CN107971016B - A kind of catalytic cracking catalyst and preparation method thereof containing phosphorous IMF structure molecular screen - Google Patents
A kind of catalytic cracking catalyst and preparation method thereof containing phosphorous IMF structure molecular screen Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- 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
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- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
- C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
- C07C4/18—Catalytic processes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- 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
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Abstract
The invention discloses a kind of catalytic cracking catalysts and preparation method thereof containing phosphorous IMF structure molecular screen, it is counted by butt and on the basis of the dry weight of the catalyst, the catalyst contains the mixed molecular sieve of the natural mineral matter of 15-65 weight %, the inorganic oxide binder of 10-60 weight % and 25-75 weight %, and the mixed molecular sieve includes Y molecular sieve and phosphorous IMF structure molecular screen.Catalytic cracking catalyst provided by the invention containing phosphorous IMF structure molecular screen productivity of propylene in petroleum hydrocarbon catalytic pyrolysis reaction is high, and Propylene Selectivity is good, while being capable of fecund BTX.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalysts and preparation method thereof containing phosphorous IMF structure molecular screen.
Background technique
For a long time, ethylene, propylene and butylene are that the basic organic chemical industry of synthetic resin, synthetic fibers and synthetic rubber is former
Material, wherein propylene is be only second to ethylene a kind of for manufacturing the important source material of petroleum chemicals.The maximum of domestic and international propylene at present
Source is the Main By product of thermal cracking production ethylene, and the second largest source of propylene provides about nearly all from FCC apparatus
30% demand, in the U.S., FCC apparatus then provides petroleum chemicals to about half demand of propylene.
Due to increasing rapidly to polyacrylic demand, make the required propylene of petrochemical industry faster than ethylene requirements, and
The construction of ethylene plant is limited to the demand of ethylene, therefore a large amount of volume increase FCC propylene will be used for the increase of meet demand.From previous generation
It has recorded since the eighties, the catalyst of the ZSM-5 containing shape-selective molecular sieve starts to put into industrial application on FCC apparatus, has reached volume increase
C3 =Purpose, but the greatest weakness of this kind of ZSM-5 molecular sieve is that activity stability is poor, in the periodic regeneration of FCC apparatus harshness
Under the conditions of easy in inactivation.
IM-5 molecular sieve is a kind of IMF structure molecular screen, is synthesized for the first time by Benazzi in 1998.2007 by
Baerlocher et al. completes the parsing work of structure.The molecular sieve is two-dimentional ten-ring cellular structure, channel diameter with
ZSM-5 molecular sieve is similar, and there is also a limited ducts on third dimension direction.Since it has and ZSM-5 molecular sieve phase
Close cellular structure, while there is higher acid amount and better hydrothermal stability, therefore show in many catalysis reaction
Characteristic.Corma et al. has carried out a series of researchs to the catalytic performance of IM-5 molecular sieve, finds it in terms of alkane cracking capability
Higher than ZSM-5 molecular sieve.
Although IM-5 molecular sieve can alkane cracking capability with higher, it is identical as other ten-ring molecular sieves, by
Narrow in its cellular structure, biggish reactant molecule such as polycyclic hydro carbons are difficult to enter in crystal duct and are reacted, and reduce
The effective affecting acreage of molecular sieve reduces the reactivity of molecular sieve；On the other hand, isoparaffin and aromatic hydrocarbons etc. are biggish
Product molecule is also not easy to diffuse out inside molecular sieve pore passage, in turn so as to cause secondary responses such as excessive hydrogen migration, cokings
Molecular sieve inactivation, reaction selectivity is caused to reduce.In the cracking reaction for being divided into raw material with macromolecular recombination, IM-5 molecular sieve pores
The defect of road hole stenostomia necessarily makes problem above more prominent.
Summary of the invention
The object of the present invention is to provide a kind of catalytic cracking catalyst containing phosphorous IMF structure molecular screen and its preparation sides
Method, the catalytic cracking catalyst provided by the invention containing phosphorous IMF structure molecular screen is third in petroleum hydrocarbon catalytic pyrolysis reaction
Alkene yield is high, and Propylene Selectivity is good, while being capable of fecund BTX.
To achieve the goals above, the present invention provides a kind of catalytic cracking catalyst containing phosphorous IMF structure molecular screen,
It is counted by butt and on the basis of the dry weight of the catalyst, the catalyst contains natural mineral matter, the 10- of 15-65 weight %
The inorganic oxide binder of 60 weight % and the mixed molecular sieve of 25-75 weight %, the mixed molecular sieve include Y molecular sieve and contain
Phosphorus IMF structure molecular screen；Wherein, the Al distribution parameter D of the phosphorous IMF structure molecular screen meets: 0.6≤D≤0.85；Its
In, D=Al (S)/Al (C), Al (S) indicate the crystal face side of the phosphorous IMF structure molecular screen crystal grain using the measurement of TEM-EDS method
Along inside H apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) indicates containing using the measurement of TEM-EDS method
The outside H of geometric center of crystal face described in phosphorus IMF structure molecular screen crystal grain contains apart from interior any aluminium greater than 100 square nanometers regions
Amount, wherein the H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The phosphorous IMF structural molecule
The ratio that the mesopore volume of sieve accounts for total pore volume is 50-80 body %, the total mesoporous of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers
The ratio of volume is greater than 85 body %；The ratio that the strong acid acid amount of the phosphorous IMF structure molecular screen accounts for total acid content is 50-80%, B
The ratio between sour amount and L acid acid amount are 7-30；With P2O5Count and on the basis of the dry weight of phosphorous IMF structure molecular screen, it is described to contain
The phosphorus content of phosphorus IMF structure molecular screen is 0.1-15 weight %.
Preferably, the Al distribution parameter D of the phosphorous IMF structure molecular screen meets: 0.65≤D≤0.82；It is described phosphorous
The ratio that the mesopore volume of IMF structure molecular screen accounts for total pore volume is 57-70 body %, the middle hole body that aperture is 2 nanometers -20 nanometers
The ratio of the product total mesopore volume of Zhan is greater than 90 body %；The strong acid acid amount of the phosphorous IMF structure molecular screen accounts for the ratio of total acid content
For 55-70%, the ratio between B acid acid amount and L acid acid amount are 8-25；With P2O5It counts and is with the dry weight of phosphorous IMF structure molecular screen
Benchmark, the phosphorus content of the phosphorous IMF structure molecular screen are 1-13 weight %.
Preferably, the mesopore volume is that aperture is greater than 2 nanometers of pore volumes less than 100 nanometers；The molecular sieve it is strong
Sour amount accounts for the ratio of total acid content using NH3- TPD method measures, and the acid site of the strong acid is NH3Desorption temperature is greater than
Acid site corresponding to 300 DEG C；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
Preferably, the natural mineral matter includes being selected from kaolin, halloysite, montmorillonite, diatomite, convex-concave stick
At least one of stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite, the inorganic oxide binder be selected from
At least one of silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina, the Y molecular sieve are selected from DASY molecule
Sieve, the DASY molecular sieve containing rare earth, USY molecular sieve, the USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve and HY points
At least one of son sieve, preferably DASY molecular sieve and/or REY molecular sieve containing rare earth.
Preferably, the dry weight ratio of the Y molecular sieve and the phosphorous IMF structure molecular screen is 1:(0.025-4).
The present invention also provides a kind of preparation method of catalytic cracking catalyst provided by the present invention, the preparation method packets
It includes: preparing after raw material and water mix for catalytic cracking catalyst is beaten and is spray-dried；Wherein, in terms of butt and with institute
It is described to prepare the natural mineral matter, the 10-60 that raw material includes 15-65 weight % on the basis of stating the dry weight for preparing raw material
The precursor of the inorganic oxide binder of weight % and the mixed molecular sieve of 25-75 weight %, the mixed molecular sieve
Including Y molecular sieve and phosphorous IMF structure molecular screen.
Preferably, the preparation step of the phosphorous IMF structure molecular screen includes: a, sodium form IMF structure molecular screen in alkali soluble
Desiliconization processing is carried out in liquid, obtains desiliconization molecular sieve；B, gained desiliconization molecular sieve in step a is subjected to ammonium exchange processing, obtained
Ammonium exchanges molecular sieve；Wherein, it is counted by sodium oxide molybdena and on the basis of total dry weight of ammonium exchange molecular sieve, the ammonium exchanges molecule
The sodium content of sieve % heavy less than 0.2；C, by gained ammonium exchange molecular sieve in step b by fluosilicic acid, organic acid and inorganic acid group
At Compound-acid dealuminzation agent solution in carry out dealumination treatment, and after being filtered and washed, obtain dealuminzation molecular sieve；D, by step
After dealuminzation molecular sieve obtained in c carries out P Modification processing and calcination process, the phosphorous IMF structure molecular screen is obtained.
Preferably, the preparation step of sodium form IMF structure molecular screen described in step a includes: and will use to have amine method crystallization institute
After IMF structure molecular screen slurries are filtered and washs, obtain washing molecular sieve；Wherein, in terms of sodium oxide molybdena and with the water
It washes on the basis of total dry weight of molecular sieve, the sodium content % heavy less than 3.0 of the washing molecular sieve；By the washing molecular sieve
It is dried and after air roasting, obtains the sodium form IMF structure molecular screen.
Preferably, aqueous slkali described in step a is selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide.
Preferably, desiliconization described in step a processing condition include: with the sodium form IMF structure molecular screen of dry basis,
The weight ratio of the water in alkali and aqueous slkali in aqueous slkali is 1:(0.1-2): the temperature of (5-20), the desiliconization processing are room temperature
To 100 DEG C, the time is 0.2-4 hours.
Preferably, desiliconization described in step a processing condition include: with the sodium form IMF structure molecular screen of dry basis,
The weight ratio of the water in alkali and aqueous slkali in aqueous slkali is 1:(0.2-1): (5-20).
Preferably, organic acid described in step c is in ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid
At least one, the inorganic acid be selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the condition of dealumination treatment described in step c includes: with the ammonium of dry basis exchange molecular sieve, organic
The weight ratio of acid, inorganic acid and fluosilicic acid is 1:(0.01-0.3): (0.01-0.3): (0.01-0.3)；The dealumination treatment
Temperature be 25-100 DEG C, the time be 0.5-6 hours.
Preferably, the condition of dealumination treatment described in step c includes: with the ammonium of dry basis exchange molecular sieve, organic
The weight ratio of acid, inorganic acid and fluosilicic acid is 1:(0.02-0.2): (0.015-0.2): (0.015-0.2).
Preferably, the processing of P Modification described in step d includes: that will be selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid
At least one of ammonium phosphorus-containing compound carries out dipping and/or ion exchange to molecular sieve.
Preferably, it is air atmosphere or steam atmosphere that the condition of the calcination process, which includes: the atmosphere of calcination process,；Roasting
Burning temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.
Preferably, the precursor of the inorganic oxide binder includes intending thin water aluminium selected from silica solution, Aluminum sol, peptization
At least one of stone, silicon-aluminum sol and phosphorated aluminiferous collosol.
Present inventors discovered unexpectedly that chemically carrying out desiliconization processing to IMF structure molecular screen, ammonium exchanges
Processing carries out the processing such as dealumination treatment and P Modification processing, prepared phosphorous IMF structural molecule in Compound-acid dealuminzation agent solution
Sieve can be used for preparing catalytic cracking catalyst and be applied in catalytic pyrolysis, improves productivity of propylene, Propylene Selectivity and BTX and produces
Rate.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of catalytic cracking catalyst containing phosphorous IMF structure molecular screen, urges in terms of butt and with this
On the basis of the dry weight of agent, the catalyst contains the inorganic oxide of the natural mineral matter of 15-65 weight %, 10-60 weight %
The mixed molecular sieve of object binder and 25-75 weight % preferably comprises the inorganic of the heavy % of natural mineral matter, 10-30 of 20-55 weight %
The mixed molecular sieve of adhesive oxides (more preferably 12-28 weight %) and 30-70 weight %, the mixed molecular sieve includes Y points
Son sieve and phosphorous IMF structure molecular screen；Wherein, the Al distribution parameter D of the phosphorous IMF structure molecular screen meets: 0.6≤D≤
0.85；Wherein, D=Al (S)/Al (C), Al (S) indicate the phosphorous IMF structure molecular screen crystal grain using the measurement of TEM-EDS method
The inside H in crystal face edge apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) indicates to use TEM-EDS method
The outside H of geometric center of crystal face described in the phosphorous IMF structure molecular screen crystal grain of measurement is arbitrarily greater than 100 square nanometers areas apart from interior
The aluminium content in domain, wherein the H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The phosphorous IMF
The ratio that the mesopore volume of structure molecular screen accounts for total pore volume is 50-80 body %, the mesopore volume that aperture is 2 nanometers -20 nanometers
The ratio of the total mesopore volume of Zhan is greater than 85 body %；The ratio that the strong acid acid amount of the phosphorous IMF structure molecular screen accounts for total acid content is
The ratio between 50-80%, B acid acid amount and L acid acid amount are 7-30；With P2O5It counts and using the dry weight of phosphorous IMF structure molecular screen as base
Standard, the phosphorus content of the phosphorous IMF structure molecular screen are 0.1-15 weight %；Preferably, the Al of the phosphorous IMF structure molecular screen
Distribution parameter D meets: 0.65≤D≤0.82；The ratio that the mesopore volume of the phosphorous IMF structure molecular screen accounts for total pore volume is
The ratio of 57-70 body %, the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers are greater than 90 body %；It is described phosphorous
The ratio that the strong acid acid amount of IMF structure molecular screen accounts for total acid content is 55-70%, and the ratio between B acid acid amount and L acid acid amount are 8-25；With
P2O5It counts and on the basis of the dry weight of phosphorous IMF structure molecular screen, the phosphorus content of the phosphorous IMF structure molecular screen is 1-
13 heavy %.
IMF structure is the topological structure of molecular sieve, such as IM-5 molecular sieve has IMF structure.
According to the present invention, using TEM-EDS method measurement molecular sieve aluminium content be it is well-known to those skilled in the art,
Wherein the geometric center is also well-known to those skilled in the art, can be calculated according to formula, and the present invention is no longer superfluous
It states, the geometric center of generally symmetrical figure is the intersection point of each opposed apexes line, for example, conventional rectangular bulk IM-5 molecular sieve is long
Point of intersection of the geometric center of rectangular crystal face in opposed apexes line.The crystal face is a face of regular crystal grain, it is described to
Interior and outwardly direction refers both to the direction inwardly or outwardly on the crystal face.
According to the present invention, the mesopore volume of the molecular sieve accounts for the ratio of total pore volume and aperture is 2 nanometers -20 nanometers
The ratio of the total mesopore volume of mesopore volume Zhan is measured using N2 adsorption BET specific surface area method, the mesopore volume finger-hole
Diameter is greater than 2 nanometers of pore volumes less than 100 nanometers；The strong acid acid amount of the molecular sieve accounts for the ratio of total acid content using NH3-TPD
Method measures, and the acid site of the strong acid is NH3Desorption temperature be greater than 300 DEG C corresponding to acid site；The B acid acid amount
It is measured with the ratio between the L acid acid amount use infrared acid process of pyridine adsorption.
According to the present invention, natural mineral matter refers under the comprehensive function of the various substances of the earth's crust and (claims geologic process) formation
Natural simple substance or compound, and distinctive chemical component and relatively-stationary chemical component with chemical formula expression, such as can
To include selected from kaolin, halloysite, montmorillonite, diatomite, convex-concave stick stone, sepiolite, galapectite, hydrotalcite, swelling
At least one of soil and rectorite；Inorganic oxide binder refers to the inorganic oxide for playing bonding each component in the catalyst
Object, such as can be for selected from least one of silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina, the Y divides
Son sieve can be the DASY molecular sieve selected from DASY molecular sieve, containing rare earth, USY molecular sieve, the USY molecular sieve containing rare earth, REY points
At least one of son sieve, REHY molecular sieve and HY molecular sieve, preferably DASY molecular sieve and/or REY molecular sieve containing rare earth,
The dry weight ratio of the Y molecular sieve and the phosphorous IMF structure molecular screen can be 1:(0.025-4).
The present invention also provides a kind of catalytic cracking catalysts provided by the present invention containing phosphorous IMF structure molecular screen
Preparation method, the preparation method include: that preparing for catalytic cracking catalyst is carried out mashing and spraying dry after raw material and water mix
It is dry；Wherein, it is counted by butt and on the basis of the dry weight for preparing raw material, the raw material for preparing includes 15-65 weight %
The precursor of the inorganic oxide binder of the heavy % of the natural mineral matter, 10-60 and the mixing point of 25-75 weight %
It is (more preferable to preferably comprise the natural mineral matter of 20-55 weight %, the precursor of the inorganic oxide binder of 10-30 weight % for son sieve
For the mixed molecular sieve of 12-28 weight %) and 30-70 weight %, the mixed molecular sieve includes Y molecular sieve and phosphorous IMF structure point
Son sieve.
According to the present invention, the preparation step of the phosphorous IMF structure molecular screen may include: a, sodium form IMF structural molecule
Sieve carries out desiliconization processing in aqueous slkali, obtains desiliconization molecular sieve；B, gained desiliconization molecular sieve in step a is carried out at ammonium exchange
Reason obtains ammonium exchange molecular sieve；Wherein, by sodium oxide molybdena count and by ammonium exchange molecular sieve total dry weight on the basis of, the ammonium
Exchange the sodium content % heavy less than 0.2 of molecular sieve；C, by step b gained ammonium exchange molecular sieve by fluosilicic acid, organic acid and
Dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of inorganic acid composition, and after being filtered and washed, obtains dealuminzation molecular sieve；
D, after dealuminzation molecular sieve obtained in step c being carried out P Modification processing and calcination process, the phosphorous IMF structural molecule is obtained
Sieve.
According to the present invention, sodium form IMF structure molecular screen is well-known to those skilled in the art, can it is commercially available can be voluntarily
Preparation, for example, the preparation step of the sodium form IMF structure molecular screen may include: that will use to have IMF structure obtained by amine method crystallization
After molecular sieve pulp is filtered and washes, washing molecular sieve is obtained；Wherein, in terms of sodium oxide molybdena and with the washing molecular sieve
On the basis of total dry weight, the sodium content % heavy less than 3.0 of the washing molecular sieve；The washing molecular sieve is dried and
After air roasting, the sodium form IMF structure molecular screen is obtained.It is described to there is amine method crystallization to refer to using template progress hydrothermal crystallizing
Prepare molecular sieve, by taking the preparation of IMF molecular sieve as an example, specific document can with reference to Chinese patent CN102452667A,
CN103708491A, CN102452666A and CN103723740A.The air roasting is used to remove the mould in washing molecular sieve
Plate agent, the temperature of the air roasting can be 400-700 DEG C, and the time can be 0.5-10 hours.
According to the present invention, part framework silicon atom and part framework silicon of the desiliconization processing for removing molecular sieve remove,
It is unobstructed to reach molecular sieve pore passage, generates more second hole effects, aqueous slkali described in step a can be inorganic base, for example,
Selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide, preferably sodium hydrate aqueous solution；Desiliconization described in step a
The condition of processing may include: with the water in the alkali and aqueous slkali in the sodium form IMF structure molecular screen of dry basis, aqueous slkali
Weight ratio can be 1:(0.1-2): (5-20), preferably 1:(0.2-1): (5-20), the temperature of desiliconization processing can be with
It is room temperature to 100 DEG C, the time can be 0.2-4 hours.
According to the present invention, ammonium exchange processing is well-known to those skilled in the art, is contained for reducing the sodium in molecular sieve
Amount.For example, the condition of the ammonium exchange processing may include: according to molecular sieve: ammonium salt: water=1:(0.1~1): (5~10)
Weight ratio filters molecular sieve after room temperature exchanges 0.5~3 hour to ammonium at 100 DEG C, and ammonium salt used can be common nothing
Machine ammonium salt, for example, the number of ammonium exchange can repeat 1~3 time selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate,
Until sodium oxide content is lower than 0.2 heavy % in molecular sieve.
According to the present invention, although desiliconization processing can make molecular sieve generate second hole, in desiliconization treatment process, point
Amorphous chips are inevitably resulted from son sieve, block molecular sieve pore passage, cover activated centre, and molecular sieve table can be made
The relatively rich aluminium in face, is unfavorable for the raising of molecular sieve reaction selectivity, it is therefore desirable to carry out subsequent dealumination treatment, dealumination treatment to it
It is well-known to those skilled in the art, but did not reported and inorganic acid, organic acid and fluosilicic acid are used for dealumination treatment together.Institute
It states dealumination treatment can be primary or to be performed in multiple times, organic acid can be exchanged first to molecular sieve with the ammonium and mixed, then by fluorine
Silicic acid and inorganic acid exchange molecular sieve mixing with the ammonium, it can exchange in molecular sieve for ammonium first is added in organic acid, then
By fluosilicic acid and inorganic acid, cocurrent is added at a slow speed, or fluosilicic acid is first added and adds inorganic acid, preferably fluosilicic acid and inorganic acid
Cocurrent is added at a slow speed.For example, organic acid described in step c can be for selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfo group water
At least one of poplar acid, preferably oxalic acid or citric acid, further preferably oxalic acid；The inorganic acid can be for selected from salt
At least one of acid, sulfuric acid and nitric acid, preferably hydrochloric acid or sulfuric acid, further preferably hydrochloric acid；The item of the dealumination treatment
Part may include: the weight ratio with the ammonium exchange molecular sieve of dry basis, organic acid, inorganic acid and fluosilicic acid for 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 temperature of the dealumination treatment can be 25-100 DEG C, and the time can be 0.5-6 hours.Pass through desiliconization processing and Compound-acid dealuminzation
Agent solution dealumination treatment, which combines, handles IMF structure molecular screen, be distributed the aluminium of molecular sieve, silica alumina ratio, Acidity and
Pore structure has carried out modulation, keeps IMF structure molecular screen reaming modified, still has preferable selective activization, thus effectively
Improve the propylene and BTX yield of IMF structure molecular screen.
According to the present invention, P Modification processing is well-known to those skilled in the art, for example, P Modification described in step d
Processing may include: will selected from least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound to point
Son sieve carries out dipping and/or ion exchange.
According to the present invention, calcination process is well-known to those skilled in the art, for example, the condition of the calcination process can
To include: the atmosphere of calcination process as air atmosphere or steam atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is
0.5-8 hours.
It is of the present invention washing be it is well-known to those skilled in the art, refer generally to wash, for example, can use 5-10 times
The water of molecular sieve elutes molecular sieve.
According to the present invention, the precursor of the inorganic oxide binder refers to for generating in catalytic cracking catalyst
The catalytic cracking catalyst of inorganic oxide binder prepares raw material, such as may include selected from silica solution, Aluminum sol, peptization
At least one of boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.
The present invention will be further illustrated by embodiment below, but the present invention is not therefore subject to any restriction,
Instrument and reagent used by the embodiment of the present invention, unless otherwise instructed, be instrument commonly used by those skilled in the art and
Reagent.
Crystallinity of the invention is measured using the standard method of ASTM D5758-2001 (2011) e1.
Phosphorus content of the invention is measured using GB/T 30905-2014 standard method.
The research method of TEM-EDS measuring method of the invention referring to solid catalyst, petrochemical industry, 29 (3), 2000:
227。
Total specific surface area (S of the inventionBET), mesopore surface area, mesoporous pore volume, total pore volume, 2-20 nanometers of Jie
The measuring method of hole pore volume is as follows:
The AS-3 produced using Quantachrome instrument company, the measurement of AS-6 static state n2 absorption apparatus.
Instrument parameter: being placed in sample processing system for sample, is evacuated to 1.33 × 10 at 300 DEG C-2Pa, heat-insulation pressure keeping
4h purifies sample.At -196 DEG C of liquid nitrogen temperature, test purification sample is not pressing P/P on year-on-year basis0Under the conditions of to the adsorbance of nitrogen
And desorption rate, obtain N2Adsorption-desorption isothermal curve.Then total specific surface area is calculated using two parameter BET formula, micropore compares table
Area and mesopore surface area take than pressing P/P0=0.98 adsorbance below is the total pore volume of sample, utilizes BJH formula meter
The pore-size distribution of mesoporous part is calculated, and mesoporous pore volume (2-100 nanometers) and 2-20 nanometers of mesoporous hole are calculated using integration method
Volume.
The measuring method of B acid acid amount and L acid acid amount of the invention is as follows:
The FTS3000 type Fourier infrared spectrograph produced using BIO-RAD company, the U.S..
Test condition: tabletted be placed in the pond in situ of infrared spectrometer of sample is sealed, is vacuumized at 350 DEG C
To 10-3Pa keeps 1h, the gas molecule of sample surfaces is desorbed clean, is cooled to room temperature.Pressure is imported into pond in situ is
The pyridine steam of 2.67Pa is warming up to 200 DEG C, is evacuated to 10 again after balancing 30min-3Pa keeps 30min, is cooled to room
Temperature, in 1400-1700cm-1Scanning, records the infrared spectrum spectrogram of 200 DEG C of pyridine adsorptions in wave-number range.Again by infrared suction
Sample in receives pond moves to heat-treatment zone, is warming up to 350 DEG C, is evacuated to 10-3Pa keeps 30min, is cooled to room temperature, records
The infrared spectrum of 350 DEG C of pyridine adsorptions.Instrument automatic integration obtains B acid acid amount and L acid acid amount.
The measuring method of total acid content and strong acid acid amount of the invention is as follows:
Using II 2920 temperature programmed desorption instrument of Merck & Co., Inc, U.S. Autochem.
Test condition: weighing 0.2g sample to be tested and be packed into sample cell, is placed in conductance cell heating furnace, and He gas is carrier gas (50mL/
Min), 600 DEG C are warming up to the rate of 20 DEG C/min, purging 60min drives away the impurity of catalyst surface absorption.Then it is cooled to
100 DEG C, constant temperature 30min switches to NH3- He gaseous mixture (10.02%NH3+ 89.98%He) absorption 30min, it is further continued for He gas
It is steady to baseline to purge 90min, the ammonia of physical absorption is desorbed.600 DEG C are warming up to 10 DEG C/min heating rate to be taken off
It is attached, 30min is kept, desorption terminates.Using TCD detector detection gas change of component, instrument automatic integration obtain total acid content and
Strong acid acid amount, the acid site of strong acid are NH3Desorption temperature be greater than 300 DEG C corresponding to acid site.
Sodium content of the invention is measured using GB/T 30905-2014 standard method.
The calculation method of D value is as follows: choosing a crystal grain in transmission electron microscope and some crystal face of the crystal grain is formed
One polygon, there are 10% distance H of geometric center, edge and geometric center to edge point is (different for the polygon
Edge point, H value are different), choose respectively any one piece in the inside H distance in the crystal face edge be greater than 100 square nanometers regions with
And any one piece in the outside H distance of crystal face geometric center is greater than 100 square nanometers regions, measures aluminium content, as Al (S1)
With Al (C1), and D1=Al (S1)/Al (C1) is calculated, chooses different crystal grain respectively and measure 5 times, calculating average value is D.
Prepare embodiment 1
The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned
Molecular sieve roasts 6 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.4 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C,
After exchange processing 1h, until Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving
Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g are added in stirring, then by 35g hydrochloric acid
(mass fraction 10%) and 28g fluosilicic acid (mass fraction 3%) cocurrent are added, and time 30min is added；65 DEG C of constant temperature are warming up to stir
1h is mixed, filtering is washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3g
H3PO4(85 weight % of concentration) is uniformly mixed with dipping, drying, 550 DEG C of calcination process 2h.Molecular sieve-4 A is obtained, physico-chemical property is listed in table
1。
Prepare comparative example 1
The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned
Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 1000g 2.4%, is warming up to 65 DEG C, after reacting 30min, is rapidly cooled to room temperature
Afterwards, it filters, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, hands over
After changing processing 1h, until Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecular sieve 50g
(butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, and oxalic acid 20g is added in stirring；It is warming up to 65 DEG C of constant temperature stirrings
1h, filtering are washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.1gH3PO4
(85 weight % of concentration), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA1 is obtained, physico-chemical property is listed in
Table 1.
Prepare comparative example 2
The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned
Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.2 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, washing to filtrate neutrality.Then obtained molecular sieve filter cake is added in HCL aqueous solution and is washed, it is specific to grasp
As the molecular sieve pulp for taking above-mentioned molecular sieve filter cake 50g (butt) plus water to be configured to the weight of solid content 10 %, it is added in stirring
180g hydrochloric acid (mass fraction 10%)；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；1500g is added in filter cake
Water mashing, is added 80g NH4After Cl is warming up to 65 DEG C of exchange washing 40min, filtering, elution to filtrate neutrality；By filter cake plus water
It is beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH3PO4(85 weight % of concentration) is uniformly mixed with dipping, dries
It is dry, 550 DEG C calcination process 2 hours.Molecular sieve DA2 is obtained, physico-chemical property is listed in table 1.
Prepare comparative example 3
The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned
Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.2 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C,
After exchange processing 1h, until Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving
Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, and 135g fluosilicic acid (mass fraction is added in stirring
3%) time 30min, is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten solid
Content is the molecular sieve pulp of 40 weight %, and 6.3gH is added3PO4(85 weight % of concentration) is uniformly mixed with dipping, drying, 550 DEG C of roastings
Burn processing 2 hours.Molecular sieve DA3 is obtained, physico-chemical property is listed in table 1.
Prepare comparative example 4
The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned
Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 1.9 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C,
After exchange processing 1h, until Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving
Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 11g are added in stirring, then by 110g salt
Sour (mass fraction 10%) is added, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；It will
Filter cake adds water to be beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH3PO4(85 weight % of concentration) is uniformly mixed
Dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA4 is obtained, physico-chemical property is listed in table 1.
Prepare comparative example 5
The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned
Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.0 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C,
After exchange processing 1h, until Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving
Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 4g are added in stirring, then by 72g fluorine silicon
Sour (mass fraction 3%) is slowly added to, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed in filtrate
Property；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH3PO4(85 weight % of concentration), uniformly
Be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA5 is obtained, physico-chemical property is listed in table 1.
Prepare comparative example 6
The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned
Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.0 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C,
After exchange processing 1h, until Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving
Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, under stirring by 42g hydrochloric acid (mass fraction 10%) and
78g fluosilicic acid (mass fraction 3%) cocurrent is added, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to
Filtrate is neutral；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH3PO4(85 weight of concentration
Measure %), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA6 is obtained, physico-chemical property is listed in table 1.
Prepare comparative example 7
The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；By above-mentioned baking
Molecular sieve roasts 8 hours in air after dry, and 550 DEG C of maturing temperature, to remove template therein.Take above-mentioned molecular sieve 100g
It is added in the NaOH solution of 1.2 weight % of 2000g, is warming up to 65 DEG C, after reacting 30min, be rapidly cooled to room temperature, filter, wash
It washs to filtrate neutrality.It takes above-mentioned molecular sieve filter cake 50g (butt) that the mashing of 500g water is added, 40g NH is added4Cl is warming up to 75
DEG C, after exchange processing 1h, filtering, repeated exchanged is washed twice to molecular sieve sodium oxide content lower than 0.1%, and filter cake plus water are beaten
Starch to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH3PO4(85 weight % of concentration), be uniformly mixed with dipping, dry,
550 DEG C obtain molecular sieve DA7 in calcination process 2 hours, and physico-chemical property is listed in table 1.
Prepare embodiment 2
The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned
Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.3 weight % of 1500g, is warming up to 60 DEG C, after reacting 45min, is quickly cooled to room
Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C,
After exchange processing 1h, until Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving
Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 4g are added in stirring, then 10g sulfuric acid
(mass fraction 10%) and 45g fluosilicic acid (mass fraction 3%) cocurrent are added, and time 30min is added；45 DEG C of constant temperature are warming up to stir
1h is mixed, filtering is washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition
6.3gH3PO4(85 weight % of concentration), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve B, materialization
Matter is listed in table 1.
Conventional alkali process will make IM-5 molecular sieve surface richness aluminium it can be seen from data in table 1, using single organic acid
Oxalic acid dealuminzation (DA1) uses single inorganic acid HCl dealumination (DA2) and uses organic acid oxalic acid and two kinds of inorganic acid hydrochloric acid
Sour compound (DA4) all can not effectively remove the Al in molecular sieve, molecular sieve still surface richness aluminium and only used fluorine silicon
Preferable dealuminzation effect could be obtained after acid, improve the distribution of molecular sieve aluminium.When fluosilicic acid dealuminzation is used alone (DA3), Ke Yigai
The aluminium distribution of kind molecular sieve, but mesoporous is relatively fewer, strong acid proportion in total acid is lower, and B acid/L acid ratio is lower.Fluorine
Silicic acid composite organic acid oxalic acid dealuminzation (DA5), is equally unable to get higher mesopore proportion and preferable acid distribution.Fluosilicic acid
Composite inorganic acid HCl dealumination (DA6), although mesopore volume increased, strong acid in total acid proportion and B acid/
It is high that L acid ratio is all not so good as molecular sieve provided by the invention.After the present invention is using first desiliconization processing is carried out to molecular sieve, reuse multiple
Acid system is closed, dealumination treatment is carried out under three kinds of sour synergistic effects, can guarantee crystal structure of molecular sieve and mesopore orbit
Improve aluminium distribution and acid distribution under the premise of structural intergrity.
The following examples illustrate catalyst provided by the invention and preparation method thereof, and wherein the property of raw materials is such as
Under: kaolin (Suzhou China Kaolin Co., Ltd, 75 weight % of solid content), (Shandong catalyst branch, aluminium oxide contain Aluminum sol
Amount is 22.5 weight %), REY molecular sieve (Shandong catalyst branch, content of rare earth 10%), DASY molecular sieve (is urged Shandong
Agent branch company, content of rare earth 1.5%).
Embodiment 1-4
Kaolin is configured to the slurries that solid content is 30 weight % with decationized Y sieve water, is stirred evenly, it will with hydrochloric acid
Slurries pH is adjusted to 2.5, keeps the pH value, and Aluminum sol is added after standing aging 1 hour at 50 DEG C, stirs 1 hour formation colloid,
The slurry of the phosphorous IMF structure molecular screen containing preparation embodiment preparation and Y molecular sieve (REY molecular sieve or DASY molecular sieve) is added
Liquid forms catalyst slurry (solid content is 35 weight %).Microspherical catalyst is made in spray drying after continuing stirring.It then will be micro-
Sphere catalyst roasts 1 hour at 500 DEG C, then washed at 60 DEG C with ammonium sulfate (wherein, ammonium sulfate: microspherical catalyst: water=
0.5:1:10) is then eluted and filtered with deionized water, later at 110 DEG C less than 0.25 weight % to sodium oxide content
Drying, obtains catalyst CA, CB, CC and CD, proportion of the specific catalyst in terms of butt is shown in Table 2.
Comparative example 1-7
Catalytic cracking catalyst is prepared according to the method for embodiment 1-4, unlike, by the phosphorous IMF in embodiment 1-4
Structure molecular screen replaces with the molecular sieve DA1-DA7 of preparation comparative example preparation, obtains catalyst CDA1-CDA7, specific catalyst
Proportion in terms of butt is shown in Table 2.
Testing example 1-4
By the catalytic cracking catalyst CA-CD of above-mentioned preparation, aging 12 is small under 800 DEG C, 100% steam atmosphere respectively
When, it is filled in small fixed flowing bed ACE device later, loadings are respectively 9g.Then, reaction temperature be 530 DEG C,
Air speed is 16h-1, agent oil weight ratio be 5:1 under conditions of to feedstock oil shown in table 3 carry out catalytic cracking reaction, reaction result
In table 4.
Test comparison example 1-7
Catalytic cracking reaction is carried out to feedstock oil according to the method for testing example 1-4, the difference is that by catalyst CA-CD
It is substituted respectively with the catalytic cracking catalyst CDA1-CDA7 of identical weight part, in reaction result such as table 4.
Table 4 the result shows that, catalyst prepared by the present invention has yield of liquefied gas high, and total conversion is high, propylene and BTX choosing
The high advantage of selecting property.
Table 1
| Molecular sieve | A | DA1 | DA2 | DA3 | DA4 | DA5 | DA6 | DA7 | B |
| Crystallinity/% | 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 |
| (VMesoporous/VTotal hole)/% | 60.4 | 53.8 | 54.7 | 57.1 | 54.5 | 56.8 | 57.8 | 52.7 | 62.3 |
| (V2nm-20nm/VMesoporous)/% | 90 | 80 | 80 | 86 | 77 | 82 | 82 | 63 | 92 |
| (strong acid acid amount/total acid content)/% | 63 | 48 | 47 | 56 | 45 | 58 | 55 | 40 | 65 |
| The sour amount of B acid/L acid acid amount | 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
| Project | Feedstock oil |
| Density (20 DEG C), g/cm3 | 0.9334 |
| Refractive power (70 DEG C) | 1.5061 |
| Four components, m% | |
| Saturated hydrocarbons | 55.6 |
| Aromatic hydrocarbons | 30 |
| Colloid | 14.4 |
| Asphalitine | <0.1 |
| Freezing point, DEG C | 34 |
| Tenor, ppm | |
| Ca | 3.9 |
| Fe | 1.1 |
| Mg | <0.1 |
| Na | 0.9 |
| Ni | 3.1 |
| Pb | <0.1 |
| V | 0.5 |
| C m% | 86.88 |
| H m% | 11.94 |
| S m% | 0.7 |
| Carbon residue m% | 1.77 |
Table 4
Claims (17)
1. a kind of catalytic cracking catalyst containing phosphorous IMF structure molecular screen, in terms of butt and with the dry basis of the catalyst
On the basis of amount, the catalyst contains the inorganic oxide binder of the natural mineral matter of 15-65 weight %, 10-60 weight %
With the mixed molecular sieve of 25-75 weight %, the mixed molecular sieve includes Y molecular sieve and phosphorous IMF structure molecular screen；Wherein,
The Al distribution parameter D of the phosphorous IMF structure molecular screen meets: 0.6≤D≤0.85；Wherein, D=Al (S)/Al (C),
Al (S) is indicated using the inside H in crystal face edge of the phosphorous IMF structure molecular screen crystal grain of TEM-EDS method measurement apart from interior any
Greater than the aluminium content in 100 square nanometers regions, Al (C) indicates brilliant using the phosphorous IMF structure molecular screen of TEM-EDS method measurement
The outside H of geometric center of the grain crystal face is apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein the H is institute
State crystal face edge point arrives the crystal face geometric center distance 10%；The mesopore volume Zhan of the phosphorous IMF structure molecular screen is total
The ratio of pore volume is 50-80%, and the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers is greater than 85%；
The ratio that the strong acid acid amount of the phosphorous IMF structure molecular screen accounts for total acid content is 50-80%, and the ratio between B acid acid amount and L acid acid amount are
7-30；With P2O5Count and on the basis of the dry weight of phosphorous IMF structure molecular screen, the phosphorus of the phosphorous IMF structure molecular screen contains
Amount is 0.1-15 weight %；The mesopore volume is that aperture is greater than 2 nanometers of pore volumes less than 100 nanometers.
2. catalytic cracking catalyst according to claim 1, wherein the Al of the phosphorous IMF structure molecular screen is distributed ginseng
Number D meets: 0.65≤D≤0.82；The ratio that the mesopore volume of the phosphorous IMF structure molecular screen accounts for total pore volume is 57-
70%, the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers is greater than 90%；The phosphorous IMF structure point
The ratio that the strong acid acid amount of son sieve accounts for total acid content is 55-70%, and the ratio between B acid acid amount and L acid acid amount are 8-25；With P2O5Count and with
On the basis of the dry weight of phosphorous IMF structure molecular screen, the phosphorus content of the phosphorous IMF structure molecular screen is 1-13 weight %.
3. catalytic cracking catalyst according to claim 1, wherein the strong acid acid amount of the molecular sieve accounts for the ratio of total acid content
Example uses NH3- TPD method measures, and the acid site of the strong acid is NH3Desorption temperature be greater than 300 DEG C corresponding in acid
The heart；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
4. catalytic cracking catalyst according to claim 1, wherein the natural mineral matter includes selected from kaolin, more
At least one of hydrokaolinite, montmorillonite, diatomite, attapulgite, sepiolite, hydrotalcite, bentonite and rectorite, it is described
Inorganic oxide binder is selected from least one of silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina, institute
Y molecular sieve is stated as the DASY molecular sieve selected from DASY molecular sieve, containing rare earth, USY molecular sieve, the USY molecular sieve containing rare earth, REY
At least one of molecular sieve, REHY molecular sieve and HY molecular sieve.
5. catalytic cracking catalyst according to claim 1, wherein the Y molecular sieve and the phosphorous IMF structural molecule
The dry weight ratio of sieve is 1:(0.025-4).
6. the preparation method of catalytic cracking catalyst described in a kind of any one of claim 1-5, the preparation method include:
Preparing after raw material and water mix for catalytic cracking catalyst is beaten and is spray-dried；Wherein, in terms of butt and with
It is described to prepare the natural mineral matter, the 10- that raw material includes 15-65 weight % on the basis of the dry weight for preparing raw material
The precursor of the inorganic oxide binder of 60 weight % and the mixed molecular sieve of 25-75 weight %, the mixing
Molecular sieve includes Y molecular sieve and phosphorous IMF structure molecular screen.
7. preparation method according to claim 6, wherein the preparation step of the phosphorous IMF structure molecular screen includes:
A, sodium form IMF structure molecular screen carries out desiliconization processing in aqueous slkali, obtains desiliconization molecular sieve；
B, gained desiliconization molecular sieve in step a is subjected to ammonium exchange processing, obtains ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena
And on the basis of total dry weight of ammonium exchange molecular sieve, the sodium content of the ammonium exchange molecular sieve is less than 0.2 weight %；
C, gained ammonium exchange molecular sieve in step b is molten in the Compound-acid dealumination agent being made of fluosilicic acid, organic acid and inorganic acid
Dealumination treatment is carried out in liquid, and after being filtered and washed, obtains dealuminzation molecular sieve；The inorganic acid is selected from hydrochloric acid, sulfuric acid
At least one of with nitric acid；
D, after dealuminzation molecular sieve obtained in step c being carried out P Modification processing and calcination process, the phosphorous IMF structure is obtained
Molecular sieve.
8. preparation method according to claim 7, wherein the preparation step of sodium form IMF structure molecular screen described in step a
Include:
After will be using there are IMF structure molecular screen slurries obtained by amine method crystallization to be filtered and wash, washing molecular sieve be obtained；Its
In, by sodium oxide molybdena count and by it is described washing molecular sieve total dry weight on the basis of, it is described washing molecular sieve sodium content be less than
3.0 weight %；
The washing molecular sieve is dried and after air roasting, obtains the sodium form IMF structure molecular screen.
9. preparation method according to claim 7, wherein aqueous slkali described in step a be selected from sodium hydrate aqueous solution,
Potassium hydroxide aqueous solution and ammonium hydroxide.
10. preparation method according to claim 7, wherein the condition of the processing of desiliconization described in step a includes: with butt
The weight ratio of the water in alkali and aqueous slkali in the sodium form IMF structure molecular screen of poidometer, aqueous slkali is 1:(0.1-2): (5-
20), the temperature of the desiliconization processing is room temperature to 100 DEG C, and the time is 0.2-4 hours.
11. preparation method according to claim 7, wherein the condition of the processing of desiliconization described in step a includes: with butt
The weight ratio of the water in alkali and aqueous slkali in the sodium form IMF structure molecular screen of poidometer, aqueous slkali is 1:(0.2-1): (5-
20)。
12. preparation method according to claim 7, wherein organic acid described in step c be selected from ethylenediamine tetra-acetic acid,
At least one of oxalic acid, citric acid and sulfosalicylic acid.
13. preparation method according to claim 7, wherein the condition of dealumination treatment described in step c includes: with butt
The weight ratio that the ammonium of poidometer exchanges molecular sieve, organic acid, inorganic acid and fluosilicic acid is 1:(0.01-0.3): (0.01-
0.3): (0.01-0.3)；The temperature of the dealumination treatment is 25-100 DEG C, and the time is 0.5-6 hours.
14. preparation method according to claim 7, wherein the condition of dealumination treatment described in step c includes: with butt
The weight ratio that the ammonium of poidometer exchanges molecular sieve, organic acid, inorganic acid and fluosilicic acid is 1:(0.02-0.2): (0.015-
0.2): (0.015-0.2).
15. preparation method according to claim 7, wherein P Modification described in step d processing include: will selected from phosphoric acid,
At least one of ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound carries out dipping to molecular sieve and/or ion is handed over
It changes.
16. preparation method according to claim 7, wherein the condition of the calcination process includes: the atmosphere of calcination process
For air atmosphere or steam atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.
17. preparation method according to claim 6, wherein the precursor of the inorganic oxide binder includes being selected from
At least one of silica solution, Aluminum sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.
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