CN111068752A - MFI structure molecular sieve rich in mesopores and preparation method thereof - Google Patents

MFI structure molecular sieve rich in mesopores and preparation method thereof Download PDF

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CN111068752A
CN111068752A CN201910122645.5A CN201910122645A CN111068752A CN 111068752 A CN111068752 A CN 111068752A CN 201910122645 A CN201910122645 A CN 201910122645A CN 111068752 A CN111068752 A CN 111068752A
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molecular sieve
treatment
ammonium
content
roasting
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CN111068752B (en
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罗一斌
欧阳颖
庄立
刘建强
李明罡
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to JP2021521117A priority Critical patent/JP7482120B2/en
Priority to KR1020217015115A priority patent/KR20210066930A/en
Priority to EP19872554.1A priority patent/EP3868711A4/en
Priority to PCT/CN2019/111725 priority patent/WO2020078434A1/en
Priority to SG11202104004SA priority patent/SG11202104004SA/en
Priority to US17/286,747 priority patent/US11975980B2/en
Priority to TW108137638A priority patent/TWI822885B/en
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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
    • 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
    • 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
    • B01J35/651—50-500 nm
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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

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Abstract

The invention relates to a kind of foodMFI structure molecular sieve containing mesopores, preparation method thereof and n (SiO) of molecular sieve2)/n(Al2O3) Greater than 15 and less than 70; with P2O5The phosphorus content of the molecular sieve is 1-15 wt% based on the dry weight of the molecular sieve; the content of the supported metal in the molecular sieve is 1-10 wt% based on the oxide of the supported metal and the dry weight of the molecular sieve, wherein the supported metal is selected from one or two of lanthanum and cerium; the proportion of the volume of mesopores of the molecular sieve to the total pore volume is 40-70% by volume, the volume of mesopores and the total pore volume of the molecular sieve are measured by a nitrogen adsorption BET specific surface area method, and the volume of mesopores is the pore volume with the pore diameter of more than 2 nanometers and less than 100 nanometers. The molecular sieve provided by the invention has better ethylene selectivity in the catalytic cracking reaction of petroleum hydrocarbon.

Description

MFI structure molecular sieve rich in mesopores and preparation method thereof
Technical Field
The invention relates to an MFI structure molecular sieve rich in mesopores and a preparation method thereof.
Background
Since the 21 st century, the rapid progress of crude oil price fluctuation and technology has promoted the development of the global petrochemical industry toward the diversification of raw materials and low cost, particularly the rapid expansion of petrochemical production energy in areas rich in middle east light hydrocarbon resources, the development of north american shale gas and the chinese coal chemical industry, etc., which has brought a huge impact on the traditional petrochemical industry using naphtha as raw material, and the large-scale marketization of ethane-to-ethylene technology has also made the steam cracking of naphtha to produce low-carbon olefins challenging. In contrast, the conventional naphtha route for ethylene production has high cash cost and poor cost competitiveness, and thus development of competitive chemical raw material production technology is receiving attention.
The cracking reaction of hydrocarbons at high temperature is an important process for converting long-chain hydrocarbons into short-chain hydrocarbons with high added value, especially low-carbon olefins and gasoline. Generally, the cracking of hydrocarbons can be classified into a carbonium ion mechanism (catalytic cracking) and a radical mechanism (steam cracking) according to the mechanism. The carbonium ion mechanism needs to be capable of occurring under the action of an acid catalyst, the required reaction temperature is relatively low, the cracking product takes propylene as a characteristic product, the free radical mechanism generally reacts under the condition of thermal initiation, and the cracking product takes ethylene as a characteristic product. In fact, hydrocarbons undergo both carbonium and free radical reactions under catalytic cracking reaction conditions. However, the reaction temperature is low, the initiation speed of free radicals is low, the reaction process is mainly based on the carbonium ion reaction, the yield of propylene is high, the yield of ethylene is low, and the ethylene/propylene ratio in the product cannot be finely and freely regulated in a large range at present.
The catalytic thermal cracking of ethylene is a new way to increase the yield of ethylene. The traditional method for preparing ethylene by steam cracking has the defects of high cracking temperature, strict requirements on raw materials and the like. It is believed that the steam cracking process produces ethylene by a radical reaction mechanism, and therefore the reaction temperature is high. In the catalytic thermal cracking catalyst for producing light olefins in high yield, ZSM-5 molecular sieve is generally used as the active component, and the molecular sieve property is adjusted to mainly increase the yield of C3-C5-olefins, so that the ethylene yield is not very high.
CN1072032C discloses a molecular sieve composition for catalytic cracking to produce ethylene and propylene in high yield, which is prepared from SiO2/Al2O3The molar ratio is 15-60The five-membered ring molecular sieve is prepared by activating and modifying P, alkaline earth metal and transition metal. P of modified molecular sieve2O52 to 10 wt%, 0.3 to 5 wt% of an alkaline earth metal oxide, and 0.3 to 5 wt% of a transition metal oxide. The structure and active center of the molecular sieve have high thermal and hydrothermal stability.
CN1147420A discloses a molecular sieve containing phosphorus and rare earth and having MFI structure, and the anhydrous chemical composition of the molecular sieve is aRE2O3bNa2OAl2O3cP2O5dSiO2Wherein a is 0.01 to 0.25, b is 0.005 to 0.02, c is 0.2 to 1.0, and d is 35 to 120. The molecular sieve has excellent hydrothermal activity stability and good low-carbon olefin selectivity when being used for high-temperature conversion of hydrocarbons.
In the prior art, the effect of modulating the properties of the molecular sieve is mostly concentrated on the improvement of the yield and the selectivity of propylene and butylene, and the effect of improving the yield and the selectivity of ethylene is not obvious enough.
Disclosure of Invention
The invention aims to provide an MFI structure molecular sieve rich in mesopores and a preparation method thereof, and the molecular sieve provided by the invention has better ethylene selectivity in the catalytic cracking reaction of petroleum hydrocarbon.
In order to achieve the aim, the invention provides an MFI structure molecular sieve rich in mesopores, and n (SiO) of the molecular sieve2)/n(Al2O3) Greater than 15 and less than 70; with P2O5The phosphorus content of the molecular sieve is 1-15 wt% based on the dry weight of the molecular sieve; the content of the supported metal in the molecular sieve is 1-10 wt% based on the oxide of the supported metal and the dry weight of the molecular sieve, wherein the supported metal is selected from one or two of lanthanum and cerium; the proportion of the volume of mesopores of the molecular sieve to the total pore volume is 40-70% by volume, the volume of mesopores and the total pore volume of the molecular sieve are measured by a nitrogen adsorption BET specific surface area method, and the volume of mesopores is the pore volume with the pore diameter of more than 2 nanometers and less than 100 nanometers.
Optionally, the RE distribution parameter D of the molecular sieve satisfies: d is more than or equal to 0.9 and less than or equal to 1.1, wherein D is RE (S)/RE (C), RE (S) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the edge of a crystal face of the molecular sieve crystal grain to the inside H by adopting a TEM-EDS method, RE (C) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the geometric center of the crystal face of the molecular sieve crystal grain to the outside H by adopting the TEM-EDS method, and H is 10 percent of the distance from a certain point of the edge of the crystal face to the geometric center of the crystal face.
Optionally, n (SiO) of the molecular sieve2)/n(Al2O3) Greater than 18 and less than 60; with P2O5The phosphorus content of the molecular sieve is 3-12 wt% based on the dry weight of the molecular sieve; the content of the loaded metal in the molecular sieve is 3-8 wt% based on the oxide of the loaded metal and the dry basis weight of the molecular sieve; the molecular sieve has a mesopore volume fraction of 45-65% by volume of the total pore volume.
The invention also provides a preparation method of the MFI structure molecular sieve rich in mesopores, which comprises the following steps:
a. filtering and washing the crystallized MFI structure molecular sieve slurry to obtain a water-washed molecular sieve; wherein the sodium content of the washed molecular sieve is less than 5 wt% based on the total dry basis weight of the washed molecular sieve calculated as sodium oxide;
b. b, desiliconizing the washed molecular sieve obtained in the step a in an alkaline solution, and filtering and washing to obtain an alkaline washed molecular sieve;
c. b, performing ammonium exchange treatment on the alkali washing molecular sieve obtained in the step b to obtain an ammonium exchange molecular sieve; wherein the ammonium exchanged molecular sieve has a sodium content of less than 0.2 wt.%, based on sodium oxide and based on total dry basis weight of the ammonium exchanged molecular sieve;
d. and c, carrying out phosphorus modification treatment, loading treatment of loaded metal and roasting treatment on the ammonium exchange molecular sieve obtained in the step c to obtain the MFI structure molecular sieve rich in mesopores.
Optionally, the step d is selected from one or more of the following modes:
mode (1): c, simultaneously carrying out the phosphorus modification treatment and the loading treatment of the loaded metal on the ammonium exchange molecular sieve obtained in the step c, and then carrying out the roasting treatment;
mode (2): c, sequentially carrying out loading treatment on the loaded metal, roasting treatment in a steam atmosphere, phosphorus modification treatment and roasting treatment in an air atmosphere on the ammonium exchange molecular sieve obtained in the step c;
mode (3): c, sequentially carrying out loading treatment, phosphorus modification treatment and roasting treatment on the loaded metal on the ammonium exchange molecular sieve obtained in the step c;
mode (4): and c, sequentially carrying out the phosphorus modification treatment, the roasting treatment in the air atmosphere, the loading treatment of the loaded metal and the roasting treatment in the steam atmosphere on the ammonium exchange molecular sieve obtained in the step c.
Optionally, the MFI structure molecular sieve in the MFI structure molecular sieve slurry obtained by crystallization is a ZSM-5 molecular sieve, and the silica-alumina ratio is less than 80.
Optionally, if the MFI structure molecular sieve slurry obtained by crystallization is prepared by a template method, step b further includes: and drying and roasting the washed molecular sieve to remove the template agent, and then carrying out desiliconization treatment.
Optionally, in step b, the alkali in the alkali solution is sodium hydroxide and/or potassium hydroxide.
Optionally, in step b, the conditions of the desiliconization treatment include: the weight ratio of alkali to water in the molecular sieve and the alkali solution is 1: (0.1-2): (5-15) the temperature is between room temperature and 100 ℃, and the time is 0.2-4 hours.
Optionally, in step c, the ammonium exchange treatment conditions include: the weight ratio of the molecular sieve, the ammonium salt and the water on a dry basis is 1: (0.1-1): (5-10) the temperature is between room temperature and 100 ℃, and the time is 0.2-4 hours.
Optionally, the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
Optionally, in step d, the phosphorus modification treatment includes: impregnating and/or ion-exchanging the molecular sieve with at least one phosphorus-containing compound selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate;
the loading treatment of the loaded metal comprises: loading a compound containing a supported metal onto the molecular sieve by impregnation and/or ion exchange one or more times;
the roasting treatment conditions comprise: the atmosphere is air atmosphere and/or water vapor atmosphere, the roasting temperature is 400-800 ℃, and the roasting temperature is 0.5-8 hours.
The inventor of the invention unexpectedly finds that the MFI structure molecular sieve containing phosphorus and rare earth prepared by desiliconizing the MFI structure molecular sieve by a chemical method, washing sodium and then carrying out phosphorus modification treatment and metal loading treatment can be applied to catalytic cracking and catalytic cracking processes and can be used as an active component of a catalyst or an auxiliary agent.
The MFI structure molecular sieve subjected to desiliconization provided by the invention has a rich mesoporous structure, is beneficial to the migration of rare earth into molecular sieve pore channels, and strengthens the synergistic effect of the rare earth and the acid center of the molecular sieve.
The modified MFI structure molecular sieve provided by the invention has the characteristics of strong cracking capability, good shape-selective performance, high ethylene yield and high ethylene selectivity.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a MFI structure molecular sieve rich in mesopores, and n (SiO) of the molecular sieve2)/n(Al2O3) Greater than 15 and less than 70; with P2O5The phosphorus content of the molecular sieve is 1-15 wt% based on the dry weight of the molecular sieve; the content of the supported metal in the molecular sieve is 1-10 wt% based on the oxide of the supported metal and the dry weight of the molecular sieve, wherein the supported metal is selected from one or two of lanthanum and cerium; mesopore volume of the molecular sieveThe proportion of the total pore volume is 40-70% by volume, and the mesopore volume and the total pore volume of the molecular sieve are measured by a nitrogen adsorption BET specific surface area method, wherein the mesopore volume is the pore volume with the pore diameter of more than 2 nanometers and less than 100 nanometers. Preferably, n (SiO) of the molecular sieve2)/n(Al2O3) Greater than 18 and less than 60; with P2O5The phosphorus content of the molecular sieve is 3-12 wt% based on the dry weight of the molecular sieve; the content of the loaded metal in the molecular sieve is 3-8 wt% based on the oxide of the loaded metal and the dry basis weight of the molecular sieve; the molecular sieve has a mesopore volume fraction of 45-65% by volume of the total pore volume.
The invention carries out modification research on the molecular sieve catalytic material, improves the performance of promoting free radical reaction, and realizes the purpose of modulating cracking activity and product distribution by modulating the proportion of a carbonium ion route and a free radical route at the catalytic cracking temperature so as to improve the yield and selectivity of ethylene.
According to the invention, the RE distribution parameter D of the molecular sieve preferably satisfies: d is more than or equal to 0.9 and less than or equal to 1.1, wherein D is RE (S)/RE (C), RE (S) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the edge of a crystal face of the molecular sieve crystal grain to the inside H by adopting a TEM-EDS method, RE (C) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the geometric center of the crystal face of the molecular sieve crystal grain to the outside H by adopting the TEM-EDS method, and H is 10 percent of the distance from a certain point of the edge of the crystal face to the geometric center of the crystal face. The molecular sieve pore passages with RE distribution parameter D satisfying the range have more rare earth, thereby improving the yield of ethylene, propylene and BTX.
According to the molecular sieve of the invention, the determination of the rare earth content of the molecular sieve by using a TEM-EDS method is well known by those skilled in the art, wherein the geometric center is also well known by those skilled in the art and can be obtained by calculation according to a formula, which is not repeated in the invention, the geometric center of a general symmetrical graph is an intersection point of connecting lines of all relative vertexes, for example, the geometric center of a hexagonal crystal face of a conventional hexagonal plate-shaped ZSM-5 is at an intersection point of three relative vertexes.
The invention also provides a preparation method of the MFI structure molecular sieve rich in mesopores, which comprises the following steps:
a. filtering and washing the crystallized MFI structure molecular sieve slurry to obtain a water-washed molecular sieve; wherein the sodium content of the washed molecular sieve is less than 5 wt% based on the total dry basis weight of the washed molecular sieve calculated as sodium oxide;
b. b, desiliconizing the washed molecular sieve obtained in the step a in an alkaline solution, and filtering and washing to obtain an alkaline washed molecular sieve;
c. b, performing ammonium exchange treatment on the alkali washing molecular sieve obtained in the step b to obtain an ammonium exchange molecular sieve; wherein the ammonium exchanged molecular sieve has a sodium content of less than 0.2 wt.%, based on sodium oxide and based on total dry basis weight of the ammonium exchanged molecular sieve;
d. and c, carrying out phosphorus modification treatment, loading treatment of loaded metal and roasting treatment on the ammonium exchange molecular sieve obtained in the step c to obtain the MFI structure molecular sieve rich in mesopores.
According to the invention, said step d may be selected in one or more of the following ways:
mode (1): and c, simultaneously carrying out the phosphorus modification treatment and the loading treatment of the loaded metal on the ammonium exchange molecular sieve obtained in the step c, and then carrying out the roasting treatment.
Mode (2): and c, sequentially carrying out loading treatment on the loaded metal, roasting treatment in a steam atmosphere, phosphorus modification treatment and roasting treatment in an air atmosphere on the ammonium exchange molecular sieve obtained in the step c. By adopting the method, more rare earth can be contained in the pore canal of the molecular sieve, thereby improving the yield of ethylene, propylene and BTX.
Mode (3): and c, sequentially carrying out loading treatment of the loaded metal, phosphorus modification treatment and roasting treatment on the ammonium exchange molecular sieve obtained in the step c.
Mode (4): and c, sequentially carrying out the phosphorus modification treatment, the roasting treatment in the air atmosphere, the loading treatment of the loaded metal and the roasting treatment in the steam atmosphere on the ammonium exchange molecular sieve obtained in the step c.
According to the present invention, the MFI structure molecular sieve slurry obtained by crystallization is well known to those skilled in the art, and may be obtained by amine-free crystallization, or may be a molecular sieve slurry prepared by a template method, for example, the MFI structure molecular sieve in the MFI structure molecular sieve slurry obtained by crystallization is a ZSM-5 molecular sieve, and the silica-alumina ratio is less than 80. If the MFI structure molecular sieve slurry obtained by the crystallization is prepared by a template method, step b may further include: the desiliconization treatment is carried out after the washed molecular sieve is dried and calcined to remove the template agent, and the drying and calcining temperature is well known to those skilled in the art and is not described in detail.
According to the present invention, the alkaline solution in step b is well known to the person skilled in the art, for example the base in said alkaline solution may be an inorganic base, such as sodium hydroxide and/or potassium hydroxide. The conditions of the desiliconization treatment may include: the weight ratio of alkali to water in the molecular sieve and the alkali solution is 1: (0.1-2): (5-15) the temperature is between room temperature and 100 ℃, and the time is 0.2-4 hours.
According to the present invention, the ammonium exchange treatment in step c is well known to those skilled in the art, for example, the conditions of the ammonium exchange treatment include: the weight ratio of the molecular sieve, the ammonium salt and the water on a dry basis is 1: (0.1-1): (5-10) at room temperature to 100 ℃ for 0.2-4 hours, and the ammonium salt may be a commonly used inorganic ammonium salt, for example, one or more selected from ammonium chloride, ammonium sulfate and ammonium nitrate. The phosphorus modification treatment is for loading phosphorus in the molecular sieve, and may include, for example: at least one phosphorus-containing compound selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate is impregnated and/or ion-exchanged with the molecular sieve. The phosphorus modification treatment and the supporting treatment may be performed together or separately.
According to the invention, in step d, the loading treatment is used for loading a metal in the molecular sieve, for example, the loading treatment of the loaded metal may comprise: loading the supported metal on the molecular sieve by impregnating and/or ion-exchanging a compound containing the supported metal once or in multiple times.
According to the invention, in step d, the calcination treatment is well known to the person skilled in the art, for example the conditions of said calcination treatment include: the atmosphere is air atmosphere and/or water vapor atmosphere, the roasting temperature is 400-800 ℃, and the roasting temperature is 0.5-8 hours.
The present invention will be further illustrated by the following examples, but the present invention is not limited thereto, and the instruments and reagents used in the examples of the present invention are those commonly used by those skilled in the art unless otherwise specified.
The influence of the molecular sieve on the yield, selectivity and BTX yield of the low-carbon olefin in the catalytic cracking of the petroleum hydrocarbon is evaluated by adopting heavy oil micro-reaction. Preparing a microspherical catalyst by taking a molecular sieve as an active component, wherein the content of the molecular sieve is 30 percent by weight, the balance is kaolin and an adhesive, carrying out aging treatment on a prepared catalyst sample on a fixed bed aging device at 800 ℃ and 100 percent of water vapor for 17 hours, and carrying out micro-reverse evaluation on heavy oil, wherein the raw material oil is VGO, the evaluation conditions are that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃ and the weight ratio of the catalyst to the oil is 3.2.
The crystallinity of the process of the invention is determined using the standard method of ASTM D5758-2001(2011) e 1.
N (SiO) of the process of the invention2)/n(Al2O3) Namely, the silicon-aluminum ratio is calculated by the contents of silicon oxide and aluminum oxide, and the contents of the silicon oxide and the aluminum oxide are measured by the GB/T30905-2014 standard method.
The phosphorus content of the method is determined by adopting a GB/T30905-2014 standard method, and the content of the load metal is determined by adopting the GB/T30905-2014 standard method.
The specific surface area of the method of the invention is determined using the GB5816 standard method.
The pore volume of the process of the invention is determined using the GB5816 standard method.
The sodium content of the method is determined by adopting the GB/T30905-2014 standard method.
The micro-inversion rate of the method of the present invention is measured by the ASTM D5154-2010 standard method.
The D value is calculated as follows: selecting a crystal grain and a certain crystal face of the crystal grain in a transmission electron mirror to form a polygon, wherein the polygon has a geometric center, an edge and a 10% distance H from the geometric center to the edge (different edge points and different H values), respectively selecting any one of regions in the inward H distance of the edge of the crystal face which is larger than 100 square nanometers and any one of regions in the outward H distance of the geometric center of the crystal face which is larger than 100 square nanometers, measuring the rare earth content (if two kinds of rare earth exist, measuring the total rare earth content), namely RE (S1) and RE (C1), calculating D1 to RE (S1)/RE (C1), respectively selecting different crystal grains to measure for 5 times, and calculating the average value to be D.
Example 1
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 9.7g of H3PO4(concentration 85% by weight) and 8.1gLa (NO)3)3·6H2And O, uniformly mixing, soaking, drying and roasting at 550 ℃ in an air atmosphere for 2 hours. Molecular sieve a was obtained and the physicochemical properties, ethylene yield, propylene yield and BTX yield data are presented in table 1.
Example 2
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, and quicklyAfter cooling to room temperature, filtration and washing were carried out until the filtrate was neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 5.8g of H3PO4(concentration 85% by weight) and 4.9gCe (NO)3)2·6H2And O, uniformly mixing, soaking, drying and roasting at 550 ℃ in an air atmosphere for 2 hours. Molecular sieve B was obtained and the physicochemical properties, micro-reverse evaluation of ethylene yield, propylene yield and BTX yield data are listed in table 1.
Example 3
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 11.6g of H3PO4(concentration 85% by weight), 8.1gLa (NO)3)3·6H2O and 4.9gCe (NO)3)2·6H2And O, uniformly mixing, soaking, drying and roasting at 550 ℃ in an air atmosphere for 2 hours. Molecular sieve C was obtained and the physicochemical properties, ethylene yield, propylene yield and BTX yield data are presented in Table 1.
Example 4
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2O content (in order)Dry basis) less than 5.0 wt%, filtering to obtain filter cake; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 5.8g of H3PO4(concentration 85% by weight) and 3.3gCe (NO)3)2·6H2And O, uniformly mixing, soaking, drying and roasting at 550 ℃ in an air atmosphere for 2 hours. Molecular sieve D was obtained and the physicochemical properties, micro-reverse evaluation of ethylene yield, propylene yield and BTX yield data are listed in table 1.
Example 5
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 5.8g of H3PO4(concentration 85% by weight) and 14.7gCe (NO)3)2·6H2And O, uniformly mixing, soaking, drying and roasting at 550 ℃ in an air atmosphere for 2 hours. Molecular sieve E was obtained and the physicochemical properties, micro-reverse evaluation of ethylene yield, propylene yield and BTX yield data are listed in table 1.
Example 6
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method,n(SiO2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 8.1gLa (NO)3)3·6H2O, uniformly mixing, soaking, drying and roasting at 550 ℃ in a steam atmosphere for 2 hours; adding water into the molecular sieve, pulping to obtain molecular sieve slurry with the solid content of 40 wt%, adding 9.7g H3PO4(concentration 85 wt.%) are mixed, dipped, dried and baked at 550 deg.C in air atmosphere for 2 h. Molecular sieve A-1 was obtained and the physicochemical properties, ethylene yield, propylene yield and BTX yield data are presented in Table 2.
Example 7
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 4.9gCe (NO)3)2·6H2O, uniformly mixing, soaking, drying and roasting at 550 ℃ in a steam atmosphere for 2 hours; adding water into the molecular sieve and pulping to obtain the product with the solid content of 40 weight percentMolecular sieve slurry, 5.8g H is added3PO4(concentration 85 wt.%) are mixed, dipped, dried and baked at 550 deg.C in air atmosphere for 2 h. Molecular sieve B-1 was obtained and the physicochemical properties, ethylene yield, propylene yield and BTX yield data are presented in Table 2.
Example 8
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 8.1gLa (NO)3)3·6H2O and 4.9gCe (NO)3)2·6H2O, uniformly mixing, soaking, drying and roasting at 550 ℃ in a steam atmosphere for 2 hours; adding water into the molecular sieve, pulping to obtain molecular sieve slurry with the solid content of 40 wt%, adding 11.6g H3PO4(concentration 85 wt.%) are mixed, dipped, dried and baked at 550 deg.C in air atmosphere for 2 h. Molecular sieve C-1 was obtained and the physicochemical properties, micro-reverse evaluation of ethylene yield, propylene yield and BTX yield data are shown in Table 2.
Example 9
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was beaten with 800g of waterSlurry, 40g NH added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 3.3gCe (NO)3)2·6H2O, uniformly mixing, soaking, drying and roasting at 550 ℃ in a steam atmosphere for 2 hours; adding water into the molecular sieve, pulping to obtain molecular sieve slurry with solid content of 40 wt%, adding 5.8g H3PO4(concentration 85 wt.%) were mixed, dipped, dried, and then calcined at 550 deg.C in air for 2h to obtain molecular sieve D-1. Physicochemical properties, slightly adverse evaluation ethylene yield, propylene yield and BTX yield data are presented in table 2.
Example 10
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 14.7gCe (NO)3)2·6H2O, uniformly mixing, soaking, drying and roasting at 550 ℃ in a steam atmosphere for 2 hours; adding water into the molecular sieve, pulping to obtain molecular sieve slurry with solid content of 40 wt%, adding 5.8g H3PO4(concentration 85 wt.%) are mixed, dipped, dried and baked at 550 deg.C in air atmosphere for 2 h. Molecular sieve E-1 was obtained and the physicochemical properties, micro-reverse evaluation of ethylene yield, propylene yield and BTX yield data are shown in Table 2.
Example 11
Crystallizing the ZSM-5 moleculesSieve (catalyst, produced by Ziru division, Aminoless Synthesis, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 8.1gLa (NO)3)3·6H2O, uniformly mixing, soaking and drying; adding water into the molecular sieve, pulping to obtain molecular sieve slurry with the solid content of 40 wt%, adding 9.7g H3PO4(concentration 85 wt.%) are mixed, dipped, dried and baked at 550 deg.C in air atmosphere for 2 h. Molecular sieve A-2 was obtained and the physicochemical properties, ethylene yield, propylene yield and BTX yield data are presented in Table 2.
Example 12
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 9.7g of H3PO4(the concentration is 85 weight percent), uniformly mixing, soaking, drying and roasting at 550 ℃ in air atmosphere for 2 hours; adding water into the molecular sieve and pulping to obtain the solid content of 408.1gLa (NO) was added to a weight percent molecular sieve slurry3)3·6H2And O, uniformly mixing, soaking, drying and roasting at 550 ℃ in a steam atmosphere for 2 hours. Molecular sieve A-3 was obtained and the physicochemical properties, ethylene yield, propylene yield and BTX yield data are presented in Table 2.
Comparative example 1
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) with NH4Cl exchange washing to Na2An O content (on a dry basis) of less than 0.2 wt.%; taking 50g (dry basis) of the molecular sieve, adding water, pulping to obtain molecular sieve pulp with the solid content of 40 weight percent, adding 7.7g H3PO4(concentration 85% by weight) and 8.1gLa (NO)3)3·6H2And O, uniformly mixing, soaking, drying and roasting at 550 ℃ in an air atmosphere for 2 hours. Molecular sieve D1 was obtained and the physicochemical properties, slightly reverse evaluated ethylene yield, propylene yield and BTX yield data are presented in table 1.
Comparative example 2
The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)2)/n(Al2O3) 27) the mother liquor was filtered off and washed with water to Na2The content of O (calculated by dry basis) is less than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added4Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na2The content of O (calculated by dry basis) is lower than 0.2 weight percent, and the molecular sieve filter cake is obtained after filtration and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 9.7g of H3PO4(concentration 85 wt.%) are mixed, dipped, dried and baked at 550 deg.C in air atmosphere for 2 h. Molecular sieve D2 was obtained and the physicochemical properties, slightly reverse evaluated ethylene yield, propylene yield and BTX yield data are presented in table 1.
As can be seen from the data in Table 1, the ZSM-5 molecular sieve rich in mesopores and modified by rare earth shows excellent property of producing more ethylene, while the ZSM-5 molecular sieve which is not modified by rare earth or modified by rare earth but not subjected to pore-expanding treatment has obviously lower ethylene yield.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the content of the present invention as long as it does not depart from the gist of the present invention.
TABLE 1
Item A B C D E D1 D2
Degree of crystallization/%) 51 53 50 53 50 51 65
n(SiO2)/n(Al2O3) 24 24 23 24 24 27 23
P2O5Content/% 10 6 12 6 6 8 10
Content of supported rare earth oxide/%) 5 3 8 2 9 5 0
SBET/(m2/g) 325 345 318 346 320 312 350
(VMesopores/VGeneral hole)/％ 56 62 50 61 58 18 60
RE distribution parameter D 1.27 1.25 1.29 1.21 1.34 2.78 -
Micro-inverse conversion/%) 86.97 86.47 86.62 86.55 86.54 85.98 86.18
Material balance/%
Dry gas 19.35 19.32 19.05 18.95 18.9 15.02 15.24
Liquefied gas 28.3 28.86 29.47 28.21 28.19 28.15 29.52
Gasoline (gasoline) 22.49 21.54 21.96 22.71 22.74 25.86 24.89
Diesel oil 9.42 9.57 9.49 9.54 9.51 10.05 10.09
Heavy oil 3.61 3.96 3.89 3.91 3.95 3.97 3.73
Coke 16.82 16.75 16.14 16.68 16.71 16.95 16.53
Ethylene yield 10.54 10.51 10.35 10.31 10.28 6.17 6.98
Propylene yield 15.53 15.35 15.98 15.14 15.11 14.89 15.95
BTX yield 9.81 9.78 9.67 9.56 9.55 8.14 9.13
TABLE 2
Item A-1 B-1 C-1 D-1 E-1 A-2 A-3
Degree of crystallization/%) 51 53 50 53 50 51 51
n(SiO2)/n(Al2O3) 24 24 23 24 24 24 24
P2O5Content/% 10 6 12 6 6 10 10
Content of supported rare earth oxide/%) 5 3 8 2 9 5 5
SBET/(m2/g) 332 349 323 351 328 325 325
(VMesopores/VGeneral hole)/％ 58 65 51 63 60 56 56
RE distribution parameter D 1.01 0.95 1.05 0.92 1.08 1.31 1.28
Micro-inverse conversion/%) 87.04 86.85 86.74 86.75 86.64 86.60 86.76
Material balance/%
Dry gas 20.54 20.49 20.21 20.13 19.95 19.02 19.17
Liquefied gas 29.08 29.02 29.53 28.98 29.01 29.21 29.00
Gasoline (gasoline) 20.91 20.71 20.41 21.03 21.1 22.12 22.17
Diesel oil 9.39 9.41 9.45 9.46 9.51 9.49 9.46
Heavy oil 3.57 3.74 3.81 3.79 3.85 3.90 3.78
Coke 16.51 16.63 16.59 16.61 16.58 16.25 16.41
Ethylene yield 11.46 11.41 11.28 11.23 11.21 10.34 10.43
Propylene yield 15.84 15.78 16.02 15.64 15.62 15.81 15.80
BTX yield 9.92 9.86 9.81 9.71 9.75 9.65 9.73

Claims (10)

1. An MFI structure molecular sieve rich in mesopores, n (SiO) of the molecular sieve2)/n(Al2O3) Greater than 15 and less than 70; with P2O5The phosphorus content of the molecular sieve is 1-15 wt% based on the dry weight of the molecular sieve; the content of the supported metal in the molecular sieve is 1-10 wt% based on the oxide of the supported metal and the dry weight of the molecular sieve, wherein the supported metal is selected from one or two of lanthanum and cerium; the ratio of the mesopore volume to the total pore volume of the molecular sieveFor example 40-70% by volume, the molecular sieve has a mesopore volume, i.e., a pore volume having a pore diameter greater than 2 nm and less than 100 nm, and a total pore volume, as measured by the nitrogen adsorption BET specific surface area method.
2. The MFI structure molecular sieve of claim 1, wherein the molecular sieve has an RE distribution parameter D that satisfies: d is more than or equal to 0.9 and less than or equal to 1.1, wherein D is RE (S)/RE (C), RE (S) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the edge of a crystal face of the molecular sieve crystal grain to the inside H by adopting a TEM-EDS method, RE (C) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the geometric center of the crystal face of the molecular sieve crystal grain to the outside H by adopting the TEM-EDS method, and H is 10 percent of the distance from a certain point of the edge of the crystal face to the geometric center of the crystal face.
3. The MFI structure molecular sieve of claim 1 or 2, wherein n (SiO) of the molecular sieve2)/n(Al2O3) Greater than 18 and less than 60; with P2O5The phosphorus content of the molecular sieve is 3-12 wt% based on the dry weight of the molecular sieve; the content of the loaded metal in the molecular sieve is 3-8 wt% based on the oxide of the loaded metal and the dry basis weight of the molecular sieve; the molecular sieve has a mesopore volume fraction of 45-65% by volume of the total pore volume.
4. A method of preparing the MFI structure molecular sieve enriched in mesopores of any of claims 1-3, comprising:
a. filtering and washing the crystallized MFI structure molecular sieve slurry to obtain a water-washed molecular sieve; wherein the sodium content of the washed molecular sieve is less than 5 wt% based on the total dry basis weight of the washed molecular sieve calculated as sodium oxide;
b. b, desiliconizing the washed molecular sieve obtained in the step a in an alkaline solution, and filtering and washing to obtain an alkaline washed molecular sieve;
c. b, performing ammonium exchange treatment on the alkali washing molecular sieve obtained in the step b to obtain an ammonium exchange molecular sieve; wherein the ammonium exchanged molecular sieve has a sodium content of less than 0.2 wt.%, based on sodium oxide and based on total dry basis weight of the ammonium exchanged molecular sieve;
d. and c, carrying out phosphorus modification treatment, loading treatment of loaded metal and roasting treatment on the ammonium exchange molecular sieve obtained in the step c to obtain the MFI structure molecular sieve rich in mesopores.
5. The method of claim 4, wherein step d is selected from one or more of the following:
mode (1): c, simultaneously carrying out the phosphorus modification treatment and the loading treatment of the loaded metal on the ammonium exchange molecular sieve obtained in the step c, and then carrying out the roasting treatment;
mode (2): c, sequentially carrying out loading treatment on the loaded metal, roasting treatment in a steam atmosphere, phosphorus modification treatment and roasting treatment in an air atmosphere on the ammonium exchange molecular sieve obtained in the step c;
mode (3): c, sequentially carrying out loading treatment, phosphorus modification treatment and roasting treatment on the loaded metal on the ammonium exchange molecular sieve obtained in the step c;
mode (4): and c, sequentially carrying out the phosphorus modification treatment, the roasting treatment in the air atmosphere, the loading treatment of the loaded metal and the roasting treatment in the steam atmosphere on the ammonium exchange molecular sieve obtained in the step c.
6. The process of claim 4 or 5, wherein the MFI structure molecular sieve in the MFI structure molecular sieve slurry obtained by the crystallization is a ZSM-5 molecular sieve and the silica-alumina ratio is less than 80.
7. The process of claim 4 or 5, wherein if the crystallized MFI structure molecular sieve slurry is prepared using a templating agent process, step b further comprises: and drying and roasting the washed molecular sieve to remove the template agent, and then carrying out desiliconization treatment.
8. The method according to claim 4 or 5, wherein in step b, the alkali in the alkali solution is sodium hydroxide and/or potassium hydroxide;
the conditions of the desiliconization treatment include: the weight ratio of alkali to water in the molecular sieve and the alkali solution is 1: (0.1-2): (5-15) the temperature is between room temperature and 100 ℃, and the time is 0.2-4 hours.
9. The method of claim 4 or 5, wherein in step c, the ammonium exchange treatment conditions comprise: the weight ratio of the molecular sieve, the ammonium salt and the water on a dry basis is 1: (0.1-1): (5-10), the temperature is between room temperature and 100 ℃, and the time is 0.2-4 hours;
the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
10. The method of claim 4 or 5, step d, the phosphorus modification treatment comprising: impregnating and/or ion-exchanging the molecular sieve with at least one phosphorus-containing compound selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate;
the loading treatment of the loaded metal comprises: loading a compound containing a supported metal onto the molecular sieve by impregnation and/or ion exchange one or more times;
the roasting treatment conditions comprise: the atmosphere is air atmosphere and/or water vapor atmosphere, the roasting temperature is 400-800 ℃, and the roasting temperature is 0.5-8 hours.
CN201910122645.5A 2018-10-18 2019-02-19 MFI structure molecular sieve rich in mesopores and preparation method thereof Active CN111068752B (en)

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KR1020217015115A KR20210066930A (en) 2018-10-18 2019-10-17 Mesopore-rich MFI structure molecular sieve, method for preparing same, catalyst containing same, and use thereof
EP19872554.1A EP3868711A4 (en) 2018-10-18 2019-10-17 Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof
PCT/CN2019/111725 WO2020078434A1 (en) 2018-10-18 2019-10-17 Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof
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