CN107973317B - 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
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- 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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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 greater than 18 less than 70；With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 1-15 weight %；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 40-70 volume %, and the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers is 85 volume % or more；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 45-75%, and the ratio between B acid acid amount and L acid acid amount are 8-30.Catalyst or auxiliary agent are prepared using phosphorous MFI structure molecular sieve provided by the invention as active component, propene yield and Propylene Selectivity can be effectively improved in catalytic cracking of petroleum hydrocarbon or catalytic cracking reaction, while increasing BTX yield.
Description
Technical field
The present invention relates to a kind of phosphorous MFI structure molecular sieves and preparation method thereof.
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.About 15% propylene is usually produced using liquid as the ethylene plant of raw material,
Propylene consumed by about 70% petrochemical industry is provided, and the second largest source of propylene mentions nearly all from FCC apparatus
The demand for having supplied about 30%, in the U.S., FCC apparatus then provides petroleum chemicals to about half demand of propylene.
Due to increasing rapidly to polyacrylic demand, increase the required propylene of petrochemical industry more than ethylene requirements
Fastly, 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 to meet the increasing of propylene demand
Add.Since the eighties in last century, the catalyst of the ZSM-5 containing shape-selective molecular sieve starts to put into industrial 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 periodic regeneration of FCC apparatus harshness.For this purpose, Sinopec Group
Research Institute of Petro-Chemical Engineering develops the sieve of the Series Molecules with excellent activity stability in succession, the catalyst that is prepared with this or
Auxiliary agent, other than applying Conventional catalytic cracking device for the purpose of to produce fuel, being also applied to preparing low-carbon olefins is mesh
Process unit on.
At home and abroad under the situation of oil supply growing tension, in conjunction with the reality that domestic crude oil is generally laid particular stress on, develop in
Between base or in the mink cell focuses such as m- naphthenic base wax oil be waste alkene technology, production market ethylene in short supply, propylene, BTX
Equal industrial chemicals, not only can solve the problem of China's ethylene raw inadequate resource, but also can make up caused by steam cracking
The contradiction of propylene/ethylene product structure imbalance, due to producing propylene and ethylene using inexpensive heavy charge, so that alkene produces
Cost sharp fall, while the industrial chemicals such as BTX can be produced, therefore the technology has significant economic benefit and society's effect
Benefit.
ZSM-5 molecular sieve is the three-dimensional meso-hole high-silica zeolite being successfully prepared at first by Mobil Corporation, 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 enters, and 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
It improves, but since its cellular structure is narrow, biggish 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 biggish production such as isoparaffin and aromatic hydrocarbons
Object molecule is also not easy to diffuse out inside molecular sieve pore passage, causes point so as to cause secondary responses such as excessive hydrogen migration, cokings
Son sieve inactivation, reaction selectivity reduce.In the new catalytic cracking process using mink cell focus as raw material, ZSM-5 molecular sieve duct hole
The defect of stenostomia necessarily makes problem above more prominent.
For this problem, there are a few class solutions at present.First is that synthesizing small-grain such as nanoscale ZSM-5 molecular sieve,
To shorten diffusion path.But there is the congenital weakness such as filtration difficulty, hydrothermal structural stability difference for small crystal grain molecular sieve.Second is that 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 also a kind of method is modified method after molecular sieve, 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
It carries 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.
Summary of the invention
The object of the present invention is to provide a kind of phosphorous MFI structure molecular sieves 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 increasing BTX yield.
To achieve the goals above, the present invention provides a kind of phosphorous MFI structure molecular sieve, the n (SiO of the molecular sieve2)/n
(Al2O3) it is greater than 18 less than 70；With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 1-
15 weight %；The Al distribution parameter D of the molecular sieve meets: 0.6≤D≤0.85, wherein D=Al (S)/Al (C), Al (S) table
Show and 100 square nanometers regions are arbitrarily greater than apart from interior using the inside H in crystal face edge of the zeolite crystal of TEM-EDS method measurement
Aluminium content, Al (C) indicate using TEM-EDS method measurement zeolite crystal described in crystal face the outside H distance of geometric center
Interior any aluminium content for being greater than 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometric center
The 10% of distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 40-70 volume %, and aperture is 2 nanometer -20 and receives
The ratio of the total mesopore volume of mesopore volume Zhan of rice is 85 volume % or more；The strong acid acid amount of the molecular sieve accounts for the ratio of total acid content
Example is 45-75%, and the ratio between B acid acid amount and L acid acid amount are 8-30.
Preferably, the n (SiO of the molecular sieve2)/n(Al2O3) it is greater than 21 less than 60；With P2O5It counts and with the dry of molecular sieve
On the basis of base weight amount, the phosphorus content of the molecular sieve is 3-12 weight %；The Al distribution parameter 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 volume %, and aperture is 2 nanometer -20 and receives
The ratio of the total mesopore volume of mesopore volume Zhan of rice is 90 volume % or more；The strong acid acid amount of the molecular sieve accounts for the ratio of total acid content
Example is 55-70%, and the ratio between B acid acid amount and L acid acid amount 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 of the total mesopore volume of volume Zhan is measured using N2 adsorption measurement pore-size distribution method, and total mesopore volume is aperture
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 NH3The side-TPD
Method measures, and the acid site of the strong acid is NH3Desorption temperature be greater than 300 DEG C corresponding to acid site；B acid acid amount with
The ratio between L acid acid amount is 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 methods
Include: that a, sodium form MFI structure molecular sieve carry 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 exchange molecular sieve；Wherein, in terms of sodium oxide molybdena and with total butt of ammonium exchange molecular sieve
On the basis of weight, the sodium content of the ammonium exchange molecular sieve is less than 0.2 weight %；C, gained ammonium in step b is exchanged into molecular sieve
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 washes
After washing, dealuminzation molecular sieve is obtained；D, it after dealuminzation molecular sieve obtained in step c being carried out P Modification processing and calcination process, obtains
To the phosphorous MFI structure molecular sieve.
Preferably, the preparation step of sodium form MFI structure molecular sieve described in step a includes: and will use to have amine method crystallization institute
After MFI structure molecular sieve pulp is filtered and wash, 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 in the washing molecular sieve is less than 3.0 weight %；By the washing point
Son 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, desiliconization described in step a processing condition include: 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): 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 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 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:(0.03-0.2): (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.
Present inventors discovered unexpectedly that chemically carrying out desiliconization processing to MFI structure molecular sieve, ammonium exchanges
Processing carries 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, as the active component of catalyst or auxiliary agent, ethylene and propylene can be improved
Yield, Propylene Selectivity and BTX yield.
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
It generates and spreads, 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 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 phosphorous MFI structure molecular sieve, the n (SiO of the molecular sieve2)/n(Al2O3) be less than greater than 18
70, preferably greater than 21 less than 60；With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 1-
15 weight %, preferably 3-12 weight %；The Al distribution parameter 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) indicate the zeolite crystal measured using TEM-EDS method
The inside H in crystal face edge indicates to survey using TEM-EDS method apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C)
The outside H of the geometric center of crystal face described in fixed zeolite crystal apart from interior any aluminium content for being greater than 100 square nanometers regions,
Described in H be the crystal face edge point to the crystal face geometric center distance 10%；The mesopore volume Zhan of the molecular sieve is total
The ratio of pore volume is 40-70 volume %, and the mesopore volume Zhan that preferably aperture 45-65 volume % is 2 nanometers -20 nanometers is always situated between
The ratio of pore volume is 85 volume % or more, preferably 90 volume % or more；The strong acid acid amount of the molecular sieve accounts for total acid content
Ratio is 45-75%, preferably 55-70%, and the ratio between B acid acid amount and L acid acid amount are 8-30, 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 method measurement molecular sieve is those skilled in the art
It is known, wherein the geometric center be also it is 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, 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.
The present invention also provides a kind of preparation method of phosphorous MFI structure molecular sieve provided by the present invention, the preparation methods
Include: that a, sodium form MFI structure molecular sieve carry 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 exchange molecular sieve；Wherein, in terms of sodium oxide molybdena and with total butt of ammonium exchange molecular sieve
On the basis of weight, the sodium content of the ammonium exchange molecular sieve is less than 0.2 weight %；C, gained ammonium in step b is exchanged into molecular sieve
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 washes
After washing, dealuminzation molecular sieve is obtained；D, it after dealuminzation molecular sieve obtained in step c being carried out P Modification processing and calcination process, obtains
To the phosphorous MFI structure molecular sieve.
According to the method for the present invention, the sodium form MFI structure molecular sieve is well-known to those skilled in the art, Ke Yiwu
Obtained by amine crystallization, gained after the molecular sieve that can also be prepared by template agent method roasts, for example, ZSM-5 molecular sieve.Institute in step a
State sodium form MFI structure molecular sieve preparation step may include: will using have MFI structure molecular sieve pulp obtained by amine method crystallization into
After row filtering and washing, washing molecular sieve is obtained；Wherein, it is in terms of sodium oxide molybdena and with total dry weight of the washing molecular sieve
Benchmark, the sodium content washed in molecular sieve is less than 3.0 weight %；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, and the time can be 0.5-10 hours.
According to the present invention, desiliconization handles the part framework silicon atom for removing molecular sieve, to generate secondary pore, step a
Described in aqueous slkali can be for selected from least one of sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide, preferably
Sodium hydrate aqueous solution；The condition of the processing of desiliconization described in step a may include: with the sodium form MFI structure of dry basis point
The weight ratio of the water in alkali and aqueous slkali in son sieve, aqueous slkali is 1:(0.1-2): (5-20), preferably 1:(0.2-1): (5-
20), the temperature of the desiliconization processing is room temperature to 100 DEG C, and the time is 0.2-4 hours.
According to the present invention, ammonium exchange is well-known to those skilled in the art, for reducing the sodium content in molecular sieve.Example
Such as, the condition of the ammonium exchange may include: according to molecular sieve: ammonium salt: water=1:(0.1-1): the weight ratio of (5-15) will divide
Son sieve filters after room temperature exchanges 0.5-3 hours to ammonium 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 of ammonium exchange can be repeated 1-3 times, until in molecular sieve
Sodium oxide content is lower than 0.2 weight %.
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, make MFI structure molecular sieve selects type impaired performance, is unfavorable for the raising of reaction selectivity, it is therefore desirable to right
It carries out subsequent 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 be primary or be performed in multiple times, can be first by organic acid and institute
Ammonium exchange molecular sieve mixing is stated, then fluosilicic acid and inorganic acid are exchanged to molecular sieve mixing with the ammonium, it can will first to have
Machine acid is added in ammonium exchange molecular sieve, and then by fluosilicic acid and inorganic acid, cocurrent is added at a slow speed, or fluosilicic acid is first added and adds
Cocurrent is added at a slow speed for inorganic acid, preferably fluosilicic acid and inorganic acid.For example, organic acid described in step c can be for selected from second two
At least one of amine tetraacethyl, oxalic acid, citric acid and sulfosalicylic acid, preferably oxalic acid or citric acid, further preferably
Oxalic acid；The inorganic acid can be selected from least one of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid or sulfuric acid, further
Preferably hydrochloric acid；The condition of the dealumination treatment may include: with the ammonium of dry basis exchange molecular sieve, organic acid, inorganic
The weight ratio of acid and fluosilicic acid is 1:(0.01-0.3): (0.01-0.3): (0.01-0.3), 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, and the time is 0.5-6 hours.Pass through desiliconization
Processing is combined with Compound-acid dealuminzation agent solution dealumination treatment handles MFI structure molecular sieve, the aluminium of molecular sieve is distributed,
Silica alumina ratio, Acidity and pore structure have carried out modulation, keep MFI structure molecular sieve reaming modified, still have preferable shape-selective choosing
Selecting property, to effectively improve the propylene of MFI structure molecular sieve, ethylene and BTX yield.
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
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 instrument commonly used by those skilled in the art and
Reagent.
The present invention using micro-reactor evaluation molecular sieve carry out petroleum hydrocarbon catalytic pyrolysis when to productivity of propylene, selectivity and
Molecular sieve is prepared into microspherical catalyst by the influence of BTX yield, and molecular sieve content 50%, remaining is kaolinite
Soil and binder, catalyst sample obtained are carried out on fixed bed aging equipment at 800 DEG C, 100% steam aging 17 hours
Reason, heavy oil it is micro- it is anti-on evaluated, feedstock oil is plus hydrogen wax oil (coming from Yangtze oil plant), evaluation condition are 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 rate) of the invention is measured using ASTM D5154-2010 standard method,
The hydro carbons composition of micro-inverse product is measured using RIPP 85-90 method.
Crystallinity of the invention is measured using the standard method of ASTM D5758-2001 (2011) e1.
N (SiO of the invention2)/n(Al2O3), i.e., silica alumina ratio is calculated by the content of silica and aluminium oxide, oxidation
The content of silicon and aluminium oxide is measured using GB/T 30905-2014 standard method.
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), 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 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.
For details, reference can be made to " petrochemical analysis method ", Yang Cui is surely equal to be compiled for RIPP standard method of the present invention, and 1990
Year version.
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.
Embodiment 1
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At 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 is added, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate
It 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),
It is even to be mixed with dipping, dry, 550 DEG C of calcination process 2h.Molecular sieve-4 A is obtained, physico-chemical property and evaluation data are listed in table 1.
Comparative example 1
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At 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；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
Measure %), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA1 is obtained, physico-chemical property and evaluation data are listed in
Table 1.
Comparative example 2
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then it takes above-mentioned molecular sieve 50g (butt) plus water to be configured to the molecular sieve pulp of the weight of solid content 10 %, adds 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 is added
The mashing of 1500g water, is added 80g NH4After Cl is warming up to 65 DEG C of exchange washing 40min, filtering, elution to filtrate neutrality；By filter cake
Water is added to be beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH3PO4(85 weight % of concentration), be uniformly mixed with dipping,
Drying, 550 DEG C calcination process 2 hours.Molecular sieve DA2 is obtained, physico-chemical property and evaluation data are listed in table 1.
Comparative example 3
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, 135g fluosilicic acid (mass fraction 3%) is added in stirring, time 30min is added；It rises
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 be 40 weight % molecular sieves
6.3gH is added in slurries3PO4(85 weight % of concentration), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve
DA3, physico-chemical property and evaluation data are listed in table 1.
Comparative example 4
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At 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, 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 to contain admittedly
Amount 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
Processing 2 hours.Molecular sieve DA4 is obtained, physico-chemical property and evaluation data are listed in table 1.
Comparative example 5
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At 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
It is added, 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 DA5 is obtained, physico-chemical property and evaluation data are listed in table 1.
Comparative example 6
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, by 42g hydrochloric acid (mass fraction 10%) and 78g fluosilicic acid (mass fraction under stirring
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 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 DA6 is obtained, physico-chemical property and evaluation data are listed in table 1.
Comparative example 7
By the good ZSM-5 molecular sieve of crystallization, (production of catalyst Jian Chang branch company has the synthesis of amine method, n (SiO2)/n(Al2O3)
=50) Na is washed with water to after filtering out mother liquor2O content is lower than 3.0 weight %, filters, drying, 550 DEG C in air, roasting
2h burns up template；It takes above-mentioned molecular sieve 100g (butt) to be added in the NaOH aqueous solution of 3000g (solution concentration 0.8%), stirs
It mixes and is 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 point for taking above-mentioned molecular sieve 50g (butt) plus water to be configured to the weight of solid content 10 %
Sub- screening the pulp liquid, is added with stirring 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, 80g NH is added4After Cl is warming up to 65 DEG C of exchange washing 40min, filtering, elution 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 DA7 is obtained, physico-chemical property and evaluation data are listed in table 1.
Comparative example 8
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 score 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；It is added in the NaOH solution of 1000g2.4%, is warming up to 60 DEG C, react 45min
Afterwards, after being rapidly cooled to room temperature, filtering, washing to filtrate neutrality.Then NH4The exchange of Cl solution is washed to Na2O content is lower than 0.1
Molecular sieve filter cake is obtained by filtration in weight %；To take above-mentioned molecular sieve filter cake 50g (butt) plus water be beaten solid content is 40 heavy %
Molecular sieve pulp, be added 6.3gH3PO4(85 weight % of concentration), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.
Molecular sieve DA8 is obtained, physico-chemical property and evaluation data are listed in table 1.
Comparative example 9
By the good ZSM-5 molecular sieve of crystallization, (production of catalyst Jian Chang branch company has the synthesis of amine method, n (SiO2)/n(Al2O3)
=37) NH is used after filtering out mother liquor4Cl exchange is washed to Na2O content is lower than 0.2 weight %, drying, 550 DEG C in air, roasting
It burns 2h and burns up template；Take above-mentioned molecular sieve 100g (butt) plus water be beaten solid content be 40 weight % molecular sieve pulps, add
Enter 12.6gH3PO4(concentration 85%), dipping drying；Gained sample 550 DEG C calcination process 2 hours to get molecular sieve DA9.Object
Change property and evaluation data are listed in table 1.
Embodiment 2
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At 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 is added, and time 30min is added；45 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate
It 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),
It is even be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve B is obtained, physico-chemical property and evaluation data are listed in table 1.
Embodiment 3
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower 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 rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 1000g water is added in filter cake, 50g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At 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 fraction
3%) cocurrent is added, and time 30min is added, 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；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 5.9gH3PO4
(85 weight % of concentration), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.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) all can not effectively 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, the distribution of molecular sieve aluminium is improved.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 lower, and B acid/L acid ratio is lower.Fluosilicic acid
Composite organic acid oxalic acid dealuminzation (DA5) is equally unable to get 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
It is high that ratio is all not so good as molecular sieve provided by the invention.To the higher ZSM-5 molecular sieve of silica alumina ratio, alkali process uses inorganic acid+nitric acid again
(DA7) is handled, although can get higher mesoporous ratio, the mesoporous diameter of molecular sieve is that the pore volume Zhan of 2nm to 20nm is total
The ratio of mesopore volume is low, i.e. the mesoporous aperture of molecular sieve becomes larger, while the Al distribution of molecular sieve is still poor, and strong acid is less, B
Acid/L acid ratio is 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, crystallinity
Low, mesoporous ratio is low, and mesoporous diameter is that the ratio of the total mesopore volume of pore volume Zhan of 2nm to 20nm is low, molecular sieve outer surface Al phase
To more.After the present invention is using first desiliconization processing is carried out to molecular sieve, compound acid system is reused, in three kinds of sour synergistic effects
Lower carry out dealuminzation can improve aluminium distribution and acid under the premise of guaranteeing crystal structure of molecular sieve and mesopore orbit structural intergrity
Property distribution.From reaction result it can be seen that molecular sieve prepared by the present invention can effectively improve heavy oil conversion rate, propylene is improved
Selectivity increases propylene, ethylene and BTX yield.
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 amount | 15 | 4.9 | 5.0 | 10 | 5.0 | 13.1 | 11.2 | 4.7 | 4.6 | 6.1 | 17.2 | 20.9 |
| D (Al distribution) | 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 yield | 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 greater than 18 less than 70；With P2O5Count and with
On the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 1-15 weight %；The Al distribution parameter D of the molecular sieve
Meet: 0.6≤D≤0.85, wherein D=Al (S)/Al (C), Al (S) indicate brilliant using the molecular sieve of TEM-EDS method measurement
The inside H in crystal face edge of grain indicates to use the side TEM-EDS apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C)
The outside H of geometric center of crystal face described in the zeolite crystal of method measurement 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 mesopore volume of the molecular sieve
The ratio for accounting for total pore volume is 40-70 volume %, and the mesopore volume is that aperture is greater than 2 nanometers of pore volumes less than 100 nanometers；
The ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers is 85 volume % or more；The strong acid of the molecular sieve
The ratio that acid amount accounts for total acid content is 45-75%, and the ratio between B acid acid amount and L acid acid amount are 8-30.
2. phosphorous MFI structure molecular sieve according to claim 1, wherein the n (SiO of the molecular sieve2)/n(Al2O3) big
In 21 less than 60；With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 3-12 weight %；
The Al distribution parameter D of the molecular sieve meets: 0.65≤D≤0.82；The mesopore volume of the molecular sieve accounts for the ratio of total pore volume
Example is 45-65 volume %, and the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers is 90 volume % or more；
The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 55-70%, and the ratio between B acid acid amount and L acid acid amount are 10-25.
3. phosphorous MFI structure molecular sieve according to claim 1, wherein the strong acid acid amount of the molecular sieve accounts for total acid content
Ratio use NH3- TPD method measures, and the acid site of the strong acid is NH3Desorption temperature be greater than 300 DEG C corresponding to acid
Center；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
4. the preparation method of phosphorous MFI structure molecular sieve described in a kind of any one of claim 1-3, the preparation method packet
It includes:
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 exchange molecular sieve；Wherein, in terms of sodium oxide molybdena and with
On the basis of ammonium exchanges total dry weight of 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 being carried out in liquid, and after being filtered and washed, obtaining 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 MFI structure is obtained
Molecular sieve.
5. the preparation method according to claim 4, wherein the preparation step of sodium form MFI structure molecular sieve described in step a
Include:
After will be using there is MFI structure molecular sieve pulp 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 in sodium content it is small
In 3.0 weight %；
The washing molecular sieve is dried and after air roasting, obtains the sodium form MFI structure molecular sieve.
6. the 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. the 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 meter, 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.
8. the 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 meter, aqueous slkali is 1:(0.2-1): (5-20).
9. the 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.
10. the preparation method according to claim 4, 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.
11. the preparation method according to claim 4, 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:(0.03-0.2): (0.015-
0.2): (0.015-0.2).
12. the preparation method according to claim 4, 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.
13. the 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；Maturing temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.
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