CN103145142A - Synthesis method of heteroatom-containing ZSM-39 molecular sieve - Google Patents

Synthesis method of heteroatom-containing ZSM-39 molecular sieve Download PDF

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CN103145142A
CN103145142A CN2013100477336A CN201310047733A CN103145142A CN 103145142 A CN103145142 A CN 103145142A CN 2013100477336 A CN2013100477336 A CN 2013100477336A CN 201310047733 A CN201310047733 A CN 201310047733A CN 103145142 A CN103145142 A CN 103145142A
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molecular sieve
zsm
heteroatom
sieve
heteroatoms
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CN103145142B (en
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沈小华
薛春峰
张彩丽
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Taiyuan University of Technology
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Taiyuan University of Technology
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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

A kind ofly contain heteroatomic ZSM-39 Zeolite synthesis method
Technical field
The present invention relates to a kind of synthetic method of ZSM-39 molecular sieve, specifically a kind of take piperidines as template, Hydrothermal Synthesis contains heteroatomic ZSM-39 Zeolite synthesis method.
Background technology
The ZSM-39 zeolite be U.S. Mobile company in a kind of supersiliceous zeolite of late nineteen seventies develop, skeleton structure is made of five-ring and the basic structural unit of six-ring, has the molecular sieve of MTN topological framework.This zeolite has stronger thermostability, can be used for the lubricating oil shortening, improves lubricants performance.
The synthetic template that needs of most of molecular sieves, a kind of template can prepare the molecular sieve of various structures, and the same molecular sieve also can be prepared by the various template agent.United States Patent (USP) 4,287, at first 166 disclose the synthetic method of ZSM-39 molecular sieve, the method is take tetraethyl ammonium hydroxide or Tri N-Propyl Amine as template, be about to silicon source, aluminium source, alkali metal source, template and water mixed with certain proportion, 160 ℃ of crystallization 70 hours, after reaction finishes, product through cooling, filter, wash with water and make.
Subsequently, United States Patent (USP) 4,259,306 to disclose under four urea cobalt complexs exist be that template has been synthesized the ZSM-39 molecular sieve with tetramethyleneimine, use X ray powder diffracting technology to provide the crystalline 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).
ZSM-39 molecular sieve with the aforesaid method preparation is Si-Al molecular sieve, has limited its application.Hetero-atom molecular-sieve is to utilize other element with the silicon in framework of molecular sieve or aluminium isomorphous substitution, 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 was replaced by other heteroatoms, its stretching vibration frequency was offset, and can be used as to judge whether heteroatoms enters the evidence of framework of molecular sieve.In the hetero-atom molecular-sieve skeleton, owing to having introduced specific nonmetal or atoms metal, acidity that can modulation parent molecule sieve, oxidation-reduction quality and catalytic activity thereof or other function.By modulation or modification, these hetero-atom molecular-sieves can become good catalytic material, or other has the functional materials 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 a kind ofly take piperidines as template, containing heteroatoms is the ZSM-39 Zeolite synthesis method of Ti, V, Cr, Fe, Co or Ni.
Realize that above-mentioned purpose of the present invention is achieved through the following technical solutions.
A kind ofly contain heteroatomic ZSM-39 Zeolite synthesis method, the heteroatoms that its described method adopts is nitrate or the muriate (representing with M) of Ti, V, Cr, Fe, Co or Ni, and the silicon source is that white carbon black is (with SiO 2Expression), alkali source is that sodium hydroxide is (with OH -Expression), organic formwork agent is piperidines (representing with PI); Its described method is to be in molar ratio: M:SiO 2 :OH -: PI :H 2O=0.01 ~ 0.3 :1 :1.5 :1.4 :19; Even hybrid reaction plastic at room temperature; Again reaction mixture was carried out hydrothermal crystallizing 3 ~ 10 days under 150 ~ 200 ℃ and autogenous pressure, washing after filtration,, drying, obtain a kind of hetero-atom molecular-sieve that contains Ti, V, Cr, Fe, Co or Ni, its XRD spectra contains the ZSM-39 structure molecular screen, 800cm in its infrared spectra (IR) -1The tetrahedral vibrational frequency of the Si-O of place is offset, and scope is at 778-813cm -1
In above-mentioned technical scheme, its described heteroatoms/SiO 2Mol ratio further elects 0.03 as; The hydrothermal crystallizing temperature is further elected 170 ~ 180 ℃ as; The hydrothermal crystallizing time is further elected 5 ~ 7 days as.
Realize a kind of heteroatomic ZSM-39 Zeolite synthesis method that contains provided by the present invention, compared with prior art, the advantage and the positively effect that have are:
It is take piperidines as template that the present invention contains heteroatomic ZSM-39 Zeolite synthesis method, what hydrothermal crystallizing synthesized under autogenous pressure, be the hetero-atom molecular-sieve of a kind of Ti of containing, V, Cr, Fe, Co or Ni, have the X ray diffracting characteristic of conventional ZSM-39 molecular sieve.Heteroatoms enters framework of molecular sieve, makes heteroatoms have higher dispersiveness and stable, to improving its reactive behavior and stability, promoter action is preferably arranged.Therefore this molecular sieve analog can be used for catalyzer and the support of the catalyst of hydrocarbon conversion reactions owing to having unique structure and acidic character, in some hydro carbons chemical reaction process, special activity and selectivity is arranged.This synthetic method simple possible, synthetic with low cost, have wide Application Areas and application prospect.
Description of 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.
Embodiment
The below is further illustrated the specific embodiment of the present invention.
Embodiment 1
With 0.41g Anhydrous Ferric Chloride, 4.99 g sodium hydroxide, 5.0g white carbon black, 9.92 g piperidines and 28.46 g water mixing and stirring, make gel, the gained reaction 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 reaction mixture is sealed in band teflon-lined stainless steel autoclave, in 180 ℃ of hydrothermal crystallizing taking-ups afterwards in 7 days under autogenous pressure, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with the ionized water washing, 100 ℃ of dried overnight, namely get product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through the xrf analysis method 2/ Fe 2O 3Be 70, the X-ray diffraction of sample (XRD) figure sees accompanying drawing 1, and the infared spectrum of sample (IR) figure sees accompanying drawing 2.
Embodiment 2
With 0.47g titanium tetrachloride, 4.99 g sodium hydroxide, 5.0g white carbon black, 9.92 g piperidines and 28.46 g water mixing and stirring, make gel, the gained reaction mixture is TiO in molar ratio 2: SiO 2: OH -: PI:H 2O is 0.03:1:1.5:1.4:19, then described reaction mixture is sealed in band teflon-lined stainless steel autoclave, took out afterwards in 6 days in 175 ℃ of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with the ionized water washing, 100 ℃ of dried overnight, namely get product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through the xrf analysis method 2/ TiO 2Be 35, the X-ray diffraction of sample (XRD) figure sees accompanying drawing 3, and the infared spectrum of sample (IR) figure sees accompanying drawing 4.
Embodiment 3
With 0.39g vanadium trichloride, 4.99 g sodium hydroxide, 5.0g white carbon black, 9.92 g piperidines and 28.46 g water mixing and stirring, make gel, the gained reaction 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 reaction mixture is sealed in band teflon-lined stainless steel autoclave, took out afterwards in 5 days in 180 ℃ of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with the ionized water washing, 100 ℃ of dried overnight, namely get product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through the xrf analysis method 2/ V 2O 5Be 71, the X-ray diffraction of sample (XRD) figure sees accompanying drawing 5, and the infared spectrum of sample (IR) figure sees accompanying drawing 6.
Embodiment 4
0.72g Cobaltous nitrate hexahydrate, 4.99 g sodium hydroxide, 5.0g white carbon black, 9.92 g piperidines and 28.19g water are mixed, stir, make gel, the gained reaction 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 reaction mixture is sealed in band teflon-lined stainless steel autoclave, took out afterwards in 6 days in 175 ℃ of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with the ionized water washing, 100 ℃ of dried overnight, namely get product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through the xrf analysis method 2/ Co 2O 3Be 68, the X-ray diffraction of sample (XRD) figure sees accompanying drawing 7, and the infared spectrum of sample (IR) figure sees accompanying drawing 8.
Embodiment 5
1.00g Chromium trinitrate nonahydrate, 4.99 g sodium hydroxide, 5.0g white carbon black, 9.92 g piperidines and 28.10g water are mixed, stir, make gel, the gained reaction 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 reaction mixture is sealed in band teflon-lined stainless steel autoclave, took out afterwards in 6 days in 180 ℃ of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with the ionized water washing, 100 ℃ of dried overnight, namely get product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through the xrf analysis method 2/ Cr 2O 3Be 73, the X-ray diffraction of sample (XRD) figure sees accompanying drawing 9, and the infared spectrum of sample (IR) figure sees accompanying drawing 10.
Embodiment 6
0.73g Nickelous nitrate hexahydrate, 4.99 g sodium hydroxide, 5.0g white carbon black, 9.92 g piperidines and 28.19g water are mixed, stir, make gel, the gained reaction mixture is NiO:SiO in molar ratio 2: OH -: PI:H 2O is 0.03:1:1.5:1.4:19, then described reaction mixture is sealed in band teflon-lined stainless steel autoclave, took out afterwards in 5 days in 170 ℃ of hydrothermal crystallizings, reactor drops to rapidly room temperature, filters out solid product, and extremely neutral with the ionized water washing, 100 ℃ of dried overnight, namely get product, verify as the crystal phase structure of ZSM-39 molecular sieve through X-ray diffraction (XRD), measure SiO through the xrf analysis method 2/ NiO is 42, and the X-ray diffraction of sample (XRD) figure sees accompanying drawing 11, and the infared spectrum of sample (IR) figure sees accompanying drawing 12.

Claims (4)

1. one kind contains heteroatomic ZSM-39 Zeolite synthesis method, and the heteroatoms that its described method adopts is nitrate or the muriate of Ti, V, Cr, Fe, Co or Ni, and the silicon source is white carbon black, and alkali source is sodium hydroxide, and organic formwork agent is piperidines; Its described method is to be in molar ratio: heteroatoms: SiO 2 :OH -: piperidines :H 2O=0.01 ~ 0.3 :1 :1.5 :1.4 :19 preparation reaction mixtures; Then reaction mixture was carried out hydrothermal crystallizing 5 ~ 10 days under 150 ~ 200 ℃ and autogenous pressure, after crystallization is completed, washing after filtration,, drying, obtain a kind of hetero-atom molecular-sieve that contains Ti, V, Cr, Fe, Co or Ni, its XRD spectra contains the ZSM-39 structure molecular screen, 800cm in its infrared spectra -1The tetrahedral vibrational frequency of the Si-O of place is offset, and scope is at 778-813cm -1
2. synthetic method as claimed in claim 1, its described heteroatoms/SiO 2Mol ratio further elects 0.03 as.
3. synthetic method as claimed in claim 1, its described hydrothermal crystallizing temperature is further elected 170 ~ 180 ℃ as.
4. synthetic method as claimed in claim 1, its described hydrothermal crystallizing time is further elected 5 ~ 7 days as.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105152181A (en) * 2015-08-27 2015-12-16 华东师范大学 Preparation method of all-silicon MTN topology structure molecular sieve
CN105217647A (en) * 2014-07-03 2016-01-06 中国石油化工股份有限公司 Sheet ZSM-39 Zeolite synthesis method
CN111870126A (en) * 2019-05-03 2020-11-03 纬创资通股份有限公司 Extraction device and extraction method

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105217647A (en) * 2014-07-03 2016-01-06 中国石油化工股份有限公司 Sheet ZSM-39 Zeolite synthesis method
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
CN105152181A (en) * 2015-08-27 2015-12-16 华东师范大学 Preparation method of all-silicon MTN topology structure molecular sieve
CN111870126A (en) * 2019-05-03 2020-11-03 纬创资通股份有限公司 Extraction device and extraction method
CN111870126B (en) * 2019-05-03 2022-07-22 纬创资通股份有限公司 Extraction device and extraction method

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