CN105883848A - Method for preparing hierarchical porous ZSM-5 zeolite microspheres through recycling of crystallization liquid - Google Patents
Method for preparing hierarchical porous ZSM-5 zeolite microspheres through recycling of crystallization liquid Download PDFInfo
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- CN105883848A CN105883848A CN201610235854.7A CN201610235854A CN105883848A CN 105883848 A CN105883848 A CN 105883848A CN 201610235854 A CN201610235854 A CN 201610235854A CN 105883848 A CN105883848 A CN 105883848A
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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
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- 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
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- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The invention provides a method for preparing hierarchical porous ZSM-5 zeolite microspheres through recycling of a crystallization liquid, belongs to the field of catalyst preparation and particularly relates to a method for preparing hierarchical porous ZSM-5 zeolite microspheres with uniform sizes through efficient cyclic utilization of a crystallization waste liquid in the presence of a surfactant. The method has main advantages as follows: (1) the recycling operation of the crystallization liquid is simple, the pollutant discharge amount is reduced, and non-crystallized silicon-aluminum sources in the crystallization liquid can be utilized again; (2) the diameters of the hierarchical porous ZSM-5 zeolite microspheres range from 2 mu m to 3 mu m, the hierarchical porous ZSM-5 zeolite microspheres are formed by gathering zeolite crystal particles about 100 nm, the microspheres have uniform sizes and are distributed uniformly, and a sample has higher crystallinity and rich mesoporous volume and is a micropore and mesopore coexisting hierarchical porous ZSM-5 molecular sieve.
Description
Technical field
The method that multi-stage porous ZSM-5 zeolite microsphere is prepared in the present invention a kind of crystallization liquid reuse, belong to field of catalyst preparation, being specifically related to one in the presence of surfactants, crystallization waste liquid efficient circulation utilizes, the method preparing the multi-stage porous ZSM-5 zeolite microsphere of size uniformity.
Background technology
ZSM-5 molecular sieve is the new construction zeolite with 3 D pore canal that 20 century 70s are researched and developed by Mobil company of the U.S..Due to the pore passage structure of its high hydrothermal stability, high reaction activity, highly acid and uniqueness, the hydrocarbon in the range of gasoline-range is had the highest selectivity, is therefore widely used in the reaction of methanol hydrocarbon (MTH).This ZSM-5 molecular sieve applied research in preparing gasoline by methanol (MTG), methanol aromatic hydrocarbons (MTA), methanol-to-olefins (MTO), preparing propylene from methanol (MTP) all has a large amount of report at present.
From the point of view of in terms of the process preparing ZSM-5 molecular sieve and commercial Application thereof, currently mainly there is a following both sides difficult problem.One is to need substantial amounts of organic formwork agent (such as four third class ammonium hydroxide (TPAOH), 4-propyl bromide (TPABr), ethylenediamine, n-butylamine etc.) in building-up process, but the most costly and there is bigger toxicity in organic amine price, therefore, from the point of view of synthesis cost and environmental friendliness, this method is not particularly suited for industrialization large-scale production.Two is the micropore canals structure of conventional its uniqueness of ZSM-5 molecular sieve, and in the range of to gasoline-range, hydrocarbon has and higher selective easily makes catalyst generation carbon distribution inactivate simultaneously as its long and narrow duct, and therefore, the single pass life of routine ZSM-5 molecular sieve is the most relatively low.
The new way that a lot of researcher explores is become from reduction synthesis cost and eco-friendly angle, non-amine method and mother solution recycle method.Wherein non-amine method mainly adds crystal seed during synthesis ZSM-5 molecular sieve, and this method not only significantly reduces preparation cost, shortens crystallization time, reduces energy consumption, and avoids the organic amine severe contamination to environment；And mother solution recycle method is a kind of method efficiently utilized by the crystallization waste liquid preparing the generation of molecular sieve process, this method largely avoids the discharge of waste liquid, and silicon and aluminum source and the nano microcrystalline in waste liquid can obtain circulating efficiently utilization, thus reduce synthesis cost from another point of view.On the other hand, from the life-span of ZSM-5 molecular sieve, its research emphasis is concentrated mainly on prepares multi-stage porous ZSM-5 zeolite and nano zeolite.Mesopore orbit in porous zeotile well promotes the diffusion of macromole product, makes catalyst have higher appearance carbon ability simultaneously, the most largely slow down rapid catalyst deactivation；And nano zeolite is due to its less crystallite dimension, make reaction molecular shorter residence time in duct, it is to avoid the generation of macromole condensed-nuclei aromatics, thus can effectively slow down the generation of carbon distribution, improve catalyst life.
But, repeatability prepared by nano zeolite is relatively low, and its nano level crystallite dimension brings the biggest difficulty to separation process, and therefore, nano zeolite application in the industry is limited by very large.
The open one that reports of CN 102001678A is under organo silane coupling agent existence condition, the method of synthesis middle hole ZSM-5 zeolite microsphere, the synthesis of nano zeolite microsphere well overcomes the problem that nano zeolite is difficult to separate during preparation and use, but silicon source is the nano silicon of non-commercialization in this method, and need in advance nano silicon to be carried out silanization treatment in alcohol-water system, add technical operation flow.
CN 102001681A is open reports the silane coupler being directly added into commercialization in ZSM-5 synthetic system, the method of synthesis multi-stage porous ZSM-5 molecular sieve, simplify preparation process, but the size heterogeneity of this method gained nano zeolite microsphere, and the waste liquid produced crystallization carries out rationally efficient utilization.
The patents such as CN 101468805A, CN 101468807A, CN 102757069A are open reports the method that the mother solution preparing HTS, beta-molecular sieve and ZSM-5 molecular sieve generation is efficiently utilized synthesis ZSM-5 molecular sieve, decreases mother solution discharge pollution on the environment.But these work are all not directed to the synthesis of hierarchical porous structure ZSM-5 zeolite, also do not provide the pattern of ZSM-5 molecular sieve.
Summary of the invention
The method that multi-stage porous ZSM-5 zeolite microsphere is prepared in the present invention a kind of crystallization liquid reuse, its object is to solve two large problems present in above-mentioned preparation and application process.Thus disclosure one is in the presence of surfactants, the method for the multi-stage porous ZSM-5 zeolite microsphere of size uniformity is prepared in crystallization liquid reuse.The method efficient circulation utilizes crystallization liquid, reduces the usage amount of template, reduces synthesis cost, it is to avoid environmental pollution, and meanwhile, the hierarchical porous structure of ZSM-5 zeolite microsphere well enhances catalyst and holds carbon ability, slow down catalyst carbon deposition inactivation；The Microsphere Size of its homogeneous 2-3 μm, overcomes nano zeolite equally and is difficult to filter the problem separated present in preparation and use process.
The method that multi-stage porous ZSM-5 zeolite microsphere is prepared in the present invention a kind of crystallization liquid reuse, it is characterized in that one is in the presence of surfactants, the method of the 2-3 μm multi-stage porous ZSM-5 zeolite microsphere of size uniformity is prepared in crystallization liquid reuse, and this synthetic method comprises the following steps:
1) surfactant is added in quantitative distilled water, stir to obtain A；
2) silicon source is added in A, stir to obtain B；
3) aluminum source and template are added in quantitative solvent, stir to obtain C；
4) being mixed by B and C, stir to obtain D；
5) adding alkali in D, the PH of regulation mixture, stir to obtain E；
6) E is loaded in autoclave, use two step variable temperature crystallization method crystallization；
7) filter, wash, be dried, roasting obtains multi-stage porous ZSM-5 zeolite microsphere.
The method that multi-stage porous ZSM-5 zeolite microsphere is prepared in above-mentioned a kind of crystallization liquid reuse, it is characterised in that described surfactant is KH-560.
Above-mentioned a kind of crystallization liquid reuse is prepared in the method for multi-stage porous ZSM-5 zeolite microsphere, it is characterised in that described silicon source is the one in Ludox, sodium silicate.
Above-mentioned a kind of crystallization liquid reuse is prepared in the method for multi-stage porous ZSM-5 zeolite microsphere, it is characterised in that source of aluminium is the one in aluminum sulfate, aluminum nitrate, sodium metaaluminate, and template is 4-propyl bromide, and solvent is ZSM-5 molecular sieve crystallization liquid or distilled water.
Above-mentioned a kind of crystallization liquid reuse is prepared in the method for multi-stage porous ZSM-5 zeolite microsphere, it is characterised in that described alkali source is sodium hydroxide, and pH value is 10-13.
Above-mentioned a kind of crystallization liquid reuse is prepared in the method for multi-stage porous ZSM-5 zeolite microsphere, it is characterised in that described crystallization is carried out in autoclave, and crystallization process is pre-crystallization 10-48h at 100 DEG C, crystallization 36-60h at 170 DEG C.
Above-mentioned a kind of crystallization liquid reuse is prepared in the method for multi-stage porous ZSM-5 zeolite microsphere, it is characterised in that the reactant molar ratio scope of described reaction system is: (40-80) SiO2:(2-8)KH-560:Al2O3:(2-4)Na2O:(800-1600)H2O:
(450-950) crystallization waste liquid: (4-7) TPABr.
The present invention a kind of crystallization liquid reuse is prepared the method for multi-stage porous ZSM-5 zeolite microsphere and is had the advantage that
The method that multi-stage porous ZSM-5 zeolite microsphere is prepared in a kind of crystallization liquid reuse the most disclosed in this invention, its crystallization waste liquid can unlimited number of efficient circulation utilize, and while reducing synthesis cost, protects natural environment.
The method that multi-stage porous ZSM-5 zeolite microsphere is prepared in a kind of crystallization liquid reuse the most disclosed in this invention, can make the usage amount of template reduce 20%-60%, reduce synthesis cost.
A kind of multi-stage porous ZSM-5 zeolite microsphere the most disclosed in this invention, its particle size is homogeneous for 2-3 μm, microsphere is formed by nanocrystalline mutual accumulation, it is to avoid nano zeolite difficulty in separation process.
A kind of multi-stage porous ZSM-5 zeolite microsphere the most disclosed in this invention, its pore passage structure enriches, and is the compound diplopore molecular sieve of a kind of micropore-mesopore, enhances appearance carbon ability and the anti-carbon performance of catalyst.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of multi-stage porous ZSM-5 zeolite microsphere of the present invention.Its 5 characteristic diffraction peaks prove that this multi-stage porous ZSM-5 zeolite microsphere is typical MFI topological structure.
Fig. 2 is the N of multi-stage porous ZSM-5 zeolite microsphere of the present invention2Adsorption-desorption curve.When its relative pressure is low, adsorbance substantially rises, and obvious hysteresis loop occurs, illustrate that measured material is micropore-mesopore composite construction when relative pressure is more than 0.4.
Fig. 3 is the electron micrograph of multi-stage porous ZSM-5 zeolite microsphere of the present invention: Fig. 3 (a) scanning electron microscope, Fig. 3 (b) transmission electron microscope.Scanning electron microscopic picture shows that this multi-stage porous ZSM-5 zeolite Microsphere Size is homogeneous and forms for 2-3 μm and by the nanocrystalline mutual accumulation of the zeolite of about 100nm；Transmission electron microscope picture shows this multi-stage porous ZSM-5 zeolite microsphere highly crystalline, has obvious lattice fringe and there is a certain amount of intergranular meso-hole structure.
Detailed description of the invention
The case study on implementation of the present invention is presented herein below, but the present invention is not limited to these case study on implementation.
Embodiment
1
Take 0.75ml silane coupler KH-560 to be dissolved in 10ml water, stir 30min, be subsequently adding 11ml alkaline silica sol JN-30(WSiO2=30%, c=6.05mol/L), continue stirring 30min and obtain homogeneous Sol A.Take 1.0996g aluminum sulfate and 3g 4-propyl bromide is dissolved in 14ml ZSM-5 crystallization waste liquid, stir 1h under room temperature and obtain homogeneous sol B.Sol A being slowly added in sol B, and add 0.396g sodium hydroxide, regulation mixed sols PH is 13, continues mix and blend 3h, and then left at room temperature 3h obtains ZSM-5 forerunner's gel of thickness state.This gel fills still, 100 DEG C of crystallization 30h, then 170 DEG C of crystallization 60h, and crystallization product solid-liquid sucking filtration separates, and crystallization waste liquid reclaims, and solid product is washed with deionized to neutrality, 100 DEG C of dry 10h, 550 DEG C of roasting 5h.
Embodiment
2
11ml alkaline silica sol JN-30 in embodiment 1 being become alkaline sodium silicate solution, and alkaline sodium silicate solution is mixed by 11ml water, 8.05g sodium silicate and 0.132g sodium hydroxide, other synthesis conditions are the most constant, synthesize multi-stage porous ZSM-5 zeolite microsphere.
Embodiment
3
1.0996g aluminum sulfate in embodiment 1 being become 0.27 sodium metaaluminate, 0.396g sodium hydroxide is become 0.265g sodium hydroxide, other synthesis conditions are constant, synthesize multi-stage porous ZSM-5 zeolite microsphere.
Embodiment
4
Take 2.3ml silane coupler KH-560 to be dissolved in 18ml water, stir 30min, be subsequently adding 16.5ml alkaline silica sol JN-30(WSiO2=30%, c=6.05mol/L), continue stirring 30min and obtain homogeneous Sol A.Take 1.0996g aluminum sulfate and 2.6g 4-propyl bromide is dissolved in 18ml ZSM-5 crystallization waste liquid, stir 1h under room temperature and obtain homogeneous sol B.Sol A being slowly added in sol B, and add 0.396g sodium hydroxide, regulation mixed sols PH is 13, continues mix and blend 3h, and then left at room temperature 3h obtains ZSM-5 forerunner's gel.This gel fills still, 100 DEG C of crystallization 24h, then 170 DEG C of crystallization 48h, and crystallization product solid-liquid sucking filtration separates, and crystallization waste liquid reclaims, and solid product is washed with deionized to neutrality, 100 DEG C of dry 10h, 550 DEG C of roasting 5h.
Embodiment
5
Take 1.5ml silane coupler KH-560 to be dissolved in 20ml water, stir 30min, be subsequently adding 22ml alkaline silica sol JN-30(WSiO2=30%, c=6.05mol/L), continue stirring 30min and obtain homogeneous Sol A.Take 1.0996g aluminum sulfate and 2g 4-propyl bromide is dissolved in 28ml ZSM-5 crystallization waste liquid, stir 1h under room temperature and obtain homogeneous sol B.Sol A being slowly added in sol B, and add 0.396g sodium hydroxide, regulation mixed sols PH is 11, continues mix and blend 3h, and then left at room temperature 3h obtains ZSM-5 forerunner's gel.This gel fills still, 100 DEG C of crystallization 10h, then 170 DEG C of crystallization 36h, and crystallization product solid-liquid sucking filtration separates, and crystallization waste liquid reclaims, and solid product is washed with deionized to neutrality, 100 DEG C of dry 10h, 550 DEG C of roasting 5h.
Embodiment
6
Take 3ml silane coupler KH-560 to be dissolved in 27ml water, stir 30min, be subsequently adding 22ml alkaline silica sol JN-30(WSiO2=30%, c=6.05mol/L), continue stirring 30min and obtain homogeneous Sol A.Take 1.0996g aluminum sulfate and 2.6g 4-propyl bromide is dissolved in 15ml ZSM-5 crystallization waste liquid, stir 1h under room temperature and obtain homogeneous sol B.Sol A being slowly added in sol B, and add 0.396g sodium hydroxide, regulation mixed sols PH is 12, continues mix and blend 3h, and then left at room temperature 3h obtains ZSM-5 forerunner's gel.This gel fills still, 100 DEG C of crystallization 10h, then 170 DEG C of crystallization 48h, and crystallization product solid-liquid sucking filtration separates, and crystallization waste liquid reclaims, and solid product is washed with deionized to neutrality, 100 DEG C of dry 10h, 550 DEG C of roasting 5h.
Claims (7)
1. the method that multi-stage porous ZSM-5 zeolite microsphere is prepared in a crystallization liquid reuse, it is characterized in that one is in the presence of surfactants, the method of the 2-3 μm multi-stage porous ZSM-5 zeolite microsphere of size uniformity is prepared in crystallization liquid reuse, and this synthetic method comprises the following steps:
1) surfactant is added in quantitative distilled water, stir to obtain A；
2) silicon source is added in A, stir to obtain B；
3) aluminum source and template are added in quantitative solvent, stir to obtain C；
4) being mixed by B and C, stir to obtain D；
5) adding alkali in D, the PH of regulation mixture, stir to obtain E；
6) E is loaded in autoclave, use two step variable temperature crystallization method crystallization；
7) filter, wash, be dried, roasting obtains multi-stage porous ZSM-5 zeolite microsphere.
2. the method preparing multi-stage porous ZSM-5 zeolite microsphere according to crystallization liquid reuse a kind of described in claim, it is characterised in that described surfactant is KH-560.
3. prepare according to crystallization liquid reuse a kind of described in claim in the method for multi-stage porous ZSM-5 zeolite microsphere, it is characterised in that described silicon source is the one in Ludox, sodium silicate.
4. prepare in the method for multi-stage porous ZSM-5 zeolite microsphere according to crystallization liquid reuse a kind of described in claim, it is characterized in that source of aluminium is the one in aluminum sulfate, aluminum nitrate, sodium metaaluminate, template is 4-propyl bromide, and solvent is ZSM-5 molecular sieve crystallization liquid or distilled water.
5. prepare according to crystallization liquid reuse a kind of described in claim in the method for multi-stage porous ZSM-5 zeolite microsphere, it is characterised in that described alkali source is sodium hydroxide, and pH value is 10-13.
6. preparing according to crystallization liquid reuse a kind of described in claim in the method for multi-stage porous ZSM-5 zeolite microsphere, it is characterised in that described crystallization is carried out in autoclave, crystallization process is pre-crystallization 10-48h at 100 DEG C, crystallization 36-60h at 170 DEG C.
7. prepare according to crystallization liquid reuse a kind of described in claim in the method for multi-stage porous ZSM-5 zeolite microsphere, it is characterised in that the reactant molar ratio scope of described reaction system is:
(40-80)SiO2:(2-8)KH-560:Al2O3:(2-4)Na2O:(800-1600)H2O:
(450-950) crystallization waste liquid: (4-7) TPABr.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673008A (en) * | 2016-12-23 | 2017-05-17 | 中国石油大学(北京) | Multilevel structure ZSM-5 zeolite molecular sieve, as well as synthetic method and application thereof |
| CN107840350A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | The synthetic method of the controllable molecular sieves of nanometer ZSM 5 of particle diameter distribution |
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| CN107840350A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | The synthetic method of the controllable molecular sieves of nanometer ZSM 5 of particle diameter distribution |
| CN106673008A (en) * | 2016-12-23 | 2017-05-17 | 中国石油大学(北京) | Multilevel structure ZSM-5 zeolite molecular sieve, as well as synthetic method and application thereof |
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