CN105293519A - Synthesis method of ZSM-5/Y composite molecular sieve without using template - Google Patents
Synthesis method of ZSM-5/Y composite molecular sieve without using template Download PDFInfo
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- CN105293519A CN105293519A CN201510803955.5A CN201510803955A CN105293519A CN 105293519 A CN105293519 A CN 105293519A CN 201510803955 A CN201510803955 A CN 201510803955A CN 105293519 A CN105293519 A CN 105293519A
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Abstract
The invention discloses a synthesis method of a ZSM-5/Y composite molecular sieve without using a template. The synthesis method comprises the following steps: (1) mixing an aluminum source, sodium hydroxide, and deionized water, evenly stirring, then adding a silicon source, stirring until a uniform gel is formed, pouring the gel into a stainless steel reactor with a polytetrafluoroethylene lining, and carrying out crystallization for 2 to 7 days at a temperature of 140 to 200 DEG C; (2) repeatedly washing the products obtained in the step (1) by deionized water until the products become neutral, and drying the products to obtain ZSM-5 type molecular sieve; (3) adding an aluminum source and a Y type molecular sieve guiding agent into the ZSM-5 type molecular sieve, and carrying out crystallization for 16 to 40 hours at a temperature of 90 to 120 DEG C to obtain a composite material containing ZSM-5/Y type molecular sieves; (4) washing the product obtained in the step (3) by deionized water until the product becomes neutral, and drying the product to obtain the ZSM-5/Y composite molecular sieve. The provided synthesis method overcomes the shortages that the conventional synthesis method uses a template, the cost is high, and the environment is polluted.
Description
Technical field
The invention belongs to the preparing technical field of molecular sieve, be specifically related to the method for a kind of Template-free method method synthesis ZSM-5/Y composite molecular screen.
Background technology
ZSM-5 molecular sieve be connected by oxo bridge key by silicon-oxy tetrahedron or aluminum-oxygen tetrahedron and formed there is two-dimentional ten-ring duct, one is ten-ring straight hole road, and another is the ten-ring duct with Z-shaped shape.ZSM-5 molecular sieve have stable skeleton structure, can the aperture of modulation, higher specific surface, preferably shape selectivity; Be mainly used in the fields such as catalytic cracking, alkylation, isomerization, aromizing, esterification and low-carbon alkene conversion.The β cage that y-type zeolite skeleton is consisted of oxo bridge primarily of silicon-oxy tetrahedron or aluminum-oxygen tetrahedron is formed; There is the advantages such as activity is high, selectivity good, good stability, be mainly used in the field such as catalytic cracking, hydrocracking.Although Y zeolite is the support of the catalyst comparatively commonly used, due to the restriction of its pore passage structure, as catalyzer in catalytic cracking reaction, the problems such as gasoline octane rating is too low, cracking is insufficient can be caused.ZSM-5 molecular sieve can make up this defect of Y zeolite just, effectively improves the octane value of product gasoline and the productive rate of C3-C4 alkene.
Prior synthesizing method will adopt expensive organic formwork agent to obtain, and cost is high, needs high-temperature roasting to remove, and removes and not exclusively easily causes duct to block, cause environmental pollution simultaneously.And high-temperature roasting also easily causes zeolite small-particle to sinter, and not easily disperses.
CN102019367A discloses the preparation method of a kind of adhesiveless ZSM-5/Y zeolite Intergrown molecular sieve catalyst, by adopting with the catalyst weight after shaping and roasting, after the compound of the ZSM-5/Y zeolite coexisting molecular sieve of 10 ~ 80%, the aluminium of 0.1 ~ 10% alkaline matter 0.5 ~ 20% and the silicon oxide mixing of 20 ~ 80%, shaping, drying, put into water vapor, carry out Crystallizing treatment at 100 ~ 180 DEG C and after 10 ~ 200 hours, obtain adhesiveless ZSM-5/Y zeolite Intergrown molecular sieve catalyst.
CN101767034A discloses a kind of preparation method containing ZSM-5/Y type composite molecular screen catalytic material, comprise the following steps: solid slag mixes with silicon source, aluminium source and pulls an oar by (1), make its stable uniform, and make it consist of: the Na containing 2.5 ~ 8wt%
2the SiO of O, 25 ~ 65wt%
2, the Al of 18 ~ 55wt%
2o
3; (2) by obtain in step (1) dry materials, 600 ~ 1100 DEG C of roastings 0.5 ~ 4 hour; (3) by the material in step (2) and sodium salt, acid or carry out ion-exchange by salt, to remove the harmful ion contained in waste residue; (4) material in step (3) is added silicon source, acid and directed agents, 90 ~ 120 DEG C of crystallization 8 ~ 48 hours, prepare the catalytic material containing Y zeolite; (5) add template again after being cooled by the catalytic material prepared in step (3) containing Y zeolite and adjust its pH value between 9.5 ~ 11.5, continue crystallization 8 ~ 36 hours at 140 ~ 180 DEG C, obtain the catalytic material containing ZSM-5/Y type composite molecular screen.
CN101239327A by kaolin after 1000 ~ 1400 DEG C of roastings, mix with Y type or ZSM-5 molecular sieve crystal seed, binding agent, structural promoter and water, extruded moulding, re-baking is carried out at 600 ~ 900 DEG C, then hydrothermal crystallizing is carried out by the synthesis condition of ZSM-5 molecular sieve or NaY molecular sieve, simultaneously containing ZSM-5 and Y zeolite in the product obtained.The feature of this patent is first to be mixed with raw materials such as kaolin by relatively large a kind of molecular sieve crystal seed, and then alternatively the crystallization condition of molecular sieve prepares the composite molecular screen of Y type and ZSM-5.
CN103043679A discloses a kind of synthetic method of Y zeolite, the method is whole silicon source using natural mineral as Zeolite synthesis and aluminium source, described natural mineral is the mixture of low silica-alumina ratio mineral and high silicon mine, the two is mixed by a certain percentage, carries out crystallization after roasting obtain product Y zeolite under hydrothermal condition.In this molecular screen material, Y zeolite is 70 ~ 95wt% relative to the relative crystallinity of the conventional Y zeolite taking chemical reagent as Material synthesis, and by regulating the ratio of two kinds of mineral in synthesis material, can the silica alumina ratio of Molecular regulator sieve product.The method extends raw material range prepared by molecular screen material, not only significantly can reduce the production cost of molecular sieve, and considerably improve the spatter property of molecular screen material production process.
Chen Honglin, Shen double-edged sword etc. (ChemistryLetters, the 32nd volume the 8th phase in 2003) in articles such as " InsituFormationofZSM-5inNayGelandCharacterizationofZSM-5/YCompositeZeolite " adopt template agent method and crystal seed method to synthesize ZSM-5/Y composite molecular screen.
Jia Wei, Guo Qun etc. (the 35th volume the 9th phase in 2006) in articles such as " taking quadrol as template synthesis Y/ZSM-5 composite molecular screen " are template with quadrol, adopt two step crystallization methods, the basis of formerly synthesizing ZSM-5 molecular sieve synthesizes the Y/ZSM-5 composite molecular screen with two microvoid structure, investigates proportioning raw materials and pH value of solution to the impact of synthetic product; Adopt X-ray diffraction, N
2adsorption-desorption, Fourier transform infrared spectroscopy, scanning electronic microscope and NH
3temperature Programmed Desorption characterizes Y/ZSM-5 composite molecular screen, and compares with the mechanical mixture of Y type and ZSM-5 molecular sieve; Have studied the catalytic performance of Y/ZSM-5 composite molecular screen to butane cracking and aromatization.
Xu Shibin, Wang Xuan etc. in articles such as " preparation of ZSM-5/Y composite molecular sieves and the explorations of composite structure Forming Mechanism thereof " (the 40th volume the 10th phase in 2012) using industrial ZSM-5 molecular sieve as silicon source, adopt hydrothermal method to prepare ZSM-5/Y composite molecular sieves, and X-ray diffraction (XRD), N have been carried out to it
2absorption (BET), nucleus magnetic resonance (NMR) and scanning electron microscope (SEM) characterize.
The part material that Pan Meng, Liu Yujian, Zheng Jiajun etc. in articles such as " ZSM-5/Y Zeolite catalytic materials are prepared in the depolymerization based on y-type zeolite " (the 31st volume the 2nd phase in 2015) grow using the industrial NaY zeolite silicon that slow depolymerization is formed under alkaline environment, aluminium species as ZSM-5 zeolite, by adding suitable silicon species and template etc., successfully obtain the ZSM-5/Y Zeolite catalytic materials with nucleocapsid structure.Adopt the material to synthesis such as XRD, FT-IR, NH3-TPD, SEM, EDS to characterize, and have rated the catalytic activity of this matrix material as catalyst for cracking using the catalytic cracking reaction of isopropyl benzene and heptane, and compare with corresponding mechanical mixture.
Summary of the invention
The object of this invention is to provide the synthetic method of a kind of Template-free method method synthesis ZSM-5/Y composite molecular screen, solve in existing composite molecular screen building-up process and use template, the problems such as cost is higher, contaminate environment.
For achieving the above object, the technical solution used in the present invention is, a kind of method of Template-free method method synthesis ZSM-5/Y composite molecular screen, comprises the following steps:
(1) by aluminium source, sodium hydroxide and deionized water mixing, and to stir, then add silicon source, be stirred to formation homogeneous gel, gel to be poured in teflon-lined stainless steel cauldron at 140 ~ 200 DEG C into crystallization 2 ~ 7 days;
(2) the product deionized water obtained in step (1) is washed repeatedly paint to neutral, dry, obtain type ZSM 5 molecular sieve;
(3) add aluminium source and Y zeolite directed agents in the type ZSM 5 molecular sieve obtained in step (2), crystallization 16 ~ 40h at 90 ~ 120 DEG C, obtains the matrix material containing ZSM-5/Y type molecular sieve;
(4) product in step (3) is extremely neutral with deionized water wash, dry, obtain ZSM-5/Y composite molecular screen.
Composition (mol ratio) Na of the product obtained in step (1)
2o:SiO
2: Al
2o
3: H
2o=8 ~ 21:25 ~ 60:1:1000 ~ 5000.
In described step (3) containing ZSM-5/Y type molecular sieve matrix material in SiO
2with Al
2o
3mol ratio be 15 ~ 40:1
In step (1) and (3), aluminium source is one or more in Alumina gel, Tai-Ace S 150, aluminum isopropylate, sodium metaaluminate and sodium aluminate.
Silicon source in described step (1) is any one or more in silicon sol, water glass, tetraethoxy, water glass and white carbon black etc.
Y zeolite directed agents general conventional directed agents during Y zeolite can be selected to synthesize in described step (3), is preferably and mole consists of Na
2o:SiO
2: Al
2o
3: H
2the Y zeolite directed agents of O=13 ~ 16:12 ~ 18:1:300 ~ 350.
The beneficial effect that the present invention produces does not use template in the present invention, solves in existing composite molecular screen building-up process and use the problems such as template, cost are higher, contaminate environment.Meanwhile, in ZSM-5/Y composite molecular screen building-up process of the present invention, the mother liquor of ZSM-5 molecular sieve obtains utilization, has saved resource, has reduced cost.
Accompanying drawing explanation
The XRD spectrum of the ZSM-5/Y composite molecular screen of Fig. 1 synthesized by embodiment 1 and control experiment 1;
Fig. 2 is the SEM photo of the ZSM-5/Y composite molecular screen product in controlled trial 1 synthesized by template agent method;
The SEM photo of the ZSM-5/Y composite molecular screen of Fig. 3 synthesized by embodiment 1.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but protection scope of the present invention is not limited thereto.
Embodiment 1
A method for Template-free method method synthesis ZSM-5/Y composite molecular screen, comprises the following steps:
(1) sodium metaaluminate, sodium hydroxide and deionized water are mixed, and stir, then tetraethoxy is added, vigorous stirring is to forming homogeneous gel, gel to be poured in teflon-lined stainless steel cauldron at 175 DEG C into crystallization 5 days, the composition (mol ratio) of the product obtained is Na
2o:SiO
2: Al
2o
3: H
2o=15:45:1:2000.；
(2) it is neutral for the product deionized water obtained in step (1) being washed repeatedly paint to pH value, dries, obtains type ZSM 5 molecular sieve;
(3) add sodium metaaluminate and Y zeolite directed agents in the type ZSM 5 molecular sieve obtained in step (2) and (mole consist of Na
2o:SiO
2: Al
2o
3: H
2o=15:16:1:320), crystallization 25h at 100 DEG C, obtains matrix material (wherein, the SiO containing ZSM-5/Y type molecular sieve
2with Al
2o
3mol ratio be 25:1);
(4) be neutral by the product deionized water wash in step (3) to pH value, dry at 100 DEG C, obtain ZSM-5/Y composite molecular screen.
Controlled trial 1
Take tetraethoxy as silicon source, sodium metaaluminate is aluminium source, and quadrol (EDA) is template, as follows for the process of ZSM-5/Y composite molecular screen by static hydrothermal synthesis legal system:
(1) be dissolved in the deionized water of 20mL by a certain amount of NaOH, the template quadrol adding metering is dissolved in above-mentioned solution, adds tetraethoxy after stirring;
(2) by NaAlO
2be dissolved in deionized water, be added dropwise in the mixing solutions of step (1), stir 5h under normal temperature, form colloidal sol, gel composition (mol ratio) is Na
2o:SiO
2: Al
2o
3: EDA:H
2o=3.5:40:1:13:1300;
(3) step (2) colloidal sol is loaded in autoclave, to be transferred in baking oven at 175 DEG C crystallization 2 days;
(4) the product deionized water wash will obtained in step (3), dries, obtains type ZSM 5 molecular sieve;
(5) add sodium metaaluminate and Y zeolite directed agents in the type ZSM 5 molecular sieve obtained in step (3) and (mole consist of Na
2o:SiO
2: Al
2o
3: H
2o=15:16:1:320), crystallization 24h at 100 DEG C, obtains matrix material (wherein, the SiO containing ZSM-5/Y type molecular sieve
2with Al
2o
3mol ratio be 25:1);
(6) after crystallization terminates, by composite molecular screen deionized water repeatedly suction filtration, wash to neutrality, to be transferred in baking oven freeze-day with constant temperature 3h under 100 DEG C of conditions, to obtain molecular screen primary powder.Molecular Sieves as Template agent is removed in retort furnace Program intensification roasting.Concrete heating schedule: be first heated to 200 DEG C with the speed of 2 DEG C/min from normal temperature condition, constant temperature 100min at this temperature.Be elevated to 550 DEG C with the speed of 2 DEG C/min from 200 DEG C again, and under the condition of 550 DEG C constant temperature 300min, naturally cool to normal temperature, obtain molecular sieve powder.
The XRD spectrum of embodiment 1 and the ZSM-5/Y composite molecular screen synthesized by control experiment 1 as shown in Figure 1, the SEM photo of the ZSM-5/Y composite molecular screen product in controlled trial 1 synthesized by template agent method as shown in Figure 2, the SEM photo of the ZSM-5/Y composite molecular screen synthesized by embodiment 1 as shown in Figure 3, as seen from Figure 1, ZSM-5/Y composite molecular screen has the characteristic peak of type ZSM 5 molecular sieve and Y molecular sieve simultaneously, wherein in 2 θ=7.80, 8.70, the diffraction peak at (23.11 ± 0.42) ° place is the characteristic peak of type ZSM 5 molecular sieve, and 2 θ=6.50, 9.77, 13.46, the diffraction peak at 26.58 ° of places is the characteristic peak of Y molecular sieve, sample synthesized by explanation is the ZSM-5/Y composite molecular screen with two microvoid structure, mainly spherical in shape as can be seen from Fig. 2 and Fig. 3, ZSM-5/Y composite molecular screen, be the shape characteristic of typical type ZSM 5 molecular sieve and Y molecular sieve mixture.
Embodiment 2
A method for Template-free method method synthesis ZSM-5/Y composite molecular screen, comprises the following steps:
(1) aluminum isopropylate, sodium hydroxide and deionized water are mixed, and stir, then silicon sol is added, vigorous stirring is to forming homogeneous gel, gel to be poured in teflon-lined stainless steel cauldron at 140 DEG C into crystallization 7 days, the composition (mol ratio) of the product obtained is Na
2o:SiO
2: Al
2o
3: H
2o=8:25:1:1000;
(2) it is neutral for the product deionized water obtained in step (1) being washed repeatedly paint to pH value, dries, obtains type ZSM 5 molecular sieve;
(3) add aluminum isopropylate and Y zeolite directed agents in the type ZSM 5 molecular sieve obtained in step (2) and (mole consist of Na
2o:SiO
2: Al
2o
3: H
2o=13:18:1:300), crystallization 40h at 90 DEG C, obtains matrix material (wherein, the SiO containing ZSM-5/Y type molecular sieve
2with Al
2o
3mol ratio be 15:1);
(4) product in step (3) is extremely neutral with deionized water wash, dry at 100 DEG C, obtain ZSM-5/Y composite molecular screen.
Embodiment 3
A method for Template-free method method synthesis ZSM-5/Y composite molecular screen, comprises the following steps:
(1) Tai-Ace S 150, sodium hydroxide and deionized water are mixed, and stir, then add water glass, vigorous stirring is to forming homogeneous gel, gel to be poured in teflon-lined stainless steel cauldron at 200 DEG C into crystallization 2 days, the composition (mol ratio) of the product obtained is Na
2o:SiO
2: Al
2o
3: H
2o=21:60:1:5000;
(2) it is neutral for the product deionized water obtained in step (1) being washed repeatedly paint to pH value, dries, obtains type ZSM 5 molecular sieve;
(3) add Tai-Ace S 150 and Y zeolite directed agents in the type ZSM 5 molecular sieve obtained in step (2) and (mole consist of Na
2o:SiO
2: Al
2o
3: H
2o=16:12:1:350), crystallization 16h at 120 DEG C, obtains matrix material (wherein, the SiO containing ZSM-5/Y type molecular sieve
2with Al
2o
3mol ratio be 40:1);
(4) product in step (3) is extremely neutral with deionized water wash, dry at 100 DEG C, obtain ZSM-5/Y composite molecular screen.
Claims (6)
1. a method for Template-free method method synthesis ZSM-5/Y composite molecular screen, is characterized in that, comprise the following steps:
(1) by aluminium source, sodium hydroxide and deionized water mixing, and to stir, then add silicon source, be stirred to formation homogeneous gel, gel to be poured in reactor at 140 ~ 200 DEG C into crystallization 2 ~ 7 days;
(2) the product deionized water wash will obtained in step (1), dries, obtains type ZSM 5 molecular sieve;
(3) add aluminium source and Y zeolite directed agents in the type ZSM 5 molecular sieve obtained in step (2), crystallization 16 ~ 40h at 90 ~ 120 DEG C, obtains the matrix material containing ZSM-5/Y type molecular sieve;
(4) by the product deionized water wash in step (3), dry, obtain ZSM-5/Y composite molecular screen.
2. the method for Template-free method method synthesis ZSM-5/Y composite molecular screen as claimed in claim 1, it is characterized in that, what described step (3) obtained contains SiO in the matrix material of ZSM-5/Y type molecular sieve
2with Al
2o
3mol ratio be 15 ~ 40:1.
3. the method for Template-free method method synthesis ZSM-5/Y composite molecular screen as claimed in claim 1, is characterized in that, the product obtained in step (1) consist of Na
2o:SiO
2: Al
2o
3: H
2o=8 ~ 21:25 ~ 60:1:1000 ~ 5000.
4. the method for Template-free method method synthesis ZSM-5/Y composite molecular screen as claimed in claim 1, is characterized in that: step (1) and the middle aluminium source of step (3) are one or more in Alumina gel, Tai-Ace S 150, aluminum isopropylate, sodium metaaluminate and sodium aluminate.
5. the method for Template-free method method synthesis ZSM-5/Y composite molecular screen as claimed in claim 1, is characterized in that: the silicon source in described step (1) is any one or more in silicon sol, water glass, tetraethoxy, water glass and white carbon black.
6. the method for Template-free method method synthesis ZSM-5/Y composite molecular screen as claimed in claim 1, is characterized in that: in described step (3), the mol ratio of each composition of Y zeolite directed agents is Na
2o:SiO
2: Al
2o
3: H
2o=13 ~ 16:12 ~ 18:1:300 ~ 350.
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| CN106824263A (en) * | 2017-01-20 | 2017-06-13 | 南华大学 | A kind of preparation method of composite molecular screen and the application in 3 picolines of synthesis |
| CN109437232A (en) * | 2018-12-13 | 2019-03-08 | 东莞理工学院 | A kind of preparation method of the ZSM-5 molecular sieve of multilevel structure |
| CN111408342A (en) * | 2020-04-27 | 2020-07-14 | 北京泷涛环境科技有限公司 | High-silicon composite molecular sieve adsorbent for removing VOCs (volatile organic compounds) and preparation method thereof |
| CN115814848A (en) * | 2021-09-17 | 2023-03-21 | 中国石油化工股份有限公司 | ZSM-5/Y composite molecular sieve and preparation method and application thereof |
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| CN111408342B (en) * | 2020-04-27 | 2022-09-16 | 北京泷涛环境科技有限公司 | High-silicon composite molecular sieve adsorbent for removing VOCs (volatile organic compounds) and preparation method thereof |
| CN115814848A (en) * | 2021-09-17 | 2023-03-21 | 中国石油化工股份有限公司 | ZSM-5/Y composite molecular sieve and preparation method and application thereof |
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Application publication date: 20160203 |