CN104386707B - A kind of synthetic method of super low-Na and high-Si nano-ZSM-5 molecular sieve - Google Patents

A kind of synthetic method of super low-Na and high-Si nano-ZSM-5 molecular sieve Download PDF

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CN104386707B
CN104386707B CN201410645467.1A CN201410645467A CN104386707B CN 104386707 B CN104386707 B CN 104386707B CN 201410645467 A CN201410645467 A CN 201410645467A CN 104386707 B CN104386707 B CN 104386707B
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zsm
silicon
molecular sieve
sol
template
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CN104386707A (en
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于海斌
裴仁彦
汪洋
臧甲忠
王银斌
郭春垒
张耀日
霍志萍
张雪梅
彭晓伟
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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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
    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The present invention is a kind of synthetic method of super low-Na and high-Si nano-ZSM-5 molecular sieve, is characterised in that: comprise step: 1) be dissolved in the water by NaOH, slowly adds silicon source and selects from silicon sol; Wherein mol ratio Na 2o:SiO 2: H 2o=0.08 ~ 0.2:1:20 ~ 26, control silicon sol rate of addition and are about 50 gram/minute; 2) treat step 1) silicon sol be uniformly dispersed in alkali, by template and aluminium source, respectively with a small amount of water dissolution, add step 1 in slow stirring) colloidal sol in, wherein feed intake silica alumina ratio 80 ~ 240, template consumption and silicon oxide mol ratio are 0.05 ~ 0.1, ageing 8 hours under room temperature; 3) by step 2) in colloidal sol shift reaction still in hydrothermal crystallizing, temperature rise rate is per minute 2 DEG C, and first control temperature pre-crystallization 110 ~ 130 DEG C time, after 3 hours, is warming up to crystallization temperature 180 ± 10 DEG C, crystallization time 40 ~ 80 hours, mechanical stirring; Namely product is obtained through the filtration of routine, washing, drying, roasting.

Description

A kind of synthetic method of super low-Na and high-Si nano-ZSM-5 molecular sieve
Technical field
The present invention relates to Zeolite synthesis technical field, what be specifically related to is a kind of synthetic method of super low-Na and high-Si nano-ZSM-5 molecular sieve.
Background technology
ZSM-5 zeolite is a kind of silico-aluminate with unique three-dimensional intersection duct and ten-ring orifice structure.Because it has good hydrothermal stability, skeleton thermostability and stronger acidity, be the ideal material of catalysis, ZSM-5 zeolite is applied to the essential industry processes such as alkylating aromatic hydrocarbon, catalytic cracking, light-hydrocarbon aromatized preparing gasoline by methanol in large quantities up to now.1972, since Mobil company of the U.S. synthesizes ZSM-5 zeolite first, investigators always continuous optimum synthesis condition obtained the catalyzer with corresponding catalytic perfomance.Wherein framework si-al ratio is the key of zeolite molecular sieve Acidity, and ZSM-5 is owing to having more acid amount and acidic site, has good application prospect in petroleum catalytic cracking field.
Nanocrystal ZSM-5 mono-aspect has the outside surface active sites that larger external surface area can provide more, on the other hand there is shorter intracrystalline duct, thus there is higher micropore diffusion speed, reactant molecule can be made to be easy to arrive catalytic active site, and the product generated can spread out very soon from duct.Therefore, nanocrystal ZSM-5 improving the utilization ratio of catalyzer, strengthen macromolecular conversion capability, reduce the deep reaction of product and reduce in catalyzer coking and deactivation speed etc. all there is superior performance.
A kind of synthetic method of nano-ZSM-5 molecular sieve is disclosed in CN101643219, the method joins in the gelling system of Template-free method synthesis of nano ZSM-5 molecular sieve by pre-crystallization crystal seed, crystallization 24 hours at 160 ~ 180 DEG C again, be cooled to the ZSM-5 molecular sieve that product centrifuging, washing, drying, roasting are obtained the nanoscale of high aggregation by room temperature, but it is comparatively complicated to there is its nanosized seeds pretreatment mode.
A kind of synthetic method of high silica alumina ratio nano-ZSM-5 molecular sieve is disclosed in CN102671693A, the party adopts organic formwork method, organosilane is directly added in molecular sieve original solution, and under condensing reflux condition silane graft on ZSM-5 molecular sieve crystal seed, roasting removing organic formwork and organosilane.The nano-ZSM-5 molecular sieve grain fineness number of this method synthesis is between 0.1 ~ 500nm, silica alumina ratio SiO2/Al2O3 is not less than 30, molecular sieve has 0.5 ~ 2nm micropore, but the ZSM-5 molecular sieve grain fineness number of the method synthesis is even not, silica alumina ratio scope is lower, the hazardness that the organic formwork agent adopted has.
CN1715186A discloses a kind of preparation method of small crystal grain ZSM-5 zeolite, that the aqueous mixture of alumino silica gel particle and organic formwork agent is carried out hydrothermal crystallizing, the method avoids the raw material using sodium ion in synthetic system, thus decrease ammonium exchange, filtration, a series of process of roasting, improve the yield of zeolite product, simplify Production Flow Chart.This preparation method adopts solid silicon aluminium glue to do raw material, and single-autoclave yield rate is high, but the cost of alumino silica gel is higher, is unfavorable for large-scale industrial production.
Summary of the invention
The present invention is a kind of synthetic method of super low-Na and high-Si nano-ZSM-5 molecular sieve, it is characterized in that: comprise step:
1) by NaOH stirring and dissolving in deionized water, slowly add silicon source; Wherein mol ratio Na 2o:SiO 2: H 2o=0.08 ~ 0.2:1:20 ~ 26, control silicon source rate of addition and are about 50 gram/minute; The one in water glass, silicon sol, White Carbon black is selected in described silicon source;
2) until step 1) silicon source be uniformly dispersed in alkali lye after, by the one that template is selected in dimethylamine, diethylamine, quadrol, TEAC, with the one that aluminium source is selected in sodium metaaluminate, sodium aluminate, Tai-Ace S 150, respectively with a small amount of water dissolution, continue in whipping process, to add step 1 slowly) in the product that obtains, wherein feed intake silica alumina ratio in 80 ~ 240 scopes, template consumption is template and silicon oxide mol ratio was 0.05 ~ 0.1, by the sol system at room temperature ageing that obtains 8 hours;
3) by step 2) in colloidal sol be transferred in high pressure dynamic agitation reactor and carry out temperature programming hydrothermal crystallizing, temperature rise rate is per minute 2 DEG C, first control temperature pre-crystallization after 3 hours 110 ~ 130 DEG C time, be warming up to crystallization temperature 180 ± 10 DEG C, crystallization time 40 ~ 80 hours, mechanical stirring rotating speed is per minute 300 ~ 450 turns; Namely the good reactant of hydrothermal crystallizing obtains product Hydrogen ZSM-5 molecular sieve through the filtration of routine, washing, drying, roasting.
According to the method described in the present invention, it is characterized in that: wherein step 1) described in silicon source be silicon sol; SiO in described silicon sol 2content is 30% massfraction; Wherein step 2) described in template be etamon chloride; Described aluminium source is Tai-Ace S 150.
Compared with prior art, the present invention has following innovative point and advantage is:
1. adopt TEAC as template in synthetic method provided by the invention, non-volatility, to environment and harm little, add Na in a small amount of product ZSM-5 type zeolite molecular sieve prepared containing sodium raw materials in reaction system +content is lower, without the need to carrying out NH 4 +exchange process, reduces the discharge of production cost and ammonia-nitrogen sewage.
2. in synthetic method provided by the invention without the need to adding ZSM-5 type zeolite molecular sieve crystal seed, simplify synthesis technique, reduce synthesis cost.
3. the ZSM-5 type zeolite molecular sieve silica alumina ratio of synthetic method synthesis provided by the invention is high, and grain-size can reach nano scale level, and even grain size.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the ZSM-5 type zeolite molecular sieve sample of synthesis in the present embodiment 1.
Fig. 2 is scanning electronic microscope (SEM) figure of the ZSM-5 type zeolite molecular sieve sample of synthesis in the present embodiment 1.
Fig. 3 is X-ray diffraction (XRD) figure of the ZSM-5 type zeolite molecular sieve sample of synthesis in the present embodiment 2.
Fig. 4 is scanning electronic microscope (SEM) figure of the ZSM-5 type zeolite molecular sieve sample of synthesis in the present embodiment 2.
Fig. 5 is X-ray diffraction (XRD) figure of the ZSM-5 type zeolite molecular sieve sample of synthesis in the present embodiment 3.
Fig. 6 is scanning electronic microscope (SEM) figure of the ZSM-5 type zeolite molecular sieve sample of synthesis in the present embodiment 3.
Fig. 7 is X-ray diffraction (XRD) figure of the ZSM-5 type zeolite molecular sieve sample of synthesis in the present embodiment 4.
Fig. 8 is scanning electronic microscope (SEM) figure of the ZSM-5 type zeolite molecular sieve sample of synthesis in the present embodiment 4.
Embodiment
Embodiment 1
Take 18gNaOH dissolution of solid in 1160g deionized water, under mechanical stirring, slowly add 520g acidic silicasol, continue to stir into colloidal sol shape.Add 25.8g template TEAC, after stirring, slowly add 7.8g Tai-Ace S 150 under stirring, reinforced process constantly carries out mechanical stirring, makes reactant be emulsion state.Then at room temperature ageing 8 hours, added in dynamic agitation reactor by the reactant of emulsion state and carry out temperature programming hydrothermal crystallizing, reactor temperature rise rate is 2 DEG C/min, at 120 DEG C of stirring heating 3h, continue to be warming up to crystallization temperature 180 DEG C, crystallization time is 48h.Products therefrom passes through and filters, washs to filtrate is neutral, obtains ZSM-5 type zeolite molecular sieve 175g after drying, roasting, through XRF analysis, and SiO 2/ Al 2o 3=133.69, Na 2o content is 0.0485%, average crystal grain diameter 50nm.
Embodiment 2
Take 22gNaOH dissolution of solid in 1160g deionized water, under mechanical stirring, slowly add 520g acidic silicasol, continue to stir into colloidal sol shape.Add 25.8g template TEAC, after stirring, slowly add 11.4g Tai-Ace S 150 under stirring, reinforced process constantly carries out mechanical stirring, makes reactant be emulsion state.Then at room temperature ageing 8 hours, added in dynamic agitation reactor by the reactant of emulsion state and carry out temperature programming hydrothermal crystallizing, reactor temperature rise rate is 2 DEG C/min, at 120 DEG C of stirring heating 3h, continue to be warming up to crystallization temperature 180 DEG C, crystallization time is 48h.Products therefrom passes through and filters, washs to filtrate is neutral, obtains ZSM-5 type zeolite molecular sieve 170g after drying, roasting, through XRF analysis, and SiO 2/ Al 2o 3=98.86, Na 2o content is 0.0694%, average crystal grain diameter 55nm.
Embodiment 3
Take 24gNaOH dissolution of solid in 1160g deionized water, under mechanical stirring, slowly add 520g acidic silicasol, continue to stir into colloidal sol shape.Add 25.8g template TEAC, after stirring, slowly add 11.4g Tai-Ace S 150 under stirring, reinforced process constantly carries out mechanical stirring, makes reactant be emulsion state.Then at room temperature ageing 8 hours, added in dynamic agitation reactor by the reactant of emulsion state and carry out temperature programming hydrothermal crystallizing, reactor temperature rise rate is 2 DEG C/min, at 120 DEG C of stirring heating 3h, continue to be warming up to crystallization temperature 180 DEG C, crystallization time is 48h.Products therefrom passes through and filters, washs to filtrate is neutral, obtains ZSM-5 type zeolite molecular sieve 175g after drying, roasting, through XRF analysis, and SiO 2/ Al 2o 3=101.27, Na 2o content is 0.114%, average crystal grain diameter 53nm.
Embodiment 4
Take 20gNaOH dissolution of solid in 1160g deionized water, under mechanical stirring, slowly add 520g acidic silicasol, continue to stir into colloidal sol shape.Add 25.8g template TEAC, after stirring, slowly add 7.8g Tai-Ace S 150 under stirring, reinforced process constantly carries out mechanical stirring, makes reactant be emulsion state.Then at room temperature ageing 8 hours, added in dynamic agitation reactor by the reactant of emulsion state and carry out temperature programming hydrothermal crystallizing, reactor temperature rise rate is 2 DEG C/min, at 120 DEG C of stirring heating 3h, continue to be warming up to crystallization temperature 180 DEG C, crystallization time is 48h.Products therefrom passes through and filters, washs to filtrate is neutral, obtains ZSM-5 type zeolite molecular sieve 160g after drying, roasting, through XRF analysis, and SiO 2/ Al 2o 3=130.42, Na 2o content is 0.105%, average crystal grain diameter 50nm.

Claims (2)

1. a synthetic method for super low-Na and high-Si nano-ZSM-5 molecular sieve, is characterized in that: comprise step:
1) by NaOH stirring and dissolving in deionized water, slowly add silicon source; Wherein mol ratio Na 2o:SiO 2: H 2o=0.08 ~ 0.2:1:20 ~ 26, controlling silicon source rate of addition is 50 gram/minute; The one in water glass, silicon sol, White Carbon black is selected in described silicon source;
2) until step 1) silicon source be uniformly dispersed in alkali lye after, by the one that template is selected in dimethylamine, diethylamine, quadrol, TEAC, with the one that aluminium source is selected in sodium metaaluminate, sodium aluminate, Tai-Ace S 150, respectively with a small amount of water dissolution, continue in whipping process, to add step 1 slowly) in the product that obtains, wherein feed intake silica alumina ratio in 80 ~ 240 scopes, template consumption is template and silicon oxide mol ratio was 0.05 ~ 0.1, by the sol system at room temperature ageing that obtains 8 hours;
3) by step 2) in colloidal sol be transferred in high pressure dynamic agitation reactor and carry out temperature programming hydrothermal crystallizing, temperature rise rate is per minute 2 DEG C, first control temperature pre-crystallization after 3 hours 110 ~ 130 DEG C time, be warming up to crystallization temperature 180 ± 10 DEG C, crystallization time 40 ~ 80 hours, mechanical stirring rotating speed is per minute 300 ~ 450 turns; Namely the good reactant of hydrothermal crystallizing obtains product Hydrogen ZSM-5 molecular sieve through the filtration of routine, washing, drying, roasting.
2. in accordance with the method for claim 1, it is characterized in that: wherein step 1) described in silicon source be silicon sol; SiO in described silicon sol 2content is 30% massfraction; Wherein step 2) described in template be etamon chloride; Described aluminium source is Tai-Ace S 150.
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CN106946273B (en) * 2016-01-07 2019-05-21 中国石油化工股份有限公司 A kind of EU-1/ZSM-5 composite molecular screen and its synthetic method
CN107970989B (en) * 2016-10-25 2021-02-09 中国石油化工股份有限公司 Preparation method of xylene isomerization catalyst
CN109678175B (en) * 2017-10-19 2020-07-07 中国石油化工股份有限公司 Synthesis method of ZSM-5 molecular sieve with special morphology
CN108238614A (en) * 2018-03-16 2018-07-03 淮阴工学院 The method that ZSM-5 zeolite is prepared as raw material slightly soluble agent using clay
CN115403053B (en) * 2022-09-13 2023-12-12 中国海洋石油集团有限公司 Monodisperse nano ZSM-5 molecular sieve accompanied by orthogonal twin crystals and preparation method thereof

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CN1056473A (en) * 1990-05-16 1991-11-27 中国石油化工总公司抚顺石油化工研究院 A kind of preparation method of low-Na and high-Si Y-type molecular sieve
CN102502696A (en) * 2011-11-16 2012-06-20 大连理工大学 Synthetic method of ZSM-5 zeolites

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CN102502696A (en) * 2011-11-16 2012-06-20 大连理工大学 Synthetic method of ZSM-5 zeolites

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