 g/l of the concentration of the W elements of meter, with NiO meter Ni elements concentration be 60 g/l, solvent is water) saturation impregnate 1 hour, Ran Houyu 120 DEG C of dryings 3 hours, it is calcined 3 hours then at 400 DEG C, obtains denitrifier 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, denitrifier 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 denitrogenation Agent.Whole reaction unit filling ratio, is that protective agent accounts for 6%, and metal remover accounts for 40% by volume, Denitrifier accounts for 54%.Reaction condition is：380 DEG C of temperature, hydrogen dividing potential drop 14MPa, volume space velocity 0.5h-1, Hydrogen to oil volume ratio is 500.
Embodiment 3
The present embodiment is used for the hydrotreating method for illustrating the high nitrogen inferior heavy oil 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 80 in 70 DEG C of hydro-thermal process 24 hours, then by the carrier after hydrothermal treatment DEG C contain 15 g/l of Ca (NO3)2The aqueous solution (pH value 8) saturation impregnate 1 hour, after 200 DEG C of dryings 8 hours, obtain being loaded with the carrier of metal promoter；
The carrier for being loaded with metal promoter obtained in step (1) is by (1-2) in 145 milliliters of temperature Dipping 1 hour in 80 DEG C of the aqueous solution (pH value 4) containing 10 g/l of hydrofluoric acid, then in 120 DEG C dry 3 hours, then at 400 DEG C be calcined 3 hours, obtain modified support S1-3, S2-3, S3-3.
(2) protective agent, metal remover and denitrifier 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 carrier in 70 DEG C of hydro-thermal process 24 hours, then will Carrier after hydrothermal treatment with 160 milliliters of temperature is 80 DEG C and pH value is 4 to contain ammonium heptamolybdate and nitre The mixed solution of sour nickel is (wherein, with MoO3The concentration of the Mo elements of meter is 100 g/l, with NiO The concentration of the Ni elements of meter be 70 g/l, solvent is water) saturation impregnate 1 hour, after 100 DEG C Dry 8 hours；Then, with the tungsten containing nitric acid and nitric acid that 140 milliliters of temperature are 80 DEG C and pH value is 8 The mixed solution of nickel is (wherein, with WO3150 g/l of the concentration of the W elements of meter, in terms of NiO The concentration of Ni elements be 70 g/l, solvent is water) saturation impregnate 1 hour, then in 120 DEG C of dryings 3 hours, it is calcined 3 hours then at 400 DEG C, obtains denitrifier 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, denitrifier 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 denitrogenation Agent.Whole reaction unit filling ratio, is that protective agent accounts for 6%, and metal remover accounts for 40% by volume, Denitrifier accounts for 54%.Reaction condition is：380 DEG C of temperature, hydrogen dividing potential drop 14MPa, volume space velocity 0.5h-1, Hydrogen to oil volume ratio is 500.
Embodiment 4
The present embodiment is used for the hydrotreating method for illustrating the high nitrogen inferior heavy oil provided by the invention.
According to the method implementation steps (1) of embodiment 2 to (3), except that, prepare denitrifier Process be：
200 grams of modified support S3-2 is taken, contains ammonium metatungstate, nickel nitrate and ammonium heptamolybdate with 200 milliliters Mixed solution (wherein, with WO3The concentration of the W elements of meter is 100 g/l, in terms of NiO The concentration of Ni elements is 60 g/l, with MoO340 g/l of the concentration of the Mo elements of meter, solvent are Water) impregnated 2 hours under room temperature (about 25 DEG C), after 120 DEG C dry 6 hours, then at 400 DEG C roasting 3 hours, obtain denitrifier CS3-4.
Embodiment 5
The present embodiment is used for the hydrotreating method for illustrating the high nitrogen inferior heavy oil provided by the invention.
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 denitrifier 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, and they are existed respectively 135 milliliters of temperature are 50 DEG C and contain 12 g/l of H3PO4The aqueous solution (pH value 2) in dipping it is 1 small When, then dry 3 hours in 120 DEG C, be calcined 3 hours then at 400 DEG C, respectively obtain reference modification Carrier DS1-1, DS2-1 and DS3-1, and these modified supports are mutually applied in subsequent step respectively.
Comparative example 3
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 155 milliliters Temperature is 50 DEG C and contains 12 g/l of KNO3The aqueous solution (pH value 10) saturation impregnate 1 hour, After 100 DEG C dry 6 hours, obtain 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 KNO in step (1-1)3The aqueous solution be in neutral (pH value 7), to respectively obtain reference modified support DS1-3, DS2-3 and DS3-3, and by these modified supports Mutually it is applied to respectively in subsequent step.
Test case 1
Using SEM-EDX methods to the Elemental redistribution in modified hydrogen at-ing catalyst carrier granular and shell and The thickness of stratum nucleare is analyzed.Due to the numeration in SEM-EDX characterization results along carrier radial direction every bit Rate is mutually corresponding with the constituent content, although the size of counting rate may not represent the true of the element Real content, but the size of counting rate reflects constituent content height.Therefore, in order to represent each element edge The regularity of distribution of carrier radial direction introduces distribution factor σ.Represent auxiliary agent on a certain position of particle with σ The ratio between concentration at the heart (R is particle radius, using at modified hydrogen at-ing catalyst carrier granular center as starting point). Concentration being averaged for certain neighbouring (position deviation≤20nm) 20 numerical point counting rate of point on a certain position Value；(position deviation≤20nm) 20 numerical point counting rates is flat near being put at center centered on concentration Average.If σ>1, then show the constituent content higher than at modified hydrogen at-ing catalyst carrier granular center； If σ=1, show that this constituent content is identical with modified hydrogen at-ing catalyst carrier granular center；If σ<1, then show that the constituent content is less than at modified hydrogen at-ing catalyst carrier granular center.Table 1 is to change The relevant parameter of property catalyst carrier for hydrgenating, wherein, the content of auxiliary agent is calculated according to inventory.Table 2 be distribution factor of the modified support at diverse location.Shell and distribution acid for being distributed metal promoter The thickness of the stratum nucleare of property auxiliary agent, shell thickness refer to the thickness of the part of the distribution factor σ of metal promoter >=2, Stratum nucleare thickness refers to the thickness of the parts of 0.5≤σ of distribution factor ＜ 1 of acid additive.
Table 1
Table 2
Numbering SZ1 SZ2 SZ3 SZ4 SZ5 DZ1 DZ2 DZ3 DZ4
R(mm) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7
σMg(R) 2.58 - - 1.97 2.81 1.04 - 1 1
σMg(2/3R) 1.96 - - 1.65 2.01 0.98 - 1 1
σMg(1/3R) 1.35 - - 1.35 1.57 1.02 - 1 1
σK(R) - 2.54 - - - - - - -
σK(2/3R) - 2.13 - - - - - - -
σK(1/3R) - 1.52 - - - - - - -
ΣCa(R) - - 2.79 - - - - - -
ΣCa(2/3R) - - 2.30 - - - - - -
ΣCa(1/3R) - - 1.16 - - - - - -
σP(R) - 0.18 - - - - - - -
σP(2/3R) - 0.41 - - - - - - -
σP(1/3R) - 0.70 - - - - - - -
σB(R) 0.25 - - 0.21 0.36 - 0.99 1 0.33
σB(2/3R) 0.38 - - 0.39 0.45 - 1.03 1 0.46
σB(1/3R) 0.89 - - 0.91 0.49 - 0.96 1 0.92
σF(R) - - 0.31 - - - - - -
σF(2/3R) - - 0.45 - - - - - -
σF(1/3R) - - 0.87 - - - - - -
By upper table 1 and 2 as can be seen that modified support provided by the invention includes carrier and is supported on institute The metal promoter and acid additive on carrier are stated, the metal promoter and acid additive are on the carrier Layer distributed, its shell are metal promoter, and its stratum nucleare is acid additive.
Test case 2
According to the method described in test case 1, unlike, measure be embodiment 1-3 denitrifier Active metal component is distributed and the thickness of stratum nucleare and shell, wherein, the thickness of shell refers to Mo point The thickness of the part of cloth factor sigma >=2.0, the thickness of stratum nucleare refer to the W parts of 0.5≤σ of distribution factor ＜ 1 Thickness.Table 3 below is the relevant parameter of denitrifier, wherein, active metal component content is according to inventory It is calculated.Table 4 is distribution factor of the denitrifier at diverse location.
Table 3
Table 4
Numbering CS3-1 CS3-2 CS3-3
R(mm) 0.55 0.55 0.55
σNi(R) 0.97 0.98 0.95
σNi(2/3R) 0.96 0.99 0.98
σNi(1/3R) 0.99 0.97 0.96
σMo(R) 2.6 2.7 2.5
σMo(2/3R) 2.1 2.2 2.2
σMo(1/3R) 1.5 1.3 1.4
σW(R) 0.2 0.3 0.1
σW(2/3R) 0.4 0.4 0.3
σW(1/3R) 0.9 0.9 0.9
Note：R refers to the grain diameter of whole denitrifier.
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 denitrification percent 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 % Denitrification percent %
Embodiment 1 71.3 90.3 69.9 76.9
Embodiment 2 72.2 91.1 69.1 77.5
Embodiment 3 71.1 90.5 69.3 76.6
Embodiment 4 70.9 89.6 68.9 75.9
Embodiment 5 69.7 88.9 67.8 74.6
Comparative example 1 64.9 80.1 56.9 50.9
Comparative example 2 66.2 82.2 59.5 53.6
Comparative example 3 66.1 81.8 58.8 53.9
Comparative example 4 66.0 82.1 58.9 53.8
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, nitrogen and carbon residue removal activity and long-term operation stability height.As can be seen here, The hydrotreating method of the high nitrogen inferior heavy oil provided by the invention can not only obtain higher metal, Nitrogen and carbon residue removal effect, more praiseworthy is catalyst stability height, and the duration of runs is grown, so as to the present invention The hydrotreating method of the high nitrogen inferior heavy oil provided has preferable prospects for commercial application.

Claims (11)

1. a kind of hydrotreating method of high nitrogen inferior heavy oil, this method include：In hydrogenation conditions Under, heavy oil feedstock is contacted with protective agent, metal remover and denitrifier successively, it is the protective agent, described Metal remover and the denitrifier are each containing catalyst carrier and the work being carried in the catalyst carrier Property metal component, it is characterised in that in the protective agent, the metal remover and the denitrifier extremely The catalyst carrier of few one is modified support, and the modified support contains the acid of layer distributed in the carrier Property auxiliary agent and metal promoter, the acid additive are distributed in stratum nucleare, and the metal promoter is distributed in shell, The acid additive is selected from least one of F components, P components and B component, and the metal promoter is Group ia metal component and/or group iia metal component, the active metal component are at least one the The combination of group vib metal component and at least one group VIII metal component.
2. according to the method for claim 1, wherein, the catalyst carrier of the denitrifier is to change Property carrier；
Preferably, the catalyst carrier of the protective agent, the metal remover and the denitrifier is to change Property carrier.
3. method according to claim 1 or 2, wherein, in the modified support, distribution The thickness of the stratum nucleare of the acid additive is 0.1-5mm, and the thickness for being distributed the shell of the metal promoter is 0.1-5mm；
Preferably, on the basis of the gross weight of the modified support, the metal in terms of metal oxide The content of auxiliary agent is 0.1-15 weight %, and the acid additive in terms of tri- kinds of elements of F, P and B contains Measure as 0.1-15 weight %；
Preferably, the metal promoter is selected from Li components, Na components, K components, Mg components and Ca One or more in component.
4. method according to claim 1 or 2, wherein, the modified support be by including with The method of lower step is made：
(1) carrier Jing Guo hydro-thermal process is provided with to the metal promoted of the metal promoter in alkaline containing Impregnated in the solution A of immunomodulator compounds, then dried；
(2) being helped containing the acidity for being provided with the acid additive in acidity by the carrier that step (1) obtains Impregnated in the solution B of immunomodulator compounds, be then dried and be calcined；
Preferably, the pH value of the solution A is 7.5-11, and the pH value of the solution B is 2-6.5.
5. 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.
6. 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 denitrifier, counted by metal oxide and on the basis of the gross weight of the denitrifier, 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 %.
7. according to the method for claim 6, wherein, in the denitrifier, 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 Ni components and W components, the active metal component of shell is Ni components and Mo components；
Preferably, counted and on the basis of the gross weight of the denitrifier by metal oxide, Ni components contain Measure as 3-15 weight %, preferably 3.1-10 weight %；The content of W components is 13-50 weight %, excellent Elect 13.1-35 weight % as；The content of Mo components is 13-30 weight %, preferably 13.1-28 weight %；
Preferably, the thickness for being distributed the shell of active metal component is 0.1-5mm, is distributed active metal group The thickness of the stratum nucleare divided is 0.1-5mm.
8. according to the method for claim 7, wherein, the denitrifier 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 is impregnated in the first solution containing nickel compound and molybdenum compound of acidity, is then done It is dry；
(b) by the dried carrier of step (a) in the of alkalescence containing nickel compound and tungsten compound Impregnated in two solution, be then dried and be calcined.
9. according to the method described in any one in claim 1-8, wherein, with the protective agent, On the basis of the total amount of the metal remover and the denitrifier, 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 Denitrifier accounts for 20-85 volume %, preferably 50-75 volumes %；
Preferably, the condition that heavy oil feedstock contacts with protective agent, metal remover and denitrifier successively 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。
10. according to the method described in any one in claim 1-8, wherein, along logistics direction, institute The catalytic activity for stating protective agent, the metal remover and the denitrifier gradually increases, and aperture is gradually reduced, Granularity is gradually reduced.
11. according to the method for claim 1, wherein, the heavy oil feedstock is that nitrogen content is 0.1-1 Weight % high nitrogen inferior heavy oil.
CN201610292644.1A 2016-05-05 2016-05-05 A kind of hydrotreating method of high nitrogen inferior heavy oil Active CN107345151B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610292644.1A CN107345151B (en) 2016-05-05 2016-05-05 A kind of hydrotreating method of high nitrogen inferior heavy oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610292644.1A CN107345151B (en) 2016-05-05 2016-05-05 A kind of hydrotreating method of high nitrogen inferior heavy oil

Publications (2)

Publication Number Publication Date
CN107345151A true CN107345151A (en) 2017-11-14
CN107345151B CN107345151B (en) 2019-06-14

Family

ID=60254126

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610292644.1A Active CN107345151B (en) 2016-05-05 2016-05-05 A kind of hydrotreating method of high nitrogen inferior heavy oil

Country Status (1)

Country Link
CN (1) CN107345151B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110404552A (en) * 2018-04-27 2019-11-05 中国石油化工股份有限公司 A kind of hydrodenitrogenation catalyst and its application
CN115608371A (en) * 2022-10-09 2023-01-17 中化泉州石化有限公司 Eggshell type residual oil hydrogenation catalyst and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362481A (en) * 2001-01-05 2002-08-07 中国石油化工股份有限公司 Catalyst sorting and loading method
CN102343284A (en) * 2010-07-28 2012-02-08 中国石油天然气股份有限公司 Hydrogenation catalyst carrier with acidic auxiliary agent in layered distribution and preparation method thereof
CN102343270A (en) * 2010-07-28 2012-02-08 中国石油天然气股份有限公司 Hydrogenation catalyst with active metal ingredient in layering distribution and preparation method thereof
CN103769235A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Shell distributed catalyst and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362481A (en) * 2001-01-05 2002-08-07 中国石油化工股份有限公司 Catalyst sorting and loading method
CN102343284A (en) * 2010-07-28 2012-02-08 中国石油天然气股份有限公司 Hydrogenation catalyst carrier with acidic auxiliary agent in layered distribution and preparation method thereof
CN102343270A (en) * 2010-07-28 2012-02-08 中国石油天然气股份有限公司 Hydrogenation catalyst with active metal ingredient in layering distribution and preparation method thereof
CN103769235A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Shell distributed catalyst and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李俊诚等: "水热改性对氧化铝载体织构和表面性质的影响", 《无机化学学报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110404552A (en) * 2018-04-27 2019-11-05 中国石油化工股份有限公司 A kind of hydrodenitrogenation catalyst and its application
CN110404552B (en) * 2018-04-27 2022-03-11 中国石油化工股份有限公司 Hydrodenitrogenation catalyst and application thereof
CN115608371A (en) * 2022-10-09 2023-01-17 中化泉州石化有限公司 Eggshell type residual oil hydrogenation catalyst and preparation method thereof
CN115608371B (en) * 2022-10-09 2024-04-30 中化泉州石化有限公司 Eggshell type residuum hydrogenation catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN107345151B (en) 2019-06-14

Similar Documents

Publication Publication Date Title
CN108745392B (en) Hydrodemetallization catalyst and preparation method thereof
CN106622308B (en) Hydrobon catalyst and its preparation method and application
CN107345151A (en) A kind of hydrotreating method of high nitrogen inferior heavy oil
CN106622266B (en) Hydrobon catalyst and its preparation method and application
CN103865568B (en) VB metal component-containing hydrogenation catalyst, preparation and application thereof
CN104226297B (en) A kind of heavy oil hydrogenating treatment catalyst and preparation and application thereof
CN107345150B (en) A kind of hydrotreating method of high nitrogen inferior heavy oil
CN106622269B (en) A kind of hydrodenitrogenation catalyst and its preparation method and application
CN107345152B (en) A kind of heavy oil hydrogenation treatment method
CN107345158B (en) A kind of heavy oil hydrogenation treatment method
CN110841651A (en) Boron-containing residual oil hydrotreating catalyst and preparation method thereof
CN104226323A (en) Heavy oil hydrotreating catalyst and preparation and application
CN106622270B (en) A kind of hydrodenitrogenation catalyst and its preparation method and application
CN106622264B (en) A kind of removal of ccr by hydrotreating catalyst and its preparation method and application
CN105749933B (en) A kind of preparation method of hydrogenation catalyst
CN106622307B (en) A kind of hydrogenation protecting agent and its preparation method and application
CN104437520B (en) A kind of heavy oil hydrogenating treatment catalyst and preparation thereof and application
CN103480409B (en) There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and method for hydrotreating hydrocarbon oil
CN106622263B (en) A kind of Hydrodemetalation catalyst and its preparation method and application
CN106622262B (en) A kind of hydrogenation protecting agent and its preparation method and application
CN106622261B (en) A kind of removal of ccr by hydrotreating catalyst and its preparation method and application
CN106622265B (en) A kind of Hydrodemetalation catalyst and its preparation method and application
CN105754641B (en) A kind of heavy oil hydrogenation treatment method
CN104588030B (en) Hydrocarbon oil hydrotreatment catalyst and preparation method thereof
CN104226298A (en) Heavy oil hydrotreatment catalyst, and preparation and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant