CN111097545A - Catalyst carrier and catalyst for residual oil hydrotreating and preparation method thereof - Google Patents

Catalyst carrier and catalyst for residual oil hydrotreating and preparation method thereof Download PDF

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CN111097545A
CN111097545A CN201811257506.5A CN201811257506A CN111097545A CN 111097545 A CN111097545 A CN 111097545A CN 201811257506 A CN201811257506 A CN 201811257506A CN 111097545 A CN111097545 A CN 111097545A
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channel
catalyst
carrier
residual oil
metal component
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朱慧红
刘铁斌
王永林
杨涛
袁胜华
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J23/883—Molybdenum and nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a catalyst carrier and a catalyst for residual oil hydrotreating and a preparation method thereof. The carrier is spherical, the outer diameter of the spherical carrier is 5.0-10.0 mm, the carrier at least comprises seven channels penetrating through the carrier, namely a first channel, a second channel, a third channel, a fourth channel, a fifth channel, a sixth channel and a seventh channel, the first channel, the second channel and the third channel penetrate through the sphere center of the catalyst carrier and are communicated with one another, the first channel, the second channel and the third channel are vertical in pairs, the fourth channel, the fifth channel, the sixth channel and the seventh channel are connected and communicated end to end, and the total volume occupied by the channels is 20-60% of the volume of the spherical carrier. The catalyst prepared by the catalyst carrier loaded with the active metal component has the characteristics of high porosity, good permeability, low bed pressure drop and uniform material distribution, is particularly suitable for the upflow residual oil hydrotreating process, and has the characteristics of high hydrogenation activity, long service cycle and the like.

Description

Catalyst carrier and catalyst for residual oil hydrotreating and preparation method thereof
Technical Field
The invention relates to a catalyst carrier and a catalyst for residual oil hydrotreatment and a preparation method thereof, in particular to a catalyst carrier and a catalyst for upflow residual oil hydrotreatment and a preparation method thereof.
Background
As crude oil gets heavier and worse, more and more heavy oil and residual oil need to be processed. The processing treatment of heavy oil and residual oil not only needs to crack the heavy oil and residual oil into low boiling point products, such as naphtha, middle distillate oil, vacuum gas oil and the like, but also needs to improve the hydrogen-carbon ratio of the heavy oil and residual oil, and the processing treatment needs to be realized by a decarburization or hydrogenation method. Wherein the decarbonization process comprises coking, solvent deasphalting, heavy oil catalytic cracking and the like; the hydrogenation process comprises hydrocracking, hydrofining, hydrotreating and the like. The hydrogenation process can not only hydrogenate and convert residual oil and improve the yield of liquid products, but also remove heteroatoms in the residual oil, has good product quality and has obvious advantages. However, the hydrogenation process is a catalytic processing process, and the problem of deactivation of the hydrogenation catalyst exists, and particularly, the problem of deactivation of the catalyst is more serious when inferior and heavy hydrocarbon raw materials are processed. In order to reduce the cost of processing heavy and poor residual oil and increase the profit of oil refineries, at present, the process for processing heavier and poor residual oil mainly uses a decarburization process, but the product quality is poor and can be utilized only by post-treatment, wherein particularly, deasphalted oil and coker gas oil fractions need to be subjected to hydrotreatment to continue to be processed by using lightening devices such as catalytic cracking or hydrocracking, and therefore, each oil refiner is additionally provided with a hydrotreatment device for deasphalted oil and coker gas oil.
The raw material cracking rate of heavy oil and residual oil hydrotreating technology is low, and the main purpose is to provide raw materials for downstream raw material lightening devices such as catalytic cracking or coking devices. The impurity content of sulfur, nitrogen, metal and the like in the inferior residual oil and the carbon residue value are obviously reduced through hydrotreating, so that the feed which can be accepted by a downstream raw material lightening device is obtained.
In the fixed bed residue hydrotreating technology, reactor types can be classified into general fixed bed reactors, i.e., a downflow mode reactor and an Upflow (UFR) reactor, according to the flow pattern of the reactant stream in the reactor. The upflow reactor is characterized in that the oil-gas mixture is fed from the bottom of the reactor to pass through the upflow catalyst bed layer upwards, the liquid phase is continuous in the reactor, the gas phase passes through the reactor in a bubbling mode, the whole catalyst bed layer slightly expands, the deposits of metal, coke and the like can be uniformly deposited on the whole catalyst bed layer, the deposits are prevented from being concentrated on a certain part, the performance of all catalysts is well exerted, and the rapid increase of the pressure drop of the catalyst bed layer is slowed down. Therefore, the catalyst is required to have not only higher hydrogenation activity but also higher crushing strength and wear resistance. Because the catalyst in the reactor is always in a micro-expansion state under high temperature and high pressure, the catalyst has more chances of collision and friction, is easy to break and wear, increases the consumption of the catalyst or brings adverse effects to downstream reactors and equipment. Further, there are also certain requirements for the bulk density, particle shape and particle size distribution of the catalyst, and it is generally considered that a preferable particle shape is a spherical shape with a fine particle size.
The upflow reactor (UFR) is generally arranged in front of the fixed bed reactor (downflow mode), which can greatly reduce the metal content in the feed entering the downflow fixed bed reactor, protect the fixed bed reactor catalyst and prevent the premature deactivation thereof. The upflow reaction has the technical characteristics that reactant flows from bottom to top, so that a catalyst bed layer is slightly expanded, and the pressure drop is small, thereby solving the problem of large pressure drop change at the initial stage and the final stage when the conventional fixed bed reactor processes inferior residual oil. The upflow reactor can better remove metal impurities so as to protect a downstream fixed bed reactor and prolong the running period of the device. The combined process can fully exert the respective advantages of the upflow reactor and the fixed bed reactor.
Hydrodesulfurization and demetalization are two important reactions in the hydrogenation process of heavy raw oil such as residual oil and the like, and are also main targets of heavy oil hydrogenation modification. A difficulty in residual oil processing is asphaltene conversion. The chemical structure of the asphaltene is very complex, and the asphaltene is composed of polymerized aromatic hydrocarbon, alkane chain and naphthene ring, and has very large molecular weight, and the average molecular size is about 6-9 nm. The asphaltene structure also contains heteroatoms such as sulfur, nitrogen, metal and the like, and 80-90% of the metal in the crude oil is enriched in the asphaltene. These impurities are "buried" within the molecule and require harsh operating conditions to remove the impurities. The rate of asphaltene decomposition during hydrogenation is related to the pore size of the catalyst used. The pore diameter of the catalyst is at least larger than 10nm, and the asphaltene is possibly diffused into the pore channels of the catalyst. The catalyst also needs to have a larger pore volume to improve diffusion performance and to accommodate more impurities. Thus, for the treatment of macromolecular compounds, the pore structure of the catalyst appears to be critical: the catalyst should have a certain number of macropores, so that larger asphalt molecules can easily approach the inner surface of the catalyst, and the maximum hydrodemetallization degree can be achieved. But the number of macropores cannot be too large, otherwise, the specific surface area is reduced, and the desulfurization activity is obviously reduced.
CN1665907A discloses an upflow hydrogenation catalyst, the carrier of which is composed of alumina, the pore volume is 0.6-1.1 mL/g, the specific surface area is 110-190 m2(ii)/g, less than 35% of the pores having a diameter greater than 1000 angstroms and a peak pore diameter of 80 to 140 angstroms, the catalyst being spherical or elliptical in shape and having a particle size of about 0.1 inch (about 2.5 mm). The catalyst is prepared by a conventional balling method. The catalyst has smaller average pore diameter, higher hydrodesulfurization activity and lower hydrodemetallization activity, and in the hydrogenation process of heavy oil, the heavy raw material is firstly contacted with the catalyst prepared according to the method of US5472928 under the condition of hydrodemetallization, and then the product is contacted with the catalyst for hydrodesulfurization. The catalyst is suitable for serving as a hydrodesulfurization catalyst, and the service life of the catalyst can be prolonged only by preparing a hydrodemetallization catalyst in a previous grading way, so that the catalyst is not suitable for being used in an upflow reactor independently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalyst carrier and a catalyst for residual oil hydrotreatment and a preparation method thereof. The catalyst provided by the invention has the characteristics of high void ratio, good permeability, low bed pressure drop, uniform material distribution, high hydrogenation activity, long service cycle and the like, and is particularly suitable for an up-flow residual oil hydrotreating process.
The invention provides a residual oil hydrotreating catalyst carrier, which is spherical, wherein the outer diameter of the spherical carrier is 5.0-10.0 mm, the carrier at least comprises seven channels penetrating through the carrier, namely a first channel, a second channel, a third channel, a fourth channel, a fifth channel, a sixth channel and a seventh channel, the first channel, the second channel and the third channel penetrate through the sphere center of the catalyst carrier and are communicated with each other, the first channel, the second channel and the third channel are vertical in pairs, the fourth channel, the fifth channel, the sixth channel and the seventh channel are connected and communicated end to end, and the total volume occupied by the channels is 20-60% of the volume of the spherical carrier, preferably 22-60%.
In the residual oil hydrotreating catalyst carrier provided by the invention, the fourth channel, the fifth channel, the sixth channel and the seventh channel can be in the same plane or not. Furthermore, the fourth channel, the fifth channel, the sixth channel and the seventh channel are square in the same plane to form a square channel, and further, the square channel and any two of the first channel, the second channel and the third channel are in the same plane and are communicated with the square channel. Further, the length of the fourth, fifth, sixth or seventh channels forming the square channels is at least 1/3 to 2/3 of the outer diameter of the carrier sphere.
In the residue oil hydrotreating catalyst carrier provided by the invention, the cross section of the channel is circular, polygonal, elliptical or irregular, preferably circular.
In the residual oil hydrotreating catalyst carrier provided by the invention, each channel is a straight channel, and the cross section of each channel is the same in shape, preferably circular; further preferably, the diameters of the first channel, the second channel and the third channel are the same, and the diameters of the fourth channel, the fifth channel, the sixth channel and the seventh channel are the same; and the maximum diameter of the fourth channel, the fifth channel, the sixth channel or the seventh channel is 20-80%, preferably 35-65% of the minimum diameter of the first channel, the second channel or the third channel.
The residual oil hydrotreating catalyst carrier of the invention is Al2O3-SiO2As a carrier, wherein SiO2The weight content is 35-80%, preferably 40-60%.
The residue hydrotreating catalyst carrier of the present invention preferably further contains a first metal component oxide, and the first metal component oxide is NiO. The first metal component oxide NiO and Al2O3Is 0.03: 1-0.13: 1, preferably 0.05: 1-0.11: 1.
in the residue oil hydrotreating catalyst carrier of the present invention, the properties are as follows: the specific surface area is 80-200 m2The pore volume is more than 0.79mL/g, preferably 0.79-1.15 mL/g, the pore volume occupied by the pore diameter of 16-100 nm is 35-60% of the total pore volume, and the average pore diameter is more than 18nm, preferably 20-30 nm.
The second aspect of the invention provides a residual oil hydrotreating catalyst, which comprises a carrier and an active metal component, wherein the carrier adopts the carrier provided by the first aspect.
The active metal component of the residual oil hydrotreating catalyst comprises a second metal component, namely a VIB group metal element and a third metal component, namely a VIII group metal element, wherein the VIB group metal element is preferably Mo, and the VIII group metal element is preferably Ni and/or Co. Wherein, the content of the second metal component calculated by oxide is 1.0-10.0%, preferably 1.5-9%, the total content of the first metal component and the third metal component calculated by oxide is 1.0-10.0%, preferably 2.0-8.0%, the content of silicon oxide is 35.0-55.0%, and the content of aluminum oxide is 35.0-55.0%.
Furthermore, the catalyst also comprises an auxiliary agent, wherein the auxiliary agent is at least one of P, B, Ti and Zr, and is preferably P.
The third aspect of the invention provides a preparation method of a residual oil hydrotreating catalyst carrier, which comprises the following steps:
(1) adding an acidic peptizing agent into a silicon source for acidification treatment;
(2) adding aluminum sol and gamma-Al into the step (1)2O3Curing agent to prepare paste material;
(3) adding the paste material obtained in the step (2) into a mould, and heating the mould containing the paste material for a certain time to solidify and form the paste material;
(4) and (4) removing the material in the step (3) from the mold, washing, drying and roasting to obtain the catalyst carrier.
In the method of the present invention, the first metal oxide is preferably introduced into the support, and the first metal source (nickel source) may be introduced in step (1) and/or step (2), and the preferred introduction method is as follows: adding a nickel source into the material obtained in the step (1), and dissolving the nickel source into the material. The nickel source can adopt soluble nickel salt, wherein the soluble nickel salt can be one or more of nickel nitrate, nickel sulfate and nickel chloride, and nickel nitrate is preferred.
In the method, the silicon source in the step (1) is one or more of water glass and silica sol, wherein the mass content of silicon in terms of silicon oxide is 20-40%, preferably 25-35%; the acid peptizing agent is one or more of nitric acid, formic acid, acetic acid and citric acid, preferably nitric acid, the mass concentration of the acid peptizing agent is 55-75%, preferably 60-65%, and the adding amount of the acid peptizing agent is that the molar ratio of hydrogen ions to silicon dioxide is 1: 1.0-1: 1.5; the pH value of the silicon source after acidification treatment is 1.0-4.0, preferably 1.5-2.5.
In the method of the invention, the aluminum sol in the step (2) can be trihydroxy aluminum chloride and contains Al (OH)3And AlCl3The colloidal solution is prepared by boiling and dissolving metal aluminum and HCl which are used as raw materials at a certain temperature, wherein the Al/Cl ratio of the aluminum sol used in the invention is 1.15-1.46, and the content of aluminum oxide is 25-30 wt%; the gamma-Al2O3The precursor is calcined to form pseudo-boehmite with the propertiesThe following were used: the pore volume is more than 0.95mL/g, the preferable pore volume is 0.95-1.2 mL/g, and the specific surface area is 270m2More than g, preferably the specific surface area is 270-330 m2(g) aluminum in the alumina sol of the support prepared, calculated as alumina, with gamma-Al2O3The mass ratio of the provided alumina is 1: 1-1: 3; the curing agent is one or more of urea and organic amine salt. The organic amine salt is hexamethylenetetramine. The addition amount of the curing agent is 1: 1.5-1: 2.0 in terms of the molar ratio of nitrogen atoms to silicon dioxide; the solid content of the prepared paste material is 25-45 percent, preferably 28-40 percent by weight of silicon dioxide and aluminum oxide, and the paste material has a plastic body with certain fluidity.
In the method, the die in the step (3) comprises a shell with a spherical cavity and a guide die capable of forming a through channel, wherein the shell is made of rigid materials, and the external shape can be any shape, preferably a spherical symmetrical geometric shape. The invention is illustrated by taking the case that the external shape is spherical, and the spherical shell can be composed of two identical hemispheres or four quarter spheres. The diameter of the spherical cavity can be adjusted according to the size of the final catalyst particles. The guide mould capable of forming the through channel is made of a material which can be burnt or dissolved by heating, such as graphite, wood, paper, paraffin, petroleum resin and the like. For example, three columns are made of the material, the length of each column is the diameter of the cavity, the centers of the three columns are intersected and perpendicular to each other, and then four columns are made of the material, the length of each column is 1/3-2/3 of the diameter of the cavity, wherein the fourth column, the fifth column, the sixth column and the seventh column are connected end to end and communicated, and can be in the same plane or different planes。Furthermore, the fourth cylinder, the fifth cylinder, the sixth cylinder and the seventh cylinder are square in the same plane, and further, any two of the square, the first cylinder, the second cylinder and the third cylinder are in the same plane and connected with the square. The total volume occupied by the column bodies is 20 to 60 percent of the volume of the spherical carrier, and preferably 30 to 60 percent%。
The structure of the guide die is matched with each through hole in the carrier, namely, a channel generated after the guide die is removed.
In the residue oil hydrotreating catalyst carrier provided by the invention, the cross section of the channel is circular, polygonal, elliptical or irregular, preferably circular.
And (3) heating the paste material containing mould in the step (3) at the temperature of 70-200 ℃, preferably 100-150 ℃, and keeping the temperature for 30-240 minutes, preferably 50-120 minutes.
In the method, in the step (4), as the pasty material in the mould is heated and releases alkaline gas, the pasty material is solidified and contracted, and then is automatically demoulded; washing in the step (4) is to wash the demolded spherical material to be neutral by using deionized water; the drying temperature is 100-150 ℃, and the drying time is 4-10 hours. The roasting temperature is 500-900 ℃, preferably 550-800 ℃, and the roasting time is 2-8 hours.
The fourth aspect of the invention provides a preparation method of a residual oil hydrotreating catalyst, which comprises the preparation of a carrier and the loading of an active metal component. The preparation method of the carrier is the same as that of the residual oil hydrotreating catalyst carrier provided by the third aspect.
In the preparation method of the residual oil hydrotreating catalyst, the loading method of the active metal component can adopt an impregnation method, namely, a step (5) is added after the catalyst carrier prepared in the step (4), and the preparation method specifically comprises the following steps: and (4) impregnating the carrier obtained in the step (4) with active metal components of the supported catalyst, and drying and roasting to obtain the residual oil hydrotreating catalyst.
In the method, the drying and roasting conditions of the carrier in the step (5) after the carrier is impregnated with the active metal component of the catalyst are as follows: drying at 100-150 ℃ for 4-10 hours, and roasting at 400-600 ℃ for 2-6 hours.
In a fifth aspect, the invention provides a residual oil hydrotreating method, wherein at least one reactor adopts an upflow reactor, and the upflow reactor is filled with at least one residual oil hydrotreating catalyst of the invention.
In the residual oil hydrotreating method of the present invention, the upflow reactor adopts the following operating conditions: the reaction pressure is 5-25 MPa, the reaction temperature is 300-420 ℃, and the liquid hourly space velocity is 0.05-5.00 h-1The volume ratio of hydrogen to oil is 150: 1-400: 1.
The residual oil hydrotreating catalyst of the present invention can treat heavy residual oil material with high metal impurity content and relatively poor performance.
Compared with the prior art, the invention has the advantages that:
1. the residual oil hydrotreating catalyst of the invention adopts the silicon-aluminum carrier with proper granularity, pore channel structure and unique channel structure, on one hand, the catalyst bed layer has higher porosity, on the other hand, the catalyst bed layer has good diffusion channel and reaction channel, the diffusion path of residual oil molecules is shortened, and simultaneously, the catalyst bed layer has higher activity.
2. The residual oil hydrotreating catalyst of the invention also has higher mechanical strength and wear resistance, so that the catalyst has good stability, is suitable for the upflow residual oil hydrotreating process, especially for the hydrodemetallization reaction, and can eliminate the influence of macromolecular diffusion on the reaction. The initial pressure reduction of the catalyst bed layer is also beneficial to the long-period stable operation of the device.
3. In the method of the invention, gamma-Al is added when preparing the formed paste material2O3The gamma-Al2O3A certain skeleton is formed in the carrier, so that the carrier can hold some gamma-Al2O3Pore volume, specific surface area and pore diameter; at the same time, gamma-Al2O3Seed crystals which can also become subsequent precipitates are added, so that the subsequent precipitates can obtain larger and uniform crystal grains, and the carrier is ensured to have larger pore volume and concentrated pore diameter; gamma-Al2O3The solid content in the paste material can be adjusted more flexibly and conveniently by adding the paste material.
4. In the method, the curing agent is added when the formed paste material is prepared, so that a certain amount of ammonia is released in the subsequent drying process, on one hand, the material is cured, the strength of the carrier is increased, on the other hand, the released ammonia gas enlarges the pore channel of the carrier and the connectivity between the pore channel of the carrier and the channel in the escape process, so that the prepared carrier has better strength, larger pore volume, larger specific surface area, larger pore diameter and pore channel connectivity, and is suitable for the diffusion and conversion of macromolecules such as asphaltene and the like.
5. In the method, a small amount of nickel salt is preferably added in the preparation process of the catalyst carrier, so that a proper amount of nickel-aluminum spinel structure is generated in the roasting process, the strength and the water resistance of the catalyst are further improved, and the catalytic performance is not influenced.
6. The residual oil hydrotreating catalyst of the invention is especially suitable for the residual oil hydrodemetallization process of an up-flow reactor, can effectively remove metal impurities under the condition of lower hydrogen-oil volume ratio, has small heat release of a catalyst bed layer, reduces quenching media between catalyst bed layers, reduces the risk of bed layer disturbance, and ensures that the device operates more stably.
Drawings
FIG. 1 is a schematic cross-sectional view of a residue hydrotreating catalyst support preparation process of the present invention;
FIG. 2 is a schematic drawing of a guided mode of a residue hydrotreating catalyst support of the present invention;
FIG. 3 is a schematic cross-sectional view of a residue hydrotreating catalyst support of the present invention;
the reference numerals are explained below:
10. a catalyst support; 100. a pasty material; 20. a mold; 30. guiding a mold; 101a, a first mandrel; 102a, a second mandrel; 103. a third channel; 103a. a third mandrel; 104a, a fourth column, 105a, a fifth column; 106a, a sixth column; 107a, seventh column.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
In the invention, the specific surface area, the pore volume, the pore diameter and the pore distribution are measured by a mercury intrusion method.
In the present invention, the volume of the spherical support is (4/3) π R3Wherein R is half of the outer diameter D of the spherical support i.e. R = D/2. The total volume occupied by each channel was measured as follows: firstly, preparing the carrier to be detected and a contrast carrier, wherein the contrast carrier is prepared by the same method except that a non-porous entity is adopted to replace the part corresponding to the guide mould of the invention. The pore volumes of the carrier and the contrast carrier are determined by a water titration method, the carrier and the contrast carrier are respectively filled in a 100mL measuring cylinder to 100mL scales, then deionized water is added in the measuring cylinder to 100mL scales, the volume of the added water minus the pore volume of the 100mL contrast carrier is the volume between 100mL contrast carrier particles, the volume of the added water minus the pore volume of the 100mL carrier is the volume between 100mL carrier particles and the total volume of each channel, the volume between the carrier and the contrast carrier particles is considered to be the same, and the difference between the two is the total volume of each channel. Although only the guide mold is different when the control carrier is prepared, the rest part outside the channel is not completely the same as the control carrier due to decomposition of the guide mold in the carrier of the present invention, but the difference from this part is considered to be negligible in the present invention.
As shown in fig. 1 to 3, the catalyst carrier 10 of this embodiment is a spheroid structure of a paste material 100 after solidification, and a first tubular channel, a second tubular channel, and a third tubular channel 103 are arranged inside the material 100, and the first tubular channel, the second tubular channel, and the third tubular channel 103 are perpendicular to each other, and all the three tubular channels penetrate through the sphere center of the catalyst carrier 10, so that the three tubular channels are completely communicated. It should be noted that: fig. 3 of this embodiment does not clearly distinguish the individual channels, and therefore the corresponding columns are identified in fig. 2. In this embodiment, seven channels are provided, except that the first, second and third channels 103 correspond to the first mandrel 101a, the second mandrel 102a and the third mandrel 103a in fig. 2, respectively, fig. 2 also shows a fourth cylinder 104a, a fifth cylinder 105a, a sixth cylinder 106a and a seventh cylinder 107a, none of the fourth to seventh channels finally formed by the four cylinders passes through the spherical center of the catalyst carrier 10, the fourth to seventh channels are connected end to form a square channel as in fig. 2, and the four channels are not only communicated with each other, but also communicated with the first to third channels.
Referring to fig. 3, the catalyst carrier 10 of this embodiment is a spheroid structure formed by solidifying the pasty material 100, and the material 100 has a first, a second and a third tubular channels 103, which are perpendicular to each other and penetrate through the center of the catalyst carrier 10, and the three channels penetrate through the center of the catalyst carrier 10, so that the three channels are completely connected. Meanwhile, the carrier 10 is also provided with a fourth channel, a fifth channel, a sixth channel and a seventh column channel which are connected with each other in an end-to-end manner and communicated with each other, the length of the fourth channel, the fifth channel, the sixth channel and the seventh column channel is 1/3-2/3 of the diameter of the carrier 10, the fourth channel, the fifth channel, the sixth channel and the seventh column channel are square in the same plane, and the square is connected with any two of the first channel, the second channel and the third channel in the same plane. The total volume occupied by the channels is 20-60%, preferably 22-60% of the volume of the spherical carrier.
It should be noted that: the channel solutions of fig. 1-3 can also have many other variations without departing from the design concept, and are not described in detail here.
In the present invention, percentages and percentages are by mass unless otherwise specifically indicated.
Throughout the specification and claims, unless explicitly described otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated step or element but not the exclusion of any other step or element.
The present invention is further illustrated by the following examples, but it should be understood that the scope of the present invention is not limited by the examples.
Example 1
Weighing a silica content of 28wt%1071g of water glass is added into a beaker, a stirring device is started, 370g of nitric acid solution with the mass concentration of 65 percent is slowly added into the beaker, the pH value of the water glass solution in the beaker after being stirred and dissolved is 2.0, 93.14g of nickel nitrate hexahydrate is added, 585g of alumina sol (with the following properties that the Al/Cl ratio is 1.40, the content of alumina is 28 weight percent) and gamma-Al are added into the solution after being dissolved2O3163.8g (properties are as follows: pore volume is 1.098mL/g, specific surface area is 302m2And/g), stirring uniformly, adding 93.6g of hexamethylene tetramine as a curing agent, adding deionized water after the hexamethylene tetramine is completely dissolved, and enabling the materials in the beaker to be in a paste shape with certain fluidity and the solid content of the materials calculated by silicon dioxide and aluminum oxide to be 33%.
The pasty material is pressed into two identical hemispheres with spherical cavities. Wherein a guide die is placed in one hemisphere, and the guide die is made of wood. The structure of the guide die is that three cylinders are made of the materials, the length of each cylinder is the diameter of a cavity, the centers of the three cylinders are intersected and perpendicular to each other, and then four cylinders are made of the materials, wherein the fourth cylinder, the fifth cylinder, the sixth cylinder and the seventh cylinder are connected end to end and communicated, the fourth cylinder, the fifth cylinder, the sixth cylinder and the seventh cylinder are square in the same plane, and the square is connected with any two of the first cylinder, the second cylinder and the third cylinder in the same plane. See the cross-sectional view of the center of the sphere of fig. 3. The pasty material is pressed into the two hemispheroidal cavities, and the two hemispheroids are combined together to form a complete sphere and fixed after the whole cavity is filled with the pasty material.
Heating the ball containing the paste material to 120 ℃, keeping the temperature for 60 minutes, releasing ammonia gas after the paste material is heated to enable the paste material to be solidified and contracted, then automatically demoulding to form spherical gel, washing the spherical gel to be neutral by deionized water, drying for 5 hours at 120 ℃, and roasting for 3 hours at 700 ℃. And burning the guide die which can form the through channel in the roasting process, and leaving the through channel required by the catalyst, thereby obtaining the spherical catalyst carrier A. The outer diameter of the obtained catalyst carrier A is about 5.5mm, wherein the lengths of the first channel, the second channel and the third channel are 5.5mm, and the diameter of the channels is about 1.6 mm; the length of the fourth channel, the fifth channel, the sixth channel and the seventh channel forming the square channel is 4mm, and the diameter of the channels is about 0.6 mm.
Soaking the carrier A in Mo-Ni-P solution, drying at 120 deg.c for 6 hr, and roasting at 500 deg.c for 3 hr to obtain the catalyst ACThe catalyst properties are shown in Table 1, and the catalyst evaluation results are shown in Table 2. Wherein the impurity removal rate of the catalyst is measured in the reaction 1620 h.
Example 2
The preparation process was as in example 1 except that 97.2g of urea was added instead of hexamethylenetetramine as a curing agent and 62.5g of nickel nitrate hexahydrate were added instead, and catalyst carrier B and catalyst B were preparedCThe properties are shown in Table 1, and the catalyst evaluation results are shown in Table 2. Wherein the impurity removal rate of the catalyst is measured in the reaction 1620 h.
Wherein the outer diameter of the obtained catalyst carrier B is about 5.5mm, the diameters of the through holes of the first channel, the second channel and the third channel are about 1.5mm, and the lengths of the first channel, the second channel and the third channel are 5.5 mm; the fourth, fifth, sixth and seventh channels forming the square channels were all 4.2mm in length and approximately 0.8mm in channel diameter.
Example 3
The preparation process was as in example 1 except that the mold was changed, the diameters of the cavity and the cylinder were increased, and the prepared catalyst carrier C and catalyst C were usedCThe properties are shown in Table 1, and the catalyst evaluation results are shown in Table 2. Wherein the impurity removal rate of the catalyst is measured in the reaction 1620 h.
Wherein the outer diameter of the obtained catalyst carrier C is about 7.5mm, the diameters of the through holes of the first channel, the second channel and the third channel are about 2.6mm, the lengths of the first channel, the second channel and the third channel are 7.5mm, the lengths of the fourth channel, the fifth channel, the sixth channel and the seventh channel which form the square channels are all 6mm, and the diameter of the channels is about 1.3 mm.
Example 4
The preparation process was as in example 1 except that the mold was changed, the diameters of the cavity and the cylinder were increased, and the prepared catalyst carrier D and the catalyst D were usedCThe properties are shown inTable 1, catalyst evaluation results are shown in table 2. Wherein the impurity removal rate of the catalyst is measured in the reaction 1620 h.
The outer diameter of the obtained catalyst carrier D is about 6.0mm, the diameters of through holes of the first channel, the second channel and the third channel are about 1.5mm, the lengths of the first channel, the second channel and the third channel are 6mm, the lengths of the fourth channel, the fifth channel, the sixth channel and the seventh channel which form the square channels are 4.5mm, and the diameter of the channels is about 0.9 mm.
Example 5
The preparation process was as in example 1 except that the amount of hexamethylenetetramine as a curing agent was changed to 127.1g, the amount of water glass was adjusted to 1400g, and the catalyst carrier E and the catalyst E were preparedCThe properties are shown in Table 1, and the catalyst evaluation results are shown in Table 2. Wherein the impurity removal rate of the catalyst is measured in the reaction 1620 h.
The outer diameter of the obtained catalyst carrier E is about 5.5mm, the diameters of through holes of the first channel, the second channel and the third channel are about 1.3mm, the lengths of the first channel, the second channel and the third channel are 5.5mm, the lengths of the fourth channel, the fifth channel, the sixth channel and the seventh channel which form the square channels are all 4mm, and the diameter of the channels is about 0.6 mm.
Example 6
The procedure was as in example 1 except that nickel nitrate was not added, and catalyst carrier F and catalyst F were preparedCThe properties are shown in Table 1, and the catalyst evaluation results are shown in Table 2. Wherein the impurity removal rate of the catalyst is measured in the reaction 1620 h.
The outer diameter of the obtained catalyst carrier F is about 5.5mm, the diameter of the through hole is about 1.6mm, the lengths of the first channel, the second channel and the third channel are 5.5mm, the lengths of the fourth channel, the fifth channel, the sixth channel and the seventh channel which form the square channel are 4mm, and the diameter of the channels is about 0.6 mm.
Comparative example 1
1071g of water glass with the silicon oxide content of 28wt% is weighed and added into a beaker, a stirring device is started, 370g of nitric acid solution with the mass concentration of 65% is slowly added into the beaker, and the water glass solution in the beaker after stirring and dissolvingWas added thereto 93.14g of nickel nitrate hexahydrate, and after dissolution, 585g of alumina sol (property: Al/Cl ratio of 1.40, alumina content of 28 wt.%) and γ -Al were added to the above solution2O3163.8g (properties are as follows: pore volume is 1.098mL/g, specific surface area is 302m2And/g), stirring uniformly, adding 93.6g of hexamethylene tetramine as a curing agent, adding deionized water after the hexamethylene tetramine is completely dissolved, and enabling the materials in the beaker to be in a paste shape with certain fluidity and the solid content of the materials calculated by silicon dioxide and aluminum oxide to be 33%.
The pasty material is pressed into two identical hemispheres with spherical cavities. The pasty material is pressed into the two hemispheroidal cavities, and the two hemispheroids are combined together to form a complete sphere and fixed after the whole cavity is filled with the pasty material.
Heating the sphere containing the paste material to 120 ℃, keeping the temperature for 60 minutes, releasing ammonia gas after the paste material is heated to enable the paste material to be solidified and contracted, then automatically demoulding to form spherical gel, washing the spherical gel to be neutral by deionized water, drying for 5 hours at 120 ℃, and roasting for 3 hours at 700 ℃ to obtain the spherical catalyst carrier G of the comparative example. The outer diameter of the resulting catalyst carrier G was about 5.5 mm.
The carrier G is dipped in Mo-Ni-P solution, dried for 6 hours at 120 ℃, and roasted for 3 hours at 500 ℃ to obtain the catalyst Gc, the properties of the catalyst are shown in Table 1, and the evaluation results of the catalyst are shown in Table 2. Wherein the impurity removal rate of the catalyst is measured in the reaction 1620 h.
Comparative example 2
1071g of water glass with the silicon oxide content of 28wt% is weighed and added into a beaker, a stirring device is started, 370g of nitric acid solution with the mass concentration of 65% is slowly added into the beaker, the pH value of the water glass solution in the beaker after stirring and dissolving is 2.0, 93.14g of nickel nitrate hexahydrate is added, 585g of alumina sol (with the following properties, the Al/Cl ratio is 1.40, the aluminum oxide content is 28%) and gamma-Al are added into the solution after dissolving2O3163.8g (properties are as follows: pore volume is 1.098mL/g, specific surface area is 302m2Perg), after stirring uniformly, adding 93.6g of hexamethylenetetramine as a curing agent until hexamethylenetetramine is obtainedAnd (3) adding deionized water after the tetramine is completely dissolved, so that the material in the beaker is in a paste state with certain fluidity, and the solid content is 33% in terms of silicon dioxide and aluminum oxide.
The pasty material is pressed into two identical hemispheres with spherical cavities. The pasty material is pressed into the two hemispheroidal cavities, and the two hemispheroids are combined together to form a complete sphere and fixed after the whole cavity is filled with the pasty material.
Heating the sphere containing the paste material to 120 ℃, keeping the temperature for 60 minutes, releasing ammonia gas after the paste material is heated to enable the paste material to be solidified and contracted, then automatically demoulding to form spherical gel, washing the spherical gel to be neutral by deionized water, drying for 5 hours at 120 ℃, and roasting for 3 hours at 700 ℃ to obtain the spherical catalyst carrier H of the comparative example. The outer diameter of the resulting catalyst carrier H was about 2.5 mm.
The carrier H is dipped in Mo-Ni-P solution, dried for 6 hours at 120 ℃, and roasted for 3 hours at 500 ℃ to obtain the catalyst Hc, the properties of the catalyst are shown in Table 1, and the evaluation results of the catalyst are shown in Table 2. Wherein the impurity removal rate of the catalyst is measured in the reaction 1620 h.
TABLE 1 Properties of catalyst supports and catalysts prepared in inventive and comparative examples
Catalyst support numbering A B C D E F G H
Pore volume, mL/g 0.814 0.808 0.813 0.801 0.798 0.815 0.784 0.787
Specific surface area, m2/g 139 141 137 139 141 141 153 155
Average pore diameter, nm 23.4 22.9 23.7 23.1 22.6 23.1 20.5 20.3
Hole distribution,%
<8.0nm 0.8 0.7 0.7 0.8 0.6 0.5 1.6 1.8
8-16 nm 34.5 34.3 34 34.4 34.4 34.4 39.3 36.5
16-100 nm 58.1 58.1 58.7 58.3 58.6 58.9 52.1 54.2
>100.0nm 6.6 6.9 6.6 6.5 6.4 6.2 7 7.5
Catalyst numbering AC BC CC Dc Ec Fc GC HC
Metal content%
MoO3 8.5 8.7 8.3 8.4 8.5 8.4 8.6 8.5
NiO 5.1 4.3 5.0 5.0 5.0 2.1 5.1 5.1
Lateral pressure strength, N/grain 45 38 34 46 48 30 87 54
Catalyst A to be preparedC-HCThe activity and stability evaluations were performed on a medium upflow residuum hydrotreater with the results shown in table 2.
TABLE 2 evaluation results of catalysts prepared in inventive examples and comparative examples
Catalyst numbering AC BC CC Dc Ec Fc GC HC
Properties of crude oil
S，wt% 3.25 3.14 3.32 3.16 3.17 3.22 3.20 3.17
N，wt% 0.28 0.29 0.28 0.26 0.29 0.27 0.27 0.28
Carbon residue in wt% 12.23 11.38 11.47 12.20 12.50 11.96 12.67 12.4
Metal (Ni + V), mg/kg 70.20 70.30 71.10 69.70 68.50 71.20 72.4 69.9
Evaluation conditions
Liquid hourly volume space velocity, h-1 0.52 0.52 0.52 0.52 0.52 0.52 0.52 0.52
Average temperature of catalyst bed, deg.C 380 380 380 380 380 380 380 380
Inlet pressure, MPa 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0
Inlet hydrogen to oil ratio, Nm3/m3 330 330 330 330 330 330 330 330
Desulfurization degree, wt% 59.2 59.8 58.5 57.4 57.8 59.6 44.7 52.3
Percent of carbon residue removal in wt% 36.6 36.2 35.8 35.4 35.6 36.8 30.2 31.1
Ni + V removal rate wt% 76.7 77.3 76.2 75.2 76.8 75.6 67.1 69.4
3700h of operating bed pressure drop, MPa 0.07 0.08 0.09 0.07 0.10 0.09 0.13 0.17
As can be seen from Table 2, the catalyst of the present invention has a high impurity removal rate and a small bed pressure drop, while the catalyst G hasCDue to no passage, prolongThe residual oil diffusion path affects the activity, and simultaneously, the bed pressure drop is increased and the catalyst H is obtained due to small void ratioCAlthough the ball is smaller, which is beneficial to residual oil diffusion, the bed layer porosity is minimum, so that the pressure drop is increased quickly, and the service life of the catalyst is influenced.

Claims (27)

1. A catalyst carrier for residual oil hydrotreatment is characterized in that the carrier is spherical, the outer diameter of the spherical carrier is 5.0-10.0 mm, the carrier at least comprises seven channels penetrating through the carrier, namely a first channel, a second channel, a third channel, a fourth channel, a fifth channel, a sixth channel and a seventh channel, the first channel, the second channel and the third channel penetrate through the sphere center of the catalyst carrier and are communicated with one another, the first channel, the second channel and the third channel are vertical in pairs, the fourth channel, the fifth channel, the sixth channel and the seventh channel are connected and communicated end to end, and the total volume occupied by the channels is 20-60% of the volume of the spherical carrier, preferably 22-60%.
2. The residue hydrotreating catalyst carrier according to claim 1, characterized in that the fourth passage, the fifth passage, the sixth passage, and the seventh passage are square in the same plane, forming a square passage; preferably, the square channel and any two of the first channel, the second channel and the third channel are in the same plane and communicated with the square channel; still more preferably, the length of the fourth, fifth, sixth or seventh channels forming the square channels is at least 1/3 to 2/3 of the outer diameter of the carrier sphere.
3. A residuum hydroprocessing catalyst support according to claim 1, characterized in that the cross-section of the channels is circular, polygonal, oval or profiled, preferably circular.
4. A residue hydroprocessing catalyst support according to claim 1, wherein each channel is a straight channel, the cross-sectional shape of each channel being the same, preferably circular; further preferably, the diameters of the first channel, the second channel and the third channel are the same, and the diameters of the fourth channel, the fifth channel, the sixth channel and the seventh channel are the same; and the maximum diameter of the fourth channel, the fifth channel, the sixth channel or the seventh channel is 20-80%, preferably 35-65% of the minimum diameter of the first channel, the second channel or the third channel.
5. The residuum hydroprocessing catalyst support of claim 1, wherein the residuum hydroprocessing catalyst support is Al2O3-SiO2As a carrier, wherein SiO2The weight content is 35-80%, preferably 40-60%.
6. The residuum hydroprocessing catalyst support of claim 5, further comprising a first metal component oxide, wherein the first metal component oxide is NiO.
7. The residue hydrotreating catalyst support of claim 6, characterized in that the first metal component oxide NiO is mixed with Al2O3Is 0.03: 1-0.13: 1, preferably 0.05: 1-0.11: 1.
8. a residue hydroprocessing catalyst support according to any one of claims 1 to 7, wherein the support has the following properties: the specific surface area is 80-200 m2The pore volume is more than 0.79mL/g, preferably 0.79-1.15 mL/g, the pore volume occupied by the pore diameter of 16-100 nm is 35-60% of the total pore volume, and the average pore diameter is more than 18nm, preferably 20-30 nm.
9. A residual oil hydrotreating catalyst comprising a carrier and an active metal component, characterized in that the carrier is the residual oil hydrotreating catalyst carrier as claimed in any one of claims 1 to 8.
10. The catalyst according to claim 9, wherein the active metal component comprises a second metal component, i.e. a group vib metal element, preferably Mo, and a third metal component, i.e. a group viii metal element, preferably Ni and/or Co.
11. The catalyst according to claim 10, wherein the second metal component is present in an amount of 1.0 to 10.0%, preferably 1.5 to 9%, in terms of oxide, the total amount of the first metal component and the third metal component is present in an amount of 1.0 to 10.0%, preferably 2.0 to 8.0%, in terms of oxide, the amount of silica is 35.0 to 55.0%, and the amount of alumina is 35.0 to 55.0%, based on the weight of the catalyst.
12. A method for preparing a residue hydroprocessing catalyst support according to any one of claims 1-8, comprising:
(1) adding an acidic peptizing agent into a silicon source for acidification treatment;
(2) adding aluminum sol and gamma-Al into the step (1)2O3Curing agent to prepare paste material;
(3) adding the paste material obtained in the step (2) into a mould, and heating the mould containing the paste material for a certain time to solidify and form the paste material;
(4) and (4) removing the material in the step (3) from the mold, and washing, drying and roasting to obtain the residual oil hydrotreating catalyst carrier.
13. A process for preparing a residuum hydroprocessing catalyst as set forth in any one of claims 9-11, comprising:
(1) adding an acidic peptizing agent into a silicon source for acidification treatment;
(2) adding aluminum sol and gamma-Al into the step (1)2O3Curing agent to prepare paste material;
(3) adding the paste material obtained in the step (2) into a mould, and heating the mould containing the paste material for a certain time to solidify and form the paste material;
(4) removing the material in the step (3) from the mold, washing, drying and roasting to obtain a residual oil hydrotreating catalyst carrier;
(5) and (4) impregnating the carrier obtained in the step (4) with active metal components of the supported catalyst, and drying and roasting to obtain the residual oil hydrotreating catalyst.
14. The method according to claim 12 or 13, characterized in that a nickel source is introduced in step (1) and/or step (2).
15. The method according to claim 14, characterized in that the introduction method is specifically as follows: adding a nickel source into the material obtained in the step (1), and dissolving the nickel source into the material; the nickel source is soluble nickel salt, wherein the soluble nickel salt is one or more of nickel nitrate, nickel sulfate and nickel chloride, and nickel nitrate is preferred.
16. The method according to claim 12 or 13, wherein the silicon source in step (1) is one or more of water glass and silica sol, wherein the mass content of silicon calculated by silica is 20-40%, preferably 25-35%.
17. The method according to claim 12 or 13, wherein the acidic peptizing agent in step (1) is one or more of nitric acid, formic acid, acetic acid and citric acid, preferably nitric acid, the mass concentration of the acidic peptizing agent is 55-75%, preferably 60-65%, and the molar ratio of the added amount of the acidic peptizing agent to the silicon dioxide calculated by hydrogen ions is 1: 1.0-1: 1.5; the pH value of the silicon source after acidification treatment is 1.0-4.0, preferably 1.5-2.5.
18. The method according to claim 12 or 13, wherein the aluminum sol of step (2) is Al (OH) -containing3And AlCl3The colloidal solution of (4); wherein the Al/Cl ratio in the aluminum sol is 1.15-1.46, and the content of aluminum oxide is 25wt% -30 wt%.
19. The method of claim 12 or 13, wherein the γ -Al of step (2)2O3The material is prepared by roasting pseudo-boehmite of a precursor thereof, and has the following properties: the pore volume is more than 0.95mL/g, the preferable pore volume is 0.95-1.2 mL/g, and the specific surface area is 270m2More than g, preferably, the specific surface area is 270 to 330m2/g。
20. The method according to claim 12 or 13, wherein the aluminum in the aluminum sol in the step (2) is mixed with γ -Al in terms of alumina2O3The mass ratio of the medium alumina is 1: 1-1: 3; the curing agent is one or more of urea and organic amine salt; the organic amine salt is hexamethylenetetramine.
21. The method according to claim 12 or 13, wherein the curing agent in the step (2) is added in an amount of 1:1.5 to 1:2.0 in terms of a molar ratio of nitrogen atoms to silicon dioxide; the solid content of the prepared paste material is 25-45 percent, preferably 28-40 percent by weight of silicon dioxide and aluminum oxide, and the paste material has a plastic body with certain fluidity.
22. The method according to claim 12 or 13, wherein the mold in step (3) comprises a shell with a spherical cavity and a guide mold capable of forming a through passage, wherein the shell is made of a rigid material, and the outer shape of the shell can be any shape, preferably a sphere; the material of the guide die is graphite, wood, paper, paraffin or petroleum resin; the structure of the guide die is matched with the shape of the required pore channel in the catalyst carrier, and the pore channel generated after the guide die is removed is a channel.
23. The method according to claim 12 or 13, wherein the temperature for heating the mold containing the paste material in step (3) is 70-200 ℃, preferably 100-150 ℃, and the constant temperature time is 30-240 minutes, preferably 50-120 minutes.
24. The method according to claim 12 or 13, wherein the washing in step (4) is to wash the demolded spherical material with deionized water to neutrality; the drying temperature is 100-150 ℃, and the drying time is 4-10 hours; the roasting temperature is 500-900 ℃, preferably 550-800 ℃, and the roasting time is 2-8 hours.
25. The process according to claim 12 or 13, wherein the drying and calcining conditions after impregnation of the support with the catalyst active metal component in step (5) are as follows: drying at 100-150 ℃ for 4-10 hours, and roasting at 400-600 ℃ for 2-6 hours.
26. A process for the hydrotreatment of a residual oil, characterized in that at least one of the reactors is an upflow reactor, in which at least one residual oil hydrotreatment catalyst according to any one of claims 9 to 11 is packed.
27. A residue hydroprocessing process according to claim 26, characterized in that the upflow reactor is operated at the following conditions: the reaction pressure is 5-25 MPa, the reaction temperature is 300-420 ℃, and the liquid hourly space velocity is 0.05-5.0 h-1The volume ratio of hydrogen to oil is 150: 1-400: 1.
CN201811257506.5A 2018-10-26 2018-10-26 Catalyst carrier and catalyst for residual oil hydrotreating and preparation method thereof Pending CN111097545A (en)

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