CN111097544A - Catalyst carrier and catalyst for residual oil hydrotreatment and preparation method thereof - Google Patents

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

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Publication number
CN111097544A
CN111097544A CN201811257505.0A CN201811257505A CN111097544A CN 111097544 A CN111097544 A CN 111097544A CN 201811257505 A CN201811257505 A CN 201811257505A CN 111097544 A CN111097544 A CN 111097544A
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carrier
catalyst
spherical
channels
channel
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朱慧红
刘铁斌
王永林
袁胜华
杨涛
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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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)

Abstract

The invention provides a catalyst carrier and a catalyst for residual oil hydrotreatment and a preparation method thereof. The carrier is spherical, and the outer diameter of the carrier is 5.0-10.0 mm; the carrier comprises at least eleven large channels, wherein the first, second, third and fourth large channels are arranged in the spherical carrier and are connected end to form a round, square, quasi-round or quasi-square, the fifth and sixth large channels are crossed at the center of the sphere, and the first to sixth large channels integrally form a quasi-shaped channel or a quasi-shaped channel; the seventh large pore channel is intersected with the fifth and sixth large pore channels and penetrates through the spherical carrier through the spherical center; the eighth, ninth, tenth and eleventh large channels extend inwards from the spherical surface and are respectively intersected with the head-tail connection parts of the first to fourth large channels; the total volume of the macropores accounts for 10-50% of the volume of the spherical carrier. The catalyst prepared by the catalyst carrier loaded with the active component has the characteristics of high hydrogenation activity, long service cycle and the like.

Description

Catalyst carrier and catalyst for residual oil hydrotreatment 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 the previous stage, so that the catalyst is not suitable for being used independentlyIn an upflow reactor.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a residual oil hydrotreating catalyst carrier, a residual oil hydrotreating catalyst and a preparation method thereof. The catalyst has high void ratio, good permeability, low bed pressure drop and uniform material distribution, is particularly suitable for the upflow residual oil hydrotreating process, and has the advantages of high hydrogenation activity, long service cycle and strong impurity deposition capability.
The first aspect of the invention provides a residual oil hydrotreating catalyst carrier, wherein the carrier is spherical, and the outer diameter of the spherical carrier is 5.0-10.0 mm; the carrier comprises at least eleven large channels, wherein the first, second, third and fourth large channels are arranged in the spherical carrier, the large channels are connected end to form a round, square, quasi-round or quasi-square shape, the fifth and sixth large channels are crossed at the center of the sphere to form a cross-shaped channel, and the first, second, third, fourth, fifth and sixth large channels integrally form a quasi-shaped channel or a quasi-shaped channel; the seventh large pore channel is intersected with the fifth and sixth large pore channels and penetrates through the whole spherical carrier through the spherical center; the eighth, ninth, tenth and eleventh large channels extend inwards from the spherical surface and are respectively intersected with the head-tail connecting parts of the first, second, third and fourth large channels; the intersections among the eleven large channels are communicated with each other; the total volume of the macropores accounts for 10-50% of the volume of the spherical carrier, and preferably 15-40%.
The first, second, third, fourth, fifth and sixth large pore channels integrally form a hole channel shaped like a Chinese character 'tian' or a hole channel shaped like a Chinese character 'tian' and are in spherical symmetry. Preferably, the first, second, third, fourth, fifth and sixth large pore channels are symmetrical by taking the sphere center as the center, the inside of the carrier forms a channel shaped like a Chinese character 'tian', the cross point of the cross pore channel in the middle of the channel shaped like a Chinese character 'tian' is positioned at the sphere center, and the eighth, ninth, tenth and eleventh large pore channels are respectively connected with four corners of the channel shaped like a Chinese character 'tian'.
Furthermore, the first, second, third, fourth, fifth and sixth macropores are symmetrical by taking the sphere center as a center, and the channels which are shaped like a Chinese character 'tian' and are formed in the carrier are in the same plane.
Furthermore, the first, second, third, fourth, fifth and sixth large channels are in the same plane and have a square shape.
Furthermore, the length of the first, second, third, fourth, fifth and sixth large pore channels accounts for 0.5-0.7 times of the outer diameter of the carrier ball.
Furthermore, the seventh large pore channel penetrates through the whole spherical carrier through the spherical center and is vertical to and communicated with the plane where the channel shaped like the Chinese character tian is located.
Furthermore, the eighth, ninth, tenth and eleventh large pore channels are on the same plane with the channel shaped like the Chinese character 'tian';
in the residual oil hydrotreating catalyst carrier provided by the invention, the cross section of the large pore passage is circular, polygonal, elliptical or irregular, preferably circular.
In the residual oil hydrotreating catalyst carrier provided by the invention, the cross sections of the large channels can be the same or different in shape, and the cross sections can be the same or different. Further, the cross section of each large pore channel is basically the same in shape, and is preferably circular;
further, the cross-sectional areas of the first, second, third, fourth, fifth and sixth large orifices are the same, the cross-sectional areas of the seventh, eighth, ninth, tenth and eleventh large orifices are the same, and the cross-sectional areas of the first, second, third, fourth, fifth and sixth large orifices forming "the field" are 1/3 to 2/3 of the cross-sectional areas of the seventh, eighth, ninth, tenth and eleventh large orifices. In the invention, the same sectional areas of the pore passages mean that the difference of the sectional areas is controlled within 2 percent of the average sectional area.
Further, the opposite-angle large pore passage of the eighth, ninth, tenth and eleventh large pore passages is on the same straight line. Furthermore, the eighth, ninth, tenth and eleventh large channels may also extend inward and extend through the channels in the shape of a Chinese character 'tian' to be connected diagonally in pairs to form two channels extending through the spherical carrier and communicated with other intersecting channels.
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 support 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 0.77/g, preferably 0.77-1.15 mL/g, the pore volume occupied by the pore diameter of 20-100 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 1.5-8.5%, the total content of the first metal component and the third metal component calculated by oxide is 1-10.0%, preferably 1.5-8.0%, 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 alumina sol into the step (1)、γ-Al2O3Curing 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 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 270-330 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 hole channel, the shell is made of rigid materials, and the external shape can be any shape, preferably a spherical symmetrical geometric shape and the like. 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 large pore passage is made of a material which can be combusted or dissolved by heating, such as graphite, wood, paper, paraffin, petroleum resin and the like. For example, six columns with the length being 0.5-0.7 times of the outer diameter of the carrier ball are made of the materials, the columns are made into a shape like a Chinese character tian in one plane, one column with the length being the diameter of a cavity is made of the materials and vertically penetrates through the Chinese character tian, the middle point of the column is intersected with the cross of the center of the Chinese character tian, four columns are made of the materials and respectively connected with four corners of the Chinese character tian and are in the same plane with the Chinese character tian, the total length of the opposite corners is ensured to be the diameter of the cavity after connection, and the cross of the Chinese character tian is located in the center of the sphere.
The structure of the guide die is matched with the through large pore channels in the carrier, namely the large pore channels generated after the guide die is removed.
In the residual oil hydrotreating catalyst carrier provided by the invention, the cross section of the pore 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 pore channel structure, on one hand, the catalyst bed layer has higher porosity, on the other hand, the catalyst bed layer has good diffusion pore channels and reaction channels, and simultaneously has higher activity. In addition, the inventor also finds that the catalyst with the unique pore channel structure, which is prepared by the invention, utilizes a special molecular diffusion path to increase the residence time of reaction materials in catalyst particles, and shows excellent hydrogenation performance and impurity deposition capability.
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 process for preparing a residue hydrotreating catalyst support A of the present invention;
FIG. 2 is a schematic diagram of a mold for a residue hydrotreating catalyst support A of the present invention;
FIG. 3 is a schematic drawing of the guided mode of a residuum hydroprocessing catalyst support A of the present invention;
FIG. 4 is a schematic sectional view of a residue hydrotreating catalyst support A of the present invention;
FIG. 5 is a schematic sectional view showing the preparation process of a residue hydrotreating catalyst support B of the present invention;
FIG. 6 is a schematic view of a mold for a residue hydrotreating catalyst support B of the present invention;
FIG. 7 is a schematic drawing of the guided mode of residue hydrotreating catalyst support B of the present invention;
FIG. 8 is a schematic sectional view of a residue hydrotreating catalyst support B of the present invention;
the reference numerals are explained below:
1. a mold housing; 2. a cavity; 10. a catalyst support; 20. a mold; 30. guiding a mold; 100. a pasty material; 101a, a first cylinder; 102a, a second post; 103a, a third column; 104a, a fourth cylinder; 105a, a fifth cylinder; 106a, a sixth column; 107a, a seventh column; 107. a seventh large pore channel; 108a eighth column; 109a, a ninth cylinder; 110a, a tenth cylinder; 111a, eleventh column.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, which are not intended to limit the scope of the present invention. In the present invention, wt% is a mass fraction.
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 large pore channel is measured by the following method: 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 pore 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 pore channel. Although only the guide mold is different when the control carrier is prepared, the rest part outside the pore 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 caused by the part is considered to be negligible in the present invention.
The residual oil hydrotreating catalyst carrier 10 according to the embodiments of the present invention has a spherical shape as a whole, and as shown in fig. 1 to 4, when the residual oil hydrotreating catalyst carrier is prepared according to the present invention, the mold 20 includes a mold housing 1 (see fig. 2) having a spherical cavity, a cavity 2, and a guide mold 30 (see fig. 3) capable of forming a pore passage. The catalyst carrier 10 is a spheroid structure formed by solidifying a pasty material 100, a first, a second, a third and a fourth tubular large pore channels are arranged in the material 100 and connected end to form a square, the fifth large pore channel and the sixth large pore channel are crossed at the sphere center to form a cross, and form a channel shaped like a Chinese character 'tian' with the four large pore channels on a plane, and a seventh large pore channel 107 is intersected with the fifth and sixth large pore channels and is vertical to each other in pairs and penetrates through the whole spherical carrier through the sphere center; the eighth, ninth, tenth and eleventh large channels extend inwards from the spherical surface and are respectively intersected with the head-tail connecting parts of the first, second, third and fourth large channels; and the intersections among the eleven large channels are communicated with each other; wherein the shape of the Chinese character tian' shaped pore canal integrally formed by the first, the second, the third, the fourth, the fifth and the sixth large pore canals is spherical symmetrical and in the same plane. It should be noted that: fig. 4 of this embodiment does not clearly distinguish the respective tunnels, and therefore the corresponding pillars are identified in fig. 3. In the present embodiment, there are provided ten channels, and each of the large channels corresponds to the first column 101a, the second column 102a, the third column 103a, the fourth column 104a, the fifth column 105a, the sixth column 106a, the seventh column 107a, the eighth column 108a, the ninth column 109a, the tenth column 110a, and the eleventh column 111a in fig. 3, respectively.
As shown in fig. 4, the catalyst carrier 10 of this embodiment is a spheroid structure formed by solidifying the paste material 100, and has a first, a second, a third and a fourth tubular large pore channels inside the material 100, which are connected end to form a square shape, and the fifth and sixth large pore channels cross at the center of the sphere to form a cross shape, and form a channel shaped like a Chinese character 'tian' with the four large pore channels integrally in a plane; the seventh large pore channel 107 is intersected with the fifth and sixth large pore channels and is vertical to each other in pairs, and penetrates through the whole spherical carrier through the spherical center; the eighth, ninth, tenth and eleventh large channels extend inwards from the spherical surface and are respectively intersected with the head-tail connecting parts of the first, second, third and fourth large channels; and the intersections among the eleven large channels are communicated with each other; wherein the shape of the Chinese character tian' shaped pore canal integrally formed by the first, the second, the third, the fourth, the fifth and the sixth large pore canals is spherical symmetrical and in the same plane. The intersections among the eleven large channels are communicated with each other; the length of each of the first, second, third, fourth, fifth and sixth macropores accounts for 0.5-0.7 times of the outer diameter of the carrier sphere, and the sectional area of each of the first, second, third, fourth, fifth and sixth macropores is 1/3-2/3 of the sectional area of the seventh, eighth, ninth, tenth and eleventh macropores; the total volume of the eleven large channels is 10-50% of the volume of the spherical carrier, and preferably 15-40%. In addition, the eighth, ninth, tenth and eleventh macro-channels may extend inward and extend through the "tian" -shaped channels to connect diagonally two-by-two, forming two channels through the spherical support and communicating with other intersecting channels, as shown in fig. 5-8.
It should be noted that: the duct scheme related to embodiment 1 may have many other variations without departing from the design concept, and will not be described herein.
Example 1
1111g of water glass with 27wt% of silicon oxide content 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 1.8, 70.3g of nickel nitrate hexahydrate is added, the solution is added with 456g of alumina sol with the Al/Cl ratio of 1.45 and the alumina content of 28% and 1.065mL/g of pore volume after dissolving, and the specific surface area is 300m2gamma-Al of/g2O3200g, stirring uniformly, adding 50.6g 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 calculated by silicon dioxide and aluminum oxide to be 32%.
The pasty material is pressed into two identical hemispheres with spherical cavities. Wherein, a hemisphere is put into a guide die, and the guide die is made of wood. The structure of the guide die is that six columns are made of the materials, wherein a first column, a second column, a third column and a fourth column are connected end to end, a fifth column and a sixth column are perpendicular to each other and are intersected at the middle points, the six columns form a 'tian' shape in a plane, a seventh column is made of the materials, the length of the seventh column is the diameter of a cavity, the seventh column, the fifth column and the sixth column are perpendicular to each other in pairs and are intersected at the middle points, an eighth column, a ninth column, a tenth column and an eleventh column are made of the materials, the eighth column, the ninth column, the tenth column and the eleventh column are connected with four corners of the 'tian' shape, the total length of the diagonal columns after connection is the diameter of the cavity in the same plane, and the center of the 'ten' shape of the center of the 'tian' shape is ensured to be coincident with the center of a. See the cross-sectional view of the center of the sphere of fig. 4. 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 750 ℃. The guide die which can form the large pore path in the roasting process is burnt, and the large pore path required by the catalyst is left, thus obtaining the spherical catalyst carrier A. The outer diameter of the obtained catalyst carrier A is about 5.5mm, the lengths of the first large pore passage, the second large pore passage, the third large pore passage, the fourth large pore passage, the fifth large pore passage and the sixth large pore passage which form the channels shaped like the Chinese character 'tian' are all 3.3mm, the diameter is about 1.0mm, the length of the seventh large pore passage is 5.5mm, the lengths of the eighth large pore passage, the ninth large pore passage, the tenth large pore passage and the eleventh large pore passage are all 0.4mm, and the diameters of the seventh large pore passage, the eighth large pore passage, the ninth large pore passage, the tenth large pore passage and the eleventh large pore passage are all 1.5 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 at reaction time 1800 h.
Example 2
The preparation process was as in example 1 except that 103.5g of urea was added instead of hexamethylenetetramine as a curing agent and 99.9g of nickel nitrate hexahydrate were added instead, and catalyst carrier B and catalyst B were preparedCProperties ofSee table 1 and catalyst evaluation results in table 2. Wherein the impurity removal rate of the catalyst is measured at reaction time 1800 h.
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 at reaction time 1800 h. The outer diameter of the obtained catalyst carrier C is about 7.5mm, the lengths of the first large pore channel, the second large pore channel, the third large pore channel, the fourth large pore channel, the fifth large pore channel and the sixth large pore channel which form the channels shaped like the Chinese character 'tian' are all 5.2mm, the diameter is about 1.5mm, the length of the seventh large pore channel is 7.5mm, the lengths of the eighth large pore channel, the ninth large pore channel, the tenth large pore channel and the eleventh large pore channel are all 0.55mm, and the diameters of the seventh large pore channel, the eighth large pore channel, the ninth large pore channel, the tenth large pore channel and the eleventh large pore channel are all 1.8 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 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 at reaction time 1800 h. The outer diameter of the obtained catalyst carrier C is about 6.0mm, the lengths of the first large pore channel, the second large pore channel, the third large pore channel, the fourth large pore channel, the fifth large pore channel and the sixth large pore channel which form the channels shaped like the Chinese character 'tian' are all 3.6mm, the diameter is about 1.0mm, the length of the seventh large pore channel is 6.0mm, the lengths of the eighth large pore channel, the ninth large pore channel, the tenth large pore channel and the eleventh large pore channel are all 0.45mm, and the diameters of the seventh large pore channel, the eighth large pore channel, the ninth large pore channel, the tenth large pore channel and the eleventh large pore channel are all 1.6 mm.
Example 5
The procedure is as in example 1, except that the amount of hexamethylenetetramine as the curing agent is changed to 90g, the amount of water glass is adjusted to 1315g, and the amount of nitric acid is adjusted to 409.8 g. Prepared catalyst carrier E and catalyst ECThe 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 at reaction time 1800 h. The lengths of the first large pore passage, the second large pore passage, the third large pore passage, the fourth large pore passage, the fifth large pore passage and the sixth large pore passage which form the channel shaped like the Chinese character 'tian' are all 3.8mm, the diameter is about 1.1mm, the length of the seventh large pore passage is 5.5mm, the lengths of the eighth large pore passage, the ninth large pore passage, the tenth large pore passage and the eleventh large pore passage are all 0.4mm, and the diameters of the seventh large pore passage, the eighth large pore passage, the ninth large pore passage, the tenth large pore passage and the eleventh large pore passage are all 1.3 mm. Wherein the eighth, ninth, tenth and eleventh macro-channels extend inwards and penetrate through the channels shaped like the Chinese character 'tian' to be connected in pairs in opposite angles to form two channels penetrating through the spherical carrier and communicated with other crossed channels. See the cross-sectional view of the center of the sphere of fig. 8.
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.
Comparative example 1
Weighing 1111g of water glass with 27wt% of silicon oxide content, adding the water glass into a beaker, starting a stirring device, slowly adding 370g of nitric acid solution with the mass concentration of 65% into the beaker, stirring the pH value of the water glass solution in the beaker after dissolution to be 1.8, adding 70.3g of nickel nitrate, adding 456g of alumina sol with the aluminum oxide content of 28% and the pore volume of 1.065mL/g into the solution after dissolution, wherein the Al/Cl ratio of the solution is 1.45, the specific surface area of the solution is 300m2gamma-Al of/g2O3200g, stirring uniformly, adding 50.6g 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 calculated by silicon dioxide and aluminum oxide to be 32%.
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 750 ℃ to obtain the spherical catalyst carrier G of the comparative example. The outer diameter of the resulting catalyst carrier A was about 5.5 mm.
Soaking the carrier G 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 GCThe catalyst properties are shown in Table 1, and the catalyst evaluation results are shown in Table 2.
Comparative example 2
Weighing 1111g of water glass with 27wt% of silicon oxide content, adding the water glass into a beaker, starting a stirring device, slowly adding 370g of nitric acid solution with the mass concentration of 65% into the beaker, stirring the pH value of the water glass solution in the beaker after dissolution to be 1.8, adding 70.3g of nickel nitrate, adding 456g of alumina sol with the aluminum oxide content of 28% and the pore volume of 1.065mL/g into the solution after dissolution, wherein the Al/Cl ratio of the solution is 1.45, the specific surface area of the solution is 300m2gamma-Al of/g2O3200g, stirring uniformly, adding 50.6g 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 calculated by silicon dioxide and aluminum oxide to be 32%.
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 750 ℃ to obtain the spherical catalyst carrier H of the comparative example. The outer diameter of the resulting catalyst carrier A was about 2.5 mm. Soaking carrier H in Mo-Ni-P solution, drying at 120 deg.C for 6 hr, and calcining at 500 deg.C for 3 hr to obtain catalyst HCThe catalyst properties are shown in Table 1, and the catalyst evaluation resultsThe results are shown in Table 2.
TABLE 1 Properties of catalysts prepared in inventive and comparative examples
Catalyst support numbering A B C D E F G H
Pore volume, mL/g 0.783 0.780 0.778 0.776 0.793 0.790 0.772 0.762
Specific surface area, m2/g 131 133 136 138 131 132 140 148
Average pore diameter, nm 23.91 23.46 22.88 22.49 24.21 23.94 22.06 20.59
Hole distribution,%
<8.0nm 1.1 1.3 1.0 1.1 0.6 1.0 1.2 1.4
8-20 nm 33.9 34.3 34.7 34.5 33.9 34.3 37.6 38.0
20-100 nm 58.6 57.9 57.7 59.3 58.7 59.1 53.4 53.1
>100.0nm 6.4 6.5 6.6 5.1 6.8 5.6 7.5 7.1
Catalyst numbering AC BC CC DC EC FC GC HC
Metal content%
MoO3 7.9 7.9 8 7.9 7.8 8 8 7.9
NiO 4.4 5.6 4.4 4.5 4.3 1.9 4.4 4.5
Lateral pressure strength, N/grain 36 38 51 40 33 29 80 56
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% 3.62 3.62 3.62 3.62 3.62 3.62 3.62 3.62
N，wt% 0.36 0.36 0.36 0.36 0.36 0.36 0.36 0.36
Carbon residue in wt% 12.86 12.86 12.86 12.86 12.86 12.86 12.86 12.86
Metal (Ni + V), mg/kg 92.2 92.2 92.2 92.2 92.2 92.2 92.2 92.2
Evaluation conditions
Liquid hourly volume space velocity, h-1 0.475 0.475 0.475 0.475 0.475 0.475 0.475 0.475
Average temperature of catalyst bed, deg.C 387 387 387 387 387 387 387 387
Inlet pressure, MPa 16.6 16.6 16.6 16.6 16.6 16.6 16.6 16.6
Inlet hydrogen to oil ratio, Nm3/m3 317 317 317 317 317 317 317 317
Desulfurization degree, wt% 57.6 56.8 57.1 56.0 57.5 59.2 43.1 50.6
Percent of carbon residue removal in wt% 40.8 40.5 41.6 40.4 39.9 39.5 28.3 32.2
Ni + V removal rate wt% 78.5 77.8 77.6 78.2 76.7 78.0 65.1 69.6
3500h bed pressure drop, MPa in operation 0.07 0.08 0.07 0.09 0.08 0.08 0.16 0.18
As can be seen from Table 2, the catalyst of the present invention has the optimized design of the diffusion path and the reaction path in combination with the pore diameter, so that the impurities can be more easily close to the active center of the catalyst, and the impurity removal rate and the reaction efficiency are higher. Meanwhile, the catalyst has smaller bed pressure drop and is beneficial to long-period operation of the catalyst. And catalyst GCBecause of no channel, it affects the activity, and because of small void ratio, the pressure drop of bed layer is increased, catalyst HCAlthough 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 (31)

1. The residual oil hydrotreating catalyst carrier is characterized in that the carrier is spherical, and the outer diameter of the spherical carrier is 5.0-10.0 mm; the carrier comprises at least eleven large channels, wherein the first, second, third and fourth large channels are arranged in the spherical carrier, the large channels are connected end to form a round, square, quasi-round or quasi-square shape, the fifth and sixth large channels are crossed at the center of the sphere to form a cross-shaped channel, and the first, second, third, fourth, fifth and sixth large channels integrally form a quasi-shaped channel or a quasi-shaped channel; the seventh large pore channel is intersected with the fifth and sixth large pore channels and penetrates through the whole spherical carrier through the spherical center; the eighth, ninth, tenth and eleventh large channels extend inwards from the spherical surface and are respectively intersected with the head-tail connecting parts of the first, second, third and fourth large channels; the intersections among the eleven large channels are communicated with each other; the total volume of the macropores accounts for 10-50% of the volume of the spherical carrier, and preferably 15-40%.
2. The residue hydrotreating catalyst support of claim 1, characterized in that the first, second, third, fourth, fifth and sixth large channels integrally form a channel shaped like a Chinese character 'tian' or a channel shaped like a Chinese character 'tian' in a spherical symmetric manner; the cross-shaped pore passages in the middle of the channel shaped like the Chinese character 'tian' are positioned at the center of the sphere, and the eighth, ninth, tenth and eleventh large pore passages are respectively connected with the four corners of the channel shaped like the Chinese character 'tian'; preferably, the first, second, third, fourth, fifth and sixth macropores are arranged in the same plane, and the "tian" -shaped pore canal formed in the carrier by taking the sphere center as the symmetry is arranged in the carrier.
3. The residue hydrotreating catalyst support of claim 1, characterized in that the first, second, third, fourth, fifth and sixth macropores are in the same plane and have a square shape.
4. The residue hydrotreating catalyst support according to claim 1, characterized in that the lengths of the first, second, third, fourth, fifth and sixth large channels account for 0.5 to 0.7 times the outer diameter of the support sphere.
5. The residue hydrotreating catalyst carrier of claim 1, characterized in that the seventh large channel runs through the entire spherical carrier through the spherical center and is perpendicular to and in communication with the plane of the "tian" -shaped channel; the eighth, ninth, tenth and eleventh large pore channels are on the same plane with the channel shaped like Chinese character 'tian'.
6. A residuum hydroprocessing catalyst support according to claim 1, characterized in that the cross-section of the macropores is circular, polygonal, oval or profiled, preferably circular; the cross section of each large pore channel is basically the same, and is preferably circular.
7. The residue hydrotreating catalyst support of claim 1 wherein the first, second, third, fourth, fifth and sixth macropores have the same cross-sectional area, the seventh, eighth, ninth, tenth and eleventh macropores have the same cross-sectional area, and the cross-sectional areas forming the "field" of the first, second, third, fourth, fifth and sixth macropores are 1/3 to 2/3 of the cross-sectional areas of the seventh, eighth, ninth, tenth and eleventh macropores.
8. The residue hydrotreating catalyst support of claim 1, characterized in that the diagonal macropores of the eighth, ninth, tenth and eleventh macropores are collinear; preferably, the eighth, ninth, tenth and eleventh macro-channels extend inwardly and are connected diagonally two by two through the channel shaped like a Chinese character 'tian', forming two channels through the spherical support and communicating with other intersecting channels.
9. 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%.
10. The residuum hydroprocessing catalyst support of claim 9, further comprising a first metal component oxide, wherein the first metal component oxide is NiO.
11. According to claim10 the residual oil hydrotreating catalyst carrier, characterized in that the first metal component oxides NiO and Al2O3Is 0.03: 1-0.13: 1, preferably 0.05: 1-0.11: 1.
12. a residue hydroprocessing catalyst support according to any one of claims 1 to 11, wherein the support has the following properties: the specific surface area is 80-200 m2The pore volume is more than 0.77mL/g, preferably 0.77-1.15 mL/g, the pore volume occupied by the pore diameter of 20-100 nm is 35-60% of the total pore volume, and the average pore diameter is more than 18nm, preferably 20-30 nm.
13. 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 12.
14. The catalyst according to claim 13, 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.
15. The catalyst of claim 13 wherein the second metal component is present in an amount of 1.0% to 10.0%, preferably 1.5% to 8.5%, as 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 1.5% to 8.0%, as 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.
16. A method for preparing a residue hydroprocessing catalyst support according to any one of claims 1-12, comprising:
(1) adding an acidic peptizing agent into a silicon source for acidification treatment;
(2) to the step of(1) Adding aluminium sol and gamma-Al2O3Curing 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.
17. A process for preparing a residuum hydroprocessing catalyst as set forth in any one of claims 13-15, 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.
18. The method according to claim 16 or 17, characterized in that a nickel source is introduced in step (1) and/or step (2).
19. The method according to claim 18, 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.
20. The method according to claim 16 or 17, 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%.
21. The method according to claim 16 or 17, wherein the acidic peptizing agent in the 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 amount of the acidic peptizing agent added 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.
22. The method according to claim 16 or 17, 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%.
23. The method of claim 16 or 17, 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。
24. The method according to claim 16 or 17, 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.
25. The method according to claim 16 or 17, 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.
26. The method according to claim 16 or 17, 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 can be any shape, preferably a spherical geometric shape with equal symmetry; 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 a large pore channel required in the catalyst carrier, and the pore channel generated after the guide die is removed is the large pore channel.
27. The method according to claim 16 or 17, 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.
28. The method according to claim 16 or 17, 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.
29. The process according to claim 16 or 17, 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.
30. 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 13 to 15 is packed.
31. A residue hydroprocessing process as recited in claim 30, wherein 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.
CN201811257505.0A 2018-10-26 2018-10-26 Catalyst carrier and catalyst for residual oil hydrotreatment and preparation method thereof Pending CN111097544A (en)

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