WO2023066225A1 - 一种zsm-5分子筛催化剂及其制备方法和应用 - Google Patents

一种zsm-5分子筛催化剂及其制备方法和应用 Download PDF

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WO2023066225A1
WO2023066225A1 PCT/CN2022/125833 CN2022125833W WO2023066225A1 WO 2023066225 A1 WO2023066225 A1 WO 2023066225A1 CN 2022125833 W CN2022125833 W CN 2022125833W WO 2023066225 A1 WO2023066225 A1 WO 2023066225A1
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catalyst
aluminum
molecular sieve
zsm
hours
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French (fr)
Chinese (zh)
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滕加伟
任丽萍
赵国良
史静
谢在库
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to EP22882831.5A priority Critical patent/EP4420780A4/en
Priority to KR1020247016507A priority patent/KR20240090507A/ko
Priority to US18/701,993 priority patent/US20250235854A1/en
Priority to JP2024523449A priority patent/JP2024538197A/ja
Publication of WO2023066225A1 publication Critical patent/WO2023066225A1/zh
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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
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    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethene
    • 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
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/05—Nuclear magnetic resonance [NMR]
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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 invention relates to the field of catalytic cracking, in particular to a ZSM-5 molecular sieve catalyst, a preparation method thereof, and an application in olefin catalytic cracking to increase the production of propylene and ethylene.
  • Propylene and ethylene are important basic raw materials for the petrochemical industry. Driven by the rapid growth of demand for polyolefins and their derivatives, the demand for propylene and ethylene has continued to be strong and has grown at a relatively rapid rate in recent years. Therefore, it is considered to have great potential. products with market potential. Mixed carbon four and above olefins are by-products of FCC units in ethylene plants and refineries. Usually they can only be used as low value-added products such as liquefied gas fuels, and they can be further processed into propylene and ethylene. Make full use of this considerable amount of precious Olefin resources undoubtedly play a significant role in promoting the development of economy and technology.
  • Olefin catalytic cracking technology can convert raw materials containing olefins into ethylene and propylene. With the continuous innovation and development of development technology, the technology of olefin catalytic cracking to increase the production of propylene and ethylene has achieved remarkable results, greatly improving production efficiency. For the development of the petrochemical industry It has a very far-reaching impact and will help promote the innovation and development of subsequent petrochemical production technologies. Catalysts are the core technology in the catalytic cracking reaction of olefins. Many scholars have carried out extensive research using various preparation methods. properties, and reduce the formation of by-products and carbon deposits, modifying elements, loading and modification methods will directly affect the catalytic performance and product distribution.
  • the catalyst used for olefin cracking the active components are molecular sieves such as hydrogen ZSM-5, ZSM-11 or SAPO-34, and the inert gas is used as a heat carrier and diluent, which is of great benefit to the improvement of various indicators of this reaction.
  • the presence of water in the reaction is unfavorable for the long-term use of the catalyst.
  • acidic molecular sieve catalysts will undergo severe skeleton dealumination under high-temperature hydrothermal conditions, which will lead to a rapid decrease in the acid density of the catalyst and cause an irreversible loss of catalyst activity.
  • EP0109059A1 discloses a method for cracking C 4 -C 12 olefins to produce propylene, wherein ZSM-5 or ZSM-11 molecular sieves are used as catalysts.
  • US6307117 discloses a method for producing propylene and ethylene by cracking C 4 -C 12 olefins, wherein the active component of the catalyst used is ZSM-5 molecular sieve containing aprotic acid and group IB metal.
  • the olefin cracking catalysts reported in the above literatures all have defects such as poor product selectivity, poor catalyst stability, easy coking and deactivation, and inability to meet long-term operation, etc., so it is difficult to realize industrialization.
  • the technical problem to be solved by the present invention is to provide a ZSM-5 molecular sieve catalyst and a preparation method thereof, and The catalyst is used in the catalytic cracking of olefins to increase the production of propylene and ethylene.
  • the catalyst of the invention When the catalyst of the invention is used in the reaction of olefin catalytic cracking to produce propylene and ethylene, it has the characteristics of low reaction hydrogen transfer index, high stability, high conversion rate of raw material olefin, and high selectivity of product propylene and ethylene.
  • the first aspect of the present invention provides a ZSM-5 molecular sieve catalyst, wherein the ratio of the amount of skeleton aluminum located at the intersection of the straight channel and the sinusoidal channel to the amount of framework aluminum in the straight channel and the sinusoidal channel is 1.4:1 to 10:1 , and the silicon-aluminum molar ratio SiO 2 /Al 2 O 3 of the ZSM-5 molecular sieve is 80-1500.
  • the ratio of the amount of skeleton aluminum located at the intersection of the straight channel and the sinusoidal channel to the amount of framework aluminum in the straight channel and the sinusoidal channel is preferably 1.4:1 to 4:1, more preferably 1.5 :1 ⁇ 3:1.
  • the amount of skeleton aluminum located at the intersection of the straight channel and the sinusoidal channel is within the ratio range of the amount of skeleton aluminum in the straight channel and the sinusoidal channel, and the non-limiting specific point value can be 1.4: 1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3.0:1, 3.2:1, 3.5:1, 4.0:1, etc.
  • the silicon-aluminum molar ratio SiO 2 /Al 2 O 3 of the ZSM-5 molecular sieve is preferably 80-1000, more preferably 96-1000, still more preferably 150-1000, and furthermore More preferably, it is 200-1000, and still more preferably, it is 250-1000.
  • the micropore volume preferably accounts for 70% to 92% of the total pore volume, more preferably 75% to 90%, and even more preferably 80% to 90%.
  • the ratio of the micropore volume to the total pore volume can be 70%, 72%, 73%, 74%, 76%, 78%, 80%, 82%, 84%. , 86%, 88%, 90%, 92% and so on.
  • the total pore volume of the catalyst is preferably 0.01-1.2 mL/g, more preferably 0.1-0.8 mL/g.
  • the ZSM-5 molecular sieve catalyst preferably includes the following components in parts by weight:
  • alkaline earth metal elements preferably 0.5-5.0 parts.
  • the silicon-aluminum molar ratio SiO 2 /Al 2 O 3 of the hydrogen type ZSM-5 molecular sieve is preferably 80-1500, more preferably 80-1000, still more preferably 96-1000, and still more preferably 150-1000. 1000, still more preferably 200-1000, still more preferably 250-1000.
  • the rare earth element is preferably selected from at least one of La, Ce, Pr and Nd.
  • the alkaline earth metal element is preferably selected from at least one of Mg, Ca, Sr and Ba.
  • the mass content of the binder of the ZSM-5 molecular sieve catalyst based on the mass of the catalyst is preferably less than 5%, more preferably less than 2%, and even more preferably less than 0.5%.
  • the ZSM-5 molecular sieve catalyst is preferably a binder-free ZSM-5 molecular sieve catalyst.
  • the ZSM-5 molecular sieve catalyst is preferably an olefin catalytic cracking catalyst.
  • the second aspect of the present invention provides the preparation method of above-mentioned ZSM-5 molecular sieve catalyst, comprises the steps:
  • step (2) mixing and kneading the former molecular sieve powder obtained in step (1) with a binder, and drying to obtain a catalyst precursor;
  • step (4) may also be included: the ZSM-5 molecular sieve obtained in step (3) is loaded with rare earth metals and/or alkaline earth metals to obtain a metal-containing ZSM-5 molecular sieve catalyst.
  • the preparation method of ZSM-5 molecular sieve former powder described in step (1) preferably comprises:
  • step (1.2) Mix the second aluminum source, the second template agent, the second alkali source and the mixture obtained after the crystallization in step (1.1), and undergo the second hydrothermal crystallization to obtain the ZSM-5 molecular sieve raw powder.
  • the first templating agent described in step (1.1) is preferably at least one of tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetraethylammonium chloride and ammoniacal liquor;
  • the aluminum source is preferably at least one of aluminum nitrate, aluminum sulfate and aluminum phosphate;
  • the silicon source is preferably at least one of water glass, tetraethyl orthosilicate and silica sol;
  • the first alkali source is preferably hydrogen at least one of sodium oxide and potassium hydroxide.
  • the first hydrothermal crystallization may be performed under autogenous pressure generated in a stainless steel autoclave.
  • the water is preferably deionized water.
  • the conditions for the first hydrothermal crystallization are preferably as follows: the crystallization temperature is 80-150° C., and the crystallization time is 2-10 h.
  • the first templating agent is counted as NH 4 +
  • the first aluminum source is counted as Al 2 O 3
  • the silicon source is counted as SiO 2
  • the first alkali source is counted as OH-
  • water is counted as H 2 O
  • the second aluminum source in step (1.2) is preferably at least one of aluminum potassium sulfate and sodium metaaluminate.
  • the potassium aluminum sulfate may be a hydrate, such as potassium aluminum sulfate dodecahydrate.
  • the second templating agent is preferably at least one of n-butylamine, hexamethylenediamine and pyridine.
  • the second alkali source is preferably at least one of sodium hydroxide and potassium hydroxide.
  • the silicon source in the step (1.1) and the second aluminum source in the step (1.2) and the first aluminum source in the step (1.1) add the total amount, according to SiO 2 /Al 2 O 3
  • the molar ratio is preferably 80 ⁇ 1500, more preferably 80 ⁇ 1000.
  • the second aluminum source in the step (1.2) is in Al 2 O
  • the total mass Preferably it is 30% or more, and more preferably 40% or more.
  • the molar ratio of the second template agent and the second aluminum source in step (1.2) is preferably 200-500:1 based on NH 4 + /Al 2 O 3 .
  • the second alkali source is used to control the pH value of the system, preferably 8-10.
  • the conditions for the second hydrothermal crystallization are preferably as follows: the crystallization temperature is 120-200° C., and the crystallization time is 10-100 h.
  • the second hydrothermal crystallization may be performed under autogenous pressure generated in a stainless steel autoclave.
  • the product obtained after the second hydrothermal crystallization can be washed, dried and calcined to obtain ZSM-5 molecular sieve raw powder.
  • the washing can be done with deionized water.
  • the drying conditions are preferably as follows: the drying temperature is 80-100° C., and the drying time is 10-20 hours.
  • the calcination conditions are preferably as follows: the calcination temperature is 500-650° C., and the calcination time is 8-15 hours.
  • the binder is preferably a silicon compound or a silicon compound and an aluminum compound.
  • the aluminum compound is preferably selected from at least one of alumina and aluminum sol, and the silicon compound is preferably selected from at least one of white carbon black and silica sol.
  • the silicon compound is counted as silicon dioxide, the aluminum compound is counted as alumina, and the silicon compound can be used in an amount of 10% to 100% by mass, or 50% to 100% by mass.
  • the added amount of the binder, based on the sum of the mass of alumina and silica preferably accounts for 8% to 45% of the total mass of the molecular sieve powder and the binder, more preferably 10% to 40%.
  • step (2) can adopt conventional molding methods, such as extrusion molding and the like.
  • step (2) according to the molding requirements, an appropriate amount of water can be added.
  • the drying conditions are preferably as follows: the drying temperature is 80-120° C., and the drying time is 5-10 hours.
  • the third template agent described in step (3) is preferably ammoniacal liquor, ethylamine, ethylenediamine, triethylamine, n-butylamine, hexamethylenediamine, tetrapropylammonium bromide and tetrapropylhydrogen at least one of ammonium oxides.
  • the third hydrothermal crystallization is preferably to place the catalyst precursor obtained in step (2) in the steam containing the third template for crystallization, and the mass ratio of the third template to the catalyst precursor is preferably 1 to 3: 1. Preferably crystallize at 130-200°C for 20-100 hours.
  • the third hydrothermal crystallization preferably adopts the gas-solid crystallization method, that is, the catalyst precursor is placed on the middle mesh of the crystallization kettle, the aqueous solution containing the third template is placed under the middle mesh, and the crystallization Under certain conditions, the lower aqueous solution containing the third template agent is formed into steam to perform crystal transformation treatment on the catalyst precursor.
  • the third hydrothermal crystallization may be performed under autogenous pressure generated in a stainless steel autoclave.
  • the mass ratio of the third template agent to water in the aqueous solution of the third template agent is preferably 1 ⁇ 2:1.
  • the product obtained after the third hydrothermal crystallization can be washed, dried and roasted.
  • the drying strip is preferably as follows: the drying temperature is 80-100° C., and the drying time is 10-20 hours.
  • the calcination conditions are preferably as follows: the calcination temperature is 450-600° C., and the calcination time is 5-10 hours.
  • the ammonium exchange in step (3) is preferably to place the product obtained after crystallization of the catalyst precursor in an aqueous ammonium salt solution for ammonium exchange, washing and drying.
  • the ammonium salt is preferably selected from one or more of ammonium chloride, ammonium nitrate and ammonium sulfate.
  • the mass content of the ammonium salt in the ammonium salt aqueous solution is preferably 5%-10%.
  • the temperature of the ammonium exchange is preferably 80-90°C; the number of ammonium exchanges can be 3-6 times.
  • the product obtained after the ammonium exchange is roasted; the roasting conditions are preferably as follows: the roasting temperature is 500-600° C., and the roasting time is 4-8 hours.
  • step (4) is an optional step, which is determined according to the composition of the catalyst.
  • the loading method of rare earth metal and/or alkaline earth metal can adopt impregnation method.
  • the catalyst contains rare earth metals and alkaline earth metals, and the loading process is as follows: first obtain the ZSM-5 molecular sieve loaded with rare earth metals, and then obtain the ZSM-5 molecular sieve loaded with rare earth metals and alkaline earth metals, that is, the ZSM-5 molecular sieve containing Metallic ZSM-5 molecular sieve catalyst.
  • the impregnation method is preferably an equal-volume impregnation method.
  • Molecular sieves are impregnated in an equal-volume solution containing rare earth metal salts or alkaline earth metal salts for 3 to 10 hours, dried at 60 to 100°C for 10 to 20 hours, and then calcined at 450 to 600°C for 8 to 20 hours. 10h that is.
  • the weight concentration of the rare earth metal is preferably 0.2%-5%.
  • the rare earth element is preferably at least one selected from La, Ce, Pr and Nd; in the alkaline earth metal salt solution, the weight concentration of the alkaline earth metal is preferably 0.2%-5%.
  • the alkaline earth metal element is preferably at least one selected from Mg, Ca, Sr and Ba.
  • the third aspect of the present invention provides an application of the above-mentioned ZSM-5 molecular sieve catalyst in the production of propylene and ethylene by catalytic cracking of olefins or a method for producing propylene and ethylene by using the above-mentioned ZSM-5 molecular sieve catalyst in the catalytic cracking of olefins.
  • the process of producing propylene and ethylene by catalytic cracking of olefins can be as follows: olefin raw materials are contacted with the above-mentioned ZSM-5 molecular sieve catalyst for reaction to obtain propylene and ethylene products.
  • the reaction temperature is 400-600°C, more preferably 420-580°C
  • the reaction pressure is 0-0.3MPa, more preferably Preferably it is 0.01 to 0.2 MPa
  • the weight space velocity is 1 to 50 h -1 , more preferably 2 to 40 h -1 .
  • the raw material passes through the catalyst bed to generate propylene and ethylene
  • the reaction hydrogen transfer index is preferably lower than 9.6%, more preferably lower than 7%; the reaction hydrogen transfer index here is the yield of propane and propylene in the product mass ratio.
  • Ordinary low-silicon aluminum has more acid centers than ZSM-5 molecular sieve, which leads to more side reactions after being used in the reaction, low product selectivity, and by-products block the pores of the molecular sieve, thereby reducing the activity of the catalyst and eventually leading to catalyst deactivation.
  • ZSM-5 molecular sieve with high silicon-aluminum ratio has fewer active centers and uneven activity distribution, resulting in low reaction activity and poor catalyst stability.
  • the inventors have found through research that in the ZSM-5 molecular sieve catalyst, the amount of skeleton aluminum at the intersection of straight channels and sinusoidal channels is significantly higher than the amount of skeleton aluminum inside the straight channels and sinusoidal channels and has a higher silicon-aluminum ratio. When cracking propylene and ethylene, it has good activity and selectivity, and the stability has been further increased. In addition, an appropriate proportion of micropore volume contributes to the increase of performance.
  • the present invention has the following technical effects:
  • the ZSM-5 molecular sieve catalyst of the present invention has the skeleton aluminum content at the intersection of the straight channel and the sinusoidal channel, which is significantly higher than the skeleton aluminum content inside the straight channel and the sinusoidal channel, and has the characteristics of a higher silicon-aluminum ratio, so that the active center of the catalyst can be utilized
  • the efficiency is greatly improved, so that the products and intermediates generated at the intersecting channels are easier to diffuse, the occurrence of side reactions and the formation of carbon deposits are significantly reduced, the hydrogen transfer index of the reaction is greatly reduced, and the catalyst activity and product selectivity are significantly improved.
  • Stable Sex also grows further.
  • the prepared molecular sieve catalyst has a composite channel structure, which is treated by crystal transformation , so that the obtained catalyst basically does not contain binder, and the amount of skeleton aluminum located at the intersection of straight channels and sinusoidal channels is significantly higher than the amount of framework aluminum inside the straight channels and sinusoidal channels, the silicon-alumina ratio is high, which makes the catalyst activity and The selectivity of the product is obviously improved, and the stability is further increased. Proper pore volume ratio of micropores further increases the performance.
  • the method for producing ethylene and propylene by olefin catalytic cracking of the present invention effectively overcomes the shortcomings of high reaction hydrogen transfer index, poor catalyst activity, and low selectivity of propylene and ethylene in the prior art.
  • the reaction hydrogen transfer index can be reduced Reduced to below 9.6%, more preferably below 7%, the conversion rate of raw material olefins is above 71%, the selectivity of target product propylene and ethylene exceeds 68%, preferably exceeds 80%, when the reaction is carried out after 75h, the activity and selectivity of the catalyst The property has not changed significantly and has good stability.
  • Fig. 1 is the skeleton aluminum 27Al NMR spectrum of the catalyst obtained in Example 1, wherein in Fig. 1, line 1 is the skeleton aluminum species at the intersection of the straight channel and the sinusoidal channel, and line 2 is the skeleton aluminum species in the straight channel and the sinusoidal channel ; Line 3 is the original curve before peak splitting;
  • Fig. 2 is the XRD figure of embodiment 1 gained catalyst
  • Figure 3 is the skeleton aluminum 27Al nuclear magnetic spectrum of the catalyst obtained in Comparative Example 5, wherein in Figure 3, line 1 is the skeleton aluminum species at the intersection of straight channels and sinusoidal channels, and line 2 is the skeleton aluminum species in straight channels and sinusoidal channels ; Line 3 is the original curve before peak splitting;
  • Figure 4 is the XRD pattern of the catalyst obtained in Comparative Example 5.
  • the mensuration of pore volume is to carry out on TriStar 3000 type physical adsorption instrument. After vacuum treatment at 300°C for 3 hours, the sample was put into the tester and liquid nitrogen was added for testing. The sample pore distribution was calculated using the Barret-Joyner-Halenda (BJH) model.
  • BJH Barret-Joyner-Halenda
  • the instrument used for 27 Al nuclear magnetic characterization is Bruker's DSX 300 nuclear magnetic resonance instrument, and the chemical shift of 27 Al refers to Al(H 2 O) 6 3+ in saturated aluminum chloride solution, and the nuclear magnetic spectrum is obtained in the magic Obtained under the condition of angular rotation speed 4kHz.
  • the skeleton aluminum located at the intersection of the straight channel and the sinusoidal channel in the catalyst corresponds to the spectral peak with a chemical shift near 54ppm (for example, the range of 54 ⁇ 0.2ppm) in the 27 Al nuclear magnetic spectrum
  • the skeleton aluminum located in the straight channel and the sinusoidal channel Corresponding to the peak in the 27Al nuclear magnetic spectrum with a chemical shift near 56ppm (for example, in the range of 56 ⁇ 0.6ppm).
  • the ratio of the amount of skeleton aluminum located at the intersection of the straight channel and the sinusoidal channel to the amount of framework aluminum located in the straight channel and the sinusoidal channel is the ratio of the corresponding area after the peaks are divided according to the peaks near 54ppm and 56ppm in the 27 Al nuclear magnetic spectrum.
  • XRD analysis is carried out on Rigaku D/MAX-1400X polycrystalline X-ray diffractometer, graphite monochromator, Cu K ⁇ ray, tube voltage 40kV, tube current 40mA, scanning speed 15° ⁇ min -1 , scanning The range 2 ⁇ is 5-50°.
  • the silicon-aluminum molar ratio SiO 2 /Al 2 O 3 is calculated by analyzing the elemental composition of the solid sample with a Magix X fluorescence spectrometer of the Netherlands Philips company, the operating voltage is 40kV, and the operating current is 40mA.
  • At least one of carbon four to carbon six olefins is used as a raw material to generate ethylene and propylene by catalytic cracking, wherein the hydrogen transfer index is the yield mass ratio of propane and propylene in the product;
  • Feedstock olefin conversion rate (%) (1-quality of olefins in product/mass of olefins in feedstock) ⁇ 100%;
  • Diene selectivity (%) mass of propylene and ethylene produced in the product and/(mass of olefin in raw material-mass of olefin remaining after reaction) ⁇ 100%.
  • Tetrapropylammonium bromide is used as the first template, aluminum nitrate is the first aluminum source, silica sol is the silicon source, sodium hydroxide is the first alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate
  • the molar ratio of SiO 2 /Al 2 O 3 is 300, and the second aluminum source potassium aluminum sulfate dodecahydrate after removing the first aluminum source is added,
  • the second template agent and the second aluminum source are added with the second template agent n-butylamine at a ratio of NH 4 + /Al 2 O 3 molar ratio of 200:1, fully mixed with the above crystallization solution, and then hydrogenated with the second alkali source Adjust the pH to 10 with sodium, then transfer to a stainless steel autoclave for the second hydrothermal crystallization, and crystallize at 120°C for 100h.
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • ethylamine Take ethylamine as the third template agent, add the mixture of 30 grams of ethylamine and 30 grams of distilled water in advance in the reaction kettle, place 20 grams of the above-mentioned strip catalyst precursors prepared above the porous stainless steel mesh in the reaction kettle and seal at 130
  • the gas-solid phase hydrothermal crystallization was carried out at °C for 100 h. After the product was taken out, it was washed with distilled water, dried at 90°C for 15h, and then calcined at 550°C for 10h in an air atmosphere.
  • ammonium was exchanged in 5wt% ammonium nitrate solution at 90°C for 3 times, and after drying, it was roasted in a muffle furnace at 500°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-form ZSM-5 molecular sieve solid was immersed in 20 g of praseodymium nitrate solution with a mass content of 1% of Pr for 10 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours.
  • the total pore volume of the catalyst is 0.3mL/g, and the micropore pore volume accounts for 86% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal tunnels to the amount of skeleton aluminum in straight and sinusoidal tunnels is 2:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 282.
  • Fig. 2 is the XRD pattern of the catalyst obtained in Example 1, illustrating that the catalyst is a ZSM-5 molecular sieve catalyst, and the binder content is lower than 0.2%.
  • the prepared catalyst was evaluated for the reaction activity of olefin catalytic cracking to produce propylene and ethylene.
  • the technological conditions used in the investigation are: 5 grams of catalyst, 500°C reaction temperature, 0.02MPa reaction pressure, and 20h -1 weight space velocity.
  • the reaction results are: the conversion rate of carbon tetraolefins is 75%, the hydrogen transfer index is 6.5%, and the selectivity of propylene and ethylene is 80.8%. Catalyst reacted for 80h, the catalyst activity and selectivity did not change significantly, and had good stability.
  • Tetrapropylammonium hydroxide is used as the first template agent, aluminum nitrate is used as the first aluminum source, tetraethyl orthosilicate is used as the silicon source, sodium hydroxide is used as the first alkali source, tetrapropylammonium hydroxide is calculated as NH 4 + , aluminum nitrate in terms of Al 2 O 3 , tetraethyl orthosilicate in terms of SiO 2 , sodium hydroxide in terms of OH - , and water in terms of H 2 O.
  • the molar ratio of SiO 2 /Al 2 O 3 is 1000, add the second aluminum source sodium metaaluminate after removing the first aluminum source, and the second
  • the template agent and the second aluminum source are added into the second template agent pyridine at a ratio of NH 4 + /Al 2 O 3 molar ratio of 300:1, fully mixed with the above crystallization solution, and the pH is adjusted with the second alkali source sodium hydroxide to 8.
  • the synthesized product was washed with water, dried at 80°C for 20 hours, and calcined at 500°C for 15 hours to obtain ZSM-5 molecular sieve powder.
  • hexamethylenediamine As the third template, add a mixture of 60 grams of hexamethylenediamine and 30 grams of distilled water in advance in the reactor, and place 20 grams of the strip-shaped catalyst precursor prepared above in the reactor and seal it above the porous stainless steel mesh Afterwards, crystallization was carried out at 150° C. for 80 h. After the product was taken out, it was washed with distilled water, dried at 100°C for 10 hours, and calcined at 600°C for 5 hours in an air atmosphere.
  • the obtained hydrogen-form ZSM-5 molecular sieve solid was immersed in 20 g of neodymium nitrate solution with a Nd mass content of 2% for 5 hours, dried at 60°C for 20 hours, and calcined at 600°C for 8 hours.
  • the above solid was immersed in 20 grams of calcium nitrate solution with a Ca weight content of 0.8% for 10 hours, dried at 100°C, and calcined at 500°C for 10 hours to obtain the catalyst.
  • the XRD pattern of the obtained catalyst is similar to that shown in Figure 2, indicating that the catalyst is a ZSM-5 molecular sieve catalyst, and the binder content is lower than 0.2%.
  • the total pore volume of the catalyst is 0.4mL/g, and the micropore pore volume accounts for 90% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 1.5:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 925.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the conversion rate of carbon tetraolefins is 73%, the hydrogen transfer index is 4.8%, and the selectivity of propylene and ethylene is 85.6%. The catalyst reacted for 78 hours, and the activity and selectivity of the catalyst did not change significantly, showing good stability.
  • Tetrapropylammonium bromide is used as the first template, aluminum nitrate is the first aluminum source, silica sol is the silicon source, sodium hydroxide is the first alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate
  • the molar ratio of SiO 2 /Al 2 O 3 is 300, and the second aluminum source potassium aluminum sulfate dodecahydrate after removing the first aluminum source is added,
  • the second template agent and the second aluminum source are added with the second template agent n-butylamine at a ratio of NH 4 + /Al 2 O 3 molar ratio of 200:1, fully mixed with the above crystallization solution, and then hydrogenated with the second alkali source Adjust the pH to 10 with sodium, then transfer to a stainless steel autoclave for the second hydrothermal crystallization, and crystallize at 120°C for 100h.
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • ethylamine Take ethylamine as the third template agent, add the mixture of 30 grams of ethylamine and 30 grams of distilled water in advance in the reaction kettle, place 20 grams of the above-mentioned strip catalyst precursors prepared above the porous stainless steel mesh in the reaction kettle and seal at 130
  • the gas-solid phase hydrothermal crystallization was carried out at °C for 100 h. After the product was taken out, it was washed with distilled water, dried at 90°C for 15h, and then calcined at 550°C for 10h in an air atmosphere.
  • the XRD pattern of the obtained catalyst is similar to that shown in Figure 2, indicating that the catalyst is a ZSM-5 molecular sieve catalyst, and the binder content is lower than 0.2%.
  • the total pore volume of the catalyst is 0.5mL/g, and the micropore pore volume accounts for 87% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 2:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 280.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the conversion rate of carbon tetraolefins is 76%, the hydrogen transfer index is 9.6%, and the selectivity of propylene and ethylene is 68.2%. Catalyst reacted for 82 hours, and the activity and selectivity of the catalyst did not change significantly, showing good stability.
  • Tetrapropylammonium bromide is used as the first template, aluminum nitrate is the first aluminum source, silica sol is the silicon source, sodium hydroxide is the first alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate
  • the molar ratio of SiO 2 /Al 2 O 3 is 300, and the second aluminum source potassium aluminum sulfate dodecahydrate after removing the first aluminum source is added,
  • the second template agent and the second aluminum source are added with the second template agent n-butylamine at a ratio of NH 4 + /Al 2 O 3 molar ratio of 200:1, fully mixed with the above crystallization solution, and then hydrogenated with the second alkali source Adjust the pH to 10 with sodium, then transfer to a stainless steel autoclave for the second hydrothermal crystallization, and crystallize at 120°C for 100h.
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • ethylamine Take ethylamine as the third template agent, add the mixture of 30 grams of ethylamine and 30 grams of distilled water in advance in the reaction kettle, place 20 grams of the above-mentioned strip catalyst precursors prepared above the porous stainless steel mesh in the reaction kettle and seal at 130
  • the gas-solid phase hydrothermal crystallization was carried out at °C for 100 h. After the product was taken out, it was washed with distilled water, dried at 90°C for 15h, and then calcined at 550°C for 10h in an air atmosphere.
  • ammonium was exchanged in 5wt% ammonium nitrate solution at 90°C for 3 times, and after drying, it was roasted in a muffle furnace at 500°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-type ZSM-5 molecular sieve solid was immersed in 20 g of Pr praseodymium nitrate solution with a weight content of 1% for 10 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours. That is the catalyst.
  • the XRD pattern of the obtained catalyst is similar to that shown in Figure 2, indicating that the catalyst is a ZSM-5 molecular sieve catalyst, and the binder content is lower than 0.2%.
  • the total pore volume of the catalyst is 0.4mL/g, and the micropore pore volume accounts for 86% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 2:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 285.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the conversion rate of carbon tetraolefins is 77.3%, the hydrogen transfer index is 8.8%, and the selectivity of propylene and ethylene is 70.2%. The catalyst reacted for 76 hours, and the activity and selectivity of the catalyst did not change significantly, showing good stability.
  • Tetrapropylammonium bromide is used as the first template, aluminum nitrate is the first aluminum source, silica sol is the silicon source, sodium hydroxide is the first alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate
  • the molar ratio of SiO 2 /Al 2 O 3 is 300, and the second aluminum source potassium aluminum sulfate dodecahydrate after removing the first aluminum source is added,
  • the second template agent and the second aluminum source are added with the second template agent n-butylamine at a ratio of NH 4 + /Al 2 O 3 molar ratio of 200:1, fully mixed with the above crystallization solution, and then hydrogenated with the second alkali source Adjust the pH to 10 with sodium, then transfer to a stainless steel autoclave for the second hydrothermal crystallization, and crystallize at 120°C for 100h.
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • ethylamine Take ethylamine as the third template agent, add the mixture of 30 grams of ethylamine and 30 grams of distilled water in advance in the reaction kettle, place 20 grams of the above-mentioned strip catalyst precursors prepared above the porous stainless steel mesh in the reaction kettle and seal at 130
  • the gas-solid phase hydrothermal crystallization was carried out at °C for 100 h. After the product was taken out, it was washed with distilled water, dried at 90°C for 15h, and then calcined at 550°C for 10h in an air atmosphere.
  • ammonium was exchanged in 5wt% ammonium nitrate solution at 90°C for 3 times, and after drying, it was roasted in a muffle furnace at 500°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-type ZSM-5 molecular sieve solid was immersed in 20 grams of magnesium nitrate solution with a Mg mass content of 2% for 8 hours, dried at 100°C for 10 hours, and calcined at 550°C for 8 hours to obtain the catalyst.
  • the XRD pattern of the obtained catalyst is similar to that shown in Figure 2, indicating that the catalyst is a ZSM-5 molecular sieve catalyst, and the binder content is lower than 0.2%.
  • the total pore volume of the catalyst is 0.6mL/g, and the micropore pore volume accounts for 83% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 1.8:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 282.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the conversion rate of carbon tetraolefins is 75.8%, the hydrogen transfer index is 9.3%, and the selectivity of propylene and ethylene is 69.5%. The catalyst reacted for 75 hours, and the activity and selectivity of the catalyst did not change significantly, showing good stability.
  • Tetrapropylammonium bromide is used as the first template, aluminum sulfate is the first aluminum source, silica sol is the silicon source, sodium hydroxide is the first alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum sulfate
  • the total amount of the silicon source, the first aluminum source and the second aluminum source according to the ratio of SiO 2 /Al 2 O 3 molar ratio of 100, add the second aluminum source potassium aluminum sulfate after removing the first aluminum source, and the second template Add the second template agent n-butylamine to the second aluminum source at a molar ratio of NH 4 + /Al 2 O 3 of 500:1, mix well with the above crystallization solution, and adjust the pH with the second alkali source sodium hydroxide 10, and then transferred to a stainless steel autoclave for the second hydrothermal crystallization at 150 ° C for 40 h.
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • hexamethylenediamine As the third template, add 60 grams of hexamethylenediamine and a mixture of 30 grams of distilled water in advance in the reactor, and place 30 grams of the above-mentioned strip-shaped catalyst precursor in the reactor and seal it above the porous stainless steel mesh Afterwards, crystallization was performed at 200° C. for 20 h. After the product was taken out, it was washed with distilled water, dried at 100°C for 10h, and then baked at 450°C for 10h in an air atmosphere.
  • ammonium was exchanged in 5% ammonium sulfate solution at 90°C for 6 times, and after drying, it was roasted in a muffle furnace at 600°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-type ZSM-5 molecular sieve solid was immersed in 20 g of neodymium nitrate solution with a mass content of 0.2% Ce for 3 hours, dried at 100°C for 10 hours, and calcined at 450°C for 10 hours.
  • the above solid was placed in 20 g of magnesium nitrate solution with a weight content of 0.2% Mg for 10 hours, dried at 100°C, and calcined at 500°C for 10 hours to obtain the catalyst.
  • the XRD pattern of the obtained catalyst is similar to that shown in Figure 2, indicating that the catalyst is a ZSM-5 molecular sieve catalyst, and the binder content is lower than 0.2%.
  • the total pore volume of the catalyst is 0.8mL/g, and the micropore pore volume accounts for 90% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 3:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 98.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the conversion rate of carbon tetraolefins is 76.3%, the hydrogen transfer index is 5.3%, and the selectivity of propylene and ethylene is 84.5%. The catalyst reacted for 77 hours, and the activity and selectivity of the catalyst did not change significantly, showing good stability.
  • Tetraethylammonium chloride is used as the first template agent, aluminum phosphate is the first aluminum source, water glass is the silicon source, sodium hydroxide is the first alkali source, tetraethylammonium chloride is calculated as NH 4 + , aluminum phosphate
  • the second aluminum source sodium metaaluminate after removing the first aluminum source, and the second
  • the template agent and the second aluminum source are added with the second template agent hexamethylenediamine at a ratio of NH 4 + /Al 2 O 3 molar ratio of 200:1, fully mixed with the above crystallization solution, and adjusted with the second alkali source sodium hydroxide
  • the pH was 10, and then transferred to a stainless steel autoclave for the second hydrothermal crystallization at 120°C for 100h.
  • the synthesized product was washed with water, dried at 100°C for 10 hours, and calcined at 650°C for 8 hours to obtain ZSM-5 molecular sieve powder.
  • triethylamine Take triethylamine as the third template agent, pre-add the mixture of 50g triethylamine and 50g distilled water in the reactor, place the above-mentioned strip catalyst precursor of 50g above the porous stainless steel mesh in the reactor and seal it at 130 The crystallization was carried out at °C for 100 h. After the product was taken out, it was washed with distilled water, dried at 80°C for 20h, and then baked at 500°C for 8h in an air atmosphere.
  • the obtained hydrogen-form ZSM-5 molecular sieve solid was immersed in 20 g of La lanthanum nitrate solution with a mass content of 5% for 10 h, dried at 100° C. for 12 h, and calcined at 500° C. for 10 h.
  • the above solid was immersed in 20 grams of barium nitrate solution with a mass content of 0.5% Ba for 10 hours, dried at 100° C., and calcined at 500° C. for 10 hours to obtain the catalyst.
  • the XRD pattern of the obtained catalyst is similar to that shown in Figure 2, indicating that the catalyst is a ZSM-5 molecular sieve catalyst, and the binder content is lower than 0.2%.
  • the total pore volume of the catalyst is 0.1mL/g, and the micropore pore volume accounts for 70% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 2:1.
  • the catalyst has a SiO 2 /Al 2 O 3 molar ratio of 96.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the conversion rate of carbon tetraolefins is 71%, the hydrogen transfer index is 5.6%, and the selectivity of propylene and ethylene is 80.3%. The catalyst reacted for 78 hours, and the activity and selectivity of the catalyst did not change significantly, showing good stability.
  • Ammonia water is used as the first template agent, aluminum nitrate is the first aluminum source, tetraethyl orthosilicate is the silicon source, sodium hydroxide is the first alkali source, ammonia water is calculated as NH4 + , aluminum nitrate is calculated as Al2O3 ,
  • the molar ratio of SiO 2 /Al 2 O 3 is 500
  • the second aluminum source potassium aluminum sulfate after removing the first aluminum source is added
  • the second template Add the second template agent pyridine to the second aluminum source at a molar ratio of NH 4 + /Al 2 O 3 of 400:1, mix well with the above crystallization solution, and adjust the pH to 8 with the second alkali source sodium hydroxide , and then transferred to a stainless steel autoclave for the second hydrothermal crystallization at 180°C for 20h.
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • hexamethylenediamine As the third template, add 50 grams of hexamethylenediamine and 30 grams of distilled water in advance in the reaction kettle, and place 20 grams of the strip-shaped catalyst precursor prepared above in the reaction kettle for sealing above the porous stainless steel mesh Afterwards, crystallization was performed at 150° C. for 80 h. After the product was taken out, it was washed with distilled water, dried at 100°C for 10 hours, and then baked at 600°C for 5 hours in an air atmosphere.
  • the obtained hydrogen-form ZSM-5 molecular sieve solid was immersed in 20 g of praseodymium nitrate solution with a mass content of 1% of Pr for 5 hours, dried at 60° C. for 20 hours, and calcined at 600° C. for 8 hours.
  • the above solid is placed in 20 grams of strontium nitrate solution with a Sr weight content of 0.3% for 10 hours, dried at 100° C., and calcined at 500° C. for 10 hours to obtain the catalyst.
  • the XRD pattern of the obtained catalyst is similar to that shown in Figure 2, indicating that the catalyst is a ZSM-5 molecular sieve catalyst, and the binder content is lower than 0.2%.
  • the total pore volume of the catalyst is 0.6mL/g, and the micropore pore volume accounts for 83% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 1.8:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 488.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the conversion rate of carbon tetraolefins is 76.5%, the hydrogen transfer index is 5.1%, and the selectivity of propylene and ethylene is 83.9%. Catalyst reacted for 80h, the catalyst activity and selectivity did not change significantly, and had good stability.
  • Adopt the catalyzer of embodiment 8 take the pentene (nitrogen and pentene volume ratio 1: 1) that is diluted with nitrogen as raw material, the prepared catalyst has been carried out olefin catalytic cracking to produce propylene and ethylene reactivity evaluation, the process condition used for investigation is : The catalyst is loaded with 5 grams, the reaction temperature is 580°C, the reaction pressure is 0.3MPa, and the weight space velocity is 40h -1 . The reaction results are as follows: the conversion rate of carbon pentaolefins is 80%, the hydrogen transfer index is 5.3%, the selectivity of propylene and ethylene is 82.8%, and the catalyst has been reacted for 78 hours. The activity and selectivity of the catalyst have not changed significantly, and the catalyst has good stability.
  • Adopt the catalyzer of embodiment 8 take the hexene (nitrogen and hexene volume ratio 1: 1) diluted with nitrogen as raw material, the prepared catalyst has been carried out olefin catalytic cracking to produce propylene and ethylene reactivity evaluation, and the technological condition used for investigation is: The catalyst is packed in 5 grams, the reaction temperature is 420°C, the reaction pressure is 0.01MPa, and the weight space velocity is 2h -1 . The reaction results are: the conversion rate of carbon hexaene is 72%, the hydrogen transfer index is 6.8%, and the selectivity of propylene and ethylene is 80.3%. The catalyst reacted for 76 hours, and the activity and selectivity of the catalyst did not change significantly, showing good stability.
  • Tetrapropylammonium bromide is used as template, aluminum nitrate is used as aluminum source, silica sol is used as silicon source, sodium hydroxide is used as alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate is calculated as Al 2 O 3
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • ethylamine Take ethylamine as the third template agent, add the mixture of 30 grams of ethylamine and 30 grams of distilled water in advance in the reaction kettle, place 20 grams of the above-mentioned strip catalyst precursors prepared above the porous stainless steel mesh in the reaction kettle and seal it at 130
  • the gas-solid phase hydrothermal crystallization was carried out at °C for 100 h. After the product was taken out, it was washed with distilled water, dried at 90°C for 15h, and then calcined at 550°C for 10h in an air atmosphere.
  • ammonium was exchanged in 5wt% ammonium nitrate solution at 90°C for 3 times, and after drying, it was roasted in a muffle furnace at 500°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-form ZSM-5 molecular sieve solid was immersed in 20 g of praseodymium nitrate solution with a mass content of 1% of Pr for 10 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours.
  • the total pore volume of the catalyst is 0.6mL/g, and the micropore pore volume accounts for 68% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 1:1.
  • XRD is similar to Fig. 2, the binder content in this catalyst is less than 0.2%.
  • the catalyst evaluation method was the same as in Example 1, and the reaction results were as follows: carbon tetraolefin conversion rate 76%, hydrogen transfer index 9.2%, propylene and ethylene selectivity 69.3%, catalyst reaction 65h, catalyst activity and selectivity began to decline.
  • Tetrapropylammonium bromide is used as the first template, aluminum nitrate is the first aluminum source, silica sol is the silicon source, sodium hydroxide is the first alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate
  • the molar ratio of SiO 2 /Al 2 O 3 is 300, adding the second aluminum source aluminum nitrate after removing the first aluminum source, and the second templating agent Add the second templating agent n-butylamine with the aluminum source at a ratio of NH 4 + /Al 2 O 3 molar ratio of 200:1, fully mix with the above crystallization solution, adjust the pH to 10 with the second alkali source sodium hydroxide, It was then transferred to a stainless steel autoclave for the second hydrothermal crystallization at 120° C. for 100 h. The synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • ethylamine Take ethylamine as the third template agent, add the mixture of 30 grams of ethylamine and 30 grams of distilled water in advance in the reaction kettle, place 20 grams of the above-mentioned strip catalyst precursors prepared above the porous stainless steel mesh in the reaction kettle and seal it at 130
  • the gas-solid phase hydrothermal crystallization was carried out at °C for 100 h. After the product was taken out, it was washed with distilled water, dried at 90°C for 15h, and then calcined at 550°C for 10h in an air atmosphere.
  • ammonium was exchanged in 5wt% ammonium nitrate solution at 90°C for 3 times, and after drying, it was roasted in a muffle furnace at 500°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-type ZSM-5 molecular sieve solid was immersed in 20 g of Pr praseodymium nitrate solution with a weight content of 1% for 10 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours.
  • the total pore volume of the catalyst is 0.8mL/g, and the micropore pore volume accounts for 77% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 0.8:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 280.
  • XRD is similar to Fig. 2, the binder content in this catalyst is less than 0.2%.
  • Catalyst evaluation method is the same as that of Example 1, and the reaction results are: carbon tetraolefin conversion rate 72%, hydrogen transfer index 7.3%, selectivity of propylene and ethylene is 75.5%, catalyst reaction 70h, catalyst activity and selectivity begin to decline.
  • Tetrapropylammonium bromide is used as the first template, aluminum nitrate is the first aluminum source, silica sol is the silicon source, sodium hydroxide is the first alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate
  • the molar ratio of SiO 2 /Al 2 O 3 is 300, and the second aluminum source potassium aluminum sulfate dodecahydrate after removing the first aluminum source is added, Add the template agent tetrapropylammonium bromide with the second aluminum source at a ratio of NH 4 + /Al 2 O 3 molar ratio of 200:1, fully mix with the above crystallization solution, and adjust the pH with the second alkali source sodium hydroxide 10, and then transferred to a stainless steel autoclave for the second hydrothermal crystallization at 120 ° C for 100 h. The synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • ethylamine Take ethylamine as the third template agent, add the mixture of 30 grams of ethylamine and 30 grams of distilled water in advance in the reaction kettle, place 20 grams of the above-mentioned strip catalyst precursors prepared above the porous stainless steel mesh in the reaction kettle and seal at 130
  • the gas-solid phase hydrothermal crystallization was carried out at °C for 100 h. After the product was taken out, it was washed with distilled water, dried at 90°C for 15h, and then calcined at 550°C for 10h in an air atmosphere.
  • ammonium was exchanged in 5wt% ammonium nitrate solution at 90°C for 3 times, and after drying, it was roasted in a muffle furnace at 500°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-type ZSM-5 molecular sieve solid was immersed in 20 g of Pr praseodymium nitrate solution with a weight content of 1% for 10 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours.
  • the above solid was immersed in 20 grams of magnesium nitrate solution with a Mg weight content of 2% for 8 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours to obtain the catalyst.
  • the XRD pattern of the obtained catalyst is similar to that in Figure 2, indicating that the catalyst is a ZSM-5 molecular sieve catalyst.
  • the total pore volume of the catalyst is 0.28mL/g, and the micropore pore volume accounts for 73% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 1.2:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 285.
  • XRD is similar to Fig. 2, the binder content in this catalyst is less than 0.2%.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the carbon tetraolefin conversion rate is 69.8%, the hydrogen transfer index is 7.2%, the selectivity of propylene and ethylene is 71.8%, and the catalyst reacts for 72 hours, and the catalyst activity and selectivity begin to decline.
  • Tetrapropylammonium bromide is used as the first template, aluminum nitrate is the first aluminum source, silica sol is the silicon source, sodium hydroxide is the first alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate
  • the second aluminum source potassium aluminum sulfate dodecahydrate after removing the first aluminum source
  • the second template agent and the second aluminum source are added with the second template agent n-butylamine at a ratio of NH 4 + /Al 2 O 3 molar ratio of 200:1, fully mixed with the above crystallization solution, and then hydrogenated with the second alkali source Adjust the pH to 10 with sodium, then transfer to a stainless steel autoclave for the second hydrothermal crystallization, and crystallize at 120°C for 100h.
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • ethylamine Take ethylamine as the third template agent, add the mixture of 30 grams of ethylamine and 30 grams of distilled water in advance in the reaction kettle, place 20 grams of the above-mentioned strip catalyst precursors prepared above the porous stainless steel mesh in the reaction kettle and seal at 130
  • the gas-solid phase hydrothermal crystallization was carried out at °C for 100 h. After the product was taken out, it was washed with distilled water, dried at 90°C for 15h, and then calcined at 550°C for 10h in an air atmosphere.
  • ammonium was exchanged in 5wt% ammonium nitrate solution at 90°C for 3 times, and after drying, it was roasted in a muffle furnace at 500°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-form ZSM-5 molecular sieve solid was immersed in 20 g of praseodymium nitrate solution with a mass content of 1% of Pr for 10 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours.
  • the above solid was immersed in 20 grams of magnesium nitrate solution with a Mg weight content of 2% for 8 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours to obtain the catalyst.
  • the XRD pattern of the obtained catalyst is similar to that in Figure 2, indicating that the catalyst is a ZSM-5 molecular sieve catalyst.
  • the total pore volume of the catalyst is 0.3mL/g, and the micropore pore volume accounts for 80% of the total pore volume.
  • the ratio of the amount of skeleton aluminum at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 1.8:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 47.
  • XRD is similar to Fig. 2, the binder content in this catalyst is less than 0.2%.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: carbon tetraolefin conversion rate 68.6%, hydrogen transfer index 12.3%, propylene and ethylene selectivity 62.5%, catalyst reaction 72h, catalyst activity and selectivity began to decline.
  • Tetrapropylammonium bromide is used as the first template, aluminum nitrate is the first aluminum source, silica sol is the silicon source, sodium hydroxide is the first alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate
  • the molar ratio of SiO 2 /Al 2 O 3 is 300, and the second aluminum source potassium aluminum sulfate dodecahydrate after removing the first aluminum source is added,
  • the second template agent and the second aluminum source are added with the second template agent n-butylamine at a ratio of NH 4 + /Al 2 O 3 molar ratio of 200:1, fully mixed with the above crystallization solution, and then hydrogenated with the second alkali source Adjust the pH to 10 with sodium, then transfer to a stainless steel autoclave for the second hydrothermal crystallization, and crystallize at 120°C for 100h.
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • the above-mentioned ZSM-5 molecular sieve raw powder 100g, 25g silica sol containing 40wt% SiO 2 and 0.056g alumina were kneaded, extruded and dried at 80°C for 10h to obtain a catalyst precursor.
  • ammonium was exchanged in 5wt% ammonium nitrate solution at 90°C for 3 times, and after drying, it was roasted in a muffle furnace at 500°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-form ZSM-5 molecular sieve solid was immersed in 20 g of praseodymium nitrate solution with a mass content of 1% of Pr for 10 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours.
  • FIG. 4 is the XRD pattern of the catalyst obtained in Comparative Example 5, which shows that the catalyst is a ZSM-5 molecular sieve catalyst with a binder content of 10%.
  • the total pore volume of the catalyst is 0.1mL/g, and the micropore pore volume accounts for 68% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal tunnels to the amount of skeleton aluminum in straight and sinusoidal tunnels is 0.8:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 282.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the conversion rate of carbon tetraolefins is 65%, the hydrogen transfer index is 15.8%, and the selectivity of propylene and ethylene is 58.5%.
  • Tetrapropylammonium bromide is used as template, aluminum nitrate is used as aluminum source, silica sol is used as silicon source, sodium hydroxide is used as alkali source, tetrapropylammonium bromide is calculated as NH 4 + , aluminum nitrate is calculated as Al 2 O 3
  • the synthesized product was washed with water, dried at 90°C for 15 hours, and calcined at 600°C for 10 hours to obtain ZSM-5 molecular sieve powder.
  • the above-mentioned ZSM-5 molecular sieve raw powder 100g, 25g silica sol containing 40wt% SiO 2 and 0.056g alumina were kneaded, extruded and dried at 80°C for 10h to obtain a catalyst precursor.
  • ammonium was exchanged in 5wt% ammonium nitrate solution at 90°C for 3 times, and after drying, it was roasted in a muffle furnace at 500°C for 4 hours to obtain hydrogen ZSM-5 molecular sieve.
  • the obtained hydrogen-form ZSM-5 molecular sieve solid was immersed in 20 g of praseodymium nitrate solution with a mass content of 1% of Pr for 10 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours.
  • the above solid was immersed in 20 grams of magnesium nitrate solution with a Mg weight content of 2% for 8 hours, dried at 100° C. for 10 hours, and calcined at 550° C. for 8 hours to obtain the catalyst.
  • the XRD pattern of the obtained catalyst is similar to that shown in Figure 4, indicating that the catalyst is a ZSM-5 molecular sieve catalyst with a binder content of 10%.
  • the total pore volume of the catalyst is 0.13mL/g, and the micropore pore volume accounts for 62% of the total pore volume.
  • the ratio of the amount of skeleton aluminum located at the intersection of straight and sinusoidal channels to the amount of skeleton aluminum in straight and sinusoidal channels is 0.7:1.
  • the SiO 2 /Al 2 O 3 molar ratio of the catalyst is 280.
  • the catalyst evaluation method is the same as in Example 1, and the reaction results are as follows: the conversion rate of carbon tetraolefins is 62.5%, the hydrogen transfer index is 16.9%, and the selectivity of propylene and ethylene is 53.5%.
  • the ZSM-5 molecular sieve catalyst of the present invention has a significantly higher ratio of the amount of framework aluminum located at the intersection of straight and sinusoidal channels to the amount of framework aluminum in straight and sinusoidal channels than conventional catalysts.

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CN119488946A (zh) * 2023-08-18 2025-02-21 中国石油化工股份有限公司 3d打印分子筛催化剂的制备方法及制备得到的3d打印分子筛催化剂与应用
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CN119657212B (zh) * 2023-09-21 2025-11-25 中国石油化工股份有限公司 一种丁烯裂解制乙烯和丙烯催化剂及其制备方法和应用
CN117563658B (zh) * 2023-11-21 2025-12-12 中国石油大学(北京) 提高催化裂解产物中乙烯丙烯比的zsm-5分子筛改性方法及其所得的分子筛和应用

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CN119488946A (zh) * 2023-08-18 2025-02-21 中国石油化工股份有限公司 3d打印分子筛催化剂的制备方法及制备得到的3d打印分子筛催化剂与应用
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