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WO2018192519A1 - Support de catalyseur d'hydrocraquage diesel optimisé et son procédé de préparation - Google Patents

Support de catalyseur d'hydrocraquage diesel optimisé et son procédé de préparation Download PDF

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Publication number
WO2018192519A1
WO2018192519A1 PCT/CN2018/083502 CN2018083502W WO2018192519A1 WO 2018192519 A1 WO2018192519 A1 WO 2018192519A1 CN 2018083502 W CN2018083502 W CN 2018083502W WO 2018192519 A1 WO2018192519 A1 WO 2018192519A1
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Prior art keywords
molecular sieve
catalyst carrier
modified
hydrocracking catalyst
carrier according
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English (en)
Chinese (zh)
Inventor
明卫星
石友良
许莉
杨伟光
赖波
王春锋
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • the invention relates to a catalyst carrier, in particular to an optimized diesel hydrocracking catalyst carrier and a preparation method thereof.
  • Hydrocracking is a very important technology for the efficient conversion of heavy oil and clean oil production in the refining industry. It can process heavy crude oil with high sulfur and high metal. It has wide source of raw materials, great production flexibility, good product quality and middle distillate. High oil yield. Hydrocracking technology can directly produce low aromatics, low sulfur, low nitrogen high quality middle distillate products from reduced pressure diesel (VGO) to meet increasingly stringent environmental requirements.
  • VGO reduced pressure diesel
  • the conventional preparation methods of the hydrocracking catalyst mainly include a dipping method, a coprecipitation method and a kneading method.
  • the preparation process of the kneading method is the simplest, and the requirements for the process and the catalyst dosing are not high, but the preparation process is relatively extensive, the catalyst The dispersibility of each component is not good, and some metal hydrogenation active centers are covered, which can not exert its activity better. It is usually used for catalysts with less hydrogenation performance; the preparation process of coprecipitation method is the most complicated.
  • the impregnation method is the most widely used method for preparing hydrocracking catalysts. Firstly, the carrier which meets the performance requirements of the catalyst, such as the shape, mechanical strength, specific surface and acidity of the carrier, is prepared, and then the metal group is supported by a saturated or supersaturated impregnation method. The metal component is enriched in the catalyst to make the catalyst have higher mechanical strength and fully exert its Hydrogen performance.
  • Both CN96109702.7 and CN97121663.0 use the impregnation method to prepare a highly active hydrocracking catalyst.
  • the catalyst carrier cracking component is Y-type molecular sieve, and the impregnation liquid is prepared by nickel nitrate and ammonium metatungstate.
  • the catalyst exhibits Good hydrocracking performance.
  • CN1351121A discloses a hydrocracking catalyst containing modified ⁇ molecular sieve and amorphous silicon aluminum and a preparation method thereof, wherein the modified ⁇ molecular sieve directly exchanges the synthesized molecular sieve slurry with ammonium, and then roasts deammonium and acid.
  • the modified ⁇ molecular sieve is obtained by treatment and hydrothermal treatment.
  • CN1393521A discloses a medium oil type hydrocracking catalyst and a preparation method thereof, wherein the carrier used for the catalyst is amorphous silicon aluminum, aluminum oxide and Y and ⁇ composite molecular sieve, wherein the composite molecular sieve is after the ⁇ molecular sieve raw powder is burned to the template.
  • the catalytic activity of the catalyst is not high, and the product quality of the middle distillate of jet fuel and diesel oil is generally required to be further improved.
  • the above-mentioned hydrocracking catalyst carrier components are simply mechanically mixed, and the components in the catalyst are easily agglomerated into secondary particles, so that the dispersibility of the active components is poor, and the prepared catalyst is difficult to exert optimal performance. .
  • the object of the present invention is to provide an optimized diesel hydrocracking catalyst carrier and a preparation method thereof, and the hydrocracking catalyst prepared by using the catalyst carrier has high catalytic activity, and can obviously reduce diesel oil under the premise of ensuring diesel oil yield.
  • the pour point of the fraction increases the cetane number of the diesel.
  • the technical scheme adopted by the present invention is: an optimized diesel hydrocracking catalyst carrier, the carrier raw material comprising the following components and the weight percentage thereof: 1 to 35% modified molecular sieve, 3 to 75% ⁇ -Al 2 O 3 , 15 to 75% amorphous silicon aluminum and 9 to 40% binder; the carrier has a specific surface area of 200 to 450 m 2 /g, and a total pore volume of 0.35 to 0.75 cm 3 /g.
  • the carrier raw material comprises the following components and their weight percentages: 5 to 9% modified molecular sieve, 15 to 32% ⁇ -Al 2 O 3 , 45 to 58% amorphous silicon aluminum and 18 to 35 % of the binder; the carrier has a specific surface area of 362 to 403 m 2 /g, and a total pore volume of 0.52 to 0.63 cm 3 /g; the carrier has a columnar shape and a length of 3 to 8 mm.
  • the modified molecular sieve is one of a modified ⁇ molecular sieve, a modified Y molecular sieve, a modified MOR molecular sieve, a modified ZSM-5 molecular sieve, a modified ZSM-22 molecular sieve, and a modified ZSM-23 molecular sieve or Several.
  • the modified ⁇ molecular sieve has a specific surface area of 450 to 750 m 2 /g and a total pore volume of 0.3 to 0.5 cm 3 /g.
  • the modified MOR molecular sieve has a specific surface area of 300 to 560 m 2 /g and a total pore volume of 0.3 to 0.45 cm 3 /g.
  • the modified Y-type molecular sieve has a specific surface area of 750 to 860 m 2 /g and a total pore volume of 0.35 to 0.55 cm 3 /g.
  • a method for preparing the above optimized diesel hydrocracking catalyst carrier comprises the following steps:
  • Step 2) After removing the template, the molecular sieve is sequentially subjected to ammonium exchange, hydrothermal treatment and aluminum salt treatment to obtain a modified molecular sieve;
  • the modified molecular sieve obtained in the step 3) is added to a mixed solution of an aluminum salt and a base to be precipitated, and the precipitate is sufficiently precipitated, and then the slurry is sequentially dried and calcined to obtain a modified molecular sieve and an alumina composite material;
  • the modified molecular sieve obtained in the step 4) is mixed with the alumina composite material, the amorphous silica alumina and the binder according to the ratio of the raw materials, and the hydrocracking catalyst carrier is obtained after molding.
  • the silicon source, the aluminum source, the sodium hydroxide, the tetraethylammonium bromide solution and the water are mixed in a molar ratio of SiO 2 :Al 2 O 3 :Na 2 O:tetraethyl bromide.
  • Ammonium:H 2 O is added in a ratio of 50 to 70: 1 : 5 to 8:15 to 20:1000 to 1200.
  • the crystallization conditions are: when the molecular sieve is a ⁇ molecular sieve, the crystallization temperature is 135 to 145 ° C; when the molecular sieve is a MOR molecular sieve, the crystallization temperature is 140 to 160 ° C; When the molecular sieve is a Y-type molecular sieve, the crystallization temperature is 80 to 120 ° C; and the calcination conditions are: heating to a temperature of 2 ° C / min to 550 ° C, and then baking for 7 to 9 h.
  • the ammonium exchange condition is: the temperature is 60 to 90 ° C, and the ammonium salt used is 0.4 to 0.6 mol/L of ammonium chloride or ammonium nitrate.
  • the hydrothermal treatment conditions are: a temperature of 630 to 750 ° C, a treatment time of 1 to 4 hours, and a gauge pressure of 0.05 to 0.4 MPa.
  • the aluminum salt treatment condition is: the aluminum salt solution used has an Al 3+ concentration of 0.5 to 1.5 mol/L, the aluminum salt to the molecular sieve has a mass ratio of 4 to 30:1, and the treatment temperature is 70 to 100 ° C, the treatment time is 1 to 5 hours.
  • the aluminum source is one or more of pseudoboehmite, aluminum sulfate and sodium metaaluminate.
  • the silicon source is one or more of white carbon black, silica sol and water glass.
  • the aluminum salt is one or more of aluminum sulfate, aluminum nitrate and aluminum chloride;
  • the base is one or more of ammonium oxalate, ammonia water, sodium hydroxide and potassium hydroxide.
  • the control temperature is 50 to 70 ° C, and the pH is 3 to 7; in the baking treatment, the baking temperature is 300 to 600 ° C, and the baking time is 2 to 4 hours.
  • drying and activation treatment are sequentially performed after the molding, the drying temperature is 100 to 120 ° C, the time is 18 to 22 hours, the activation temperature is 450 to 600 ° C, and the activation time is 4 to 6 hours. .
  • the present invention has the following advantages:
  • the catalyst carrier of the present invention is prepared by adding a modified molecular sieve to an inorganic aluminum salt solution for preparing ⁇ -Al 2 O 3 , precipitating, drying and calcining to obtain a composite material of a modified molecular sieve and ⁇ -Al 2 O 3 , and then According to the proportion of the material of the catalyst carrier, the remaining material is mixed with the composite material, compacted, formed, dried and activated to obtain a catalyst carrier.
  • the modified molecular sieve in the catalyst carrier of the invention has a high silicon to aluminum ratio, a large specific surface area, and the modified molecular sieve is The dispersion in the carrier is high, so that the carrier has a more uniform acidity, and the alumina is more closely contacted with the molecular sieve.
  • the hydrocracking catalyst prepared by the carrier of the invention has suitable cracking action and good isomerization effect on long-chain alkyl groups of long-chain alkanes, aromatic hydrocarbons and cycloalkanes, and the middle distillate has good selectivity and can be more Producing high-quality middle distillate products with high catalytic activity, can significantly reduce the freezing point of diesel fraction and improve the cetane number of diesel fuel under the premise of ensuring high yield of diesel.
  • the hydrocracking catalyst prepared by using the carrier of the present invention has a higher synergistic effect on hydrogenation activity and cracking activity.
  • the specific surface area and pore volume were determined by low temperature N 2 physical adsorption method, the molar ratio of silicon to aluminum was chemical, and the amount of infrared acid, B acid and L acid was determined by pyridine adsorption infrared spectroscopy. Plasma emission spectroscopy, molecular sieve relative crystallinity was determined by XRD method.
  • modified molecular sieve Preparation of modified ⁇ molecular sieve by hydrothermal synthesis method (specific surface area: 450-750 m 2 /g, total pore volume: 0.3-0.5 cm 3 /g), modified Y-type molecular sieve (specific surface area) of 750 ⁇ 860m 2 / g, a total pore volume of 0.35 ⁇ 0.55cm 3 / g), modified MOR zeolite (specific surface area of 300 ⁇ 560m 2 / g, a total pore volume of 0.3 ⁇ 0.45cm 3 / g), change
  • One or more of the ZSM-5 molecular sieve, the modified ZSM-22 molecular sieve and the modified ZSM-23 molecular sieve, according to the molar ratio of the molecular sieve ingredients, the template or the directing agent, the aluminum salt, and the water are mixed and stirred to clarify Solution (in which the modified Y-type molecular sieve needs to use hydrochloric
  • the crystallization is carried out when the molecular sieve is ⁇ molecular sieve, the crystallization temperature is 135-145 ° C, the crystallization temperature is 140-160 ° C when the molecular sieve is MOR molecular sieve, and the crystallization temperature is 80-120 ° C when the molecular sieve is Y-type molecular sieve.
  • the obtained solid product is washed, centrifuged, dried, and calcined to remove the template (roasting strip)
  • the temperature is raised to 550 ° C at a heating rate of 2 ° C / min, calcined for 7 ⁇ 9 h), and the template is removed for ammonium exchange (temperature is 60-90 ° C, ammonium salt is 0.4-0.6 mol / L ammonium chloride) Or ammonium nitrate), hydrothermal treatment (temperature 630 ⁇ 750 ° C, treatment time is 1-4 hours, gauge pressure is 0.05 ⁇ 0.4MPa), aluminum salt treatment (Al 3 + concentration of 0.5 ⁇ 1.5mol / L, aluminum salt
  • the molecular sieve has a specific gravity of 4 to 30:1, a treatment temperature of 70 to 100 ° C, and a time of 1 to 5 hours to obtain a modified molecular sieve.
  • modified molecular sieve and alumina composite material Preparation of modified molecular sieve and alumina composite material: mixing the aluminum salt solution and the alkali precipitating agent, adding the above modified molecular sieve to the mixed solution, stirring, the temperature is controlled at 50-70 ° C, and the pH value is controlled at 3-7. Evaporation is carried out at a temperature of 50 to 90 ° C, dried at 100 ° C, and the precipitate is calcined at a temperature of 300 to 600 ° C for 2 to 4 hours to obtain a modified molecular sieve and an alumina composite material.
  • catalyst carrier According to the mixing ratio of the catalyst carrier, the modified molecular sieve is mixed with the alumina composite material, the amorphous silicon aluminum and the binder, and crushed in a wheel mill for 20 to 60 minutes. Columnar, the carrier length is 3 to 8 mm, and the strip carrier is dried at 120 ° C for 20 hours and calcined at 450 to 600 ° C for 5 to 6 hours to obtain a catalyst carrier.
  • the ammonium exchange was carried out twice at a concentration of 0.5 mol/L ammonium chloride solution at 80 ° C, and the liquid-solid ratio was 10:1. Further, hydrothermal treatment is carried out at a water vapor pressure of 0.15 MPa, a treatment temperature of 600 ° C, and a treatment time of 2.5 hours, followed by treatment with an aluminum salt, and the hydrothermally treated molecular sieve is placed in a flask with a reflux device and can be sealed, and added.
  • the mixing ratio of the catalyst carrier, the molecular sieve and the alumina composite material were mixed with 159.1 g (dry basis 93%), amorphous silicon aluminum 204.5 g (dry basis 88%), and binder 240 g (dry basis 30%).
  • the mill was milled for 40 minutes, crushed into a extrudable paste, extruded into strips, the shape of the carrier was columnar, the length was 3-8 mm, and the strip carrier was dried at 120 ° C for 20 hours and calcined at 550 ° C for 5 hours.
  • the catalyst carrier was obtained, numbered Z-1, and the properties are shown in Table 2.
  • the molecular sieve modification process was the same as in Example 1. 140 g of ammonium oxalate and 3000 ml of aluminum chloride solution (concentration: 1.5 mol/L) were weighed and mixed in a 5000 ml beaker, and 13.5 g (dry basis 98%) modified molecular sieve was added to the mixed solution. At a constant temperature of 70 ° C, continuously add 2 mol / L of ammonia water until the pH value is 4, evaporate at 85 ° C, dry the aspirated white solid at 100 ° C for 3 hours, and calcine at 500 ° C for 4 hours to obtain molecular sieve and alumina composite.
  • the molecular sieve modification process was the same as in Example 1. 140 g of ammonium oxalate and 3000 ml of aluminum chloride solution (concentration: 1.5 mol/L) were weighed and mixed in a 5000 ml beaker, and 39.4 g (dry basis 98%) modified molecular sieve was added to the mixed solution. At a constant temperature of 70 ° C, continuously add 2 mol / L of ammonia water until the pH value is 4, evaporate at 85 ° C, dry the aspirated white solid at 100 ° C for 3 hours, and calcine at 500 ° C for 4 hours to obtain molecular sieve and alumina composite.
  • the molecular sieve modification process was the same as in Example 1. 140 g of ammonium oxalate and 3000 ml of aluminum chloride solution (concentration of 1.5 mol/L) were weighed and mixed in a 5000 ml beaker, and 110.4 g (dry basis 98%) modified molecular sieve was added to the mixed solution. At a constant temperature of 70 ° C, continuously add 2 mol / L of ammonia water until the pH value is 4, evaporate at 85 ° C, dry the aspirated white solid at 100 ° C for 3 hours, and calcine at 500 ° C for 4 hours to obtain molecular sieve and alumina composite.
  • the preparation process of the modified ⁇ molecular sieve was the same as that in Example 1. 140 g of ammonium oxalate and 3000 ml of aluminum chloride solution (concentration: 1.5 mol/L) were mixed and mixed in a 5000 ml beaker at a constant temperature of 70 ° C, and 2 mol/L of ammonia water was continuously added until The pH value was 4, and the solution was evaporated at 85 ° C. The aspirated white solid was dried at 100 ° C for 3 hours, and calcined at 500 ° C for 4 hours to obtain alumina. Finally, 18.7 g of modified molecular sieve (dry basis) was used according to the ratio of the catalyst carrier material.
  • Example 1 The carrier of Example 1 and Comparative Example 1 was subjected to supersaturated impregnation to carry the hydrogenation of the metal, and the hydrogenation metal was a tungsten-nickel system.
  • the catalyst numbers were respectively CZ-1 and CZ-5, and the composition thereof is shown in Table 2.
  • the catalytic activities of the catalysts CZ-1 and CZ-5 prepared in the carrier obtained in Example 1 and Comparative Example 1 were evaluated: evaluation was carried out on a fixed bed hydrogenation experimental apparatus under the following conditions: the total reaction pressure was 10 MPa, and the volume of hydrogen oil was The ratio is 1000, the volumetric space velocity is 1.0 h -1 , and the vacuum distillate oil (VGO) is used as the raw material oil.
  • the properties of the raw material oil are shown in Table 3.
  • Catalysts CZ-1 and CZ-5 were evaluated under the same process conditions, and the evaluation results are shown in Table 4.
  • Raw material oil Vacuum distillate Density (20 ° C), kg / m 3 912.3 Distillation range, °C IBP/10% 315/403 30%/50% 442/461 70%/90% 495/526 95%/EBP 532/544 Freezing point, °C 32 Nitrogen, ⁇ g/g 1568 Carbon, wt% 84.53 Hydrogen, wt% 11.72 Carbon residue, wt% 0.32 BMCI value 43

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un support de catalyseur d'hydrocraquage diesel optimisé et son procédé de préparation. Les matières premières du support comprennent les composants suivants en pourcentage en poids : 1-35 % de tamis moléculaire modifié, de 3 à 75 % de γ-Al2O3, de 15 à 75 % de silice-alumine amorphe et de 9 à 40 % de liant. La surface spécifique du support est de 200-450 m2/g et le volume poreux total est de 0,35-0,75 cm3/g. Un tamis moléculaire modifié est ajouté à une solution de sel d'aluminium inorganique utilisée pour préparer γ-Al2O3 et la précipitation, le séchage et le rôtissage sont effectués pour obtenir un composite de tamis moléculaire et de γ-Al2O3 ; puis les matériaux restants sont mélangés avec le composite selon la proportion de matériau du support de catalyseur et le laminage, la formation, le séchage et l'activation sont effectués pour obtenir le support de catalyseur. Le tamis moléculaire dans le support a un rapport silice/alumine élevé et une surface spécifique élevée et est hautement dispersé dans le support ; ainsi, le support a des sites acides plus uniformes et l'alumine est en contact plus étroit avec le tamis moléculaire. Un catalyseur d'hydrocraquage préparé peut réduire remarquablement le point d'écoulement d'une fraction diesel et améliorer l'indice de cétane du diesel tout en garantissant un rendement diesel élevé.
PCT/CN2018/083502 2017-04-21 2018-04-18 Support de catalyseur d'hydrocraquage diesel optimisé et son procédé de préparation Ceased WO2018192519A1 (fr)

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CN201710264295.7 2017-04-21
CN201710264295.7A CN106964397A (zh) 2017-04-21 2017-04-21 优化型柴油加氢裂化催化剂载体及其制备方法

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CN115990517A (zh) * 2021-10-19 2023-04-21 中国石油化工股份有限公司 一种制备非临氢液相烷基芳烃异构化催化剂的方法以及由此制备的催化剂及其用途
CN116020540A (zh) * 2021-10-25 2023-04-28 中国石油化工股份有限公司 一种负载型催化剂及其制备方法和应用
CN116060115A (zh) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 一种临氢降凝催化剂及其制法和应用
CN116060103A (zh) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 一种改性β分子筛及其制备方法和应用
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CN116212937A (zh) * 2023-03-06 2023-06-06 青岛惠城环保科技集团股份有限公司 一种多产柴油催化裂化催化剂的制备方法
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CN116251564A (zh) * 2022-12-26 2023-06-13 美埃(中国)环境科技股份有限公司 一种半导体VOCs废气吸附剂的制备方法
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CN119972167A (zh) * 2023-11-10 2025-05-13 中国石油天然气股份有限公司 Y/zsm-22/p-kit-1复合分子筛及其制备方法、催化剂载体、催化剂和加氢裂化的方法
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