CN116474753A - Alumina carrier and forming method and application thereof - Google Patents

Alumina carrier and forming method and application thereof Download PDF

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Publication number
CN116474753A
CN116474753A CN202210038225.0A CN202210038225A CN116474753A CN 116474753 A CN116474753 A CN 116474753A CN 202210038225 A CN202210038225 A CN 202210038225A CN 116474753 A CN116474753 A CN 116474753A
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China
Prior art keywords
pore volume
alumina carrier
alumina
microsphere
pores
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CN202210038225.0A
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Chinese (zh)
Inventor
李安琪
王志武
袁胜华
王欣
曹禹
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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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Priority to CN202210038225.0A priority Critical patent/CN116474753A/en
Publication of CN116474753A publication Critical patent/CN116474753A/en
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—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
    • B01J23/882—Molybdenum and cobalt
    • 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
    • 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
    • B01J23/888—Tungsten
    • 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
    • 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
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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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)
  • Catalysts (AREA)

Abstract

The invention discloses an alumina carrier, a forming method and application thereof. The alumina carrier has a through double-peak pore structure, and the pore volume of the alumina carrier is 0.8-1.3 mL/g; the pore volume occupied by the pores with the diameter of 1-15 nm is 40-92% of the total pore volume; the pore volume of the pores with the pore diameter of 50-900 nm is 5-56% of the total pore volume. The alumina carrier has an adjustable through double-peak pore structure in a certain range, has hundred-nanometer-scale pores with a high proportion, can meet the diffusion requirement of macromolecular substances, and has the characteristics of high demetallization activity and long service life of a catalyst when being applied to residual oil hydrogenation reaction.

Description

Alumina carrier and forming method and application thereof
Technical Field
The invention relates to an alumina carrier and a forming method and application thereof, in particular to an alumina carrier of a hydrogenation catalyst suitable for petrochemical industry and a forming method and application thereof.
Background
In the oil refining industry, heavy oils, especially residuum, contain significant amounts of metals, such as Fe, ca, ni, V, na, where metals are primarily enriched in asphaltenes and gums. In the residual oil hydrogenation process, the downstream heavy oil catalytic cracking device has strict metal content limitation on the feed oil, so that most metal impurities are removed in the residual oil hydrogenation process, and asphaltene molecules containing metal can reach ten nanometers, so that the pores of the existing alumina carrier are mainly concentrated between 2 and 12 nanometers, the asphaltene molecules are subjected to serious internal diffusion control and are easily concentrated on the outer surface of the catalyst to react, serious pore opening blockage is generated, the pressure drop is rapidly increased, and the normal operation of the device is influenced, and therefore, the residual oil hydrogenation catalyst is required to have a large number of hundred nanometer pore channels suitable for the asphaltene molecule diffusion reaction.
The existing macroporous alumina carrier can not meet the requirement of directly producing hundred-nanometer pore canal, so that pore diameter distribution of ten-nanometer and hundred-nanometer double-peak pores is a good choice when the existing alumina carrier is reamed. However, no matter a physical pore-expanding agent or a chemical pore-expanding agent is adopted, the existing pore-expanding means have the problems that the efficiency of the pore-expanding agent is low, a higher proportion of the pore-expanding agent is required, the penetration of oversized pores is poor, ink bottle-shaped pores are formed, and the like, so that the mechanical strength of the catalyst is reduced. For example, CN 102861615B discloses a preparation method of alumina carrier, which adopts pseudo-boehmite, extrusion aid, chemical pore-expanding agent, ammonium salt, physical pore-expanding agent carbon black powder and water mixing extrusion strip, but pores formed by thermal decomposition of ammonium salt and pores formed by ablation of carbon black have poor penetrability, low mechanical strength and low utilization efficiency of pore-expanding agent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an alumina carrier, a forming method and application thereof. The alumina carrier has an adjustable through double-peak pore structure in a certain range, has hundred-nanometer-scale pores with a high proportion, can meet the diffusion requirement of macromolecular substances, and has the characteristics of high demetallization activity and long service life of a catalyst when being applied to residual oil hydrogenation reaction.
