CN107500312A - A kind of fluorine richness molecular sieve H ZSM 35 and preparation method thereof - Google Patents
A kind of fluorine richness molecular sieve H ZSM 35 and preparation method thereof Download PDFInfo
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- CN107500312A CN107500312A CN201710682733.1A CN201710682733A CN107500312A CN 107500312 A CN107500312 A CN 107500312A CN 201710682733 A CN201710682733 A CN 201710682733A CN 107500312 A CN107500312 A CN 107500312A
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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
- C01B39/44—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
- C01B39/445—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38 using at least one organic template directing agent
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- 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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- 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
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Abstract
The invention discloses a kind of fluorine richness molecular sieve H ZSM 35 preparation method, fluorine richness molecular sieve H ZSM 35 preparation method is：H ZSM 35 are by 1.56Na2O:Al2O3:SiO2:600H2O:18.96Py proportionings are synthesized, and are added alkali source in aqueous, are continuously added silicon source, silicon source and template, then said mixture is stirred and is sufficiently mixed, and crystallization 48h, are filtered, and are washed, and are dried, are calcined and produce H ZSM 35.Modifying agent is continuously added, stirs 5 h, until molecular sieve H ZSM 35 and modifying agent are sufficiently mixed, is stood, is evaporated and fluorine richness molecular sieve H ZSM 35 are made.Fluorine richness molecular sieve H ZSM 35 obtained by the present invention are compared in the reaction of chloromethane propylene with unmodified H ZSM 35 has preferable catalytic performance and life-span.Unmodified H ZSM 35 conversion ratios in chloromethane are 57.4%, Propylene Selectivity 20.2%, propene yield 16.3%.Conversion ratio is up to 88.4% in chloromethane by fluorine richness molecular sieve H ZSM 35, and for Propylene Selectivity up to 38%, propene yield does not have deactivation phenomenom up to 32% in 11h.And this method has the advantages of simple process, production efficiency is high.
Description
Technical field
The present invention relates to energy catalytic field, and in particular to a kind of fluorine richness molecular sieve H-ZSM-35 preparation method.
Background technology
Propylene can be used for producing the important chemical products such as polypropylene, expoxy propane, acetone, isopropanol, phenol, glycerine, be
The indispensable Chemical Manufacture raw material of development of modern society economy, but the less efficient of propylene is prepared at present, cause for should not
Ask, it is therefore desirable to the method for the efficient production propylene of exploitation.
The production path of halide propylene is ripe at present, and halide propylene needs molecular sieve catalyst,
Although this method improves the yield of propylene, but due to reasons such as the pore passage structure of molecular sieve catalyst, acidity, make its easy
Inactivation, therefore it is particularly important to prepare long catalytic life, stability is good, catalytic performance is high molecular sieve catalyst.
The content of the invention
The present invention is overcomes the shortcomings of that existing molecular sieve catalyst provides a kind of fluorine richness molecular sieve H-ZSM-35's
Preparation method.
Realize that technical solution of the invention is：A kind of fluorine richness molecular sieve H-ZSM-35 preparation method, including with
Lower step：
1. adding alkali source in aqueous, silicon source, silicon source and template are continuously added, stirs into uniform mixture colloid, then
By said mixture colloid crystallization 48h, filter, wash, dry, be calcined and produce molecular sieve H-ZSM-35；
2. molecular sieve H-ZSM-35 is pressed into solid-to-liquid ratio 1:20 are added in 0.02-0.04mol/L modifier aqueous solutions, stir 5 h,
Until molecular sieve H-ZSM-35 and modifying agent are sufficiently mixed, stand, be evaporated and fluorine richness molecular sieve H-ZSM-35 is made.
Preferably, 1. middle silicon source is sodium metaaluminate to the step, and silicon source is Ludox, and alkali source is sodium hydroxide, template
For pyrrolidines.
2. middle modifying agent can be that ammonium fluoride, fluosilicic acid or ammonium fluosilicate are any one or several to the step.
Preferably, the mol ratio of the step 1. middle mixture colloid is n (Na2O): n(Al2O3):n(SiO2) : n
(H2O):N (template)=1.56:1:50:600: 18.96.
Preferably, the step 2. in modifier aqueous solution be 0.03 mol/L ammonium fluoride aqueous solutions.
It is of the invention to be relative to beneficial effect caused by prior art：Add modifying agent, obtained fluorine richness molecular sieve H-
ZSM-35 has unique pore passage structure, suitable acidity, good stability and larger specific surface area, is chloromethane
Potential excellent catalysts in propylene reaction processed.In addition the catalysis of hydro carbons is can be also used for, is had wide range of applications.Adding
On the basis of fluorine so that the molecular sieve stability improves, and catalytic performance improves, and the life-span is elongated.Unmodified H-ZSM-35 is in chlorine
It is 57.4% for conversion ratio in methane, Propylene Selectivity 20.2%, propene yield 16.3%.Fluorine richness molecular sieve H-ZSM-35
Conversion ratio is up to 88.4% in chloromethane, and up to 38%, propene yield does not lose Propylene Selectivity up to 32% in 11h
Appear vividly as.And this method has the advantages of simple process, production efficiency is high.
Embodiment
The embodiment of form by the following examples, the above of the present invention is described in further details,
But the scope that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiment, all to be based on the above of the present invention
The technology of realization belongs to the scope of the present invention.
Embodiment 1
A kind of fluorine richness molecular sieve H-ZSM-35 preparation method, comprises the following steps：
1. adding alkali source in aqueous, silicon source, silicon source and pyrrolidines are continuously added, stirs into uniform mixture colloid, then
By said mixture colloid crystallization 48h, filter, wash, dry, be calcined and produce molecular sieve H-ZSM-35；Mixture colloid is rubbed
Your ratio is n (Na2O): n(Al2O3):n(SiO2) : n(H2O):N (pyrrolidines)=1.56:1:50:600: 18.96；Silicon source
For sodium metaaluminate, silicon source is Ludox, and alkali source is sodium hydroxide；
2. molecular sieve H-ZSM-35 is pressed into solid-to-liquid ratio 1:20 are added in 0.02mol/L ammonium fluoride aqueous solutions, stir 5 h, until
Molecular sieve H-ZSM-35 and modifying agent are sufficiently mixed, and are stood, and are evaporated and fluorine richness molecular sieve H-ZSM-35 is made.
Fluorine richness molecular sieve H-ZSM-35 catalyst prepared by embodiment 1 is used for the reaction of chloromethane propylene, chlorine
For conversion ratio in methane up to 76.1%, up to 24.7%, propene yield does not lose Propylene Selectivity up to 18.8% in 6h
Appear vividly as.
Embodiment 2
A kind of fluorine richness molecular sieve H-ZSM-35 preparation method, comprises the following steps：
1. adding alkali source in aqueous, silicon source, silicon source and pyrrolidines are continuously added, stirs into uniform mixture colloid, then
By said mixture colloid crystallization 48h, filter, wash, dry, be calcined and produce molecular sieve H-ZSM-35；Mixture colloid is rubbed
Your ratio is n (Na2O): n(Al2O3):n(SiO2) : n(H2O):N (pyrrolidines)=1.56:1:50:600: 18.96；Silicon source
For sodium metaaluminate, silicon source is Ludox, and alkali source is sodium hydroxide；
2. molecular sieve H-ZSM-35 is pressed into solid-to-liquid ratio 1:20 are added in 0.03mol/L ammonium fluoride aqueous solutions, stir 5 h, until
Molecular sieve H-ZSM-35 and modifying agent are sufficiently mixed, and are stood, and are evaporated and fluorine richness molecular sieve H-ZSM-35 is made.
Fluorine richness molecular sieve H-ZSM-35 catalyst prepared by embodiment 2 is used for the reaction of chloromethane propylene, chlorine
For conversion ratio in methane up to 88.4%, for Propylene Selectivity up to 38%, propene yield is existing without inactivation up to 32%, and in 11h
As.
Embodiment 3
A kind of fluorine richness molecular sieve H-ZSM-35 preparation method, comprises the following steps：
1. adding alkali source in aqueous, silicon source, silicon source and pyrrolidines are continuously added, stirs into uniform mixture colloid, then
By said mixture colloid crystallization 48h, filter, wash, dry, be calcined and produce molecular sieve H-ZSM-35；Mixture colloid is rubbed
Your ratio is n (Na2O): n(Al2O3):n(SiO2) : n(H2O):N (pyrrolidines)=1.56:1:50:600: 18.96；Silicon source
For sodium metaaluminate, silicon source is Ludox, and alkali source is sodium hydroxide；
2. molecular sieve H-ZSM-35 is pressed into solid-to-liquid ratio 1:20 are added in 0.04mol/L ammonium fluoride aqueous solutions, stir 5 h, until
Molecular sieve H-ZSM-35 and modifying agent are sufficiently mixed, and are stood, and are evaporated and fluorine richness molecular sieve H-ZSM-35 is made.
Fluorine richness molecular sieve H-ZSM-35 catalyst prepared by embodiment 3 is used for the reaction of chloromethane propylene, chlorine
For methane conversion up to 68%, up to 45%, propene yield starts to inactivate Propylene Selectivity up to 30%, 2h.
Reference examples 1
Alkali source is added in aqueous, continuously adds silicon source, silicon source and pyrrolidines, stirs into uniform mixture colloid, then will
Said mixture colloid crystallization 48h, filter, wash, dry, be calcined and produce molecular sieve H-ZSM-35；Mole of mixture colloid
Than for n (Na2O): n(Al2O3):n(SiO2) : n(H2O):N (pyrrolidines)=1.56:1:50:600: 18.96；Silicon source is
Sodium metaaluminate, silicon source are Ludox, and alkali source is sodium hydroxide.
Molecular sieve H-ZSM-35 catalyst prepared by reference examples 1 is used for the reaction of chloromethane propylene, chloromethane
Middle conversion ratio is 57.4%, Propylene Selectivity 20.2%, propene yield 16.3%, and 5h starts to inactivate.
Above example is explained and described to the synthetic ratio and method of modifying of the present invention, and of the present invention one
Kind fluorine richness molecular sieve H-ZSM-35 preparation method, there is provided catalytic performance is preferable, the fluorine richness molecular sieve lasted a long time, when
When Oil repellent is 0.03ml/L in modifier solution, prepared fluorine richness molecular sieve H-ZSM-35 performances are best, longest-lived,
Its in the reaction of chloromethane propylene conversion ratio up to 88.4%, Propylene Selectivity up to 38%, propene yield up to 32%, and
There is no deactivation phenomenom in 11h.This method technique is simple, method is convenient, has a good application prospect.
Claims (6)
1. a kind of fluorine richness molecular sieve H-ZSM-35 preparation method, it is characterised in that comprise the following steps：
1. adding alkali source in aqueous, silicon source, silicon source and template are continuously added, stirs into uniform mixture colloid, then
By said mixture colloid crystallization 48h, filter, wash, dry, be calcined and produce molecular sieve H-ZSM-35；
2. molecular sieve H-ZSM-35 is pressed into solid-to-liquid ratio 1:20 are added in 0.02-0.04mol/L modifier aqueous solutions, stir 5 h,
Stand, be evaporated and fluorine richness molecular sieve H-ZSM-35 is made.
2. fluorine richness molecular sieve H-ZSM-35 as claimed in claim 1 preparation method, it is characterised in that：The step 1. middle aluminium
Source is sodium metaaluminate, and silicon source is Ludox, and alkali source is sodium hydroxide, and template is pyrrolidines.
3. fluorine richness molecular sieve H-ZSM-35 as claimed in claim 1 preparation method, it is characterised in that：The step 2. in change
Property agent can be ammonium fluoride, fluosilicic acid or ammonium fluosilicate it is any one or several.
4. fluorine richness molecular sieve H-ZSM-35 as claimed in claim 1 preparation method, it is characterised in that the step 1. in mix
The mol ratio of compound colloid is n (Na2O): n(Al2O3):n(SiO2) : n(H2O):N (template)=1.56:1:50:
600: 18.96。
5. fluorine richness molecular sieve H-ZSM-35 as claimed in claim 1 preparation method, it is characterised in that the step 2. in
Modifier aqueous solution is 0.03 mol/L ammonium fluoride aqueous solutions.
6. the fluorine richness molecular sieve H-ZSM-35 prepared using claim 1-5 either method.
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Cited By (6)
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| CN108689416A (en) * | 2018-05-24 | 2018-10-23 | 河南师范大学 | A kind of preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves |
| CN108906119A (en) * | 2018-05-29 | 2018-11-30 | 河南师范大学 | A kind of preparation method of SAPO-34 composite molecular screen |
| CN110013875A (en) * | 2019-05-28 | 2019-07-16 | 河南师范大学 | A kind of preparation method of fluorine richness molecular sieve FER |
| CN110038629A (en) * | 2019-05-27 | 2019-07-23 | 河南师范大学 | A kind of preparation method of rare earth metal Nd doping H-ZSM-34 molecular sieve |
| CN113045392A (en) * | 2019-12-27 | 2021-06-29 | 中国科学院大连化学物理研究所 | Application of hierarchical pore molecular sieve in preparation of cyclopentadiene and JP-10 aviation fuel |
| CN114073976A (en) * | 2020-08-10 | 2022-02-22 | 中国科学院大连化学物理研究所 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689416A (en) * | 2018-05-24 | 2018-10-23 | 河南师范大学 | A kind of preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves |
| CN108906119A (en) * | 2018-05-29 | 2018-11-30 | 河南师范大学 | A kind of preparation method of SAPO-34 composite molecular screen |
| CN110038629A (en) * | 2019-05-27 | 2019-07-23 | 河南师范大学 | A kind of preparation method of rare earth metal Nd doping H-ZSM-34 molecular sieve |
| CN110013875A (en) * | 2019-05-28 | 2019-07-16 | 河南师范大学 | A kind of preparation method of fluorine richness molecular sieve FER |
| CN113045392A (en) * | 2019-12-27 | 2021-06-29 | 中国科学院大连化学物理研究所 | Application of hierarchical pore molecular sieve in preparation of cyclopentadiene and JP-10 aviation fuel |
| CN114073976A (en) * | 2020-08-10 | 2022-02-22 | 中国科学院大连化学物理研究所 | Modified ZSM-5 molecular sieve and preparation method and application thereof |
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Application publication date: 20171222 |