CN107973311B - A kind of Y molecular sieve and preparation method thereof - Google Patents
A kind of Y molecular sieve and preparation method thereof Download PDFInfo
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- 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
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Abstract
Present disclose provides a kind of Y molecular sieve and preparation method thereof, the cell parameter of the molecular sieve is 24.35-24.55 angstroms；The Al distribution parameter D of the molecular sieve meets: 0.3≤D≤0.8；The mesopore volume of the molecular sieve is 0.15-1.0 mls/g；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 30%-70%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 30-60%, and the ratio between B acid acid amount and L acid acid amount are 20-100.Prepare catalyst as active component using the Y molecular sieve of the disclosure, for heavy oil catalytic cracking, be hydrocracked when with excellent conversion capability and higher midbarrel oil yield, low coke yield.
Description
Technical field
This disclosure relates to a kind of Y molecular sieve and preparation method thereof.
Background technique
Molecular sieve is due to being widely used in catalysis, absorption with Shape-selective, higher specific surface and stronger acidity
With separation etc. fields.Y molecular sieve (HY, REY, USY) since the sixties in last century of use for the first time, just always catalytic cracking,
The chief active constituent element of hydrocracking catalyst.However, the polycyclic compound content with the aggravation of crude oil heaviness, in raw material
It dramatically increases, the diffusivity in molecular sieve pore passage is but remarkably decreased.And the Y molecular sieve aperture as predominant cracking group member
Only 0.74nm, being used to heavy ends, the accessibilities of catalyst active center such as process residual oils will become contained therein polycyclic
The major obstacle of compound (such as polycyclic aromatic hydrocarbon, polycyclic ring alkane) cracking；Simultaneously as molecular sieve outer surface acidity is deposited
So that the heavy oil molecules that cannot enter duct occur to react without selection on surface, product distribution is being influenced.
Poromerics aperture is smaller, surface has more polyoxybiontic weakness in order to overcome, surface Silicon-rich and rich in mesoporous
The synthesis of catalysis material is increasingly subject to the attention of people.
A kind of preparation side of the Y molecular sieve of containing mesopore is disclosed in United States Patent (USP) US5,069,890 and US5,087,348
Method is mainly comprised the processes of using commercially available USY as raw material, in the atmosphere of 100% vapor, is handled for 24 hours at 760 DEG C.This method
Obtained Y molecular sieve mesopore volume increases to 0.14mL/g by 0.02mL/g, but crystallinity drops to 70% by 100%, compares table
Area is by 683m2/ g is reduced to 456m2/ g, sour density more drop to 6% by 28.9%.
United States Patent (USP) US5 is original with HY or USY in the method for the Y molecular sieves of 601,798 disclosed preparation containing mesopores
Material, is placed in autoclave and NH4NO3Solution or NH4NO3With HNO3Mixed solution mix, 115 DEG C -250 DEG C at a temperature of
2h-20h is handled, the mesopore volume of obtained Y molecular sieve is up to 0.2mL/g-0.6mL/g, but crystallinity and specific surface area have
It is remarkably decreased.
Chinese patent CN101722022 discloses a kind of alkali treatment modifying method of Y molecular sieve, including according to molecular sieve
(butt): highly basic: distilled water=(0.1-2): (0.05-2): Y molecular sieve and strong alkali aqueous solution are beaten by the mass ratio of (4-15)
It is uniformly mixed, the alkali process 0.1-24h at 0-120 DEG C, obtained molecular sieve has higher N compared with parent Y molecular sieve2
Adsorbance.
The method that skeleton rich silicon Y molecular sieve is prepared disclosed in Chinese patent CN 101723399, first with lye to NaY points
Son sieve carries out desiliconization pretreatment, then carries out ammonium exchange, dealumination complement silicon processing, obtained Y molecular sieve to the molecular sieve after alkali process
It is mesoporous to increased, but amplification is little.
Chinese patent CN103172082 discloses a kind of preparation method of the Y molecular sieve of containing mesopore, first to sodium form Y points
Son sieve carries out ammonium exchange, handles followed by aqueous solutions of organic acids, is carrying out NaOH processing to the molecular sieve after acid processing, most
It is handled afterwards using aqueous ammonium nitrate solution, obtains the Y molecular sieve of containing mesopore.Obtained Y molecular sieve, micropore rich in are mesoporous
Pore volume can arrive 0.5mL/g-1.5mL/g.
Chinese patent CN104760973 discloses a kind of Y molecular sieve and preparation method thereof of mesoporous content of superelevation, first will
Y-type zeolite pre-processes 1-5h at 300-600 DEG C；It is cooled to 200-600 DEG C；In dried over anhydrous environment, to by pre-processing
Y-type zeolite in be passed through by dealumination complement silicon be saturated dry gas, react 0.5-7h, obtain crude product；Or in dried over anhydrous ring
Under border, while temperature to be at the uniform velocity warming up to 250-700 DEG C, satisfied to by being passed through in pretreated y-type zeolite by dealumination complement silicon
The dry gas of sum reacts 0.5-7h, obtains crude product；Crude product carries out sour processing；Alkali is carried out to acid treated crude product
Processing, obtains Y molecular sieve.Y molecular sieve made from this method has the mesoporous content of superelevation, but micro pore volume is lower.
Summary of the invention
Purpose of this disclosure is to provide a kind of Y molecular sieves and preparation method thereof, using the Y molecular sieve of the disclosure as active group
Member prepares catalyst, for heavy oil catalytic cracking, be hydrocracked when with excellent conversion capability and higher midbarrel
Oil yield, low coke yield.
To achieve the goals above, the disclosure provides a kind of Y molecular sieve, and the cell parameter of the molecular sieve is 24.35-
24.55 angstroms；The Al distribution parameter D of the molecular sieve meets: 0.3≤D≤0.8, wherein D=Al (S)/Al (C), Al (S) are indicated
The inside H in crystal face edge using the zeolite crystal of TEM-EDS method measurement is arbitrarily greater than 100 square nanometers regions apart from interior
Aluminium content, Al (C) are indicated in the outside H distance of the geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method
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 geometrical center to center
From 10%；The mesopore volume of the molecular sieve is 0.15-1.0 mls/g；The mesopore volume of the molecular sieve accounts for total pore volume
Ratio be 30%-70%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 30-60%, B acid acid amount and L acid acid
The ratio between amount is 20-100.
Preferably, the cell parameter of the molecular sieve is 24.40-24.52 angstroms；The Al distribution parameter D of the molecular sieve is full
Foot: 0.35≤D≤0.75；The mesopore volume of the molecular sieve is 0.2-0.8 mls/g；The mesopore volume of the molecular sieve accounts for
The ratio of total pore volume is 35%-65%；The strong acid acid amount of the molecular sieve account for total acid content example be 35-55%, B acid acid amount with
The ratio between L acid acid amount is 60-80.
Preferably, it is described it is mesoporous for aperture be greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；The molecular sieve it is strong
Sour amount accounts for the ratio of total acid content using NH3- TPD method measures, and the acid site of the strong acid is NH3Desorption temperature is greater than
Acid site corresponding to 300 DEG C；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
The disclosure also provides a kind of preparation method of Y molecular sieve provided by the disclosure, which includes: a, will
NaY molecular sieve carries out ammonium exchange processing, and after being filtered and washed, and obtains ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena simultaneously
On the basis of the dry weight of ammonium exchange molecular sieve, the sodium oxide content of the ammonium exchange molecular sieve is less than 5 weight %；b,
Gained ammonium exchange molecular sieve in step a is subjected to hydrothermal calcine processing in steam atmosphere, obtains water roasting molecular sieve；It c, will step
Gained water roasting molecular sieve carries out the first dealumination treatment in the acid solution being made of organic acid and inorganic acid in rapid b, and carries out
After filter and washing, the first dealuminzation molecular sieve is obtained；D, by the first dealuminzation molecular sieve obtained in step c in inorganic alkali solution into
Row alkali process, and after being filtered and washed, obtain alkali process molecular sieve；E, by step d gained alkali process molecular sieve by
The second dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of fluosilicic acid, organic acid and inorganic acid composition, and is filtered and washes
After washing, the Y molecular sieve is obtained.
Preferably, the organic acid in acid solution described in step c is selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulphur
At least one of base salicylic acid, inorganic acid are selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the condition of the first dealumination treatment described in step c includes: with the molecular sieve of dry basis, organic acid
Weight ratio with inorganic acid is 1:(0.03-0.3): (0.02-0.4)；First dealumination treatment temperature is 25-100 DEG C, and first is de-
The aluminium processing time is 0.5-6 hours.
Preferably, the condition of the first dealumination treatment described in step c includes: with the molecular sieve of dry basis, organic acid
Weight ratio with inorganic acid is 1:(0.05-0.25): (0.05-0.25).
Preferably, inorganic alkali solution described in step d is selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide
At least one of solution and ammonium hydroxide.
Preferably, the condition of alkali process described in step d includes: the weight with the molecular sieve of dry basis and inorganic base
The ratio between be 1:(0.02-0.6)；Alkali purification temp is 25-100 DEG C, and the alkali process time is 0.5-6 hours.
Preferably, organic acid described in Compound-acid dealuminzation agent solution described in step e is selected from ethylenediamine tetra-acetic acid, grass
At least one of acid, citric acid and sulfosalicylic acid, inorganic acid are selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the condition of the second dealumination treatment described in step e include: with the molecular sieve of dry basis, fluosilicic acid,
The weight ratio of organic acid and inorganic acid is 1:(0.03-0.3): (0.05-0.3): (0.05-0.25)；Second dealumination treatment temperature
Degree is 25-100 DEG C, and the second dealumination treatment time was 0.5-6 hours.
Preferably, the condition of the second dealumination treatment described in step e include: with the molecular sieve of dry basis, fluosilicic acid,
The weight ratio of organic acid and inorganic acid is 1:(0.035-0.2): (0.06-0.2): (0.1-0.2).
Preferably, it is 450-750 DEG C that the condition of the processing of hydrothermal calcine described in step b, which includes: temperature, time 0.5-6
Hour, steam atmosphere is 100 volume % steam atmospheres.
The disclosure provide by ammonium exchange, hydrothermal calcine, the first dealumination treatment, alkali process and the second dealumination treatment Y
Molecular sieve, molecular sieve surface Silicon-rich can inhibit the generation of the non-selective side reaction in surface, and mesoporous abundant to be conducive to residual oil cracking anti-
It should be with the progress of hydrocracking reaction.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The specific embodiment of the disclosure is described in detail below.It should be understood that described herein specific
Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of Y molecular sieve, and the cell parameter of the molecular sieve is 24.35-24.55 angstroms；The molecular sieve
Al distribution parameter D meets: 0.3≤D≤0.8, wherein D=Al (S)/Al (C), Al (S) indicate to measure using TEM-EDS method
Zeolite crystal the inside H in crystal face edge apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) expression is adopted
The outside H of geometric center of crystal face described in the zeolite crystal measured with TEM-EDS method is arbitrarily greater than 100 square nanometers apart from interior
The aluminium content in region, wherein the H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The molecular sieve
Mesopore volume be 0.15-1.0 mls/g；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 30%-70%；
The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 30-60%, and the ratio between B acid acid amount and L acid acid amount are 20-100；It is preferred that
Ground, the cell parameter of the molecular sieve are 24.40-24.52 angstroms；The Al distribution parameter D of the molecular sieve meets: 0.35≤D≤
0.75；The mesopore volume of the molecular sieve is 0.2-0.8 mls/g；The mesopore volume of the molecular sieve accounts for the ratio of total pore volume
Example is 35%-65%；The example that the strong acid acid amount of the molecular sieve accounts for total acid content is 35-55%, the ratio between B acid acid amount and L acid acid amount
For 60-80.
According to the disclosure, the aluminium content using TEM-EDS method measurement molecular sieve be it is well-known to those skilled in the art,
Wherein the geometric center is also well-known to those skilled in the art, can be calculated according to formula, and the disclosure is no longer superfluous
It states, the geometric center of generally symmetrical figure is the intersection point of each opposed apexes line, and the crystal face is a face of regular crystal grain,
The direction inwardly or outwardly refers both to the direction inwardly or outwardly on the crystal face.
According to the disclosure, the mesopore volume of the molecular sieve account for the ratio of total pore volume using nitrogen adsorption desorption method into
Row measurement, it is described it is mesoporous for aperture be greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；The strong acid acid amount of the molecular sieve accounts for
The ratio of total acid content uses NH3- TPD method measures, and the acid site of the strong acid is NH3It is right that desorption temperature is greater than 300 DEG C of institutes
The acid site answered；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
The disclosure also provides a kind of preparation method of Y molecular sieve provided by the disclosure, which includes: a, will
NaY molecular sieve carries out ammonium exchange processing, and after being filtered and washed, and obtains ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena simultaneously
On the basis of the dry weight of ammonium exchange molecular sieve, the sodium oxide content of the ammonium exchange molecular sieve is less than 5 weight %；b,
Gained ammonium exchange molecular sieve in step a is subjected to hydrothermal calcine processing in steam atmosphere, obtains water roasting molecular sieve；It c, will step
Gained water roasting molecular sieve carries out the first dealumination treatment in the acid solution being made of organic acid and inorganic acid in rapid b, and carries out
After filter and washing, the first dealuminzation molecular sieve is obtained；D, by the first dealuminzation molecular sieve obtained in step c in inorganic alkali solution into
Row alkali process, and after being filtered and washed, obtain alkali process molecular sieve；E, by step d gained alkali process molecular sieve by
The second dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of fluosilicic acid, organic acid and inorganic acid composition, and is filtered and washes
After washing, the Y molecular sieve is obtained.
According to the disclosure, the processing of ammonium exchange described in step a is well-known to those skilled in the art, for example, can incite somebody to action
NaY molecular sieve is according to molecular sieve: ammonium salt: H2O=1:(0.1-1): the weight ratio of (5-10) is in room temperature to exchanging 0.5- at 100 DEG C
It is filtered after 2 hours, this exchange process can repeat 1-4 times, make the Na on molecular sieve2O content % heavy less than 5.The ammonium salt
It can be common inorganic ammonium salt, for example, selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate.
According to the disclosure, organic acid and inorganic acid in acid solution described in step c are that those skilled in the art institute is ripe
Know, for example, the organic acid in the acid solution can be in ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid
At least one, preferably citric acid；Inorganic acid is selected from least one of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid.
According to the disclosure, dealumination treatment be it is well-known to those skilled in the art, first dealumination treatment can be primary
Or be performed in multiple times, first organic acid can be mixed with water roasting molecular sieve, inorganic acid and the water are then roasted into molecular sieve
Mixing；First inorganic acid can also be mixed with water roasting molecular sieve, then mix organic acid with water roasting molecular sieve；
Inorganic acid, organic acid can be mixed with water roasting molecular sieve simultaneously.The condition of first dealumination treatment can be with are as follows: with dry basis
The weight ratio of the molecular sieve of meter, organic acid and inorganic acid is 1:(0.03-0.3): (0.02-0.4), preferably 1:(0.05-
0.25):(0.05-0.25)；First dealumination treatment temperature is 25-100 DEG C, and the first dealumination treatment time was 0.5-6 hours.
According to the disclosure, what inorganic alkali solution described in step d was well known to those skilled in the art, such as can be choosing
From at least one of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and ammonium hydroxide, preferably sodium hydroxide is molten
Liquid.The condition of alkali process described in step d may include: with the weight ratio of the molecular sieve of dry basis and inorganic base for 1:
(0.02-0.6), preferably 1:(0.05-0.4)；Alkali purification temp is 25-100 DEG C, and the alkali process time is 0.5-6 hours.
According to the disclosure, although dealumination treatment be it is well-known to those skilled in the art, do not reported inorganic acid, had
Machine acid and fluosilicic acid are used for dealumination treatment together.Second dealumination treatment can be primary or be performed in multiple times, and will can first have
Machine acid is mixed with the alkali process molecular sieve, then mixes fluosilicic acid and inorganic acid with the alkali process molecular sieve, it can
For first organic acid is added in alkali process molecular sieve, then by fluosilicic acid and inorganic acid, cocurrent is added at a slow speed, or fluorine silicon is first added
Acid adds inorganic acid, and preferably cocurrent is added at a slow speed for fluosilicic acid and inorganic acid.In Compound-acid dealuminzation agent solution described in step e
The organic acid can be for selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably grass
Acid or citric acid, further preferably citric acid, inorganic acid can be excellent for selected from least one of hydrochloric acid, sulfuric acid and nitric acid
It is selected as hydrochloric acid or sulfuric acid, further preferably hydrochloric acid.The condition of second dealumination treatment can be with are as follows: with point of dry basis
Sub sieve, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.03-0.3): (0.05-0.3): (0.05-0.25), it is excellent
It is selected as 1:(0.035-0.2): (0.06-0.2): (0.1-0.2)；Second dealumination treatment temperature is 25-100 DEG C, at the second dealuminzation
Managing the time is 0.5-6 hours.
According to the disclosure, hydrothermal calcine be it is well-known to those skilled in the art, for keeping molecular sieve more stable, step
Hydrothermal calcine treatment conditions described in b can be with are as follows: temperature is 450-750 DEG C, and preferably 550-700 DEG C, the time is that 0.5-6 is small
When, preferably 1-2 hours, steam atmosphere was 100 volume % steam atmospheres, and hydrothermal calcine processing also has the work of de- ammonium
With, make by ammonium exchange processing ammonium exchange molecular sieve (NH4NaY) processing is that water roasts molecular sieve (HNaY), optimum condition are as follows: temperature
Degree be 500 DEG C -600 DEG C, steam atmosphere be 100 volume %, the time be 1-3 hour, more preferably use flowing water steam into
Row processing consumes 1-2 times of weight that the weight of vapor can exchange molecular sieve for ammonium per hour.
Washing described in the disclosure is well-known to those skilled in the art, refers generally to wash, for example, 5-10 times can be used
30-60 DEG C of water of molecular sieve elutes molecular sieve.
The disclosure will be further illustrated by embodiment below, but therefore the disclosure is not any way limited,
Instrument and reagent used by the embodiment of the present disclosure, unless otherwise instructed, be instrument commonly used by those skilled in the art and
Reagent.
Influence of the molecular sieve in catalytic cracking of petroleum hydrocarbon to heavy oil conversion ratio, gasoline yield, coke yield uses heavy oil
It is micro- counter to be evaluated.Feedstock oil is to mix slag VGO, and molecular sieve passes through 800 DEG C, 17h, and the processing of 100% vapor hydrothermal aging is evaluated
Condition be 500 DEG C of reaction temperature, 600 DEG C of regeneration temperature, oil ratio 5.92.
Influence of the molecular sieve in petroleum hydrocarbon is hydrocracked to heavy oil conversion ratio, reaction product selectivity of ring-opening uses pure hydrocarbon
It is micro- it is counter simulated, be measured using ASTM D5154-2010 standard method.Feedstock oil is naphthane, reaction pressure
4.0MPa, 300-410 DEG C of reaction temperature, air speed 6.0h-1.The selectivity of ring-opening of reaction product=mononuclear aromatics products collection efficiency/turn
Rate × 100.
The cell parameter of the disclosure is measured using RIPP145-90 standard method, and the measuring method is shown in " petrochemical industry point
Analysis method (RIPP test method) ", Yang Cui delimits the organizational structure, Science Press, and nineteen ninety publishes.
Research method of the TEM-EDS measuring method of the disclosure referring to solid catalyst, petrochemical industry, 29 (3), 2000:
227。
The mesoporous pore volume of the disclosure, the measuring method of total pore volume are as follows:
The AS-3 produced using Quantachrome instrument company, the measurement of AS-6 static state n2 absorption apparatus.
Instrument parameter: being placed in sample processing system for sample, is evacuated to 1.33 × 10 at 300 DEG C-2Pa, heat-insulation pressure keeping
4h purifies sample.At -196 DEG C of liquid nitrogen temperature, test purification sample is not pressing P/P on year-on-year basis0Under the conditions of to the adsorbance of nitrogen
And desorption rate, obtain N2Adsorption-desorption isothermal curve.Then total specific surface area is calculated using two parameter BET formula, micropore compares table
Area and mesopore surface area take than pressing P/P0=0.98 adsorbance below is the total pore volume of sample, utilizes BJH formula meter
The pore-size distribution of mesoporous part is calculated, and mesoporous pore volume (2-100 nanometers) and 2-20 nanometers of mesoporous hole are calculated using integration method
Volume.
The B acid acid amount of the disclosure and the measuring method of L acid acid amount are 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 total acid content of the disclosure and the measuring method of strong acid acid amount are 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.
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 Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 3g is added in stirring, 400g hydrochloric acid (matter is then added
Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By sample plus water
Be beaten solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature
0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 5g is added in stirring
Then oxalic acid is slowly added dropwise 50g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) simultaneously, is warming up to 50 DEG C of perseverances
Temperature stirring 1h, filtration washing are dried to obtain sieve sample A, and physico-chemical property, the heavy oil micro anti-evaluation heavy oil of sieve sample A turns
Rate, midbarrel oil yield, coke yield are listed in table 1.
Comparative example 1
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %；Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be beaten solid content be 10 weight % molecular sieve pulp, be added 10.42gNaOH (purity 96%), be warming up to 50 DEG C of perseverances
Temperature stirring 0.5h, filtration washing to neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 20 weight %, slow drop
Adding 127g fluosilicic acid (concentration 20%), is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing is dried to obtain sieve sample DB1, point
The physico-chemical property of son sieve sample DB1, heavy oil micro anti-evaluation heavy oil conversion rate, midbarrel oil yield, coke yield are listed in table 1.
Comparative example 2
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g is added in stirring, 400g hydrochloric acid (quality is then added
Score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten
Starch solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature
0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, be added in stirring
146g fluosilicic acid (concentration 20%), is warming up to 50 DEG C of constant temperature stirring 1h, and filtration washing is dried to obtain sieve sample DB2, molecule
The physico-chemical property of sieve sample DB2, heavy oil micro anti-evaluation heavy oil conversion rate, midbarrel oil yield, coke yield are listed in table 1.
Comparative example 3
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g is added in stirring, 400g hydrochloric acid (quality is then added
Score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten
Starch solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature
0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, grass is added in stirring
Then 178g hydrochloric acid (mass fraction 10%) is added in sour 12g, be warming up to 50 DEG C of constant temperature stirring 1h, and filtration washing is dried to obtain point
Son sieve sample DB3, the physico-chemical property of sieve sample DB3, heavy oil micro anti-evaluation heavy oil conversion rate, midbarrel oil yield, coke
Charcoal yield is listed in table 1.
Comparative example 4
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 15g is added in stirring, 200g hydrochloric acid (quality is then added
Score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten
Starch solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature
0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, grass is added in stirring
Sour 29g, is warming up to 50 DEG C of constant temperature stirring 1h, and filtration washing is dried to obtain sieve sample DB4, the materialization of sieve sample DB4
Property, heavy oil micro anti-evaluation heavy oil conversion rate, midbarrel oil yield, coke yield are listed in table 1.
Comparative example 5
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 3g is added in stirring, 400g hydrochloric acid (quality is then added
Score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten
Starch solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature
0.5h；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 245g hydrochloric acid (mass fraction is added in stirring
10%) 50 DEG C of constant temperature stirring 1h, are warming up to, filtration washing is dried to obtain sieve sample DB5, the materialization of sieve sample DB5
Property, heavy oil micro anti-evaluation heavy oil conversion rate, midbarrel oil yield, coke yield are listed in table 1.
Comparative example 6
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 3g is added in stirring, 400g hydrochloric acid (quality is then added
Score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten
Starch solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature
0.5h；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 30g oxalic acid is added in stirring, then slowly
It being added dropwise 100g fluosilicic acid (concentration 20%), is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing is dried to obtain sieve sample DB6,
The physico-chemical property of sieve sample DB6, heavy oil micro anti-evaluation heavy oil conversion rate, midbarrel oil yield, coke yield are listed in table
1。
Comparative example 7
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 3g is added in stirring, 400g hydrochloric acid (quality is then added
Score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten
Starch solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature
0.5h；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 188g hydrochloric acid (mass fraction is added in stirring
10%) 100g fluosilicic acid (concentration 20%), is then slowly added dropwise, is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing is dried to obtain
The physico-chemical property of sieve sample DB7, sieve sample DB7, heavy oil micro anti-evaluation heavy oil conversion rate, midbarrel oil yield,
Coke yield is listed in table 1.
Embodiment 2
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g is added in stirring, 200g sulfuric acid (quality is then added
Score 10%), time 30min is added；30 DEG C of constant temperature stirring 2h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten
Starch solid content be 10 weight % molecular sieve pulps, be added 31.25gKOH (purity 96%), be warming up to the stirring of 70 DEG C of constant temperature
0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, be added in stirring
Then 100g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) is slowly added dropwise simultaneously in 15g ethylenediamine tetra-acetic acid,
50 DEG C of constant temperature stirring 1h are warming up to, filtration washing is dried to obtain sieve sample B, and physico-chemical property, the heavy oil of sieve sample B is micro-
Anti- evaluation heavy oil conversion rate, midbarrel oil yield, coke yield are listed in table 2.
Embodiment 3
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 25g is added in stirring, 250g nitric acid (quality is then added
Score 10%), time 30min is added；90 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten
Molecular sieve pulp of the solid content for 10 weight % is starched to obtain, addition 35gNaOH (purity 96%) is warming up to 80 DEG C of constant temperature stirring 0.5h,
Filtration washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 20g grass is added in stirring
Then acid is slowly added dropwise 105g hydrochloric acid (mass fraction 10%) and 49g fluosilicic acid (concentration 20%) simultaneously, is warming up to 70 DEG C of constant temperature
1h is stirred, filtration washing is dried to obtain sieve sample C, the physico-chemical property of sieve sample C, heavy oil micro anti-evaluation heavy oil conversion
Rate, midbarrel oil yield, coke yield are listed in table 2.
Embodiment 4
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, by sample filtering, washing, drying.Take above-mentioned molecular sieve 600 DEG C,
2h is roasted under 100% vapor.Molecular sieve 100g (butt quality) plus water after taking roasting are configured to point of the weight of solid content 10 %
Oxalic acid 30g is added in stirring for sub- screening the pulp liquid, and 100g sulfuric acid (mass fraction 10%) then is added, and time 1min is added；It is warming up to
55 DEG C of constant temperature stir 2h, and filtering is washed to filtrate neutrality；By sample plus water be beaten solid content be 10 weight % molecular sieve pulps,
It is added 41gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing to neutrality；Filter cake plus water are beaten
Solid content is the molecular sieve pulp of 20 weight %, and 30g sulfosalicylic acid is added in stirring, 100g hydrochloric acid is then slowly added dropwise simultaneously
(mass fraction 10%) and 62g fluosilicic acid (concentration 20%), is warming up to 50 DEG C of constant temperature stirring 1h, and filtration washing is dried to obtain molecule
Sieve sample D, the physico-chemical property of sieve sample D, heavy oil micro anti-evaluation heavy oil conversion rate, midbarrel oil yield, coke yield
It is listed in table 2.
Embodiment 5
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1:
1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small
In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting
Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 20g is added in stirring, 220g nitric acid matter is then added
Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By sample plus water
It is beaten to obtain molecular sieve pulp of the solid content for 10 weight %, addition 23gLiOH is warming up to 400 DEG C of constant temperature stirring 2h, and filtration washing is extremely
It is neutral；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 5g ethylenediamine tetra-acetic acid is added in stirring, so
148g sulfuric acid (mass fraction 10%) and 125g fluosilicic acid (concentration 20%) is slowly added dropwise simultaneously afterwards, is warming up to 80 DEG C of constant temperature stirrings
1h, filtration washing are dried to obtain sieve sample E, the physico-chemical property of sieve sample E, heavy oil micro anti-evaluation heavy oil conversion rate,
Midbarrel oil yield, coke yield are listed in table 2.
Embodiment 6
The sieve sample F obtained using the solution saturation dipping embodiment 3 of four thio ammonium molybdate, then in 120 DEG C, N2
Dry 6h under atmosphere, catalyst F needed for being made.Physico-chemical property, the naphthane micro anti-evaluation conversion ratio, reaction product of catalyst F
Selectivity of ring-opening be listed in table 3.
Comparative example 8
Using the solution saturation dipping obtained sieve sample DF of comparative example 1 of four thio ammonium molybdate, then in 120 DEG C,
N2Dry 6h under atmosphere, catalyst DF needed for being made.The physico-chemical property of catalyst DF, naphthane relative evaluation conversion ratio, reaction
The selectivity of ring-opening of product is listed in table 3.
It is de- using single organic acid oxalic acid for the Y molecular sieve after alkali process desiliconization it can be seen from data in table 1-2
Aluminium (DB4), using single inorganic acid HCl dealumination (DB5) and using organic acid oxalic acid and two kinds of acid of inorganic acid hydrochloric acid it is compound
(DB3) all effectively the Al in molecular sieve can not be removed, and preferable dealuminzation effect could be obtained after only having used fluosilicic acid
Fruit.When fluosilicic acid dealuminzation is used alone (DB2), mesoporous relatively fewer, strong acid proportion in total acid is lower, B acid/L acid ratio
Example is lower.Fluosilicic acid composite organic acid oxalic acid dealuminzation (DB6) and fluosilicic acid composite inorganic acid HCl dealumination (DB7), though allow Jie
Pore volume increased, but strong acid proportion and B acid/L acid ratio in total acid are all not so good as the molecule of disclosure offer
Sieve is high.The disclosure uses compound acid system, under three kinds of sour synergistic effects, can guarantee crystal structure of molecular sieve and mesoporous
Aluminium distribution is effectively adjusted under the premise of cellular structure integrality, improves acid distribution, it is non-that molecular sieve surface Silicon-rich can inhibit surface
The generation of selective side reaction, it is mesoporous abundant, be conducive to the progress of residual oil cracking reaction, can be improved heavy oil conversion rate, reduces
Coke yield.
Can be seen that the molecular sieve that the disclosure provides from the data of table 3 can promote naphthane to convert and improve reaction
The selectivity of ring-opening of product.
Table 1
| Molecular sieve | A | DB1 | DB2 | DB3 | DB4 | DB5 | DB6 | DB7 |
| Cell parameter/angstrom | 24.47 | 24.44 | 24.43 | 24.45 | 24.46 | 24.44 | 24.45 | 24.45 |
| Mesopore volume/(mL/g) | 0.18 | 0.03 | 0.11 | 0.21 | 0.20 | 0.26 | 0.19 | 0.18 |
| VIt is mesoporous/VTotal hole | 0.33 | 0.08 | 0.21 | 0.58 | 0.4 | 0.62 | 0.37 | 0.34 |
| (strong acid acid amount/total acid content)/% | 41 | 35 | 39 | 29 | 31 | 36 | 38 | 39 |
| The sour amount of B acid/L acid acid amount | 35 | 16 | 19 | 8 | 9 | 5 | 18 | 14 |
| D (Al distribution) | 0.75 | 0.82 | 0.81 | 0.81 | 0.86 | 0.82 | 0.89 | 0.85 |
| Heavy oil conversion rate/w% | 65.01 | 50.01 | 58.3 | 46.06 | 42.33 | 38.14 | 61.78 | 61.1 |
| Midbarrel oil yield/w% | 21.9 | 17.3 | 18.0 | 14.1 | 15.1 | 13.2 | 17.1. | 16.9 |
| Coke yield/w% | 7.7 | 9.8 | 8.9 | 14 | 13 | 12.2 | 10.3 | 11.5 |
Table 2
| Molecular sieve | B | C | D | E |
| Cell parameter/A angstroms | 24.48 | 24.43 | 24.39 | 24.35 |
| Mesopore volume/(mL/g) | 0.27 | 0.34 | 0.68 | 0.21 |
| VIt is mesoporous/VTotal hole | 0.38 | 0.51 | 0.59 | 0.32 |
| (strong acid acid amount/total acid content)/% | 39 | 42 | 48 | 55 |
| The sour amount of B acid/L acid acid amount | 40 | 51 | 86 | 74 |
| D (Al distribution) | 0.71 | 0.65 | 0.38 | 0.35 |
| Heavy oil conversion rate/w% | 67.15 | 68.98 | 71.23 | 66.84 |
| Midbarrel oil yield/w% | 26.86 | 28.13 | 31.13 | 25.89 |
| Coke yield/w% | 7.1 | 6.6 | 6.3 | 6.1 |
Table 3
| Catalyst | F | DF |
| Cell parameter/angstrom | 24.43 | 24.49 |
| Mesopore volume/(mL/g) | 0.3 | 0.05 |
| (VIt is mesoporous/VTotal hole)/% | 0.5 | 0.08 |
| D (Al distribution) | 0.75 | 0.82 |
| Naphthane relative conversion rate/w% | 58.01 | 56.83 |
| The selectivity of ring-opening of reaction product | 27.47 | 15.06 |
Claims (13)
1. a kind of Y molecular sieve, the cell parameter of the molecular sieve is 24.35-24.55 angstroms；The Al distribution parameter D of the molecular sieve is full
Foot: 0.3≤D≤0.8, 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 of the molecular sieve is
0.15-1.0 mls/g, the ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 30%-70%, described mesoporous for hole
Diameter is greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 30-
The ratio between 60%, B acid acid amount and L acid acid amount are 20-100.
2. Y molecular sieve according to claim 1, wherein the cell parameter of the molecular sieve is 24.40-24.52 angstroms；Institute
The Al distribution parameter D for stating molecular sieve meets: 0.35≤D≤0.75；The mesopore volume of the molecular sieve is 0.2-0.8 mls/g；
The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 35%-65%；The strong acid acid amount of the molecular sieve accounts for total acid content
Example be 35-55%, B acid acid amount with L acid acid amount the ratio between be 60-80.
3. Y molecular sieve according to claim 1, wherein 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 be greater than 300 DEG C corresponding to acid site；The B
The ratio between sour amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
4. the preparation method of Y molecular sieve described in a kind of any one of claim 1-3, the preparation method include:
A, NaY molecular sieve is subjected to ammonium exchange processing, and after being filtered and washed, obtains ammonium exchange molecular sieve；Wherein, with oxygen
Change sodium meter and on the basis of the dry weight of ammonium exchange molecular sieve, the sodium oxide content of ammonium exchange molecular sieve is less than 5
Weight %；
B, gained ammonium exchange molecular sieve in step a is subjected in steam atmosphere hydrothermal calcine processing, obtains water roasting molecular sieve；
C, gained water roasting molecular sieve in step b is carried out at the first dealuminzation in the acid solution being made of organic acid and inorganic acid
Reason, and after being filtered and washed, obtain the first dealuminzation molecular sieve；
D, the first dealuminzation molecular sieve obtained in step c is subjected in inorganic alkali solution alkali process, and be filtered and washed
Afterwards, alkali process molecular sieve is obtained；
E, gained alkali process molecular sieve in step d is molten in the Compound-acid dealumination agent being made of fluosilicic acid, organic acid and inorganic acid
The second dealumination treatment being carried out in liquid, and after being filtered and washed, obtaining the Y molecular sieve, inorganic acid is selected from hydrochloric acid, sulfuric acid
At least one of with nitric acid.
5. the preparation method according to claim 4, wherein the organic acid in acid solution described in step c is selected from second two
At least one of amine tetraacethyl, oxalic acid, citric acid and sulfosalicylic acid, inorganic acid are in hydrochloric acid, sulfuric acid and nitric acid
It is at least one.
6. the preparation method according to claim 4, wherein the condition of the first dealumination treatment described in step c includes: with dry
The weight ratio of the molecular sieve of base weight meter, organic acid and inorganic acid is 1:(0.03-0.3): (0.02-0.4)；At first dealuminzation
Managing temperature is 25-100 DEG C, and the first dealumination treatment time was 0.5-6 hours.
7. the preparation method according to claim 4, wherein the condition of the first dealumination treatment described in step c includes: with dry
The weight ratio of the molecular sieve of base weight meter, organic acid and inorganic acid is 1:(0.05-0.25): (0.05-0.25).
8. the preparation method according to claim 4, wherein inorganic alkali solution described in step d is molten selected from sodium hydroxide
At least one of liquid, potassium hydroxide solution, lithium hydroxide solution and ammonium hydroxide.
9. the preparation method according to claim 4, wherein the condition of alkali process described in step d includes: with dry weight
The molecular sieve of meter and the weight ratio of inorganic base are 1:(0.02-0.6)；Alkali purification temp is 25-100 DEG C, and the alkali process time is
0.5-6 hours.
10. the preparation method according to claim 4, wherein organic described in Compound-acid dealuminzation agent solution described in step e
Acid is selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid.
11. the preparation method according to claim 4, wherein the condition of the second dealumination treatment described in step e include: with
The molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.03-0.3): (0.05-0.3):
(0.05-0.25)；Second dealumination treatment temperature is 25-100 DEG C, and the second dealumination treatment time was 0.5-6 hours.
12. the preparation method according to claim 4, wherein the condition of the second dealumination treatment described in step e include: with
The molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.035-0.2): (0.06-0.2):
(0.1-0.2)。
13. the preparation method according to claim 4, wherein the condition of the processing of hydrothermal calcine described in step b includes: temperature
Degree is 450-750 DEG C, and the time is 0.5-6 hours, and steam atmosphere is 100 volume % steam atmospheres.
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| CN103285909A (en) * | 2012-03-01 | 2013-09-11 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing mesoporous-microporous molecular sieve and preparation method thereof |
| CN104229823A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Combined modification method of rich-mesoporous ultrastable Y molecular sieve |
| CN105329912A (en) * | 2015-12-10 | 2016-02-17 | 中国海洋石油总公司 | Method for preparing meso-microporous composite Y molecular sieve |
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