CN109879295A - A kind of ZSM-5 molecular sieve - Google Patents
A kind of ZSM-5 molecular sieve Download PDFInfo
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- CN109879295A CN109879295A CN201910339314.7A CN201910339314A CN109879295A CN 109879295 A CN109879295 A CN 109879295A CN 201910339314 A CN201910339314 A CN 201910339314A CN 109879295 A CN109879295 A CN 109879295A
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Abstract
The present invention relates to a kind of ZSM-5 molecular sieves, and in particular to a kind of ZSM-5 molecular sieve standby by coal ash for manufacturing belongs to field of solid waste comprehensive utilization.The preparation method of the ZSM-5 molecular sieve includes the following steps: that (1) mixes flyash with dilute alkaline soln and is activated in a kettle, obtains primary zeolite after filtering；(2) the primary zeolite is uniformly mixed with supplement silicon source, aqueous slkali and at least one of template or crystal seed, obtains precursors；(3) precursors are subjected to crystallization；(4) product after the crystallization cool down, be separated by solid-liquid separation, wash, dry, roasted, obtain ZSM-5 molecular sieve.ZSM-5 molecular sieve large specific surface area of the invention, micro- mesoporous prosperity, and it is prepared by flyash for raw material, not only realize the efficient utilization of flyash, and reduce the energy consumption of flyash activating process, coal ash for manufacturing is simplified for the process flow of molecular sieve, makes full use of the sial resource in flyash.
Description
Technical field
The present invention relates to a kind of ZSM-5 molecular sieves, and in particular to a kind of ZSM-5 molecular sieve standby by coal ash for manufacturing belongs to
Field of solid waste comprehensive utilization.
Background technique
Coal accounts for 70% or more of China's non-renewable energy total quantity consumed as the most important non-renewable energy in China.Coal combustion
A large amount of solid by-product flyash can be generated by burning power generation.The flyash yield in China in 2017 is more than 600,000,000 tons.It expects
The year two thousand twenty, the accumulative accumulating amount of China's flyash will be more than 3,000,000,000 tons.The flyash of stockpiling occupies farmland, causes land resource
Waste.The microelements such as lead, mercury can permeate the ground with rainwater or flow into surface water in flyash, cause water pollution.Powder
Dust pollution air in coal ash, endangers human health.To the efficient disposition of flyash and green composite using always by pass
Note.The chemical constituent of flyash is mainly the metallic compounds such as silica, aluminium oxide, iron oxide, charcoal and a small amount of calcium, magnesium,
Middle SiO2、Al2O3The two accounts for 60wt% or more, very close in composition with molecular sieve, can be high added value zeolite molecular sieve
Synthesis necessary sial is provided, to open the utilization ways of synthetic zeolite from flyash molecular sieve.
Zeolite molecular sieve is a kind of inorganic porous material with orderly, uniform cellular structure, is widely used in being catalyzed
With the fields such as adsorbing separation, it is the key material for solving the problems, such as energy and environment.The zeolite molecular sieve quilt of low, middle silica alumina ratio
Referred to as first generation zeolite has caged cellular structure；The zeolite molecular sieve of high silica alumina ratio is referred to as second generation zeolite, with ZSM system
The molecular sieve of column is representative.ZSM-5 molecular sieve be Mobile company, the U.S. in 1972 for the first time succeed research and develop a kind of high sial
Than the aluminosilicate zeolite molecular sieve of, three-dimensional straight channels structure, since it is with uniform cellular structure, higher specific surface
Product, molecule shape selectivity, good ion exchangeable and hydrothermal stability, surface have adjustable Lewis andIt is acid
The properties such as center become a kind of catalyst haveing excellent performance, and are widely used in the neck such as petrochemical industry, fine chemistry industry, environmental protection
Domain.It is at high cost since zeolite molecular sieve generallys use the synthesis of the industrial chemicals such as waterglass, sodium aluminate or aluminium hydroxide, be not suitable for
Large-scale production.Many scholars have carried out using flyash as the research of Material synthesis molecular sieve.
SiO in flyash2And Al2O3Mainly exist in the form of amorphous mineral glass body, vitreous surface is one layer of smooth heavily fortified point
Solid protective film, hinder internal SiO2And Al2O3Dissolution, on a small quantity with crystalline phase substance such as mullite and quartz form deposit
In property stabilization, it is difficult to be utilized.It must be activated when therefore, using flyash as Material synthesis molecular sieve, make it
In silicon, aluminium can be released effectively to being fully used.Currently, the activation method of flyash have it is following several: 1) mechanical grinding
Mill is destroyed the internal structure of flyash by mechanical energy, increases the contact point of reaction, increase the unordered degree of sial, to mention
Its high reactivity.This method sial activation effect is low, easily causes dust pollution；2) hydro-thermal activation is usually in aqueous slkali or acid
Under solution condition, it can also be aided with microwave or ultrasonication, sial is promoted to be dissolved.The disadvantage is that the dosage of alkali or acid is larger, week
Phase is longer；3) high-temperature activation includes alkali fusion and salt melting, and the two is all using alkali as activator, and wherein salt melting is alkali and salt
Mixture, salt are used as stabilizer.The activation effect of (500~800 DEG C) at high temperature, sial is good, and utilization rate is high.But alkali
(salt) dosage is big, and aftertreatment technology increases, and cost increases.
CN 106517237 A, CN 106587098 B and 106587099 B of CN individually disclose a kind of flyash acid system
Residue of aluminum-extracted prepares NaY type coproduction ZSM-5 molecular sieve, 13X type coproduction ZSM-5 molecular sieve and sodalite coproduction ZSM-5 type point
The method of son sieve.Flyash acid system residue of aluminum-extracted is subjected to alkaline process roasting at (830~890 DEG C), obtains roasting slag charge, successively into
The water logging of row high temperature and heat preservation filtering, obtain the first filtrate；First filtrate is subjected to NaY type, 13X type, sodalite type molecule
Hydrothermal crystallizing is sieved, NaY type, 13X type, sodalite type molecular sieve and molecular sieve filtrate are respectively obtained；By the molecular sieve filtrate into
Row type ZSM 5 molecular sieve hydrothermal crystallizing, obtains type ZSM 5 molecular sieve.But the process is in flyash acid system residue of aluminum-extracted
Sial is silicon source, silicon source prepares ZSM-5 molecular sieve, and flyash extracts aluminium through overpickling, then carries out high-temperature alkali calcination activation, preparation
The zeolite molecular sieve of low out, middle silica alumina ratio, the filtrate of preparation process, which is further processed, prepares ZSM-5 molecular sieve.Operating process is numerous
Trivial, energy consumption is high, soda acid usage amount is big, is not suitable for industrialized production.
103435064 A of CN discloses a kind of method using coal ash for manufacturing for nanoscale ZSM-5 molecular sieve, by fine coal
Ash is ground, the pretreatment such as 600-900 DEG C of calcination activation, washing, then mixed using pretreated flyash and sodium carbonate
It closes and is roasted at 600-900 DEG C, chlorohydric acid pickling is filtered to remove the obtained Silicon-rich gel of insoluble matter and thick AlCl3Solution, respectively to Silicon-rich
Gel and AlCl3Solution carries out a series of processing and prepares aluminium hydroxide, sodium metasilicate, then using aluminium hydroxide, sodium metasilicate as silicon source,
Silicon source prepares nanoscale ZSM-5 molecular sieve by addition water, template.103394367 A of CN discloses a kind of using fine coal
Flyash is carried out the pretreatment such as 800 DEG C of high-temperature roastings, washings by the method that ash prepares ZSM-5 molecular sieve nucleocapsid double-layer catalyst
Afterwards with Na2CO3Mixing carries out 800 DEG C of high-temperature roastings, acid processing obtains silica solution and AlCl3, it is further processed preparation Al (OH)3
And Na2SiO3, addition water, tetrapropylammonium hydroxide prepare ZSM-5 molecular sieve shell structurre.But operating process is complicated, acid consumption
Measure larger, high-temperature roasting activation energy consumption height.The two patents be all aluminium hydroxide and sodium metasilicate is made by raw material of flyash, then
It is prepared for nanoscale ZSM-5 molecular sieve and nucleocapsid bilayer ZSM-5 molecular sieve using it as raw material, although improving product purity,
It is that step is more, process is complicated, energy consumption is high, acid and alkali consumption amount is big.
108892151 A of CN discloses a kind of coal ash for manufacturing for the method for ZSM-5 molecular sieve, and flyash is ground
And sieve, 800 DEG C of roastings, the pretreatment such as heating washing, it will filtering gained filter residue and activator Na2CO3Mixing, heating roasting are lived
Change, acid solution is added in flyash after activation and post-processes to obtain silicic acid precipitating, supplement tetrapropylammonium hydroxide, silicon source and steaming
Distilled water prepares ZSM-5 molecular sieve.But this method prepares ZSM-5 molecule by additional silicon source merely with the silicon in flyash
Sieve, it is lower to the utilization rate of flyash.
Existing technical method is all to be activated by high-temperature roasting to flyash, and energy consumption is higher；Secondly, with powder
Coal ash is that Al (OH) is made in raw material3And Na2SiO3ZSM-5 molecular sieve is prepared using it as raw material again afterwards, step is more, process is complicated.With
Flyash acid system residue of aluminum-extracted is that raw material prepares ZSM-5 molecular sieve, and the sial in flyash is separately utilized, big portion in flyash
Silicon and a small amount of aluminium is divided to be used to synthesis of molecular sieve.And it is that silicon source prepares ZSM-5 molecular sieve that silicic acid is made by raw material of flyash,
The silicon in flyash is just only utilized, it is still necessary to improve for the utilization rate of flyash.
Therefore, existing coal ash for manufacturing is for the method for molecular sieve, and activation method is it is still necessary to improve, to reduce energy consumption；Preparation
Method also needs to simplify, to reduce cost；Sial utilization rate in flyash is badly in need of improving, to economize on resources.
Summary of the invention
The object of the present invention is to provide a kind of ZSM-5 molecular sieve, the ZSM-5 molecular sieve large specific surface area, micro- mesoporous hair
It reaches, and is prepared by flyash for raw material, not only realize the efficient utilization of flyash, and reduce flyash activating process
Energy consumption, simplify coal ash for manufacturing for the process flow of molecular sieve, make full use of the sial resource in flyash.
To achieve the above object, the present invention provides the following technical scheme that
A kind of ZSM-5 molecular sieve, preparation method include the following steps:
(1) flyash is mixed with dilute alkaline soln and is activated in a kettle, obtain primary zeolite after filtering；
The reaction kettle is usually high-temperature high-pressure reaction kettle, and pressure resistance is generally 0-20MPa, and pressure limit is generally in 1- in reaction
15MPa。
75 μm of the partial size ﹤ of the flyash；The dilute alkaline soln is generally sodium hydroxide or potassium hydroxide solution.
The concentration of the dilute alkaline soln is 0.1-1.0mol/L；The liquid-solid ratio of the dilute alkaline soln and flyash is 10-
60mL/g。
The temperature of the activation is 200-350 DEG C, activation time 10-180min.Compared to conventional activation roasting technique,
Energy consumption substantially reduces.
The primary zeolite is the filter cake after the filtering.
After the filtering, filtrate can supplement suitable alkali and/or water, be used as follow again by measuring its alkali concentration
Ring lye activating fly ash.Water described herein is preferably deionized water.
(2) the primary zeolite is uniformly mixed with supplement silicon source, aqueous slkali and at least one of template or crystal seed,
Obtain precursors；In the mixed process, the template and crystal seed can choose one of addition, be also possible to two
It plants while being added.
After mixing, precursors are obtained by ageing.The aging condition is about 1-50 DEG C of Aging Temperature, when ageing
Between about 0.5-10h.
Further, the supplement silicon source includes white carbon black, silica solution, tetraethyl orthosilicate, SiO2, waterglass or silicic acid
Sodium etc. is one such or several；The aqueous slkali is sodium hydroxide or potassium hydroxide solution；The template is tetrapropyl hydrogen
Amine-oxides (TPAOH), tetraethyl ammonium hydroxide (TEAOH), 4-propyl bromide (TPABr), n-butylamine (NBA) or ethylenediamine
(EDA) etc. one such or several；The crystal seed is ZSM-5 molecular sieve or Silicalite-1 molecular sieve.
The aqueous slkali is sodium hydroxide or potassium hydroxide solution.It can choose and mix solid base NaOH or KOH etc. with water
It closes and obtains.
Regardless of whether addition crystal seed, when adding template, the primary zeolite and supplement silicon source, aqueous slkali and template
The molar ratio of each compound in mixed process are as follows: (1-10) Na2O ﹕ 1Al2O3﹕ (10-200) SiO2﹕ (0-10) Mo Ban Ji ﹕
(1000-6000)H2O.Wherein, the primary zeolite provides whole silicon source and part silicon source.
Regardless of whether addition template, when adding crystal seed, the 0- of the total silicon source quality of the additive amount Zhan of the crystal seed
10wt%.
Total silicon source is made of the silicon source provided in the primary zeolite and the supplement silicon source.
(3) precursors are subjected to crystallization；Crystallization can be generally carried out in hydrothermal reaction kettle.
The temperature of the crystallization is 110-210 DEG C, crystallization time 6-240h.
(4) product after the crystallization cool down, be separated by solid-liquid separation, wash, dry, roasted, obtain ZSM-5 molecule
Sieve.
The cooling is generally cooled to room temperature；The separation of solid and liquid generally uses vacuum filtration machine or centrifuge
It is separated by solid-liquid separation；The washing is in neutrality to wash the filter cake after the separation of solid and liquid, it is preferable to use deionized water is washed；
Dry 8-24h at usually in an oven 80-110 DEG C of the drying, described be roasted at 500-600 DEG C roast 5-10h, preferably
It is roasted in Muffle furnace.
Through characterizing, total specific surface area of the ZSM-5 molecular sieve is greater than 288m2/G, micropore specific area are greater than 224m2/ g,
External surface area is greater than 57m2/ g, pore volume are greater than 0.15cm3/ g, average pore size is between 1.72-2.10nm.
ZSM-5 molecular sieve provided by the invention activates to obtain primary zeolite using flyash as raw material by a step lye,
Hydro-thermal turns brilliant synthesis after supplementing silicon source.Compared with prior art: (1) made ZSM-5 molecular sieve large specific surface area, micro- mesoporous hair
It reaches；(2) in preparation process, activation efficiency is high, and low energy consumption；Hydro-thermal turns brilliant process and uses crystal seed method, only adds a small amount of template, no
Crystallization velocity is improved only, cost is also greatly reduced；Under conditions of without complicated technologies such as purifications, flyash is made full use of
In sial resource；(3) carbon of flyash itself is used as mesoporous template during the reaction, so that the micro- mesoporous prosperity of product,
Specific surface increases, and the carbon for being conducive to mass transfer, while solving flyash itself is burnt up in vain in conventional activation roasting process
The problem of.
Detailed description of the invention
The X-ray diffractogram of the made primary zeolite of Fig. 1 the embodiment of the present invention 1；
The scanning electron microscope (SEM) photograph of the made primary zeolite of Fig. 2 the embodiment of the present invention 1；
The X-ray diffractogram of the made ZSM-5 molecular sieve of Fig. 3 the embodiment of the present invention 1-6；
The scanning electron microscope (SEM) photograph of the made ZSM-5 molecular sieve of Fig. 4 the embodiment of the present invention 1；
The graph of pore diameter distribution of the made ZSM-5 molecular sieve of Fig. 5 the embodiment of the present invention 1-6.
Specific embodiment
Below by embodiment combination attached drawing, the technical scheme of the present invention will be explained in further detail, but is not limited to this
The content of embodiment.
Embodiment 1
A kind of ZSM-5 molecular sieve, preparation method include the following steps:
(1) NaOH solution of the flyash by partial size less than 75 μm and 0.2mol/L are mixed in the ratio that liquid-solid ratio is 60mL/g
It closes, is activated in high-temperature high-pressure reaction kettle, activation temperature is 350 DEG C, reactor pressure activates 10min under being 15MPa, instead
Mixture is cooled to room temperature after answering, and primary zeolite is obtained after filtering.As shown in Figure 1, the angle of diffraction (2 θ) of primary zeolite is respectively
For 15.795 °, 26.010 °, 30.586 °, and crystallinity is higher.As shown in Fig. 2, primary zeolite morphology is spherical shape.
Filtered filtrate supplement trace NaOH and deionized water can be used as circulation alkali liquor activating fly ash again.
(2) the primary zeolite is rubbed with silica solution, NaOH solution, template tetraethyl ammonium hydroxide according to each compound
You are than being 1Na2O ﹕ 1Al2O3﹕ 10SiO2﹕ 10TEAOH ﹕ 1000H2The ZSM-5 molecular sieve crystal seed of the total silicon source 1.0wt% of O and Zhan is mixed
It closes uniformly, is aged 10h at being then 10 DEG C in temperature, obtains precursors.
(3) precursors are transferred in hydrothermal reaction kettle, the crystallization 240h at 110 DEG C.
(4) it by the reactant cooled to room temperature after the crystallization, is separated by solid-liquid separation, will be consolidated using vacuum filtration machine
Filter cake after liquid separation is washed to and is in neutrality, the dry 8h at 110 DEG C in an oven of the filter cake after washing, finally by the filter after drying
Cake roasts 5h in Muffle furnace and obtains ZSM-5 molecular sieve, number A at 600 DEG C.
Through characterizing, pore property is shown in Table 1.Synthetic product ZSM-5 molecular sieve not only contains micropore, but also containing mesoporous, is in
Existing multi-stage porous state.Multi-stage porous ZSM-5 molecular sieve not only have the unique three dimensional intersection cellular structure of micropore ZSM-5 molecular sieve,
High specific surface area, stronger acidity and good shape selective catalysis performance, while biggish mesoporous pore size overcomes micropore ZSM-5
Molecular sieve bore diameter is smaller, molecular mass-transfer and the shortcomings that diffusion limited, shortens the mass transfer distance of molecular sieve, improves molecular sieve
Catalytic efficiency makes it have broad application prospect.
As shown in figure 3, synthetic product matches with ZSM-5 molecular sieve characteristic diffraction peak, angle of diffraction (2 θ) is respectively
7.972 °, 8.818 °, 8.920 °, 9.122 °, 23.083 °, 23.321 °, 23.724 °, 23.949 °, 24.418 °, and product knot
Brilliant degree is higher.As shown in figure 4, synthetic product is the shape characteristic of typical ZSM-5 molecular sieve.As shown in figure 5, synthetic product was both
Containing micropore, and containing mesoporous.
Embodiment 2
A kind of ZSM-5 molecular sieve, preparation method include the following steps:
(1) KOH solution of the flyash by partial size less than 75 μm and 0.4mol/L are mixed in the ratio that liquid-solid ratio is 50mL/g
It closes, is activated in high-temperature high-pressure reaction kettle, activation temperature is 325 DEG C, reactor pressure activates 40min under being 12MPa, instead
Mixture is cooled to room temperature after answering, and primary zeolite is obtained after filtering.
Filtered filtrate supplement trace KOH and deionized water can be used as circulation alkali liquor activating fly ash again.
(2) it is according to each compound mole ratio with white carbon black, KOH solution, template n-butylamine by the primary zeolite
3K2O ﹕ 1Al2O3﹕ 50SiO2﹕ 8NBA ﹕ 2000H2The Silicalite-1 molecular sieve seed of the total silicon source 3.0wt% of O and Zhan mixes
Uniformly, it is aged 5h at being then 1 DEG C in temperature, obtains precursors.
(3) precursors are transferred in hydrothermal reaction kettle, the crystallization 180h at 130 DEG C.
(4) it by the reactant cooled to room temperature after the crystallization, is separated by solid-liquid separation using centrifuge, by solid-liquid point
Filter cake from after, which is washed to, to be in neutrality, the dry 12h at 105 DEG C in an oven of the filter cake after washing, finally by the filter cake after drying
6h is roasted at 600 DEG C in Muffle furnace and obtains ZSM-5 molecular sieve, number B.
Through characterizing, pore property is shown in Table 1.Synthetic product ZSM-5 molecular sieve not only contains micropore, but also containing mesoporous, is in
Existing multi-stage porous state, is conducive to mass transfer.
As shown in figure 3, synthetic product matches with ZSM-5 molecular sieve characteristic diffraction peak, angle of diffraction (2 θ) is respectively
7.972 °, 8.818 °, 8.920 °, 9.122 °, 23.083 °, 23.321 °, 23.724 °, 23.949 °, 24.418 °, and product knot
Brilliant degree increases.As shown in figure 5, synthetic product not only contains micropore, but also containing mesoporous, and mesoporous content increases.
Embodiment 3
A kind of ZSM-5 molecular sieve, preparation method include the following steps:
(1) KOH solution of the flyash by partial size less than 75 μm and 0.5mol/L are mixed in the ratio that liquid-solid ratio is 40mL/g
It closes, is activated in high-temperature high-pressure reaction kettle, activation temperature is 300 DEG C, reactor pressure activates 60min under being 9MPa, instead
Mixture is cooled to room temperature after answering, and primary zeolite is obtained after filtering.
Filtered filtrate supplement trace KOH and deionized water can be used as circulation alkali liquor activating fly ash again.
(2) by the primary zeolite and sodium metasilicate, KOH solution, template 4-propyl bromide according to each compound mole
Than for 5K2O ﹕ 1Al2O3﹕ 80SiO2﹕ 6TPABr ﹕ 3000H2O is uniformly mixed, and is aged 0.5h at being then 50 DEG C in temperature, is obtained anti-
Answer presoma.
(3) precursors are transferred in hydrothermal reaction kettle, the crystallization 120h at 150 DEG C.
(4) it by the reactant cooled to room temperature after the crystallization, is separated by solid-liquid separation, will be consolidated using vacuum filtration machine
Filter cake after liquid separation is washed to and is in neutrality, the dry 14h at 100 DEG C in an oven of the filter cake after washing, finally will be after drying
Filter cake roasts 7h in Muffle furnace and obtains ZSM-5 molecular sieve, number C at 550 DEG C.
Through characterizing, pore property is shown in Table 1.Synthetic product ZSM-5 molecular sieve not only contains micropore, but also containing mesoporous, is in
Existing multi-stage porous state, is conducive to mass transfer.
As shown in figure 3, synthetic product matches with ZSM-5 molecular sieve characteristic diffraction peak, angle of diffraction (2 θ) is respectively
7.972 °, 8.818 °, 8.920 °, 9.122 °, 23.083 °, 23.321 °, 23.724 °, 23.949 °, 24.418 °, and product knot
Brilliant degree further increases.As shown in figure 5, synthetic product not only contains micropore, but also containing mesoporous, and mesoporous content obviously increases.
Embodiment 4
A kind of ZSM-5 molecular sieve, preparation method include the following steps:
(1) NaOH solution of the flyash by partial size less than 75 μm and 0.6mol/L are mixed in the ratio that liquid-solid ratio is 30mL/g
It closes, is activated in high-temperature high-pressure reaction kettle, activation temperature is 250 DEG C, reactor pressure activates 120min under being 4MPa, instead
Mixture is cooled to room temperature after answering, and primary zeolite is obtained after filtering.
Filtered filtrate supplement trace NaOH and deionized water can be used as circulation alkali liquor activating fly ash again.
(2) by the primary zeolite and SiO2Powder, NaOH solution, template tetrapropylammonium hydroxide are according to each compound
Molar ratio is 7Na2O ﹕ 1Al2O3﹕ 150SiO2﹕ 4TPAOH ﹕ 4000H2The ZSM-5 crystal seed of O and 5.0wt.% is uniformly mixed, and is then existed
Temperature is to be aged 0.5h at 50 DEG C, obtains precursors.
(3) precursors are transferred in hydrothermal reaction kettle, the crystallization 96h at 170 DEG C.
(4) it by the reactant cooled to room temperature after the crystallization, is separated by solid-liquid separation using centrifuge, by solid-liquid point
Filter cake from after, which is washed to, to be in neutrality, and the dry 18h at 95 DEG C in an oven of the filter cake after washing finally exists the filter cake after drying
8h is roasted in Muffle furnace at 550 DEG C and obtains ZSM-5 molecular sieve, number D.
Through characterizing, pore property is shown in Table 1.Synthetic product ZSM-5 molecular sieve not only contains micropore, but also containing mesoporous, is in
Existing multi-stage porous state, is conducive to mass transfer.
As shown in figure 3, synthetic product matches with ZSM-5 molecular sieve characteristic diffraction peak, angle of diffraction (2 θ) is respectively
7.972 °, 8.818 °, 8.920 °, 9.122 °, 23.083 °, 23.321 °, 23.724 °, 23.949 °, 24.418 °, and product knot
Brilliant degree further increases.As shown in figure 5, synthetic product not only contains micropore, but also containing mesoporous, and mesoporous content further increases.
Embodiment 5
A kind of ZSM-5 molecular sieve, preparation method include the following steps:
(1) NaOH solution of the flyash by partial size less than 75 μm and 0.8mol/L are mixed in the ratio that liquid-solid ratio is 20mL/g
It closes, is activated in high-temperature high-pressure reaction kettle, activation temperature is 225 DEG C, reactor pressure activates 150min under being 3MPa, instead
Mixture is cooled to room temperature after answering, and primary zeolite is obtained after filtering.
Filtered filtrate supplement trace NaOH and deionized water can be used as circulation alkali liquor activating fly ash again.
(2) by the primary zeolite and tetraethyl orthosilicate, NaOH solution, template ethylenediamine according to each compound mole
Than for 9Na2O ﹕ 1Al2O3﹕ 180SiO2﹕ 2EDA ﹕ 5000H2The ZSM-5 crystal seed of O and 10.0wt.% is uniformly mixed, then in temperature
It is to be aged 1h at 25 DEG C, obtains precursors.
(3) precursors are transferred in hydrothermal reaction kettle, the crystallization 72h at 180 DEG C.
(4) it by the reactant cooled to room temperature after the crystallization, is separated by solid-liquid separation, will be consolidated using vacuum filtration machine
Filter cake after liquid separation is washed to and is in neutrality, the dry 20h at 90 DEG C in an oven of the filter cake after washing, finally by the filter after drying
Cake roasts 9h in Muffle furnace and obtains ZSM-5 molecular sieve, number E at 500 DEG C.
Through characterizing, pore property is shown in Table 1.Synthetic product ZSM-5 molecular sieve not only contains micropore, but also containing mesoporous, is in
Existing multi-stage porous state, is conducive to mass transfer.
As shown in figure 3, synthetic product matches with ZSM-5 molecular sieve characteristic diffraction peak, angle of diffraction (2 θ) is respectively
7.972 °, 8.818 °, 8.920 °, 9.122 °, 23.083 °, 23.321 °, 23.724 °, 23.949 °, 24.418 °, product crystallization
Degree slightly reduces.As shown in table 1 and Fig. 5, synthetic product not only contains micropore, but also containing mesoporous, and mesoporous content further increases,
External surface area is up to 122.59m2/g。
Embodiment 6
A kind of ZSM-5 molecular sieve, preparation method include the following steps:
(1) KOH solution of the flyash by partial size less than 75 μm and 1.0mol/L are mixed in the ratio that liquid-solid ratio is 10mL/g
It closes, is activated in high-temperature high-pressure reaction kettle, activation temperature is 200 DEG C, reactor pressure activates 180min under being 1MPa, instead
Mixture is cooled to room temperature after answering, and primary zeolite is obtained after filtering.
Filtered filtrate supplement trace KOH and deionized water can be used as circulation alkali liquor activating fly ash again.
It (2) is 10K according to each compound mole ratio by the primary zeolite and waterglass, KOH solution2O ﹕ 1Al2O3﹕
200SiO2﹕ 6000H2The ZSM-5 crystal seed of O and 10.0wt.% is uniformly mixed, and is aged 1h at being then 25 DEG C in temperature, is obtained anti-
Answer presoma.
(3) precursors are transferred in hydrothermal reaction kettle, the crystallization 6h at 210 DEG C.
(4) it by the reactant cooled to room temperature after the crystallization, is separated by solid-liquid separation using centrifuge, by solid-liquid point
Filter cake from after, which is washed to, to be in neutrality, the filter cake after washing in an oven at 80 DEG C it is dry for 24 hours, finally the filter cake after drying is existed
10h is roasted in Muffle furnace at 500 DEG C and obtains ZSM-5 molecular sieve, number F.
Through characterizing, pore property is shown in Table 1.Synthetic product ZSM-5 molecular sieve not only contains micropore, but also containing mesoporous, is in
Existing multi-stage porous state, is conducive to mass transfer.
As shown in figure 3, synthetic product matches with ZSM-5 molecular sieve characteristic diffraction peak, angle of diffraction (2 θ) is respectively
7.972 °, 8.818 °, 8.920 °, 9.122 °, 23.083 °, 23.321 °, 23.724 °, 23.949 °, 24.418 °, product crystallization
Degree decreases.As shown in table 1 and Fig. 5, synthetic product not only contains micropore, but also contains mesoporous, mesoporous content decline, Extra specific surface area
Product is down to 63.93m2/g。
The pore structure parameter of ZSM-5 molecular sieve in 1 embodiment 1-6 of table
Claims (10)
1. a kind of ZSM-5 molecular sieve, which is characterized in that preparation method includes the following steps:
(1) flyash is mixed with dilute alkaline soln and is activated in a kettle, obtain primary zeolite after filtering；
(2) the primary zeolite is uniformly mixed with supplement silicon source, aqueous slkali and at least one of template or crystal seed, is obtained
Precursors；
(3) precursors are subjected to crystallization；
(4) product after the crystallization cool down, be separated by solid-liquid separation, wash, dry, roasted, obtain ZSM-5 molecular sieve.
2. ZSM-5 molecular sieve according to claim 1, it is characterised in that in the step (1), the partial size of the flyash
75 μm of ﹤；The dilute alkaline soln is sodium hydroxide or potassium hydroxide solution.
3. ZSM-5 molecular sieve according to claim 1 or 2, it is characterised in that in the step (1), the dilute alkaline soln
Concentration be 0.1-1.0mol/L；The liquid-solid ratio of the dilute alkaline soln and flyash is 10-60mL/g.
4. ZSM-5 molecular sieve according to claim 1 or 2, it is characterised in that in the step (1), the temperature of the activation
Degree is 200-350 DEG C, activation time 10-180min.
5. ZSM-5 molecular sieve according to claim 1, it is characterised in that in the step (2), the supplement silicon source includes
White carbon black, silica solution, tetraethyl orthosilicate, SiO2, waterglass or sodium metasilicate；The aqueous slkali is sodium hydroxide or potassium hydroxide
Solution；The template is tetrapropylammonium hydroxide, tetraethyl ammonium hydroxide, 4-propyl bromide, n-butylamine or ethylenediamine；Institute
Stating crystal seed is ZSM-5 molecular sieve or Silicalite-1 molecular sieve.
6. ZSM-5 molecular sieve according to claim 1 or 5, it is characterised in that in the step (2), the primary zeolite
With the molar ratio of each compound in supplement silicon source, aqueous slkali and template mixed process are as follows: (1-10) Na2O ﹕ 1Al2O3﹕ (10-
200)SiO2﹕ (0-10) Mo Ban Ji ﹕ (1000-6000) H2O。
7. ZSM-5 molecular sieve according to claim 1, it is characterised in that the total silicon source quality of the additive amount Zhan of the crystal seed
0-10wt%.
8. ZSM-5 molecular sieve according to claim 1, it is characterised in that in the step (3), the temperature of the crystallization is
110-210 DEG C, crystallization time 6-240h.
9. ZSM-5 molecular sieve according to claim 1, it is characterised in that in the step (4), the washing is will be described
Filter cake washing after separation of solid and liquid is in neutrality；Described be roasted at 500-600 DEG C roasts 5-10h.
10. ZSM-5 molecular sieve according to claim 1, it is characterised in that total large specific surface area of the ZSM-5 molecular sieve
In 288m2/ g, micropore specific area are greater than 224m2/ g, external surface area are greater than 57m2/ g, pore volume are greater than 0.15cm3/ g is put down
Equal aperture is between 1.72-2.10nm.
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