CN103145142B - Synthesis method of heteroatom-containing ZSM-39 molecular sieve - Google Patents
Synthesis method of heteroatom-containing ZSM-39 molecular sieve Download PDFInfo
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- CN103145142B CN103145142B CN201310047733.6A CN201310047733A CN103145142B CN 103145142 B CN103145142 B CN 103145142B CN 201310047733 A CN201310047733 A CN 201310047733A CN 103145142 B CN103145142 B CN 103145142B
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- molecular sieve
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- heteroatom
- sieve
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Abstract
The invention relates to a synthesis method of a heteroatom-containing ZSM-39 molecular sieve. The method comprises: mixing a silicon source, a heteroatom source, an alkali source, piperidine and water evenly into a gel, under certain temperature, subjecting the reaction mixture to hydrothermal crystallization under a self-generated pressure, and carrying out filtering, washing and drying so as to obtain a Ti, V, Cr, Fe, Co or Ni-containing heteroatom molecular sieve, the X-ray diffraction (XRD) spectrum of which has a structure of a ZSM-39 molecular sieve. The vibration frequency of an Si-O tetrahedron at the 800cm<-1> site in an infrared spectrum (IR) of the molecular sieve undergoes offset in a range of 778-813cm<-1>. The method disclosed in the invention is simple, practical and low in cost. Until now, no published report on the synthesis method of a heteroatom-containing ZSM-39 molecular sieve can be acquired.
Description
Technical field
The present invention relates to a kind of synthetic method of ZSM-39 molecular sieve, specifically a kind of taking piperidines as template, Hydrothermal Synthesis contains heteroatomic ZSM-39 Zeolite synthesis method.
Background technology
ZSM-39 zeolite is a kind of silica-rich zeolite that Mobile company of the U.S. successfully develops in late nineteen seventies, and skeleton structure is made up of five-membered ring and the basic construction unit of hexatomic ring, has the molecular sieve of MTN topological structure.This zeolite has stronger heat endurance, can be used for lubricating oil catalytic hydrogenation, improves lubricants performance.
The synthetic template that needs of most of molecular sieves, a kind of template can be prepared the molecular sieve of various structures, and same molecular sieve also can be prepared by various template agent.United States Patent (USP) 4,287, first 166 disclose the synthetic method of ZSM-39 molecular sieve, the method is taking tetraethyl ammonium hydroxide or n-propylamine as template, by silicon source, aluminium source, alkali metal source, template and water mixed with certain proportion, 160 DEG C of crystallization 70 hours, after reaction finishes, product through cooling, filter, wash with water and make.
Subsequently, United States Patent (USP) 4,259,306 disclose four urea cobalt complexs exist under be that template has synthesized ZSM-39 molecular sieve with pyrrolidines, use X ray powder diffracting technology to provide the crystal structure (J.L.Schlenker of ZSM-39 molecular sieve, F.G.D.wyer, E.F.Jwnkina, W.J.Rohrbaugh and G.T.kokotailo, Nature, 246,340,1981).
The ZSM-39 molecular sieve of preparing with said method, is Si-Al molecular sieve, has limited its application.Hetero-atom molecular-sieve is to utilize other element that the silicon in framework of molecular sieve or the aluminium isomorphous are replaced, and keeps the skeleton structure of molecular sieve not change.Symmetrical stretching vibration frequency 800 cm of Si-O limbs face in framework of molecular sieve
-1, after framework silicon is replaced by other hetero atom, its stretching vibration frequency is offset, and can be used as and judges whether hetero atom enters the evidence of framework of molecular sieve.In hetero-atom molecular-sieve skeleton, owing to having introduced specific nonmetal or metallic atom, can modulation parent molecule the acidity of sieve, oxidation-reduction quality and catalytic activity thereof or other function.By modulation or modification, these hetero-atom molecular-sieves can become good catalysis material, or other has the functional material of property.Up to the present, also fail to obtain disclosed relevant contain heteroatomic ZSM-39 molecular sieve and synthetic method thereof.
Summary of the invention
The object of the present invention is to provide one taking piperidines as template, containing hetero atom is the ZSM-39 Zeolite synthesis method of Ti, V, Cr, Fe, Co or Ni.
Realizing above-mentioned purpose of the present invention is achieved through the following technical solutions.
One contains heteroatomic ZSM-39 Zeolite synthesis method, and the hetero atom that described in it, method adopts is nitrate or the chloride (representing with M) of Ti, V, Cr, Fe, Co or Ni, and silicon source is that white carbon is (with SiO
2represent), alkali source is that NaOH is (with OH
-represent), organic formwork agent is piperidines (representing with PI); Described in it, method is to be in molar ratio: M:SiO
2 :oH
-: PI
:h
2o=0.01 ~ 0.3
:1
:1.5
:1.4
:19; At room temperature even hybrid reaction plastic; Again reactant mixture is carried out to hydrothermal crystallizing 3 ~ 10 days under 150 ~ 200 DEG C and self-generated pressure, washing after filtration,, dry, obtain a kind of hetero-atom molecular-sieve that contains Ti, V, Cr, Fe, Co or Ni, its XRD spectra contains ZSM-39 structure molecular screen, 800cm in its infrared spectrum (IR)
-1the tetrahedral vibration frequency of the Si-O of place is offset, and scope is at 778-813cm
-1.
In above-mentioned technical scheme, hetero atom/SiO described in it
2mol ratio further elects 0.03 as; Hydrothermal crystallizing temperature is further elected 170 ~ 180 DEG C as; The hydrothermal crystallizing time is further elected 5 ~ 7 days as.
Realize one provided by the present invention and contain heteroatomic ZSM-39 Zeolite synthesis method, compared with prior art, the advantage and the good effect that have are:
It is taking piperidines as template that the present invention contains heteroatomic ZSM-39 Zeolite synthesis method, hydrothermal crystallizing synthesized under self-generated pressure, be the hetero-atom molecular-sieve of a kind of Ti of containing, V, Cr, Fe, Co or Ni, there is the X ray diffracting characteristic of conventional ZSM-39 molecular sieve.Hetero atom enters framework of molecular sieve, makes hetero atom have higher dispersiveness and stability, has good facilitation to improving its reactivity and stability.This molecular sieve analog, owing to having unique structure and acidic character, therefore can, for the catalyst in hydrocarbon conversion reactions and catalyst carrier, have special activity and selectivity in some hydro carbons chemical reaction process.This synthetic method simple possible, synthetic with low cost, there is wide application and application prospect.
Brief description of the drawings
Fig. 1 is the XRD figure of the embodiment of the present invention 1 sieve sample that obtains.
Fig. 2 is the IR figure of the embodiment of the present invention 1 sieve sample that obtains.
Fig. 3 is the XRD figure of the embodiment of the present invention 2 sieve sample that obtains.
Fig. 4 is the IR figure of the embodiment of the present invention 2 sieve sample that obtains.
Fig. 5 is the XRD figure of the embodiment of the present invention 3 sieve sample that obtains.
Fig. 6 is the IR figure of the embodiment of the present invention 3 sieve sample that obtains.
Fig. 7 is the XRD figure of the embodiment of the present invention 4 sieve sample that obtains.
Fig. 8 is the IR figure of the embodiment of the present invention 4 sieve sample that obtains.
Fig. 9 is the XRD figure of the embodiment of the present invention 5 sieve sample that obtains.
Figure 10 is the IR figure of the embodiment of the present invention 5 sieve sample that obtains.
Figure 11 is the XRD figure of the embodiment of the present invention 6 sieve sample that obtains.
Figure 12 is the IR figure of the embodiment of the present invention 6 sieve sample that obtains.
Detailed description of the invention
Below the specific embodiment of the present invention is further illustrated.
Embodiment 1
By 0.41g anhydrous ferric chloride, 4.99 g NaOH, 5.0g white carbon, 9.92 g piperidines and 28.46 g water mixing and stirring, make gel, gained reactant mixture is Fe in molar ratio
2o
3: SiO
2: OH
-: PI: H
2o is 0.015
:1
:1.5
:1.4
:19, then described reactant mixture is sealed in band teflon-lined stainless steel autoclave, in 180 DEG C of hydrothermal crystallizing taking-ups afterwards in 7 days under self-generated pressure, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with ionized water washing, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through xrf analysis method
2/ Fe
2o
3be 70, X-ray diffraction (XRD) figure of sample is shown in accompanying drawing 1, and infared spectrum (IR) figure of sample is shown in accompanying drawing 2.
Embodiment 2
By 0.47g titanium tetrachloride, 4.99 g NaOH, 5.0g white carbon, 9.92 g piperidines and 28.46 g water mixing and stirring, make gel, gained reactant mixture is TiO in molar ratio
2: SiO
2: OH
-: PI:H
2o is 0.03:1:1.5:1.4:19, then described reactant mixture is sealed in band teflon-lined stainless steel autoclave, within 6 days, take out afterwards in 175 DEG C of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with ionized water washing, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through xrf analysis method
2/ TiO
2be 35, X-ray diffraction (XRD) figure of sample is shown in accompanying drawing 3, and infared spectrum (IR) figure of sample is shown in accompanying drawing 4.
Embodiment 3
By 0.39g vanadium trichloride, 4.99 g NaOH, 5.0g white carbon, 9.92 g piperidines and 28.46 g water mixing and stirring, make gel, gained reactant mixture is V in molar ratio
2o
5: SiO
2: OH
-: PI:H
2o is 0.015:1:1.5:1.4:19, then described reactant mixture is sealed in band teflon-lined stainless steel autoclave, within 5 days, take out afterwards in 180 DEG C of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with ionized water washing, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through xrf analysis method
2/ V
2o
5be 71, X-ray diffraction (XRD) figure of sample is shown in accompanying drawing 5, and infared spectrum (IR) figure of sample is shown in accompanying drawing 6.
Embodiment 4
0.72g cabaltous nitrate hexahydrate, 4.99 g NaOH, 5.0g white carbon, 9.92 g piperidines and 28.19g water are mixed, stir, make gel, gained reactant mixture is Co in molar ratio
2o
3: SiO
2: OH
-: PI:H
2o is 0.015:1:1.5:1.4:19, then described reactant mixture is sealed in band teflon-lined stainless steel autoclave, within 6 days, take out afterwards in 175 DEG C of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with ionized water washing, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through xrf analysis method
2/ Co
2o
3be 68, X-ray diffraction (XRD) figure of sample is shown in accompanying drawing 7, and infared spectrum (IR) figure of sample is shown in accompanying drawing 8.
Embodiment 5
1.00g Chromium nitrate (Cr(NO3)3),nonahydrate, 4.99 g NaOH, 5.0g white carbon, 9.92 g piperidines and 28.10g water are mixed, stir, make gel, gained reactant mixture is Cr in molar ratio
2o
3: SiO
2: OH
-: PI:H
2o is 0.015:1:1.5:1.4:19, then described reactant mixture is sealed in band teflon-lined stainless steel autoclave, within 6 days, take out afterwards in 180 DEG C of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with ionized water washing, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through xrf analysis method
2/ Cr
2o
3be 73, X-ray diffraction (XRD) figure of sample is shown in accompanying drawing 9, and infared spectrum (IR) figure of sample is shown in accompanying drawing 10.
Embodiment 6
0.73g Nickelous nitrate hexahydrate, 4.99 g NaOH, 5.0g white carbon, 9.92 g piperidines and 28.19g water are mixed, stir, make gel, gained reactant mixture is NiO:SiO in molar ratio
2: OH
-: PI:H
2o is 0.03:1:1.5:1.4:19, then described reactant mixture is sealed in band teflon-lined stainless steel autoclave, within 5 days, take out afterwards in 170 DEG C of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with ionized water washing, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through xrf analysis method
2/ NiO is 42, and X-ray diffraction (XRD) figure of sample is shown in accompanying drawing 11, and infared spectrum (IR) figure of sample is shown in accompanying drawing 12.
Claims (1)
1. contain a heteroatomic ZSM-39 Zeolite synthesis method, the hetero atom that described in it, method adopts is nitrate or the chloride of Ti, V, Cr, Fe, Co or Ni, and silicon source is white carbon, and alkali source is NaOH, and organic formwork agent is piperidines; Described in it, method is to be in molar ratio: hetero atom: SiO
2 :oH
-: piperidines
:h
2o=0.3
:1
:1.5
:1.4
:19 preparation reactant mixtures; Then reactant mixture is carried out to hydrothermal crystallizing 5 ~ 7 days under 170 ~ 180 DEG C and self-generated pressure, after crystallization completes, washing after filtration,, dry, obtain a kind of hetero-atom molecular-sieve that contains Ti, V, Cr, Fe, Co or Ni, its XRD spectra contains ZSM-39 structure molecular screen, 800cm in its infrared spectrum
-1the tetrahedral vibration frequency of the Si-O of place is offset, and scope is at 778-813cm
-1.
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| CN105217647B (en) * | 2014-07-03 | 2017-07-14 | 中国石油化工股份有限公司 | The Zeolite synthesis methods of sheet ZSM 39 |
| CN105152181B (en) * | 2015-08-27 | 2017-10-10 | 华东师范大学 | A kind of preparation method of the MTN topological structure molecular sieves of total silicon type |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806918A (en) * | 2005-12-21 | 2006-07-26 | 华东师范大学 | Synthesis method of titanium-containing molecular sieve |
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806918A (en) * | 2005-12-21 | 2006-07-26 | 华东师范大学 | Synthesis method of titanium-containing molecular sieve |
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
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