CN104556096A - Method for synthesizing sub-micron BEA zeolite by virtue of two-step crystallization - Google Patents

Method for synthesizing sub-micron BEA zeolite by virtue of two-step crystallization Download PDF

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Publication number
CN104556096A
CN104556096A CN201410815718.6A CN201410815718A CN104556096A CN 104556096 A CN104556096 A CN 104556096A CN 201410815718 A CN201410815718 A CN 201410815718A CN 104556096 A CN104556096 A CN 104556096A
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source
several
crystallization
bea zeolite
bea
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唐颐
张斌
宋坤山
郭肖
张亚红
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Fudan University
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Fudan University
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    • 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
    • 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
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention belongs to the technical field of material chemistry, and particularly discloses a synthesis preparation method for sub-micron BEA zeolite crystals with good morphology. According to the method, sub-micron BEA zeolite is synthesized under the condition of two-step crystallization of low-temperature pre-crystallization nucleation and high-temperature crystallization growth, the sub-micron BEA zeolite is dimensionally uniform and structurally complete, and has the good dual-pyramid-shaped morphology of BEA zeolite crystals, and the method is significant for scientific researches and industrial application.

Description

A kind of method of two step crystallization synthesizing submicron BEA zeolites
Technical field
The invention belongs to technical field of preparation for inorganic material, be specifically related to a kind of method of synthesizing submicron BEA zeolite.
Background technology
BEA zeolite is a kind of important microporous crystalline zeolite, has the twelve-ring pore passage structure of three dimensional intersection.BEA zeolite also has good acidity, higher thermostability, hydrothermal stability simultaneously.BEA zeolite demonstrates higher using value in the catalyzed reactions such as petroleum naphtha isomerization, Cumene cracking, alkylation, ethylbenzene isomerization, toluene disproportionation, amination.
Before the BEA zeolite of industrial use be generally alkaline system under synthesize the short grained aggregate of the nano zeolite obtained, reunion size heterogeneity, lack regular crystal morphology structure, in scientific research, do not possess typical meaning.And high catalyzed reaction is required for selectivity, lower micropore canals continuity and the integrity of crystal formation are difficult to the requirement meeting selecting property.And reported in document there is perfect crystal and good pattern BEA zeolite need synthesize under fluorine-containing system, the BEA zeolite obtained is generally micron-sized macrocrystal, but due to oversize, in catalyzed reaction, reactant or the product molecule the evolving path in zeolite crystal is long, diffusional resistance is large, easily causes deep reaction and produces carbon distribution, causing catalyst deactivation to accelerate.Therefore synthesize the less and better crystallinity degree of size, the homogeneous submicron BEA zeolite of regular appearance is significant.The BEA zeolite that two step crystallization method synthesis obtain submicron order is proposed here first, size uniformity, structural integrity, defective bit is few, and have the good pattern of two pyramid of typical BEA zeolite crystal, scientific research and industrial application are all had very important significance.
Summary of the invention
The object of the present invention is to provide that a kind of better crystallinity degree, size are little, the method for the employing crystallization method synthesizing submicron BEA zeolite of regular appearance.
The method of employing crystallization method synthesizing submicron BEA zeolite provided by the present invention, concrete steps are as follows:
(1) quadrivalent element, trivalent element, alkali source and water are mixed as raw material;
Described quadrivalent element is one or more in silicon source, germanium source and tin source; Described trivalent element is one or more the mixing in aluminium source, boron source, source of iron and gallium source;
(2) in above-mentioned mixed solution, mineralizer HF or NH is added 4f, adjustment basicity is to OK range 0.1 ~ 0.5;
(3) the pre-crystallization of hydro-thermal 12 ~ 720 hours at the mixture obtained in step (2) being placed in 60 ~ 120 DEG C;
(4) hydrothermal crystallizing reaction 120 ~ 480 hours at the sample in step (3) being placed in 120 ~ 200 DEG C;
(5) by the sample separation after crystallization in step (4), massive laundering is washed to neutrality, and dries, and obtains submicron BEA zeolite.
In the present invention, described raw material adds by following mol ratio:
Quadrivalent element/trivalent element is 2 ~ 1000, and alkali source/quadrivalent element is 0.1 ~ 0.8, and water/quadrivalent element is 10 ~ 100, and mineralizer/quadrivalent element is 0.3 ~ 0.7.
Described silicon source is selected from one or more the mixing in tetraethoxy, silica gel, silicic acid, white carbon black, silicon sol, water glass and diatomite;
Described germanium source is selected from germanium oxide;
Described Xi Yuan is selected from one or more the mixing in stannic oxide and tin chloride;
Described aluminium source is selected from one or more the mixing in aluminum isopropylate, sodium aluminate, aluminium foil, Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminium hydroxide, boehmite and pseudo-boehmite;
Described boron source is selected from one or more the mixing in boric acid, Sodium Tetraborate, boron oxide, boron trichloride and borophosphoric acid;
Described source of iron is selected from one or more the mixing in iron(ic) chloride, ferric sulfate, iron nitrate, ferric oxide, ironic hydroxide and iron powder;
Described gallium is derived from one or more the mixing in gallium chloride, gallium sulfate and gallium nitrate;
Described alkali source is selected from alkali metal hydroxide or alkaline earth metal hydroxides.
In the inventive method step (2), the pre-crystallization process of low temperature is conducive to inducing a large amount of nucleation thus obtains the less submicron BEA of crystal grain after crystallization growth.
The invention has the advantages that two step crystallization method synthesis obtain the BEA zeolite of submicron order, size uniformity, structural integrity, defective bit is few, and have the good pattern of two pyramid of typical BEA zeolite crystal, scientific research and industrial application are all had very important significance.
Accompanying drawing explanation
Fig. 1 is the XRD spectra that example 1 of the present invention prepares submicron order BEA zeolite.
Fig. 2 is the submicron BEA zeolite SEM image of example 1 of the present invention preparation.
Fig. 3 is the TEM image of the submicron BEA zeolite of example 1 of the present invention preparation.
Fig. 4 is the N of the submicron BEA zeolite of example 1 of the present invention preparation 2isothermal adsorption desorption curve.
Embodiment
Below by example, the inventive method is illustrated, the restriction of embodiment not to content of the present invention.
Embodiment 1
By molar ratio preparation Primogel: SiO below 2: 0.025Al 2o 3: 0.45TEAOH:0.40NH 4f:5.8H 2white carbon black and aluminium foil are dissolved in the mixing of TEAOH solution by O respectively, at room temperature stir aging 12 hours, then in tape loaded teflon-lined stainless steel static crystallization still, in 100 DEG C of pre-crystallization, 140 DEG C of crystallization 10 days after 48 hours, after end, cooling, filters and uses deionized water wash 3 ~ 4 times, then at 80 ~ 120 DEG C, drying gained sample.Product, in retort furnace or tubular type kiln roasting removing template, to be generally in air atmosphere 550 DEG C of roastings 4 ~ 6 hours.Obtain the BEA zeolite of 500nm.
Embodiment 2
Step in the present embodiment is identical with above-described embodiment 1.Unlike: the pre-crystallization time adopted changes 12 hours into, obtains the BEA zeolite of 700nm.
Embodiment 3
Step in the present embodiment is identical with above-described embodiment 1.Unlike: the pre-crystallization time adopted changes 96 hours into, obtains the BEA zeolite of 500nm.
Embodiment 4
Step in the present embodiment is identical with above-described embodiment 1.Unlike: the pre-crystallization temperature adopted changes 60 DEG C of pre-crystallization into, obtains the BEA zeolite of 700nm.
Embodiment 5
Step in the present embodiment is identical with above-described embodiment 1.Unlike: the pre-crystallization temperature adopted changes 90 DEG C into, obtains the BEA zeolite of 600nm.
Embodiment 6
Step in the present embodiment is identical with above-described embodiment 1.Unlike: Primogel formula changes SiO into 2: 0.02Al 2o 3: 0.005B 2o 3: 0.45TEAOH:0.40NH 4f:5.8H 2o, obtains the B-BEA zeolite of 500nm.
Embodiment 7
Step in the present embodiment is identical with above-described embodiment 1.Unlike: Primogel formula changes SiO into 2: 0.02Al 2o 3: 0.005Fe 2o 3: 0.45TEAOH:0.40NH 4f:5.8H 2o, obtains the Fe-BEA zeolite of 500nm.
Embodiment 8
Step in the present embodiment is identical with above-described embodiment 1.Unlike: Primogel formula changes SiO into 2: 0.025Al 2o 3: 0.01SnO 2: 0.45TEAOH:0.40NH 4f:5.8H 2o, obtains the Sn-BEA zeolite of 500nm.
Comparison example 1
Step in the present embodiment is identical with above-described embodiment 1.Unlike: identical proportioning is fluoridize system not, similarity condition crystallization, cannot obtain submicron BEA zeolite, can only obtain undersized nano zeolite aggregate.
Comparison example 2
Step in the present embodiment is identical with above-described embodiment 1.Unlike: without low-temperature zone, directly 140 DEG C of crystallization, submicron BEA zeolite cannot be obtained, large-sized micron order zeolite can only be obtained.

Claims (4)

1. a method for two step crystallization synthesizing submicron BEA zeolites, is characterized in that concrete steps are as follows:
(1) quadrivalent element, trivalent element, alkali source and water are mixed as raw material;
Described quadrivalent element is the one in silicon source, germanium source and tin source, or wherein several; Described trivalent element is the one in aluminium source, boron source, source of iron and gallium source, wherein several;
(2) in above-mentioned mixed solution, mineralizer HF or NH is added 4f, adjustment basicity is to OK range 0.1 ~ 0.5;
(3) the pre-crystallization of hydro-thermal 12 ~ 720 hours at the mixture obtained in step (2) being placed in 60 ~ 120 DEG C;
(4) hydrothermal crystallizing reaction 120 ~ 480 hours at the sample in step (3) being placed in 120 ~ 200 DEG C;
(5) by the sample separation after crystallization in step (4), massive laundering is washed to neutrality, and dries, and obtains submicron BEA zeolite;
Described raw material adds by following mol ratio:
Quadrivalent element/trivalent element is 2 ~ 1000, and alkali source/quadrivalent element is 0.1 ~ 0.8, and water/quadrivalent element is 10 ~ 100, and mineralizer/quadrivalent element is 0.3 ~ 0.7.
2. the method for two step crystallization synthesizing submicron BEA zeolites as claimed in claim 1, is characterized in that in quadrivalent element:
Described silicon source is selected from the one in tetraethoxy, silica gel, silicic acid, white carbon black, silicon sol, water glass and diatomite, or wherein several;
Described germanium source is selected from germanium oxide;
Described Xi Yuan is selected from the one in stannic oxide and tin chloride, or wherein several.
3. the method for two step crystallization synthesizing submicron BEA zeolites as claimed in claim 1, is characterized in that in trivalent element:
Described aluminium source is selected from the one in aluminum isopropylate, sodium aluminate, aluminium foil, Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminium hydroxide, boehmite and pseudo-boehmite, or wherein several;
Described boron source is selected from the one in boric acid, Sodium Tetraborate, boron oxide, boron trichloride and borophosphoric acid, or wherein several;
Described source of iron is selected from the one in iron(ic) chloride, ferric sulfate, iron nitrate, ferric oxide, ironic hydroxide and iron powder, or wherein several;
Described gallium is derived from the one in gallium chloride, gallium sulfate and gallium nitrate, or wherein several multiple.
4. the method for two step crystallization synthesizing submicron BEA zeolites as claimed in claim 1, is characterized in that described alkali source is selected from alkali metal hydroxide or alkaline earth metal hydroxides.
CN201410815718.6A 2014-12-25 2014-12-25 Method for synthesizing sub-micron BEA zeolite by virtue of two-step crystallization Pending CN104556096A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2772519C2 (en) * 2016-09-30 2022-05-23 Джонсон Мэтти Паблик Лимитед Компани Synthesis of zeolite with fluoride source
US11345605B2 (en) 2019-11-14 2022-05-31 Saudi Arabian Oil Company Systems and methods for preparing nano-sized crystals of BEA zeolite
US11452996B2 (en) 2016-09-30 2022-09-27 Johnson Matthey Public Limited Company Zeolite synthesis with a fluoride source

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0438818A2 (en) * 1989-12-21 1991-07-31 ENIRICERCHE S.p.A. Preparation of crystalline porous boro-silicates
CN1154341A (en) * 1996-01-11 1997-07-16 中国石油化工总公司 Method for synthesis of beta-zeolite
CN1377827A (en) * 2001-04-04 2002-11-06 中国石油化工股份有限公司 Process for preparing beta-zeolite
CN102757066A (en) * 2012-07-16 2012-10-31 大连理工大学 Method for synthesizing B-beta-heteroatom molecular sieve

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0438818A2 (en) * 1989-12-21 1991-07-31 ENIRICERCHE S.p.A. Preparation of crystalline porous boro-silicates
CN1154341A (en) * 1996-01-11 1997-07-16 中国石油化工总公司 Method for synthesis of beta-zeolite
CN1377827A (en) * 2001-04-04 2002-11-06 中国石油化工股份有限公司 Process for preparing beta-zeolite
CN102757066A (en) * 2012-07-16 2012-10-31 大连理工大学 Method for synthesizing B-beta-heteroatom molecular sieve

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙宁: "表面润湿法合成β 沸石的研究", 《石油炼制与化工》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2772519C2 (en) * 2016-09-30 2022-05-23 Джонсон Мэтти Паблик Лимитед Компани Synthesis of zeolite with fluoride source
US11452996B2 (en) 2016-09-30 2022-09-27 Johnson Matthey Public Limited Company Zeolite synthesis with a fluoride source
US11345605B2 (en) 2019-11-14 2022-05-31 Saudi Arabian Oil Company Systems and methods for preparing nano-sized crystals of BEA zeolite

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