CN106830002A - Illite microwave synthesizes the method for the molecular sieves of ZSM 5 - Google Patents

Illite microwave synthesizes the method for the molecular sieves of ZSM 5 Download PDF

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Publication number
CN106830002A
CN106830002A CN201710242687.3A CN201710242687A CN106830002A CN 106830002 A CN106830002 A CN 106830002A CN 201710242687 A CN201710242687 A CN 201710242687A CN 106830002 A CN106830002 A CN 106830002A
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China
Prior art keywords
illite
microwave
zsm
molecular sieve
alkali
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CN201710242687.3A
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Chinese (zh)
Inventor
姜男哲
孟万
石慧男
刘新辉
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Yanbian University
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Yanbian University
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Priority to CN201710242687.3A priority Critical patent/CN106830002A/en
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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
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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

Abstract

The invention discloses a kind of method that illite microwave synthesizes the molecular sieves of ZSM 5, belong to technical field of inorganic nonmetallic materials, comprise the following steps：(1) by illite and alkali admixture activation, obtain alkali and burn illite；(2) alkali burning illite is mixed with acid solution, carries out acidification；(3) pretreatment illite is mixed with template, distilled water, in 100 DEG C~150 DEG C microwave crystallization 5min~2h, obtains crystallization product.After by crystallization product suction filtration, washing, drying, the molecular sieves of ZSM 5 are obtained.The present invention solves the problems, such as to need additional silicon source, silicon source during illite synthesis zeolite, and the energy consumption for overcoming conventional hydrothermal synthetic method again is big, with serious pollution shortcoming.

Description

Illite microwave synthesizes the method for ZSM-5 molecular sieve
Technical field
The invention belongs to technical field of inorganic nonmetallic materials, and in particular to a kind of illite microwave synthesizes ZSM-5 molecules The method of sieve.
Background technology
ZSM-5 molecular sieve has unique pore passage structure, highly acid, good heat endurance and hydrothermal stability etc. excellent Good catalytic performance is shown in the reaction such as point, catalytic cracking, alkylation, disproportionation, isomerization in hydro carbons, by domestic and international The extensive concern of research worker.ZSM-5 molecular sieve is typically mixed with silicon source, silicon source, mineralizer by template and formed, and is passed Controlling Preparation Method is Hydrothermal Synthesiss, and the method can prepare the ZSM-5 molecular sieve that crystallinity is high, pattern is homogeneous, but have energy simultaneously Consumption is big and the shortcomings of environmental pollution, and the microwave-assisted synthesis used time is short, energy consumption is low and environmental protection.Therefore, synthesized using microwave technology ZSM-5 molecular sieve catalyst, as the ideal route of synthesis of ZSM-5 molecular sieve.
Illite is the 2 of a kind of rich potassium：The dioctahedron silicate mica-group clay minerals of 1 type interlayer missing, belong to two Individual silicon-oxy tetrahedron presss from both sides an alumina octahedral structure.Illitic chemical structural formula is KyAl4(Si8-y, Aly)O20(OH)4, lead to Normal 1<y<1.5, in the case of possible charge unbalance, Ca and Mg can replace K.Illitic chemical composition is SiO2、 Al2O3、K2O.It has been investigated that, illite provides silicon source and silicon source for synthesis zeolite, is dropped significantly compared to chemical raw material Low cost, so that the preferable synthesis material as zeolite molecular sieve.
At present, Duanmu closes and uses the illite of Shaanxi Chunhua ore deposit that 4A zeolite molecular sieves are prepared for for raw material along seminar, Additional silicon source is reaching suitable silica alumina ratio in building-up process.Mezni seminars are prepared for X-type with Tunisia natural illites The zeolite molecular sieves such as zeolite, synthetic method is hydrothermal solution reaction and conventional hydrothermal synthesis after alkali fusion.
In sum, with reference to it is existing with illite as raw material prepare the pertinent literature of zeolite molecular sieve it can be found that she Additional silicon source, silicon source etc. are generally required during the zeolite molecular sieves such as profit standby 4A made of stones, synthetic method is Hydrothermal Synthesiss, and is utilized The research that illite prepares ZSM-5 molecular sieve is not yet reported.
The content of the invention
The technical problems to be solved by the invention are directed to the deficiency of above-mentioned prior art presence and provide a kind of illite Microwave synthesizes the method for ZSM-5 molecular sieve, and solving needs additional silicon source, silicon source during illite synthesis zeolite Problem, overcomes the energy consumption of conventional hydrothermal synthetic method, heavy-polluted shortcoming again.
The present invention is to solve the problems, such as that used technical scheme set forth above is：
Illite microwave synthesizes the method for ZSM-5 molecular sieve, comprises the following steps that：
(1) by illite and alkali admixture activation, obtain alkali and burn illite；
(2) alkali burning illite is mixed with acid solution, carries out acidification；
(3) illite for crossing acidification mixes with template, distilled water, in 100 DEG C~150 DEG C microwave crystallization 5min ~2h, obtains crystallization product；After by crystallization product suction filtration, washing, drying, ZSM-5 molecular sieve is obtained.
Preferably, the alkali in the step (1) is NaOH or sodium carbonate, and the alkali is with illitic mass ratio 0.5~2：1.
Preferably, activation method is calcining or microwave in the step (1), and temperature range is 600~1100 DEG C, time model It is 5~10h to enclose.
Preferably, the acid in the step (2) is hydrochloric acid or sulfuric acid, and described use acid concentration is 6~12mol/L, described Volume and the alkali of acid solution to burn illitic quality than scope be 10:1.
Preferably, the template in the step (3) is organic amine, quaternary ammonium salt or industrial molecular sieve.
Preferably, the template in the step (3) and illitic mass ratio are 0.05~1：1.
Compared with prior art, beneficial effects of the present invention are as follows：
The present invention is to have synthesized ZSM-5 molecular sieve as raw material microwave using illite, solves illite synthetic zeolite point Additional silicon source, the problem of silicon source are needed during son sieve, the energy consumption that conventional hydrothermal synthetic method is overcome again is big, with serious pollution Shortcoming, while the ZSM-5 molecular sieve for preparing shows more excellent catalytic performance in fixed bed reactors.
Brief description of the drawings
Fig. 1 is the XRD of illite raw material；
Fig. 2 is the XRD spectra of the ZSM-5 molecular sieve that embodiment 1 is prepared；
Fig. 3 is the SEM image of the ZSM-5 molecular sieve that embodiment 1 is prepared；
Specific embodiment
For a better understanding of the present invention, below in conjunction with example the present invention is furture elucidated content, but present disclosure It is not limited solely to the following examples.
Illite raw material sources used in following examples are divided in autonomous prefecture of Yanbian, Jilin Province Korean nationality Antu County by Fig. 1 Analysis understands, consisting of illite 95%, kaolin 3%, chlorite 2%.
Embodiment 1
Illite microwave synthesizes the method for ZSM-5 molecular sieve, comprises the following steps that：
(1) 10g illites are mixed with 20g sodium carbonate particles, in 950 DEG C of calcining and activating 5h, obtains alkali and burn illite；
(2) 10g alkali is burnt into illite with 100ml molar concentrations for the hydrochloric acid solution of 6mol/L mixes, carries out acidification；
(3) illite obtained in 10g steps (2) is mixed with 10ml TPAOHs and appropriate distilled water, in 130 DEG C of microwave crystallization 2h, obtain crystallization product, after crystallization product suction filtration, washing, drying, obtain 9.24gZSM-5 molecular sieves.
With reference to accompanying drawing, Fig. 2 is used for characterizing molecular sieve crystalline structure, as seen from Figure 2, ZSM-5 molecules is contained in product Sieve (θ of diffraction maximum position 2 is 7.96 °, 8.90 °, 23.1 °, 23.9 ° and 24.3 °)；Fig. 3 is used for characterizing zeolite crystal pattern, by Fig. 3 can be seen that grain morphology rule, the size uniformity of ZSM-5 molecular sieve.
Embodiment 2
Condition is same as Example 1, and difference is that template is ethylenediamine, obtains the ZSM-5 molecular sieve of 9.37g.
Embodiment 3
Condition is same as Example 1, and difference is that template is industrial molecular sieve, obtains ZSM-5 points of 10.12g Son sieve.
Embodiment 4
Condition is same as Example 1, and difference is that acid used is sulfuric acid, obtains the ZSM-5 molecular sieve of 9.21g.
Embodiment 5
Condition is same as Example 2, and difference is that acid used is sulfuric acid, obtains the ZSM-5 molecular sieve of 9.28g.
Embodiment 6
Condition is same as Example 3, and difference is that acid used is sulfuric acid, obtains the ZSM-5 molecular sieve of 10.06g.

Claims (6)

1. the method that illite microwave synthesizes ZSM-5 molecular sieve, it is characterised in that comprise the following steps that：
(1) by illite and alkali admixture activation, obtain alkali and burn illite；
(2) alkali burning illite is mixed with acid solution, carries out acidification；
(3) illite for crossing acidification mixes with template, distilled water, in 100 DEG C~150 DEG C microwave crystallization 5min~ 2h, obtains crystallization product；After by crystallization product suction filtration, washing, drying, ZSM-5 molecular sieve is obtained.
2. the method that illite microwave as claimed in claim 1 synthesizes ZSM-5 molecular sieve, it is characterised in that the step (1) In alkali be NaOH or sodium carbonate, the alkali and illitic mass ratio are 0.5~2：1.
3. the method that illite microwave as claimed in claim 1 synthesizes ZSM-5 molecular sieve, it is characterised in that the step (1) Middle activation method is calcining or microwave, and temperature range is 600~1100 DEG C, and time range is 5~10h.
4. the method that illite microwave as claimed in claim 1 synthesizes ZSM-5 molecular sieve, it is characterised in that the step (2) In acid be hydrochloric acid or sulfuric acid, described use acid concentration is 6~12mol/L, and the volume of described acid solution burns illite with alkali Quality than scope be 10:1.
5. the method that illite microwave as claimed in claim 1 synthesizes ZSM-5 molecular sieve, it is characterised in that the step (3) In template for organic amine, quaternary ammonium salt or industrial molecular sieve.
6. the method that illite microwave as claimed in claim 1 synthesizes ZSM-5 molecular sieve, it is characterised in that the step (3) In template and illitic mass ratio be 0.05~1：1.
CN201710242687.3A 2017-04-14 2017-04-14 Illite microwave synthesizes the method for the molecular sieves of ZSM 5 Pending CN106830002A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109336129A (en) * 2018-12-20 2019-02-15 延边大学 A kind of method of the illite without templated synthesis multi-stage porous ZSM-5 zeolite molecular sieve
CN110482564A (en) * 2019-09-09 2019-11-22 延边大学 A kind of method of microwave heating class solid phase acid vapor conversion method processing illite synthesis zeolite
CN112174164A (en) * 2020-10-19 2021-01-05 中国矿业大学 ZSM-5 molecular sieve and preparation method thereof
CN112723380A (en) * 2020-12-24 2021-04-30 西安科技大学 Method for preparing hierarchical pore SAPO-20 molecular sieve from illite
CN114873605A (en) * 2022-06-14 2022-08-09 延边大学 Method for preparing illite clay-based integral hierarchical pore nano H-ZSM-5 zeolite by utilizing two-stage temperature-changing crystallization technology

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CN103435064A (en) * 2013-08-20 2013-12-11 东北石油大学 Method for preparing nano-scale ZSM-5 molecular sieve by using coal ash
CN104843739A (en) * 2014-02-13 2015-08-19 中国科学院过程工程研究所 Preparation method of ZSM-5 molecular sieve
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109336129A (en) * 2018-12-20 2019-02-15 延边大学 A kind of method of the illite without templated synthesis multi-stage porous ZSM-5 zeolite molecular sieve
CN109336129B (en) * 2018-12-20 2021-08-10 延边大学 Method for synthesizing hierarchical pore ZSM-5 zeolite molecular sieve by illite template-free method
CN110482564A (en) * 2019-09-09 2019-11-22 延边大学 A kind of method of microwave heating class solid phase acid vapor conversion method processing illite synthesis zeolite
CN110482564B (en) * 2019-09-09 2021-05-14 延边大学 Method for synthesizing zeolite molecular sieve by treating illite through microwave heating solid-phase acid steam conversion method
CN112174164A (en) * 2020-10-19 2021-01-05 中国矿业大学 ZSM-5 molecular sieve and preparation method thereof
CN112174164B (en) * 2020-10-19 2022-05-17 中国矿业大学 ZSM-5 molecular sieve and preparation method thereof
CN112723380A (en) * 2020-12-24 2021-04-30 西安科技大学 Method for preparing hierarchical pore SAPO-20 molecular sieve from illite
CN114873605A (en) * 2022-06-14 2022-08-09 延边大学 Method for preparing illite clay-based integral hierarchical pore nano H-ZSM-5 zeolite by utilizing two-stage temperature-changing crystallization technology
CN114873605B (en) * 2022-06-14 2022-12-27 延边大学 Method for preparing illite clay-based integral hierarchical pore nano H-ZSM-5 zeolite by utilizing two-stage temperature-changing crystallization technology

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