CN106140271B - A kind of phosphorous MFI structure molecular sieve and preparation method thereof - Google Patents
A kind of phosphorous MFI structure molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN106140271B CN106140271B CN201510198783.3A CN201510198783A CN106140271B CN 106140271 B CN106140271 B CN 106140271B CN 201510198783 A CN201510198783 A CN 201510198783A CN 106140271 B CN106140271 B CN 106140271B
- Authority
- CN
- China
- Prior art keywords
- acid
- molecular sieve
- ratio
- ammonium
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses the preparation method of a kind of phosphorous MFI structure molecular sieve and the molecular sieve, the n (SiO of the molecular sieve2)/n(Al2O3) it is greater than 100；With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-5 weight %；The Al distribution parameter D of the molecular sieve meets: 0.5≤D≤0.8；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 15-30 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60-80%, and the ratio between B acid acid amount and L acid acid amount are 20-100.Phosphorous MFI structure molecular sieve of the invention is prepared into catalyst or auxiliary agent as active component, while keeping yield of gasoline in catalytic cracking of petroleum hydrocarbon reaction, moreover it is possible to effectively improve octane number, or improve yield of gasoline while keeping octane number.
Description
Technical field
The present invention relates to a kind of phosphorous MFI structure molecular sieves and preparation method thereof.
Background technique
In recent years, domestic motor vehicles ownership continues to support domestic gasoline terminal consumption demand to keep prosperous in the situation that raises up
It contains.It is expected that motor vehicle volume of production and marketing and ownership will keep growing trend during " 12th Five-Year Plan ", gasoline demand will keep upper uptrend
Head.Automobile sales volume increases by 11% every year during " 12th Five-Year Plan ", drives gasoline demand to keep average annual 5% steady growth, it is contemplated that arrive
Gasoline Apparent con- sumption is up to 98Mt within 2015.It goes into operation as a new round specially produces propylene production capacity, the coming five years whole world propylene supplies
Should measure will increase significantly beyond anticipated demand.It was predicted that the coming five years whole world propylene production capacity will increase 30Mt, and demand growth is pre-
Meter only has 22Mt, drops since this gap between Supply and Demand may result in propylene price.
Under the promotion of the market demand and economic benefit, oil refining enterprise takes voluminous gasoline to produce the producer of liquefied gas less
Case.For the purpose for realizing voluminous gasoline, on the one hand technological parameter can be adjusted, on the other hand adjustable catalyst is matched
The most direct effective means of side, catalyst formulation adjustment is exactly to reduce ZSM-5 molecular sieve dosage.
ZSM-5 molecular sieve has shape slective cracking, isomerization, flexibly uses in catalytic cracking catalyst or auxiliary agent,
The octane number of catalytically cracked gasoline can be effectively improved.ZSM-5 molecular sieve is the three-dimensional mesoporous being successfully prepared at first by Mobil Corporation
High-silica zeolite, there is ten-ring duct on [100] and [010] direction, and aperture about 0.51nm × 0.55nm and 0.53nm ×
0.56nm, the especially unique duct Z in [100] direction lead to its efficient shape selective catalysis property.Linear paraffin is allowed to enter, together
When limit more side chain hydrocarbon and cyclic hydrocarbon, be preferentially C3 and C4 alkene by low octane rating alkane in gasoline and olefin cracking, while will be straight
Olefine is isomerized to the high octane olefins with more side chain.ZSM-5 molecular sieve is applied in catalytic cracking catalysts, and one
Aspect improves density of propylene in yield of liquefied gas and liquefied gas, on the other hand improves octane number.Reduce ZSM-5 molecule
The purpose that sieve dosage can achieve and reduce yield of liquefied gas, improves yield of gasoline, but octane number can also drop at the same time
It is low.
Octane number is an important indicator for indicating the capability of antidetonance quality of engine fuel.With gasoline octane number not
Disconnected to improve, automobile factory can increase accordingly the compression ratio of engine, and engine power both can be improved in this way, increased mileage
Number, but it is capable of saving fuel, it is of great significance to the power economy performance for improving gasoline.
It is required by environmental regulation and automobile industry requires tight promotion to fuel mass, in recent years global motor petrol matter
Amount promotion is very rapid, and oil quality upgrading paces in China's are also obviously accelerated.External gasoline pool compositing characteristic is: catalytic cracking vapour
Oily ratio is lower, as U.S.'s FCC gasoline only accounts for 1/3 or so；Average RON higher, about 93~94；Other antiknock components compared with
More, the development of especially other antiknock component technologies constantly promotes the raising of octane number.But the main oil product in China
Quality still has certain gap compared with developed countries, currently, China FCC (fluid catalytic cracking) gasoline accounts for about motor petrol total amount
70% or more, Reformed Gasoline and other high-quality high octane gasoline component contents are too low, and less than 9%, and low octane rating is straight
It is higher to evaporate gasoline proportion, reaches about 13%.Therefore, the height of FCC gasoline octane plays octane number total level
Very important effect.The FCC gasoline octane (RON) in China is up to 90~92, and minimum 87~88, average out to 89~
90；MON is up to 80.6, and minimum 78, average out to 79, there are biggish compared with the quality of gasoline of some other developed country
Therefore gap improves octane number, realize that gasoline upgrading is trend of the times.In addition, during gasoline cleaning,
Some measures such as control content of olefin in gasoline, desulfurization, result in the different degrees of loss of octane number, the contradiction of octane number shortage will
It is more prominent.
Isomerization is to improve an effective way of octane number.Due to the isomeric olefine with side chain and isoparaffin ratio
Corresponding normal olefine has higher octane number, so if lytic activity and the hydrogen migration of ZSM-5 molecular sieve can be reduced suitably
Activity, while isomerization ability is improved, isomeric olefine and isoparaffin concentration increase in product, so that it may improve gasoline octane
While value, the loss of yield of light oil is reduced.
The ZSM-5 molecular sieve of high silica alumina ratio is advantageous to improving octane number while reducing light oil loss.This is because
It is improved with silica alumina ratio, the acid site density of ZSM-5 molecular sieve can be reduced, improve acid strength, to reduce lytic activity, inhibit hydrogen
Transfer reaction enhances isomerization ability.The ZSM-5 molecular sieve of high silica alumina ratio is based on isomerization reaction, therefore octane number mentions
Height is primarily due to the increase of isomeric olefine and isoparaffin concentration in product, so yield of light oil loss is low.
CN 101269340A discloses a kind of ZSM-5 zeolite catalyst and preparation method thereof of high silica alumina ratio.The catalyst
Using active pure silicon compound as silicon source, Trace Aluminum is added, hydrothermal synthesis method is made.Zeolite skeleton silica alumina ratio reaches in catalyst
1000 or more, the grain particles of sub-micron, duct is open, large specific surface area, and molecular diffusivity is good.
CN 1046922C discloses a kind of method for improving ZSM-5 molecular sieve silica alumina ratio.The molecular sieve be high silica alumina ratio and
The molecular sieve of high-crystallinity, it is made after hydro-thermal process with pressure, then with the method for acid processing, is had no or only in product few
Non-framework aluminum is measured to exist.
CN 103480411A discloses a kind of containing mesopore ZSM-5 molecular sieve catalyst and preparation method thereof.The invention will be honest and clean
Silicon and aluminum source, sylvite and the organic formwork agent of valence are dissolved in the water, and using the cavitation of ultrasonic wave, it is super to carry out heating to the system
Sound assists mechanical stirring, while generating structure-directing effect using the salting-out effect of sylvite, synthesizes finally by hydro-thermal method
The containing mesopore ZSM-5 of high silica alumina ratio with MFI structure property.
CN 101857243A discloses a kind of method that surface dealumination complement silicon adjusts ZSM-5 molecular sieve surface apertures, the hair
The bright processing means for being carried out dealumination complement silicon to ZSM-5 zeolite molecular sieve surface using ammonium fluosilicate solution, are realized to its surface holes
The accurate control of diameter.Using ammonium fluosilicate modify ZSM-5 zeolite molecular sieve, by the Al isomorphous substitution in molecular sieve surface skeleton at
Si, so the diameter in molecular sieve surface aperture can be reduced, forms one in molecular sieve surface since the bond distance of Si-O is less than Al-O
The superthin layer of layer Silicon-rich.By finely controlling treatment conditions, the shrinkage degree in molecular sieve surface aperture can control.
In the prior art, direct synthesizing high-silicon aluminium is needed than ZSM-5 molecular sieve using expensive template, cost
Height, production difficulty is big, and three waste discharge is high, and the usual crystal grain of ZSM-5 molecular sieve being synthesized is relatively thin (100~300nm), water
Thermal stability is poor, it is difficult to be promoted and applied in catalytic cracking catalyst.
In order to achieve the purpose that voluminous gasoline produces liquefied gas less while improving octane number, the present invention is de- by Compound-acid
Aluminium method has carried out modulation to the Acidity and pore structure of ZSM-5 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, by phosphorous MFI of the invention
Structure molecular screen prepares catalyst or auxiliary agent as active component, keeps the same of yield of gasoline in catalytic cracking of petroleum hydrocarbon reaction
When, moreover it is possible to octane number is effectively improved, or improves yield of gasoline while keeping octane number.
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 100；With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-5
Weight %；The Al distribution parameter D of the molecular sieve meets: 0.5≤D≤0.8, wherein D=Al (S)/Al (C), Al (S) expression are adopted
The inside H in crystal face edge of the zeolite crystal measured with TEM-EDS method is apart from interior any aluminium for being greater than 100 square nanometers regions
Content, Al (C) indicate that the outside H distance of the geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method is interior and appoint
Meaning is greater than the aluminium content in 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometric center distance
10%；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 15-30 body %；The strong acid acid amount of the molecular sieve accounts for
The ratio of total acid content is 60-80%, and the ratio between B acid acid amount and L acid acid amount are 20-100.
Preferably, molecular sieve according to the present invention, wherein the n (SiO of the molecular sieve2)/n(Al2O3) it is greater than 120；With P2O5
It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-4 weight %；The Al of the molecular sieve is distributed
Parameter D meets: 0.55≤D≤0.75；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 20-25 body %；It is described
The ratio that the strong acid acid amount of molecular sieve accounts for total acid content is 70-75%, and the ratio between B acid acid amount and L acid acid amount are 30-80.
Preferably, molecular sieve according to the present invention, wherein the ratio that the mesopore volume of the molecular sieve accounts for total pore volume is adopted
It is measured with N2 adsorption BET specific surface area method, the mesopore volume is that aperture is greater than 2 nanometers of hole bodies less than 100 nanometers
Product；The strong acid acid amount of the molecular sieve accounts for the ratio of total acid content using NH3- TPD method measures, the acid site of the strong acid
For NH3Desorption temperature be greater than 300 DEG C corresponding to acid site；The ratio between the B acid acid amount and L acid acid amount are infrared using pyridine adsorption
Acid process measures.
The present invention also provides the preparation methods of the phosphorous MFI structure molecular sieve described in one kind, this method comprises:
A, sodium form MFI structure molecular sieve 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 % heavy less than 0.2 of the ammonium exchange molecular sieve；
B, by gained ammonium exchange molecular sieve in step a in the Compound-acid dealuminzation being made of fluosilicic acid, organic acid and inorganic acid
Dealumination treatment is carried out in agent solution, and after being filtered and washed, obtains dealuminzation molecular sieve；
C, after dealuminzation molecular sieve obtained in step b being carried out P Modification processing and calcination process, the phosphorous MFI is obtained
Structure molecular screen.
Preferably, according to the method for the present invention, wherein the step of dealumination treatment described in step b further include: first will be organic
It is sour that molecular sieve mixing is exchanged with the ammonium, then fluosilicic acid and inorganic acid are exchanged to molecular sieve mixing with the ammonium.
Preferably, according to the method for the present invention, wherein organic acid described in step b 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, according to the method for the present invention, wherein organic acid described in step b is oxalic acid, and inorganic acid is hydrochloric acid.
Preferably, according to the method for the present invention, wherein the condition of dealumination treatment described in step b are as follows: with dry basis
Molecular sieve, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.02-0.5): (0.05-0.5): (0.05-0.5)；
Treatment temperature is 25-100 DEG C, and the processing time is 0.5-6 hours.
Preferably, according to the method for the present invention, wherein the condition of dealumination treatment described in step b are as follows: with dry basis
Molecular sieve, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.05-0.3): (0.1-0.3): (0.1-0.3).
Preferably, according to the method for the present invention, wherein P Modification processing include: will selected from phosphoric acid, ammonium hydrogen phosphate,
At least one of ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound carry out dipping and/or ion exchange to molecular sieve.
Preferably, according to the method for the present invention, wherein the condition of the calcination process includes: that the atmosphere of calcination process is
Air atmosphere or steam atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.
Present inventors discovered unexpectedly that chemically carrying out dealumination treatment to MFI structure molecular sieve, then carry out
P Modification processing, prepared phosphorous MFI structure molecular sieve can be applied in catalytic cracking process, as catalyst or auxiliary agent
Active component.
Modification MFI structure molecular sieve provided by the invention after Compound-acid dealumination treatment, molecular sieve silica alumina ratio are high, total
Acid amount is low to reduce cracking activity, and surface Silicon-rich can inhibit the generation of the non-selective side reaction in surface, activated carbon with rich mesoporous, strong acid center
Ratio height and B acid/L acid ratio height are all conducive to the progress of isomerization reaction.
Modified MFI structure molecular sieve provided by the invention has cracking capability weak, and the strong feature of isomerism ability can be used as
High octane number bucket catalysis material, while keeping yield of gasoline in catalytic cracking of petroleum hydrocarbon reaction, moreover it is possible to effectively mention
High octane number, or yield of gasoline is improved while keeping octane number.
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) it is greater than 100, preferably
Greater than 120；With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-5 weight %, preferably
For 0.1-4 weight %；The Al distribution parameter D of the molecular sieve meets: 0.5≤D≤0.8 preferably satisfies: 0.55≤D≤0.75,
In, D=Al (S)/Al (C), Al (S) indicate the inside H distance in crystal face edge of the zeolite crystal using the measurement of TEM-EDS method
Interior any aluminium content for being greater than 100 square nanometers regions, Al (C) indicate the zeolite crystal institute using the measurement of TEM-EDS method
The outside H of geometric center of crystal face is stated apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein the H is the crystalline substance
Face edge point arrives the 10% of the crystal face geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is
15-30 body %, preferably 20-25 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60-80%, preferably
The ratio between 70-75%, B acid acid amount and L acid acid amount are 20-100, preferably 30-80.
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.
Molecular sieve according to the present invention, well-known to those skilled in the art to be, the mesopore volume of the molecular sieve accounts for always
The ratio of pore volume can be measured using N2 adsorption BET specific surface area method, and the mesopore volume is that aperture is greater than 2 nanometers
Pore volume less than 100 nanometers；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content can use NH3- TPD method carries out
Measurement, the acid site of the strong acid are NH3Desorption temperature be greater than 300 DEG C corresponding to acid site；The B acid acid amount and L acid acid
The ratio between amount can be 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, this method comprises: a, by sodium form
MFI structure molecular sieve carries out ammonium exchange, obtains ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena and with the total of ammonium exchange molecular sieve
On the basis of dry weight, the sodium content % heavy less than 0.2 of the ammonium exchange molecular sieve；B, gained ammonium in step a is exchanged into molecule
Sieve carry out dealumination treatment in the Compound-acid dealuminzation agent solution being made of fluosilicic acid, organic acid and inorganic acid, and be filtered and
After washing, dealuminzation molecular sieve is obtained；C, after dealuminzation molecular sieve obtained in step b being carried out P Modification processing and calcination process,
Obtain 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, silica alumina ratio is less than
100。
According to the method for the present invention, the ammonium exchange is well-known to those skilled in the art, for example, can be by sodium form
MFI structure 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 handing at 100 DEG C
It is filtered after changing 0.5~2 hour, this exchange process repeats 1~4 time, makes the Na on zeolite2O content % heavy less than 0.2.Described
Ammonium salt can be common inorganic ammonium salt, for example, selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate.
According to the method for the present invention, organic acid described in step b and inorganic acid are well known to the skilled person, example
Such as, the organic acid can be selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably
For oxalic acid；Inorganic acid can be for selected from least one of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid.
According to the method for the present invention, dealumination treatment described in step b is well-known to those skilled in the art, but is not reported
It crosses and inorganic acid, organic acid and fluosilicic acid is used for dealumination treatment together.The dealumination treatment can be primary or be performed in multiple times, can
Organic acid first to be exchanged to molecular sieve mixing with the ammonium, fluosilicic acid and inorganic acid are then exchanged into molecular sieve with the ammonium and mixed
It closes, it can exchanged in molecular sieve for ammonium first is added in organic acid, then by fluosilicic acid and inorganic acid, cocurrent is added at a slow speed, or first
Fluosilicic acid is added and adds inorganic acid, preferably cocurrent is added at a slow speed for fluosilicic acid and inorganic acid.The condition of the dealumination treatment can
With are as follows: the weight ratio with the molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid is 1:(0.02-0.5):
(0.05-0.5): (0.05-0.5), preferably 1:(0.05-0.3): (0.1-0.3): (0.1-0.3)；Treatment temperature is 25-100
DEG C, the processing time is 0.5-6 hours.
According to the method for the present invention, washing described in step b is well-known to those skilled in the art, and mode can be with
Are as follows: 5-10 times 30-60 DEG C of water elutes molecular sieve after filtering.
According to the method for the present invention, roasting described in step c is also well-known to those skilled in the art, and condition can be with
Are as follows: the atmosphere of calcination process is air atmosphere or steam atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is that 0.5-8 is small
When.
According to the method for the present invention, the processing of P Modification described in step c is well-known to those skilled in the art, be can wrap
It includes: molecular sieve will be soaked selected from least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound
Stain and/or ion exchange.
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.
Influence of the molecular sieve in catalytic cracking of petroleum hydrocarbon to gasoline yield and octane number counter is evaluated using heavy oil is micro-.
It is prepared into assistant for calalytic cracking using molecular sieve as active component, molecular sieve content 50%, remaining is kaolin and carrying alumina
Body, auxiliary agent sample obtained carries out 800 DEG C, 100% steam aging 17 hours on fixed bed aging equipment and handles, then with not
Equilibrium catalyst for catalytic cracking process (come from Shandong catalyst plant, trade mark DVI catalyst) containing shape-selective molecular sieve makees base catalyst, and helps
Agent is uniform by the weight ratio mix and convert of 95:5, then catalytic cracking fluidized bed it is micro- it is anti-on evaluated, feedstock oil is to mix slag VGO, is commented
Valence condition be 500 DEG C of reaction temperature, 600 DEG C of regeneration temperature, oil ratio 5.92.Blank is evaluated as 100% equilibrium catalyst for catalytic cracking process.
The crystallinity of the method for the present invention is measured using the standard method of ASTM D5758-2001 (2011) e1.
N (the SiO of the method for the present invention2)/n(Al2O3), i.e., silica alumina ratio is calculated by the content of silica and aluminium oxide,
The content of silica and aluminium oxide is measured using GB/T 30905-2014 standard method.
The phosphorus content of the method for the present invention is measured using GB/T 30905-2014 standard method.
Research method of the TEM-EDS measuring method of the method for the present invention referring to solid catalyst, petrochemical industry, 29 (3),
2000:227.
The specific surface of the method for the present invention is measured using GB5816 standard method.
The pore volume of the method for the present invention is measured using GB5816 standard method.
The strong acid acid amount and total acid content of the method for the present invention use NH3- TPD method is measured, referring to solid catalyst
Research method, petrochemical industry, 30 (12), 2001:952.
The B acid acid amount of the method for the present invention is measured with L acid acid amount using Pyridine adsorption IR spectra method, is urged referring to solid
The research method of agent, petrochemical industry, 29 (8), 2000:621.
The sodium content of the method for the present invention is measured using GB/T 30905-2014 standard method.
Micro- reactivity of the method for the present invention is measured using ASTM D5154-2010 standard method, micro-inverse product
Octane number is measured using RIPP 85-90 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 ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 20g is added in stirring, then by 200g hydrochloric acid (mass fraction 10%)
It is added with 167g fluosilicic acid (mass fraction 3%) cocurrent, time 30min is added；It is warming up to 65 DEG C of constant temperature stirring 1h, filtering washing
To filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 2.4gH3PO4(85 weight of concentration
Measure %), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve-4 A is obtained, physico-chemical property, micro anti-evaluation gasoline are received
Rate and octane Value Data are listed in table 1.
Comparative example 1
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 48g is added in stirring；65 DEG C of constant temperature stirring 1h are warming up to, drainage is crossed
It is washed till filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 2.4gH3PO4(85 weight of concentration
Measure %), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve DA1, physico-chemical property, micro anti-evaluation gasoline
Yield and octane Value Data are listed in table 1.
Comparative example 2
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, 390g hydrochloric acid (mass fraction 10%) is added in stirring；It is warming up to 65 DEG C of perseverances
Temperature stirring 1h, filtering are washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition
2.4gH3PO4(85 weight % of concentration), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve DA2, materialization
Property, micro anti-evaluation yield of gasoline and octane Value Data are listed in table 1.
Comparative example 3
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, 670g fluosilicic acid (mass fraction 3%) is added in stirring, the time is added
30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water be beaten solid content be 40 heavy %
Molecular sieve pulp, be added 2.4gH3PO4(85 weight % of concentration), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.
Molecular sieve DA3 is obtained, physico-chemical property, micro anti-evaluation yield of gasoline and octane Value Data are listed in table 1.
Comparative example 4
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 20g is added in stirring, then by 200g hydrochloric acid (mass fraction 10%)
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 2.4gH is added3PO4(85 weight % of concentration) is uniformly mixed with dipping, drying, 550 DEG C of roastings
Burn processing 2 hours.Molecular sieve DA4 is obtained, physico-chemical property, micro anti-evaluation yield of gasoline and octane Value Data are listed in table 1.
Comparative example 5
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 20g is added in stirring, then by 334g fluosilicic acid (mass fraction
3%) it is slowly added to, 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 2.4gH3PO4(85 weight % of concentration) is uniformly mixed with dipping, dries
It is dry, 550 DEG C calcination process 2 hours.Molecular sieve DA5 is obtained, physico-chemical property, micro anti-evaluation yield of gasoline and octane Value Data are listed in table
1。
Comparative example 6
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, by 200g hydrochloric acid (mass fraction 10%) and 334g fluosilicic acid (matter under stirring
Measure score 3%) cocurrent addition, time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；It will filter
Cake adds water to be beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 2.4gH3PO4(85 weight % of concentration), uniformly mixing leaching
Stain, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve DA6, physico-chemical property, micro anti-evaluation yield of gasoline and octane Value Data
It is listed in table 1.
Comparative example 7
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, is slowly added to 1332g fluosilicic acid (mass fraction 3%) under stirring, is added
Time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water be beaten solid content be 40
The molecular sieve pulp of weight %, is added 1.5gH3PO4(85 weight % of concentration) is uniformly mixed with dipping, drying, 550 DEG C of calcination process 2
Hour.Molecular sieve DA7 is obtained, physico-chemical property, micro anti-evaluation yield of gasoline and octane Value Data are listed in table 1.
Embodiment 2
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 40g is added in stirring, then by 100g sulfuric acid (mass fraction
10%) it is added with 500g fluosilicic acid (mass fraction 3%) cocurrent, time 30min is added；It is warming up to 45 DEG C of constant temperature stirring 1h, mistake
Drainage is washed till filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 2.0gH3PO4(concentration
85 weight %), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve B, physico-chemical property, micro anti-evaluation vapour
Oil yield and octane Value Data are listed in table 1.
Embodiment 3
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, ethylenediamine tetra-acetic acid 10g is added in stirring, then by 1000g fluosilicic acid (matter
Measure score 3%) stream addition, time 30min is added, is eventually adding 400g hydrochloric acid (mass fraction 10%)；It is warming up to 85 DEG C of constant temperature
6h is stirred, filtering is washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition
1.6gH3PO4(85 weight % of concentration), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve C, materialization
Matter, micro anti-evaluation yield of gasoline and octane Value Data are listed in table 1.
Comparative example 8
This comparative example explanation carries out P Modification processing than molecular sieve using direct synthesizing high-silicon aluminium.
By ZSM-5 molecular sieve, (production of catalyst Jian Chang branch company has the synthesis of amine method, n (SiO2)/n(Al2O3)=210) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 1.6gH3PO4(concentration 85%), dipping drying；Gained sample exists
550 DEG C calcination process 2 hours to get molecular sieve D.Physico-chemical property, micro anti-evaluation yield of gasoline and octane Value Data are listed in table 1.
Single organic acid oxalic acid dealuminzation (DA1) and single inorganic acid HCl dealumination (DA2) it can be seen from data in table 1
And organic acid oxalic acid and two kinds of acid of inorganic acid hydrochloric acid compound (DA4) all can not effectively remove the Al in ZSM-5 molecular sieve, silicon
Aluminium does not change than substantially, and could obtain preferable dealuminzation effect after only having used fluosilicic acid.It is de- that fluosilicic acid is used alone
When aluminium (DA3), the ZSM-5 molecular sieve of available high silica alumina ratio, but mesoporous is less, strong acid in total acid proportion compared with
Low, B acid/L acid ratio is lower.Fluosilicic acid composite organic acid oxalic acid dealuminzation (DA5), is equally unable to get higher mesopore volume.
Fluosilicic acid composite inorganic acid HCl dealumination (DA6), though allow mesopore volume increased, strong acid in total acid proportion with
And B acid/L acid ratio is all not so good as molecular sieve height provided by the invention.Relying solely on improving fluosilicic acid dosage also can be obtained higher silicon
The ZSM-5 molecular sieve (DA7) of aluminium ratio, but molecular sieve crystallinity loss is serious, mesopore proportion and acid distribution are not changed
It is kind.The present invention uses compound acid system, can be in the premise for guaranteeing molecular sieve structure integrality under three kinds of sour synergistic effects
Under effectively improve molecular sieve silica alumina ratio, adjust aluminium distribution, improve mesopore proportion, improve acid distribution.It is received from micro anti-evaluation gasoline
Rate and octane Value Data can be seen that molecular sieve prepared by the present invention while keeping yield of gasoline, moreover it is possible to effectively improve
Octane number.
Claims (11)
1. a kind of phosphorous MFI structure molecular sieve, the n (SiO of the molecular sieve2)/n(Al2O3) it is greater than 100；With P2O5It counts and with molecule
On the basis of the dry weight of sieve, the phosphorus content of the molecular sieve is 0.1-5 weight %；The Al distribution parameter D of the molecular sieve meets:
0.5≤D≤0.8, wherein D=Al (S)/Al (C), Al (S) indicate the crystalline substance of the zeolite crystal using the measurement of TEM-EDS method
Edge inside H in face indicates to measure using TEM-EDS method apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C)
Zeolite crystal described in crystal face the outside H of geometric center apart from interior any aluminium content for being greater than 100 square nanometers regions, 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 accounts for total hole
The ratio of volume is 15-30 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60-80%, B acid acid amount and L
The ratio between sour amount is 20-100.
2. molecular sieve according to claim 1, wherein the n (SiO of the molecular sieve2)/n(Al2O3) it is greater than 120；With P2O5Count and with
On the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-4 weight %；The Al distribution parameter D of the molecular sieve
Meet: 0.55≤D≤0.75；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 20-25 body %；The molecular sieve
Strong acid acid amount account for total acid content ratio be 70-75%, B acid acid amount with L acid acid amount the ratio between be 30-80.
3. molecular sieve according to claim 1, wherein the ratio that the mesopore volume of the molecular sieve accounts for total pore volume is inhaled using nitrogen
Attached BET specific surface area method measures, and the mesopore volume is that aperture is greater than 2 nanometers of pore volumes less than 100 nanometers；It is described
The strong acid acid amount of molecular sieve accounts for the ratio of total acid content using NH3- TPD method measures, and the acid site of the strong acid is NH3It is de-
Enclosure temperature be greater than 300 DEG C corresponding to acid site；The ratio between the B acid acid amount and L acid acid amount use the infrared acidic side of pyridine adsorption
Method measures.
4. the preparation method of phosphorous MFI structure molecular sieve described in a kind of claim 1-3 any one, this method comprises:
A, sodium form MFI structure molecular sieve is subjected to ammonium exchange, obtains ammonium exchange molecular sieve；Wherein, it is handed in terms of sodium oxide molybdena and with ammonium
It changes on the basis of total dry weight of molecular sieve, the sodium content % heavy less than 0.2 of the ammonium exchange molecular sieve；
B, the Compound-acid dealumination agent that is made of again fluosilicic acid, organic acid and inorganic acid of gained ammonium exchange molecular sieve in step a is molten
Dealumination treatment is carried out in liquid, and after being filtered and washed, obtains dealuminzation molecular sieve；
C, after dealuminzation molecular sieve obtained in step b being carried out P Modification processing and calcination process, the phosphorous MFI structure is obtained
Molecular sieve.
5. method according to claim 4, wherein the step of dealumination treatment described in step b further include: 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.
6. method according to claim 4, wherein organic acid described in step b is selected from ethylenediamine tetra-acetic acid, oxalic acid, lemon
At least one of acid and sulfosalicylic acid, inorganic acid are selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
7. method according to claim 4, wherein organic acid described in step b is oxalic acid, and inorganic acid is hydrochloric acid.
8. method according to claim 4, wherein the condition of dealumination treatment described in step b are as follows: with the molecule of dry basis
Sieve, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.02-0.5): (0.05-0.5): (0.05-0.5)；Processing temperature
Degree is 25-100 DEG C, and the processing time is 0.5-6 hours.
9. method according to claim 4, wherein the condition of dealumination treatment described in step b are as follows: with the molecule of dry basis
Sieve, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.05-0.3): (0.1-0.3): (0.1-0.3).
10. method according to claim 4, wherein the P Modification processing includes: will be selected from phosphoric acid, ammonium hydrogen phosphate, di(2-ethylhexyl)phosphate
At least one of hydrogen ammonium and ammonium phosphate phosphorus-containing compound carry out dipping and/or ion exchange to molecular sieve.
11. method according to claim 4, wherein the condition of the calcination process includes: that the atmosphere of calcination process is air gas
Atmosphere or steam atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510198783.3A CN106140271B (en) | 2015-04-23 | 2015-04-23 | A kind of phosphorous MFI structure molecular sieve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510198783.3A CN106140271B (en) | 2015-04-23 | 2015-04-23 | A kind of phosphorous MFI structure molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106140271A CN106140271A (en) | 2016-11-23 |
| CN106140271B true CN106140271B (en) | 2019-02-01 |
Family
ID=57346943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510198783.3A Active CN106140271B (en) | 2015-04-23 | 2015-04-23 | A kind of phosphorous MFI structure molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106140271B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097482B (en) * | 2018-10-26 | 2021-08-06 | 中国石油化工股份有限公司 | Phosphorus-containing high-silicon molecular sieve and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147420A (en) * | 1995-10-06 | 1997-04-16 | 中国石油化工总公司 | Phosphorus and RE containing molecular sieve with MFI structure |
| CN1194181A (en) * | 1997-03-24 | 1998-09-30 | 中国石油化工总公司 | Phosphorus containing molecular sieve with MFI structure |
| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
| CN1611299A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphor and metal component and its use |
| CN101234764A (en) * | 2007-01-31 | 2008-08-06 | 中国石油化工股份有限公司 | Method of preparing MFI structure molecular sieve containing phosphorus and transition metal |
| EP2047905A1 (en) * | 2007-10-10 | 2009-04-15 | Petroleo Brasileiro S.A. Petrobras | Additive for maximizing light olefins in FCC and process for preparation thereof |
| CN102452669A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal as well as its preparation method |
-
2015
- 2015-04-23 CN CN201510198783.3A patent/CN106140271B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147420A (en) * | 1995-10-06 | 1997-04-16 | 中国石油化工总公司 | Phosphorus and RE containing molecular sieve with MFI structure |
| CN1194181A (en) * | 1997-03-24 | 1998-09-30 | 中国石油化工总公司 | Phosphorus containing molecular sieve with MFI structure |
| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
| CN1611299A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphor and metal component and its use |
| CN101234764A (en) * | 2007-01-31 | 2008-08-06 | 中国石油化工股份有限公司 | Method of preparing MFI structure molecular sieve containing phosphorus and transition metal |
| EP2047905A1 (en) * | 2007-10-10 | 2009-04-15 | Petroleo Brasileiro S.A. Petrobras | Additive for maximizing light olefins in FCC and process for preparation thereof |
| CN102452669A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal as well as its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106140271A (en) | 2016-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107971015B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107971001B (en) | It is a kind of to contain the assistant for calalytic cracking and preparation method thereof for being rich in mesoporous Beta molecular sieve | |
| CN107971028A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107971018A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107971011A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN107973318A (en) | MFI structure molecular screens a kind of phosphorous and containing carried metal and preparation method thereof | |
| CN107970978B (en) | Phosphorus-containing and metal-loaded MFI structure molecular sieve and preparation method thereof | |
| CN107973317A (en) | A kind of phosphorous MFI structure molecular sieve and preparation method thereof | |
| CN107973308A (en) | A kind of phosphorous MFI structure molecular sieve and preparation method thereof | |
| CN106140271B (en) | A kind of phosphorous MFI structure molecular sieve and preparation method thereof | |
| CN106140270B (en) | Phosphorous and a kind of MFI structure molecular sieve and preparation method thereof containing carried metal | |
| CN106587147B (en) | A kind of Y/ZrO of directing agent method synthesis2Composite and preparation method thereof | |
| CN107970984B (en) | Catalytic cracking auxiliary agent for improving gasoline octane number barrel and preparation method thereof | |
| CN107974274B (en) | Phosphorus-containing and metal-loaded MFI structure molecular sieve and preparation method thereof | |
| CN107971031B (en) | A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket | |
| CN107971027A (en) | A kind of aromatisation auxiliary agent and preparation method thereof | |
| CN107970982A (en) | A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof | |
| CN106669775B (en) | A kind of Y/ZrO of crystal seed method synthesis2Composite material and preparation method | |
| CN107583666B (en) | A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket | |
| CN107971032B (en) | Catalytic cracking auxiliary agent for improving gasoline octane number barrel and preparation method thereof | |
| CN107970983B (en) | Catalytic cracking auxiliary agent for improving gasoline octane number barrel and preparation method thereof | |
| CN107970985A (en) | A kind of aromatisation auxiliary agent and preparation method thereof | |
| CN107583668B (en) | A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket | |
| CN107115886B (en) | A kind of Y/ZrO of two sections of crystallization methods synthesis2Composite material and preparation method | |
| CN107971022A (en) | A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |