WO2004037408A1 - A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support - Google Patents

A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support Download PDF

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Publication number
WO2004037408A1
WO2004037408A1 PCT/CN2003/000839 CN0300839W WO2004037408A1 WO 2004037408 A1 WO2004037408 A1 WO 2004037408A1 CN 0300839 W CN0300839 W CN 0300839W WO 2004037408 A1 WO2004037408 A1 WO 2004037408A1
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Prior art keywords
silicon
alumina support
catalyst
nano
aluminum
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PCT/CN2003/000839
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English (en)
French (fr)
Inventor
Dengling Wei
Shaozhong Peng
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Priority claimed from CN 02133122 external-priority patent/CN1219028C/zh
Priority claimed from CN 02133144 external-priority patent/CN1197650C/zh
Priority claimed from CN 02133125 external-priority patent/CN1282732C/zh
Priority claimed from CN 02133118 external-priority patent/CN1201865C/zh
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to EP03753239.7A priority Critical patent/EP1552880B1/en
Priority to JP2004545680A priority patent/JP5006516B2/ja
Priority to CA2501973A priority patent/CA2501973C/en
Priority to AU2003272858A priority patent/AU2003272858A1/en
Publication of WO2004037408A1 publication Critical patent/WO2004037408A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/182—Phosphorus; Compounds thereof with silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J35/615—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
    • B01J35/633—Pore volume less than 0.5 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
    • B01J35/635—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
    • B01J35/66—Pore distribution

Definitions

  • the present invention relates to a silica-containing alumina carrier, a method for preparing the same, and a catalyst containing the alumina carrier.
  • the invention relates to a silica-containing alumina support and a preparation method thereof, and a catalyst containing the alumina support, particularly a catalyst for hydrotreating a hydrocarbon. Background technique
  • Alumina support is a common type of catalyst support. Its surface properties, such as specific surface area, surface acid content, acid strength, and pore properties, such as average pore diameter and pore size distribution, are decisive for the properties of the catalyst containing it. influences.
  • silicon, phosphorus, boron, titanium, zirconium and other additives are often used to modify it. Among them, silicon is one of the most commonly used additives. Studies have shown that the additive silicon can change the surface properties of the aluminum oxide support.
  • auxiliary silicon to alumina according to the prior art affects the microstructure of the alumina support. For example, it is easy to diffuse the pore size distribution of the alumina support, which is not conducive to sufficiently improving its surface properties.
  • Alumina supports are commonly used in hydrocarbon hydroprocessing catalysts.
  • the active components are oxides of Group VIB metals and Group VIII metals.
  • one method is to modify the alumina support.
  • the introduction of silica in alumina supports has significant effects on the catalyst in terms of acid properties, metal dispersion, and pore size distribution.
  • the silica after adding silica to the alumina support, the silica must first interact with the strong active center on the surface of the alumina support, weakening the surface active center of the alumina support, and as a result, the alumina support
  • the interaction with the active metal is relatively mild, which is conducive to metal dispersion and activity. Therefore, the use of silicon modified alumina support is one of the directions to improve the performance of hydrocarbon hydrotreating catalysts.
  • auxiliary source of silicon mainly as silicates or silica sols.
  • the method of introducing auxiliary silicon mainly consists of coprecipitation of aluminum-containing compounds and sodium silicate (commonly known as water glass)
  • Silicon-containing aluminum hydroxide is mixed with aluminum hydroxide or alumina and silica sol to prepare silicon-containing aluminum hydroxide.
  • the content of silicon dioxide in the catalyst is generally 1-10%.
  • USP 4, 758, 544 describes a method for preparing an alumina-aluminum stearate-silica support and supporting a tungsten-nickel-fluorine catalyst by a co-precipitation method.
  • silicon and stele elements are added to the support by the co-precipitation method, most of the silicon and phosphorus elements are bound to be dispersed in the alumina support body phase, which reduces the utilization rate of the auxiliary agent and cannot fully exert its role.
  • the addition of both silicon and phosphorus will inevitably affect the microstructure of the alumina support itself, resulting in dispersed pore size distribution, small pore volume, and low specific surface area, reducing the dispersion of the additive, and failing to fully play the role of the additive.
  • CN1048651C describes a production process using silicon sulfate and sodium metaaluminate as raw materials to prepare silicon-containing and aluminophosphorus oxide-containing hafnium by a precipitation method.
  • the silicon source introduced during this preparation is sodium silicate, which has the same problems as described above.
  • US4,134,856 also uses a co-precipitation method to prepare alumina support containing silica, which also has similar problems as described above.
  • the pore size distribution of the catalyst support described in this patent is relatively diffuse, and the pore volume and specific surface area are relatively large, which belongs to an amorphous silicon aluminum structure.
  • CN1030395C and other methods use silica sol to be mixed into aluminum hydroxide during the formation of the support or catalyst, and the auxiliary silicon is introduced. Since the silica sol expands the pores during the subsequent drying and firing of the support or catalyst, the pore diameter of the support or catalyst Dispersed distribution is not conducive to improving the reaction performance of the catalyst.
  • the present invention provides a silicon-containing alumina support in which the auxiliary silicon is enriched on the surface of the alumina support, a preparation method thereof, and a hydrocarbon hydrotreating catalyst prepared from the alumina support.
  • a silicon-containing alumina carrier which comprises a ⁇ -alumina carrier as a main component and silica as an auxiliary agent, and is characterized in that the weight of the alumina carrier is used as a reference 10 ⁇ , Generally, the alumina carrier contains silica 0.5 to 10. 0%, the auxiliary silicon is enriched on the surface of the alumina carrier, and the difference between the surface phase silicon aluminum atomic ratio and the average silicon aluminum atomic ratio is 0.10 or more, generally 12 ⁇ 0. 20 ⁇ 0. 10 ⁇ 0. 25, preferably 0. 12 ⁇ 0. 20.
  • a method for preparing a silicon-containing alumina carrier comprises mixing and / or kneading aluminum hydroxide or alumina, adding nano silicon-containing compounds, and adding a peptizing acid, etc., to form a plastic.
  • the body is then shaped, dried, and fired to obtain the silicon-containing alumina support of the present invention.
  • a silicon-containing alumina support in the preparation of a hydrocarbon hydrotreating catalyst, such as a hydrocracking catalyst, a hydrorefining catalyst, and the like, is provided.
  • a hydrocarbon hydrotreating catalyst uses the silicon-containing alumina carrier of the present invention as a carrier, and the VIB group metal and the group metal as active components.
  • the silica-containing alumina carrier of the present invention uses a ⁇ -alumina carrier as a main component and silica as an auxiliary agent, and is characterized in that the silica-containing alumina carrier of the present invention contains 0.5 to 10.0% of silica, preferably 1 ⁇ 0 ⁇ 7 ⁇ 0%, the auxiliary silicon is enriched on the surface of the alumina support, and the difference between the surface phase silicon aluminum atomic ratio and the average silicon aluminum atomic ratio is more than 0.10, generally 0.10 to 0.25, preferably 0.12 to 0.20 .
  • the surface phase silicon-aluminum atomic ratio is above 0.15, generally 0.15 to 0.30, and preferably 0.16 to 0.25.
  • the pore volume of the silica-containing alumina carrier of the present invention is 0.55-0.68ml / g, the specific surface area is 270-320m7g, and the average pore diameter is 6.5-9.5nm. Among them, the pore volume of 3-15nm accounts for the total pore volume. Above 90%, generally 90 ⁇ 96%.
  • the silica-containing alumina carrier of the present invention optionally further contains an auxiliary phosphorus, which contains 0.3 to 3.0% of phosphorus pentoxide by weight.
  • the silicon-containing alumina carrier of the present invention optionally further contains additives such as titanium, boron, zirconium and the like.
  • silicon-containing alumina carrier of the present invention aluminum hydroxide or alumina is mixed and / or kneaded, and at the same time, a nano silicon-containing compound is added, and a peptizing acid is added, etc., and mixed to form a plastic body.
  • a silicon-containing alumina support of the present invention was prepared.
  • the nano silicon-containing compound can be added in one of the following ways: (a) the nano silicon-containing compound is mixed with an aluminum-containing source material (aluminum hydroxide or alumina); or
  • the nano silicon-containing compound is preferably nano silica, and its particle size is 6 to 100 nm.
  • the amount of nano silica added can be determined according to the specific use of the alumina carrier.
  • the method of the present invention can prepare alumina carriers with a silica auxiliary content of 0.5 to 40%, generally 0.5 to 10%, and preferably 1.0 to 7.0%. . .
  • Auxiliary ringworm can be added during the preparation of the alumina support.
  • phosphorus-containing aluminum hydroxide can be used.
  • the production process of scale-containing aluminum hydroxide is: according to the neutralization methods known in the art, hydrogen is obtained by, for example, reacting aluminum sulfate with sodium metaaluminate or reacting aluminum chloride with ammonia. The alumina precipitate is then filtered, the filter cake is slurried, and the phosphorus-containing compound is added to control the slurry temperature to 30-90 ° C, and then filtered, dried, and roasted to obtain phosphorus-containing aluminum hydroxide.
  • the aluminum hydroxide support contains 0.3-3.0% of phosphorus pentoxide by weight.
  • a silica-containing alumina carrier is prepared in the following manner: mixing macroporous aluminum hydroxide powder and / or small-pore aluminum hydroxide powder, adding a peptizer containing nano-silica, or An aqueous solution of an inorganic acid and nano-silica are mixed to form a plastic body, and extruded into a bar on an extruder.
  • the shaped bar is dried at 90 ° C-150 ° C for 8-16 hours, and then calcined at 450-650 ° C for 1-6 hours, and finally the silicon-containing alumina carrier of the present invention is obtained.
  • the pore volume of macroporous aluminum hydroxide is 0.7-l.lml / g, the average pore diameter is 6.0-ll. Onm, and the specific surface area is 300-380m 2 / g; the pore volume of small-pore aluminum hydroxide is 0.2- 0.6ml / g, average pore diameter is 2.0-10.0nm, and specific surface area is 200-300m 2 / g.
  • Macroporous aluminum hydroxide The weight mixing ratio with the small pore aluminum hydroxide is 1: 1-1: 5.
  • the ratio of the mixed part of the small pore aluminum hydroxide and the large pore aluminum hydroxide to the solvent part is 5: 1 ⁇ 25: 1.
  • the method of the present invention changes the preparation method of the traditional silicon-containing alumina carrier.
  • the silicon element is enriched and uniformly dispersed on the surface of the alumina carrier, and the modulation and oxidation are performed.
  • the effect of the surface properties of the aluminum support further improves the interaction between the metal component and the alumina support in the catalyst containing the support. It has the following advantages:
  • the nano-silica used has the characteristics of small particle size, high dispersion and excellent stability, it has little effect on the microstructure of the alumina support, and the pore size distribution of the alumina support is more uniform, which can effectively control the product properties.
  • the restrictions on the precursor of alumina carrier-pseudoboehmite or alumina can be relaxed, and the production cost can be reduced.
  • the alumina support prepared by adding nano-silica to prepare a catalyst after the alumina (or aluminum hydroxide) is generated is beneficial to the enrichment and uniform dispersion of silicon on the surface of the alumina support and plays a role in modulating the surface properties of the alumina support. effect.
  • auxiliary silicon of the present invention can also be applied to auxiliary agents such as titanium, boron, zirconium, and phosphorus.
  • auxiliary agents such as titanium, boron, zirconium, and phosphorus.
  • nano titanium-containing substances, nano boron-containing substances, nano zirconium-containing substances, and nano phosphorus-containing substances are used as oxidation agents.
  • the silica-containing alumina support of the present invention can be used for preparing hydrocarbons-such as petroleum hydrocarbons-hydrotreating catalysts, such as hydrocracking catalysts, hydrorefining catalysts, and the like.
  • the hydrocarbon hydrotreating catalyst of the present invention uses the silicon-containing alumina carrier of the present invention as a support.
  • a carrier VIB group metals and Vin group metals are used as active components, and optional auxiliary component phosphorus may be contained.
  • the Group VIB metal is preferably tungsten and / or molybdenum, and the Group metal is preferably nickel and / or cobalt.
  • the group VIB metal oxide for example, Tungsten and / or molybdenum oxide
  • group metal oxides such as nickel and / or cobalt oxide
  • the hydrocarbon hydrotreating catalyst may contain 0.5 to 8.0% of phosphorus pentoxide.
  • the catalyst of the present invention has a specific surface area of 150 to 200 m 2 / g, and a pore volume of 0.30 to 0.40 ml / g, preferably 0.32 to 0.38 ml / g. It is preferably 92-96%.
  • the catalyst surface silicon-aluminum atomic ratio is greater than 0.15, preferably 0.15-0.25.
  • the difference between the surface silicon atomic ratio of the catalyst and the average silicon aluminum atomic ratio is 0.10-0.20.
  • the impregnation method known in the art is adopted, and the silicon-containing alumina carrier of the present invention is used as a carrier, and the alumina carrier is, for example, a solution containing molybdenum-nickel and optional phosphorus.
  • the alumina support is dried at 90 to 150 ° C for 1 to 5 hours, and then calcined at 430 to 550 ° C for 1 to 5 hours to obtain the catalyst of the present invention.
  • the activity of the hydrocarbon hydrotreating catalyst obtained from the silica-containing alumina carrier of the present invention is remarkably improved, and experiments show that the hydrodenitrogenation activity is about 20% higher than that of the prior art.
  • the silica (Si0 2 ) content of the alumina support and catalyst of the present invention is determined by colorimetric method; the pore structure is determined by nitrogen adsorption method, using the American Michel Instrument Company ASAP2400 full-automatic physical adsorption meter; the acidity and acid content distribution are vacuumed Determination of ammonia adsorption and programmed temperature desorption by NH 3 -TG-TPD technique. JSW-6310F cold-field emission scanning electron microscope was used to observe the element distribution in the oxidized catalyst body phase.
  • Surface phase silicon-aluminum atomic ratio measurement method Measured by X-ray photoelectron energy (XPS) method, the average silicon-aluminum atomic ratio is obtained by converting the silica content and alumina content. The difference between the surface phase silicon-aluminum atomic ratio and the average silicon-aluminum atomic ratio is ASi / Al (the above silicon-aluminum atomic ratio is the ratio of silicon-aluminum atoms).
  • Example 1 is intended to further illustrate the invention, but do not limit the invention in any way.
  • Example 1 is intended to further illustrate the invention, but do not limit the invention in any way.
  • Og pore volume 0.458ml / g, average pore diameter is 8. Onm, specific surface area is 228m 2 / g), nanometer silica with an average particle diameter of 30nm 4.0% (based on the weight of the final support), 75.
  • the properties are shown in the table 1.
  • Example 1 4.0% of nano-silica was replaced by 6.2% (average particle diameter of 15 nm), which is a cost example.
  • Example 1 4.0% of nano-silica was replaced by 2.3% (average particle diameter of 45 nm), which is a cost example.
  • Example 1 the nano-silica was changed to 8.5%, and the firing temperature was changed to 550, which is a cost example.
  • Example 1 the firing temperature was changed to 580 ° C, which is a cost example.
  • Example 1 the method for adding nano-silica is: mixing the nano-silica with a nitric acid solution, and then adding the macro-porous aluminum hydroxide and the micro-porous aluminum hydroxide, and the other steps are the same as those in the embodiment 1, which is a cost example.
  • Example 1 the nano-silica was replaced by 5.5%, and a peptizer was prepared based on the nano-silica and 10% of small-pore aluminum hydroxide and a nitric acid solution, and then mixed with large-pore aluminum hydroxide and the remaining small-pore hydrogen.
  • the alumina was mixed, and the other examples were the same as in Example 1, which is a cost example.
  • Example 1 the nano-silica was replaced by 3.0%, wherein the nano-dioxide was Silicon is divided into two equal parts, one is added to the aluminum hydroxide material after wetting with deionized water, and the other is made into a peptizer with a 5% solution of small-pore aluminum hydroxide and nitric acid and added to the aluminum hydroxide material.
  • the other steps are the same as those in Embodiment 1, namely, the cost example.
  • Example 1 instead of nano-silica, 85.0 g of silica sol containing 20% of silica was used, and 325 g of water was changed to 340 g, which is a cost example.
  • Example 1 the macroporous aluminum hydroxide powder was replaced with a macroporous silicon-containing aluminum hydroxide powder produced by precipitation method using aluminum trichloride, ammonia water, and sodium silicate as raw materials.
  • the silica content was 5.2%.
  • 325 g of water was changed to 400 g, which is a cost example.
  • Step 1 In a clean container, add 1200 ml of deionized water, raise the temperature to 65, and add an aqueous solution of sodium metaaluminate having a specific gravity of 1.35 at a flow rate of 30 ml / min and an aqueous solution of aluminum sulfate having a specific gravity of 1.15 at a flow rate of 65 ml / min.
  • deionized water the temperature was maintained at 65 ° C, the pH was 8.5, and the feeding time was 90 minutes.
  • Step 2 After the feeding is stopped, the system is aged for 90 minutes at the above pH and temperature conditions.
  • the filtered cake is dehydrated with deionized water, washed with sodium carbonate solution and / or ammonia solution for 5 times, and washed to the alumina carrier.
  • the Na + content ⁇ Q. G5m%, S0 4 content ⁇ 1.2m%, Fe +++ content ⁇ 0.08m%.
  • Step 3 Add the aluminum hydroxide filter cake obtained in the previous step to a solution of 2.5 L of deionized water and 42 g of 85m% phosphoric acid, beat and homogenize, control the temperature of the slurry to 65 ° C, and filter for 40 minutes to obtain phosphorous aluminum hydroxide. Filter cake.
  • Step 4 The filter cake is directly dried at 120 ⁇ for 8 hours and then used.
  • Step 5 Weigh 142g of phosphorous aluminum hydroxide, 252g of small-pore aluminum hydroxide, 7.5g of nano-silica (average particle size 30nm) and 90g of deionized water, mix well, add 24g of 40% nitric acid solution and 340g of deionized The solution prepared with water was kneaded into a plastic body, extruded into a bar using a stick extruder, dried at a temperature of 120 * C for 8 hours, and then baked at 500 ° C for 4 hours, which is a cost example.
  • Step 1 is the same as Step 1 and Step 2 of Embodiment 9.
  • Step 2 The 42.0 g 85 m% phosphoric acid in step 3 of Example 9 was changed to 56 g 85 m% phosphoric acid.
  • Step 3 is the same as Step 4 and Step 5 in Example 9.
  • Step 1 is the same as Step 1 and Step 2 of Embodiment 9.
  • Step 2 Change 42.0 g of 85 m% phosphoric acid in Step 3 of Example 9 to 7 5 g of 8 5 m% phosphoric acid
  • Step 3 is the same as the step 9 in step 9 and step 5.
  • Step 1 is the same as that in the embodiment 9. Step 1, step 2, step 3, step 4.
  • Step 2 The baking temperature in Step 5 of Example 9 was changed to 550 ° C, and the baking was performed for 4 hours.
  • Step 1 is the same as that in the embodiment 9. Step 1, step 2, step 3, step 4.
  • Step 2 The baking temperature in Step 9 of Example 9 was changed to 600, and the baking was performed for 3 hours.
  • Example 9 the nano-silica was replaced with 13 g (average particle size: 20 nm).
  • the nano-silica was mixed with a nitric acid solution, and then added to the macroporous aluminum hydroxide and the microporous aluminum hydroxide. .
  • Example 9 the nano-silica was replaced with 20 g (average particle diameter of 45 nm), and the nano-silica was mixed with 10% of small-pore aluminum hydroxide and a nitric acid solution to make a peptizer, and then mixed with large-pore aluminum hydroxide. It was mixed with the remaining small-pore aluminum hydroxide.
  • Example 9 the nano-silica was replaced with 25 g, wherein the nano-silica was divided into two equal parts, one part was wetted with deionized water and added to the aluminum hydroxide material, and the other part was with small holes. After adding 5% of aluminum hydroxide and nitric acid solution to make a peptizer, add hydroxide In the aluminum material, other steps are the same as in Example 9.
  • Example 9 the nano-silica in step 5 was changed to 95 g of 20% silica sol, 430 g of deionized water was changed to 390 g, and the auxiliary brick was added by the co-precipitation method (the method described in US 4,758,544 ).
  • the catalyst needs to be pre-sulfided before evaluation.
  • the pre-sulfurization process is as follows: Use a lamp oil containing 1.8% carbon disulfide, and perform pre-sulfidation at a hydrogen partial pressure of 13.7 MPa and a volumetric space velocity of 1.2 h-hydrogen oil volume ratio of 1200: 1. 230 ° C constant temperature vulcanization for 8 hours, 360 ° C constant temperature vulcanization for 4 hours.
  • the oxidation state element composition is the percentage of the mass of an element in the cross section micro area of the oxidation state catalyst body phase in the total mass of the elements contained.
  • the content of nano-silica was increased so that the content of silica in the silica-containing alumina carrier was 10% and 15%.
  • the main properties of the alumina support are shown in Table 6 (19, 20).
  • the amount of silica sol was increased so that the silica content in the silica-containing alumina carrier was 10% and 15%.
  • the main properties of the alumina support are shown in Table 6 (ratio 5, ratio 6).
  • Table 6 Physicochemical properties of alumina supports of Examples 19, 20 and Comparative Examples 5, 6 Pore volume ratio Surface average pore total acid amount 'Average average surface phase Example Pore size ASi / Al ral / g Product m 2 / g Diameter nm mmo 1 / g si0,% Si / Al Si / Al

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Description

一种含硅氧化铝载体、 其制法及含有该氧化铝载体的催化剂 技术领域
本发明涉及一种含硅氧化铝载体及其制备方法， 以及含有该氧 化铝载体的催化剂， 特别是用于烃类加氢处理的催化剂。 背景技术
氧化铝载体是一类常用的催化剂载体， 其表面性质， 如比表 面积、 表面酸量、 酸强度等， 以及孔性质， 如平均孔直径、 孔径 分布等， 对含有它的催化剂的性质具有决定性的影响。 为改进氧 -化铝载体的性能， 常采用硅、 磷、 硼、 钛、 锆等助剂对其进行改 性， 其中硅是最常用的助剂之一。 研究表明， 助剂硅可以改变氧 化铝载体的表面性质。 但按现有技术将助剂硅加入到氧化铝中影 响氧化铝载体的微观结构， 例如， 容易使氧化铝载体的孔径分布 较弥散， 不利于充分地改善其表面性质。
氧化铝载体常用于烃类加氢处理催化剂。 在该类催化剂中， 活性组分为第 VIB 族金属和第稷族金属的氧化物。 为了提高催化 剂的性能， 其中一种方法是对氧化铝载体进行改性。 研究表明， 在氧化铝载体中引入二氧化硅， 在酸性质、 金属分散情况及孔径 分布等方面对催化剂产生明显影响。 具体而言， 根据体系能量最 低原理， 在氧化铝载体中加入二氧化硅后， 二氧化硅首先要与氧 化铝载体表面强活性中心作用， 削弱了氧化铝载体表面活性中 心， 结果使氧化铝载体与活性金属间的相互作用较緩和， 有利于 金属分散及活性的发挥。 因此， 采用硅改性氧化铝载体是改进烃 类加氢处理催化剂性能的方向之一。
现有烃类加氢处理催化剂引入助剂硅的硅源主要为硅酸盐类 或硅溶胶类， 助剂硅的引入方式主要是，含铝化合物与硅酸钠（俗 名水玻璃） 共沉淀制备含硅氢氧化铝， 和氢氧化铝或氧化铝与硅 溶胶混合制备含硅氢氧化铝， 二氧化硅在催化剂中的含量一般为 1 - 10%。 USP 4, 758, 544 描述了一种用共沉淀法制备氧化铝 -碑酸铝- 二氧化硅载体， 并负载钨-镍-氟的催化剂的方法。 由于是采用共 沉淀法将硅和碑元素加入到载体中的， 势必有大部分硅和磷元素 分散在氧化铝载体体相中， 降低了助剂的利用率， 不能充分发挥 其作用。 此外， 这种既加硅又加磷势必影响氧化铝载体本身的微 观结构， 导致孔径分布弥散、 孔容小、 比表面积低， 降低了助剂 的分散度， 也不能充分发挥助剂的作用。
CN1048651C 描述了以硫酸铝和偏铝酸钠为原料， 采用沉淀法 制备含硅和磷氧化铝载侔的生产过程， 此制备过程中引入的硅源 为硅酸钠， 存在上述相同的问题。
US4, 134, 856 也采用共沉淀法制备含二氧化硅的氧化铝载体， 也存在上述类似问题。 该专利描述的催化剂载体的孔径分布较为 弥散， 孔容和比表积较大， 属于一种无定形硅铝结构。
CN1030395C 等采用在载体或催化剂成型时向氢氧化铝中混入 硅溶胶的方法引入助剂硅， 由于硅溶胶在载体或催化剂的后续干 燥及焙烧过程中起到扩孔作用， 使得载体或催化剂的孔径分布弥 散， 不利于提高催化剂的反应性能。
上述现有技术助剂硅的硅源及其加入方式同时存在的一个问 题是， 助剂硅分散在体相中的量较大， 在表相的量较少， 因此， 影响了助剂硅对催化剂表面性质调节作用的发挥。 发明内容
针对现有技术的不足， 本发明提供一种其中助剂硅富集在氧化 铝载体表面的含硅氧化铝载体及其制备方法， 以及由该氧化铝载体 制备的烃类加氢处理催化剂。
因此， 根据本发明的第一方面， 提供一种含硅氧化铝载体， 它以 γ-氧化铝载体为主要组分， 以二氧化硅为助剂， 其特征在于， 以氧化铝载体重量为基准， 氧化铝载体含二氧化硅 0. 5 - 10. 0%， 助剂硅富集在氧化铝载体表面， 表相硅铝原子比与平均硅铝原子 比的差值为 0. 10以上， 一般为 0. 10 ~ 0. 25， 优选为 0. 12 ~ 0. 20。 根据本发明的第二方面， 提供一种制备含硅氧化铝载体的方 法， 包括混合和 /或混捏氢氧化铝或氧化铝， 同时加入纳米含硅 化合物， 并加入胶溶酸等， 混合形成可塑体， 然后成型、 干燥、 焙烧， 即制得本发明的含硅氧化铝载体。
根据本发明的第三方面， 提供一种含硅的氧化铝载体在制备 烃类加氢处理催化剂， 例如加氢裂化催化剂、 加氢精制催化剂等 中的应用。
根据本发明的第四方面， 提供一种烃类加氢处理催化剂， 该 催化剂以本发明的含硅氧化铝载体作为载体， 以 VIB 族金属和權 族金属为活性组分。
具体实施方式
本发明的含硅氧化铝载体以 γ-氧化铝载体为主要组分， 以二 氧化硅为助剂， 其特征在于， 本发明的含硅氧化铝载体含二氧化 硅 0.5 - 10.0%， 优选为 1· 0~ 7· 0%， 助剂硅富集在氧化铝载体表 面， 表相硅铝原子比与平均硅铝原子比的差值为 0.10 以上， 一 般为 0.10~ 0.25， 优选为 0.12 ~ 0.20。 在本发明的优选含硅氧 化铝载体中， 表相硅铝原子比在 0.15 以上， 一般为 0.15 ~ 0.30， 优选为 0.16 ~ 0.25。
本发明的含硅氧化铝载体的孔容为 0.55 - 0.68ml/g, 比表面 积为 270 - 320m7g, 平均孔直径为 6.5 - 9.5nm, 其中， 孔径为 3 - 15nm的孔容占总孔容的 90%以上， 一般为 90~ 96%。
本发明的含硅氧化铝载体还任选含有助剂磷， 以重量计含五 氧化二磷 0.3 - 3.0%。
本发明的含硅氧化铝载体还任选含有助剂钛、 硼、 锆等。
为制备本发明含硅氧化铝载体， 混合和 /或混捏氢氧化铝或氧 化铝， 同时， 加入纳米含硅化合物， 并加入胶溶酸等， 混合形成 可塑体， 然后成型、 干燥、 焙烧， 即制得本发明的含硅氧化铝载 体。
上述纳米含硅化合物的加入方式可以采用下列方式中的一 种： ( a ) 纳米含硅化合物与含铝源物料 （氢氧化铝或氧化铝） 混 合； 或
( b ) 纳米含硅化合物用去离子水润湿后加入含铝源物料中；
( C ) 纳米含硅化合物与胶溶酸溶液混合后加入含铝源物料 中， 或
( d ) 将全部或部分小孔氢氧化铝与胶溶酸溶液和纳米含硅化 合物混合 （做胶溶剂） ， 然后与大孔氢氧化铝混合； 或
( e ) 分步加入， 在上述（a ) 、 （b ) 、 （c ) 和 （d ) 中任两 步或两步以上中分别加入。
上述纳米含硅化合物优选为纳米二氧化硅， 其粒径为 6 - 100nm。 纳米二氧化硅加入量可以 据氧化铝载体的具体用途确 定， 本发明方法可以制备二氧化硅助剂含量为 0.5 ~ 40%的氧化铝 载体， 一般为 0.5~ 10%， 优选为 1.0 ~ 7.0%。 。
可以在氧化铝载体制备过程中加入助剂癬。 为此， 可以使用 含磷氢氧化铝， 含鱗氢氧化铝的制备过程为： 按照本领域公知的 中和方法， 由例如硫酸铝与偏铝酸钠反应或由氯化铝与氨反应获 得氢氧化铝沉淀物， 然后将氢氧化铝沉淀物过滤， 滤饼打浆， 加 入含磷化合物， 控制浆液温度为 30~ 90°C, 然后过滤并干燥、 焙 烧得到含磷的氢氧化铝。 以重量计， 氢氧化铝载体含五氧化二磷 0.3- 3.0%。
在本发明的一个优选实施方式中， 含硅氧化铝载体以下列方 式制备： 混合大孔氢氧化铝粉和 /或小孔氢氧化铝粉， 加入含有 纳米二氧化硅的胶溶剂， 或混入含无机酸的水溶液和纳米二氧化 硅， 混合形成可塑体， 在挤条机上挤成条状物。 成形后的条状物 在 90°C - 150°C下干燥 8- 16小时， 然后于 450 - 650°C焙烧 1 - 6 小时， 最后得到本发明的含硅氧化铝载体。 其中， 大孔氢氧化铝 的孔容为 0.7- l.lml/g， 平均孔直径为 6.0- ll. Onm, 比表面积 为 300 - 380m2/g; 小孔氢氧化铝的孔容为 0.2 - 0.6ml/g， 平均孔 直径为 2.0- 10.0nm， 比表面积为 200 - 300m2/g。 大孔氢氧化铝 与小孔氢氧化铝的重量混合比为 1 : 1 - 1： 5。 小孔氢氧化铝与大 孔氢氧化铝的混合部分与做胶溶剂部分的比例为 5 : 1 ~ 25： 1。
本发明方法改变了传统含硅氧化铝载体的制备方法， 通过采 取新的硅源及独特的添加助剂硅的技术， 使硅元素富集于氧化铝 载体表面且分散均匀， 起到了调变氧化铝载体的表面性质的作 用， 进而有效地改善含有该载体的催化剂中金属组分与氧化铝载 体间的相互作用。 具体具有如下优点：
( 1 ) 与现有技术相比， 不增加额外步驟， 简便易行， 容易掌 握。
( 2 ) 由于使用的纳米二氧化硅具有粒度小、 高度分散性及优 异的稳定性等特点， 对氧化铝载体微观结构的影响小， 氧化铝载 体孔径分布更加均勾， 可以有效控制产品性质， 同时可放宽对氧 化铝载体前身物-拟薄水铝石或氧化铝的限制， 降低生产成本。
( 3 ) 在氧化铝 （或氢氧化铝） 生成后加入纳米二氧化硅制备 催化剂的氧化铝载体， 有利于氧化铝载体表面硅富集且分散均 匀， 起到了调变氧化铝载体的表面性质的作用。
( 4 ) 用于制备催化剂， 可有效地改善活性组分与氧化铝载体 间的相互作用， 提供更多的表面活性中心。
( 5 ) 用于制备含磷的含硅氧化铝载体时， 在氧化铝载体制备 过程中采用先加入助剂磷后加入纳米二氧化硅的方法， 解决了用 现有技术中氧化铝载体同时加入助剂磷和硅使孔径分布弥散的缺 点。
本发明关于助剂硅的加入方法还可以适用于助剂钛、 硼、 锆、 磷等助剂， 例如采用纳米含钛物质、 纳米含硼物质、 纳米含锆物 质、 纳米含磷物质等作为氧化铝载体助剂来源， 制备含上述一种 或几种助剂的催化剂或催化剂载体。
本发明的含有二氧化硅的氧化铝载体可用于制备烃类 -例如 石油烃类 -加氢处理催化剂， 例如加氢裂化催化剂、 加氢精制催 化剂等。
本发明的烃类加氢处理催化剂以本发明的含硅氧化铝载体作 为载体， 以 VIB 族金属和 Vin族金属为活性组分， 还可含有可选择 助剂组分磷。 在本发明的烃类加氢处理催化剂中， 第 VIB 族金属 优选为钨和 /或钼， 第爾族金属优选是镍和 /或钴， 以最终催化剂 重量计， 含 VIB 族金属氧化物 （例如钨和 /或钼氧化物） 18.0 - 28.0%, 覆族金属氧化物 （例如镍和 /或钴氧化物） 2.0 - 6.0%， 二氧化硅 0.3 - 7.0%， 其余为氧化铝载体。 在本发明的优选实施 方案中， 烃类加氢处理催化剂可以含五氧化二磷 0.5 - 8.0%。
本发明的催化剂的比表面积为 150 - 200m2/g， 孔容为 0.30- 0.40ml/g, 优选 0.32 - 0.38ml/g， 孔径为 3 - 15nm的孔容占总孔 容的 90%以上， 优选为 92 - 96%。 催化剂表相硅铝原子比大于 0.15， 优选为 0.15 - 0.25。 催化剂表相硅铝原子比与平均硅铝原 子比的差值为 0.10- 0.20。
为制备本发明的烃类加氢处理催化剂， 采用本领域公知的浸渍 法， 以本发明含硅氧化铝载体作为载体， 使用例如含有钼-镍及任 选的磷的溶液对所述氧化铝载体进行浸渍， 浸渍后氧化铝载体在 90 - 150°C干燥 1 - 5 小时， 再于 430 - 550°C焙烧 1 - 5 小时， 即制得 本发明的催化剂。
由本发明的含硅氧化铝载体得到的烃类加氢处理催化剂的活性 显著提高， 实验表明， 加氢脱氮活性比现有技术高 20%左右。
分析及表征方法
本发明氧化铝载体和催化剂的二氧化硅 （ Si02 ) 含量用比色 法测定；孔结构用氮吸附法测定，采用美国迈克仪器公司 ASAP2400 型全自动物理吸附仪； 酸度和酸量分布采用真空氨吸附和程序升 温解吸的 NH3- TG- TPD技术测定。 采用 JSW-6310F冷场发射扫描电 子显微镜观测氧化态催化剂体相中元素分布。 表相硅铝原子比测 定方法： 用 X 光电子能语 ( XPS ) 方法测定， 平均硅铝原子比按 二氧化硅含量与氧化铝含量换算得到。 表相硅铝原子比与平均硅 铝原子比的差值为 ASi/Al (上述硅铝原子比为硅铝原子数比）。
下述实施例旨在进一步说明本发明， 但是不以任何方式限制 本发明。 实施例 1
将以硫酸铝中和偏铝酸钠所制备的大孔氢氧化铝粉 188· Og (孔容 0.825ml/g， 平均孔直径为 9.4nm， 比表面积为 350m2/g) , 小孔氢氧化铝粉 226. Og (孔容 0.458ml/g, 平均孔直径为 8. Onm, 比表面积为 228m2/g) ， 平均粒径 30nm的纳米二氧化硅 4.0% (基 于最终载体重量） ， 75. Og去离子水和 8g柠檬酸， 混合均匀， 加 入由 26.0g40°/。硝酸与 325.0g 去离子水配制成的溶液， 混捏成可 塑体， 在挤条机上挤成条形物， 在干燥温度 110°C条件下干燥 8 小时， 然后在 500Ό下焙烧 4小时， 性质见表 1。
实施例 2
在实施例 1 中， 把纳米二氧化硅 4.0%换成 6.2% (平均粒径 15nm ) ， 即成本例。
实施例 3
在实施例 1 中， 把纳米二氧化硅 4.0%换成 2.3% (平均粒径 45nm) ， 即成本例。
实施例 4
在实施例 1中， 将纳米二氧化硅换成 8.5%, 焙烧温度改为 550 , 即成本例。
实施例 5
在实施例 1中， 焙烧温度改为 580°C, 即成本例。
实施例 6
在实施例 1 中， 纳米二氧化硅的加入方法为： 纳米二氧化硅 与硝酸溶液混合， 然后加入大孔氢氧化铝和小孔氢氧化铝中， 其 它步骤同实施例 1， 即成本例。
实施例 7
在实施例 1 中， 将纳米二氧化硅换成 5.5%， 按纳米二氧化硅 与小孔氢氧化铝的 10%及硝酸溶液制成胶溶剂， 然后与大孔氢氧 化铝和剩余小孔氢氧化铝混合， 其它同实施例 1， 即成本例。
实施例 8
在实施例 1 中， 将纳米二氧化硅换成 3.0%, 其中纳米二氧化 硅分为两等份， 一份与加去离子水润湿后加入氢氧化铝物料中， 另一份与小孔氢氧化铝的 5%及硝酸溶液制成胶溶剂后加入氢氧化 铝物料中， 其它步骤同实施例 1， 即成本例。
比较例 1
在实施例 1中， 不用纳米二氧化硅， 用 85· Og含二氧化硅 20% 的硅溶胶， 水 325g改为 340g, 即成本例。
比较例 2
在实施例 1 中， 大孔氢氧化铝粉换成以三氯化铝、 氨水和硅 酸钠为原料， 采用沉淀法生产的大孔含硅氢氧化铝粉， 二氧化硅 含量为 5.2%， 不加纳米二氧化硅， 水 325g改为 400g, 即成本例。
比较例 3
比较例 1中硅溶胶的用量增加至 130g。
实施例 9
步骤 1 在一干净容器中加入 1200ml去离子水，升温至 65 以 30ml/分钟流速将比重为 1.35 的偏铝酸钠水溶液及以 65ml/分 钟流速将比重为 1.15 的硫酸铝水溶液， 同时加入到搅拌的去离 子水中， 保持温度 65°C, pH为 8.5， 加料时间为 90分钟。
步骤 2 停止加料后， 体系在上述 pH值和温度条件下老化 90 分钟， 过滤后的滤饼加去离子水浆化， 并加入碳酸钠溶液和 /或 氨水溶液洗涤 5次， 洗涤至氧化铝载体中 Na+含量 < Q. G5m%, S04 = 含量 < 1.2m%， Fe+++含量 < 0.08m%为止。
步骤 3 将上步得到的氢氧化铝滤饼加入到 2.5 L 去离子水 和 42g 85m%磷酸的溶液中打浆均勾， 控制浆液温度为 65Ό, 浆 化 40分钟后过滤， 得到含磷氢氧化铝滤饼。
步骤 4 滤饼直接在 120Ό干燥 8小时后待用。
步骤 5 称量上述含磷氢氧化铝 142g, 小孔氢氧化铝 252g, 纳米二氧化硅 7.5g (平均粒径 30nm)和 90g去离子水， 混合均匀， 加入由 24g40%硝酸溶液和 340g 去离子水配制成的溶液， 混捏成 可塑体， 用挤条机挤成条形物， 在 120*C温度条件下干燥 8 小时， 然后在 500Ό下焙烧 4小时， 即成本例。 步骤 1 同实施例 9步骤 1、 步骤 2。
步骤 2 将实施例 9步骤 3中的 42. Og 85 m%磷酸改为 56 g 85m% 磷酸。
步骤 3 同实施例 9步骤 4、 步骤 5。
实施例 11
步骤 1 同实施例 9步驟 1、 步骤 2。
步骤 2 将实施例 9步骤 3 中的 42. 0g85m%磷酸改为 75g8 5m% 磷酸
步骤 3 同实施例 9步膝 4、 步骤 5。
实施例 12
步骤 1 同实施例 9步骤 1、 步骤 2、 步驟 3、 步骤 4。
步驟 2 将实施例 9步驟 5 中的焙烧温度改为 550 °C， 焙烧 4 小时。
实施例 13
步骤 1 同实施例 9步骤 1、 步骤 2、 步骤 3、 步骤 4。
步驟 2 将实施例 9步骤 5 中的焙烧温度改为 600 ， 焙烧 3 小时。
实施例 14
在实施例 9 中， 将纳米二氧化硅换成 13g (平均粒径 20nm) , 纳米二氧化硅与硝酸溶液混合， 然后加入大孔氢氧化铝和小孔氢 氧化铝中， 其它同实施例 9。
实施例 15
在实施例 9中， 将纳米二氧化硅换成 20g (平均粒径 45nm ) , 纳米二氧化硅与小孔氢氧化铝的 1 0%及硝酸溶液制成胶溶剂， 然 后与大孔氢氧化铝和剩余小孔氢氧化铝混合， 其它同实施例 9。
实施例 16
在实施例 9 中， 将纳米二氧化硅换成 25 g， 其中纳米二氧化 硅分为两等份， 一份与加去离子水润湿后加入氢氧化铝物料中， 另一份与小孔氢氧化铝的 5%及硝酸溶液制成胶溶剂后加入氢氧化 铝物料中， 其它步骤同实施例 9。
比较例 4
在实施例 9 中将步骤 5 中的纳米二氧化硅改用 95g20%的硅溶 胶， 去离子水 430g 改为 390g， 助剂磚采用共沉淀法加入 （同 US4， 758， 544中所述的方法） 。
实施例 17
将取实施例 1、 2、 3、 7、 9、 12、 14、 15和比较例 2、 的氧 化铝载体各 100 克， 用 Mo03含量为 38g/100ml、 NiO 含量为 7.2g/100ml、P含量为 3.0g/100ml的溶液 250ml浸渍 2.0小时（含 磷的氧化铝载体 9、 12、 14、 15、 比较例 4 的浸渍溶液碑含量减 少为 2.0g/100ml ) ， 然后在 110°C干燥 4 小时， 在 500。C焙烧 4 小时， 得到最终加氢处理催化剂 C1 ~ C10。 各催化剂性盾及组成 见表 3。 催化剂 C3、 C4、 C7> C9和 C10的氧化态体相中元素分布 电镜观测结果见表 4。
表 3 结果看出， 在催化剂二氧化硅总含量为 1.7 - 5.0%的情 况下， 表相硅铝原子比较大， 一般为 0.16 ~ 0.20， 硅富集于催化 剂表面， 表相硅铝原子比与平均硅铝原子比的差值为 0.10 以上， 明显高于现有技术； 从表 4 氧化态催化剂体相中元素分布电镜观 测结果看出， 催化剂沿条形物径向方向由里向外各种元素含量变 化梯度也较小， 说明本发明纳米二氧化硅具有促进催化剂中各元 素分散均匀， 表面性质均一的作用。
实施例 18
实施例 17得到的各催化剂的性能评价。
催化剂在评价前需要进行预硫化处理， 预硫化过程为： 用含 1.8%二硫化碳的灯油， 在氢分压 13.7MPa， 体积空速 1.2h— 氢 油体积比 1200: 1条件下进行预硫化。 230Ό恒温硫化 8小时， 360 °C恒温硫化 4小时。
在氢分压 14.7MPa， 体积空速 1.0h_1, 氢油体积比 1000: 1 的工艺条件下处理伊朗 VG0油（硫 1.1%, 氮 0.12%, 芳烃 42· 8%)。 反应结果见表 5。
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比表 平均
P 0 TPD-NH3 3 - 15nm孔径占 孔容 总含量 平均 表相 实例 面积 孔径 ASi/Al
% (总酸量） Mmol/g 总孔容分率 ¾ ml/g Si02% Si/Al Si/Al m /g nm
9 1.00 0.67 95.6 0.597 320 7.9 2.19 °- 0190 0· 169 0.150
10 1.32 o.65 95.7 0.613 325 8.0 2.17 0.0188 0.170 0.151
11 1.74 0 62 94.9 0.625 318 8.1 2.19 0.0190 0.168 0.149
12 1.10 0> 64 95.0 0.637 315 8.2 2.18 0.0189 0.168 0.149
13 1.07 o.66 94.0 0.645 305 8.4 2.20 0.0191 0.167 0.148
14 1.09 o.70 95.8 0.611 339 7.8 4.08 0.0362 0.165 0.129
15 1.08 0.73 95.4 0.619 337 7.9 5.88 0.0531 0.205 0.152
16 1.11 0 75 94.9 0.624 334 8.0 7.21 0.0660 0.213 0.147 比 4 1.61 o 5 81.2 0.650 290 8.6 5.90 0.0542 0.125 0.071
表 3 实施例 17各催化剂組成及性质 催化剂 氧化铝载体 S i02% Mo03% Ni0% A1203%
C1 实施例 1 3. 1 5. 2 25 4 余量
C2 实施例 1 4. 8 5. 2 25 4 余量
C 3 实施例 3 1. 7 5. 2 25 4 余量
C4 实施例 7 4. 2 5. 2 25 4 余量
C5 实施例 9 1. 7 5. 5 25 4 余量
C6 实施例 12 1. 7 5. 5 25 4 余量
C7 实施例 14 3. 2 5. 5 25 4 余量
C8 实施例 15 4. 5 5. 5 25 4 余量
C9 比较例 2 1. 9 5. 2 25 4 余量
C10 比较例 4 4. 5 5. 5 25 4 余量
5¾ 催化剂 孔容 比表面 3 - 15nm TPD-NH3 平均 表相 AS i/Al 积 raVg 孔径占总 S i /Al S i/Al ml/g (总酸量）
孔容分率
mmo 1 /g
%
CI 0. 35 164 92. 7 0. 64 0. 0416 0. 172 0. 130
C2 0. 36 157 92. 3 0. 74 0. 0661 0. 196 0. 130
C3 0. 37 155 96. 1 0. 65 0. 0223 0. 168 0. 146
C4 0. 34 168 94. 7 0. 73 0. 0587 0. 186 0. 127
169 0. 147
0. 31 182 96. 7 0. 0223 0.
C5 0. 75
0. 33 178 97. 0 0. 0223 0. 168 0. 146
C6 0. 73
185 96. 2 0. 0416 0. 166 0. 124
0. 32
C7 0. 75
0. 30 187 95. 6 0. 0588 0. 206 0. 147
C8 0. 77
C9 0. 38 167 86. 4 0. 56 0. 0225 0. 087 0. 065
CI O 0. 39 163 81. 7 0. 54 0. 0588 0. 125 0. 066
表 4 氧化态催化剂体相中元素分布电镜观测结果
C 3 C4 C7 C9 C10 元
中心 1 / 2 中心 1 /2 中心 1 /2 中心 1 /2 中心 素 边位 1/2位 边位 边位 边位 边位
位 位 位 位 位 位 位 位 位
S i 1. 13 1. 21 1. 09 1. 78 1. 87 1. 69 1. 47 1. 55 1. 39 0. 77 0. 98 0. 69 1. 24 1. 31 1. 09
Ni 2. 27 2. 05 2. 18 2. 33 2. 12 2. 21 2. 20 2. 09 2. 11 2. 09 3. 23 2. 71 1. 89 3. 01 2. 51
Mo 14. 2 13. 1 14. 3 13. 8 12. 9 14. 5 15. 8 14. 5 16. 2 14. 3 9. 8 11. 0 15. 9 10. 5 12. 1
※氧化态元素组成为氧化态催化剂体相中某一横断面微区上某种元素质量占所含元素总质量 的百分数。
催化剂活性对比评价结果 反应温度， 生成油含疏 生成油含氮 催化剂
°c , 量， μ g/g 量， μ g/g
C1 370 57 9. 7
C2 370 + 2 43 6. 5
C3 370 + 1 65 8. 2
C4 370 + 1 55 6. 0
C5 370 + 1 71 7. 4
C6 370 + 2 65 7. 7
C7 370 45 7. 3
C8 370 + 1 45 5. 5
C9 370 + 5 97 9. 5
C10 370 + 6 82 9. 0 实施例 19、 20
按照实施例 1 的方法， 增加纳米二氧化硅的含量， 使含二氧 化硅氧化铝载体中的二氧化硅含量为 10%、 15%。 氧化铝载体主要 性质见表 6 ( 19、 20 ) 。
比较例 5、 6
按照比较例 1 的方法， 增加硅溶胶的用量， 使含二氧化硅氧 化铝载体中的二氧化硅含量为 10%、 15%。 氧化铝载体主要性质见 表 6 (比 5、 比 6 ) 。 表 6 实施例 19、 20及比较例 5、 6氧化铝载体的理化性质 孔容 比表面 平均孔 总酸量 ' 食 平均 表相 实例 孔径占孔 ASi/Al ral/g 积 m2/g 径 nm mmo 1/g si0,% Si/Al Si/Al
容分率％
19 0.615 316 8.0 91.1 0.81 9.62 0.090 0.294 0.204
20 0.623 323 8.1 89.5 0.84 14.60 0.145 0.372 0.227 比 5 0.666 290 8.6 79.2 0.62 9.87 0.093 0.182 0.089 比 6 0.691 275 8.9 75.3 0.64 14.79 0.148 0.283 0.135

Claims

权 利 要 求
1. 一种含硅的氧化铝载体， 其特征在于， 以氧化铝载体重量 为基准， 氧化铝载体含二氧化硅 0.5 - 10.0%, 氧化铝载体表相硅 铝原子比与平均硅铝原子比的差值为 0.10以上。
2. 按照权利要求 1 的氧化铝载体， 其特征在于所述的表相 硅铝原子比与平均硅铝原子比的差值为 0.10- 0.25。
3. 按照权利要求 1的氧化铝载体， 其特征在于表相硅铝原子 比与平均硅铝原子比的差值为 0.12 - 0.20。
4. 按照权利要求 1的氧化铝载体， 其特征在于氧化铝载体以 重量计含二氧化硅为 1.0- 7.0°/0。
5. 按照权利要求 1的氧化铝载体， 其特征在于氧化铝载体表 相硅铝原子比大于 0.15。
6. 按照权利要求 5的氧化铝载体， 其特征在于氧化铝载体表 相硅铝原子比为 0.15 - 0.30。
7. 按照权利要求 1的氧化铝载体， 其特征在于氧化铝载体比 表面积为 270 - 320m2/g， 孔容为 0· 55 - 0.68ml/g， 其中孔径为 3 - 15nm的孔容占总孔容的 90%以上。
8. 按照权利要求 7 的氧化铝载体， 其特征在于所述的孔径 为 3 - 15nm的孔容占总孔容的 90 - 96%。
9. 一种制备含硅氧化铝载体的方法， 包括混合和 /或混捏氢 氧化铝或氧化铝， 同时加入纳米含硅化合物， 并加入胶溶酸等， 混合形成可塑体， 然后成型、 干燥、 焙烧， 即制得本发明的含硅 氧化铝载体， 纳米含硅化合物加入量以最终氧化铝载体重量计为 含二氧化硅 0.5 - 40.0%。
10. 按照权利要求 9 的方法， 其特征在于所述的纳米含硅化 合物为纳米二氧化硅， 粒径为 6 - 100nm。
11. 按照权利要求 8 的方法， 其特征在于所述氧化铝载体二 氧化硅含量为 0.5 - 10%。
12. 按照杈利要求 9 的方法， 其特征在于所述氢氧化铝为以 下列方式制得的含有 0.3- 3.0 重量％五氧化二磷的含磷氢氧化 铝： 将氢氧化铝沉淀物打浆， 加入含磷化合物， 控制浆液温度为
30 - 90 , 然后过滤、 干燥并焙烧得到含磷的氢氧化铝。
13. 按照权利要求 9 的方法， 其特征在于所述的纳米含硅化 合物的加入方式釆用下列方式中的一种： （a) 纳米含硅化合物 与含铝源物料混合， 或 （b) 纳米含硅化合物用去离子水润湿后 加入含铝源物料中， 或 （ c) 纳米含硅化合物与胶溶酸溶液混合 后加入含铝源物料中， 或 （d) 用全部或部分小孔氢氧化铝与胶 溶酸溶液和纳米含硅化合物混合作为胶溶剂， 然后与大孔氢氧化 铝混合， 或 ( e) 分步加入， 在上述 ( a ) 、 ( b) 、 (c) 和 (d) 中任两步或两步以上中分别加入。
14. 按照权利要求 13的方法， 其特征在于所述的大孔氢氧化 铝的孔容为 0.7- l. lml/g， 平均孔直径为 6- llnm， 比表面积为 300 - 380m2/g; 小孔氢氧化铝的孔容为 0.2 - 0.6ml/g, 平均孔直 径为 2 - 10nm, t匕表面积为 200 - 300m2/g; 大孑 LiL氧化 与' J、孑 L 氢氧化铝的重量比为 1: 1 - 1: 5; 小孔氢氧化铝与大孔氢氧化铝 的混合部分与做胶溶剂部分的比例为 5: 1 - 25: 1。
15. 按照权利要求 9 的方法， 其特征在于所述的干燥过程为 在 90°C - 150°C下干燥 8 - 16 小时， 焙烧过程为在 450 - 650Ό焙 烧 1 - 6小时。
16. 按照权利要求 9 的方法， 其特征在于采用氧化铝或拟薄 水铝石与纳米助剂原料混合的方式引入助剂， 所述的助剂为钛、 硼、 锆和磷中的一种或几种， 纳米助剂原料为纳米含钛物质、 纳 米含硼物质、 纳米含锆物质、 纳米含碑物质。
17. 权利要求 1的含硅氧化铝载体在催化剂中的应用。
18. 权利要求 17的应用， 其特征在于所述催化剂为烃类加氢 处理催化剂。
19. 一种烃类加氢处理催化剂， 含有权利要求 1 的含硅氧化 铝载体， 和第 VIB族金属和 Vffl族金属作为活性组分。
20. 按照权利要求 19的催化剂， 其特征在于催化剂含二氧化 硅 0.3 - 7.0%， 表相硅铝原子比大于 0.15， 孔容为 0.30 - 0.40ml/g, 孔径为 3 - 15nm的孔容占总孔容的 90%以上。
21. 按照权利要求 20的催化剂， 其特征在于表相硅铝原子比 为 0.15— 0.25。
22. 按照权利要求 20的催化剂， 其特征在于表相硅铝原子比 与平均硅铝原子比的差值为 0.10- 0.20。
23. 按照权利要求 19的催化剂， 其特征在于所述催化剂还含 有助剂組分磷。
24. 按照权利要求 19的催化剂， 其特征在于， 以最终催化剂 重量计， 催化剂含有 2.0- 6.0%第 VIB 族金属钨和 /或钼， 18.0- 28.0%第预族金属镍和 /或钴， 以及 0.5 - 8.0%五氧化二磷。
25. 按照权利要求 19 的催化剂， 其特征在于催化剂的 比表面积在 150 - 200m2/g, 孔容为 0.32 - 0.38ml/g, 孔径 为 3 - 15nm的孔容占总孔容的 92 - 96%。
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CN 02133144 CN1197650C (zh) 2002-10-10 2002-10-10 一种含硅氧化铝载体及其制备方法
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CN 02133125 CN1282732C (zh) 2002-10-10 2002-10-10 重质油加氢处理催化剂及其制备方法
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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20051410A1 (it) * 2005-07-22 2007-01-23 Eni Spa Procedimento per la preparazione di catalizzatori di fischer-tropsch ad alta stabilita' meccanica, termica e chimica
EP2199650A1 (en) * 2008-12-19 2010-06-23 Borealis AG Layer for pipes made of multimodal polyethylene composition
WO2010088013A1 (en) 2009-01-29 2010-08-05 W. R. Grace & Co.-Conn. Catalyst on silica clad alumina support
US9365664B2 (en) 2009-01-29 2016-06-14 W. R. Grace & Co. -Conn. Catalyst on silica clad alumina support
EP2665555A4 (en) * 2010-11-16 2017-03-29 Rhodia Operations Porous inorganic composite oxide
US8895468B2 (en) * 2011-09-20 2014-11-25 Basf Corporation Chromia alumina catalysts for alkane dehydrogenation
JP5922372B2 (ja) * 2011-10-24 2016-05-24 日揮触媒化成株式会社 水素化処理触媒及びその製造方法
JP6413168B2 (ja) * 2013-09-27 2018-10-31 コスモ石油株式会社 重質炭化水素油の水素化処理触媒、及び重質炭化水素油の水素化処理方法
CA2986556A1 (en) * 2015-05-29 2016-12-08 Jxtg Nippon Oil & Energy Corporation Method for producing hydrotreated oil and method for producing catalytic cracked oil
US9630166B1 (en) * 2016-02-03 2017-04-25 Institute of Nuclear Energy Research, Atomic Energy Council, Executive Yuan, R.O.C. Method of fabricating catalyst carrier for generating hydrogen through methane reformation
KR102113122B1 (ko) * 2017-01-20 2020-05-21 효성화학 주식회사 탈수소 촉매의 제조방법
RU2726374C1 (ru) * 2020-01-17 2020-07-13 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") Способ приготовления носителя для катализатора гидроочистки
CN114453017B (zh) * 2020-10-21 2023-09-01 中国石油化工股份有限公司 一种加氢裂化催化剂及其制备方法及应用

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755196A (en) 1971-04-01 1973-08-28 Union Oil Co Hydrotreating catalyst
US3755150A (en) 1971-04-01 1973-08-28 Union Oil Co Hydrogenative desulfurization
US4446248A (en) 1982-08-16 1984-05-01 Union Oil Company Of California Hydrotreating catalyst
US4513097A (en) 1982-08-16 1985-04-23 Union Oil Company Of California Hydrotreating catalyst and a method for preparing the catalyst
US4568449A (en) 1982-08-16 1986-02-04 Union Oil Company Of California Hydrotreating catalyst and process
EP0201762A2 (en) * 1985-05-06 1986-11-20 American Cyanamid Company Catalyst for hydroconversion of heavy oils
US4758544A (en) 1985-07-17 1988-07-19 Chevron Research Company Catalyst composition and hydroprocessing of oils using same
WO1993005878A1 (en) * 1991-09-24 1993-04-01 Union Oil Company Of California Resid hydroprocessing catalyst
CN1085594A (zh) * 1992-10-14 1994-04-20 中国石油化工总公司抚顺石油化工研究院 一种蜡料加氢精制催化剂
CN1110304A (zh) * 1994-04-13 1995-10-18 中国石油化工总公司 一种重油加氢处理催化剂
WO2002009870A2 (en) * 2000-07-28 2002-02-07 Akzo Nobel N.V. Hydroprocessing catalyst for heavy oils and its use
CN1350882A (zh) * 2000-10-26 2002-05-29 中国石油化工股份有限公司 大孔径含钛、硅氧化铝载体及其制备方法
CN1451717A (zh) * 2002-04-12 2003-10-29 石油大学(北京) 新型钛硅复合氧化物加氢催化剂及其制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4242236A (en) * 1979-03-29 1980-12-30 Chevron Research Company 65-130 Angstrom mean radius silica-alumina catalyst support
EP0605723A4 (en) 1991-09-24 1995-07-05 Dainippon Pharmaceutical Co Blood lipid metabolism ameliorant.
US5401388A (en) * 1991-11-21 1995-03-28 Uop Selective upgrading of naphtha
US5498810A (en) * 1991-11-21 1996-03-12 Uop Selective isoparaffin synthesis from naphtha
US5827421A (en) * 1992-04-20 1998-10-27 Texaco Inc Hydroconversion process employing catalyst with specified pore size distribution and no added silica
CN1030395C (zh) 1992-11-05 1995-11-29 中国石油化工总公司抚顺石油化工研究院 一种重油加氢脱氮催化剂
JPH06218282A (ja) * 1993-01-26 1994-08-09 Kurosaki Refract Co Ltd 耐熱性触媒担体及びその製造方法
CN1048651C (zh) 1994-06-29 2000-01-26 中国石油化工总公司抚顺石油化工研究院 一种加氢催化剂载体的制备方法
US5831139A (en) * 1995-06-07 1998-11-03 Uop Llc Production of aliphatic gasoline
JPH1030083A (ja) * 1996-07-15 1998-02-03 Yokohama Rubber Co Ltd:The 絶縁耐熱性接着剤
WO1999019061A1 (fr) * 1997-10-14 1999-04-22 Japan Energy Corporation Catalyseur d'hydrotraitement pour huile lourde, support de catalyseur et procede de preparation de ce catalyseur

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755196A (en) 1971-04-01 1973-08-28 Union Oil Co Hydrotreating catalyst
US3755150A (en) 1971-04-01 1973-08-28 Union Oil Co Hydrogenative desulfurization
US4446248A (en) 1982-08-16 1984-05-01 Union Oil Company Of California Hydrotreating catalyst
US4513097A (en) 1982-08-16 1985-04-23 Union Oil Company Of California Hydrotreating catalyst and a method for preparing the catalyst
US4568449A (en) 1982-08-16 1986-02-04 Union Oil Company Of California Hydrotreating catalyst and process
EP0201762A2 (en) * 1985-05-06 1986-11-20 American Cyanamid Company Catalyst for hydroconversion of heavy oils
US4758544A (en) 1985-07-17 1988-07-19 Chevron Research Company Catalyst composition and hydroprocessing of oils using same
WO1993005878A1 (en) * 1991-09-24 1993-04-01 Union Oil Company Of California Resid hydroprocessing catalyst
CN1085594A (zh) * 1992-10-14 1994-04-20 中国石油化工总公司抚顺石油化工研究院 一种蜡料加氢精制催化剂
CN1110304A (zh) * 1994-04-13 1995-10-18 中国石油化工总公司 一种重油加氢处理催化剂
WO2002009870A2 (en) * 2000-07-28 2002-02-07 Akzo Nobel N.V. Hydroprocessing catalyst for heavy oils and its use
CN1350882A (zh) * 2000-10-26 2002-05-29 中国石油化工股份有限公司 大孔径含钛、硅氧化铝载体及其制备方法
CN1451717A (zh) * 2002-04-12 2003-10-29 石油大学(北京) 新型钛硅复合氧化物加氢催化剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1552880A4

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