CN116262622A - Nanoscale high-silicon Y molecular sieve, and preparation method and application thereof - Google Patents

Nanoscale high-silicon Y molecular sieve, and preparation method and application thereof Download PDF

Info

Publication number
CN116262622A
CN116262622A CN202111521721.3A CN202111521721A CN116262622A CN 116262622 A CN116262622 A CN 116262622A CN 202111521721 A CN202111521721 A CN 202111521721A CN 116262622 A CN116262622 A CN 116262622A
Authority
CN
China
Prior art keywords
molecular sieve
silicon
source
days
aluminum
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.)
Pending
Application number
CN202111521721.3A
Other languages
Chinese (zh)
Inventor
崔文浩
田鹏
王林英
朱大丽
刘中民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202111521721.3A priority Critical patent/CN116262622A/en
Publication of CN116262622A publication Critical patent/CN116262622A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The application discloses a nanoscale high-silicon Y molecular sieve and a synthesis method and application thereof. The silicon-aluminum ratio of the nano-grade high-silicon molecular sieve is 5-25, the size of the nano-grade high-silicon Y molecular sieve is 10-100 nm, and the nano-grade high-silicon Y molecular sieve has inter-crystal mesopores. The synthesis method of the Y molecular sieve comprises the steps of preparing a guiding agent, and then adding the guiding agent into a synthesis system for crystallization to synthesize the nanoscale high-silicon Y-type molecular sieve. In addition, the application provides application of the Y molecular sieve in catalytic cracking of isopropylbenzene and triisopropylbenzene. The preparation method of the Y molecular sieve is simple, and the product has higher crystallinity and purity and has higher catalytic activity in catalytic cracking reaction.

Description

Nanoscale high-silicon Y molecular sieve, and preparation method and application thereof
Technical Field
The application relates to a nanoscale high-silicon Y molecular sieve and a preparation method and application thereof, in particular to a method for directly synthesizing the nanoscale high-silicon Y molecular sieve in one step by directly introducing a molecular sieve growth inhibitor and adding a guiding agent into a synthesis system, belonging to the field of catalysis.
Background
Molecular sieves are a class of microporous solid materials with crystalline structures that use silicon oxide and aluminum oxide tetrahedra as structural units. Molecular sieves are widely used in the fields of adsorption separation, ion exchange, catalytic conversion and the like because of the high specific surface area, rich active sites and good thermal stability. The Y molecular sieve is a silicon-aluminum molecular sieve with a FAU topological structure, is mainly applied to Fluidized Catalytic Cracking (FCC) reaction, and is the molecular sieve material with the largest current use amount. The framework silicon-aluminum ratio of the Y molecular sieve plays a decisive role in the catalytic performance, wherein the higher the silicon-aluminum ratio is, the better the catalytic activity and the stability are.
In catalytic reactions, the microporous structure of the molecular sieve itself is small, typically less than 1nm, limiting the contact of the macromolecular reactants with the active sites and product diffusion. Compared with the conventional molecular sieve, the nano-scale molecular sieve has the advantages of high number of exposed active sites, small diffusion limitation and the like. And the specific surface area, the available active site number and the catalytic reaction efficiency of the nano molecular sieve are obviously increased along with the reduction of the size of the nano molecular sieve.
The Y molecular sieve commonly used in the industry at present is mainly obtained by dealuminizing by a post-treatment method, and the post-treatment can not only improve the silicon-aluminum ratio of the molecular sieve framework, but also generate a multi-level pore structure. The treatment processes are complex in operation, time-consuming and energy-consuming, the crystallization degree of the obtained product is drastically reduced, dealumination gradients exist on the surface and inside of the crystal of the product, and uneven distribution of acid centers is easily caused.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the application provides a method for directly synthesizing a nanoscale high-silicon Y molecular sieve, which has low energy consumption, good adjustable nanoscale size in the synthesized molecular sieve, uniform aluminum distribution in the molecular sieve, rich available active sites, good thermal stability and hydrothermal stability, and high crystallinity, and is an ideal catalytic material.
According to a first aspect of the present application, there is provided a high-silicon Y molecular sieve having a nano-scale size, which can be applied to reactions such as catalytic cracking (e.g., cumene and triisopropylbenzene), hydrocracking, and the like, and has good catalytic reactivity.
Specifically, the anhydrous chemical composition of the nanoscale high-silicon Y molecular sieve is shown as a formula I:
kM·mR1·nR2·pT·(Si x Al y )O 2 i is a kind of
Wherein M is selected from at least one of alkali metal elements;
t represents a molecular sieve growth inhibitor;
r1 represents a first organic template; r2 represents a second organic templating agent, and R1 is different from R2;
k represents a molar ratio of (Si x Al y )O 2 K=0.01 to 0.20 corresponding to the mole number of the alkali metal element;
m, n represent each mole (Si x Al y )O 2 Corresponding to the mole number of the organic template agent R1 and R2, wherein m=0.01-0.2; n=0.01 to 0.4;
p represents a group represented by a formula of (Si x Al y )O 2 P=0.001 to 0.20 corresponding to the mole number of the growth-suppressing monomer;
x and y respectively represent mole fractions of Si and Al, 2 x/y=5-25, and x+y=1;
the size of the nanoscale high-silicon Y molecular sieve is 10-100 nm;
the nanoscale high-silicon Y molecular sieve has inter-crystalline mesopores.
Optionally, micropores are included in the nanoscale high-silicon Y molecular sieve;
the specific surface area of the micropores is 480-820 m 2 /g；
The volume of the micropores is 0.23-0.40 cm 3 /g；
The external surface area is 50-415 m 2 /g；
The volume of the inter-crystal mesopores is 0.05-0.30 cm 3 /g。
Alternatively, k=0.01 to 0.15; m=0.01 to 0.12; n=0.01 to 0.30; p=0.002 to 0.15.
Alternatively, under the condition that x+y=1, the upper limit of 2x/y is selected from 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7 or 6, and the lower limit is selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24.
Optionally, the size of the nanoscale high-silicon Y molecular sieve is 10-50 nm.
Optionally, the nanoscale high-silicon Y molecular sieve has a size of any two values or any one value of a range of values determined by any two values of 10nm, 50nm and 100 nm.
Alternatively, M is Li, na, K and/or Cs, preferably Na or K.
Alternatively, T is selected from one of polydiallyl dimethyl ammonium chloride, dimethyl diallyl ammonium chloride-acrylamide copolymer, polyquaternium-11, polyquaternium-39 and polyquaternium-28.
Optionally, R1 and R2 are independently selected from at least one of the compounds of formula II:
[NR 4 ] a X q- II (II)
Wherein R is selected from C 1 ～C 8 Alkyl, C of (2) 1 ～C 8 At least one of the alkoxy groups of (a); x is X q- Selected from OH - 、Cl - 、Br - 、I - 、NO 3 - 、HSO 4 - 、SO 4 2- 、H 2 PO 3 - 、HPO 3 2- And PO (PO) 3 3- At least one of them.
Optionally, R1 is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
Alternatively, R2 is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium bromide.
According to a second aspect of the present application, there is provided a method of nano-scale high silicon Y molecular sieve according to the above, the method comprising the steps of:
1) Obtaining Al containing an aluminum source 1 Si as silicon source 1 An initial gel mixture a of the raw materials of alkali metal source M, first organic template R1 and water;
aging the initial gel mixture A at a predetermined temperature for a predetermined time to obtain a guiding agent A';
2) Obtaining the guiding agent A' containing the step 1) and the aluminum source Al 2 Si as silicon source 2 An initial gel mixture B of additional alkali metal source M, molecular sieve growth inhibitor T, second organic template R2 and water feedstock;
3) Placing the initial gel mixture B obtained in the step 2) into a reaction kettle, and crystallizing at a preset temperature for a preset time;
4) After crystallization is completed, separating, washing and drying the solid product to obtain the nanoscale high-silicon Y molecular sieve.
Optionally, the step 2) includes: firstly, guiding agent A' containing step 1) and aluminum source Al are obtained 2 Si as silicon source 2 A mixture B 'of raw materials of an alkali metal source M, an organic template agent R2 and water, and then adding a molecular sieve growth inhibitor T into the mixture B', and uniformly mixing to obtain the initial gel mixture B.
Optionally, the step 2) includes: the initial gel mixture B was obtained in the following order: mixing additional water with an alkali metal source M and an aluminum source Al 2 After being uniformly mixed, the organic template agent R2 is added, and then the silicon source Si is added 2 Finally adding the directing agent A 'obtained in step 1) to obtain a mixture B'; then adding molecular sieve growth inhibitor T into the mixture B' and uniformly mixing to obtain the primary productStarting gel mixture B.
Optionally, the preparation method of the nanoscale high-silicon Y molecular sieve comprises the following steps:
1) Will contain Al as an aluminum source 1 Si as silicon source 1 Mixing the raw materials of the alkali metal source M, the organic template agent R1 and water to prepare an initial gel mixture A; aging the mixture A at a preset temperature for a preset time to obtain a guiding agent A';
2) Will contain Al as an aluminum source 2 Si as silicon source 2 Mixing the raw materials of an alkali metal source M, a molecular sieve growth inhibitor T, an organic template agent R2 and water to prepare an initial gel mixture;
3) Adding the guiding agent A' obtained in the step 1) into the initial gel mixture obtained in the step 2) to obtain an initial gel mixture B, uniformly mixing, and then placing the mixture in a preset temperature for crystallization for a preset time;
4) After crystallization, separating, washing and drying the solid product to obtain the high-silicon Y molecular sieve with the nanoscale structure.
The specific types of R1 and R2 used in the process are as described above, and the molecular sieve growth inhibitor T used is also as described above and will not be described in detail herein.
Optionally, after obtaining the initial gel mixture of step 2), stirring for 0.5-4 hours, adding the directing agent A' and stirring for 0.5-4 hours to obtain the initial gel mixture B.
Alternatively, the number of moles of the aluminum source in steps 1) and 2) is calculated as Al 2 O 3 Counting; mole number of silicon source is calculated as SiO 2 Counting; template R1 mole number is calculated by mole number of R1 itself; the mole number of the alkali metal source is calculated as the corresponding metal oxide M of the alkali metal M 2 Moles of O; the mole number of the molecular sieve growth inhibitor T is calculated by the mole number of the corresponding monomer;
in step 1), al as an aluminum source in the raw material 1 Si as silicon source 1 The alkali metal source M, the organic template agent R1 and water have the following molar ratio:
SiO 2 /Al 2 O 3 ＝5～30；
M 2 O/SiO 2 =0.01 to 0.5, wherein M is selected from at least one of alkali metal elements;
R1/SiO 2 ＝0.02～2；
H 2 O/SiO 2 ＝18～400。
optionally, in step 2), the aluminum source Al in the feedstock 2 Si as silicon source 2 The alkali metal source M, the molecular sieve growth inhibitor T, the organic template agent R2 and water have the following molar ratio:
SiO 2 /Al 2 O 3 ＝10～200；
M 2 O/SiO 2 =0.01 to 0.5, wherein M is selected from at least one of alkali metal elements;
R2/SiO 2 ＝0.02～2；
T/SiO 2 ＝0.001～0.22；
H 2 O/SiO 2 ＝10～800；
the amount of director A 'of step 1) added is such that SiO in director A' of step 1) 2 Is contained in the initial gel mixture B in an amount of SiO 2 3 to 20 weight percent of the total weight of the mixture.
Optionally, in step 2), the aluminum source Al in the feedstock 2 Si as silicon source 2 The alkali metal source M, the molecular sieve growth inhibitor T, the organic template agent R2 and water have the following molar ratio:
SiO 2 /Al 2 O 3 ＝10～200；
M 2 O/SiO 2 =0.01 to 0.3, wherein M is selected from at least one of alkali metal elements;
R2/SiO 2 ＝0.02～1；
T/SiO 2 ＝0.002～0.15；
H 2 O/SiO 2 ＝10～500。
optionally, in step 3), the directing agent A 'of step 1) is added in such an amount that SiO in directing agent A' of step 1) is present 2 Is contained in the initial gel mixture B in an amount of SiO 2 The upper limit of the percentage of the content is selected from 20wt%, 19wt%, 18wt%, 17The lower limit of the weight percent is 3 weight percent, 4 weight percent, 5 weight percent, 6 weight percent, 7 weight percent, 8 weight percent, 9 weight percent, 10 weight percent, 11 weight percent, 14 weight percent, 13 weight percent, 12 weight percent, 11 weight percent, 10 weight percent, 9 weight percent, 8 weight percent, 7 weight percent, 6 weight percent, 5 weight percent, 4 weight percent, and the lower limit is 3 weight percent, 4 weight percent, 5 weight percent, 6 weight percent, 7 weight percent, 8 weight percent, 9 weight percent, 10 weight percent, 11 weight percent, 12 weight percent, 13 weight percent, 14 weight percent, 15 weight percent, 16 weight percent, 17 weight percent, 18 weight percent, and 19 weight percent.
Optionally, the aluminum source Al described in step 1) and step 2) 1 And Al 2 Independently selected from at least one of sodium metaaluminate, aluminum isopropoxide, gamma-alumina, aluminum hydroxide, aluminum 2-butoxide, aluminum chloride, aluminum sulfate, sodium aluminate, aluminum nitrate, aluminum powder and pseudo-boehmite.
Optionally, the silicon source Si in step 1) and step 2) 1 And Si (Si) 2 Independently selected from at least one of methyl orthosilicate, silica sol, ethyl orthosilicate, solid silica gel, sodium silicate and white carbon black.
Optionally, the alkali metal source M described in step 1) and step 2) is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide.
Optionally, in step 1), the aging temperature is 25 to 140 ℃ and the aging time is 0.5 to 20 days.
Optionally, in step 1), the aging temperature is 30 to 120 ℃ and the aging time is 1 to 10 days.
Optionally, in step 3), the crystallization temperature is 80-170 ℃ and the crystallization time is 1-30 days.
Optionally, in step 3), the crystallization temperature is 90-140 ℃ and the crystallization time is 2-15 days.
Optionally, in step 1), the upper limit of the aging temperature is selected from 140 ℃, 130 ℃, 120 ℃, 110 ℃,100 ℃, 90 ℃, 80 ℃, 70 ℃, 60 ℃,50 ℃, 40 ℃, 30 ℃, and the lower limit is selected from 25 ℃, 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃, 85 ℃, 95 ℃, 105 ℃, 115 ℃, 125 ℃, 135 ℃.
Alternatively, in step 1), the upper limit of the aging time is selected from 20 days, 19 days, 18 days, 17 days, 16 days, 15 days, 14 days, 13 days, 12 days, 11 days, 10 days, 9 days, 8 days, 7 days, 6 days, 5 days, 4 days, 3 days, 2 days, and the lower limit is selected from 0.5 days, 1.5 days, 2.5 days, 3.5 days, 4.5 days, 5.5 days, 6.5 days, 7.5 days, 8.5 days, 9.5 days, 10.5 days, 11.5 days, 12.5 days, 13.5 days, 14.5 days, 15.5 days, 16.5 days, 17.5 days, 18.5 days, 19.5 days.
Optionally, the aging in step 1) is performed in one of dynamic, static or a combination of dynamic and static.
In this application, static aging refers to the slurry in the reaction vessel being in a state of rest. Dynamic aging refers to the slurry in the reaction vessel being in a non-stationary state, such as magnetic stirring or rotating.
Optionally, in step 3), the upper limit of the crystallization temperature is selected from 170 ℃, 160 ℃, 150 ℃, 140 ℃, 130 ℃, 120 ℃, 110 ℃,100 ℃, 90 ℃; the lower limit is selected from 80 ℃, 85 ℃, 95 ℃, 105 ℃, 115 ℃, 125 ℃, 135 ℃, 145 ℃, 155 ℃ and 165 ℃.
Alternatively, in step 3), the upper limit of crystallization time is selected from 30 days, 29 days, 28 days, 27 days, 26 days, 25 days, 24 days, 23 days, 22 days, 21 days, 20 days, 19 days, 18 days, 17 days, 16 days, 15 days, 14 days, 13 days, 12 days, 11 days, 10 days, 9 days, 8 days, 7 days, 6 days, 5 days, 4 days, 3 days, 2 days, and the lower limit is selected from 1 day, 1.5 days, 2.5 days, 3.5 days, 4.5 days, 5.5 days, 6.5 days, 7.5 days, 8.5 days, 9.5 days, 10.5 days, 11.5 days, 12.5 days, 13.5 days, 14.5 days, 15.5 days, 16.5 days, 17.5 days, 18.5 days, 19.5 days, 20.5 days, 21.5 days, 22.5 days, 23.5 days, 24.5 days, 25.5 days, 26.5 days, 27.5 days, and 28.5 days.
Optionally, the crystallization in step 3) is performed under autogenous pressure.
Optionally, the crystallization in step 3) is performed in a dynamic, static or a combination of dynamic and static modes.
In the present application, static crystallization refers to the slurry in the reaction vessel being in a static state. Dynamic crystallization refers to the slurry in the reactor being in a non-stationary state, such as magnetic stirring or rotation.
Alternatively, the separation, washing and drying in step 4) are all conventional operations, wherein the separation and washing can be performed by centrifugation or filtration. Drying may be carried out by standing at 80-115℃for 12 hours.
According to a third aspect of the present application, there is provided a catalyst comprising at least one of the nanoscale high-silicon Y molecular sieves described above and nanoscale high-silicon Y molecular sieves prepared according to the method described above.
According to a fourth aspect of the present application there is provided the use of the above catalyst in a catalytic cracking reaction.
Alternatively, the reaction conditions of the catalyst in the catalytic cracking reaction are as follows: the reaction temperature is 160-350 ℃ and the reaction time is 8-150 hours.
Alternatively, the reaction time is any two values determined for the range of values and any value therein of 25 hours, 50 hours, 75 hours, 100 hours and 150 hours.
In the present application, the term "silica to alumina ratio" means that in molecular sieves, siO 2 And Al 2 O 3 The molar ratio of silicon to aluminum is the same as "2x/y" and "silicon to aluminum oxide ratio" in the present application.
Benefits that can be produced by the present application include, but are not limited to:
(1) The application provides a direct synthesis method of a nanoscale high-silicon Y molecular sieve, which has the advantages of simple synthesis process and high crystallization speed.
(2) The crystallinity and purity of the nanoscale high-silicon Y molecular sieve provided by the application are high; the thermal stability and the hydrothermal stability are good; can effectively relieve the catalyst deactivation caused by diffusion limitation. Can be applied to the reactions such as fluid catalytic cracking, hydrocracking and the like.
(3) The preparation method of the nanoscale high-silicon Y molecular sieve is simple and convenient, and has practical value in the field of industrial production.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the synthesized product of example Y1.
FIG. 2 is a Scanning Electron Microscope (SEM) of the synthesized product of example Y1.
FIG. 3 is a Scanning Electron Microscope (SEM) of the synthesized product of comparative example S8.
FIG. 4 is a Scanning Electron Microscope (SEM) of the synthesized product of comparative example S9.
FIG. 5 is a Transmission Electron Microscope (TEM) image of the synthesized product of example Y1.
FIG. 6 is a plot of the physical adsorption and desorption of nitrogen (BET) for the synthetic product of example Y1.
FIG. 7 is a graph comparing the catalytic cracking performance of triisopropylbenzene with that of example Y1, comparative example S8 and commercial USY.
FIG. 8 is a graph comparing the catalytic cracking performance of cumene for example Y1, comparative example S8 and commercial USY.
FIG. 9 is a graph comparing the thermal and hydrothermal stability of example Y1 with that of commercial USY.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are for illustration only and the invention is not limited to these examples.
The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Under the condition that special description is not made, all raw materials used in the method are purchased through commercial paths and are directly used without special treatment, and part of raw material information is as follows:
solid silica gel (analytically pure, chinese medicine (group) Shanghai chemical reagent company); ethyl orthosilicate (analytically pure, division of dense euler chemical reagent, of the division of the Tianjin); white carbon black (325 mesh, shanghai microphone Biochemical technologies Co., ltd.); silica sol (29% -31% aqueous solution, shanghai microphone Biochemical technology Co., ltd.); alumina (analytically pure, shanghai microphone Biochemical technologies Co., ltd.); aluminum nitrate (nonahydrate, analytically pure, shanghai Meilin Biochemical technologies Co., ltd.); anhydrous aluminum chloride (analytically pure, shanghai microphone Biochemical technologies Co., ltd.); aluminum powder (99.9%, shanghai Ala Biochemical technologies Co., ltd.); aluminum isopropoxide (analytically pure, shanghai Ala Biochemical technologies Co., ltd.); sodium metaaluminate (analytically pure, shanghai Ala Biochemical technologies Co., ltd.); sodium hydroxide (analytically pure, shanghai Ala Biochemical technologies Co., ltd.); potassium hydroxide (analytically pure, shanghai Ala Biochemical technologies Co., ltd.); cesium hydroxide (analytically pure, shanghai Ala Biochemical technologies Co., ltd.); tetramethyl ammonium hydroxide (25 wt% aqueous solution, an Naiji, anhui Hirship Co., ltd.); tetraethylammonium hydroxide (35 wt% aqueous solution, shanghai chemical reagent company, china medicine (group)), is added to the mixture; tetrapropylammonium hydroxide (40 wt% aqueous solution, an Naiji, anhui Hirshine Co., ltd.); tetrabutylammonium hydroxide (40 wt% aqueous solution, an Naiji, anhui Hirship Co., ltd.); tetramethyl ammonium bromide (analytically pure, shanghai Ala Biochemical technologies Co., ltd.); tetrapropylammonium chloride (97%, shanghai Ala Biochemical technologies Co., ltd.); tetrabutylammonium chloride (97%, shanghai Ala Biochemical technologies Co., ltd.); tetrabutylammonium bromide (analytically pure, shanghai Ala Biochemical technologies Co., ltd.); polydiallyl dimethyl ammonium chloride (20 wt% aqueous solution, shanghai Ala Biotechnology Co., ltd.), polydiallyl ammonium chloride-acrylamide copolymer (20 wt% aqueous solution, shanghai Ala Biotechnology Co., ltd.), polyquaternium-11 (20 wt% aqueous solution, shanghai Ala Biotechnology Co., ltd.), polyquaternium-39 (10 wt% aqueous solution, shanghai Michelin Biotechnology Co., ltd.), polyquaternium-28 (20 wt% aqueous solution, shanghai Ala Biotechnology Co., ltd.).
Without specific description, the test conditions of the present application are as follows:
an X-ray powder diffraction phase analysis (XRD) was performed using an X' Pert PRO X-ray diffractometer, cu target, kα radiation source (λ=0.15418 nm), voltage 40kV, current 40mA, company pamanaceae, pamalytical, netherlands.
The X-ray photoelectron spectrum was measured by using a Thermofisher Escalab xi+ quasi-in-situ X-ray photoelectron spectrometer of Siemens Feier Co.
Scanning Electron Microscope (SEM) morphology analysis used a Hitachi SU8020 scanning electron microscope with an acceleration voltage of 2kV.
Elemental composition was determined using a Magix 2424X-ray fluorescence analyzer (XRF) from Philips.
A Transmission Electron Microscope (TEM) was used as a JEM2100 transmission electron microscope of JEOL corporation of japan.
Physical adsorption was measured using ASAP 2020 physical adsorption apparatus from Micromeritics, USA, and the specific surface area and pore size distribution of the sample. Before analysis, the sample is subjected to vacuum heating pretreatment for 4 hours at 350 ℃, and the free volume of the sample tube is measured by taking helium as a medium. When analyzing the sample, physical adsorption and desorption measurement were performed at a liquid nitrogen temperature (77K) using nitrogen as an adsorption gas. Determining the specific surface area of the material by adopting a BET formula; using relative pressure (P/P 0 ) The total pore volume of the material was calculated for a nitrogen adsorption amount of 0.99. Calculating the micropore surface area and micropore volume by using a t-plot method, subtracting the micropore volume from the total pore volume to obtain the mesoporous volume, and subtracting the micropore surface area from the total specific surface area to obtain the external specific surface area. When calculating, N 2 The molecular cross-sectional area is 0.162nm 2 。
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Examples in the formulation table, the amount of director added was such that the director was SiO 2 Occupying SiO in the initial gel 2 The molecular sieve growth inhibitor is added in the mass percent of the molecular sieve growth inhibitor monomer to SiO 2 Wherein the polydiallyl dimethyl ammonium chloride is calculated as the number of diallyl dimethyl ammonium chloride monomers, the dimethyldiallyl ammonium chloride acrylamide copolymer is calculated as the number of dimethyldiallyl ammonium chloride monomers, the polyquaternium-11 is calculated as the number of N, N-dimethylaminoethyl methacrylate (DMAEMA) cationic monomers, the polyquaternium-28 is calculated as the number of dimethyldiallyl ammonium chloride monomers, and the polyquaternium-39 is calculated as the number of dimethyldiallyl ammonium chloride monomers.
Examples: d1-19
The proportion of the guiding agent D1-19, the aging temperature, the aging mode and the aging time are shown in the table 1.
Preparation of guiding agent D1: 6.8g of aluminum isopropoxide is added into 84.15g of tetraethylammonium hydroxide aqueous solution, 0.133g of sodium hydroxide is added, stirring is carried out for 2 hours, 34.72g of tetraethoxysilane is added dropwise, stirring is carried out at room temperature for 2 hours, then the solution is transferred into a sealed stainless steel reaction kettle, static aging is carried out for 0.5 days at 50 ℃ and static aging is carried out for 2.5 days at 100 ℃ to obtain the required directing agent D1.
Table 1 proportion of the directing agent, aging temperature, aging method, aging time
Figure BDA0003407738840000111
Si 1 O 2 Tetraethoxysilane Si 2 O 2 Solid silica gel Si 3 O 2 White carbon black Si 4 O 2 Silica sol
Al 1 2 O 3 Aluminum isopropoxide Al 2 2 O 3 Alumina Al 3 2 O 3 Sodium aluminate Al 4 2 O 3 Aluminum nitrate Al 5 2 O 3 Aluminum chloride Al 6 2 O 3 Aluminum powder
R1 1 Tetraethylammonium hydroxide R1 2 Tetrapropylammonium hydroxide R1 3 Tetramethyl ammonium hydroxide R1 4 Tetrabutylammonium hydroxide
M 1 2 O: sodium hydroxide M 2 2 O: potassium hydroxide M 3 2 Cesium hydroxide
Examples Y1 to 34
Wherein the specific formulation of example Y1 is as follows:
11.40g of deionized water, 0.132g of sodium hydroxide and 0.307g of sodium metaaluminate are mixed, 3.9g of tetrabutylammonium hydroxide aqueous solution (40 wt%) is added, after uniform stirring, 1.8g of solid silica gel is added, after uniform stirring, 2.26g of the prepared directing agent is added dropwise (SiO in the directing agent 2 The mass of the (B) is SiO in the mixed solution 2 10wt% of the mass). After stirring at room temperature for 1 hour, 2.7g of polydiallyl dimethyl ammonium chloride solution (10 wt%) was added dropwise, stirring was carried out for another 4 hours, and the mixture was transferred into a sealed high-pressure stainless steel reaction kettle, and dynamic crystallization was carried out at 120℃under autogenous pressure for 6 days.
The specific formulation of the remaining examples is similar to example Y1, the proportions being as shown in Table 2The addition of the directing agent is carried out in such an amount that SiO in the directing agent 2 Is based on the mass of SiO in the initial gel 2 Mass fraction of (a) is calculated.
Figure BDA0003407738840000131
Figure BDA0003407738840000141
Comparative examples S1 to 9
The specific formulation of comparative examples S1 to 8 was similar to example Y1, the formulation was carried out according to Table 3, the addition amount of the directing agent being such that SiO in the directing agent 2 Is based on the mass of SiO in the initial gel 2 Mass fraction of (a) is calculated.
The specific formulation procedure of comparative example S9 was similar to example Y1, except that the order of addition of S9 was deionized water, sodium hydroxide, sodium metaaluminate, aqueous tetrabutylammonium hydroxide solution, solid silica gel, aqueous polydiallyl dimethyl ammonium chloride solution, and after stirring for 1 hour at room temperature, the corresponding directing agent was added and stirring was continued for another 4 hours.
TABLE 3 Synthesis ratio of molecular sieves, crystallization conditions, and Structure of the obtained product
Figure BDA0003407738840000161
Note that: si (Si) 1 O 2 Tetraethoxysilane Si 2 O 2 Solid silica gel Si 3 O 2 White carbon black Si 4 O 2 Silica sol
Al 1 2 O 3 Aluminum isopropoxide Al 2 2 O 3 Alumina Al 3 2 O 3 Sodium aluminate Al 4 2 O 3 Aluminum nitrate
R2 1 Tetraethylammonium hydroxide R2 2 Tetrapropylammonium hydroxide R2 3 Tetramethyl ammonium hydroxide
M 1 2 O: hydrogen oxidationSodium M 2 2 O: potassium hydroxide M 3 2 Cesium hydroxide
T 1 Poly (diallyl dimethyl ammonium chloride) T 2 Dimethyldiallylammonium chloride-acrylamide copolymer
The sample of example Y1 was subjected to XRD analysis, and the XRD diffraction pattern is shown in FIG. 1, and shows typical peaks characteristic of the FAU topology. Roasting the Y1 sample at 600 ℃ for 4 hours to remove the template agent, measuring the specific surface area and pore volume of the sample, and calculating the sample according to a t-plot method to obtain a micropore specific surface area of 575m 2 g -1 The micropore volume is 0.28cm 3 g -1 Mesoporous volume of 0.24cm 3 g -1 An external specific surface area of 159m 2 g -1 。
The scanning electron microscope photograph of the obtained Y1 sample is shown in FIG. 2, and the obtained sample is in a nano-scale size, and the particle size of the sample is about 10-50 nm.
As shown in FIG. 3, the scanning electron micrograph of comparative example S8 shows that the size of the sample obtained is about 100 to 400 nm. The addition of growth inhibition T is described as a necessary condition for synthesizing nanoscale high-silicon Y molecular sieves according to the present application. No molecular sieve growth inhibitor is added, and the prepared samples are large in size and uneven in size.
The scanning electron micrograph of the obtained comparative example S9 is shown in FIG. 4, and it can be seen that the obtained sample size is a mixture of 10-50nm and 100-400 nm. The molecular sieve growth inhibitor is added at last as a necessary condition for preparing the nanoscale high-silicon Y molecular sieve with uniform particle size, and the molecular sieve growth inhibitor is added before the guiding agent to obtain a product with the particle size of 10-50nm and 100-400nm which are mixed, so that the particle size is nonuniform.
The transmission electron micrograph of the obtained Y1 sample is shown in FIG. 5, obvious lattice fringes can be seen, and small grains of 10-50nm are proved to have a crystal structure, and the small grains are known to be nano Y molecular sieves by combining the XRD diffraction pattern of FIG. 1.
The nitrogen physical adsorption and desorption curves of the obtained Y1 sample are shown in fig. 6, the I type adsorption and desorption curves and the IV type adsorption and desorption curves can be seen, and an H3 type hysteresis loop exists, so that the mesoporous is a particle stacking hole, namely an intergranular mesoporous. The nitrogen physisorption and desorption curves of samples Y2-Y34 are similar to those of FIG. 6, and are not repeated here, which illustrates that the Y-type molecular sieve prepared by the present application has inter-crystalline mesopores.
The samples obtained in example Y1 and comparative example S8 were subjected to calcination to remove the template agent by a conventional method in the prior art, and the ammonium-exchanged ammonium-type sample was subjected to calcination to obtain a hydrogen-type catalyst. A hydrogen form sample and a commercial USY (silica to alumina ratio 10.7) sample were used in the catalytic cracking reaction of triisopropylbenzene. The specific experimental procedure and conditions are as follows: tabletting and granulating the sample, weighing 50mg of the sample with 60-80 meshes, mixing with 0.5g of quartz sand with 60-80 meshes, and loading into a fixed bed reactor. The reaction was started by nitrogen activation at 500℃for one hour and then cooling to 160 ℃. The triisopropylbenzene is prepared from 150mLmin -1 Nitrogen was carried through a saturated bottle of triisopropylbenzene in a water bath at 80℃and the reaction tail gas was analyzed by Agilent7890A weather chromatography from Agilent company, PONA (100 m. Times.0.25 mm. Times.0.5 μm), and the results are shown in FIG. 7, it can be seen that example Y1 and comparative example S8 had better triisopropylbenzene conversion and life than commercial USY (silica alumina: 10.7) and that the Y1 sample was most inactivated.
The hydrogen form Y1 and S8 samples obtained above and commercial USY samples were used in the cumene catalytic cracking reaction. The specific experimental procedure and conditions are as follows: tabletting and granulating the sample, weighing 50mg of the sample with 40-60 meshes, mixing with 0.5g of quartz sand with 40-60 meshes, and loading into a fixed bed reactor. The reaction was started by nitrogen activation at 500℃for one hour and then cooling to 350 ℃. The isopropyl benzene is prepared from 100mLmin -1 Nitrogen was carried through a saturated vial of cumene in a 60℃water bath, and the reaction tail gas was analyzed by Agilent7890A weather chromatography, PONA (100 m 0.25mm 0.5 μm) from Agilent, inc., and the results are shown in FIG. 8, where the initial activity of the three samples was seen to be near, but the Y1 sample had the slowest rate of deactivation.
Sample Y1 and commercial USY were calcined in a muffle furnace at 900℃for 6 hours in an air atmosphere, and the two molecular sieve samples were treated with saturated steam at 700℃for 8 hours on a fixed bed unit. The thermal stability and hydrothermal stability of the samples were compared by measuring the retention of micropore volume using physical adsorption, and the results are shown in fig. 9. It can be seen that the example Y1 sample has better thermal stability and hydrothermal stability.
The samples obtained in examples Y1-34 and comparative examples S1-9 were subjected to comparative analysis by XRD diffraction, and the results showed that examples Y1-34 and comparative example S8 were both high purity FAU samples, examples S1-7 were amorphous, and comparative samples Y1-34 revealed that the addition of a directing agent was necessary in the synthesis of the nanoscale high-silicon Y molecular sieve according to the present application; in preparing the directing agent, it is necessary that the directing agent be aged at a predetermined temperature; the crystallization process requires a preset temperature, and the room temperature cannot be crystallized; template agent R2, alkali metal M 2 Aluminum source Al 2 Silicon source Si 2 The addition of (3) is also necessary, and crystallization is not possible without any addition.
The results of the nitrogen physical adsorption of Y1, Y4, Y14, Y20, S8, S9, USY and XRF and XPS are shown in Table 4. As can be seen from comparison of the physical adsorption results of S8 and Y1, when no growth inhibitor is added, the obtained product basically has no mesoporous existence, and the external specific surface area is extremely low. Comparing USY with the surface of Y1, Y4, Y14 and Y20 and the silicon-aluminum ratio of the bulk phase, the nano-grade high-silicon Y molecular sieve prepared by the method has uniform aluminum distribution.
TABLE 4 structural Properties of the products
Figure BDA0003407738840000181
Figure BDA0003407738840000191
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (10)

1. The nanoscale high-silicon Y molecular sieve is characterized in that the anhydrous chemical composition of the nanoscale high-silicon Y molecular sieve is shown as a formula I:
kM·mR1·nR2·pT·(Si x Al y )O 2 i is a kind of
Wherein M is selected from at least one of alkali metal elements;
t represents a molecular sieve growth inhibitor;
r1 represents a first organic template; r2 represents a second organic templating agent, and R1 is different from R2;
k represents a molar ratio of (Si x Al y )O 2 K=0.01 to 0.20 corresponding to the mole number of the alkali metal element;
m, n represent each mole (Si x Al y )O 2 Corresponding to the mole number of the organic template agent R1 and R2, wherein m=0.01-0.2; n=0.01 to 0.4;
p represents a group represented by a formula of (Si x Al y )O 2 P=0.001 to 0.20 corresponding to the mole number of the molecular sieve growth inhibitor monomer;
x and y respectively represent mole fractions of Si and Al, 2 x/y=5-25, and x+y=1;
the size of the nanoscale high-silicon Y molecular sieve is 10-100 nm;
the nanoscale high-silicon Y molecular sieve has inter-crystalline mesopores.
2. The nanoscale high-silicon Y molecular sieve of claim 1 wherein the size of the nanoscale high-silicon Y molecular sieve is from 10 to 50nm.
3. The nanoscale high-silicon Y molecular sieve of claim 1 wherein M is selected from one of Li, na, K, and Cs.
4. The nanoscale high-silicon Y molecular sieve of claim 1 wherein T is selected from one of polydiallyl dimethyl ammonium chloride, dimethyl diallyl ammonium chloride-acrylamide copolymer, polyquaternium-11, polyquaternium-39, and polyquaternium-28.
5. The nanoscale high-silicon Y molecular sieve according to claim 1, wherein R1 and R2 are independently selected from at least one of the compounds of formula II;
[NR 4 ] q X q- II (II)
Wherein R1 and R2 are independently selected from C 1 ～C 8 Alkyl, C of (2) 1 ～C 8 At least one of the alkoxy groups of (a); x is X q- Selected from OH - 、Cl - 、Br - 、I - 、NO 3 - 、HSO 4 - 、SO 4 2- 、H 2 PO 3 - 、HPO 3 2- And PO (PO) 3 3- At least one of (a) and (b);
preferably, R1 is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide;
preferably, R2 is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium bromide.
6. A process for preparing a nanoscale high silicon Y molecular sieve according to any one of claims 1 to 5, characterized in that it comprises the steps of:
1) Obtaining Al containing an aluminum source 1 Si as silicon source 1 An initial gel mixture a of the raw materials of alkali metal source M, first organic template R1 and water;
aging the initial gel mixture A at a predetermined temperature for a predetermined time to obtain a guiding agent A';
2) Obtaining the guiding agent A' containing the step 1) and the aluminum source Al 2 Si as silicon source 2 An initial gel mixture B of additional alkali metal source M, molecular sieve growth inhibitor T, second template R2 and water feedstock;
3) Placing the initial gel mixture B obtained in the step 2) into a reaction kettle, and crystallizing at a preset temperature for a preset time;
4) After crystallization is completed, separating, washing and drying the solid product to obtain the nanoscale high-silicon Y molecular sieve.
7. The method according to claim 6, wherein the step 2) includes: firstly, guiding agent A' containing step 1) and aluminum source Al are obtained 2 Si as silicon source 2 A mixture B 'of raw materials of an additional alkali metal source M, a second organic template agent R2 and water, and then adding a molecular sieve growth inhibitor T to the mixture B' and uniformly mixing to obtain the initial gel mixture B.
8. The method according to claim 6, wherein the number of moles of the aluminum source in steps 1) and 2) is expressed as Al 2 O 3 Counting; mole number of silicon source is calculated as SiO 2 Counting; the mole numbers of the first organic template R1 and the second organic template R2 are calculated by the mole numbers of R1 and R2 per se respectively; the mole number of the alkali metal source is calculated as the corresponding metal oxide M of the alkali metal M 2 Moles of O; the mole number of the molecular sieve growth inhibitor T is calculated by the mole number of the corresponding monomer;
in step 1), al as an aluminum source in the raw material 1 Si as silicon source 1 The alkali metal source M, the first organic template R1 and water have the following molar ratio:
SiO 2 /Al 2 O 3 ＝5～30；
M 2 O/SiO 2 =0.01 to 0.5, wherein M is selected from at least one of alkali metal elements;
R1/SiO 2 ＝0.02～2；
H 2 O/SiO 2 ＝18～400；
preferably, in step 2), the aluminum source Al in the feedstock 2 Si as silicon source 2 The additional alkali metal source M, the molecular sieve growth inhibitor T, the second organic template R2 and water have the following molar ratios:
SiO 2 /Al 2 O 3 ＝10～200；
M 2 O/SiO 2 =0.01 to 0.5, wherein M is selected from at least one of alkali metal elements;
R2/SiO 2 ＝0.02～2；
T/SiO 2 ＝0.001～0.22；
H 2 O/SiO 2 ＝10～800；
the amount of director A 'of step 1) added is such that SiO in director A' of step 1) 2 Is contained in the initial gel mixture B in an amount of SiO 2 3-20wt% of the content;
preferably, the aluminum source Al described in step 1) and step 2) 1 And Al 2 At least one selected from the group consisting of sodium metaaluminate, aluminum isopropoxide, gamma-alumina, aluminum hydroxide, aluminum 2-butoxide, aluminum chloride, aluminum sulfate, sodium aluminate, aluminum nitrate, aluminum powder and pseudo-boehmite;
preferably, the silicon source Si described in step 1) and step 2) 1 And Si (Si) 2 At least one selected from methyl orthosilicate, silica sol, ethyl orthosilicate, solid silica gel, sodium silicate and white carbon black independently;
more preferably, the alkali metal source M in step 1) and step 2) is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide;
preferably, in step 1), the aging temperature is 25 to 140 ℃ and the aging time is 0.5 to 20 days;
more optionally, in step 1), the aging temperature is 30 to 120 ℃ and the aging time is 1 to 10 days;
preferably, in step 3), the crystallization temperature is 80-170 ℃ and the crystallization time is 1-30 days;
more preferably, in step 3), the crystallization temperature is 90 to 140℃and the crystallization time is 2 to 15 days.
9. A catalyst comprising at least one of the nanoscale high-silicon Y molecular sieves according to any one of claims 1 to 5, prepared according to the method of any one of claims 6 to 8.
10. Use of the catalyst according to claim 9 in catalytic cracking reactions.
CN202111521721.3A 2021-12-13 2021-12-13 Nanoscale high-silicon Y molecular sieve, and preparation method and application thereof Pending CN116262622A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111521721.3A CN116262622A (en) 2021-12-13 2021-12-13 Nanoscale high-silicon Y molecular sieve, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111521721.3A CN116262622A (en) 2021-12-13 2021-12-13 Nanoscale high-silicon Y molecular sieve, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116262622A true CN116262622A (en) 2023-06-16

Family

ID=86723250

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111521721.3A Pending CN116262622A (en) 2021-12-13 2021-12-13 Nanoscale high-silicon Y molecular sieve, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116262622A (en)

Similar Documents

Publication Publication Date Title
RU2601462C2 (en) Emm-22 molecular sieve, its synthesis and application
EP2837596A1 (en) Beta zeolite and method for producing same
JP2016536240A (en) Molecular sieve, its manufacture and its use
KR20110042740A (en) Method of zsm-5 preparation using crystalline nano-sized zsm - 5 seed
CN108002396B (en) Method for synthesizing Silicalite-1 molecular sieve by taking TPABr as template agent
EP3257813B1 (en) Method for producing beta zeolite
WO2016145619A1 (en) Method for preparation of, and application of, mordenite having mesopores and micropores
Chaida-Chenni et al. Synthesis of mesoporous-zeolite materials using Beta zeolite nanoparticles as precursors and their catalytic performance in m-xylene isomerization and disproportionation
JP6108411B2 (en) Method for producing MAZ type zeolite
CN112239215B (en) SCM-27 molecular sieves, methods of making, and uses thereof
WO2019121939A1 (en) Process for the manufacture of hollow zsm-5 and ts-1 zeolites
CN116262622A (en) Nanoscale high-silicon Y molecular sieve, and preparation method and application thereof
JP2010155759A (en) Method for synthesizing mesoporous aluminosilicate
CN112520754B (en) Aluminum-rich ZSM-5 molecular sieve and synthesis method thereof
JP7196090B2 (en) Beta-type zeolite, method for producing the same, and catalyst
CN116262623A (en) Metal modified hierarchical porous high-silicon Y molecular sieve and preparation method and application thereof
CN114426293B (en) SCM-35 molecular sieve, preparation method and application thereof
EP2837597B1 (en) Method for producing pau zeolite
JP2012136409A (en) MICROCRYSTALLINE AND HIGHLY CRYSTALLINE β-ZEOLITE AND METHOD FOR PRODUCING THE SAME
CN116177561A (en) ZSM-5 nanocrystalline material with hollow multistage holes and preparation method and application thereof
CN117583021A (en) Beta molecular sieve catalyst and preparation method and application thereof
WO2023218312A1 (en) Synthesis of aluminum-containing cit-13 and cit-15 molecular sieves
WO2023168174A1 (en) Emm-73 molecular sieve compositions, syntheses, and uses
KR20220135693A (en) A manufacturing process using TEA and Zeolite using thereof
WO2023059961A1 (en) Emm-68 aluminosilicate zeolites, syntheses, and uses

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination