WO2023036154A1 - Catalyseur hautement actif et thermiquement stable et son procédé de préparation - Google Patents

Catalyseur hautement actif et thermiquement stable et son procédé de préparation Download PDF

Info

Publication number
WO2023036154A1
WO2023036154A1 PCT/CN2022/117397 CN2022117397W WO2023036154A1 WO 2023036154 A1 WO2023036154 A1 WO 2023036154A1 CN 2022117397 W CN2022117397 W CN 2022117397W WO 2023036154 A1 WO2023036154 A1 WO 2023036154A1
Authority
WO
WIPO (PCT)
Prior art keywords
precursor
highly active
rare earth
hydrothermally stable
silicon
Prior art date
Application number
PCT/CN2022/117397
Other languages
English (en)
Chinese (zh)
Inventor
吴青
臧甲忠
李滨
范景新
孙振海
赵云
郭健
周微
宫毓鹏
侯立伟
Original Assignee
中海油天津化工研究设计院有限公司
中国海洋石油集团有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中海油天津化工研究设计院有限公司, 中国海洋石油集团有限公司 filed Critical 中海油天津化工研究设计院有限公司
Publication of WO2023036154A1 publication Critical patent/WO2023036154A1/fr

Links

Classifications

    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J35/61—Surface area
    • B01J35/617—500-1000 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/30—Ion-exchange
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Definitions

  • the invention relates to the field of catalysts, in particular to a high-activity, high-temperature, hydrothermally stable catalyst and a preparation method thereof.
  • Catalysts are the soul of catalytic technology and the key core materials in the chemical industry.
  • Porous materials are the most common catalytic materials, such as mesoporous molecular sieve catalysts, microporous molecular sieve catalysts, macroporous alumina catalysts, etc., because of their developed pore structure , high specific surface advantage, and high activity in the catalytic reaction process, so that it has broad application prospects in many fields.
  • the above-mentioned highly active catalytic materials have poor hydrothermal stability, and are particularly prone to skeleton collapse under high-temperature hydrothermal conditions (>800°C), resulting in the destruction of the entire material structure.
  • CN108163869A discloses a method for improving the hydrothermal stability of silicon-based mesoporous materials.
  • the silicon-based mesoporous materials and ionic liquids are placed in a closed reactor, and the reactor is heated and heat-insulated. Roasting at high temperature.
  • the method of the invention uses environmentally friendly ionic liquids to carry out high-temperature secondary treatment on silicon-based mesoporous materials, and utilizes the dehydration and condensation of silicon hydroxyl groups on the surface of the pore walls of silicon-based mesoporous materials under the high temperature conditions of ionic liquids to improve the interaction of the pore walls.
  • the joint degree increases the structural stability of the material, and then achieves the purpose of improving the hydrothermal stability of the silicon-based mesoporous material.
  • the SBA series silicon-based mesoporous material treated by the method of the invention is treated with 100% water vapor at 900° C. for 17 hours, the material can still maintain a good ordered mesoporous structure.
  • CN109650422A discloses a method for improving the hydrothermal stability of mesoporous alumina materials.
  • the three-block polymer template, aluminum source, inorganic acid, and solvent are mixed and stirred in a certain mass ratio, and the resulting slurry is left to stand for 12- After 48 hours, the obtained solid and ionic liquid were mixed according to ionic liquid and placed in a closed reaction kettle for treatment at 80-180°C. Then, it is filtered and dried, and finally calcined at a high temperature to obtain a mesoporous alumina material with high hydrothermal stability.
  • CN110817885A discloses a method for improving the hydrothermal stability of mesoporous silicon molecular sieves. Firstly, hydrothermal carbonization is used to load a hydrothermal carbon layer on the surface of mesoporous silicon molecular sieves, and then the hydrothermal stability is improved by high-temperature roasting. This method can not only significantly improve the hydrothermal stability of the mesoporous silicon molecular sieve, but also well maintain the mesoporous structure of the molecular sieve.
  • the hydrothermal carbonization method is characterized in that an aminated molecular sieve is used as a carrier, biomass is used as a carbon source, water is used as a reaction medium, and a hydrothermal carbon layer is loaded on the surface of the mesoporous silicon molecular sieve.
  • the method has the advantages of simple operation, convenience, low cost, wide application range and easy industrialization, and has broad application prospects in the fields of catalysis and the like.
  • CN104891525A discloses a method for preparing a strongly acidic and highly stable mesoporous molecular sieve.
  • the preparation method first synthesizes the Y-type molecular sieve precursor, and then uses the seed crystal method to assemble the Y-type molecular sieve precursor under acidic conditions to obtain the first-step crystallization product, and finally adjusts the pH value of the first-step crystallization product to carry out the second step
  • the product is obtained after crystallization.
  • the mesoporous molecular sieve prepared by the invention shows excellent hydrothermal stability. After 800°C and 100% steam hydrothermal treatment, the specific surface area retention rate is more than 46%, and it has a good performance as a component of catalytic cracking catalyst for heavy oil. performance.
  • the existing methods for improving hydrothermal stability include high-temperature treatment of ionic liquids, surface coating of carbon layers, and doping of aluminum atoms.
  • Treatment of mesoporous silica, mesoporous alumina, and mesoporous molecular sieves can Significantly improve its hydrothermal stability.
  • ionic liquid surface treatment, carbonization layer coverage, in-situ crystallization and other treatments the activity of the catalyst is greatly reduced. How to improve the hydrothermal stability of the catalytic material while maintaining high activity has become a major technical problem that needs to be solved at present.
  • the purpose of the present invention is to overcome the disadvantages of high activity and hydrothermal stability of catalysts in the prior art, and provide a catalyst with high activity and hydrothermal stability and a preparation method thereof.
  • the high-activity hydrothermal stability catalyst of the present invention adopts surface covering, metal doping, and rare earth modification methods to treat the catalyst precursor gel, improve the hydrothermal stability of the catalyst, and use transition metals and rare earth metals to increase catalyst metal active centers .
  • a high-activity hydrothermal-resistant and stable catalyst is prepared by mixing high-active hydrothermal-resistant and stable catalyst powder with a binder and a forming aid through molding equipment to prepare a spherical or strip-shaped catalyst, and then dried and roasted; wherein,
  • the highly active hydrothermally stable catalyst powder is composed of covering components, doped metals, rare earth metals, and precursors.
  • the covering components are 0.02 to 20 wt% based on the mass percentage of the total solid content of the catalyst powder, and the doped 0.02-10wt% for metals, 0.02-10wt% for rare earth metals, and 60-99.4wt% for precursors;
  • the covering component is one or more of ethyl orthosilicate, silicon tetrachloride, titanium tetrachloride, and n-butyl titanate;
  • the doping metal is one or more of manganese, tungsten, molybdenum, titanium, zirconium, germanium, tin and lead;
  • the rare earth metal is one or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;
  • the precursor is one or more of silicon-containing composite oxides, high-silicon molecular sieves, silicon dioxide, mesoporous silica, and mesoporous alumina;
  • the described highly active hydrothermally stable catalyst powder is prepared by the following preparation steps:
  • the precursor is prepared by the sol-gel method.
  • silicon/titanium is first used to cover the surface and pores, that is, the water in the precursor hydrogel is replaced with an alcohol solvent, and then the Alcohol solvent treatment containing covering components, and finally replacing the alcohol solvent with water and catalyzing the hydrolysis of the covering components to obtain a surface-covered precursor.
  • the alcohol solvents are methanol, ethanol, propanol, isopropanol, butanol, One or more of ethylene glycol;
  • Metal doping Add soluble doped metal salt-inorganic acid solution to the surface-covered precursor during the gel generation process or gel aging stage, so that the doped metal is bonded to the silicon-aluminum precursor skeleton, and then washed with water to remove Unreacted soluble doping metal salt and inorganic acid to obtain metal doping precursor;
  • Rare earth modification introducing a rare earth metal salt into the metal-doped precursor by ion exchange, impregnation or coprecipitation to obtain a rare earth modified precursor;
  • the silicon-containing composite oxide is one or more of silicon-aluminum composite oxide, silicon-magnesium composite oxide, and silicon-titanium composite oxide.
  • the high-silicon molecular sieve is a high-silicon Y molecular sieve with a SiO 2 /Al 2 O 3 molar ratio greater than 5.0, a ⁇ molecular sieve with a SiO 2 /Al 2 O 3 molar ratio greater than 40, or a SiO 2 /Al 2 O 3 molar ratio greater than 60
  • One or more of ZSM-5 molecular sieves are ZSM-5 molecular sieves.
  • the mesoporous silica is one or more of MCM-41 and SBA-15.
  • the present invention also provides a preparation method of the above-mentioned highly active hydrothermally stable catalyst, the preparation method comprising the following steps:
  • the precursor is covered with silicon/titanium on the surface and pores in the gel stage.
  • the steps include first replacing the water in the precursor hydrogel with an alcohol solvent, and then using an alcohol containing the covering component. Solvent treatment, and finally replace the alcohol solvent with water and catalyze the hydrolysis of the covering component to obtain a surface-covered precursor.
  • the alcohol solvent is one of methanol, ethanol, propanol, isopropanol, butanol, and ethylene glycol or several;
  • Metal doping After the surface of the precursor is covered, add a soluble doped metal salt-inorganic acid solution during the gel generation process or the gel aging stage, so that the doped metal is bonded to the silicon-aluminum precursor skeleton, and then washed with water to remove Unreacted soluble doping metal salt and inorganic acid to obtain metal doping precursor;
  • the rare earth metal salt is introduced into the metal-doped precursor by ion exchange, impregnation, and coprecipitation to obtain a rare earth modified precursor;
  • the highly active hydrothermally stable catalyst powder is mixed with a binder and a molding aid to prepare a spherical or strip-shaped catalyst through a molding device, and then dried and roasted to obtain a highly active hydrothermally stable catalyst.
  • the doping metal of the soluble doping metal salt-inorganic acid is one or more of manganese, tungsten, molybdenum, titanium, zirconium, germanium, tin, and lead;
  • the rare earth metal salt is one or more soluble metal salts of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu .
  • the soluble doped metal salt-inorganic acid is a manganese nitrate dilute sulfuric acid solution with a concentration of 0.15-0.25 mol/L.
  • the rare earth metal salt described in step 4) is cerium nitrate, the calcination is at 350-700° C., and the calcination time is 4-24 hours.
  • the present invention further provides the application of the above-mentioned highly active hydrothermal stability catalyst in the catalytic reaction under the high temperature hydrothermal process condition of 500-850°C.
  • the conversion rate of heavy oil is greater than 80wt%
  • the selectivity of low-carbon olefins is greater than 80%
  • the coke yield is less than 10wt% .
  • Highly active, water-resistant and thermally stable catalysts can be molded by spray drying, rolling ball molding, extrusion molding, and powerful granulation.
  • the highly active hydrothermally stable catalyst used for fluidized catalytic cracking reaction is a microspherical catalyst with a particle size distribution of 20-200 ⁇ m.
  • the molding method is spray drying. It is 90-280°C.
  • the highly active hydrothermally stable catalyst of the present invention has relatively high pore wall thickness, and has good hydrothermal stability in a high-temperature hydrothermal environment.
  • the catalyst also has a skeleton-doped metal, which forms a bond with the skeleton elements such as silicon and aluminum in the carrier through the doping of the metal skeleton.
  • the metal doping can slow down the damage of the skeleton elements by water vapor under high-temperature hydrothermal conditions, and can also generate defects. position, has catalytic activity, and further improves the hydrothermal stability and catalytic activity of the catalyst.
  • rare earth metals are introduced to further protect the doping metals and catalyst skeleton elements, and improve the activity and stability of the catalyst again.
  • the surface and pores of the catalyst carrier are covered with silicon/titanium, which increases the wall thickness of the carrier pores and improves the hydrothermal stability of the catalyst. Afterwards, the transition metal skeleton is doped and the rare earth metal is loaded to further improve the hydrothermal stability.
  • the specific surface area of the catalyst powder is maintained at 100-390m 2 /g when the catalyst powder is treated under the hydrothermal condition of 800°C for a long time, and the high-temperature hydrothermal stability is very excellent.
  • the highly active hydrothermal stability catalyst prepared by the present invention has the following advantages:
  • the catalyst carrier has undergone pore wall thickness, transition metal skeleton doping and rare earth metal loading, and the hydrothermal stability has been greatly improved.
  • the surface area reaches up to 390m 2 /g, and the molded catalyst is treated under hydrothermal conditions at 800°C for a long time, and the specific surface area reaches up to 250m 2 /g
  • the catalyst is doped with transition metal skeleton and rare earth metal, and the transition metal doped with skeleton is used to generate defect center to form a highly active catalytic center, and the rare earth metal loading further improves the activity and stability of the catalyst.
  • the conversion rate of heavy oil is greater than 80wt%, and the catalyst has high activity.
  • the catalyst with high activity and high hydrothermal stability is especially suitable for the catalytic cracking reaction process of heavy oil such as residue oil and oil sand bitumen under high temperature hydrothermal environment.
  • the olefin selectivity is greater than 80%, the coke yield is less than 10wt%, and has high activity and hydrothermal stability.
  • the invention adopts surface covering, metal doping and rare earth modification methods to treat the catalyst precursor gel to improve the hydrothermal stability of the catalyst, and utilizes transition metals and rare earth metals to increase catalyst metal active centers, surface covering and metal doping 1.
  • the method of rare earth modification can be impregnation method, washing replacement method, ion exchange method, co-precipitation method, or other metal loading and modification methods.
  • the catalyst performance evaluation method of high activity hydrothermal stability of the present invention is as follows:
  • a fluidized bed pilot plant was used to evaluate the highly active hydrothermally stable catalyst.
  • the properties of the heavy oil raw material used are shown in Table 1.
  • the catalyst used for the catalytic cracking performance reaction of heavy oil is pre-aged at 800°C and 100% water vapor for 24 hours.
  • the samples before and after hydrothermal treatment are used to measure the BET specific surface area and pore volume by nitrogen adsorption, and the specific surface area and pore volume after hydrothermal treatment are calculated. See Table 2 for relevant data.
  • Performance evaluation of highly active hydrothermally stable catalysts was carried out on a fluidized bed pilot plant.
  • Process conditions reaction pressure 0.2MPa, reaction temperature 550°C, steam/feedstock oil weight ratio 0.3:1, agent-oil ratio 12:1, The contact time is 2s.
  • the collected gas phase products were measured by refinery gas chromatography, the liquid products were measured by true boiling point distillation, and the liquid product family composition was determined by chromatography-mass spectrometry.
  • the product analysis data of each embodiment are shown in Table 3.
  • mesoporous silica hydrogel was selected as the precursor, and the precursor was dried at 120°C for 12 hours, and then crushed to obtain a comparative catalyst powder: the measured BET specific surface area was 687m 2 /g, and the pore volume was 0.71cm 3 /g, the mesoporous silica powder is subjected to hydrothermal aging treatment first, and first undergoes 800°C, 100% water vapor aging treatment for 24 hours, then tests the specific surface area and pore volume of the catalyst after hydrothermal treatment, and calculates the specific surface area after hydrothermal treatment and pore volume retention rate, the relevant data are shown in Table 2.
  • microsphere catalyst was sprayed, dried at 120° C. for 12 hours, and calcined at 650° C. for 4 hours to obtain a comparative catalyst.
  • Catalyst evaluation and product analysis The raw material of the evaluation catalyst is , and the specific analysis data are shown in Table 1.
  • the catalyst has been aged at 800°C and 100% water vapor for 24 hours in advance, simulating the high temperature hydrothermal conditions of industrial equipment. After hydrothermal treatment, catalyst reaction performance evaluation was carried out on a fluidized bed pilot plant. Process conditions: reaction pressure 0.2MPa, temperature 550°C, steam/raw material oil weight ratio 0.3:1, agent-oil ratio 12:1, contact time 2s
  • the collected gas phase products are measured by refinery gas chromatography, the liquid products are measured by true boiling point distillation, and the liquid product family composition is determined by chromatography-mass spectrometry.
  • the product analysis data of each embodiment are shown in Table 3.
  • the highly active hydrothermally stable catalyst powder is composed of covering components, doping metals, rare earth metals, and precursors.
  • the covering components are 0.77wt%
  • the doping metals are 0.86 wt%
  • the rare earth metal is 0.25wt%
  • the remaining components are precursors
  • the precursors are mesoporous silicon dioxide.
  • Precursor surface coverage use mesoporous silica hydrogel 1000g (mesoporous silica hydrogel is the same as the comparative example), the solid content of silica in the gel is 15wt%, and the remaining components are water.
  • Rare earth modification prepare rare earth modified precursor by ion exchange method, prepare 5000g cerium nitrate concentration as 0.15wt% cerium nitrate solution, contact with the transition metal doped precursor of step (3) at 80°C, After the cerium nitrate solution was circulated for 12 hours, it was washed with deionized water to obtain a rare earth modified precursor, and the mass of the rare earth metal cerium oxide was detected to be 0.38 g.
  • the rare earth modified precursor prepared in step (4) was dried at 120° C. for 12 hours, then calcined at 550° C. for 4 hours, and pulverized to obtain a highly active hydrothermally stable catalyst powder.
  • the powder is subjected to hydrothermal aging treatment first, and the treatment conditions are the same as those of the comparative example.
  • the specific surface area and pore volume retention rate after hydrothermal treatment are calculated. The relevant data are shown in Table 2.
  • High-silicon ZSM-5 molecular sieve hydrogel is selected.
  • the physical properties of the molecular sieve are that the molar ratio of SiO 2 to Al 2 O 3 is 92, the content of sodium oxide is 0.02wt%, the BET specific surface area is 347m 2 /g, and the pore volume 0.30 cm 3 /g.
  • the highly active hydrothermally stable catalyst powder is composed of covering components, doping metals, rare earth metals, and precursors.
  • the covering components are 1.01wt%
  • the doping metals are 0.76 wt%
  • the rare earth metal is 0.28wt%
  • the remaining components are precursors.
  • Precursor surface coverage use high silicon ZSM-5 molecular sieve hydrogel 1000g, the solid content of silicon dioxide in the gel is 22wt%, and the rest is water, first use the moisture in the high silicon ZSM-5 molecular sieve gel as ethanol solvent , treated with an ethanol solvent with a n-butyl titanate concentration of 0.2wt%, consuming 5000 g of solvent, and finally replacing the alcohol solvent with water and catalyzing the hydrolysis of n-butyl titanate to obtain a surface-covered precursor.
  • the mass of the covered component was detected as 2.28g (based on the mass of titanium dioxide), and the mass of the precursor is 220g (based on the total mass of silica and alumina).
  • Rare earth modification prepare rare earth modified precursor by ion exchange method, prepare 5000g of cerium nitrate concentration as 0.15wt% cerium nitrate solution, contact with the transition metal doped precursor of step (4) at 80°C, After the cerium nitrate solution was circulated for 12 hours, it was washed with deionized water to obtain a rare earth modified precursor, and the mass of the rare earth metal cerium oxide was detected to be 0.64 g.
  • step (6) The rare earth modified precursor prepared in step (5) was dried at 120° C. for 12 hours, then calcined at 550° C. for 4 hours, and pulverized to obtain a highly active hydrothermally stable catalyst powder.
  • the powder is subjected to hydrothermal aging treatment first, and the treatment conditions are the same as those of the comparative example.
  • the specific surface area and pore volume retention rate after hydrothermal treatment are calculated. The relevant data are shown in Table 2.
  • the spray molding of the catalyst is the same as that of the comparative example, and the drying and calcination conditions are the same as those of the comparative example.
  • silicon-aluminum composite oxide hydrogel the physical properties of silicon-aluminum composite oxide are SiO 2 content 84.15wt%, Al2O3 content 15.62wt%, sodium oxide content 0.23wt%, BET specific surface area 315m 2 /g, pores Capacity 0.57cm 3 /g.
  • the highly active hydrothermally stable catalyst powder is composed of covering components, doped metals, rare earth metals, and precursors.
  • the covering components are 1.59 wt%
  • the doping metals are 0.91 wt%.
  • the rare earth metal is 0.40wt%
  • the remaining components are precursors.
  • Precursor surface coverage use 1000g of silicon-aluminum composite oxide hydrogel, the solid content of silicon dioxide in the gel is 18wt%, and the rest is water.
  • the mass of the covered component was detected to be 2.86 g (based on the mass of titanium dioxide), and the mass of the precursor is 180 g (based on the sum of the mass of silica and alumina).
  • Rare earth modification Prepare rare earth modified precursor by ion exchange method, prepare 5000g cerium nitrate concentration as 0.20wt% cerium nitrate solution, contact with the transition metal doped precursor of step (4) at 80°C, After the cerium nitrate solution was circulated for 12 hours, it was washed with deionized water to obtain a rare earth modified precursor, and the mass of the rare earth metal cerium oxide was detected to be 0.72 g.
  • step (6) The rare earth modified precursor prepared in step (5) was dried at 120° C. for 12 hours, then calcined at 550° C. for 4 hours, and pulverized to obtain a highly active hydrothermally stable catalyst powder.
  • the powder is subjected to hydrothermal aging treatment first, and the treatment conditions are the same as those of the comparative example.
  • the specific surface area and pore volume retention rate after hydrothermal treatment are calculated. The relevant data are shown in Table 2.
  • the spray molding of the catalyst is the same as that of the comparative example, and the drying and calcination conditions are the same as those of the comparative example.
  • SiO2 is selected as the precursor, the SiO2 content is 99.8wt%, the sodium oxide content is 0.2wt%, the BET specific surface area is 663m2/g, and the pore volume is 0.74cm3/g.
  • the highly active hydrothermally stable catalyst powder is composed of covering components, doping metals, rare earth metals, and precursors.
  • the covering components are 2.34wt%
  • the doping metals are 0.84 wt%
  • the rare earth metal is 0.33wt%
  • the remaining components are precursors.
  • Precursor surface coverage use 1000g of silica hydrogel, the solid content of silica in the gel is 17wt%, the rest is water, first replace the moisture in the silica gel with ethanol solvent, and The butyl ester concentration is 0.35wt% ethanol solvent treatment, consumes 5000g of solvent, finally replaces alcoholic solvent with water and catalyzes the hydrolysis of n-butyl titanate, obtains the precursor of surface coverage, detects that the mass of covering component is 4.08g (as titanium dioxide mass), the mass of the precursor is 170g (based on the total mass of silica and alumina).
  • Rare earth modification Prepare rare earth modified precursor by ion exchange method, prepare 5000g cerium nitrate concentration as 0.25wt% cerium nitrate solution, contact with the transition metal doped precursor of step (4) at 80°C, After circulating the cerium nitrate solution for 12 hours, it was washed with deionized water to obtain a rare earth modified precursor, and the mass of the rare earth metal cerium oxide was detected to be 0.58 g.
  • step (6) The rare earth modified precursor prepared in step (5) was dried at 120° C. for 12 hours, then calcined at 550° C. for 4 hours, and pulverized to obtain a highly active hydrothermally stable catalyst powder.
  • the powder is subjected to hydrothermal aging treatment first, and the treatment conditions are the same as those of the comparative example.
  • the specific surface area and pore volume retention rate after hydrothermal treatment are calculated. The relevant data are shown in Table 2.
  • the spray molding of the catalyst is the same as that of the comparative example, and the drying and calcination conditions are the same as those of the comparative example.
  • the highly active hydrothermally stable catalyst powder is composed of covering components, doped metals, rare earth metals, and precursors.
  • the covering components are 1.01 wt%
  • the doping metals are 0.61 wt%.
  • the rare earth metal is 0.28wt%
  • the remaining components are precursors.
  • step (6) The rare earth modified precursor prepared in step (5) was dried at 120° C. for 12 hours, then calcined at 550° C. for 4 hours, and pulverized to obtain a highly active hydrothermally stable catalyst powder.
  • the powder is subjected to hydrothermal aging treatment first, and the treatment conditions are the same as those of the comparative example.
  • the specific surface area and pore volume retention rate after hydrothermal treatment are calculated. The relevant data are shown in Table 2.
  • the spray molding of the catalyst is the same as that of the comparative example, and the drying and calcination conditions are the same as those of the comparative example.
  • the highly active hydrothermally stable catalyst powder is composed of covering components, doping metals, rare earth metals, and precursors.
  • the covering components are 1.01wt%
  • the doping metals are 1.53 wt%
  • the rare earth metal is 0.28wt%
  • the remaining components are precursors.
  • step (6) The rare earth modified precursor prepared in step (5) was dried at 120° C. for 12 hours, then calcined at 550° C. for 4 hours, and pulverized to obtain a highly active hydrothermally stable catalyst powder.
  • the powder is subjected to hydrothermal aging treatment first, and the treatment conditions are the same as those of the comparative example.
  • the specific surface area and pore volume retention rate after hydrothermal treatment are calculated. The relevant data are shown in Table 2.
  • the spray molding of the catalyst is the same as that of the comparative example, and the drying and calcination conditions are the same as those of the comparative example.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur hautement actif et thermiquement stable et son procédé de préparation. Le catalyseur est préparé en mélangeant une poudre de catalyseur hautement active et thermiquement stable avec un liant et un agent de formation et en formant un catalyseur sphérique ou en forme de bande au moyen d'un dispositif de moulage, puis en séchant et en calcinant le catalyseur sphérique ou en forme de bande, les pourcentages en masse des composants de la poudre de catalyseur hautement active et stable hydrothermiquement étant : 0,02 à 20 % en poids d'un composant de revêtement, 0,02 à 10 % en poids de métal dopant, 0,02 à 10 % en poids de métal des terres rares, et 60 à 99,4 % en poids de précurseur. Le catalyseur hautement actif et thermiquement stable présente une surface spécifique de 200 à 390 m2/g après traitement dans des conditions hydrothermiques à haute température, présente une activité élevée et une stabilité hydrothermique élevée, et est applicable à des réactions catalytiques dans des conditions de traitement hydrothermique à haute température.
PCT/CN2022/117397 2021-09-07 2022-09-06 Catalyseur hautement actif et thermiquement stable et son procédé de préparation WO2023036154A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111040727.9 2021-09-07
CN202111040727.9A CN113477247B (zh) 2021-09-07 2021-09-07 一种高活性耐水热稳定性催化剂及制备方法

Publications (1)

Publication Number Publication Date
WO2023036154A1 true WO2023036154A1 (fr) 2023-03-16

Family

ID=77947345

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/117397 WO2023036154A1 (fr) 2021-09-07 2022-09-06 Catalyseur hautement actif et thermiquement stable et son procédé de préparation

Country Status (2)

Country Link
CN (1) CN113477247B (fr)
WO (1) WO2023036154A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113477247B (zh) * 2021-09-07 2021-12-03 中海油天津化工研究设计院有限公司 一种高活性耐水热稳定性催化剂及制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101905175A (zh) * 2010-07-28 2010-12-08 中国石油天然气集团公司 一种重馏分油加氢处理催化剂的制备方法
CN106145153A (zh) * 2015-03-31 2016-11-23 中国石油化工股份有限公司 改性y沸石及其制备和应用
CN111715204A (zh) * 2020-06-11 2020-09-29 华北电力大学 高温烟气用平板式scr脱硝催化剂及其制备方法
CN112495365A (zh) * 2020-11-22 2021-03-16 浙江盛旺环境工程有限公司 一种中低温钒钛基scr脱硝催化剂及其制备方法
CN113072653A (zh) * 2018-04-16 2021-07-06 切弗朗菲利浦化学公司 利用水合试剂制备催化剂的方法
CN113477247A (zh) * 2021-09-07 2021-10-08 中海油天津化工研究设计院有限公司 一种高活性耐水热稳定性催化剂及制备方法
CN113509925A (zh) * 2021-09-07 2021-10-19 中海油天津化工研究设计院有限公司 一种固体碱催化剂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10308571B4 (de) * 2003-02-24 2014-05-08 Volkswagen Ag Verfahren zur Herstellung eines Komposit-Materials für die Speicherung von Stickoxiden, mit dem Verfahren hergestelltes Kompositmaterial sowie seine Verwendung
CN101428238B (zh) * 2007-11-07 2011-02-09 中国石油化工股份有限公司上海石油化工研究院 热稳定性的层状复合载体
CN101898144B (zh) * 2009-05-27 2013-02-13 中国石油天然气股份有限公司 一种含骨架杂原子的y型分子筛的催化裂化催化剂及其制备方法
CN105749958A (zh) * 2016-02-04 2016-07-13 中国海洋石油总公司 一种移动床甲醇制芳烃球形催化剂及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101905175A (zh) * 2010-07-28 2010-12-08 中国石油天然气集团公司 一种重馏分油加氢处理催化剂的制备方法
CN106145153A (zh) * 2015-03-31 2016-11-23 中国石油化工股份有限公司 改性y沸石及其制备和应用
CN113072653A (zh) * 2018-04-16 2021-07-06 切弗朗菲利浦化学公司 利用水合试剂制备催化剂的方法
CN111715204A (zh) * 2020-06-11 2020-09-29 华北电力大学 高温烟气用平板式scr脱硝催化剂及其制备方法
CN112495365A (zh) * 2020-11-22 2021-03-16 浙江盛旺环境工程有限公司 一种中低温钒钛基scr脱硝催化剂及其制备方法
CN113477247A (zh) * 2021-09-07 2021-10-08 中海油天津化工研究设计院有限公司 一种高活性耐水热稳定性催化剂及制备方法
CN113509925A (zh) * 2021-09-07 2021-10-19 中海油天津化工研究设计院有限公司 一种固体碱催化剂及其制备方法

Also Published As

Publication number Publication date
CN113477247B (zh) 2021-12-03
CN113477247A (zh) 2021-10-08

Similar Documents

Publication Publication Date Title
Zhang et al. SO42−/ZrO2 supported on γ‐Al2O3 as a catalyst for CO2 desorption from CO2‐loaded monoethanolamine solutions
CN113509925B (zh) 一种固体碱催化剂及其制备方法
CN109110808B (zh) 一种锆溶胶及其制备方法和应用
WO2023036154A1 (fr) Catalyseur hautement actif et thermiquement stable et son procédé de préparation
CN105439168A (zh) 一种制备高硅铝比y型分子筛的方法
CN105582973B (zh) 一种重油裂化催化剂及其制备方法
CN106140254B (zh) 改性y沸石、其制备方法及含该改性y沸石的裂化催化剂
JPH11564A (ja) 接触分解触媒
CN106145153B (zh) 改性y沸石及其制备和应用
CN113546672B (zh) 催化裂解催化剂及其制备方法和应用及催化裂解的方法
CN105618110B (zh) 一种裂化催化剂及其制备方法
CN106145154B (zh) 一种改性y沸石及其制备方法
CN105126900B (zh) 一种汽油烷基化催化剂的制备方法
JPH08229405A (ja) 炭化水素接触分解用触媒組成物
CN110876926B (zh) 锆铝复合溶胶及其制备方法和应用以及催化裂化催化剂的制备方法
CN102786064A (zh) 一种加氢裂化催化剂载体及其制备方法
CN106145152B (zh) 改性y沸石及其制备方法和应用
CN100388973C (zh) 改性氧化铝组合物及其制备方法
CN106140256B (zh) 一种改性y沸石及其制备方法
CN111203267B (zh) 一种催化γ-戊内酯脱羧制丁烯的固体酸催化剂及其制备方法和应用
CN114272919A (zh) 催化裂化助剂及其制备方法、使用方法
JP4541688B2 (ja) イソパラフィン−オレフィンアルキル化法
Valente et al. Sulfated Nanocapsular Aluminas: Controlling their Bronsted and Lewis Acidity
CN107866211B (zh) 一种TiO2溶胶和催化裂化催化剂以及它们制备方法
TW202009218A (zh) 改性y型分子篩、包含它的催化裂解催化劑、及其製備和用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22866617

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE