CN107973317A - A kind of phosphorous MFI structure molecular sieve and preparation method thereof - Google Patents
A kind of phosphorous MFI structure molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN107973317A CN107973317A CN201610920226.2A CN201610920226A CN107973317A CN 107973317 A CN107973317 A CN 107973317A CN 201610920226 A CN201610920226 A CN 201610920226A CN 107973317 A CN107973317 A CN 107973317A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- acid
- ratio
- mfi structure
- ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of phosphorous MFI structure molecular sieve and preparation method thereof, the n (SiO of the molecular sieve2)/n(Al2O3) it is more than 18 less than 70；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 1 15 heavy %；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 40 70 body %, and the ratio that the mesopore volume that aperture is 2 nanometers 20 nanometers accounts for total mesopore volume is more than 85 body %；The molecular sieve strong acid acid amount account for total acid content ratio be 45 75%, B acid acid amount with L acid acid amount the ratio between be 8 30.Phosphorous MFI structure molecular sieve provided by the invention is prepared into catalyst or auxiliary agent as active component, propene yield and Propylene Selectivity can be effectively improved in catalytic cracking of petroleum hydrocarbon or catalytic cracking reaction, while increase BTX yields.
Description
Technical field
The present invention relates to a kind of phosphorous MFI structure molecular sieve and preparation method thereof.
Background technology
For a long time, ethene, propylene and butylene are that the basic organic chemical industry of synthetic resin, synthetic fibers and synthetic rubber is former
Material, wherein propylene are a kind of important source materials for being used to manufacture petroleum chemicals for being only second to ethene.The maximum of domestic and international propylene at present
Source is the Main By product of thermal cracking production ethene.Ethylene plant using liquid as raw material usually produces about 15% propylene,
The propylene that about 70% petrochemical industry is consumed is provided, and the second largest source of propylene nearly all comes from FCC apparatus, carries
About 30% demand is supplied, in the U.S., FCC apparatus then provides petroleum chemicals to the propylene demand of about half.
Due to increasing rapidly to polyacrylic demand, the required propylene of petrochemical industry is set to increase more than ethylene requirements
It hurry up, and the construction of ethylene plant is limited to the demand of ethene, therefore a large amount of FCC propylene that increase production are by the increasing for meeting propylene demand
Add.Since the eighties in last century, the catalyst of the ZSM-5 containing shape-selective molecular sieve starts to put into commercial Application on FCC apparatus, reaches
Volume increase C is arrived3 =And C4 =Yield, and the purpose of octane number is improved, but the greatest weakness of this kind of ZSM-5 molecular sieve is activity
Stability is poor, the easy in inactivation under the conditions of the periodic regeneration of FCC apparatus harshness.For this reason, Sinopec Group
Research Institute of Petro-Chemical Engineering develops the Series Molecules sieve with excellent activity stability in succession, the catalyst that is prepared with this or
Auxiliary agent, except applying in addition to the Conventional catalytic cracking device for the purpose of producing fuel, it is mesh to be also applied to preparing low-carbon olefins
Process unit on.
At home and abroad under the situation of oil supply growing tension, the reality that is generally laid particular stress on reference to domestic crude oil is developed in
Between base or in the mink cell focus such as m- cycloalkyl wax oil be waste alkene technology, production market ethene in short supply, propylene, BTX
Deng industrial chemicals, the problem of China's ethylene raw inadequate resource can be not only solved, but also caused by steam cracking being made up
The contradiction of propylene/ethylene product structure imbalance, due to using inexpensive heavy charge production propylene and ethene so that alkene produces
Cost significantly declines, while can produce the industrial chemicals such as BTX, therefore there is the technology significant economic benefit and society to imitate
Benefit.
ZSM-5 molecular sieve is the three-dimensional meso-hole high-silica zeolite being successfully prepared at first by Mobil Corporation, its unique duct
Structure makes it have excellent performance on shape slective cracking, isomerization and Aromatization Activity.The duct of ZSM-5 molecular sieve allows straight
Alkane enters, and limits more side chain hydrocarbon and cyclic hydrocarbon and enters, can be preferentially C by low octane rating alkane in gasoline and olefin cracking3And C4
Alkene.ZSM-5 molecular sieve is applied in catalytic cracking and catalytic cracking catalyst, can effectively increase yield of liquefied gas, improves
Density of propylene in liquefied gas.
Although conventional ZSM-5 molecular sieve can enable productivity of propylene by the type effect of selecting in higher silica alumina ratio and duct
Improve, but since its pore passage structure is narrow, larger reactant molecule, which is difficult to enter in crystal duct, to be reacted, and is reduced point
The effective affecting acreage of son sieve, reduces the reactivity of molecular sieve；On the other hand, the larger production such as isoparaffin and aromatic hydrocarbons
Thing molecule is not easy to come out from molecular sieve pore passage diffusion inside, so as to cause the secondary responses such as excessive hydrogen migration, coking to cause point
Son sieve inactivation, reaction selectivity reduce.Using mink cell focus as in the new catalytic cracking process of raw material, ZSM-5 molecular sieve duct hole
The defects of stenostomia, necessarily makes problem above more prominent.
For this problem, there are several classes to solve method at present.When for example nano level ZSM-5 molecular sieve of synthesizing small-grain,
To shorten diffusion path.But there is the congenital weakness such as filtration difficulty, hydrothermal structural stability difference for small crystal grain molecular sieve.It is second, straight
It is bonded into the ZSM-5 molecular sieve material containing multi-stage porous.But such method needs to add template and complex process, cost compared with
It is high.In addition it is molecular sieve post-modification method to also have a kind of method, mainly uses desiliconization method or desiliconization dealuminzation coupled method.
Chinese patent CN103848438A discloses a kind of modified zsm-5 zeolite for preparing high mesoporous area and its preparation
Method, this method is first swapped the molecular sieve after roasting with acid solutions such as nitric acid, hydrochloric acid and repeatedly washed, after drying
Carry out second to roast, molecular sieve desiliconization is handled with inorganic base after roasting, it is multiple with weak acid scrubbing molecular sieve after desiliconization filtering
Afterwards, drying carries out third time roasting, is repeatedly exchanged with Ammonium Salt Ionic again after roasting, and the 4th roasting is carried out after drying, obtains height
Mesoporous area molecular sieve.
The content of the invention
The object of the present invention is to provide a kind of phosphorous MFI structure molecular sieve and preparation method thereof, contain provided by the invention
Phosphorus MFI structure molecular sieve prepares catalyst or auxiliary agent as active component, in catalytic cracking of petroleum hydrocarbon or catalytic cracking reaction
Propene yield and Propylene Selectivity can be effectively improved, while increases BTX yields.
To achieve these goals, the present invention provides a kind of phosphorous MFI structure molecular sieve, the n (SiO of the molecular sieve2)/n
(Al2O3) it is more than 18 less than 70；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 1-
15 heavy %；The Al distributed constants D of the molecular sieve meets：0.6≤D≤0.85, wherein, D=Al (S)/Al (C), Al (S) are represented
The inside H in crystal face edge using the zeolite crystal of TEM-EDS methods measure is arbitrarily more than 100 square nanometers regions apart from interior
Aluminium content, Al (C) are represented in the outside H distances of geometric center using crystal face described in the zeolite crystal of TEM-EDS methods measure
Any aluminium content for being more than 100 square nanometers regions, wherein the H arrives the crystal face geometrical center to center for the crystal face edge point
From 10%；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 40-70 body %, and aperture is 2 nanometers -20 nanometers
The ratio that mesopore volume accounts for total mesopore volume is more than 85 body %；The strong acid acid amount of the molecular sieve accounts for the ratio of total acid content and is
The ratio between 45-75%, B acid acid amount and L acid acid amounts are 8-30.
Preferably, the n (SiO of the molecular sieve2)/n(Al2O3) it is more than 21 less than 60；With P2O5Count and with the dry of molecular sieve
On the basis of base weight amount, the phosphorus content of the molecular sieve is 3-12 weights %；The Al distributed constants D of the molecular sieve meets：0.65≤D
≤0.82；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 45-65 body %, and aperture is 2 nanometers -20 nanometers of Jie
The ratio that pore volume accounts for total mesopore volume is more than 90 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 55-
The ratio between 70%, B acid acid amount and L acid acid amounts are 10-25.
Preferably, the mesopore volume of the molecular sieve accounts for the ratio of total pore volume and aperture is 2 nanometers -20 nanometers mesoporous
The ratio that volume accounts for total mesopore volume is measured using N2 adsorption measure pore-size distribution method, and total mesopore volume is aperture
It is less than 100 nanometers of pore volume more than 2 nanometers；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content uses NH3- TPD sides
Method measures, and the acid site of the strong acid is NH3Desorption temperature is more than the acid site corresponding to 300 DEG C；B acid acid amount with
The ratio between L acid acid amounts are measured using the infrared acid process of pyridine adsorption.
The present invention also provides a kind of preparation method of phosphorous MFI structure molecular sieve provided by the present invention, the preparation method
Including：A, sodium form MFI structure molecular sieve carries out desiliconization processing in aqueous slkali, obtains desiliconization molecular sieve；B, by gained in step a
Desiliconization molecular sieve carries out ammonium exchange, obtains ammonium and exchanges molecular sieve；Wherein, total butt of molecular sieve is exchanged in terms of sodium oxide molybdena and with ammonium
On the basis of weight, the sodium content that the ammonium exchanges molecular sieve is less than 0.2 heavy %；C, gained ammonium in step b is exchanged molecular sieve to exist
Dealumination treatment is carried out in the Compound-acid dealuminzation agent solution being made of fluosilicic acid, organic acid and inorganic acid, and is filtered and is washed
Afterwards, dealuminzation molecular sieve is obtained；D, after the dealuminzation molecular sieve of gained in step c being carried out P Modification processing and calcination process, obtain
The phosphorous MFI structure molecular sieve.
Preferably, the preparation process of sodium form MFI structure molecular sieve described in step a includes：To use has amine method crystallization institute
After MFI structure molecular sieve pulp filtered and washed, obtain washing molecular sieve；Wherein, in terms of sodium oxide molybdena and with the water
Wash on the basis of total butt weight of molecular sieve, the sodium content in the washing molecular sieve is less than 3.0 heavy %；By the washing molecule
Sieve is dried and after air roasting, obtains the sodium form MFI structure molecular sieve.
Preferably, aqueous slkali described in step a is selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide.
Preferably, the condition of the processing of desiliconization described in step a includes：With the sodium form MFI structure molecular sieve of dry basis,
The weight ratio of the water in alkali and aqueous slkali in aqueous slkali is 1：(0.1-2)：(5-20), the temperature of the desiliconization processing is room temperature
To 100 DEG C, when the time is 0.2-4 small.
Preferably, the condition of the processing of desiliconization described in step a includes：With the sodium form MFI structure molecular sieve 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 includes described in step c：Molecular sieve, organic is exchanged with the ammonium of dry basis
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 for 0.5-6 it is small when.
Preferably, the condition of dealumination treatment includes described in step c：Molecular sieve, organic is exchanged with the ammonium of dry basis
The weight ratio of acid, inorganic acid and fluosilicic acid is 1：(0.03-0.2)：(0.015-0.2)：(0.015-0.2).
Preferably, the processing of P Modification described in step d includes：Phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid will be selected from
Molecular sieve is impregnated at least one of ammonium phosphorus-containing compound and/or ion exchange.
Preferably, the condition of the calcination process includes：The atmosphere of calcination process is air atmosphere or steam atmosphere；Roasting
It is 400-800 DEG C to burn temperature, when roasting time is 0.5-8 small.
Present inventors discovered unexpectedly that desiliconization processing is chemically carried out to MFI structure molecular sieve, ammonium exchanges
Processing, carry out dealumination treatment and P Modification processing in Compound-acid dealuminzation agent solution, prepared phosphorous MFI structure molecular sieve, can be with
Applied in catalytic cracking and Deep Catalytic Cracking process, the active component as catalyst or auxiliary agent, it is possible to increase ethene and propylene
Yield, Propylene Selectivity and BTX yields.
Phosphorous MFI structure molecular sieve surface Silicon-rich provided by the invention can inhibit the generation of the non-selective side reaction in surface,
Be conducive to giving full play to for MFI structure molecular sieve Shape-selective；Molecular sieve is mesoporous abundant, is conducive to reaction intermediates and product
Generation and diffusion, reduce coking and deactivation；Strong acid center ratio is high and B acid/L acid ratio is high, is conducive to molecular sieve cracking reaction
Generation, improve cracking activity.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of phosphorous MFI structure molecular sieve, the n (SiO of the molecular sieve2)/n(Al2O3) be less than more than 18
70, preferably greater than 21 are less than 60；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 1-
15 heavy %, are preferably 3-12 weights %；The Al distributed constants D of the molecular sieve meets：0.6≤D≤0.85, preferably satisfies：0.65
≤D≤0.82；Wherein, D=Al (S)/Al (C), Al (S) represent the crystal face of the zeolite crystal using TEM-EDS methods measure
The inside H in edge is represented using TEM-EDS methods measure apart from interior any aluminium content for being more than 100 square nanometers regions, Al (C)
The outside H of geometric center of crystal face described in zeolite crystal is apart from interior any aluminium content for being more than 100 square nanometers regions, wherein institute
It is that the crystal face edge point arrives the 10% of the crystal face geometric center distance to state H；The mesopore volume of the molecular sieve accounts for total hole body
Long-pending ratio is 40-70 body %, is preferably that the mesopore volume that 45-65 body % apertures are 2 nanometers -20 nanometers accounts for total mesopore volume
Ratio is more than 85 body %, is preferably more than 90 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 45-
75%, it is preferably 55-70%, the ratio between B acid acid amounts and L acid acid amounts are 8-30, are preferably 10-25.
MFI structure is the topological structure of molecular sieve, such as ZSM-5 molecular sieve has MFI structure.
Molecular sieve according to the present invention, the aluminium content using TEM-EDS methods measure molecular sieve is those skilled in the art
Known, wherein the geometric center is also well-known to those skilled in the art, can be calculated according to formula, this hair
Bright to repeat no more, the geometric center of generally symmetrical figure is the intersection point of each opposed apexes line, for example, conventional six square shape sheet ZSM-
Point of intersection of the geometric center of 5 hexagon crystal face in three opposed apexes lines.The crystal face is one of regular crystal grain
Face, the direction inwardly or outwardly refer both to the direction inwardly or outwardly on the crystal face.
According to the present invention, it is 2 nanometers -20 nanometers that the mesopore volume of the molecular sieve, which accounts for the ratio of total pore volume and aperture,
The ratio that mesopore volume accounts for total mesopore volume is measured using N2 adsorption BET specific surface area method, the mesopore volume finger-hole
Footpath is more than 2 nanometers of pore volumes for being less than 100 nanometers；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content uses NH3-TPD
Method measures, and the acid site of the strong acid is NH3Desorption temperature is more than the acid site corresponding to 300 DEG C；The B acid acid amount
Measured with the ratio between the L acid acid amounts use infrared acid process of pyridine adsorption.
The present invention also provides a kind of preparation method of phosphorous MFI structure molecular sieve provided by the present invention, the preparation method
Including：A, sodium form MFI structure molecular sieve carries out desiliconization processing in aqueous slkali, obtains desiliconization molecular sieve；B, by gained in step a
Desiliconization molecular sieve carries out ammonium exchange, obtains ammonium and exchanges molecular sieve；Wherein, total butt of molecular sieve is exchanged in terms of sodium oxide molybdena and with ammonium
On the basis of weight, the sodium content that the ammonium exchanges molecular sieve is less than 0.2 heavy %；C, gained ammonium in step b is exchanged molecular sieve to exist
Dealumination treatment is carried out in the Compound-acid dealuminzation agent solution being made of fluosilicic acid, organic acid and inorganic acid, and is filtered and is washed
Afterwards, dealuminzation molecular sieve is obtained；D, after the dealuminzation molecular sieve of gained in step c being carried out P Modification processing and calcination process, obtain
The phosphorous MFI structure molecular sieve.
The method according to the invention, the sodium form MFI structure molecular sieve are well-known to those skilled in the art, Ke Yiwu
, can also be by gained after the molecular sieve roasting of template agent method preparation, for example, ZSM-5 molecular sieve obtained by amine crystallization.Institute in step a
Stating the preparation process of sodium form MFI structure molecular sieve can include：To use have MFI structure molecular sieve pulp obtained by amine method crystallization into
After row filtering and washing, washing molecular sieve is obtained；Wherein, in terms of sodium oxide molybdena and using it is described washing molecular sieve total butt weight as
Benchmark, the sodium content washed in molecular sieve are less than 3.0 heavy %；The washing molecular sieve is dried and air roasting
Afterwards, the sodium form MFI structure molecular sieve is obtained.The air roasting is used to remove the template in washing molecular sieve, the sky
The temperature of gas roasting can be 400-700 DEG C, when the time can be 0.5-10 small.
According to the present invention, desiliconization processing is used for the part framework silicon atom for removing molecular sieve, to produce secondary pore, step a
Described in aqueous slkali can be selected from least one of sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide, be preferably
Sodium hydrate aqueous solution；The condition of the processing of desiliconization described in step a can include：With the sodium form MFI structure point of dry basis
The weight ratio of the water in alkali and aqueous slkali in son sieve, aqueous slkali is 1：(0.1-2)：(5-20), is preferably 1：(0.2-1)：(5-
20), the temperature of desiliconization processing is room temperature to 100 DEG C, the time for 0.2-4 it is small when.
According to the present invention, it is well-known to those skilled in the art that ammonium, which exchanges, for reducing the sodium content in molecular sieve.Example
Such as, the condition that the ammonium exchanges can include：According to molecular sieve：Ammonium salt：Water=1：(0.1-1)：The weight ratio of (5-15), will divide
Son sieve is filtered in room temperature to after when ammonium exchange 0.5-3 is small at 100 DEG C, and ammonium salt used can be common inorganic ammonium salt, for example,
Selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate, the number that ammonium exchanges can repeat 1-3 times, until in molecular sieve
Sodium oxide content is less than 0.2 heavy %.
According to the present invention, although desiliconization processing can obtain the MFI structure molecular sieve with secondary pore, molecular sieve will be made
The relatively rich aluminium in surface, makes the raising selected type impaired performance, be unfavorable for reaction selectivity of MFI structure molecular sieve, it is therefore desirable to right
It carries out follow-up dealumination treatment.Dealumination treatment is well-known to those skilled in the art, but is not reported inorganic acid, organic acid
It is used for dealumination treatment together with fluosilicic acid.The dealumination treatment can carry out once or several times, can be first by organic acid and institute
State ammonium and exchange molecular sieve mixing, then fluosilicic acid and inorganic acid are exchanged to molecular sieve with the ammonium mixed, you can with will first to have
Machine acid adds ammonium and exchanges in molecular sieve, and then by fluosilicic acid and inorganic acid, cocurrent adds at a slow speed, or first adds fluosilicic acid and add
Inorganic acid, is preferably that cocurrent adds at a slow speed for fluosilicic acid and inorganic acid.For example, organic acid described in step c can be selected from second two
At least one of amine tetraacethyl, oxalic acid, citric acid and sulfosalicylic acid, are preferably oxalic acid or citric acid, are more preferably
Oxalic acid；The inorganic acid can be selected from least one of hydrochloric acid, sulfuric acid and nitric acid, be preferably hydrochloric acid or sulfuric acid, further
Preferably hydrochloric acid；The condition of the dealumination treatment can include：Molecular sieve, organic acid, inorganic is exchanged with the ammonium of dry basis
The weight ratio of acid and fluosilicic acid is 1：(0.01-0.3)：(0.01-0.3)：(0.01-0.3), is preferably 1：(0.03-0.2)：
(0.015-0.2)：(0.015-0.2)；The temperature of the dealumination treatment is 25-100 DEG C, when the time is 0.5-6 small.Pass through desiliconization
Processing is combined with Compound-acid dealuminzation agent solution dealumination treatment MFI structure molecular sieve is handled, the aluminium of molecular sieve is distributed,
Silica alumina ratio, Acidity and pore structure have carried out modulation, make MFI structure molecular sieve reaming modified, still have preferable shape-selective choosing
Selecting property, so as to be effectively improved the propylene of MFI structure molecular sieve, ethene and BTX yields.
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 can include：At least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound will be selected to dividing
Son sieve is impregnated 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
With including：The atmosphere of calcination process is air atmosphere or steam atmosphere；Calcination temperature is 400-800 DEG C, and roasting time is
When 0.5-8 is small.
Washing of the present invention is well-known to those skilled in the art, refers generally to wash, it is for instance possible to use 5-10 times
30-60 DEG C of water of molecular sieve elutes molecular sieve.
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 those skilled in the art's common instrument of institute and
Reagent.
The present invention using micro-reactor evaluation molecular sieve carry out petroleum hydrocarbon catalytic pyrolysis when to productivity of propylene, selectivity and
The influence of BTX yields, is prepared into microspherical catalyst, molecular sieve content 50%, remaining is kaolinite using molecular sieve as active component
Soil and binding agent, obtained catalyst sample carried out on fixed bed aging equipment 800 DEG C, 100% steam aging 17 it is small when at
Reason, heavy oil it is micro- it is anti-on evaluated, feedstock oil is hydrogenation wax oil (coming from Yangtze oil plant), and appreciation condition is reaction temperature 620
DEG C, 620 DEG C of regeneration temperature, oil ratio 1.3.Propylene Selectivity is the mass fraction of propylene in liquefied gas.
Micro- reversion rate (i.e. heavy oil conversion ratio) of the present invention is measured using ASTM D5154-2010 standard methods,
The hydro carbons composition of micro-inverse product is measured using RIPP 85-90 methods.
The crystallinity of the present invention is measured using the standard method of ASTM D5758-2001 (2011) e1.
N (the SiO of the present invention2)/n(Al2O3), i.e., silica alumina ratio is obtained by the content calculation of silica and aluminium oxide, oxidation
The content of silicon and aluminium oxide is measured using GB/T 30905-2014 standard methods.
The phosphorus content of the present invention is measured using GB/T 30905-2014 standard methods.
The TEM-EDS assay methods of the present invention are referring to the research method of solid catalyst, petrochemical industry, 29 (3), and 2000：
227。
Total specific surface area (S of the present inventionBET), the survey of mesoporous pore volume, total pore volume, 2-20 nanometers of mesoporous pore volume
It is as follows to determine method：
The AS-3 produced using Quantachrome instrument companies, AS-6 static state n2 absorption apparatus measure.
Instrument parameter：Sample is placed in sample processing system, 1.33 × 10 are evacuated 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/P0Less than=0.98 adsorbance is the total pore volume of sample, utilizes BJH formula meters
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 B acid acid amounts of the present invention and the assay method of L acid acid amounts are as follows：
The FTS3000 type Fourier infrared spectrographs produced using BIO-RAD companies of 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 totally, is cooled to room temperature.Pressure is imported into pond in situ is
The pyridine steam of 2.67Pa, after balancing 30min, is warming up to 200 DEG C, is evacuated to 10 again-3Pa, keeps 30min, is cooled to room
Temperature, in 1400-1700cm-1Scanning in wave-number range, records the infrared spectrum spectrogram of 200 DEG C of pyridine adsorptions.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 amounts and L acid acid amounts.
The assay method of total acid content and strong acid the acid amount of the present invention is as follows：
Using II 2920 temperature programmed desorption instrument of Merck ＆ Co., Inc of U.S. Autochem.
Test condition：Weigh 0.2g samples to be tested and load sample cell, be placed in conductance cell heating furnace, He gas is carrier gas (50mL/
Min), 600 DEG C are warming up to the speed 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 mixtures (10.02%NH3+ 89.98%He) absorption 30min, it is further continued for He gas
It is steady to baseline to purge 90min, to be desorbed the ammonia of physical absorption.600 DEG C are warming up to 10 DEG C/min heating rates 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 is NH3Desorption temperature is more than the acid site corresponding to 300 DEG C.
The sodium content of the present invention is measured using GB/T 30905-2014 standard methods.
RIPP standard methods of the present invention for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, and 1990
Year version.
The computational methods of D values are as follows：A crystal grain is chosen 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 values are different), choose respectively any one piece in the inside H distances in the crystal face edge be more than 100 square nanometers regions with
And any one piece in the outside H distances of crystal face geometric center is more than 100 square nanometers regions, measures aluminium content, is Al (S1)
With Al (C1), and D1=Al (S1)/Al (C1) is calculated, choose different crystal grain respectively and measure 5 times, it is D to calculate average value.
Embodiment 1
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being quickly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, filter cake is added into the mashing of 800g water, adds 40g NH4Cl, is warming up to 75 DEG C, after exchanging processing 1h, extremely
Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
Into the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 4g is added in stirring, then by 45g hydrochloric acid (mass fraction 10%) and 30g
Fluosilicic acid (mass fraction 3%) cocurrent adds, and adds time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate
It is neutral；By filter cake plus water be beaten solid content is the molecular sieve pulps of 40 weight %, add 6.3g H3PO4(85 weight % of concentration),
Uniformly it is mixed with dipping, dries, 550 DEG C of calcination process 2h.Molecular sieve-4 A is obtained, physico-chemical property and evaluating data are listed in table 1.
Comparative example 1
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being quickly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, filter cake is added into the mashing of 800g water, adds 40g NH4Cl, is warming up to 75 DEG C, after exchanging processing 1h, extremely
Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
Into the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 27g is added in stirring；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to
Filtrate is neutral；By filter cake plus water be beaten solid content for 40 weight % molecular sieve pulps, add 6.1gH3PO4(85 weight of concentration
Measure %), when uniformly hybrid infusion, drying, 550 DEG C of calcination process 2 are small.Molecular sieve DA1 is obtained, physico-chemical property and evaluating data are listed in
Table 1.
Comparative example 2
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.2%, 65 DEG C are warming up to, after reacting 30min, after being quickly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then take above-mentioned molecular sieve 50g (butt) plus water to be configured to the molecular sieve pulp of the weight of solid content 10 %, add in stirring
Enter 215g hydrochloric acid (mass fraction 10%)；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake adds
1500g water is beaten, and adds 80g NH4After Cl is warming up to 65 DEG C of exchange washing 40min, filtering, elutes neutral to filtrate；By filter cake
Add water be beaten solid content for 40 weight % molecular sieve pulps, add 6.3gH3PO4(85 weight % of concentration), be uniformly mixed with dipping,
When drying, 550 DEG C of calcination process 2 are small.Molecular sieve DA2 is obtained, physico-chemical property and evaluating data are listed in table 1.
Comparative example 3
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.2%, 65 DEG C are warming up to, after reacting 30min, after being quickly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, filter cake is added into the mashing of 800g water, adds 40g NH4Cl, is warming up to 75 DEG C, after exchanging processing 1h, extremely
Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
Into the molecular sieve pulp of the weight of solid content 10 %, 135g fluosilicic acid (mass fraction 3%) is added in stirring, adds time 30min；Rise
Temperature to 65 DEG C of constant temperature stir 1h, and filtering is washed to filtrate neutrality；By filter cake plus water be beaten solid content for 40 weight % molecular sieves
Slurries, add 6.3gH3PO4(85 weight % of concentration), when uniformly hybrid infusion, drying, 550 DEG C of calcination process 2 are small.Obtain molecular sieve
DA3, physico-chemical property and evaluating data are listed in table 1.
Comparative example 4
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 1.9%, 65 DEG C are warming up to, after reacting 30min, after being quickly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, filter cake is added into the mashing of 800g water, adds 40g NH4Cl, is warming up to 75 DEG C, after exchanging processing 1h, extremely
Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
Into the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 11g is added in stirring, then adds 110g hydrochloric acid (mass fraction 10%)
Enter, add time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten to consolidate and contained
Measure as the molecular sieve pulp of 40 weight %, addition 6.3gH3PO4(85 weight % of concentration), is uniformly mixed with dipping, dries, 550 DEG C of roastings
Handle 2 it is small when.Molecular sieve DA4 is obtained, physico-chemical property and evaluating data are listed in table 1.
Comparative example 5
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being quickly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, filter cake is added into the mashing of 800g water, adds 40g NH4Cl, is warming up to 75 DEG C, after exchanging processing 1h, extremely
Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
Into the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 3g is added in stirring, it is then that 72g fluosilicic acid (mass fraction 3%) is slow
Add, add time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water, which are beaten, to be consolidated
Content is the molecular sieve pulp of 40 weight %, adds 6.3gH3PO4(85 weight % of concentration), is uniformly mixed with dipping, dries, 550 DEG C of roastings
When burning processing 2 is small.Molecular sieve DA5 is obtained, physico-chemical property and evaluating data are listed in table 1.
Comparative example 6
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being quickly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, filter cake is added into the mashing of 800g water, adds 40g NH4Cl, is warming up to 75 DEG C, after exchanging processing 1h, extremely
Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
Into the molecular sieve pulp of the weight of solid content 10 %, by 42g hydrochloric acid (mass fraction 10%) and 78g fluosilicic acid (mass fractions under stirring
3%) cocurrent adds, and adds time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water
Be beaten solid content for 40 weight % molecular sieve pulps, add 6.3gH3PO4(85 weight % of concentration), is uniformly mixed with dipping, dries
It is dry, when 550 DEG C of calcination process 2 are small.Molecular sieve DA6 is obtained, physico-chemical property and evaluating data are listed in table 1.
Comparative example 7
By the good ZSM-5 molecular sieve of crystallization, (catalyst Jian Chang branch companies produce, and have the synthesis of amine method, n (SiO2)/n(Al2O3)
=50) Na is washed with water to after filtering out mother liquor2O content is less than 3.0 weight %, filters, drying, 550 DEG C in air, roasting
2h burns up template；Take above-mentioned molecular sieve 100g (butt) to add in the NaOH aqueous solutions of 3000g (solution concentration 0.8%), stir
Mix and be warming up to 80 DEG C, after reacting 30min, be cooled to room temperature, filter, elution, obtains filter cake；Obtained molecular sieve filter cake is added
Aqueous solution of nitric acid is washed, and concrete operations are to take above-mentioned molecular sieve 50g (butt) plus water to be configured to point of the weight of solid content 10 %
Sub- screening the pulp liquid, stirs lower addition 550g2.3% nitric acid；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake
The mashing of 1500g water is added, adds 80g NH4After Cl is warming up to 65 DEG C of exchange washing 40min, filtering, elutes neutral to filtrate；Will
Filter cake add water be beaten solid content for 40 weight % molecular sieve pulps, add 6.3gH3PO4(85 weight % of concentration), uniformly mixing
When dipping, drying, 550 DEG C of calcination process 2 are small.Molecular sieve DA7 is obtained, physico-chemical property and evaluating data are listed in table 1.
Comparative example 8
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
Water is configured to the molecular sieve pulp of the weight of solid content 10 %, ethylenediamine tetra-acetic acid 3g is added in stirring, then by 400g fluosilicic acid (matter
Measure fraction 3%) cocurrent addition, time 30min is added, is eventually adding 140g hydrochloric acid (mass fraction 10%)；It is warming up to 85 DEG C of perseverances
Temperature stirring 6h, filtering are washed to filtrate neutrality；Add in the NaOH solution of 1000g2.4%, be warming up to 60 DEG C, react 45min
Afterwards, after being quickly cooled to room temperature, filtering, is washed neutral to filtrate.Then NH4Cl solution exchanges washing to Na2O content is less than 0.1
Weight %, is obtained by filtration molecular sieve filter cake；To take above-mentioned molecular sieve filter cake 50g (butt) plus water be beaten solid content is 40 heavy %
Molecular sieve pulp, add 6.3gH3PO4(85 weight % of concentration), when uniformly hybrid infusion, drying, 550 DEG C of calcination process 2 are small.
Molecular sieve DA8 is obtained, physico-chemical property and evaluating data are listed in table 1.
Comparative example 9
By the good ZSM-5 molecular sieve of crystallization, (catalyst Jian Chang branch companies produce, and have the synthesis of amine method, n (SiO2)/n(Al2O3)
=37) NH is used after filtering out mother liquor4Cl exchanges washing to Na2O content is less than 0.2 weight %, drying, 550 DEG C in air, roasting
Burn 2h burn-up templates；Take above-mentioned molecular sieve 100g (butt) plus water be beaten solid content is the molecular sieve pulps of 40 weight %, add
Enter 12.6gH3PO4(concentration 85%), dipping drying；Gained sample is when 550 DEG C of calcination process 2 are small, up to molecular sieve DA9.Thing
Change property and evaluating data is listed in table 1.
Embodiment 2
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1500g 2.3%, 60 DEG C are warming up to, after reacting 45min, after being quickly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, filter cake is added into the mashing of 800g water, adds 40g NH4Cl, is warming up to 75 DEG C, after exchanging processing 1h, extremely
Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
Into the molecular sieve pulp of the weight of solid content 10 %, citric acid 4g is added in stirring, then 10g sulfuric acid (mass fraction 10%) and 45g
Fluosilicic acid (mass fraction 3%) cocurrent adds, and adds time 30min；45 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate
It is neutral；By filter cake plus water be beaten solid content for 40 weight % molecular sieve pulps, add 6.3gH3PO4(85 weight % of concentration),
When even hybrid infusion, drying, 550 DEG C of calcination process 2 are small.Molecular sieve B is obtained, physico-chemical property and evaluating data are listed in table 1.
Embodiment 3
By the good ZSM-5 molecular sieve of crystallization, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, is washed to Na2O content is less than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1200g 2.2%, 55 DEG C are warming up to, after reacting 60min, after being quickly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, filter cake is added into the mashing of 1000g water, adds 50g NH4Cl, is warming up to 75 DEG C, after exchanging processing 1h, extremely
Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
Into the molecular sieve pulp of the weight of solid content 10 %, ethylenediamine tetra-acetic acid 2g is added in stirring, then by 140g fluosilicic acid (mass fractions
3%) cocurrent adds, and adds time 30min, is eventually adding 60g hydrochloric acid (mass fraction 10%)；It is warming up to 85 DEG C of constant temperature stirrings
6h, filtering are washed to filtrate neutrality；By filter cake plus water be beaten solid content for 40 weight % molecular sieve pulps, add 5.9gH3PO4
(85 weight % of concentration), when uniformly hybrid infusion, drying, 550 DEG C of calcination process 2 are small.Obtain molecular sieve C, physico-chemical property and evaluation
Data are listed in table 1.
For the ZSM-5 molecular sieve after alkali process desiliconization it can be seen from data in table 1, using single organic acid oxalic acid
Dealuminzation (DA1) is answered using single inorganic acid HCl dealumination (DA2) and using two kinds of acid of organic acid oxalic acid and inorganic acid hydrochloric acid
Closing (DA4) effectively can not all remove the Al in molecular sieve, molecular sieve still surface richness aluminium and after only having used fluosilicic acid
Preferable dealuminzation effect could be obtained, improves the distribution of molecular sieve aluminium.When fluosilicic acid dealuminzation is used alone (DA3), it can improve point
The aluminium distribution of son sieve, but it is mesoporous relatively fewer, and strong acid proportion in total acid is relatively low, and B acid/L acid ratios are relatively low.Fluosilicic acid
Composite organic acid oxalic acid dealuminzation (DA5), can not equally obtain higher mesoporous ratio and preferable acid distribution.Fluosilicic acid is compound
Inorganic acid HCl dealumination (DA6), although mesopore volume increased, strong acid proportion and B acid/L acid in total acid
Ratio is all be not as high as molecular sieve provided by the invention.The ZSM-5 molecular sieve higher to sial, alkali process is again with inorganic acid+nitric acid
(DA7) is handled, although the mesoporous ratio of higher can be obtained, the mesoporous footpath of molecular sieve is that the pore volume of 2nm to 20nm accounts for always
The ratio of mesopore volume is low, i.e. the mesoporous aperture of molecular sieve becomes larger, while the Al distributions of molecular sieve are still poor, and strong acid is less, B
Acid/L acid ratios are low, and molecular sieve stability is poor, and reactivity is low.And the technology path of first dealuminzation desiliconization again is used, to contain fluorine
The molecular sieve (DA8) that desiliconization is handled again after the Compound-acid of silicic acid improves the silica alumina ratio of ZSM-5 molecular sieve, its crystallinity
Low, mesoporous ratio is low, and the ratio that the pore volume that mesoporous footpath is 2nm to 20nm accounts for total mesopore volume is low, molecular sieve outer surface Al phases
To more.After the present invention to molecular sieve using first desiliconization processing is carried out, compound acid system is reused, in three kinds of sour synergistic effects
Lower carry out dealuminzation, can improve aluminium distribution and acid on the premise of crystal structure of molecular sieve and mesopore orbit structural intergrity is ensured
Property distribution.From reaction result it can be seen that the molecular sieve prepared by the present invention can effectively improve heavy oil conversion ratio, propylene is improved
Selectivity, increase propylene, ethene and BTX yields.
Table 1
| Molecular sieve | A | DA1 | DA2 | DA3 | DA4 | DA5 | DA6 | DA7 | DA8 | DA9 | B | C |
| Crystallinity/% | 87 | 80 | 78 | 83 | 83 | 83 | 85 | 77 | 78 | 90 | 90 | 87 |
| n(SiO2)/n(Al2O3) | 35 | 24 | 23 | 42 | 24 | 39 | 43 | 29 | 29 | 37 | 23 | 50 |
| P2O5Content/% | 7.5 | 7.2 | 7.5 | 7.5 | 7.5 | 7.5 | 7.5 | 7.5 | 7.5 | 7.5 | 7.5 | 7.0 |
| SBET/(m2/g) | 420 | 380 | 371 | 389 | 381 | 405 | 398 | 380 | 360 | 364 | 452 | 437 |
| (VIt is mesoporous/VTotal hole)/% | 58 | 41 | 39 | 49 | 45 | 50 | 54 | 72 | 45 | 11.4 | 55 | 60 |
| (V2nm-20nm/VIt is mesoporous)/% | 90 | 80 | 80 | 86 | 77 | 82 | 82 | 63 | 74 | 77 | 95 | 90 |
| (strong acid acid amount/total acid content)/% | 60 | 40 | 39 | 51 | 37 | 55 | 51 | 40 | 43 | 48 | 58 | 65 |
| The sour amount of B acid/L acid acid amounts | 15 | 4.9 | 5.0 | 10 | 5.0 | 13.1 | 11.2 | 4.7 | 4.6 | 6.1 | 17.2 | 20.9 |
| D (Al distributions) | 0.75 | 1.1 | 1.1 | 0.95 | 1.1 | 0.87 | 0.91 | 1.2 | 1.1 | 1.0 | 0.80 | 0.72 |
| Micro- reversion rate/% | 77.2 | 71.9 | 69.5 | 74.8 | 73.2 | 75.5 | 75.1 | 71.6 | 69.1 | 65.4 | 78.5 | 76.4 |
| Ethylene yield | 6.7 | 5.1 | 4.8 | 6.1 | 4.8 | 6.2 | 5.9 | 4.7 | 4.3 | 3.8 | 6.5 | 6.5 |
| Productivity of propylene | 20.5 | 17.6 | 16.7 | 18.5 | 16.4 | 19.1 | 18.7 | 16.5 | 16.1 | 14.2 | 21.0 | 20.1 |
| BTX yields | 7.5 | 5.3 | 5.0 | 6.2 | 5.1 | 6.4 | 6.2 | 4.8 | 4.9 | 4.0 | 7.2 | 7.1 |
| Propylene Selectivity | 62.1 | 56.4 | 55.6 | 58.7 | 55.2 | 59.5 | 59.2 | 54.9 | 55.2 | 56.5 | 60.8 | 63.7 |
Claims (13)
1. a kind of phosphorous MFI structure molecular sieve, the n (SiO of the molecular sieve2)/n(Al2O3) it is more than 18 less than 70；With P2O5Count and with
On the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 1-15 weights %；The Al distributed constants D of the molecular sieve expires
Foot：0.6≤D≤0.85, wherein, D=Al (S)/Al (C), Al (S) represent the zeolite crystal using TEM-EDS methods measure
The inside H in crystal face edge represent to use TEM-EDS methods apart from interior any aluminium content for being more than 100 square nanometers regions, Al (C)
The outside H of the geometric center of crystal face described in the zeolite crystal of measure apart from interior any aluminium content for being more than 100 square nanometers regions,
Wherein described H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The mesopore volume of the molecular sieve accounts for
The ratio of total pore volume is 40-70 body %, and aperture is that the ratio that 2 nanometers -20 nanometers of mesopore volume accounts for total mesopore volume is 85
More than body %；The ratio that the sour amount of the strong acid of the molecular sieve accounts for total acid content is 45-75%, and the ratio between B acid acid amounts and L acid acid amounts are 8-
30。
2. phosphorous MFI structure molecular sieve according to claim 1, wherein, the n (SiO of the molecular sieve2)/n(Al2O3) big
It is less than 60 in 21；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 3-12 weights %；Institute
The Al distributed constants D for stating molecular sieve meets：0.65≤D≤0.82；The mesopore volume of the molecular sieve accounts for the ratio of total pore volume
For 45-65 body %, aperture is that the ratio that 2 nanometers -20 nanometers of mesopore volume accounts for total mesopore volume is more than 90 body %；Described point
The ratio that the sour amount of strong acid of son sieve accounts for total acid content is 55-70%, and the ratio between B acid acid amounts and L acid acid amounts are 10-25.
3. phosphorous MFI structure molecular sieve according to claim 1, wherein, the mesopore volume is more than 2 nanometers small for aperture
In 100 nanometers of pore volume；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content uses NH3- TPD methods measure,
The acid site of the strong acid is NH3Desorption temperature is more than the acid site corresponding to 300 DEG C；The ratio between the B acid acid amount and L acid acid amounts
Measured using the infrared acid process of pyridine adsorption.
4. a kind of preparation method of the phosphorous MFI structure molecular sieve in claim 1-3 described in any one, the preparation method bag
Include：
A, sodium form MFI structure molecular sieve carries out desiliconization processing in aqueous slkali, obtains desiliconization molecular sieve；
B, gained desiliconization molecular sieve in step a is subjected to ammonium exchange, obtains ammonium and exchange molecular sieve；Wherein, in terms of sodium oxide molybdena and with
On the basis of ammonium exchanges total butt weight of molecular sieve, the sodium content that the ammonium exchanges molecular sieve is less than 0.2 heavy %；
C, it is 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 being washed, obtains dealuminzation molecular sieve；
D, after the dealuminzation molecular sieve of gained in step c being carried out P Modification processing and calcination process, the phosphorous MFI structure is obtained
Molecular sieve.
5. preparation method according to claim 4, wherein, the preparation process of sodium form MFI structure molecular sieve described in step a
Including：
It will use after thering is MFI structure molecular sieve pulp obtained by amine method crystallization to be filtered and washed, and obtain washing molecular sieve；Its
In, counted by sodium oxide molybdena and on the basis of total butt weight of the washing molecular sieve, the sodium content in the washing molecular sieve is small
In 3.0 heavy %；
The washing molecular sieve is dried and after air roasting, obtains the sodium form MFI structure molecular sieve.
6. preparation method according to claim 4, wherein, aqueous slkali described in step a be selected from sodium hydrate aqueous solution,
Potassium hydroxide aqueous solution and ammonium hydroxide.
7. preparation method according to claim 4, wherein, the condition of the processing of desiliconization described in step a includes：With dry basis
The weight ratio of the water in alkali and aqueous slkali in the sodium form MFI structure molecular sieve of gauge, aqueous slkali is 1：(0.1-2)：(5-20),
The temperature of desiliconization processing is room temperature to 100 DEG C, the time for 0.2-4 it is small when.
8. preparation method according to claim 4, wherein, the condition of the processing of desiliconization described in step a includes：With dry basis
The weight ratio of the water in alkali and aqueous slkali in the sodium form MFI structure molecular sieve of gauge, aqueous slkali is 1：(0.2-1)：(5-20).
9. preparation method according to claim 4, wherein, organic acid described in step c is selected from ethylenediamine tetra-acetic acid, grass
At least one of acid, citric acid and sulfosalicylic acid, the inorganic acid are at least one in hydrochloric acid, sulfuric acid and nitric acid
Kind.
10. preparation method according to claim 4, wherein, the condition of dealumination treatment includes described in step c：With butt
The weight ratio that the ammonium of weight meter 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, when the time is 0.5-6 small.
11. preparation method according to claim 4, wherein, the condition of dealumination treatment includes described in step c：With butt
The weight ratio that the ammonium of weight meter exchanges molecular sieve, organic acid, inorganic acid and fluosilicic acid is 1：(0.03-0.2)：(0.015-
0.2)：(0.015-0.2).
12. preparation method according to claim 4, wherein, the processing of P Modification described in step d includes：Will be selected from phosphoric acid,
At least one of ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound impregnates molecular sieve and/or ion is handed over
Change.
13. preparation method according to claim 4, wherein, the condition of the calcination process includes：The atmosphere of calcination process
For air atmosphere or steam atmosphere；Calcination temperature is 400-800 DEG C, when roasting time is 0.5-8 small.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610920226.2A CN107973317B (en) | 2016-10-21 | 2016-10-21 | A kind of phosphorous MFI structure molecular sieve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610920226.2A CN107973317B (en) | 2016-10-21 | 2016-10-21 | A kind of phosphorous MFI structure molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107973317A true CN107973317A (en) | 2018-05-01 |
| CN107973317B CN107973317B (en) | 2019-11-15 |
Family
ID=62004538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610920226.2A Active CN107973317B (en) | 2016-10-21 | 2016-10-21 | A kind of phosphorous MFI structure molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107973317B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020078434A1 (en) * | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
| CN113526522A (en) * | 2020-04-13 | 2021-10-22 | 中国石油化工股份有限公司 | Phosphorus modified MFI structure molecular sieve and preparation method thereof |
| JP2022505333A (en) * | 2018-10-18 | 2022-01-14 | 中国石油化工股▲ふん▼有限公司 | Phosphorus / rare earth-containing MFI structural molecular sieves rich in mesopores and methods for producing them, and catalysts containing the molecular sieves and their utilization. |
| RU2800606C2 (en) * | 2018-10-18 | 2023-07-25 | Чайна Петролеум Энд Кемикал Корпорейшн | Molecular sieve having mfi structure and high mesopore content, method for its production, catalyst containing it and its application |
| TWI822885B (en) * | 2018-10-18 | 2023-11-21 | 大陸商中國石油化工科技開發有限公司 | A kind of mesopore-rich MFI structure molecular sieve, preparation method, catalyst containing the molecular sieve and its use |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073024A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN104307560A (en) * | 2014-10-20 | 2015-01-28 | 丁泳 | Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst |
-
2016
- 2016-10-21 CN CN201610920226.2A patent/CN107973317B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073024A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN104307560A (en) * | 2014-10-20 | 2015-01-28 | 丁泳 | Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020078434A1 (en) * | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
| JP2022505174A (en) * | 2018-10-18 | 2022-01-14 | 中国石油化工股▲ふん▼有限公司 | MFI-structured molecular sieves rich in mesopores and methods for producing them, and catalysts containing the molecular sieves and their use. |
| JP2022505333A (en) * | 2018-10-18 | 2022-01-14 | 中国石油化工股▲ふん▼有限公司 | Phosphorus / rare earth-containing MFI structural molecular sieves rich in mesopores and methods for producing them, and catalysts containing the molecular sieves and their utilization. |
| EP3868711A4 (en) * | 2018-10-18 | 2022-07-06 | China Petroleum & Chemical Corporation | Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
| RU2800606C2 (en) * | 2018-10-18 | 2023-07-25 | Чайна Петролеум Энд Кемикал Корпорейшн | Molecular sieve having mfi structure and high mesopore content, method for its production, catalyst containing it and its application |
| TWI822885B (en) * | 2018-10-18 | 2023-11-21 | 大陸商中國石油化工科技開發有限公司 | A kind of mesopore-rich MFI structure molecular sieve, preparation method, catalyst containing the molecular sieve and its use |
| JP7429693B2 (en) | 2018-10-18 | 2024-02-08 | 中国石油化工股▲ふん▼有限公司 | A phosphorus/rare earth-containing MFI structured molecular sieve rich in mesopores, a method for producing the same, a catalyst containing the molecular sieve, and its use |
| US11964262B2 (en) | 2018-10-18 | 2024-04-23 | China Petroleum & Chemical Corporation | Phosphorus-containing rare-earth-containing MFI structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof |
| US11975980B2 (en) | 2018-10-18 | 2024-05-07 | China Petroleum & Chemical Corporation | MFI structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
| JP7482120B2 (en) | 2018-10-18 | 2024-05-13 | 中国石油化工股▲ふん▼有限公司 | MFI-structured molecular sieve rich in mesopores, its preparation method, catalyst containing said molecular sieve and its use |
| CN113526522A (en) * | 2020-04-13 | 2021-10-22 | 中国石油化工股份有限公司 | Phosphorus modified MFI structure molecular sieve and preparation method thereof |
| CN113526522B (en) * | 2020-04-13 | 2023-02-21 | 中国石油化工股份有限公司 | Phosphorus modified MFI structure molecular sieve and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107973317B (en) | 2019-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107971015B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107973318B (en) | Phosphorous and a kind of MFI structure molecular sieve and preparation method thereof containing carried metal | |
| CN107971028B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107973317B (en) | A kind of phosphorous MFI structure molecular sieve and preparation method thereof | |
| CN107973314B (en) | A kind of phosphorous and rare earth Y molecular sieve and preparation method thereof | |
| CN107971016B (en) | A kind of catalytic cracking catalyst and preparation method thereof containing phosphorous IMF structure molecular screen | |
| CN107971018A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107971011A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107971000A (en) | A kind of assistant for calalytic cracking containing phosphorous Beta molecular sieves and preparation method thereof | |
| CN107971014A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107973308A (en) | A kind of phosphorous MFI structure molecular sieve and preparation method thereof | |
| CN107971008A (en) | A kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method | |
| CN107970978B (en) | Phosphorus-containing and metal-loaded MFI structure molecular sieve and preparation method thereof | |
| CN104944435B (en) | Silicon-phosphorus-aluminum molecular sieve with ITH structure and synthesis method thereof | |
| CN107973307B (en) | Phosphorous and a kind of Beta molecular sieve and preparation method thereof containing carried metal | |
| CN107970986A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN103787359B (en) | A kind of phosphorous Silicon-rich beta-molecular sieve | |
| CN107970996A (en) | One kind phosphorous and IMF containing carried metal structure molecular screens and preparation method thereof | |
| CN107974274A (en) | MFI structure molecular sieve a kind of phosphorous and containing carried metal and preparation method thereof | |
| CN107973306B (en) | A kind of phosphorous IMF structure molecular screen and preparation method thereof | |
| CN107973311A (en) | A kind of Y molecular sieve and preparation method thereof | |
| CN103771437B (en) | A kind of phosphorous modified beta molecular sieve | |
| CN107970987A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107971022B (en) | Catalytic cracking auxiliary agent for increasing propylene yield and preparation method thereof | |
| CN106140271B (en) | A kind of phosphorous MFI structure molecular sieve and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |