CN111825100B - High-silicon Y molecular sieve with FAU topological structure and preparation method thereof - Google Patents

High-silicon Y molecular sieve with FAU topological structure and preparation method thereof Download PDF

Info

Publication number
CN111825100B
CN111825100B CN201910312157.0A CN201910312157A CN111825100B CN 111825100 B CN111825100 B CN 111825100B CN 201910312157 A CN201910312157 A CN 201910312157A CN 111825100 B CN111825100 B CN 111825100B
Authority
CN
China
Prior art keywords
silicon
aluminum
source
molecular sieve
hydroxide
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
Application number
CN201910312157.0A
Other languages
Chinese (zh)
Other versions
CN111825100A (en
Inventor
朱大丽
田鹏
刘中民
王林英
张建明
赵学斌
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
Priority to CN201910312157.0A priority Critical patent/CN111825100B/en
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to JP2021558687A priority patent/JP7261316B2/en
Priority to EP19925079.6A priority patent/EP3957603A4/en
Priority to KR1020217033741A priority patent/KR102622825B1/en
Priority to US17/604,377 priority patent/US20220306481A1/en
Priority to AU2019441814A priority patent/AU2019441814B2/en
Priority to PCT/CN2019/106165 priority patent/WO2020211281A1/en
Publication of CN111825100A publication Critical patent/CN111825100A/en
Application granted granted Critical
Publication of CN111825100B publication Critical patent/CN111825100B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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

Abstract

The application discloses a high-silicon Y molecular sieve with an FAU topological structure, wherein the anhydrous chemical composition of the molecular sieve is shown as a formula I: kM.mR1.nR2 (Si x Al y )O 2 A formula I; wherein M is at least one selected from alkali metal elements; r1 and R2 represent organic template agents; k represents a molar ratio of (Si x Al y )O 2 K=0 to 0.20 corresponding to the mole number of the alkali metal element M; m, n represent each mole (Si x Al y )O 2 Corresponding to the mole number of the template agent R1 and R2, m=0.00-0.20, n=0.01-0.20; x and y represent mole fractions of Si and Al, respectively, 2 x/y=7 to 40, and x+y=1. And a synthesis method of the high-silicon Y molecular sieve with the FAU topological structure.

Description

High-silicon Y molecular sieve with FAU topological structure and preparation method thereof
Technical Field
The application relates to a high-silicon Y molecular sieve with a FAU topological structure and a method for synthesizing the high-silicon Y molecular sieve by introducing an organic template agent into a synthesis gel system and adding a silicon-aluminum molecular sieve with a topological structure of FAU or EMT as a seed crystal.
Background
Y zeolite is a silica alumina zeolite with FAU topology, and is the zeolite material currently used most in Fluid Catalytic Cracking (FCC). 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. The high-silicon Y zeolite used in the industry at present is mainly obtained by dealumination and the like through a chemical/physical method, the post-treatment method has complicated process, high energy consumption and heavy pollution, and the direct hydrothermal method synthesis effectively avoids the defects and simultaneously maintains the integrity of a crystal structure and the uniformity of aluminum distribution. Therefore, the exploration of the direct method for synthesizing the Y-type molecular sieve with high silicon-aluminum ratio has very important significance for the catalytic cracking process.
For the direct method for synthesizing the high-silicon Y-type molecular sieve, the high-silicon Y-type molecular sieve is synthesized in a non-template system, namely, no organic template agent is added into the reaction gel, the crystallization time, the preparation method of the seed crystal or the inorganic guiding agent and the like are adjusted only by adjusting the gel proportion, so that the purpose of improving the silicon-aluminum ratio of the Y-type molecular sieve is achieved, but the effect is very little, and the silicon-aluminum ratio is difficult to reach 6.
The use of organic structure directing agents brings Y-type molecular sieve synthesis into a new field, and U.S. Pat. No. 3,182,1987 discloses a FAU polymorphism named ECR-4 with a silicon to aluminum ratio of greater than 6, which is obtained by hydrothermal crystallization at 70-120 ℃ in the presence of seed crystals using alkyl or hydroxyalkyl quaternary ammonium salt as a template agent.
U.S. Pat. No. 3,182,62, 1990, discloses a FAU polymorph named ECR-32 having a silicon to aluminum ratio of greater than 6, which is obtained by hydrothermal crystallization at 90-120 ℃ using tetrapropyl and/or tetrabutylammonium hydroxide as a structure directing agent, and has high thermal stability.
FAU zeolite with cubic structure was synthesized for the first time in 1990 by French Delprato et al (Zeolite. 1990,10 (6): 546-552) using crown ether as template agent, and the framework silica-alumina ratio was close to 9.0, which is the highest value that can be achieved by the one-step method reported in the literature, but the expensive and extremely toxic crown ether has limited its industrial application. Thereafter, U.S. Pat. No. 3,182,62 synthesized a Y zeolite having a silica to alumina ratio of greater than 6 using polyethylene oxide as a template.
Disclosure of Invention
According to one aspect of the present application, a high silicon Y molecular sieve having a FAU topology is provided.
The high-silicon Y molecular sieve with the FAU topological structure is characterized in that the anhydrous chemical composition of the molecular sieve is shown as a formula I:
kM·mR1·nR2·(Si x Al y )O 2 i is a kind of
Wherein M is at least one selected from alkali metal elements;
r1 and R2 represent organic template agents;
k represents a molar ratio of (Si x Al y )O 2 K=0 to 0.20 corresponding to the mole number of the alkali metal element M;
m, n represent each mole (Si x Al y )O 2 Corresponding to the mole number of the template agent R1 and R2, m=0.00-0.20, n=0.01-0.20;
x and y respectively represent mole fractions of Si and Al, 2 x/y=7-40, and x+y=1;
r1 and R2 are independently selected from one of quaternary ammonium compounds;
the structural formula of the quaternary ammonium compound is shown as a formula II;
in the formula II, R 21 ，R 22 ，R 23 ，R 24 Independently selected from C 1 ～C 12 Alkyl, C of (2) 1 ～C 12 Alkoxy, C 1 ～C 12 At least one of hydroxyalkyl, aryl, adamantyl; x is X n- Selected from OH - 、Cl - 、Br - 、I - 、NO 3 - 、HSO 4 - 、H 2 PO 3 - 、SO 4 2- 、HPO 3 2- 、PO 3 3- 。
Alternatively, m=0.01 to 0.20.
Optionally, the "C 1 ～C 12 The alkyl group of (C) includes C 7 ～C 12 Phenylalkyl groups.
Alternatively, the "aryl" includes "C 7 ～C 12 Aryl groups of (a).
Optionally, the "C 7 ～C 12 The aryl group of (C) includes C 7 ～C 12 Alkylaryl groups of (a).
Optionally, M is at least one selected from Na, K, cs, 2 x/y=8 to 30.
Optionally, the upper limit of 2x/y is selected from 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 26, 27, 28, 29 or 30; the lower limit is selected from 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 26, 27, 28 or 29.
Alternatively, R1, R2 is independently selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrapentylammonium bromide, tripropyl-isobutylammonium bromide, tributyl-cyclohexane-based ammonium hydroxide, dibutyl-dihexylammonium hydroxide, choline, triethyl-hydroxyethylammonium hydroxide, tripropyl-hydroxyethylammonium hydroxide, tributyl-benzylammonium hydroxide, triethyl-benzylammonium hydroxide, tripropyl-benzylammonium hydroxide, N-triethyl-adamantylammonium chloride, N-tripropyl-adamantylammonium chloride.
Optionally, R1 is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, choline;
r2 is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrapentylammonium bromide, tripropyl-isobutylammonium bromide, tributyl-cyclohexane-ylammonium hydroxide, dibutyl-dihexylammonium hydroxide, choline, triethyl-hydroxyethyl-ammonium hydroxide tripropyl-hydroxyethyl-ammonium hydroxide, tributyl-benzylammonium hydroxide, triethyl-benzylammonium hydroxide, tripropyl-benzylammonium hydroxide, N-triethyl-adamantylammonium chloride, N-tripropyl-adamantylammonium chloride.
Optionally, the high-silicon Y molecular sieve with FAU topology is in a platy structure.
Optionally, the size of the high-silicon Y molecular sieve with the FAU topological structure is 50 nm-2500 nm.
According to another aspect of the present application, there is provided a method for synthesizing a high silicon Y molecular sieve having a FAU topology, which hydrothermally synthesizes a high silicon (molar ratio of silicon to aluminum oxide is 7 to 40) Y molecular sieve under alkaline conditions by using a silicon to aluminum molecular sieve having a topology of FAU or EMT as a seed crystal and introducing an organic template.
The synthesis method of the high-silicon Y molecular sieve with the FAU topological structure comprises the following steps:
a) Mixing raw materials containing an aluminum source, a silicon source, an alkali metal source, an organic template agent R and water to prepare an initial gel mixture I; the raw materials comprise an aluminum source, a silicon source, an alkali metal source, an organic template agent R and water in the following molar ratio:
SiO 2 /Al 2 O 3 ＝10～200；
M 2 O/Al 2 O 3 =0 to 30, wherein M is selected from at least one of alkali metal elements;
R/Al 2 O 3 ＝1～45；
H 2 O/Al 2 O 3 ＝100～8000；
b) Adding a silicon-aluminum molecular sieve seed crystal with a FAU or EMT structure into the initial gel mixture I obtained in the step a), and mixing to obtain a mixture II;
c) Placing the mixture II obtained in the step b) into a sealed reaction kettle for crystallization to obtain the high-silicon Y molecular sieve with the FAU topological structure;
wherein the mole number of the silicon source is SiO 2 Counting; mole number of aluminum source is calculated as Al 2 O 3 Counting; the mole number of the template agent R is calculated by the mole number of R per se; the mole number of the alkali metal source is calculated as the corresponding metal oxide M of the corresponding alkali metal M 2 O moles.
Optionally, the organic template R in the step a) is at least one selected from quaternary ammonium compounds;
the structural formula of the quaternary ammonium compound is shown as a formula II;
in the formula II, R 21 ，R 22 ，R 23 ，R 24 Independently selected from C 1 ～C 12 Alkyl, C of (2) 1 ～C 12 Alkoxy, C 1 ～C 12 At least one of hydroxyalkyl, aryl, adamantyl;
X n- selected from OH - 、Cl - 、Br - 、I - 、NO 3 - 、HSO 4 - 、H 2 PO 3 - 、SO 4 2- 、HPO 3 2- 、PO 3 3- 。
Optionally, the "C 1 ～C 12 The alkyl group of (C) includes C 7 ～C 12 Phenylalkyl groups.
Alternatively, the "aryl" includes "C 7 ～C 12 Aryl groups of (a).
Optionally, the "C 7 ～C 12 The aryl group of (C) includes C 7 ～C 12 Alkylaryl groups of (a).
Optionally, the organic template R in step a) is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrapentylammonium bromide, tripropyl-isobutylammonium bromide, tributyl-cyclohexane-based ammonium hydroxide, dibutyl-dihexylammonium hydroxide, choline, triethyl-hydroxyethyl ammonium hydroxide tripropyl-hydroxyethyl ammonium hydroxide, tributyl-benzylammonium hydroxide, triethyl-benzylammonium hydroxide, tripropyl-benzylammonium hydroxide, N-triethyl-adamantylammonium chloride, N-tripropyl-adamantylammonium chloride.
Optionally, the silicon source in the step a) is at least one selected from methyl orthosilicate, ethyl orthosilicate, silica sol, solid silica gel, white carbon black and sodium silicate;
the aluminum source in the step a) is at least one selected from sodium metaaluminate, aluminum oxide, aluminum hydroxide, aluminum isopropoxide, aluminum 2-butoxide, aluminum chloride, aluminum sulfate, aluminum nitrate and pseudo-boehmite;
the alkali metal source in the step a) is at least one selected from sodium hydroxide, potassium hydroxide and cesium hydroxide.
Optionally, step a) comprises: mixing an aluminum source, an alkali metal source, an organic template agent R and water, then adding a silicon source, and mixing to prepare an initial gel mixture I.
Optionally, the aluminum source, the silicon source, the alkali metal source, the organic template R and the water in the raw materials in step a) have the following molar ratios:
SiO 2 /Al 2 O 3 ＝10～200；
M 2 O/Al 2 O 3 =0 to 30, wherein M is selected from at least one of alkali metal elements;
R/Al 2 O 3 ＝1～45；
H 2 O/Al 2 O 3 ＝100～6000。
alternatively, siO 2 /Al 2 O 3 The upper molar ratio limit of (c) is selected from 15, 20, 30, 40, 45, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200; the lower limit is selected from 10, 15, 20, 30, 40, 45, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, or 190.
Alternatively, M 2 O/Al 2 O 3 The upper molar ratio limit of (2) is selected from 1.8, 2.0, 3.0, 4.0, 4.5, 4.8, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29 or 30; the lower limit is selected from 0.1, 1.8, 2.0, 3.0, 4.0, 4.5, 4.8, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25 or 28.
Alternatively, R/Al 2 O 3 The upper molar ratio limit of (2), 3, 3.6, 4, 4.5, 4.8, 5, 5.2, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29, 30, 32, 35, 38, 40, 42 or 45; the lower limit is selected from 1, 2, 3, 3.6, 4, 4.5, 4.8, 5, 5.2, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 29, 30, 32, 35, 38, 40 or 42.
Alternatively, H 2 O/Al 2 O 3 The upper molar ratio limit of (2) is selected from 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400,2500. 2600, 2700, 2800, 2900, 3000, 3200, 3500, 3800, 4000, 5000, or 6000; the lower limit is selected from 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3200, 3500, 3800, 4000, or 5000.
Optionally, the mass ratio of the addition of the silicon-aluminum molecular sieve seed crystal with FAU or EMT structure in the mixture II in the step b) to the silicon source in the initial gel mixture I is 0.05-0.3:1;
wherein the mass of the silicon source in the initial gel mixture I is SiO 2 Is a mass of (c) a (c).
Optionally, the mass ratio of the added amount of the silicon-aluminum molecular sieve seed crystal with FAU or EMT structure in the mixture II in step b) to the silicon source (in terms of silica) in the initial gel mixture I is in the range of values between any ratio of 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.11:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, 0.20:1, 0.30:1 and any two ratios thereof.
Alternatively, the aluminosilicate molecular sieve seeds having FAU or EMT structure in step b) have a silica to alumina molar ratio SiO 2 /Al 2 O 3 Is 2 to infinity.
Alternatively, the aluminosilicate molecular sieve seeds having FAU or EMT structure in step b) have a silica to alumina molar ratio SiO 2 /Al 2 O 3 2.5 to 200.
Alternatively, the aluminosilicate molecular sieve seeds having FAU or EMT structure in step b) have a silica to alumina molar ratio SiO 2 /Al 2 O 3 2.5 to 30.
Alternatively, the aluminosilicate molecular sieve seeds having FAU or EMT structure in step b) have a silica to alumina molar ratio SiO 2 /Al 2 O 3 2.5 to 20.
Alternatively, the aluminosilicate molecular sieve seeds having FAU or EMT structure in step b) have a silica to alumina molar ratio SiO 2 /Al 2 O 3 The upper limit is selected from 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20. 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30; the lower limit is selected from 2.2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28 or 29.
Alternatively, the aluminosilicate molecular sieve seed having FAU or EMT structure in step b) has a silica to alumina molar ratio SiO 2 /Al 2 O 3 3 to 10.
Optionally, the crystallization temperature in step c) is 90-180 ℃ and the crystallization time is 0.1-15 days.
Alternatively, the upper limit of the crystallization temperature in step c) is selected from 100 ℃, 120 ℃, 140 ℃, 160 ℃ or 180 ℃; the lower limit is selected from 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 140 ℃ or 160 ℃.
Optionally, the upper limit of the crystallization time in step c) is selected from 0.1 day, 0.5 day, 1 day, 1.5 day, 2.5 days, 4 days, 5 days, 6 days; the lower limit is selected from 2 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days or 10 days.
Optionally, the crystallization in step c) is dynamic crystallization and/or static crystallization.
Optionally, the crystallization in step c) is rotational crystallization.
As an embodiment, the method comprises the steps of:
a) Mixing raw materials of an aluminum source, a silicon source, an alkali metal source, an organic template agent R and water to prepare an initial gel mixture I; the raw materials comprise an aluminum source, a silicon source, an alkali metal source, an organic template agent R and water in the following molar ratio:
SiO 2 /Al 2 O 3 ＝10～200；
M 2 O/Al 2 O 3 =0 to 30, wherein M is selected from at least one of alkali metal elements;
R/Al 2 O 3 ＝1～45；
H 2 O/Al 2 O 3 ＝100～8000
b) Adding a silicon-aluminum molecular sieve seed crystal with a FAU or EMT structure into the initial gel mixture I obtained in the step a), and mixing to obtain a mixture II;
c) Placing the mixture II obtained in the step b) into a sealed reaction kettle for crystallization, wherein the crystallization temperature is 80-180 ℃, the crystallization pressure is autogenous pressure, and the crystallization time is 0.1-15 days; after crystallization is completed, separating, washing and drying the obtained product to obtain the high-silicon Y molecular sieve with the FAU topological structure;
wherein the mole number of the silicon source is SiO 2 Counting; mole number of aluminum source is calculated as Al 2 O 3 Counting; the mole number of the template agent R is calculated by the mole number of R per se; the number of moles of alkali metal being the corresponding metal oxide M 2 O moles.
As an implementation mode, the synthesis process of the high-silicon Y molecular sieve with the FAU topology structure is as follows:
a) Preparation of initial gel: the aluminum source, the silicon source, the alkali metal source, the organic template agent R and deionized water are mixed according to the following proportion:
SiO 2 /Al 2 O 3 ＝10～200；
M 2 O/Al 2 O 3 =0 to 30, wherein M is selected from at least one of alkali metal elements;
R/Al 2 O 3 ＝1～45；
H 2 O/Al 2 O 3 ＝100～8000
mixing and stirring uniformly at room temperature to obtain initial gel;
b) Adding a seed crystal of a silicon aluminum molecular sieve with a FAU or EMT structure into the initial gel mixture obtained in the step a), and uniformly stirring, wherein the adding amount of the seed crystal is equal to that of SiO in the initial gel mixture 2 The mass ratio of (2) is 0.05-0.3:1;
c) Crystallizing the mixture obtained in the step b) for 0.1-15 days under the autogenous pressure at the temperature of 80-180 ℃, filtering and separating a solid product after crystallization is completed, washing the solid product with deionized water to be neutral, and drying the solid product to obtain the high-silicon Y molecular sieve.
The high-silicon Y molecular sieve with the FAU topological structure prepared by the method can be used for a fluid catalytic cracking catalyst and a carrier and a catalyst for difunctional catalysis reactions such as hydrocracking, hydrodesulfurization and the like.
According to another aspect of the present application, there is provided a catalyst comprising at least one of the high silicon Y molecular sieve having FAU topology, and the high silicon Y molecular sieve having FAU topology prepared according to the method.
According to a further aspect of the present application, there is provided a fluid catalytic cracking catalyst comprising at least one of said high silicon Y molecular sieve having a FAU topology, and a high silicon Y molecular sieve having a FAU topology prepared according to the method.
In the application, C 1 ～C 12 、C 7 ～C 12 And the like refer to the number of carbon atoms included. Such as "C 1 ～C 12 The term "alkyl" as used herein means an alkyl group having 1 to 12 carbon atoms.
In the present application, an "alkyl group" is a group formed by losing any one of hydrogen atoms on an alkane compound molecule. The alkane compound comprises straight-chain alkane, branched alkane, cycloparaffin and cycloparaffin with branched chains.
In the present application, an "alkoxy group" is a group formed by losing a hydrogen atom on an-OH group on an alkyl alcohol compound molecule. Such as CH 3 methoxy-OCH formed by loss of hydrogen atom on-OH group on OH molecule 3 。
In the present application, "hydroxyalkyl" is a group formed by the loss of any one of the hydrogen atoms on the non-OH group on the alkyl alcohol compound molecule. Such as CH 3 Hydroxymethyl HOCH formed by loss of hydrogen atom on methyl group on OH molecule 2 —。
In the present application, an "aryl" group is a group formed by the removal of one hydrogen atom from an aromatic ring on an aromatic compound molecule; such as p-tolyl formed by the loss of a hydrogen atom para to the methyl group on the phenyl ring by toluene.
In the present application, "alkylphenyl" is a group formed by a benzene ring containing a substituent losing one hydrogen atom; such as p-tolyl formed by the loss of a hydrogen atom para to the methyl group on the phenyl ring by toluene.
In the present application, "phenylalkyl" is a group formed by losing any hydrogen atom from an alkyl substituent on the benzene ring; such as benzyl (benzyl) formed by the loss of one hydrogen atom from methyl on toluene.
The application has the beneficial effects that:
1) According to the application, the high silicon Y molecular sieve with the silicon-aluminum oxide ratio of 7-30 is synthesized by introducing an organic template agent into the synthetic gel and adding the silicon-aluminum molecular sieve with the topological structure of FAU as a seed crystal.
2) The high silicon-aluminum ratio Y molecular sieve synthesized by the method has higher crystallinity and purity, better hydrothermal/thermal stability, can be applied to reactions such as Fluid Catalytic Cracking (FCC), hydrocracking, hydrodesulfurization and the like, avoids complex post-treatment processes with high energy consumption and heavy pollution, and has important significance in the field of actual chemical production.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of sample X1.
Fig. 2 is a Scanning Electron Microscope (SEM) image of sample X1.
FIG. 3 shows the silicon nuclear magnetism of sample X1 29 Si-NMR) spectra.
FIG. 4 is an X-ray diffraction (XRD) pattern of sample V1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The analysis method in the embodiment of the application is as follows:
the X-ray powder diffraction phase analysis (XRD) of the product was performed using an X' Pert PRO X-ray diffractometer, cu target, K.alpha.radiation source (λ=0.15418 nm), voltage 40KV, current 40mA, company PANalytical, netherlands.
The Scanning Electron Microscope (SEM) test uses Hitachi SU8020 field emission scanning electron microscope with acceleration voltage of 2kV.
Elemental composition was determined using a Magix 2424X-ray fluorescence analyzer (XRF) from Philips.
Silicon nuclear magnetism [ ] 29 Si-NMR experiments were performed on a Bruker Avance III (14.1 Tesla) spectrometer using a 7mm dual resonance probe at a speed of 6kHz. Adopts a high-power proton decoupling program and adoptsThe number of samples was 1024, the pulse width of pi/4 was 2.5. Mu.s, the sampling delay was 10s, and the sample was corrected to 0ppm with sodium 4, 4-dimethyl-4-propanesulfonate (DSS) as a chemical shift reference.
Carbon nuclear magnetism 13 C MAS NMR experiments at Bruker Avance III (14.1 Tesla)
The experiment on the spectrometer adopts a 4mm triple resonance probe with the rotating speed of 12kHz and uses amantadine as chemical displacement reference to correct to 0ppm.
Example 1: preparation of sample X1
Preparing synthetic gel: 0.7g of sodium aluminate (Al 2 O 3 ：48.3wt％，Na 2 O:36.3wt%, shanghai chemical reagent company of China medicine (group), 0.20g sodium hydroxide, 13.0g tetrapropylammonium hydroxide (25 wt%) are dissolved in 2.40g deionized water, stirred until clear, and 13.3g silica Sol (SiO) is added dropwise 2 :30wt%, shenyang chemical Co., ltd.) was stirred for 0.5 hours, and 0.4g of zeolite Y having a silica alumina ratio of 3 was added as seed crystal, and stirring was continued for 2 hours.
Synthesis of high silicon Y zeolite: transferring the synthetic gel into a stainless steel reaction kettle, rotating and crystallizing for 5d at 130 ℃, separating solid from liquid after crystallization, washing to be neutral, drying for 12h at 100 ℃, and marking as a sample X1.
The X-ray powder diffraction pattern (XRD) of sample X1 is shown in fig. 1, indicating that sample 1 is a molecular sieve having a FAU framework structure. As shown in FIG. 2, the particles of sample 1 were small pieces and had a size of 50nm to 200nm. 29 The Si MAS NMR spectrum is shown in FIG. 3, and the Si/Al ratio of the skeleton obtained by fitting calculation is consistent with that obtained by XRF calculation, and the Si/Al ratio is calculated according to XRF and XRF 13 The elemental composition of sample 1 normalized by C MAS NMR analysis was: 0.07 Na. 0.07R2 1 ·(Si 0.86 Al 0.14 )O 2 Wherein R2 1 Is tetrapropylammonium hydroxide.
Example 2 preparation of samples X2-X30
The gel preparation process of samples X2-X30 is the same as in example 1, and the raw material types, the molar ratio and the seed crystal addition amount (seed crystal and SiO in gel) of samples X2-X30 2 Mass ratio), crystallization conditions, crystal structure, silicon-aluminum ratio (product silicon-aluminum ratio is X-ray fluorescence analyzer (XR)F) The measurement results) and the product composition are shown in Table 1.
Silicon-aluminum molecular sieves with FAU structures in silicon-aluminum oxide ratios of 3, 2.8, 3, 3.5, 45, 6, 7, 70, 10, 4, 5, 6, 8, 3.5, 35, 12 and 20 are used as seed crystals in the preparation of samples X1 to X20, and the seed crystals of the molecular sieves are purchased from Zibotun Xin chemical technology Co. Silicon-aluminum molecular sieves with EMT structures in silicon-aluminum oxide ratios of 10, 8, 8.5, 7, 8, 21, 7, 8, 22 were used as seed crystals in the preparation of samples X21 to X30, respectively, and the molecular sieve seed crystals were purchased from Henan Ring molecular sieve Co., ltd.
Comparative example 1 preparation of comparative samples V1-V30
The specific synthesis gel raw material types, the molar ratio, the batching process and the crystallization conditions are the same as those of the sample 1# in the example 1, no seed crystal adding step is adopted, and the samples obtained by synthesizing the raw material types, the molar ratio, the crystallization conditions and the product crystal structures of all the products are shown in the table 2 and are recorded as comparative samples V1-V30.
Example 3 characterization analysis of samples X1-X30 and comparative sample V1
The phases of samples X1-X30 and comparative samples V1-V30 were analyzed by X-ray diffraction.
The results show that samples X1-X30 prepared in examples 1 and 2 are both high purity and high crystallinity Y-type molecular sieves, typically representing XRD patterns of sample X1 as in FIG. 1, FIG. 2 is an SEM of X1, and FIG. 3 is the silicon core magnetism of the X1 sample. The XRD spectrum results of the samples X2-X30 are similar to those of the samples shown in the figure 1, namely the diffraction peak positions and the diffraction peak shapes are basically the same, the relative peak intensity fluctuates within +/-5% according to the change of synthesis conditions, the samples X1-X30 are shown to have the structural characteristics of Y-type zeolite and have no mixed crystals, the silicon-aluminum ratio is far higher than that of the conventional Y-type zeolite, and the introduction of an organic template agent is the key for synthesizing high-silicon Y-type zeolite.
The V1-V30 products in Table 2 are all amorphous and typically represent the XRD patterns of comparative sample V1 as in FIG. 4, thus, it can be seen that in high silica Y zeolite synthesis, the addition of seed crystals is necessary in addition to the organic template.
TABLE 1 raw material types, molar ratios, seed crystal addition amounts, crystallization conditions, crystal structures, silica-alumina ratios, and product compositions of X1-X30 samples
TABLE 2 raw material types, molar ratios, crystallization conditions, crystal structures of V1-V30 samples
/>
/>
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (4)

1. The synthesis method of the high-silicon Y molecular sieve with the FAU topological structure is characterized by comprising the following steps of:
a) Mixing raw materials containing an aluminum source, a silicon source, an alkali metal source, an organic template agent R and water to prepare an initial gel mixture I; the raw materials comprise an aluminum source, a silicon source, an alkali metal source, an organic template agent R and water in the following molar ratio:
SiO 2 /Al 2 O 3 ＝40～200；
M 2 O/Al 2 O 3 =0 to 30, wherein M is selected from at least one of alkali metal elements;
R/Al 2 O 3 ＝16～45；
H 2 O/Al 2 O 3 ＝500～6000；
wherein the organic template agent R is at least one selected from tetrahexylammonium hydroxide, tripropyl-isobutyl ammonium bromide, tributyl-cyclohexane ammonium hydroxide, dibutyl-dihexyl ammonium hydroxide, choline, triethyl-hydroxyethyl ammonium hydroxide, tripropyl-hydroxyethyl ammonium hydroxide, tributyl-benzyl ammonium hydroxide, triethyl-benzyl ammonium hydroxide, tripropyl-benzyl ammonium hydroxide, N, N, N-triethyl-adamantyl ammonium chloride, N, N, N-tripropyl-adamantyl ammonium chloride;
b) Adding a silicon-aluminum molecular sieve seed crystal with a FAU or EMT structure into the initial gel mixture I obtained in the step a), and mixing to obtain a mixture II;
silicon-aluminum molar ratio SiO of the silicon-aluminum molecular sieve seed crystal with FAU or EMT structure 2 /Al 2 O 3 3 to 10;
the mass ratio of the addition amount of the silicon-aluminum molecular sieve seed crystal with the FAU or EMT structure to the silicon source in the initial gel mixture I is 0.05-0.3:1;
wherein the mass of the silicon source in the initial gel mixture I is SiO 2 Is a mass meter of (2);
c) Placing the mixture II obtained in the step b) into a sealed reaction kettle for crystallization, wherein the crystallization temperature is 110-140 ℃, and the crystallization time is 2-6 days, so that the high-silicon Y molecular sieve with the FAU topological structure is obtained;
wherein the mole number of the silicon source is SiO 2 Counting; mole number of aluminum source is calculated as Al 2 O 3 Counting; the mole number of the template agent R is calculated by the mole number of R per se; the mole number of the alkali metal source is calculated as the corresponding metal oxide M of the corresponding alkali metal M 2 O moles.
2. The method according to claim 1, wherein the silicon source in step a) is selected from at least one of methyl orthosilicate, ethyl orthosilicate, silica sol, solid silica gel, white carbon black, sodium silicate;
the aluminum source in the step a) is at least one selected from sodium metaaluminate, aluminum oxide, aluminum hydroxide, aluminum isopropoxide, aluminum 2-butoxide, aluminum chloride, aluminum sulfate, aluminum nitrate and pseudo-boehmite;
the alkali metal source in the step a) is at least one selected from sodium hydroxide, potassium hydroxide and cesium hydroxide.
3. The method according to claim 1, wherein step a) comprises: mixing an aluminum source, an alkali metal source, an organic template agent R and water, then adding a silicon source, and mixing to prepare an initial gel mixture I.
4. The method according to claim 1, characterized in that the crystallization in step c) is dynamic crystallization and/or static crystallization.
CN201910312157.0A 2019-04-18 2019-04-18 High-silicon Y molecular sieve with FAU topological structure and preparation method thereof Active CN111825100B (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN201910312157.0A CN111825100B (en) 2019-04-18 2019-04-18 High-silicon Y molecular sieve with FAU topological structure and preparation method thereof
EP19925079.6A EP3957603A4 (en) 2019-04-18 2019-09-17 High-silica y molecular sieve having fau topology and preparation method therefor
KR1020217033741A KR102622825B1 (en) 2019-04-18 2019-09-17 High-silica Y molecular sieve with FAU topological structure and method for producing the same
US17/604,377 US20220306481A1 (en) 2019-04-18 2019-09-17 High-silica y molecular sieve having fau topology and preparation method therefor
JP2021558687A JP7261316B2 (en) 2019-04-18 2019-09-17 High silica Y molecular sieve with FAU topology structure and its preparation method
AU2019441814A AU2019441814B2 (en) 2019-04-18 2019-09-17 High-silica Y molecular sieve having FAU topology and preparation method therefor
PCT/CN2019/106165 WO2020211281A1 (en) 2019-04-18 2019-09-17 High-silica y molecular sieve having fau topology and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910312157.0A CN111825100B (en) 2019-04-18 2019-04-18 High-silicon Y molecular sieve with FAU topological structure and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111825100A CN111825100A (en) 2020-10-27
CN111825100B true CN111825100B (en) 2023-10-31

Family

ID=72915061

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910312157.0A Active CN111825100B (en) 2019-04-18 2019-04-18 High-silicon Y molecular sieve with FAU topological structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111825100B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4931267A (en) * 1987-11-19 1990-06-05 Exxon Research And Engineering Company Process for preparing a high silica zeolite having the faujasite topology, ECR-32
US4965059A (en) * 1984-05-04 1990-10-23 Exxon Research & Engineering Company High silica faujasite aluminosilicate, ECR-4, and a process for making it
US5447709A (en) * 1992-10-26 1995-09-05 Societe Nationale Elf Aquitaine Process for the synthesis of zeolites belonging to the faujasite structural family
CN1145278A (en) * 1996-06-28 1997-03-19 太原工业大学 Synthesis of hypersilicon zeolit and hetero-atom isomorphism substituted derivative
CN1951812A (en) * 2005-10-19 2007-04-25 中国石油化工股份有限公司 High silica/ aluminum ratio octagonal zeolite synthesizing method
CN1951813A (en) * 2005-10-19 2007-04-25 中国石油化工股份有限公司 High-silica octagonal zeolite and synthesizing method thereof
CN101618882A (en) * 2008-07-04 2010-01-06 中国石油化工股份有限公司 Method for in-situ synthesis of Y-type molecular sieve
CN106145155A (en) * 2015-04-23 2016-11-23 中国科学院大连化学物理研究所 A kind of prepare the method for high silica alumina ratio Y type molecular sieve, product and application thereof
CN108862309A (en) * 2017-05-11 2018-11-23 中国石油大学(北京) A kind of NaY molecular sieve aggregation and preparation method thereof with nano-micro structure

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4965059A (en) * 1984-05-04 1990-10-23 Exxon Research & Engineering Company High silica faujasite aluminosilicate, ECR-4, and a process for making it
US4931267A (en) * 1987-11-19 1990-06-05 Exxon Research And Engineering Company Process for preparing a high silica zeolite having the faujasite topology, ECR-32
US5447709A (en) * 1992-10-26 1995-09-05 Societe Nationale Elf Aquitaine Process for the synthesis of zeolites belonging to the faujasite structural family
CN1145278A (en) * 1996-06-28 1997-03-19 太原工业大学 Synthesis of hypersilicon zeolit and hetero-atom isomorphism substituted derivative
CN1951812A (en) * 2005-10-19 2007-04-25 中国石油化工股份有限公司 High silica/ aluminum ratio octagonal zeolite synthesizing method
CN1951813A (en) * 2005-10-19 2007-04-25 中国石油化工股份有限公司 High-silica octagonal zeolite and synthesizing method thereof
CN101618882A (en) * 2008-07-04 2010-01-06 中国石油化工股份有限公司 Method for in-situ synthesis of Y-type molecular sieve
CN106145155A (en) * 2015-04-23 2016-11-23 中国科学院大连化学物理研究所 A kind of prepare the method for high silica alumina ratio Y type molecular sieve, product and application thereof
CN108862309A (en) * 2017-05-11 2018-11-23 中国石油大学(北京) A kind of NaY molecular sieve aggregation and preparation method thereof with nano-micro structure

Also Published As

Publication number Publication date
CN111825100A (en) 2020-10-27

Similar Documents

Publication Publication Date Title
CN1162325C (en) Step crystallizing process for synthesizing composite mesaporous and microporous molecular sieve composition
CN103191776A (en) Preparation method of ZSM-5 molecular sieve catalyst
CN102947224A (en) Uzm-35 zeolitic composition, method of preparation and processes
JP2017525651A (en) Method for producing high silica alumina ratio Y-type molecular sieve
CN103384644A (en) A method for the preparation of MWW type zeolite
WO2022104580A1 (en) Mordenite molecular sieve, and preparation method and use therefor
CN112645351A (en) SCM-30 molecular sieve and preparation method and application thereof
JP6190545B2 (en) Method for producing NaY type molecular sieve having high silica-alumina ratio and product thereof
CN108928830A (en) Molecular sieve SCM-17, its preparation method and use
CN101444748A (en) Beta/ZSM-5 compound borosilicate molecular sieve and preparation method thereof
CN112209397A (en) CHA type topological structure zinc-silicon molecular sieve with high zinc-silicon ratio and synthesis method thereof
CN111825100B (en) High-silicon Y molecular sieve with FAU topological structure and preparation method thereof
CN111825105B (en) Preparation of Y molecular sieve with FAU structure by guide agent method
CN105668580A (en) Composite-structure molecular sieve and synthetic method thereof
KR102622825B1 (en) High-silica Y molecular sieve with FAU topological structure and method for producing the same
CN111825102B (en) Dry glue conversion synthesis method of high-silicon Y molecular sieve
CN111825104B (en) Method for preparing high-silicon Y molecular sieve by seed crystal method
CN103508466A (en) Synthesis method of MCM (Mobil Composition of Matter)-22 molecular sieve
CN111825101B (en) High-silicon Y molecular sieve and preparation method thereof
CN106145133A (en) A kind of H beta molecular sieve and preparation method thereof
CN112624148B (en) SCM-29 molecular sieve and preparation method and application thereof
CN111825103B (en) Fluorine-containing high-silicon Y molecular sieve and preparation method thereof
WO2020227886A1 (en) Method for rapidly preparing high crystallinity ecr-1 molecular sieve
CN113880110A (en) Nanometer hierarchical pore MOR/MTW eutectic molecular sieve and preparation method and application thereof
CN111099609B (en) Synthesis method of beta molecular sieve

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant