CN107970998B - Catalytic cracking auxiliary agent for increasing propylene yield and preparation method thereof - Google Patents

Catalytic cracking auxiliary agent for increasing propylene yield and preparation method thereof Download PDF

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CN107970998B
CN107970998B CN201610920655.XA CN201610920655A CN107970998B CN 107970998 B CN107970998 B CN 107970998B CN 201610920655 A CN201610920655 A CN 201610920655A CN 107970998 B CN107970998 B CN 107970998B
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molecular sieve
acid
phosphorus
aluminum
clay
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CN107970998A (en
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任飞
陈振宇
朱玉霞
田辉平
庄立
罗一斌
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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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  • General Chemical & Material Sciences (AREA)
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  • Silicates, Zeolites, And Molecular Sieves (AREA)
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Abstract

The catalytic cracking assistant for increasing the yield of propylene comprises, based on the dry weight of the assistant, 10-75 wt% of phosphorus-containing IMF structure molecular sieve, 3-40 wt% of phosphorus-aluminum inorganic binder, 1-30 wt% of other inorganic binders, and 0-60 wt% of second clay. When the auxiliary agent provided by the disclosure is used in a catalytic cracking process, the propylene yield and the propylene selectivity can be effectively improved.

Description

Catalytic cracking auxiliary agent for increasing propylene yield and preparation method thereof
Technical Field
The invention relates to a catalytic cracking auxiliary agent for increasing the yield of propylene and a preparation method thereof.
Background
Ethylene, propylene and butylene have long been the basic organic chemicals for synthetic resins, synthetic fibers and synthetic rubbers, with propylene being one of the next most important raw materials for the manufacture of petrochemicals than ethylene. The largest source of propylene at home and abroad is currently the major byproduct of ethylene production by thermal cracking, with the second largest source of propylene coming almost exclusively from FCC units, which provide about 30% of the demand, and in the united states, the FCC unit provides about half of the demand for propylene from petrochemicals.
The production of FCC propylene in large quantities will be used to meet the increasing demand due to the rapidly growing demand for polypropylene, which makes the demand for propylene faster than for ethylene, which is the limit of ethylene plant construction. Since the 80 s of the last century, catalysts containing shape selective molecular sieves ZSM-5 began to be put into industrial application on FCC devices, achieving the purpose of increasing yield C3 ＝However, the biggest weakness of such ZSM-5 molecular sieves is their poor stability of activity and their tendency to deactivate under the harsh periodic regeneration conditions of FCC units.
The IM-5 molecular sieve is an IMF structure molecular sieve, which was first synthesized by Benazzi in 1998. The structural analysis was done in 2007 by Baerlocher et al. The molecular sieve is of a two-dimensional ten-membered ring channel structure, the diameter of a channel of the molecular sieve is similar to that of a ZSM-5 molecular sieve, and a limited channel also exists in the third dimension direction. The catalyst has a pore channel structure similar to that of a ZSM-5 molecular sieve, and has higher acid content and better hydrothermal stability, so the catalyst has characteristics in a plurality of catalytic reactions. A series of studies by Corma et al on the catalytic performance of IM-5 molecular sieves have shown that it is higher than ZSM-5 molecular sieves in alkane cracking capacity.
Although the IM-5 molecular sieve has higher alkane cracking capability, the IM-5 molecular sieve is the same as other ten-membered ring molecular sieves, and larger reactant molecules such as polycyclic hydrocarbons are difficult to enter crystal pore channels for reaction due to the narrow pore channel structure, so that the effective reaction area of the molecular sieve is reduced, and the reaction activity of the molecular sieve is reduced; on the other hand, the molecules of the larger products such as isoparaffin and aromatic hydrocarbon are not easy to diffuse out from the inside of the molecular sieve pore channel, so that secondary reactions such as excessive hydrogen transfer, coking and the like are caused, and the molecular sieve is inactivated, and the reaction selectivity is reduced. In the cracking reaction using macromolecular recombinant as raw material, the above problems are inevitably made more prominent by the defect of narrow openings of IM-5 molecular sieve pores.
Disclosure of Invention
The invention aims to provide a catalytic cracking auxiliary agent for increasing the yield of propylene and a preparation method thereof.
In order to achieve the above object, the present disclosure provides a catalytic cracking assistant for increasing propylene yield, which comprises, based on the dry weight of the assistant, 10 to 75 wt% of a phosphorus-containing IMF structure molecular sieve, 3 to 40 wt% of a phosphorus-aluminum inorganic binder, 1 to 30 wt% of other inorganic binders, calculated as oxides, and 0 to 60 wt% of a second clay, calculated as dry weight; wherein the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay, and the phosphorus-aluminum inorganic binder containing first clay comprises Al based on the dry weight of the phosphorus-aluminum inorganic binder containing first clay2O315-40% by weight, calculated as P, of an aluminium component2O545-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis weight, and the P/Al weight ratio is 1.0-6.0, pH value is 1-3.5, solid content is 15-60 wt%; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.6 and less than or equal to 0.85; wherein, D ═ al (s)/al (c), al(s) represents the aluminum content in the region arbitrarily greater than 100 square nanometers within the distance H inward from the crystal face edge of the molecular sieve crystal grain measured by TEM-EDS method, and al (c) represents the aluminum content in the region arbitrarily greater than 100 square nanometers within the distance H outward from the geometric center of the crystal face of the molecular sieve crystal grain measured by TEM-EDS method, where H is 10% of the distance from a certain point of the crystal face edge to the geometric center of the crystal face; the proportion of the mesopore volume of the molecular sieve to the total mesopore volume is 50-80% by volume, and the proportion of the mesopore volume with the pore diameter of 2-20 nm to the total mesopore volume is more than 85% by volume; the proportion of the strong acid amount of the molecular sieve to the total acid amount is 50-80%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 7-30; with P2O5The molecular sieve has a phosphorus content of from 0.1 to 15 wt.% based on the dry weight of the molecular sieve.
Preferably, the molecular sieve has an Al distribution parameter D that satisfies: d is more than or equal to 0.65 and less than or equal to 0.82; the ratio of mesopore volume of the molecular sieve to the total pore volume is 57-70% by volume, and the ratio of mesopore volume with pore diameter of 2-20 nm to the total mesopore volumeE.g., greater than 90 volume%; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 55-70%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 8-25; with P2O5The molecular sieve has a phosphorus content of 1-13 wt.% based on the dry weight of the molecular sieve.
Preferably, the first clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite; the second clay is at least one selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite; the other inorganic binder is at least one selected from pseudo-boehmite, alumina sol, silica-alumina sol and water glass.
Preferably, the auxiliary agent also contains P based on the dry weight of the auxiliary agent2O5Up to 5 wt% of a phosphorus additive.
Preferably, the auxiliary agent comprises 8-25 wt% of phosphorus-aluminum inorganic binder, 20-60 wt% of phosphorus-containing IMF structure molecular sieve, 10-45 wt% of second clay, 5-25 wt% of other inorganic binder and 0-3 wt% of phosphorus additive.
The present disclosure also provides a method for preparing a catalytic cracking aid for increasing propylene yield, the method comprising: mixing the phosphorus-containing IMF structure molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders, adding or not adding second clay, pulping, and spray-drying; wherein, a phosphorus additive is introduced or not introduced; based on the total dry weight of the preparation raw materials of the auxiliary agent, the preparation raw materials of the auxiliary agent comprise 10-75 wt% of phosphorus-containing IMF structure molecular sieve based on the dry weight, 3-40 wt% of phosphorus-aluminum inorganic binder based on the dry weight, 1-30 wt% of other inorganic binders based on oxides, 0-60 wt% of second clay based on the dry weight, and the preparation raw materials of the auxiliary agent or the auxiliary agent do not comprise P2O5Up to 5 wt% of a phosphorus additive; wherein the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay, and the phosphorus-aluminum inorganic binder containing first clay comprises Al based on the dry weight of the phosphorus-aluminum inorganic binder containing first clay2O315-40% by weight, calculated as P, of an aluminium component2O545-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis weight, and the P/Al weight ratio is 1.0-6.0, pH value is 1-3.5, solid content is 15-60 wt%; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.6 and less than or equal to 0.85; wherein, D ═ al (s)/al (c), al(s) represents the aluminum content in the region arbitrarily greater than 100 square nanometers within the distance H inward from the crystal face edge of the molecular sieve crystal grain measured by TEM-EDS method, and al (c) represents the aluminum content in the region arbitrarily greater than 100 square nanometers within the distance H outward from the geometric center of the crystal face of the molecular sieve crystal grain measured by TEM-EDS method, where H is 10% of the distance from a certain point of the crystal face edge to the geometric center of the crystal face; the proportion of the mesopore volume of the molecular sieve to the total mesopore volume is 50-80% by volume, and the proportion of the mesopore volume with the pore diameter of 2-20 nm to the total mesopore volume is more than 85% by volume; the proportion of the strong acid amount of the molecular sieve to the total acid amount is 50-80%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 7-30; with P2O5The molecular sieve has a phosphorus content of from 0.1 to 15 wt.% based on the dry weight of the molecular sieve.
Preferably, the preparation step of the molecular sieve with the phosphorus-containing IMF structure comprises the following steps: a. carrying out desiliconization treatment on the sodium type IMF structure molecular sieve in an alkali solution to obtain a desiliconized molecular sieve; b. b, performing ammonium exchange treatment on the desiliconized molecular sieve obtained in the step a 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; c. b, dealuminizing the ammonium exchange molecular sieve obtained in the step b in a composite acid dealuminizing agent solution consisting of fluosilicic acid, organic acid and inorganic acid, and filtering and washing to obtain a dealuminized molecular sieve; d. and c, carrying out phosphorus modification treatment and roasting treatment on the dealuminized molecular sieve obtained in the step c to obtain the phosphorus-containing IMF structure molecular sieve.
Preferably, the preparation step of the sodium type IMF structure molecular sieve in step a comprises: filtering and washing the slurry of the IMF structure molecular sieve obtained by amine crystallization to obtain a washed molecular sieve; wherein the sodium content of the washed molecular sieve is less than 3.0 wt% based on the total dry basis weight of the washed molecular sieve calculated as sodium oxide; and drying and air roasting the water-washed molecular sieve to obtain the sodium type IMF structure molecular sieve.
Preferably, the alkali solution in step a is selected from the group consisting of aqueous sodium hydroxide solution, aqueous potassium hydroxide solution and aqueous ammonia.
Preferably, the conditions of the desilication treatment in the step a include: the weight ratio of the sodium type IMF structure molecular sieve, alkali in the alkali solution and water in the alkali solution is 1: (0.1-2): (5-20), wherein the desiliconization treatment temperature is between room temperature and 100 ℃, and the time is 0.2-4 hours.
Preferably, the conditions of the desilication treatment in the step a include: the weight ratio of the sodium type IMF structure molecular sieve, alkali in the alkali solution and water in the alkali solution is 1: (0.2-1): (5-20).
Preferably, the organic acid in step c is at least one selected from the group consisting of ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the dealumination treatment conditions in step c include: the weight ratio of the ammonium exchange molecular sieve, the organic acid, the inorganic acid and the fluosilicic acid is 1: (0.01-0.3): (0.01-0.3): (0.01-0.3); the dealuminization treatment temperature is 25-100 ℃, and the time is 0.5-6 hours.
Preferably, the dealumination treatment conditions in step c include: the weight ratio of the ammonium exchange molecular sieve, the organic acid, the inorganic acid and the fluosilicic acid is 1: (0.02-0.2): (0.015-0.2): (0.015-0.2).
Preferably, the phosphorus modification treatment in step d comprises: at least one phosphorus-containing compound selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate is used to impregnate and/or ion-exchange the molecular sieve.
Preferably, the conditions of the calcination treatment include: the atmosphere of the roasting treatment is air atmosphere or water vapor atmosphere; the roasting temperature is 400-800 ℃, and the roasting time is 0.5-8 hours.
Preferably, the preparation step of the first clay-containing aluminophosphate inorganic binder comprises: (1) pulping and dispersing an alumina source, first clay and water into slurry with the solid content of 8-45 wt%; the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, first clay and Al which are calculated by dry weight2O3The weight ratio of the alumina source is (more than 0-40) to (15-40); (2) adding concentrated phosphoric acid into the slurry obtained in the step (1) according to the weight ratio of P/Al to 1-6 under stirring; (3) and (3) reacting the slurry obtained in the step (2) at the temperature of 50-99 ℃ for 15-90 minutes.
The catalytic cracking auxiliary agent provided by the disclosure has good catalytic cracking performance, is used for catalytic cracking reaction of hydrocarbon oil after being mixed with a main agent, and can effectively improve propylene yield and propylene selectivity.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a catalytic cracking assistant for increasing yield of propylene, which comprises, based on the dry weight of the assistant, 10-75 wt% of phosphorus-containing IMF structure molecular sieve, 3-40 wt% of phosphorus-aluminum inorganic binder, 1-30 wt% of other inorganic binders, and 0-60 wt% of second clay; wherein the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay, and the phosphorus-aluminum inorganic binder containing first clay comprises Al based on the dry weight of the phosphorus-aluminum inorganic binder containing first clay2O315-40% by weight, calculated as P, of an aluminium component2O545-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis weight, and the P/Al weight ratio is 1.0-6.0, pH value is 1-3.5, solid content is 15-60 wt%; al distribution of the molecular sieveThe parameter D satisfies: d is more than or equal to 0.6 and less than or equal to 0.85; wherein, D ═ al (s)/al (c), al(s) represents the aluminum content in the region arbitrarily greater than 100 square nanometers within the distance H inward from the crystal face edge of the molecular sieve crystal grain measured by TEM-EDS method, and al (c) represents the aluminum content in the region arbitrarily greater than 100 square nanometers within the distance H outward from the geometric center of the crystal face of the molecular sieve crystal grain measured by TEM-EDS method, where H is 10% of the distance from a certain point of the crystal face edge to the geometric center of the crystal face; the proportion of the mesopore volume of the molecular sieve to the total mesopore volume is 50-80% by volume, and the proportion of the mesopore volume with the pore diameter of 2-20 nm to the total mesopore volume is more than 85% by volume; the proportion of the strong acid amount of the molecular sieve to the total acid amount is 50-80%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 7-30; with P2O5The molecular sieve has a phosphorus content of from 0.1 to 15 wt.% based on the dry weight of the molecular sieve. Preferably, the molecular sieve has an Al distribution parameter D that satisfies: d is more than or equal to 0.65 and less than or equal to 0.82; the proportion of the mesopore volume of the molecular sieve in the total pore volume is 57-70% by volume, and the proportion of the mesopore volume with the pore diameter of 2-20 nm in the total mesopore volume is more than 90% by volume; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 55-70%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 8-25; with P2O5The molecular sieve has a phosphorus content of 1-13 wt.% based on the dry weight of the molecular sieve.
According to the present disclosure, the aluminophosphate inorganic binder is a aluminophosphate inorganic binder and/or a aluminophosphate gel comprising a first clay.
In one embodiment, the phosphorus-aluminum inorganic binder comprises Al based on the dry weight of the phosphorus-aluminum inorganic binder2O315-40% by weight, calculated as P, of an aluminium component2O545-80 wt% of phosphorus component and 0-40 wt% of first clay calculated by dry basis weight, and the P/Al weight ratio is 1.0-6.0, pH value is 1-3.5, and solid content is 15-60 wt%; for example, including Al2O315-40% by weight, calculated as P, of an aluminium component2O545-80 wt% of a phosphorus component and 1-40 wt% of a first clay, based on dry weight; preferably contains Al2O315-35% by weight, calculated on the basis of the total weight of the composition,with P2O5A phosphorus component in an amount of 50 to 75 wt% and a first clay in an amount of 8 to 35 wt% on a dry basis, preferably having a P/Al weight ratio of 1.2 to 6.0, more preferably 2.0 to 5.0, and a pH value of 1.5 to 3.0.
In another embodiment, the phosphorus aluminum inorganic binder comprises Al based on the dry weight of the phosphorus aluminum inorganic binder2O320-40% by weight, calculated as P, of an aluminium component2O560-80% by weight of a phosphorus component.
The IMF structure is the topology of the molecular sieve, for example, the IM-5 molecular sieve has an IMF structure.
According to the present disclosure, it is well known to those skilled in the art to determine the aluminum content of the molecular sieve by using the TEM-EDS method, wherein the geometric center is also well known to those skilled in the art, and can be calculated according to a formula, which is not repeated in the present disclosure, and the geometric center of the general symmetric graph is the intersection point of the connection lines of the relative vertexes, for example, the geometric center of the rectangular crystal face of the conventional rectangular block IM-5 molecular sieve is at the intersection point of the connection lines of the relative vertexes. The crystal plane is a plane of regular crystal grains, and the inward and outward directions are both inward and outward directions on the crystal plane.
In accordance with the present disclosure, the ratio of mesopore volume to total pore volume and the ratio of mesopore volume having a pore diameter of from 2 nm to 20 nm to total mesopore volume of the molecular sieve are measured using the nitrogen adsorption BET specific surface area method, the mesopore volume generally referring to the pore volume having a pore diameter of greater than 2 nm and less than 100 nm; the strong acid amount of the molecular sieve is NH in proportion to the total acid amount3The TPD method, the acid centre of which may be NH3Desorbing the corresponding acid center at the temperature of more than 300 ℃; and the ratio of the acid amount of the B acid to the acid amount of the L acid is measured by adopting a pyridine adsorption infrared acidity method.
Clays are well known to those skilled in the art in light of this disclosure, and the first clay may be at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth, preferably including rectorite, more preferably rectorite; the second clay may be at least one selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, rectorite, diatomaceous earth, halloysite, saponite, bentonite and hydrotalcite, preferably at least one selected from kaolin, metakaolin, diatomaceous earth, sepiolite, attapulgite, montmorillonite and rectorite; the additional inorganic binder may be selected from one or more of the inorganic oxide binders conventionally used in catalytic cracking promoters or catalyst binder components other than the aluminophosphate and aluminophosphate inorganic binders, preferably from at least one of pseudoboehmite, alumina sol, silica alumina sol, and water glass, more preferably from at least one of pseudoboehmite and alumina sol.
In accordance with the present disclosure, the first clay-containing aluminophosphate inorganic binder preferably contains Al2O315-35% by weight, calculated as P, of an aluminium component2O5A phosphorus component in an amount of 50 to 75 wt% and a first clay in an amount of 8 to 35 wt% on a dry basis, preferably having a P/Al weight ratio of 1.2 to 6.0, more preferably 2.0 to 5.0, and a pH value of 1.0 to 3.5.
According to the disclosure, the adjuvant may further comprise P on a dry weight basis2O5Up to 5 wt% of a phosphorus additive. The phosphorus additive may be selected from phosphorus compounds, such as one or more of inorganic compounds and organic compounds including phosphorus, which may be readily soluble in water, or may be a poorly water-soluble or water-insoluble phosphorus compound, such as one or more selected from phosphorus oxides, phosphoric acid, orthophosphates, phosphites, hypophosphites, basic phosphates, acid phosphates, and phosphorus-containing organic compounds. Preferred phosphorus compounds are one or more of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and aluminum phosphate. The resulting adjuvant has a phosphorus additive in the form of a phosphorus compound such as phosphorus oxide, orthophosphate, phosphite, basic phosphate and acid phosphate. The phosphorus additive may be present in any location where a promoter may be present, such as within the channels of the zeolite, on the surface of the zeolite, in the matrix material (i.e., the material of the promoter other than the molecular sieve), or may be present in the zeolite at the same timeInside the channels, on the surface of the zeolite and in the matrix material. The phosphorus additive is not included in the content of phosphorus in the molecular sieve, nor is the phosphorus introduced by the phosphorus-aluminum inorganic binder included.
According to the present disclosure, the adjuvant preferably comprises 8-25 wt% of a phosphorus aluminum inorganic binder, 20-60 wt% of a phosphorus-containing IMF structure molecular sieve, 10-45 wt% of a second clay, 5-25 wt% of other inorganic binders, and 0-3 wt% of a phosphorus additive.
The present disclosure also provides a method for preparing a catalytic cracking aid for increasing propylene yield, the method comprising: mixing the phosphorus-containing IMF structure molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders, adding or not adding second clay, pulping, and spray-drying; wherein, a phosphorus additive is introduced or not introduced; based on the total dry weight of the preparation raw materials of the auxiliary agent, the preparation raw materials of the auxiliary agent comprise 10-75 wt% of phosphorus-containing IMF structure molecular sieve based on the dry weight, 3-40 wt% of phosphorus-aluminum inorganic binder based on the dry weight, 1-30 wt% of other inorganic binders based on oxides, 0-60 wt% of second clay based on the dry weight, and the preparation raw materials of the auxiliary agent or the auxiliary agent do not comprise P2O5Up to 5 wt% of a phosphorus additive; wherein the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay, and the phosphorus-aluminum inorganic binder containing first clay comprises Al based on the dry weight of the phosphorus-aluminum inorganic binder containing first clay2O315-40% by weight, calculated as P, of an aluminium component2O545-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis weight, and the P/Al weight ratio is 1.0-6.0, pH value is 1-3.5, solid content is 15-60 wt%; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.6 and less than or equal to 0.85; wherein, D ═ Al (S)/Al (C), Al (S) represents the aluminum content in the region of more than 100 square nanometers in the distance H from the edge of the crystal face of the molecular sieve crystal grain to the inside measured by TEM-EDS method, Al (C) represents the aluminum content in the region of more than 100 square nanometers in the distance H from the geometric center of the crystal face of the molecular sieve crystal grain to the outside measured by TEM-EDS method, wherein H is the aluminum content in the region from a certain point of the edge of the crystal face to several points of the crystal faceWhich center distance is 10%; the proportion of the mesopore volume of the molecular sieve to the total mesopore volume is 50-80% by volume, and the proportion of the mesopore volume with the pore diameter of 2-20 nm to the total mesopore volume is more than 85% by volume; the proportion of the strong acid amount of the molecular sieve to the total acid amount is 50-80%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 7-30; with P2O5The molecular sieve has a phosphorus content of from 0.1 to 15 wt.% based on the dry weight of the molecular sieve.
According to the present disclosure, the preparation step of the phosphorus-containing IMF structure molecular sieve may include: a. carrying out desiliconization treatment on the sodium type IMF structure molecular sieve in an alkali solution to obtain a desiliconized molecular sieve; b. b, performing ammonium exchange treatment on the desiliconized molecular sieve obtained in the step a 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; c. b, dealuminizing the ammonium exchange molecular sieve obtained in the step b in a composite acid dealuminizing agent solution consisting of fluosilicic acid, organic acid and inorganic acid, and filtering and washing to obtain a dealuminized molecular sieve; d. and c, carrying out phosphorus modification treatment and roasting treatment on the dealuminized molecular sieve obtained in the step c to obtain the phosphorus-containing IMF structure molecular sieve.
The sodium IMF structure molecular sieve is well known to those skilled in the art and is commercially available and can be prepared by itself, for example, the sodium IMF structure molecular sieve can be prepared by steps including: filtering and washing the slurry of the IMF structure molecular sieve obtained by amine crystallization to obtain a washed molecular sieve; wherein the sodium content of the washed molecular sieve is less than 3.0 wt% based on the total dry basis weight of the washed molecular sieve calculated as sodium oxide; and drying and air roasting the water-washed molecular sieve to obtain the sodium type IMF structure molecular sieve. The amine crystallization refers to the preparation of a molecular sieve by hydrothermal crystallization with a template agent, and specific references to the preparation of the IMF molecular sieve include chinese patents CN102452667A, CN103708491A, CN102452666A and CN 103723740A. The air roasting is used for removing the template agent in the washed molecular sieve, and the temperature of the air roasting can be 400-700 ℃, and the time can be 0.5-10 hours.
According to the present disclosure, the desiliconization treatment is used to remove part of framework silicon atoms of the molecular sieve and part of framework silicon, so as to achieve the purpose of unobstructed pore channels of the molecular sieve and generate more secondary pore effects, and the alkali solution in step a can be an inorganic alkali, for example, selected from sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and ammonia water, preferably sodium hydroxide aqueous solution; the conditions of the desiliconization treatment in step a may include: the weight ratio of the sodium-type IMF structure molecular sieve, the alkali in the alkali solution and the water in the alkali solution based on the dry weight can be 1: (0.1-2): (5-20), preferably 1: (0.2-1): (5-20), the desiliconization treatment temperature can be from room temperature to 100 ℃, and the time can be 0.2-4 hours.
Ammonium exchange treatments are well known to those skilled in the art in light of this disclosure for reducing the sodium content of molecular sieves. For example, the conditions of the ammonium exchange treatment may include: according to the molecular sieve: ammonium salt: water 1: (0.1-1): (5-10) filtering the molecular sieve after ammonium exchange for 0.5-3 hours at room temperature to 100 ℃, wherein the ammonium salt used can be common inorganic ammonium salt, for example, at least one selected from ammonium chloride, ammonium sulfate and ammonium nitrate, and the number of ammonium exchanges can be repeated for 1-3 times until the content of sodium oxide in the molecular sieve is less than 0.2 wt%.
Although the desiliconization treatment according to the present disclosure can generate secondary pores in the molecular sieve, amorphous fragments are inevitably generated in the molecular sieve during the desiliconization treatment to block the molecular sieve channels, cover active centers, and make the surface of the molecular sieve relatively rich in aluminum, which is not favorable for the improvement of the reaction selectivity of the molecular sieve, so that it is necessary to perform a subsequent dealumination treatment, which is well known to those skilled in the art, but the use of inorganic acid, organic acid and fluosilicic acid together for the dealumination treatment has not been reported. The dealumination treatment can be carried out once or for multiple times, organic acid can be firstly mixed with the ammonium exchange molecular sieve, and then fluosilicic acid and inorganic acid are mixed with the ammonium exchange molecular sieve, namely, the organic acid is firstly added into the ammonium exchange molecular sieve, and then the fluosilicic acid and the inorganic acid are slowly and concurrently added, or the fluosilicic acid is firstly added and then the inorganic acid is added, preferably the fluosilicic acid and the inorganic acid are slowly and concurrently added. For example, the organic acid in step c may be at least one selected from the group consisting of ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably oxalic acid or citric acid, and more preferably oxalic acid; the inorganic acid may be at least one selected from hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid or sulfuric acid, and more preferably hydrochloric acid; the dealumination treatment conditions may include: the weight ratio of the ammonium exchange molecular sieve, the organic acid, the inorganic acid and the fluosilicic acid is 1: (0.01-0.3): (0.01-0.3): (0.01-0.3), preferably 1: (0.02-0.2): (0.015-0.2): (0.015-0.2); the dealumination treatment temperature can be 25-100 ℃, and the time can be 0.5-6 hours. The molecular sieve with the IMF structure is treated by combining desiliconization treatment and composite acid dealuminization treatment, so that the aluminum distribution, the silicon-aluminum ratio, the acid property and the pore structure of the molecular sieve are modulated, and the molecular sieve with the IMF structure still has good shape selection selectivity after pore expansion modification, thereby effectively improving the yield of propylene, ethylene and BTX of the molecular sieve with the IMF structure.
Phosphorus modification treatments are well known to those skilled in the art in light of this disclosure, for example, the phosphorus modification treatment in step d may include: at least one phosphorus-containing compound selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate is used to impregnate and/or ion-exchange the molecular sieve.
Calcination treatments are well known to those skilled in the art in light of this disclosure, and the conditions of the calcination treatment may include, for example: the atmosphere of the roasting treatment is air atmosphere or water vapor atmosphere; the roasting temperature is 400-800 ℃, and the roasting time is 0.5-8 hours.
Washing as described herein is well known to those skilled in the art and generally refers to water washing, e.g., the molecular sieve may be rinsed with 5 to 10 times the weight of the molecular sieve.
According to the present disclosure, the step of preparing the first clay-containing aluminophosphate inorganic binder may comprise: (1) pulping and dispersing an alumina source, first clay and water into slurry with the solid content of 8-45 wt%; the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the weight is calculated according to the dry weightThe first clay and Al2O3The weight ratio of the alumina source is (more than 0-40) to (15-40); (2) adding concentrated phosphoric acid into the slurry obtained in the step (1) according to the weight ratio of P/Al to 1-6 under stirring; wherein P in the P/Al is the weight of phosphorus in the phosphoric acid by simple substance, and Al is the weight of aluminum in the alumina source by simple substance; (3) and (3) reacting the slurry obtained in the step (2) at the temperature of 50-99 ℃ for 15-90 minutes.
According to the present disclosure, the alumina source may be at least one selected from the group consisting of rho-alumina, chi-alumina, eta-alumina, gamma-alumina, kappa-alumina, delta-alumina, theta-alumina, gibbsite, metazoite, nordstrandite, diaspore, boehmite, and pseudoboehmite from which the aluminum component of the first clay-containing aluminophosphate inorganic binder is derived. The first clay can be one or more of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite, and preferably rectorite. The concentrated phosphoric acid may be present in a concentration of 60 to 98 wt.%, more preferably 75 to 90 wt.%. The feeding rate of phosphoric acid is preferably 0.01 to 0.10Kg of phosphoric acid per minute per Kg of alumina source, and more preferably 0.03 to 0.07Kg of phosphoric acid per minute per Kg of alumina source.
According to the disclosure, due to the introduction of the clay, the phosphorus-aluminum inorganic binder containing the first clay not only improves mass transfer and heat transfer among materials in the preparation process, but also avoids binder solidification caused by nonuniform local instant violent reaction of the materials, heat release and overtemperature, and the obtained binder has the same binding performance as the phosphorus-aluminum binder prepared by a method without introducing the clay; in addition, the method introduces clay, especially rectorite with a layered structure, improves the heavy oil conversion capability of the catalyst composition, and enables the obtained auxiliary agent to have better selectivity.
The preparation method of the catalytic cracking assistant provided by the present disclosure mixes and pulps the phosphorus-containing IMF structure molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders, and the order of addition thereof has no special requirement, for example, the phosphorus-aluminum inorganic binder, other inorganic binders, the molecular sieve, the second clay may be mixed (when the second clay is not included, the relevant addition step may be omitted) and then pulps, preferably, the second clay, the molecular sieve and other inorganic binders are mixed and pulped, and then the phosphorus-aluminum inorganic binder is added, which is beneficial to improving the activity and selectivity of the assistant.
The preparation method of the catalytic cracking assistant provided by the disclosure further comprises the step of spray drying the slurry obtained by pulping. Methods of spray drying are well known to those skilled in the art and no particular requirement of the present disclosure exists.
When the promoter contains the phosphorus additive, the phosphorus additive can be introduced by one of the following methods or a combination of several methods, but is not limited to the methods for introducing the phosphorus additive into the promoter:
1. adding a phosphorus compound to the slurry before the spray drying and forming of the auxiliary agent;
2. after the spray drying and forming of the auxiliary agent, the phosphorus compound is impregnated or chemically adsorbed, and the phosphorus compound is introduced through solid-liquid separation (if needed), drying and roasting processes, wherein the drying temperature can be between room temperature and 400 ℃, preferably 100-300 ℃, the roasting temperature can be between 400-700 ℃, preferably 450-650 ℃, and the roasting time can be between 0.5 and 100 hours, preferably between 0.5 and 10 hours. The phosphorus compound may be selected from one or more of various inorganic and organic compounds of phosphorus. The phosphorus compound may be either readily water-soluble or poorly water-soluble or water-insoluble. Examples of the phosphorus compound include oxides of phosphorus, phosphoric acid, orthophosphates, phosphites, hypophosphites, phosphorus-containing organic compounds, and the like. Preferred phosphorus compounds are selected from one or more of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate and the like.
Thus, the phosphorus additive may be present in any location where an adjunct may be present, such as may be present inside the pores of the zeolite, on the surface of the zeolite, in the matrix material, and may also be present both inside the pores of the zeolite, on the surface of the zeolite and in the matrix material. The phosphorus additive is present in the form of a phosphorus compound (e.g., an oxide of phosphorus, an orthophosphate, a phosphite, a basic phosphate, an acid phosphate).
The catalytic cracking auxiliary agent provided by the disclosure is suitable for catalytic cracking of various hydrocarbon oils. When the catalyst is used in the catalytic cracking process, the catalyst can be added into a catalytic cracking reactor independently or can be mixed with a catalytic cracking catalyst for use. In general, the adjunct provided by the present disclosure comprises no more than 30 wt%, preferably 1 to 25 wt%, more preferably 3 to 15 wt% of the total amount of FCC catalyst and adjunct mixture provided by the present disclosure, and the hydrocarbon oil is selected from one or more of various petroleum fractions, such as crude oil, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, straight run wax oil, propane light/heavy deoiling, coker wax oil, and coal liquefaction products. The hydrocarbon oil may contain heavy metal impurities such as nickel and vanadium, and sulfur and nitrogen impurities, for example, the content of sulfur may be as high as 3.0 wt%, the content of nitrogen may be as high as 2.0 wt%, and the content of metal impurities such as vanadium and nickel may be as high as 3000 ppm.
The catalytic cracking assistant provided by the disclosure is used in a catalytic cracking process, and the catalytic cracking conditions of the hydrocarbon oil can be conventional catalytic cracking conditions. Generally, the hydrocarbon oil catalytic cracking conditions include a reaction temperature of 400-600 ℃, preferably 450-550 ℃, and a weight hourly space velocity of 8-120 hours-1Preferably 8 to 80 hours-1The ratio of the solvent to the oil (weight ratio) is 1-20, preferably 3-15. The catalytic cracking auxiliary agent provided by the present disclosure can be used in various existing catalytic cracking reactors, such as in fixed bed reactors, fluidized bed reactors, riser reactors, multi-reaction zone reactors, and the like.
The present disclosure is further illustrated by the following examples, which are not intended to be limiting and the instruments and reagents used in the examples of the present disclosure are those commonly used by those skilled in the art unless otherwise specified.
Total specific surface (S) of the present disclosureBET) The mesoporous pore volume, the total pore volume and the mesoporous pore volume of 2-20 nm are measured by an AS-3, AS-6 static nitrogen adsorption instrument produced by Quantachrome instruments. The instrument parameters are as follows: the sample was placed in a sample handling system and evacuated to 1.33X 10 at 300 deg.C-2Pa, keeping the temperature and the pressure for 4h, and purifying the sample. The purified sample was tested at-196 ℃ in liquid nitrogenSame specific pressure P/P0The adsorption quantity and the desorption quantity of the nitrogen under the condition are obtained to obtain N2Adsorption-desorption isotherm curve. Then, the total specific surface area, the micropore specific surface area and the mesopore specific surface area are calculated by utilizing a two-parameter BET formula, and the specific pressure P/P is taken0The adsorption capacity below 0.98 is the total pore volume of the sample, the pore size distribution of the mesoporous part is calculated by using BJH formula, and the mesoporous pore volume (2-100 nm) and the mesoporous pore volume of 2-20 nm are calculated by adopting an integration method.
The acid content and total acid content of the strong acid disclosed by the disclosure are measured by an Autochem II 2920 temperature programmed desorption instrument of Michman, USA. And (3) testing conditions are as follows: weighing 0.2g of a sample to be detected, putting the sample into a sample tube, putting the sample tube into a thermal conductivity cell heating furnace, taking He gas as carrier gas (50mL/min), heating the sample tube to 600 ℃ at the speed of 20 ℃/min, and purging the sample tube for 60min to remove impurities adsorbed on the surface of the catalyst. Then cooling to 100 ℃, keeping the temperature for 30min, and switching to NH3-He mixed gas (10.02% NH)3+ 89.98% He) for 30min, and then continuing to purge with He gas for 90min until the baseline is stable, so as to desorb the physically adsorbed ammonia gas. And (4) heating to 600 ℃ at the heating rate of 10 ℃/min for desorption, keeping for 30min, and finishing desorption. Detecting gas component change by TCD detector, automatically integrating by instrument to obtain total acid amount and strong acid amount, wherein acid center of strong acid is NH3The desorption temperature is higher than 300 ℃ of the corresponding acid center.
The amount of acid B and the amount of acid L of the present disclosure were measured by FTS3000 Fourier Infrared Spectroscopy manufactured by BIO-RAD, USA. And (3) testing conditions are as follows: pressing the sample into tablet, sealing in an in-situ cell of an infrared spectrometer, and vacuumizing to 10 deg.C at 350 deg.C-3Pa, keeping for 1h to enable gas molecules on the surface of the sample to be desorbed completely, and cooling to room temperature. Introducing pyridine vapor with pressure of 2.67Pa into the in-situ tank, balancing for 30min, heating to 200 deg.C, and vacuumizing to 10 deg.C-3Pa, keeping for 30min, cooling to room temperature at 1400-1700cm-1Scanning in wave number range, and recording infrared spectrogram of pyridine adsorption at 200 ℃. Then the sample in the infrared absorption cell is moved to a heat treatment area, the temperature is raised to 350 ℃, and the vacuum is pumped to 10 DEG-3Pa, keeping for 30min, cooling to room temperature, and recording the infrared spectrogram of pyridine adsorption at 350 ℃. Automatic integration of instrumentTo the acid amount of B and the acid amount of L.
The phosphorus content of the present disclosure is determined by the GB/T30905-2014 standard method.
The sodium content of the present disclosure is determined using the GB/T30905-2014 standard method.
See methods for solid catalyst investigation, petrochemical, 29(3), 2000: 227.
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 (different edge points and different H values) from the geometric center to a certain point of the edge, 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 are respectively selected, measuring the aluminum content, namely Al (S1) and Al (C1), calculating D1 to Al (S1)/Al (C1), respectively selecting different crystal grains to measure for 5 times, and calculating the average value to be D.
When the auxiliary agent disclosed by the invention is used for evaluating the performance of catalytic cracking reaction, a reaction product is N2Carrying out gas-liquid separation in a liquid receiving bottle at the temperature of minus 10 ℃, and collecting a gas product to finish on-line analysis by an Agilent 6890GC (TCD detector); collecting liquid products, weighing off-line, and performing simulated distillation and gasoline monomer hydrocarbon analysis (testing by RIPP81-90 testing method) respectively, wherein the cut points of gasoline and diesel oil are 221 ℃ and 343 ℃ respectively; the coke-forming catalyst is burnt and regenerated on line, and the coke mass is calculated according to the flow rate and the composition of the flue gas; the mass balance was calculated by summing all product masses.
The RIPP standard method disclosed in the disclosure can be found in petrochemical analysis methods, edition such as Yangcui, 1990 edition.
Some of the raw materials used in the examples had the following properties:
the pseudoboehmite is an industrial product produced by Shandong aluminum industry company, and the solid content is 60 percent by weight; the aluminum sol is an industrial product, Al, produced by the Qilu division of the medium petrochemical catalyst2O3The content was 21.5 wt%; the silica sol is a medium petrochemical catalystCommercial products of manufacture, SiO2The content was 28.9% by weight, Na2The O content is 8.9 percent; the kaolin is kaolin specially used for a catalytic cracking catalyst produced by Suzhou kaolin company, and the solid content is 78 weight percent. Hydrochloric acid concentration of 36 wt%, rectorite as product of Hubei Zhongxiang famous flow rectorite development Limited company, and quartz sand content<3.5 wt.% of Al2O339.0 wt.% of Fe2O3The content of Na was 2.0 wt%2The O content was 0.03% by weight, and the solid content was 77% by weight; SB aluminum hydroxide powder: al from Condex, Germany2O3The content was 75% by weight; gamma-alumina powder: al from Condex, Germany2O3The content was 95% by weight. Hydrochloric acid: chemical purity, concentration of 36-38 wt%, and is produced in Beijing chemical plant.
Examples 1-2 provide the phosphorus-containing IMF structure molecular sieves of the present disclosure, and comparative examples 1-7 provide comparative molecular sieves.
Example 1
Filtering mother liquor of crystallized IM-5 molecular sieve (produced by Changling catalyst factory), washing with water, filtering and drying; roasting the dried molecular sieve in air for 6 hours at the roasting temperature of 550 ℃ to remove the template agent; adding 100g (dry basis) of the molecular sieve into 1000g of 2.4 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 O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 5g of oxalic acid while stirring, then adding 35g of hydrochloric acid (mass fraction is 10%) and 28g of fluosilicic acid (mass fraction is 3%) in a concurrent flow manner, and adding for 30 min; heating to 65 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with solid content of 40 wt%, adding 6.3gH3PO4(concentration 85 wt%), mixing, soaking, oven drying, and baking at 550 deg.C for 2 h. The molecular sieve A is obtained, and the physicochemical properties are shown in Table 1.
Comparative example 1
Filtering mother liquor of crystallized IM-5 molecular sieve (produced by Changling catalyst factory), washing with water, filtering and drying; roasting the dried molecular sieve in air for 8 hours at the roasting temperature of 550 ℃ to remove the template agent; adding 100g (dry basis) of the molecular sieve into 1000g of 2.4% 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 O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve, adding water to prepare molecular sieve slurry with the solid content of 10 weight percent, and adding 20g of oxalic acid while stirring; heating to 65 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with solid content of 40 wt%, adding 6.1gH3PO4(concentration: 85 wt.%), mixing, immersing, baking, and calcining at 550 deg.C for 2 hr. Molecular sieve DA1 was obtained, and the physicochemical properties are shown in Table 1.
Comparative example 2
Filtering mother liquor of crystallized IM-5 molecular sieve (produced by Changling catalyst factory), washing with water, filtering and drying; roasting the dried molecular sieve in air for 8 hours at the roasting temperature of 550 ℃ to remove the template agent; adding 100g (dry basis) of the molecular sieve into 1000g of 2.2 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then adding the obtained molecular sieve filter cake into HCl aqueous solution for washing, and specifically, adding water into 50g (dry basis) of the molecular sieve filter cake to prepare molecular sieve slurry with the solid content of 10 weight percent, and adding 180g of hydrochloric acid (the mass fraction is 10%) during stirring; heating to 65 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding 1500g of water into the filter cake, pulping, adding 80g of NH4Heating Cl to 65 ℃, exchanging and washing for 40min, filtering, and leaching until the filtrate is neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with solid content of 40 wt%, adding 6.3gH3PO4(concentration 85 wt.%), mixing, immersing, baking at 550 deg.C for 2 hr. Molecular sieve DA2 was obtained, and the physicochemical properties are shown in Table 1.
Comparative example 3
Filtering mother liquor of crystallized IM-5 molecular sieve (produced by Changling catalyst factory), washing with water, filtering and drying; roasting the dried molecular sieve in air for 8 hours at the roasting temperature of 550 ℃ to remove the template agent; adding 100g (dry basis) of the molecular sieve into 1000g of 2.2 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 O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; adding water into 50g (dry basis) of the molecular sieve filter cake to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 135g of fluosilicic acid (the mass fraction is 3 percent) while stirring, and adding for 30 min; heating to 65 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with solid content of 40 wt%, adding 6.3gH3PO4(concentration: 85 wt.%), mixing, immersing, baking, and calcining at 550 deg.C for 2 hr. Molecular sieve DA3 was obtained, and the physicochemical properties are shown in Table 1.
Comparative example 4
Filtering mother liquor of crystallized IM-5 molecular sieve (produced by Changling catalyst factory), washing with water, filtering and drying; roasting the dried molecular sieve in air for 8 hours at the roasting temperature of 550 ℃ to remove the template agent; adding 100g (dry basis) of the molecular sieve into 1000g of 1.9 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 O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 11g of oxalic acid while stirring, then adding 110g of hydrochloric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 65 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into the filter cake and pulping to obtain the solid content of40 weight percent molecular sieve slurry, 6.3gH3PO4(concentration: 85 wt.%), mixing, immersing, baking, and calcining at 550 deg.C for 2 hr. Molecular sieve DA4 was obtained, and the physicochemical properties are shown in Table 1.
Comparative example 5
Filtering mother liquor of crystallized IM-5 molecular sieve (produced by Changling catalyst factory), washing with water, filtering and drying; roasting the dried molecular sieve in air for 8 hours at the roasting temperature of 550 ℃ to remove the template agent; 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 O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; adding water into 50g (dry basis) of the molecular sieve filter cake to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 4g of oxalic acid while stirring, and slowly adding 72g of fluosilicic acid (the mass fraction is 3 percent) for 30 min; heating to 65 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with solid content of 40 wt%, adding 6.3gH3PO4(concentration: 85 wt.%), mixing, immersing, baking, and calcining at 550 deg.C for 2 hr. Molecular sieve DA5 was obtained, and the physicochemical properties are shown in Table 1.
Comparative example 6
Filtering mother liquor of crystallized IM-5 molecular sieve (produced by Changling catalyst factory), washing with water, filtering and drying; roasting the dried molecular sieve in air for 8 hours at the roasting temperature of 550 ℃ to remove the template agent; 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 O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; 50g (dry basis) of the molecular sieve filter cake is taken and added with water to prepare molecular sieve slurry with the solid content of 10 weight percent, and 42g of the molecular sieve slurry is stirredAdding hydrochloric acid (10 mass percent) and 78g of fluosilicic acid (3 mass percent) in a concurrent flow manner for 30 min; heating to 65 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with solid content of 40 wt%, adding 6.3gH3PO4(concentration: 85 wt.%), mixing, immersing, baking, and calcining at 550 deg.C for 2 hr. Molecular sieve DA6 was obtained, and the physicochemical properties are shown in Table 1.
Comparative example 7
Filtering out mother liquor of the crystallized IM-5 molecular sieve (produced by Changling catalyst factory), washing with water, filtering and drying; and roasting the dried molecular sieve in air for 8 hours at the roasting temperature of 550 ℃ to remove the template agent. Adding 100g of the molecular sieve into 2000g of 1.2 weight percent NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Taking 50g (dry basis) of the molecular sieve filter cake, adding 500g of water for pulping, adding 40g of NH4Heating Cl, heating to 75 ℃, performing exchange treatment for 1h, filtering, repeating exchange washing twice until the content of the molecular sieve sodium oxide is lower than 0.1%, adding water into a filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 wt%, and adding 6.3g of H3PO4(concentration 85 wt%), uniformly mixing, soaking, drying, and roasting at 550 deg.C for 2 hours to obtain molecular sieve DA7, the physicochemical properties of which are shown in Table 1.
Example 2
Filtering mother liquor of crystallized IM-5 molecular sieve (produced by Changling catalyst factory), washing with water, filtering and drying; roasting the dried molecular sieve in air for 8 hours at the roasting temperature of 550 ℃ to remove the template agent; adding 100g (dry basis) of the molecular sieve into 1500g of 2.3 weight percent NaOH solution, heating to 60 ℃, reacting for 45min, 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 O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 4g of citric acid while stirring, and then 10g of sulfuric acid (the mass fraction is 10 percent) and 45g of fluosilicic acid (the mass fraction is 10 percent)Fraction 3%) and adding for 30 min; heating to 45 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with solid content of 40 wt%, adding 6.3gH3PO4(concentration: 85 wt.%), mixing, immersing, baking, and calcining at 550 deg.C for 2 hr. The molecular sieve B is obtained, and the physicochemical properties are shown in Table 1.
As can be seen from the data in Table 1, the conventional alkali treatment can enrich the aluminum on the surface of the IM-5 molecular sieve, the single organic acid oxalic acid dealumination (DA1) or the single inorganic acid hydrochloric acid dealumination (DA2) and the combination of the organic acid oxalic acid and the inorganic acid hydrochloric acid (DA4) can not effectively remove the Al in the molecular sieve, the surface of the molecular sieve is still enriched with the aluminum, and the molecular sieve can obtain a good dealumination effect only after the fluosilicic acid is used, so that the aluminum distribution of the molecular sieve is improved. When fluosilicic acid alone is used for dealumination (DA3), the aluminum distribution of the molecular sieve can be improved, but the mesopores are relatively less, the proportion of strong acid in the total acid is lower, and the proportion of B acid/L acid is lower. The fluosilicic acid and organic acid composite oxalic acid dealumination (DA5) can not obtain higher mesopore proportion and better acidity distribution. Fluosilicic acid complex mineral acid salt dealumination (DA6) showed an increase in mesopore volume, but neither the proportion of strong acid in the total acid nor the B acid/L acid ratio was as high as the molecular sieve provided by the present disclosure. According to the method, after the molecular sieve is subjected to desiliconization treatment, a composite acid system is used, and dealuminization treatment is performed under the synergistic effect of three acids, so that the aluminum distribution and the acid distribution can be improved on the premise of ensuring the integrity of a molecular sieve crystal structure and a mesoporous pore structure.
Examples 3-6 provide a phosphoaluminate inorganic binder for use in the present disclosure.
Example 3
This example prepared a phosphoaluminate inorganic binder as described in the present disclosure.
1.91 kg of pseudoboehmite (containing Al)2O3Pulping 1.19 Kg), 0.56 Kg kaolin (0.50 Kg on a dry basis) and 3.27 Kg decationized water for 30 minutes, adding 5.37 Kg concentrated phosphoric acid (85% by mass) to the slurry under stirring at a rate of 0.04Kg phosphoric acid/min/Kg alumina source, heating to 70 deg.C, and reacting at that temperatureAnd obtaining the phosphorus-aluminum inorganic binder after 45 minutes. The material ratio is shown in Table 2, and the Binder Binder1 is obtained.
Examples 4 to 6
The phosphor-aluminum inorganic Binder was prepared by the method of example 3, the material ratio is shown in table 2, and Binder2-4 was obtained.
Examples 7-11 provide catalytic cracking aids of the present disclosure, and comparative examples 8-14 provide comparative catalytic cracking aids.
Example 7
Adding decationized water and aluminum sol into molecular sieve A, kaolin and pseudo-boehmite, pulping for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, continuously pulping for 45 minutes, adding the phosphorus-aluminum inorganic binder prepared in example 3, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, roasting the microspheres at 500 ℃ for 1 hour to obtain ZJ1The compounding ratio is shown in Table 3.
Comparative examples 8 to 14
A catalytic cracking assistant was prepared as described in example 7, except that molecular sieves DA1, DA2, DA3, DA4, DA5, DA6 and DA7 were used in place of A to prepare assistant DZJ1-DZJ7The compounding ratio is shown in Table 3.
Example 8
Adding decationized water and aluminum sol into molecular sieve B, kaolin and pseudo-boehmite, pulping for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, continuously pulping for 45 minutes, adding the phosphorus-aluminum inorganic binder prepared in the embodiment 3, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, roasting the microspheres at 500 ℃ for 1 hour to obtain ZJ2The compounding ratio is shown in Table 3.
Example 9
Adding decationized water and aluminum sol into molecular sieve A, kaolin and pseudo-boehmite, pulping for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, continuously pulping for 45 minutes, adding the phosphorus-aluminum inorganic binder prepared in example 4, stirring for 30 minutes, and then mixing the obtained mixtureSpray drying the slurry to obtain microspheres, and roasting the microspheres at 500 ℃ for 1 hour to obtain ZJ3The compounding ratio is shown in Table 3.
Example 10
Adding decationized water and aluminum sol into molecular sieve A, kaolin and pseudo-boehmite, pulping for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, continuously pulping for 45 minutes, adding the phosphorus-aluminum inorganic binder prepared in example 5, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, roasting the microspheres at 500 ℃ for 1 hour to obtain ZJ4The compounding ratio is shown in Table 3.
Example 11
Adding decationized water and silica sol into molecular sieve A, kaolin and pseudo-boehmite, pulping for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, continuously pulping for 45 minutes, adding the phosphorus-aluminum inorganic binder prepared in example 6, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, adding the microspheres into 7.5 weight percent diammonium hydrogen phosphate aqueous solution, heating to 60 ℃ under stirring, reacting for 20 minutes at the temperature, vacuum-filtering and drying the slurry, and roasting for 2 hours at 500 ℃ to obtain ZJ5The compounding ratio is shown in Table 3.
Blank test example, examples 12-16 incorporation of 100% Balancing agent and Balancing agent into adjuvant ZJ prepared in examples of the present disclosure using a small fixed fluidized bed reaction apparatus1-ZJ5The reaction performance evaluation was conducted to demonstrate the catalytic cracking reaction effect of the catalytic cracking aids provided by the present disclosure.
Blank test example, examples 12 to 16
Respectively mixing auxiliary agents ZJ1-ZJ5The aging treatment was carried out at 800 ℃ under a 100% steam atmosphere for 17 hours. Taking the aged ZJ1-ZJ6Separately mixed with an industrial FCC equilibrium catalyst (commercial grade DVR-3 FCC equilibrium catalyst, micro-reverse activity 63). 100% of the balance agent and catalyst mixture was charged into a small fixed fluidized bed reactor, and the sources shown in Table 4 were usedThe material oil is catalytically cracked under the following reaction conditions: the reaction temperature is 500 ℃, and the weight hourly space velocity is 8h-1And the weight ratio of the solvent to the oil is 6. The weight composition of the individual catalyst mixtures and the reaction results are given in Table 5.
Comparative examples 15-21A small fixed fluidized bed reactor was used to incorporate the balancing agent into the formulation DZJ prepared in the comparative examples of the present disclosure1-DZJ7Performance evaluations were conducted to illustrate the case where the comparative aid was used.
Comparative examples 15 to 21
The same feed oil was catalytically cracked in the same manner as in example 12, except that the catalysts used were DZJ each which was an aid obtained by aging in the same manner as in example 121-DZJ7Mixtures with commercial FCC equilibrium catalysts. The weight composition of the individual catalyst mixtures and the reaction results are given in Table 5.
As can be seen from table 5, compared with the comparative assistant, the catalytic assistant provided by the present disclosure can effectively increase the yields of catalytically cracked propylene and liquefied gas, and simultaneously significantly increase the concentration of propylene in the catalytically cracked liquefied gas.
TABLE 1
Molecular sieves A DA1 DA2 DA3 DA4 DA5 DA6 DA7 B
Degree of crystallization/%) 87 80 78 83 83 83 85 83 90
P2O5Content/% 7.5 7.2 7.5 7.5 7.5 7.5 7.5 7.5 7.5
SBET/(m2/g) 510 462 451 473 469 477 491 413 521
(VMesopores/VGeneral hole)/％ 60.4 53.8 54.7 57.1 54.5 56.8 57.8 52.7 62.3
(V2nm-20nm/VMesopores)/％ 90 80 80 86 77 82 82 63 92
(amount of strong acid/total acid)/% 63 48 47 56 45 58 55 40 65
Acid content of B acid/LAmount of acid and acid 13 4.9 5.0 8 5.0 10.1 9.2 2.3 14.2
D (Al distribution) 0.75 1.1 1.1 0.95 1.1 0.87 0.91 1.1 0.80
TABLE 2
TABLE 3
TABLE 4
Item Numerical value Item Numerical value
Density (20 ℃ C.)/(g. cm)-3) 0.9104 Distillation range/. degree.C
Refractive index (70 ℃ C.) 1.4917 Initial boiling point 251
Viscosity (80 ℃ C.)/(mm)2·s-1) 18.54 5％ 325
Viscosity (100 ℃ C.)/(mm)2·s-1) 10.89 10％ 355
Freezing point/. degree.C 38 30％ 416
Carbon residue value/weight% 3.1 50％ 452
Four components composition/weight% End point of distillation 544
Saturated hydrocarbons 63.7 Metal content/(μ g. g)-1)
Aromatic hydrocarbons 21.6 Al 0.6
Glue 14.5 Ca 21.5
Asphaltenes 0.2 Fe 16.4
Element composition/weight% Mg 0.6
C 86.12 Na 1.8
H 12.64 Ni 7.9
S 0.65 V 0.6
N 0.277 Pb 2.1
TABLE 5

Claims (16)

1. A catalytic cracking assistant for increasing the yield of propylene, which comprises 10-75 wt% of a phosphorus-containing IMF structure molecular sieve based on the dry weight of the assistant, 3-40 wt% of a phosphorus-aluminum inorganic binder based on the dry weight, 1-30 wt% of other inorganic binders based on oxides and 0-60 wt% of second clay based on the dry weight; wherein,
the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay, and the phosphorus-aluminum inorganic binder containing the first clay comprises Al based on the dry weight of the phosphorus-aluminum inorganic binder containing the first clay2O315-40% by weight, calculated as P, of an aluminium component2O545-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis weight, and the P/Al weight ratio is 1.0-6.0, pH value is 1-3.5, solid content is 15-60 wt%;
the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.6 and less than or equal to 0.85; wherein D = Al (S)/Al (C), Al (S) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the distance H from the edge of the crystal face of the molecular sieve crystal grain to the inside measured by a TEM-EDS method, and Al (C) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the distance H from the geometric center of the crystal face of the molecular sieve crystal grain to the outside measured by the TEM-EDS method, wherein H is 10% of the distance from a certain point of the edge of the crystal face to the geometric center of the crystal face; the proportion of the mesopore volume of the molecular sieve to the total pore volume is 50-80%, and the proportion of the mesopore volume with the pore diameter of 2-20 nm to the total mesopore volume is more than 85%; the proportion of the strong acid amount of the molecular sieve to the total acid amount is 50-80%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 7-30; with P2O5The molecular sieve has a phosphorus content of from 0.1 to 15 wt.% based on the dry weight of the molecular sieve.
2. The adjuvant according to claim 1, wherein the molecular sieve has an Al distribution parameter D satisfying: d is more than or equal to 0.65 and less than or equal to 0.82; the proportion of the mesopore volume of the molecular sieve in the total pore volume is 57-70%, and the proportion of the mesopore volume with the pore diameter of 2-20 nm in the total mesopore volume is more than 90%; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 55-70%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 8-25; with P2O5The molecular sieve has a phosphorus content of from 1 to 13 weight percent, based on the dry weight of the molecular sieve.
3. The adjuvant according to claim 1, wherein the first clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth; the second clay is at least one selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite; the other inorganic binder is at least one selected from pseudo-boehmite, alumina sol, silica-alumina sol and water glass.
4. The adjuvant according to any one of claims 1 to 3, wherein the adjuvant is selected from the group consisting ofBased on the dry weight of the raw materials, and the auxiliary agent also contains P2O5Up to 5 wt% of a phosphorus additive.
5. The adjuvant of claim 4, wherein the adjuvant comprises 8-25 wt% of a phosphorus aluminum inorganic binder, 20-60 wt% of a phosphorus-containing IMF structure molecular sieve, 10-45 wt% of a second clay, 5-25 wt% of other inorganic binders, and 0-3 wt% of a phosphorus additive.
6. A preparation method of a catalytic cracking auxiliary agent for increasing the yield of propylene comprises the following steps:
mixing the phosphorus-containing IMF structure molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders, adding or not adding second clay, pulping, and spray-drying; wherein, a phosphorus additive is introduced or not introduced;
based on the total dry weight of the preparation raw materials of the auxiliary agent, the preparation raw materials of the auxiliary agent comprise 10-75 wt% of phosphorus-containing IMF structure molecular sieve based on the dry weight, 3-40 wt% of phosphorus-aluminum inorganic binder based on the dry weight, 1-30 wt% of other inorganic binders based on oxides, 0-60 wt% of second clay based on the dry weight, and the preparation raw materials of the auxiliary agent or the auxiliary agent do not comprise P2O5Up to 5 wt% of a phosphorus additive; wherein,
the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay, and the phosphorus-aluminum inorganic binder containing the first clay comprises Al based on the dry weight of the phosphorus-aluminum inorganic binder containing the first clay2O315-40% by weight, calculated as P, of an aluminium component2O545-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis weight, and the P/Al weight ratio is 1.0-6.0, pH value is 1-3.5, solid content is 15-60 wt%;
the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.6 and less than or equal to 0.85; wherein D = Al (S)/Al (C), Al (S) represents the content of aluminum in the region of more than 100 square nanometers arbitrarily within the distance H from the crystal face edge of the molecular sieve crystal grain measured by the TEM-EDS method, and Al (C) represents the content of aluminum in the region of more than 100 square nanometers arbitrarilyThe aluminum content of a region which is arbitrarily greater than 100 square nanometers within the distance H from the geometric center of the crystal face of the molecular sieve crystal grain to the outside determined by a TEM-EDS method, wherein the H is 10% of the distance from a certain point on the edge of the crystal face to the geometric center of the crystal face; the proportion of the mesopore volume of the molecular sieve to the total pore volume is 50-80%, and the proportion of the mesopore volume with the pore diameter of 2-20 nm to the total mesopore volume is more than 85%; the proportion of the strong acid amount of the molecular sieve to the total acid amount is 50-80%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 7-30; with P2O5The molecular sieve has a phosphorus content of from 0.1 to 15 wt.% based on the dry weight of the molecular sieve.
7. The preparation method of claim 6, wherein the preparation step of the phosphorous-containing IMF structure molecular sieve comprises:
a. carrying out desiliconization treatment on the sodium type IMF structure molecular sieve in an alkali solution to obtain a desiliconized molecular sieve;
b. b, performing ammonium exchange treatment on the desiliconized molecular sieve obtained in the step a 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;
c. b, dealuminizing the ammonium exchange molecular sieve obtained in the step b in a composite acid dealuminizing agent solution consisting of fluosilicic acid, organic acid and inorganic acid, and filtering and washing to obtain a dealuminized molecular sieve; the organic acid is at least one selected from ethylenediamine tetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid is at least one selected from hydrochloric acid, sulfuric acid and nitric acid;
d. and c, carrying out phosphorus modification treatment and roasting treatment on the dealuminized molecular sieve obtained in the step c to obtain the phosphorus-containing IMF structure molecular sieve.
8. The preparation method of claim 7, wherein the preparation of the sodium-type IMF structure molecular sieve in the step a comprises:
filtering and washing the slurry of the IMF structure molecular sieve obtained by amine crystallization to obtain a washed molecular sieve; wherein the sodium content of the washed molecular sieve is less than 3.0 wt% based on the total dry basis weight of the washed molecular sieve based on sodium oxide;
and drying and air roasting the water-washed molecular sieve to obtain the sodium type IMF structure molecular sieve.
9. The method according to claim 7, wherein the alkali solution in the step a is selected from the group consisting of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution and aqueous ammonia.
10. The production method according to claim 7, wherein the conditions of the desiliconization treatment in the step a include: the weight ratio of the sodium type IMF structure molecular sieve, alkali in the alkali solution and water in the alkali solution is 1: (0.1-2): (5-20), wherein the desiliconization treatment temperature is between room temperature and 100 ℃, and the time is 0.2-4 hours.
11. The production method according to claim 7, wherein the conditions of the desiliconization treatment in the step a include: the weight ratio of the sodium type IMF structure molecular sieve, alkali in the alkali solution and water in the alkali solution is 1: (0.2-1): (5-20).
12. The preparation method according to claim 7, wherein the dealumination treatment conditions in step c include: the weight ratio of the ammonium exchange molecular sieve, the organic acid, the inorganic acid and the fluosilicic acid is 1: (0.01-0.3): (0.01-0.3): (0.01-0.3); the dealuminization treatment temperature is 25-100 ℃, and the time is 0.5-6 hours.
13. The preparation method according to claim 7, wherein the dealumination treatment conditions in step c include: the weight ratio of the ammonium exchange molecular sieve, the organic acid, the inorganic acid and the fluosilicic acid is 1: (0.02-0.2): (0.015-0.2): (0.015-0.2).
14. The method of claim 7, wherein the phosphorus modification treatment in step d comprises: at least one phosphorus-containing compound selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate is used to impregnate and/or ion-exchange the molecular sieve.
15. The production method according to claim 7, wherein the conditions of the baking treatment include: the atmosphere of the roasting treatment is air atmosphere or water vapor atmosphere; the roasting temperature is 400-800 ℃, and the roasting time is 0.5-8 hours.
16. The method of claim 6, wherein the first clay-containing aluminophosphate inorganic binder is prepared by a method comprising:
(1) pulping and dispersing an alumina source, first clay and water into slurry with the solid content of 8-45 wt%; the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, first clay and Al which are calculated by dry weight2O3The weight ratio of the alumina source is (0-40) to (15-40), and the first clay is not used in 0;
(2) adding concentrated phosphoric acid into the slurry obtained in the step (1) according to the weight ratio of P/Al =1-6 under stirring;
(3) and (3) reacting the slurry obtained in the step (2) at the temperature of 50-99 ℃ for 15-90 minutes.
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CN102616804A (en) * 2011-01-27 2012-08-01 中国石油化工股份有限公司 Copper-containing beta molecular sieve and preparation method thereof
CN103007989A (en) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 Cracking assistant for improving low-carbon olefin concentration
CN105732349A (en) * 2014-12-12 2016-07-06 中国科学院大连化学物理研究所 Method for preparing anhydrous formaldehyde through methanol dehydrogenation

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