The first aspect of the invention provides an alumina carrier, which has a through double-peak pore structure, wherein the pore volume of the alumina carrier is 0.8-1.3 mL/g; the pore volume occupied by the pores with the diameter of 1-15 nm is 40-92% of the total pore volume; the pore volume of the pores with the pore diameter of 50-900 nm is 5-56% of the total pore volume.
According to the present invention, preferably, the alumina carrier has a pore volume of 0.9 to 1.2mL/g.
According to the invention, preferably, in the alumina carrier, the pore volume occupied by the pores with the pore diameter of 1-15 nm is 43% -77% of the total pore volume; the pore volume of the pores with the pore diameter of 50-900 nm is 22-53% of the total pore volume.
According to the present invention, in the alumina carrier, the concentration of the distribution of macropores having a pore diameter of 50 to 900nm can be adjusted, for example, the distribution of macropores is concentrated at 60 to 400nm, and further, for example, the distribution of macropores is concentrated at 60 to 120nm,60 to 140nm,60 to 150nm,150 to 300nm, or 150 to 400nm, etc.
According to the invention, the specific surface area of the alumina carrier is 80-300 m 2 Preferably 100 to 180m 2 /g。
According to the invention, the mechanical strength of the alumina carrier is 10 to 30N/mm, preferably 10 to 20N/mm.
According to the present invention, the shape of the alumina carrier may be any shape conventional in the art, such as a column, sphere, ellipsoid, cylinder, bar, vane, tooth sphere, clover, etc., and may have holes formed therein, grooves formed on the outer surface thereof, etc.
The second aspect of the present invention provides a method for forming the alumina carrier, comprising the following steps:
(1) Uniformly mixing the alumina dry gel powder and the microsphere expanding agent;
(2) Kneading and molding the materials obtained after the step (1) are mixed;
(3) Drying and roasting the formed product obtained in the step (2) to obtain an alumina carrier;
the microsphere expanding agent in the step (1) has a core-shell structure, wherein the shell is thermoplastic acrylic ester polymer, and the inner core is hydrocarbon.
According to the present invention, the microsphere expansion agent in step (1) is a high temperature type. The shell temperature resistance limit value of the microsphere expanding agent in the step (1) is 155-210 ℃, preferably 160-185 ℃; the initial volatilizing temperature of the hydrocarbon in the core is 110-145 ℃, preferably 120-135 ℃. The volume fraction of the hydrocarbon in the core to the shell volume is 0.0001% to 0.1%, preferably 0.0002% to 0.001%.
According to the invention, the particle size of the microsphere expansion agent in step (1) is 1 μm to 100. Mu.m, preferably 5 μm to 50. Mu.m.
According to the invention, the microsphere expansion agent in step (1) may be commercially available or prepared according to the prior art. The commercial product can be at least one of Clocell high temperature type foaming microsphere of PolyCHEM company, U.S.A., expancel DU series high temperature type foaming microsphere of Nouryon company, switzerland. For example, the product types 186DU20, 180DU25, 186DU35, 186DU45 of Clocell high temperature expanded microspheres of PolyCHEM company, USA, and for example, the product types 920DU20, 920DU40, 920DU80, 920DU120 of Expancel DU series high temperature expanded microspheres of Nouryon company, switzerland, etc.
According to the present invention, preferably, the property of the microsphere expansion agent in step (1) has at least one of a to D:
numbering device Particle size/. Mu.m Core onset volatilization temperature/°c Temperature limit value/DEGC of shell
A 15～25 130～140 180～190
B 20～39 120～129 175～185
C 40～50 120～129 175～185
D 40～50 110～119 165～175
According to the present invention, preferably, the property of the microsphere expansion agent in step (1) has at least one of E to H:
according to the invention, the weight of the microsphere expanding agent added in the step (1) is 2-30% of the weight of the alumina dry gel powder, and is preferably 3-15%.
According to the invention, the alumina dry gel powder in the step (1) is macroporous aluminum hydroxide.
According to the invention, step (1) requires the addition of water, preferably deionized water; the water addition amount is 70-160% of the weight of the alumina dry adhesive powder, and is preferably 110-130%. Water is added together with the other raw materials in step (1).
According to the invention, an extrusion aid can be added in the step (1), wherein the extrusion aid is one or more of sesbania powder, cellulose, polyvinyl alcohol, polyacrylamide, methylcellulose and hydroxypropyl methylcellulose; the addition amount of the extrusion aid is 1-5% of the weight of the alumina dry adhesive powder, and is preferably 2-4%. The extrusion aid is added together with other raw materials in the step (1).
According to the invention, in the step (1), a peptizing agent can be added, wherein the peptizing agent is one or more of nitric acid, citric acid, sulfuric acid, acetic acid and hydrochloric acid, and the adding amount of the peptizing agent is 1-5% of the weight of the dry alumina powder, and is preferably 2-3%. The peptizing agent is added together with other raw materials in the step (1).
According to the invention, the shaping process in step (2) should be controlled to a temperature which is 10 ℃ to 50 ℃, preferably 20 ℃ to 40 ℃, above the initial volatilization temperature of the microsphere expander core in step (1).
According to the invention, the shaping process in step (2) should be controlled to a temperature which is 5 to 40 ℃, preferably 5 to 25 ℃, above the shell temperature limit of the microsphere expansion agent in step (1).
According to the invention, the shaping in step (2) may be extrusion; the forming process is carried out in high-temperature resistant forming equipment capable of measuring temperature, cooling and heating materials. The temperature range of the high temperature resistance of the molding equipment is 100-350 ℃, preferably 120-300 ℃. The molding equipment is a strip extruder; the thickness of the orifice plate of the extruder is conventional, such as 0.1-0.5 cm.
According to the present invention, preferably, the molding process in the step (2) should be controlledThe pressure is 100kg/cm 2 ～180kg/cm 2 。
According to the invention, the drying in the step (3) is performed at 50-150 ℃ for 1-5 hours; the calcination is carried out at 500-1000 ℃ for 2-5 hours, preferably 800-1000 ℃.
According to a third aspect of the present invention there is provided the use of the alumina carrier described above or the alumina carrier prepared by the method described above in a hydrogenation catalyst.
When used as a hydrogenation catalyst according to the present invention, the catalyst can be obtained by a method commonly used in the art, that is, by supporting an active metal component with a carrier. The active metal is a group VIB and/or a group VIII metal, preferably molybdenum and/or tungsten, and the group VIII metal is preferably cobalt and/or nickel. The weight of the carrier is taken as the reference, the content of the VIB group metal oxide is 1 to 20 percent, and the content of the VIII group metal oxide is 0.1 to 8 percent.
According to the invention, the hydrotreated feedstock is a residuum having the following properties: the Ni+V content is 20-150 ppm. The content is mass content.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the invention, the alumina carrier has a bimodal pore structure with good penetrability, and the pore volume of the alumina carrier is 0.8-1.3 mL/g; the pore volume occupied by the pores with the diameter of 1-15 nm is 40-92% of the total pore volume; the pore volume of the pores with the pore diameter of 50-900 nm is 5-56% of the total pore volume. The alumina carrier has a bimodal pore structure with adjustable penetrability in a certain range and high proportion of hundred-nanometer pores, can meet the diffusion requirement of macromolecular substances, and has the characteristics of high demetallization activity and long service life of a catalyst when applied to residual oil hydrogenation reaction.
(2) In the forming method of the alumina carrier, a small amount of microsphere expanding agent is added into the alumina dry rubber powder, and the microsphere expanding agent is controlled to perform moderate and controllable reaming by controlling the proper temperature and the profile limitation of a strip extruding machine and the strip extruding pressure during strip extruding forming, so that the alumina carrier with adjustable through double-peak hole distribution and high mechanical strength is obtained. The method of the invention avoids the problems of large consumption of the reaming agent, poor mechanical strength, poor penetration of oversized holes, formation of ink bottle shaped holes and the like in the existing reaming means when the traditional reaming agent is adopted for reaming to obtain hundred-nanometer holes. Alumina reamed by the microsphere expansion agent is particularly suitable for being used as a heavy oil hydrogenation catalyst carrier. The hydrogenation catalyst obtained by loading the active metal on the alumina carrier is used for the residual oil hydrogenation reaction and has the characteristics of high demetallization activity and long service life.
(3) In the invention, the alumina carrier is suitable for being used as a heavy oil hydrogenation catalyst carrier. The hydrogenation catalyst obtained by loading the active metal component on the alumina carrier is used in residual oil hydrogenation reaction and has the characteristics of high demetallization activity and long catalyst life.
Detailed Description
The operation and effect of the method of the present invention will be further illustrated by the following examples, but is not limited thereto.
In the invention, pore volume and pore distribution are measured by mercury intrusion; the mechanical strength is measured by a particle strength tester; the specific surface area is measured by the BET method.
The alumina dry gel powder used in the examples and comparative examples of the present invention was macroporous aluminum hydroxide having a specific surface area of 245m 2 Per g, pore volume of 0.89mL/g, and pore diameter of 12.5nm; pore distribution: the diameter of the hole is 1-15 nm and 96.7%, and the diameter of the hole is 16-900 nm and 3.3%.
In the invention, the microsphere expanding agent of the embodiment 4 is Clocell high-temperature foaming microsphere of the American PolyCHEM company, the model is 180DU45, the particle size of the batch is 45 mu m, the initial volatilization temperature of the core hydrocarbon is 125 ℃, and the temperature-resistant limit value of the thermoplastic acrylate polymer of the shell is 180 ℃.
In the invention, the expansion agent of the microspheres in examples 1, 2, 3, 5 and 6 is an Expancel DU series high-temperature foaming microsphere of Nouryon company, switzerland, the model is 920DU20, the average particle diameter of the batch is 7 mu m, the initial volatilization temperature of the hydrocarbon of the inner core is 130 ℃, and the temperature-resistant limit value of the thermoplastic acrylate polymer of the outer shell is 170 ℃.
In the present invention, the process control pressure for molding in each example was 140kg/cm 2 。
In the present invention, ni-free ratio/% and V-free ratio/% of the examples and comparative examples were:
ni removal rate/% = 1- (mass content of Ni in product oil/mass content of Ni in raw oil) ×100%;
the V removal rate/% =1- (V mass content in the product oil/V mass content in the raw oil) ×100%.
In each example of the present invention, the thickness of the orifice plate of the bar extruder was 0.5cm.
Example 1
3g of 920DU20 microspheres are weighed, and the volume fraction of the hydrocarbon in the inner core accounting for the spherical shell of the thermoplastic acrylic polymer is 0.001%. And mixing 100g of microspheres, 100g of alumina dry gel powder and 120g of deionized water, fully kneading, and putting the kneaded material into a Gao Wenji strip-resistant machine capable of measuring temperature, cooling and heating for strip extrusion molding. And controlling the temperature in the molding process to 170 ℃ to obtain the reamed alumina wet strip. Drying in a baking oven at the normal pressure and 110 ℃ for 2 hours, and roasting at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier.
The pore volume of the prepared alumina carrier is 0.95mL/g, the pore volume occupied by the pores with the diameter of 1-15 nm accounts for 84.9% of the total pore volume, the pores with the diameter of more than 15nm are mainly distributed at 60-150 nm, and the pore volume occupied by the pores with the diameter of 60-150 nm accounts for 13.1% of the total pore volume. The mechanical strength of the alumina carrier is 18N/mm, and the specific surface area is 130m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of molybdenum oxide and 2wt% of nickel oxide based on the mass of the carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil of the residual oil hydrogenation reaction are shown in table 1, and the hydrogenation reaction conditions are as follows: temperature 380 ℃, pressure 15MPa and liquid hourly space velocity 1h -1 Hydrogen oil volume ratio 760. The hydrogenation effect is shown in Table 2.
Example 2
15g of 920DU20 microspheres are weighed, and the volume fraction of the hydrocarbon in the inner core accounting for the spherical shell of the thermoplastic acrylic polymer is 0.001%. And mixing 100g of microspheres, 100g of alumina dry gel powder and 120g of deionized water, fully kneading, and putting the kneaded material into a Gao Wenji strip-resistant machine capable of measuring temperature, cooling and heating for strip extrusion molding. And controlling the temperature in the molding process to 170 ℃ to obtain the reamed alumina wet strip. Drying in a baking oven at the normal pressure and 110 ℃ for 2 hours, and roasting at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier.
The pore volume of the prepared alumina carrier is 1.19mL/g, the pore volume occupied by the pores with the diameter of 1-15 nm is 44.1% of the total pore volume, the pores with the diameter of more than 15nm are mainly distributed at 60-150 nm, and the pore volume occupied by the pores with the diameter of 60-150 nm is 51.1% of the total pore volume. The mechanical strength of the carrier is 10N/mm, and the specific surface area is 105m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of tungsten oxide and 2wt% of cobalt oxide based on the mass of a carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil for the residual oil hydrogenation reaction and the hydrogenation reaction conditions are the same as in example 1. The hydrogenation effect is shown in Table 2.
Example 3
3g of 920DU20 microspheres are weighed, and the volume fraction of the hydrocarbon in the inner core accounting for the spherical shell of the thermoplastic acrylic polymer is 0.001%. And mixing 100g of microspheres, 100g of alumina dry gel powder and 120g of deionized water, fully kneading, and putting the kneaded material into a Gao Wenji strip-resistant machine capable of measuring temperature, cooling and heating for strip extrusion molding. Controlling the temperature in the molding process to 185 ℃ to obtain the reamed alumina wet strip. Drying in a baking oven at the normal pressure and 110 ℃ for 2 hours, and roasting at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier.
The pore volume of the prepared alumina carrier is 0.93mL/g, the pore volume occupied by the pores with the pore diameter of 1-15 nm accounts for 87.6% of the total pore volume, the pores with the pore diameter of more than 15nm are mainly distributed at 60-120 nm, and the pore volume occupied by the pores with the pore diameter of 60-120 nm accounts for 11.9% of the total pore volume. The mechanical strength of the carrier is 19N/mm, and the specific surface area is135m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of tungsten oxide and 2wt% of nickel oxide based on the mass of the carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil for the residual oil hydrogenation reaction and the hydrogenation reaction conditions are the same as in example 1. The hydrogenation effect is shown in Table 2.
Example 4
3g of 180DU45 microsphere is weighed, and the volume fraction of the hydrocarbon in the inner core accounting for the spherical shell of the thermoplastic acrylic polymer is 0.0002 percent. 100g of microspheres, 100g of alumina dry rubber powder, 120g of deionized water, 2g of sesbania powder and 2ml of nitric acid are mixed and kneaded fully, and the kneaded material is put into a Gao Wenji strip-resistant machine capable of measuring temperature, cooling and heating of the material to be extruded and formed. Controlling the temperature of the molding process to be 185 ℃, drying the reamed alumina wet strips in a baking oven at the normal pressure of 110 ℃ for 2 hours, and roasting the alumina wet strips at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier.
The pore volume of the prepared alumina carrier is 0.94mL/g, the pore diameter of the alumina carrier is 86.7 percent, the pore diameter of the alumina carrier is larger than that of the alumina carrier, the pore diameter of the alumina carrier is mainly distributed between 60nm and 140nm, and the pore volume of the alumina carrier is 11.2 percent of the total pore volume. The mechanical strength of the carrier is 18N/mm, and the specific surface area is 138m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of molybdenum oxide and 2wt% of cobalt oxide based on the mass of a carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil for the residual oil hydrogenation reaction and the hydrogenation reaction conditions are the same as in example 1. The hydrogenation effect is shown in Table 2.
Example 5
3g of 920DU20 microspheres are weighed, and the volume fraction of the hydrocarbon in the inner core accounting for the spherical shell of the thermoplastic acrylic polymer is 0.001%. And mixing 100g of microspheres, 100g of alumina dry gel powder and 120g of deionized water, fully kneading, and putting the kneaded material into a Gao Wenji strip-resistant machine capable of measuring temperature, cooling and heating for strip extrusion molding. Controlling the temperature of the molding process to 160 ℃, drying the reamed alumina wet strips in a baking oven at the normal pressure of 110 ℃ for 2 hours, and roasting the alumina wet strips at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier.
The pore volume of the prepared alumina carrier is 0.98mL/g, the pore diameter of the alumina carrier is 68.8 percent, the pore diameter of the alumina carrier is larger than that of the alumina carrier, the alumina carrier is mainly distributed between 150nm and 400nm, and the pore volume of the alumina carrier is 24.3 percent of the total pore volume. The mechanical strength of the carrier is 14N/mm, and the specific surface area is 120m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of molybdenum oxide and 2wt% of nickel oxide based on the mass of the carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil for the residual oil hydrogenation reaction and the hydrogenation reaction conditions are the same as in example 1. The hydrogenation effect is shown in Table 2.
Example 6
3g of 920DU20 microspheres are weighed, and the volume fraction of the hydrocarbon in the inner core accounting for the spherical shell of the thermoplastic acrylic polymer is 0.001%. And mixing 100g of microspheres, 100g of alumina dry gel powder and 120g of deionized water, fully kneading, and putting the kneaded material into a Gao Wenji strip-resistant machine capable of measuring temperature, cooling and heating for strip extrusion molding. Controlling the temperature of the molding process to be 195 ℃, drying the reamed alumina wet strips in a baking oven at the normal pressure of 110 ℃ for 2 hours, and roasting the alumina wet strips at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier.
The pore volume of the prepared alumina carrier is 0.97mL/g, the pores with the diameter of 1-15 nm account for 70.9%, the pores with the diameter larger than 15nm are mainly distributed in 150-300 nm, and the pore volume occupied by 150-300 nm accounts for 23.1% of the total pore volume. The mechanical strength of the carrier is 15N/mm, and the specific surface area is 122m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of molybdenum oxide and 2wt% of nickel oxide based on the mass of the carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil for the residual oil hydrogenation reaction and the hydrogenation reaction conditions are the same as in example 1. The hydrogenation effect is shown in Table 2.
Comparative example 1
3g of 920DU20 microspheres are weighed, and the volume fraction of the hydrocarbon in the inner core accounting for the spherical shell of the thermoplastic acrylic polymer is 0.001%. And mixing 100g of microspheres, 100g of alumina dry gel powder and 120g of deionized water, fully kneading, and putting the kneaded material into a Gao Wenji strip-resistant machine capable of measuring temperature, cooling and heating for strip extrusion molding. Controlling the temperature of the molding process to be 100 ℃ to obtain the reamed alumina wet strip. Drying in a baking oven at the normal pressure and 110 ℃ for 2 hours, and roasting at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier.
The pore volume of the prepared alumina carrier is 0.90mL/g, the pore volume of the alumina carrier is 93.9% when the pore diameter is 1-15 nm, the pore volume of the alumina carrier is 6.1% when the pore diameter is larger than 15nm, the pore volume of the alumina carrier is mainly distributed between 1 μm and 10 μm, and the pore volume of the alumina carrier is 2.8% when the pore diameter is larger than 15 nm. The mechanical strength of the carrier is 21N/mm, and the specific surface area is 128m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of molybdenum oxide and 2wt% of nickel oxide based on the mass of the carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil for the residual oil hydrogenation reaction and the hydrogenation reaction conditions are the same as in example 1. The hydrogenation effect is shown in Table 2.
Comparative example 2
3g of 920DU20 microspheres are weighed, and the volume fraction of the hydrocarbon in the inner core accounting for the spherical shell of the thermoplastic acrylic polymer is 0.001%. Mixing microspheres with 100g of alumina dry rubber powder and 120g of deionized water, fully kneading, putting the kneaded material into a Gao Wenji strip machine capable of measuring temperature, cooling and heating, extruding and molding, and controlling the molding temperature to 225 ℃ to obtain the reamed alumina wet strip. Drying in a baking oven at the normal pressure and 110 ℃ for 2 hours, and roasting at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier.
The pore volume of the prepared alumina carrier is 0.90mL/g, the pore volume of the alumina carrier is 93.5% when the pore diameter is 1-15 nm, the pore volume of the alumina carrier is 6.5% when the pore diameter is larger than 15nm, the pore volume of the alumina carrier is mainly distributed between 1 μm and 10 μm, and the pore volume of the alumina carrier is 2.6% when the pore diameter is larger than 15 nm. The mechanical strength of the carrier is 21N/mm, and the specific surface area is 129m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of molybdenum oxide and 2wt% of nickel oxide based on the mass of the carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil for the residual oil hydrogenation reaction and the hydrogenation reaction conditions are the same as in example 1. The hydrogenation effect is shown in Table 2.
Comparative example 3
3g of 920DU20 microspheres are weighed, and the volume fraction of the hydrocarbon in the inner core accounting for the spherical shell of the thermoplastic acrylic polymer is 10%. Mixing microspheres with 100g of alumina dry rubber powder and 120g of deionized water, fully kneading, putting the kneaded material into a Gao Wenji strip machine capable of measuring temperature, cooling and heating, extruding and molding, and controlling the molding temperature to 170 ℃ to obtain the reamed alumina wet strip. Drying in a baking oven at the normal pressure and 110 ℃ for 2 hours, and roasting at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier. The aluminum oxide carrier obtained by extruding strips has the phenomenon of strip explosion, irregular appearance, macroscopic millimeter holes on the surface and mechanical strength of 5N/mm. Specific surface area of 99m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of molybdenum oxide and 2wt% of nickel oxide based on the mass of the carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil for the residual oil hydrogenation reaction and the hydrogenation reaction conditions are the same as in example 1. The hydrogenation effect is shown in Table 2.
Comparative example 4
Weighing 3g of acrylonitrile-methacrylonitrile copolymer, mixing 100g of alumina dry gel powder and 120g of deionized water, fully kneading, and putting the kneaded material into a Gao Wenji strip machine capable of measuring temperature, cooling and heating for strip extrusion molding. And controlling the temperature in the molding process to 170 ℃ to obtain the reamed alumina wet strip. Drying in a baking oven at the normal pressure and 110 ℃ for 2 hours, and roasting at the temperature of 850 ℃ for 3 hours after the drying is finished to obtain the alumina carrier.
The pore volume of the prepared alumina carrier is 0.90mL/g, the pores with the diameter of 1-15 nm account for 96.1%, the pores with the diameter larger than 15nm are mainly distributed in 16-25 nm, and the pore volume occupied by the pores with the diameter of 16-25 nm accounts for 2.1% of the total pore volume. The mechanical strength of the alumina carrier was 24N/mm. Specific surface area of 131m 2 /g。
Impregnating the alumina carrier with an impregnating solution containing active metal to obtain the hydrogenation catalyst. The hydrogenation catalyst comprises 5wt% of molybdenum oxide and 2wt% of nickel oxide based on the mass of the carrier.
The hydrogenation catalyst is applied to the residual oil hydrogenation reaction. The properties of the raw oil for the residual oil hydrogenation reaction and the hydrogenation reaction conditions are the same as in example 1. The hydrogenation effect is shown in Table 2.
TABLE 1 oil Properties of raw materials
Properties of (C) Raw oil-sand normal slag
Density (20 ℃ C.)/g.cm -3 0.9718
S/wt％ 3.3
Ni/ppm 22.4
V/ppm 73.7
Table 2 hydrogenation effects obtained in examples
Ni removal rate/% V removal rate/%
Example 1 54 80
Example 2 62 91
Example 3 55 83
Example 4 56 80
Example 5 60 88
Example 6 58 88
Comparative example 1 40 68
Comparative example 2 42 65
Comparative example 3 38 70
Comparative example 4 41 61
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (14)

1. An alumina carrier, wherein the alumina carrier has a through double-peak pore structure, and the pore volume of the alumina carrier is 0.8-1.3 mL/g; the pore volume occupied by the pores with the diameter of 1-15 nm is 40-92% of the total pore volume; the pore volume of the pores with the pore diameter of 50-900 nm is 5-56% of the total pore volume.
2. The alumina carrier of claim 1, wherein the alumina carrier has a pore volume of 0.9 to 1.2mL/g; the pore volume occupied by the pores with the diameter of 1-15 nm is 43-77% of the total pore volume; the pore volume of the pores with the pore diameter of 50-900 nm is 22-53% of the total pore volume.
3. Alumina support according to claim 1 or 2, characterized in that the mechanical strength of the alumina support is 10-30N/mm, preferably 10-20N/mm.
4. A method of forming the alumina carrier of any one of claims 1 to 3, comprising the steps of:
(1) Uniformly mixing the alumina dry gel powder and the microsphere expanding agent;
(2) Kneading and molding the materials obtained after the step (1) are mixed;
(3) Drying and roasting the formed product obtained in the step (2) to obtain an alumina carrier;
the microsphere expanding agent in the step (1) has a core-shell structure, wherein the shell is thermoplastic acrylic ester polymer, and the inner core is hydrocarbon.
5. The molding method as claimed in claim 4, wherein the volume fraction of the hydrocarbon in the core to the shell is 0.0001% to 0.1%, preferably 0.0002% to 0.001%.
6. The molding process of claim 4, wherein the shell temperature limit of the microsphere expansion agent in step (1) is 155 ℃ to 210 ℃, preferably 160 ℃ to 185 ℃; the initial volatilizing temperature of the hydrocarbon in the core is 110-145 ℃, preferably 120-135 ℃.
7. The molding method as claimed in claim 4, wherein the property of the microsphere expansion agent in the step (1) has at least one of A to D:
8. the molding method of claim 4, wherein the microsphere expansion agent of step (1) has at least one of the properties E to H:
9. the molding method as claimed in claim 4, wherein the weight of the microsphere expanding agent added in the step (1) is 2-30% of the weight of the dry alumina powder, preferably 3-15%.
10. The molding method as claimed in claim 4, wherein the particle size of the microsphere expansion agent in the step (1) is 1 μm to 100. Mu.m, preferably 5 μm to 50. Mu.m.
11. The molding process of claim 4, wherein the molding process of step (2) is controlled to a temperature of 10 ℃ to 50 ℃, preferably 20 ℃ to 40 ℃, above the initial volatilization temperature of the microsphere expander core of step (1).
12. The molding process according to claim 4, wherein the molding process in step (2) is controlled to a temperature higher than the shell temperature limit of the microsphere expansion agent in step (1) by 5 to 40 ℃, preferably 5 to 25 ℃.
13. The molding method according to claim 4, wherein the drying in the step (3) is performed at 50 to 150 ℃ for 1 to 5 hours; the calcination is carried out at 500-1000 ℃ for 2-5 hours, preferably 800-1000 ℃.
14. Use of an alumina support according to any one of claims 1 to 3 or an alumina support prepared by a shaping process according to any one of claims 4 to 13 in a hydrogenation catalyst.
CN202210038225.0A 2022-01-13 2022-01-13 Alumina carrier and forming method and application thereof Pending CN116474753A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101237927A (en) * 2005-08-10 2008-08-06 科学设计有限责任两合公司 Process for preparation of a catalyst carrier
CN102614934A (en) * 2011-01-30 2012-08-01 中国石油化工股份有限公司 Alumina carrier with composite pore structure and preparation method thereof
US20160220985A1 (en) * 2013-09-27 2016-08-04 Cosmo Oil Co., Ltd Hydrogenation catalyst for heavy hydrocarbon oil and hydrogenation method for heavy hydrocarbon oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101237927A (en) * 2005-08-10 2008-08-06 科学设计有限责任两合公司 Process for preparation of a catalyst carrier
CN102614934A (en) * 2011-01-30 2012-08-01 中国石油化工股份有限公司 Alumina carrier with composite pore structure and preparation method thereof
US20160220985A1 (en) * 2013-09-27 2016-08-04 Cosmo Oil Co., Ltd Hydrogenation catalyst for heavy hydrocarbon oil and hydrogenation method for heavy hydrocarbon oil

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