WO2023124747A1 - Catalyseur de production d'oléfine à faible teneur en carbone au moyen d'un craquage catalytique, son procédé de préparation et son utilisation - Google Patents

Catalyseur de production d'oléfine à faible teneur en carbone au moyen d'un craquage catalytique, son procédé de préparation et son utilisation Download PDF

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WO2023124747A1
WO2023124747A1 PCT/CN2022/135848 CN2022135848W WO2023124747A1 WO 2023124747 A1 WO2023124747 A1 WO 2023124747A1 CN 2022135848 W CN2022135848 W CN 2022135848W WO 2023124747 A1 WO2023124747 A1 WO 2023124747A1
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catalyst
treatment
lanthanum
raw material
phosphorus
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PCT/CN2022/135848
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English (en)
Chinese (zh)
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代跃利
汲永钢
张永军
孙恩浩
李振业
万书宝
徐显明
连奕新
孙淑坤
褚洪岭
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中国石油天然气股份有限公司
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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
    • B01J29/40—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
    • B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • 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
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present application relates to a catalyst, in particular to a catalyst for producing light olefins by catalytic cracking and its preparation method and application, belonging to the technical field of catalysts.
  • Low-carbon olefins represented by ethylene and propylene are important chemical raw materials and occupy an important position in the national economy.
  • the overall demand for ethylene and propylene in my country has shown a steady growth trend.
  • my country's ethylene and propylene have been in a tight supply situation and have a high degree of dependence on foreign countries. Therefore, the development of new technologies for the production of low-carbon olefins is an inevitable trend in the development of my country's energy industry at this stage.
  • the non-petroleum route represented by MTO has become an important part of the production of low-carbon olefins in my country, but the profit of MTO is restricted by the raw material methanol.
  • the price of methanol has fluctuated greatly, and its price can reach more than 3,000 yuan/ton, which makes the economic benefits of the MTO industry unsatisfactory. Due to poor profits, low operating rates and even production stagnation often occur.
  • catalytic cracking can lower the reaction temperature and obtain higher yields of low-carbon olefins under milder conditions than thermal cracking conditions, and has attracted widespread attention.
  • catalytic cracking is still a strong endothermic reaction process that requires high energy consumption, and the system still has problems such as heating and water supply.
  • the catalytic cracking activity of the existing catalysts used in the coupling process is poor, especially for some feed oils with complex compositions, it is difficult to crack macromolecules and cyclic molecules; on the other hand, it is difficult for these catalysts to significantly improve the selection of light olefins Therefore, it is often necessary to increase the amount of methanol used to increase the yield of low-carbon olefins, which in turn keeps the cost of raw materials high.
  • This application provides a catalyst for the production of low-carbon olefins by catalytic cracking.
  • the catalyst has a special mesopore distribution and loading elements, and can be used as a catalyst in a coupled process without increasing the cost of raw materials, and finally with low energy consumption and high Activity and high selectivity enable the production of light olefins.
  • the present application also provides a method for preparing the above-mentioned catalyst.
  • the catalyst prepared by the method can realize the production of low-carbon olefins with low cost, low energy consumption, high activity and high selectivity.
  • the present application also provides a composite catalyst, which includes the above-mentioned catalyst, and has a catalytic effect similar to that of the above-mentioned catalyst.
  • the present application also provides a method for producing low-carbon olefins, which can realize the production of low-carbon olefins with low cost, low energy consumption, high activity and high selectivity.
  • the application provides a catalyst for catalytic cracking to produce low-carbon olefins, the catalyst includes an MFI molecular sieve and lanthanum and phosphorus loaded on the MFI molecular sieve, and the mass percentage of the lanthanum in the catalyst is 0.5 -1.5%, the mass percentage of the phosphorus in the catalyst is 0.5-0.9%;
  • the catalyst includes a first mesopore distribution of 2-4 nm and a second mesopore distribution of 7-20 nm.
  • the present application also provides a preparation method of a catalyst for producing light olefins by catalytic cracking described in any one of the above, comprising the following steps:
  • the gel system including silicon source, aluminum source, polymer stabilizer, templating agent, deionized water, and sodium hydroxide aqueous solution is sequentially subjected to crystallization treatment, first roasting treatment, ammonium ion exchange treatment, and second roasting treatment , to obtain a molecular sieve; the quality of the polymer stabilizer is 5-20% of the quality of the silicon source;
  • the loading treatment of the lanthanum element includes impregnating the molecular sieve with a lanthanum salt solution, and the impregnation amount of the lanthanum salt solution is 0.2-0.5ml/g;
  • the loading treatment of the phosphorus element includes impregnating the intermediate catalyst with a phosphorus salt solution, and the impregnation amount of the phosphorus salt solution is 0.2-0.5ml/g.
  • the preparation method as described above, wherein, the molar ratio of the silicon source, aluminum source, sodium hydroxide, templating agent, and deionized water is 100: (1.11-1.82): (5-12.5): (5-10) : (1000-3000).
  • the crystallization treatment includes the first crystallization treatment and the second crystallization treatment performed in sequence; wherein, the temperature of the first crystallization treatment is 120-140°C, and the time is 8- 16 hours, the temperature of the second crystallization treatment is 170-200° C., and the time is 28-40 hours.
  • polymer stabilizer is selected from at least one of polyethylene glycol 2000, polyethylene glycol 4000, and polyethylene glycol 6000.
  • the application provides a composite catalyst, the composite catalyst includes the catalyst for the production of low-carbon olefins by catalytic cracking described in any one of the above, and the mass percentage of the catalyst for the production of low-carbon olefins by catalytic cracking in the composite catalyst The content is not less than 42%.
  • the present application provides a method for producing light olefins, using the catalyst described in any one of the above and/or the composite catalyst to carry out catalytic cracking of the raw material system at 560-640°C and normal pressure.
  • the raw material system includes a first raw material and a second raw material
  • the first raw material is selected from methanol
  • the second raw material is selected from petroleum products with a distillation range of 40-220°C
  • the mass ratio of the first raw material to the second raw material is (0-2):1
  • the mass space velocity of the second raw material is 1-5h -1 .
  • the catalyst for producing light olefins by catalytic cracking of the present application can be used for the production of light olefins, and is especially suitable for the coupling process of MTO and thermal cracking.
  • the catalyst has a double-segment mesopore distribution, which is beneficial to the diffusion of raw materials inside it, and then can achieve excellent catalytic activity and low carbon selectivity at a lower catalytic temperature without increasing methanol raw materials.
  • the quantitative loading of special elements of the catalyst can make the catalyst have suitable acidity, thereby further improving the catalytic activity and low-carbon selectivity of the catalyst by inhibiting the carbon deposition of the catalyst.
  • Fig. 1 is the XRD spectrogram of the catalyst prepared by comparative example 1 and embodiment 1 of the present application;
  • Figure 2 is the NH 3 -TPD spectrogram of the molecular sieve catalysts prepared in Comparative Example 1, Comparative Example 4 and Example 1 of the present application;
  • Fig. 3 is the nitrogen adsorption-desorption curve of the molecular sieve catalyst prepared in Example 1 of the present application;
  • Example 4 is a DFT model pore size distribution curve of the molecular sieve catalyst prepared in Example 1.
  • the first aspect of the present application provides a catalyst for catalytic cracking to produce low-carbon olefins
  • the catalyst includes MFI molecular sieve and lanthanum and phosphorus loaded on the MFI molecular sieve, and the mass percentage of the lanthanum in the catalyst The content is 0.5-1.5%, and the mass percentage of the phosphorus in the catalyst is 0.5-0.9%.
  • the catalyst includes the first mesopore distribution of 2-4nm and the second mesopore distribution of 7-20nm.
  • the catalyst of the present application is used for catalytic cracking to produce low-carbon olefins (mainly referring to ethylene and propylene), and is especially suitable for catalytic cracking of a coupled raw material system of methanol and petroleum products (such as naphtha) to produce low-carbon olefins.
  • the catalyst includes an MFI molecular sieve, and lanthanum and phosphorus supported on the MFI molecular sieve.
  • the inventors found that when the mass percentage of lanthanum in the catalyst was 0.5-1.5%, and the mass percentage of phosphorus in the catalyst was 0.5-0.9%, the catalyst had a suitable acid site (weak acid site temperature 170-210°C, strong acid site temperature is 390-410°C), the acidic site is beneficial to inhibit the carbon deposition of the catalyst during use, thus ensuring the catalytic activity of the catalyst and the selectivity of low-carbon olefins, and reducing The regeneration frequency of the catalyst is improved, the service life of the catalyst is extended, and finally a high conversion rate of the raw material and a high yield of low-carbon olefins are realized at a lower raw material cost.
  • the catalyst of the present application has a two-segment mesopore distribution, specifically a first mesopore distribution of 2-4 nm and a second mesopore distribution of 7-20 nm. This kind of mesoporous distribution is helpful for the diffusion of raw materials inside the catalyst, especially for the macromolecules of cycloalkanes to enter the inside of the catalyst and diffuse. Catalytic activity and yield of low carbon olefins.
  • the catalyst with the above composition and structure in the present application is conducive to the improvement of the conversion rate of raw materials and the yield of low-carbon olefins.
  • the generation of low-carbon olefins also has a significant effect on the reduction of cost and energy consumption.
  • mesopore volume of the catalyst of the present application is 0.08-0.20 cm 3 /g.
  • the catalyst of the present application also has micropores, and the pore volume of the micropores is 0.08-0.15 cm 3 /g.
  • the catalyst of the present application has the above-mentioned mesoporous pore volume and/or micropore pore volume, even in a hydrothermal environment with high temperature, the mesopores and micropores are not easy to collapse and destroy, and the hydrothermal stability is good, thereby contributing to The guarantee of catalytic stability and the extension of service life of the catalyst.
  • the catalyst of the present application realizes the high-efficiency preparation of low-carbon olefins at low cost and low energy consumption through its own special composition and structure, and the catalyst is especially suitable for coupling raw materials of methanol and petroleum products.
  • the second aspect of the present application provides a method for preparing the catalyst described in any one of the above, comprising the following steps:
  • the gel system including silicon source, aluminum source, polymer stabilizer, templating agent, deionized water, and sodium hydroxide aqueous solution is sequentially subjected to crystallization treatment, first calcination treatment, ammonium ion exchange treatment, and second calcination processing to obtain molecular sieves; the mass of the polymer stabilizer is 5-20% of the mass of the silicon source;
  • the loading treatment of the lanthanum element includes impregnating the molecular sieve with a lanthanum salt solution, and the impregnation amount of the lanthanum salt solution is 0.2-0.5ml/g;
  • the loading treatment of the phosphorus element includes impregnating the intermediate catalyst with a phosphorus salt solution, and the impregnation amount of the phosphorus salt solution is 0.2-0.5ml/g.
  • the preparation method of the catalyst of the present application mainly includes three steps, which are respectively preparation of molecular sieve, loading of lanthanum element and loading of phosphorus element.
  • the present application does not limit the preparation method of the gel system in step 1), for example, it can be mixed with silicon source, aluminum source, polymer stabilizer, templating agent, deionized water and fully stirred, then add sodium hydroxide aqueous solution and stir After 2-4h, the gel system was obtained.
  • the addition of polymer stabilizers helps to uniformly disperse silicon and aluminum sources in the gel system, which not only reduces the formation of miscellaneous crystals, but also helps to introduce mesopores and Formation of mesopore distribution of catalyst bisections.
  • the mass of the polymer stabilizer is 5-20% of the mass of the silicon source.
  • the above-mentioned silicon source, aluminum source, and templating agent can be commonly used raw materials in the field, which are not specifically limited in this application.
  • the silicon source is selected from at least one of silica sol, coarse-pore silica gel, white carbon black, orthosilicate
  • the aluminum source is selected from sodium aluminate, sodium metaaluminate, aluminum chloride, aluminum nitrate, isopropyl
  • the templating agent is selected from at least one of tetrapropylammonium hydroxide, hexamethylenediamine, and tetrapropylammonium bromide, preferably tetrapropylammonium bromide.
  • the aforementioned polymer stabilizer is selected from at least one of polyethylene glycol 2000, polyethylene glycol 4000, and polyethylene glycol 6000.
  • the gel system is subjected to crystallization treatment, first calcination treatment, ammonium ion exchange treatment, and second calcination treatment in sequence to prepare a molecular sieve having an MFI structure.
  • the lanthanum element is loaded on the molecular sieve to obtain an intermediate catalyst.
  • the loading treatment of the lanthanum element includes impregnating the molecular sieve with a lanthanum salt solution.
  • lanthanum salt for example can be at least one in lanthanum chloride, lanthanum nitrate, lanthanum sulfate solution.
  • the intermediate catalyst is subjected to loading treatment of phosphorus element, and then dried to a constant weight and then subjected to a third calcination treatment to obtain the catalyst of the present application.
  • the phosphorus loading treatment includes impregnating the molecular sieve with a phosphorus salt solution.
  • the present application does not specifically limit the phosphorus salt, for example, it may be at least one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate.
  • the present application does not use equal volume immersion in the immersion treatment of the lanthanum salt solution and the phosphorus salt solution, but uses the hygroscopic method to complete the immersion (stirring or standing for 8-24h).
  • the way of hygroscopicity means that the molecular sieve and the intermediate catalyst are stirred or left standing for 8-24 hours with only a very small volume of impregnation solution, wherein the impregnation amount of the lanthanum salt solution is 0.2-0.5ml/g, that is, every gram
  • the molecular sieve is impregnated with 0.2-0.5ml of lanthanum salt solution to prepare the intermediate catalyst; the impregnation amount of phosphorus salt solution is 0.2-0.5ml/g, that is, each gram of intermediate catalyst is impregnated with 0.2-0.5ml of phosphorus salt solution to prepare the catalyst .
  • this hygroscopic impregnation method can effectively prevent the enrichment of modifying elements on the surface of the molecular sieve, so that more modifying elements enter the interior to form more active centers, so finally a small amount of modifying elements (lanthanum in The mass percentage in the catalyst is 0.5-1.5%, and the mass percentage of phosphorus in the catalyst is 0.5-0.9%) to realize the efficient loading modification of the molecular sieve, so that the catalyst has a lower content of modifying elements It can still have excellent catalytic activity, and improve the economic benefits of catalytic cracking to produce low-carbon olefins by reducing the production cost of the catalyst. It can be understood that the concentrations of the lanthanum salt solution and the phosphorus salt solution are determined according to the target loads of lanthanum and phosphorus.
  • the molar ratio of silicon source, aluminum source, sodium hydroxide, templating agent and deionized water is 100: (1.11-1.82): (5-12.5): (5- 10): (1000-3000).
  • the silicon source is counted as SiO 2
  • the aluminum source is counted as Al 2 O 3
  • the sodium hydroxide is counted as Na 2 O, that is, the molar ratio of SiO 2 , Al 2 O 3 , Na 2 O, template agent and deionized water is 100: (1.11-1.82): (5-12.5): (5-10): (1000-3000).
  • the crystallization treatment and the ammonium ion exchange treatment can be carried out in the usual manner in the art.
  • the crystallization treatment of the present application includes the first crystallization treatment and the second crystallization treatment in sequence, and the temperature of the first crystallization treatment is 120-140°C, and the time is 8-16h, the second crystallization treatment When the temperature is 170-200°C and the time is 28-40h, it is helpful to further optimize the mesopore volume and micropore volume of the dual-section mesopore distribution.
  • the process of performing amine ion exchange treatment refers to using an ammonium salt solution to exchange the crystallized product, wherein the ammonium salt is selected from at least one of ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium carbonate solutions.
  • an ammonium salt solution with an ion molar concentration of 1-2 mol/L can be used for multiple exchange treatments.
  • each gram of crystallized product is ion-exchanged with 5-20ml of ammonium salt solution, the temperature of each ion-exchange is 50-80°C, and the time is 1-4h, and finally the Na2O mass content is less than 0.2% molecular sieves.
  • the preparation process of the catalyst also includes drying treatment and calcination treatment.
  • the system after the crystallization treatment is washed, dried and first roasted in sequence, and then ammonium ion exchange treatment is performed.
  • the drying temperature is 80-120° C., and the time is 3-12 hours;
  • the temperature of the first roasting treatment is 550-600° C., and the time is 4-6 hours, and the heating rate is 0.5-2° C./min.
  • the system after the ammonium ion exchange treatment is washed, dried and second roasted in sequence to obtain molecular sieves.
  • the drying temperature is 80-120° C., and the time is 3-12 hours; the temperature of the second roasting treatment is 550-600° C., and the time is 4-6 hours, and the heating rate is 0.5-2° C./min.
  • the loading system is dried at 80-120° C. to a constant weight to obtain an intermediate catalyst.
  • the loading system is dried at 80-120° C. to constant weight, and the third calcination treatment is carried out at 550-600° C. (0.5-2° C./min) for 4-6 hours to obtain the catalyst.
  • the salt solution in this application is an aqueous salt solution.
  • the third aspect of the present application also provides a composite catalyst, the composite catalyst includes the catalyst of the first aspect, and the mass percentage of the catalyst in the composite catalyst is not less than 42%.
  • the composite catalyst may include, for example, a binder, an inert carrier, and the like.
  • the composite catalyst of the present application includes the above-mentioned catalyst, it can realize high-efficiency preparation of low-carbon olefins with low cost and low energy consumption, and the composite catalyst is especially suitable for coupling raw materials of methanol and petroleum products.
  • the fourth aspect of the present application provides a method for producing light olefins. Specifically, at 560-640° C. and normal pressure, the catalyst of the first aspect or the composite catalyst of the third aspect is used to carry out catalytic cracking of the raw material system.
  • This production method can realize the high-efficiency cracking of the raw material system at a lower temperature and normal pressure due to the catalytic cracking of the raw material system with the catalyst described in the aforementioned first aspect and/or the composite catalyst described in the aforementioned third aspect , and finally realized the production of low-carbon olefins with low energy consumption, low cost and high yield.
  • the raw material system of the production method is a coupled raw material system.
  • the raw material system comprises a first raw material and a second raw material, the first raw material is selected from methanol, and the second raw material is selected from at least one of petroleum products with a distillation range of 40 to 220°C, and the mass ratio of the first raw material and the second raw material is ( 0-2): 1, the mass space velocity of the second raw material is 1-5h -1 .
  • the above-mentioned petroleum products with a distillation range of 40-200°C are, for example, naphtha and hydrogenated gasoline.
  • the gel was transferred to a crystallization kettle for crystallization at elevated temperature.
  • the crystallization temperature was controlled at 140° C. and maintained for 12 hours, then the crystallization temperature was raised to 180° C. and maintained for 32 hours.
  • the crystallized product was washed, dried at 110°C for 5 hours, and calcined at 550°C for 6 hours at a heating rate of 1°C/min to obtain a sodium molecular sieve;
  • the dried sample was pulverized in a beaker, and 2.5ml of a solution in which 0.30g of ammonium phosphate was dissolved in advance was added dropwise to it, and after stirring evenly, the beaker was sealed with a plastic wrap and left to stand for 12h; the plastic wrap was removed, and the sample was placed at 120 °C and dried to constant weight; afterward, the dried sample was placed at 550 °C and roasted for 6 hours at a heating rate of 1 °C/min to obtain the catalyst SS-1 of this embodiment, with a lanthanum loading of 1.5% and a phosphorus loading of 0.9% .
  • the gel was transferred to a crystallization kettle for crystallization at elevated temperature.
  • the crystallization temperature was controlled at 120° C. and maintained for 16 hours, and then the crystallization temperature was raised to 170° C. and maintained for 40 hours.
  • the crystallized product was washed, dried at 80°C for 12 hours, and calcined at 600°C for 4 hours at a heating rate of 0.5°C/min to obtain a sodium molecular sieve;
  • the dried sample was pulverized in a beaker, and 1.0ml of a solution in which 0.11g of diammonium hydrogen phosphate was dissolved in advance was added dropwise to it, and after stirring evenly, the beaker was sealed with a plastic wrap and left to stand for 24 hours; the plastic wrap was removed, and the sample was placed Dry at 80°C to constant weight; then, place the dried sample at 600°C for 4 hours and roast at a rate of 0.5°C/min to obtain the catalyst SS-2 of this example, with a lanthanum loading of 0.5% and a phosphorus loading of 0.5%. 0.5%.
  • the gel was transferred to a crystallization kettle for crystallization at elevated temperature.
  • the crystallization temperature was controlled at 130° C. and maintained for 8 hours, and then the crystallization temperature was raised to 200° C. and maintained for 28 hours.
  • the crystallized product was washed, dried at 120°C for 3 hours, and calcined at 580°C for 5 hours at a heating rate of 2°C/min to obtain a sodium molecular sieve;
  • the dried sample was pulverized in a beaker, and 2.0ml of a solution in which 0.15g of ammonium dihydrogen phosphate was dissolved in advance was added dropwise to it, and after stirring evenly, the beaker was sealed with a plastic wrap and left to stand for 8 hours; the plastic wrap was removed, and the sample was placed Dry at 110°C to constant weight; then, place the dried sample at 580°C for 5 hours and calcinate at a heating rate of 2°C/min to obtain catalyst SS-3 with a lanthanum loading of 1.0% and a phosphorus loading of 0.8%.
  • the preparation method of the catalyst of this embodiment is basically the same as the preparation method of Example 1 (the molar ratio of the raw materials is consistent with that of Example 1), the difference is that the present embodiment uses aluminum nitrate as the aluminum source, and ethyl orthosilicate is Silicon source, hexamethylenediamine as template, lanthanum sulfate as lanthanum salt, phosphoric acid as phosphorus salt, lanthanum loading 1.2%, phosphorus loading 0.6%, catalyst SS-6.
  • the preparation method of the molecular sieve is basically the same as that of the molecular sieve in the embodiment 2 (the molar ratio of the raw materials is consistent with the embodiment 2), the difference is that the present embodiment uses aluminum chloride as the aluminum source, and silica sol is the source of silicon. Then adopt the method of Example 3 to carry out the loading of lanthanum element and phosphorus element, and the loading amount of the lanthanum and phosphorus elements is the same as that of Example 3, and the catalyst SS-7 is obtained.
  • the catalyst of this comparative example is prepared according to the following method:
  • the gel was transferred to a crystallization kettle for crystallization at elevated temperature.
  • the crystallization temperature was controlled at 140° C. and maintained for 12 hours, and then the crystallization temperature was raised to 180° C. and maintained for 32 hours.
  • the crystallized product was washed, dried, and calcined at 550°C for 6 hours at a rate of 1°C/min to obtain a sodium molecular sieve;
  • the catalyst of this comparative example is prepared according to the following method:
  • the catalyst of this comparative example is prepared according to the following method:
  • the catalyst of this comparative example is prepared according to the following method:
  • the catalyst of this comparative example is prepared according to the following method:
  • the dried sample was pulverized in a beaker, and 2.5ml of a solution in which 0.30g of ammonium phosphate was dissolved in advance was added dropwise to it, and after stirring evenly, the beaker was sealed with a plastic wrap and left to stand for 12h; the plastic wrap was removed, and the sample was placed at 120 °C and dry to constant weight; afterward, the dried sample was placed at 550 °C for 6 h and the rate of heating was 1 °C/min to obtain the catalyst DB-5 of this embodiment, with a lanthanum load of 1.5% and a phosphorus load of 0.9% .
  • Fig. 1 is the XRD spectrogram of the catalyst prepared in Comparative Example 1 and Example 1 of the present application. It can be seen from Figure 1 that Example 1 of the present application has a typical MFI topology, and under the same raw material gel silica-alumina formula as that of Comparative Example 1, the crystallinity of the catalyst obtained in Example 1 of the present application is higher.
  • Fig. 2 is the NH 3 -TPD spectra of the molecular sieve catalysts prepared in Comparative Example 1, Comparative Example 4 and Example 1 of the present application.
  • the acid properties of the catalyst obtained in Example 1 of the present application are suitable (the weak acid site temperature is 203 °C and the strong acid site temperature is 409 °C), between Between Comparative Example 1 and Comparative Example 4, and compared with Comparative Example 1, the number and proportion of strong acid sites decreased, and the temperature of strong acid sites shifted slightly to the left, and the strength of strong acid sites decreased slightly.
  • Fig. 3 is the nitrogen adsorption-desorption curve of the molecular sieve catalyst prepared in Example 1 of the present application. It can be seen from FIG. 3 that the nitrogen adsorption-desorption process of the molecular sieve catalyst prepared in Example 1 of the present application has an obvious hysteresis loop, indicating the existence of mesopores.
  • Fig. 4 is the DFT model pore size distribution curve of the molecular sieve catalyst prepared in Example 1, indicating that the mesopore distribution of the molecular sieve catalyst in Example 1 of the present application is two sections of 2-4nm and 7-20nm.
  • the catalysts of Examples 1-7 and Comparative Examples 1-5 were compressed into tablets under a pressure of 5Mpa, and the samples after compression were crushed and sieved; samples between 20-60 mesh were collected into a fixed-bed reactor, and passed
  • the gas inlet rate is 50ml/min nitrogen; the reactor is heated to 600°C for activation for 2 hours; after the activation, adjust the instrumentation parameters of the device to control the catalytic cracking reaction to produce light olefins.
  • the reaction conditions are: reaction temperature 600°C, normal pressure, methanol
  • the mass ratio to the oil feed is 1:1, the oil feed mass space velocity is 2h -1 , and the feed methanol mass concentration is 99.5%.
  • the oil products are n-hexane, cyclohexane and naphtha.
  • the composition of naphtha is shown in Table 2, and the results after 4 hours of reaction are shown in Table 3.
  • the catalyst of the present application has high catalytic conversion performance for alkanes and cycloalkanes, and the conversion rate of raw materials and the selectivity of product ethylene and propylene are relatively high. It also has a good catalytic effect on naphtha.
  • the gas production rate (conversion rate) of naphtha is relatively high, and the content of ethylene and propylene in its cracked gas phase products is relatively high.
  • reaction conditions for controlling the catalytic cracking reaction to produce light olefins are as follows: reaction temperature 640°C, normal pressure, mass ratio of methanol to naphtha feedstock 2:1, naphtha feed mass space velocity 1h -1 , feed The mass concentration of methanol is 95%. After 4 hours of reaction, the conversion rate of naphtha was 93.05%, and the selectivity of ethylene and propylene was 59.43%.
  • reaction conditions of controlling the catalytic cracking reaction to produce light olefins are: reaction temperature 550°C, normal pressure, mass ratio of methanol to naphtha feedstock 0.5:1, naphtha feed mass space velocity 5h -1 , feed The mass concentration of feed methanol is 50%. After 3.5 hours of reaction, the conversion rate of naphtha was 92.37%, and the selectivity of ethylene and propylene was 58.93%.
  • Example 7 After the catalyst SS-7 in Example 7 was tabletted and sieved, the catalyst was placed in a fixed bed, and the gas flow rate was 50ml/min nitrogen; the reactor was heated to 600°C for activation for 2 hours; the activation was completed Finally, adjust the instrumentation parameters of the device, and control the reaction conditions as follows: reaction temperature 610°C, normal pressure, methanol to naphtha feed mass ratio 2:1, naphtha feed mass space velocity 3h -1 , feed methanol The mass concentration is 80%. After reacting for 5 hours, the conversion rate of naphtha was 93.51%, and the selectivity of ethylene and propylene was 59.33%.

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Abstract

La présente demande concerne un catalyseur pour la production d'une oléfine à faible teneur en carbone au moyen d'un craquage catalytique, ainsi que son procédé de préparation et son utilisation. Le catalyseur comprend un tamis moléculaire à structure MFI et du lanthane et du phosphore, qui sont chargés sur le tamis moléculaire à structure MFI, la teneur en pourcentage en masse de lanthane dans le catalyseur étant de 0,5 à 1,5 % et la teneur en pourcentage en masse de phosphore dans le catalyseur étant de 0,5 à 0,9 %. Le catalyseur comprend une première distribution mésoporeuse de 2 à 4 nm et une seconde distribution mésoporeuse de 7 à 20 nm. Le catalyseur peut réaliser la production d'oléfines à faible teneur en carbone à une faible consommation d'énergie, un faible coût, une activité élevée et une sélectivité élevée.
PCT/CN2022/135848 2021-12-29 2022-12-01 Catalyseur de production d'oléfine à faible teneur en carbone au moyen d'un craquage catalytique, son procédé de préparation et son utilisation WO2023124747A1 (fr)

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CN103769192A (zh) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 一种催化裂化催化剂及其制备方法
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CN103028433B (zh) * 2011-09-29 2016-01-06 乐天化学株式会社 具有微孔和介孔的zsm-5催化剂、其制备方法及使用该催化剂催化裂化烃类生产轻烯烃的方法
CN103055929B (zh) * 2011-10-24 2015-04-08 中国石油化工股份有限公司 催化裂解制烯烃的流化床催化剂及其制备方法
CN103071523B (zh) * 2013-01-31 2015-04-22 惠生工程（中国）有限公司 一种镧、磷双杂原子zsm-5分子筛催化剂及其制备方法
KR20210066927A (ko) * 2018-10-18 2021-06-07 차이나 페트로리움 앤드 케미컬 코포레이션 메조포어가 풍부한 인-함유 희토류-함유 mfi 구조 분자체, 이의 제조 방법, 및 이를 함유하는 촉매 및 이의 용도

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US20130085311A1 (en) * 2011-09-29 2013-04-04 Honam Petrochemical Corporation Zsm-5 catalyst with micropores and mesopores, preparation method thereof and production method of light olefins through catalytic cracking of hydrocarbons using the catalyst
CN103769192A (zh) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 一种催化裂化催化剂及其制备方法
CN112850742A (zh) * 2019-11-12 2021-05-28 中国石油天然气股份有限公司 一种多级孔y型分子筛及其合成方法

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