CN110510628A - A kind of Beta zeolite of big crystal grain and its preparation method and application - Google Patents
A kind of Beta zeolite of big crystal grain and its preparation method and application Download PDFInfo
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Abstract
The present invention provides Beta zeolites of a kind of big crystal grain and its preparation method and application.Preparation method includes: to mix micropore organic formwork agent, water, and silicon source is added after stirring, stirs to clarify, obtains silicon source solution；Sodium hydroxide and/or ammonium hydroxide is added in Xiang Shuizhong, and the halide of potassium hydroxide or potassium is added, adds silicon source, stirs, obtains silicon source solution；Silicon source solution and silicon source solution are mixed, the crystal seed of Beta zeolite is added in stirring, carries out crystallization；Crystallization product is separated, washed, dried, roast, ammonium ion exchange is then carried out, obtains big crystal grain Beta zeolite.The big crystal grain Beta zeolite obtained by above-mentioned preparation method of the invention, activity and stability with higher in catalysis levulic acid esterification reaction.
Description
Technical field
The present invention relates to a kind of zeolites more particularly to a kind of Beta zeolite and preparation method thereof, belong to zeolite technology of preparing
Field.
Background technique
Beta zeolite has unique cellular structure of three-dimensional twelve-ring, due to its special structure, Acidity and shape-selective
Property, have in the important reactions such as the relevant alkylation of petrochemical industry, hydrofinishing, esterification, hydroisomerizing, disproportionation, dewaxing extensively
Using.
Traditional Beta zeolite grain size is substantially in 500nm hereinafter, this little crystal grain zeolite has large specific surface area, outer
The features such as surface acidity position is more, catalytic activity are high.But zeolite grain size reduces, and will lead to acidic site ratio in outside hole and hole
It improves, the shape-selective effect of zeolite weakens, and will appear catalyst bed temperature runaway significantly now in the big reaction of catalytic exothermic amount
As being easy to cause catalyst stability to be deteriorated even and inactivating.Therefore, suitably increase the size of zeolite grain, synthesize big crystal grain
Beta zeolite has important practical significance.
Since researchers for the first time synthesis Beta zeolite, more and more methods are used for the synthesis of Beta zeolite.Its
Middle main method are as follows: hydrothermal crystallizing synthetic method, directed agents synthetic method, dry gum method, microwave process for synthesizing.Hydrothermal crystallizing synthetic method is boiling
The method of stone synthesis most original.1967, Mobil company just synthesized Beta zeolite with hydrothermal crystallizing synthetic method for the first time.Hydro-thermal
Crystallization synthetic method is easy to operate, system is uniform, products obtained therefrom performance is stablized, but consumption of template agent is big, so that synthesis cost
It is higher, constrain the industrial application of Beta zeolite.Directed agents synthetic method also needs hydrothermal crystallization process, synthesizes with hydrothermal crystallizing
The dosage of template in conventional hydrothermal synthesis is reduced unlike method by being introduced into directed agents.(Zhou Qun, Li Baozong, the fur coat such as all groups
Formula synthetic fibre waits directing agent method synthesizing low silicon aluminium ratio Beta zeolite [J] Chemical Journal of Chinese Universities, 1999,20 (5): 693-695.)
Directed agents are synthesized by template of quaternary ammonium base, no longer add quaternary ammonium base in synthesis Beta zeolite materials, it is only necessary to which addition is led on a small quantity
Beta zeolite can be obtained to agent.Directed agents synthetic method has many advantages, such as that crystallization is fast, template dosage is few, but its technique is multiple
Miscellaneous, silica alumina ratio narrow range can only be limited in 5-50.Dry gum method is first that each material of synthetic zeolite is mixed with sequence according to a certain ratio
Conjunction forms gel, then is dried and dry glue is made, and then dry glue is placed in small polytetrafluoroethylene (PTFE) cup, is put into polytetrafluoroethyl-ne
In alkene crystallizing kettle, water and template is added in bottom, is not contacted directly with dry glue, dry glue carries out crystalline substance in high temperature and high pressure steam
Change.(Xu W, Dong J, Li J, the et al.A novel method for the preparation of Zeolite such as Xu
beta in fluoride media under microwave irradiation[J].Microporous&Mesoporous
Materials, 2004,68 (1-3): 77-82.) ZSM-5 zeolite has been synthesized using dry gum method for the first time.Dry gum method is received with zeolite
The advantages that rate is high, crystallization time is short, template dosage is few, but operating process is complicated.Microwave process for synthesizing have crystallization rate it is fast,
The advantages that reaction condition is mild, but microwave is used in synthesis process, it consumes energy higher, synthesis cost is high.
F- mineralizer is mainly added in the method for synthesis big crystal grain Beta zeolite into synthetic system at present.But it is fluorine-containing
Mineralizer general toxicity is larger, and is easy to pollute the environment.(Jian S, Zhu G, the Chen Y, et such as Jian
al.Synthesis,surface and crystal structure investigation of the large zeolite
Beta crystal [J] .Microporous and Mesoporous Materials, 2007,102 (1): 242-248.) it adopts
It is silicon source with monocrystalline silicon piece, maximum Beta zeolite so far is successfully synthesized in fluorine-containing system, uses optical microphotograph for the first time
Mirror directly observes the hourglass phenomenon of Beta zeolite grain.
CN102923728A discloses a kind of big crystal grain Beta molecular sieve and preparation method thereof, and this method is by alkali metal, four
Ethyl ammonium cations, tertiary alkanolamine chelating agent, silica, water and aluminium oxide are mixed with ingredient sequence by a certain percentage, are added appropriate
It is uniformly mixing to obtain reaction mixture gel system after crystal seed, reaction mixture gel is fitted into stainless steel cauldron, reacts
Mixture carries out crystallization in closed environment, has obtained big crystal grain Beta molecular sieve.This method is gone back other than needing that crystal seed is added
Chelating agent is added as silicon source, increases the complexity of preparation.
CN107032369A discloses a kind of mesoporous Beta zeolite and preparation method thereof, this method by tetraethylammonium bromide,
Silicon source, sodium hydroxide, sesbania powder, alcohol and water are mixed and stirred for clear solution, and silicon source is then added, and continue to stir to get silicon
Silica-alumina gel is fitted into stainless steel cauldron by alumina gel, and silica-alumina gel crystallization under certain temperature in closed environment obtains
Mesoporous Beta zeolite.This method is not enough to increase the crystallite dimension of Beta zeolite.
CN106672992A discloses a kind of Beta zeolite, and preparation process is divided into multiple stages, and constantly regulate each
The pressure in a stage prepares Beta zeolite.Its mesoporous specific surface of the Beta zeolite of preparation is 200-600m2/ g, mesopore volume with
The volume ratio of total pore volume is 0.56-0.9, and acid amount is 0.30-0.85mmol/g.But the operating process of this method is complicated, system
Standby Beta zeolite size and tradition Beta zeolite out does not have significant difference.
Currently, the research for the preparation of big crystal grain Beta zeolite is not still very thorough, it is simple to develop a kind of synthesis process, right
Environmental-friendly, the synthetic method of the good Beta zeolitic material of catalytic performance is to expand the key point of its application.
Summary of the invention
In order to solve the above-mentioned technical problem, the purpose of the present invention is to provide a kind of Beta zeolite of big crystal grain, (partial size is
0.6 μm -1.1 μm) preparation method, which does not need to add fluorine-containing mineralizer.
In order to achieve the above technical purposes, the present invention provides a kind of preparation method of big crystal grain Beta zeolite, the preparations
Method the following steps are included:
Micropore organic formwork agent, water are mixed, silicon source is added after stirring, stirs to clarify, obtains silicon source solution；
Sodium hydroxide and/or ammonium hydroxide is added in Xiang Shuizhong, and the halide of potassium hydroxide or potassium is added, adds silicon source, stirs,
Obtain silicon source solution；
Silicon source solution and silicon source solution are mixed, the crystal seed of Beta zeolite is added in stirring, carries out crystallization；
Crystallization product is separated, washed, dried, roast, ammonium ion exchange is then carried out, obtains the Beta of big crystal grain
Zeolite.
In the preparation method of big crystal grain Beta zeolite of the invention, by introducing potassium ion in alkaline solution, change silicon
The depolymerization and polycondensation state of acid ion, obtain specific silicate ion state；Effect of the silicon source in alkaline organic formwork agent
Under, obtain specific hydrolysate；After silicon source and silicon source mixing, under the auxiliary of crystal seed, promote the growth of crystal.Make final obtain
The Beta zeolite arrived has biggish crystallite dimension (partial size be 0.6 μm -1.1 μm), while catalytic activity with higher and steady
It is qualitative.
The preparation method of Beta zeolite of the invention includes the steps that preparing silicon source solution.Wherein, in alkaline organic formwork
Under the action of agent, specific hydrolysate-silicon source solution is obtained.
In a specific embodiment of the invention, the micropore organic formwork agent used is tetraethyl ammonium hydroxide or tetrem
Base ammonium bromide.
Specifically, with SiO in silicon source2, Al in silicon source2O3With mole of tetraethylammonium cation in micropore organic formwork agent
Than meter:
When using tetraethyl ammonium hydroxide as micropore organic formwork agent, alkaline environment can be provided by sodium hydroxide,
In, tetraethyl ammonium hydroxide, water, silicon source, silicon source, the molar ratio of sodium ion and potassium ion are (0.15-0.55): (2.25-
4.25): (0.014-0.017): 1:(0.01-0.04): (0.04-0.08).
Specifically, with SiO in silicon source2, Al in silicon source2O3With mole of tetraethylammonium cation in micropore organic formwork agent
Than meter:
When using tetraethylammonium bromide as micropore organic formwork agent, alkalinity can be provided jointly by sodium hydroxide and ammonium hydroxide
Environment, wherein tetraethylammonium bromide, water, silicon source, silicon source, ammonium hydroxide, sodium ion and potassium ion molar ratio be (0.15-0.55):
(17-26): (0.02-0.1): 1:(0.6-0.8): (0.15-0.25): (0.07-0.14).
In a specific embodiment of the invention, the silicon source used is sodium aluminate or boehmite.
The preparation method of Beta zeolite of the invention includes the steps that preparing silicon source solution.By drawing in alkaline solution
Enter potassium ion, changes the depolymerization and polycondensation state of silicate ion, obtain specific silicate ion state.
When using tetraethyl ammonium hydroxide for micropore organic formwork agent, it can choose sodium hydroxide and alkaline environment be provided.
When using tetraethylammonium bromide for micropore organic formwork agent, it can choose ammonium hydroxide and sodium hydroxide provide alkali jointly
Property environment.
When preparing silicon source solution, it is ensured that after sodium hydroxide, ammonium hydroxide, sylvite dissolution, add silicon source.
When preparing silicon source solution, sodium hydroxide is added, ammonium hydroxide can promote acid silicon source that dissolution or depolymerization, shape occurs
At condensation silicate anion.
In a specific embodiment of the invention, the silicon source used is silochrom or white carbon black.
When preparing silicon source solution, the rate that potassium ion can be generated and be grown with modulation nucleus is introduced, to boil to Beta
The crystallite dimension of stone carries out modulation.
The preparation method of Beta zeolite of the invention includes mixing silicon source solution and silicon source solution, and introduce Beta zeolite
Crystal seed the step of.
In a specific embodiment of the invention, the crystal seed of Beta zeolite is through the following steps that be prepared:
Micropore organic formwork agent, water are mixed, silicon source is added after stirring, stirs to clarify, obtains silicon source solution；
Sodium hydroxide is added in Xiang Shuizhong, adds silicon source, stirs, obtains silicon source solution；
Silicon source solution and silicon source solution are mixed, stirring carries out crystallization；
Crystallization product is separated, washed, dried, roast, the crystal seed of Beta zeolite is obtained.
In the preparation process of the crystal seed of Beta zeolite of the invention, the micropore organic formwork agent used is tetraethyl hydrogen-oxygen
Change ammonium.
In the preparation process of the crystal seed of Beta zeolite of the invention, tetraethyl ammonium hydroxide, water, silicon source, silicon source, sodium from
The molar ratio of son is 0.031568:0.637778:0.00353080:0.163062:0.0112511.
In the preparation process of the crystal seed of Beta zeolite of the invention, the silicon source used is sodium aluminate or boehmite.
In the preparation process of the crystal seed of Beta zeolite of the invention, the time of crystallization is -80h for 24 hours.
In a specific embodiment of the invention, the crystal seed of the Beta zeolite used and the mass ratio of silicon source is (0.02-
0.15): 1.
In a specific embodiment of the invention, the temperature of crystallization is 130 DEG C -150 DEG C, the time of crystallization be for 24 hours -
80h。
The preparation method of Beta zeolite of the invention includes the steps that carrying out crystallization product post-processing and ion exchange.Its
In, it is to separate, wash, dry, roast crystallization product, obtains big crystal grain Beta zeolite powder, big crystal grain Beta is boiled
Stone original powder carries out ammonium exchange, obtains big crystal grain Beta zeolite.
In a specific embodiment of the invention, ammonium ion exchange is followed the steps below:
With the mass ratio of 1:20-40,0.5mol/ is added into the crystallization product (big crystal grain Beta zeolite powder) after roasting
The NH of L-1.5mol/L4Cl solution stirs 2h-4h under 80 DEG C of -100 DEG C of water bath conditions and carries out ion exchange, separated, washed
It washs, dry, roast, it is primary to repeat ammonium exchange.
In a specific embodiment of the invention, in post-processing and ammonium ion exchange step, washing to solution ph is
7-8。
In a specific embodiment of the invention, post-processing and ammonium ion exchange step in, dry temperature be 60 DEG C-
100 DEG C, the dry time is 8h-12h.
In a specific embodiment of the invention, in post-processing and ammonium ion exchange step, roasting is with 1 DEG C/min-4
DEG C/after the rate of min is warming up to 500 DEG C -600 DEG C, constant temperature calcining 4h-6h.
It is the preparation method of Beta zeolite through the invention the present invention also provides a kind of Beta zeolite of big crystal grain
It is prepared.The Beta zeolite has biggish crystallite dimension, and partial size is 0.6 μm -1.1 μm.
Beta zeolite of the invention can be used for being catalyzed levulic acid esterification reaction.
The preparation method of Beta zeolite of the invention can be closed in the case where not adding fluorine-containing mineralizer using hydro-thermal method
At big crystal grain Beta zeolite, this method process is simple, nontoxic, while also avoiding the pollution to environment.
The big crystal grain Beta zeolite of the preparation method preparation of Beta zeolite of the invention is relative to small crystalline substance common in the market
Grain Beta zeolite (< 500nm), thermal stability is good, shape selectivity is more prominent.
It is anti-that the Beta zeolite that the preparation method of Beta zeolite of the invention is prepared can be used for being catalyzed levulic acid esterification
It answers, relative to the little crystal grain tradition Beta zeolite of identical silica alumina ratio, Beta zeolite of the invention is with good stability and urges
Change activity.
Detailed description of the invention
Fig. 1 is the XRD diagram of the product of embodiment 1.
Fig. 2 is the XRD diagram of the product of embodiment 2.
Fig. 3 is the SEM figure of the product of embodiment 2.
Fig. 4 is the SEM figure of the product of embodiment 3.
Fig. 5 is the SEM figure of the product of embodiment 4.
Fig. 6 is the XRD diagram of the product of embodiment 5.
Fig. 7 is the SEM figure of the product of embodiment 5.
Fig. 8 is the SEM figure of the product of embodiment 6.
Fig. 9 is the SEM figure of the product of comparative example 1.
Figure 10 is the SEM figure of the product of comparative example 2.
Figure 11 is the SEM figure of the product of comparative example 3.
Figure 12 is the SEM figure of the product of comparative example 4.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
A kind of preparation method of the crystal seed of Beta zeolite is present embodiments provided, specifically includes the following steps:
Taking the 25wt% tetraethyl ammonium hydroxide solution of 27.90g, (0.031568mol is equivalent to the 0.19 of silochrom
Times) the 0.8g sodium aluminate (Al of 0.00353080mol is added2O3, it is equivalent to 0.014 times of silochrom), stir 5-10min shape
At uniform silicon source solution.
It takes in 11.48g deionized water (0.637778mol is equivalent to 2.61 times of silochrom), 0.45g hydrogen-oxygen is added
Change sodium (0.0112511mol is equivalent to 0.046 times of silochrom), is slowly added to gross porosity silicon after stirring 5min-10min dissolution
Glue 15g (0.163062mol) stirs 10min, forms mixed solution.
Silicon source solution is added into mixed solution, at the uniform velocity stirring 3h, is transferred in the baking oven for be placed in reaction kettle 140 DEG C brilliant
Change 48h.
Product after crystallization is subjected to conventional suction filtration or centrifuge separation, being washed with deionized to product leacheate pH is 7-8,
The dry 12h in 100 DEG C of baking oven, is finally warming up to after 550 DEG C with the rate of 2 DEG C/min in Muffle furnace and continues to roast 6h,
Obtain the crystal seed of Beta zeolite.
Fig. 1 is the XRD diagram for the crystal seed being prepared, it can be seen that sample has typical Beta zeolite characteristic diffraction peak,
And without other stray crystal diffraction maximums, illustrate that sample crystal phase is good.
Embodiment 2
The preparation method of big crystal grain Beta zeolite is present embodiments provided, specifically includes the following steps:
Taking the tetraethyl ammonium hydroxide solution of the 25wt% of 18.60g, (0.031568mol is equivalent to the 0.19 of silochrom
Times) the 0.533g sodium aluminate (Al of 0.00235239mol is added2O3, it is equivalent to 0.014 times of silochrom), stir 5-10min
Form uniform silicon source solution.
It takes in 7.95g deionized water (0.441667mol is equivalent to 2.71 times of silochrom), 0.16g hydrogen is then added
Sodium oxide molybdena (0.00400029mol is equivalent to 0.025 times of silochrom), 0.495g potassium hydroxide (0.0074986mol, phase
When in 0.046 times of silochrom), silochrom 10g (0.163062mol) is added after stirring 5-10min dissolution, stirring
10min is added silicon source solution and at the uniform velocity stirs 3h.
The crystal seed of Beta zeolite prepared by embodiment 1 is added, dosage 0.2g is sufficiently stirred.
It is transferred to crystallization 48h in the baking oven for be placed in reaction kettle 140 DEG C.
Product after crystallization is subjected to conventional suction filtration or centrifuge separation, being washed with deionized to product leacheate pH is 7-8,
The dry 12h in 100 DEG C of baking oven later, is warming up to after 550 DEG C with the rate of 2 DEG C/min in Muffle furnace and continues to roast 6h,
Obtain big crystal grain Beta zeolite powder；
Obtained big crystal grain Beta zeolite powder is put into conical flask, the NH of 1mol/L is added in 1:20 in mass ratio4Cl
Solution stirs 3h under 90 DEG C of water bath conditions and carries out ion exchange, and sample is separated, washed, dried, roast, and repeats ammonium and hands over
It changes once, obtains big crystal grain Beta zeolite.
Fig. 2 is the XRD diagram for the big crystal grain Beta zeolite being prepared, it can be seen that sample has typical Beta zeolite special
Diffraction maximum is levied, and without other stray crystal diffraction maximums, illustrates that sample crystal phase is good.
Fig. 3 is the scanning electron microscope (SEM) photograph for the big crystal grain Beta zeolite being prepared, and shows that sample particle diameter is uniform in figure, is in ball
Shape, crystallite dimension are 0.7 μm -1.0 μm.
Embodiment 3
Present embodiments provide a kind of preparation method of big crystal grain Beta zeolite comprising following steps:
The 25wt% tetraethyl ammonium hydroxide solution (0.031568mol is equivalent to 0.19 times of white carbon black) of 18.6g is taken to add
Enter the 0.533g sodium aluminate (Al of 0.00235239mol2O3, it is equivalent to 0.014 times of white carbon black), stirring 5-10min is formed uniformly
Silicon source solution.
7.95g deionized water (0.441667mol is equivalent to 2.71 times of white carbon black) is taken, 0.16g hydroxide is then added
Sodium (0.00400029mol is equivalent to 0.025 times of silochrom), (0.00749866mol is equivalent to 0.495g potassium hydroxide
0.046 times of white carbon black) and 0.170g potassium chloride (0.00228035mol is equivalent to 0.014 times of white carbon black) with adjust
Potassium content is slowly added to white carbon black 10g (0.163062mol) after stirring 5-10min dissolution, stirs 10min, silicon source is added
Solution at the uniform velocity stirs 3h.
The crystal seed of Beta zeolite prepared by embodiment 1 is added, dosage 0.2g is sufficiently stirred.
It is transferred to crystallization 48h in the baking oven for be placed in reaction kettle 140 DEG C.
Product after crystallization is subjected to conventional suction filtration or centrifuge separation, being washed with deionized to product leacheate pH is 7-8,
The dry 12h in 90 DEG C of baking oven later, is finally warming up to after 550 DEG C with the rate of 2 DEG C/min in Muffle furnace and continues to roast
6, obtain big crystal grain Beta zeolite powder；
Big crystal grain Beta zeolite powder is put into conical flask, the NH of 1mol/L is added in 1:20 in mass ratio4Cl solution, In
2h is stirred under 90 DEG C of water bath conditions carries out ion exchange, sample is separated, washed, dried, roast, repeat ammonium exchange once,
Obtain final big crystal grain Beta zeolite.
Fig. 4 is the scanning electron microscope (SEM) photograph for the big crystal grain Beta zeolite being prepared, and shows that sample particle diameter is uniform in figure, in spherical
And fusiform, crystallite dimension are about 0.8 μm -1.1 μm.
Embodiment 4
A kind of preparation method of big crystal grain Beta zeolite is present embodiments provided, specifically includes the following steps:
Taking the 25wt% tetraethyl ammonium hydroxide solution of 26.3g, (0.0446368mol is equivalent to the 0.27 of silochrom
Times) the 0.616g sodium aluminate (Al of 0.00271871mol is added2O3, it is equivalent to 0.017 times of silochrom), stir 5-10min
Form uniform silicon source solution.
7.66g deionized water (0.425556mol is equivalent to 2.61 times of silochrom) is taken, 0.16g hydrogen-oxygen is then added
Change sodium (0.00400029mol is equivalent to 0.025 times of silochrom), and 0.48g potassium hydroxide (0.00727143mol, quite
In 0.045 times of silochrom), it is slowly added to silochrom 10g (0.163062mol), stirs after stirring 5-10min dissolution
10min is added silicon source solution and at the uniform velocity stirs 3h.
The crystal seed of Beta zeolite prepared by embodiment 1 is added, dosage 0.2g is sufficiently stirred.
It is transferred to crystallization 48h in the baking oven for be placed in reaction kettle 140 DEG C.
Product after crystallization is subjected to conventional suction filtration or centrifuge separation, being washed with deionized to product leacheate pH is 7-8,
The dry 12h in 100 DEG C of baking oven later, is finally warming up to after 550 DEG C with the rate of 3 DEG C/min in Muffle furnace and continues to roast
5h obtains big crystal grain Beta zeolite powder；
Obtained big crystal grain Beta zeolite powder is put into conical flask, the NH of 1mol/L is added in 1:20 in mass ratio4Cl
Solution stirs 3.5h under 80 DEG C of water bath conditions and carries out ion exchange, and sample is separated, washed, dried, roast, and ammonium is repeated
Exchange is primary, obtains final big crystal grain Beta zeolite.
Fig. 5 is the scanning electron microscope (SEM) photograph for the big crystal grain Beta zeolite being prepared, and shows that sample particle diameter is uniform in figure, is in ball
Shape, crystallite dimension are about 0.8 μm -1.1 μm.
Embodiment 5
A kind of preparation method of big crystal grain Beta zeolite is present embodiments provided, specifically includes the following steps:
5.2g tetraethylammonium bromide (0.0247431mol is equivalent to 0.30 times of silochrom) is taken to be added to 12.23g
In ionized water (0.6794441mol is equivalent to 8.33 times of silochrom), addition 0.74g sodium aluminate be (0.00326599mol's
Al2O3, it is equivalent to 0.040 times of silochrom), stirring 5-10min forms uniform silicon source solution.
16.35g deionized water (0.908333mol is equivalent to 11.14 times of silochrom) is taken, 4.00g ammonia is then added dropwise
Water (0.0587199molNH3, it is equivalent to 0.72 times of silochrom), 0.61g sodium hydroxide is then added
(0.00636250mol is equivalent to gross porosity for (0.0152515mol is equivalent to 0.19 times of silochrom) and 0.42g potassium hydroxide
0.078 times of silica gel), it is slowly added to silochrom 5g (0.0815308mol) after stirring 5-10min dissolution, stirs 10min, add
Enter silicon source solution and at the uniform velocity stirs 3h.
The crystal seed of Beta zeolite prepared by embodiment 1 is added, dosage 0.5g is sufficiently stirred.
It is transferred to crystallization 72h in the baking oven for be placed in reaction kettle 140 DEG C.
Product after crystallization is subjected to conventional suction filtration or centrifuge separation, being washed with deionized to product leacheate pH is 7-8,
The dry 12h in 100 DEG C of baking oven later, is finally warming up to after 550 DEG C with the rate of 2 DEG C/min in Muffle furnace and continues to roast
6h obtains big crystal grain Beta zeolite powder；
Big crystal grain Beta zeolite powder is put into conical flask, the NH of 1mol/L is added in 1:30 in mass ratio4Cl solution, In
3h is stirred under 90 DEG C of water bath conditions carries out ion exchange, sample is separated, washed, dried, roast, repeat ammonium exchange once,
Obtain big crystal grain Beta zeolite.
Fig. 6 is the XRD diagram of big crystal grain Beta zeolite, it can be seen that sample has typical Beta zeolite characteristic diffraction peak,
And without other stray crystal diffraction maximums, illustrate that sample crystal phase is good.
Fig. 7 is the scanning electron microscope (SEM) photograph for the big crystal grain Beta zeolite being prepared, and shows that sample particle diameter is unevenly distributed in Fig. 7
Even, generally in spherical form, crystallite dimension is about 0.8 μm -1.1 μm.
Embodiment 6
A kind of preparation method of big crystal grain Beta zeolite is present embodiments provided, specifically includes the following steps:
The tetraethylammonium bromide (0.0247431mol is equivalent to 0.30 times of silochrom) of 5.2g is taken to be added to 12.23g
In deionized water (1.587778mol is equivalent to 19.47 times of silochrom), 0.74g sodium aluminate (0.00326599mol is added
Al2O3, it is equivalent to 0.040 times of silochrom), stirring 5-10min forms uniform silicon source solution.
16.35g deionized water (1.587778mol is equivalent to 19.47 times of silochrom) is taken, 4.00g ammonia is then added dropwise
Water (the NH of 0.0587199mol3, it is equivalent to 0.72 times of silochrom), the sodium hydroxide of 0.61g is then added
(0.00636250mol is equivalent to gross porosity for (0.0152515mol is equivalent to 0.19 times of silochrom) and 0.42g potassium hydroxide
0.078 times of silica gel) and 0.32g potassium chloride (0.00429242mol is equivalent to 0.053 times of silochrom) to adjust potassium
Ion concentration is slowly added to silochrom 5g (0.0815308mol) after stirring 5-10min dissolution, stirs 10min, silicon source is added
Solution at the uniform velocity stirs 3h.
The crystal seed of Beta zeolite prepared by embodiment 1 is added, dosage 0.5g is sufficiently stirred.
It is transferred to crystallization 72h in the baking oven for be placed in reaction kettle 130 DEG C.
Product after crystallization is subjected to conventional suction filtration or centrifuge separation, being washed with deionized to product leacheate pH is 7-8,
The dry 12h in 100 DEG C of baking oven later, is finally warming up to after 550 DEG C with the rate of 2 DEG C/min in Muffle furnace and continues to roast
6h obtains big crystal grain Beta zeolite powder；
Obtained big crystal grain Beta zeolite powder is put into conical flask, the NH of 1mol/L is added in 1:20 in mass ratio4Cl
Solution stirs 3h under 90 DEG C of water bath conditions and carries out ion exchange, and sample is separated, washed, dried, roast, and repeats ammonium and hands over
It changes once, obtains big crystal grain Beta zeolite.
Fig. 8 is the scanning electron microscope (SEM) photograph for the big crystal grain Beta zeolite being prepared, and shows that sample particle diameter is unevenly distributed in figure,
Generally in spherical form, crystallite dimension is about 0.7 μm -1.1 μm
Comparative example 1
This comparative example provides a kind of routine Beta zeolite.
Fig. 9 is the scanning electron microscope (SEM) photograph of routine Beta zeolite, shows that sample particle diameter is evenly distributed in figure, generally in spherical form, brilliant
Particle size is less than 0.5 μm.
Comparative example 2
This comparative example provides a kind of Beta zeolite, specifically includes the following steps:
Hydrothermal synthesis system is made according to the embodiment 2 of the Chinese patent application of Publication No. CN102923728, crystallization,
The methods of filtering and its molar ratio refer to the embodiment of the invention, specifically:
By sodium aluminate, tetraethyl ammonium hydroxide, tetraethylammonium bromide, deionized water, sodium hydroxide, triethanolamine by mole
Than: SiO2/Al2O3=120, TEA+/SiO2=0.90, H2O/SiO2=15, Na+/SiO2=0.17, triethanolamine/SiO2=
0.25 mixing, is then added the crystal seed of mass fraction 2%, is to react 85 hours under 80 revs/min with 150 DEG C, revolving speed, is located later
Reason obtains Beta zeolite.
Figure 10 is the electron microscope that big grain Beta zeolite is prepared, and shows that sample crystallite dimension is about 0.45 μm in figure.
Comparative example 3
This comparative example provides a kind of method that no crystal seed introduces synthesizing small-grain Beta zeolite, specifically includes following step
It is rapid:
Taking the tetraethyl ammonium hydroxide solution of the 25wt% of 18.60g, (0.031568mol is equivalent to the 0.19 of silochrom
Times) the 0.533g sodium aluminate (Al of 0.00235239mol is added2O3, it is equivalent to 0.014 times of silochrom) and form uniform silicon source
Solution.
It takes in 7.95g deionized water (0.441667mol is equivalent to 2.71 times of silochrom), 0.16g hydrogen is then added
Sodium oxide molybdena (0.00400029mol is equivalent to 0.025 times of silochrom), 0.49g potassium hydroxide (0.00749866mol, phase
When in 0.046 times of silochrom), it is slowly added to silochrom 10g (0.163062mol), stirs after stirring 5-10min dissolution
10min is added silicon source solution and at the uniform velocity stirs 3h.
Above-mentioned raw material prepares liquid and is transferred to crystallization 48h in the baking oven for be placed in reaction kettle 140 DEG C.
Product after crystallization is subjected to conventional suction filtration or centrifuge separation, being washed with deionized to product leacheate pH is 7-8,
The dry 12h in 100 DEG C of baking oven later, is finally warming up to after 550 DEG C with the rate of 2 DEG C/min in Muffle furnace and continues to roast
6h obtains Beta zeolite powder；
Beta zeolite powder is put into conical flask, the NH of 1mol/L is added in 1:20 in mass ratio4Cl solution, in 90 DEG C of water
3h is stirred under the conditions of bath and carries out ion exchange, and sample is separated, washed, dried, roast, and is repeated ammonium exchange once, is obtained most
Whole Beta zeolite.
Figure 11 is the scanning electron microscope (SEM) photograph for the Beta zeolite being prepared, and shows that sample particle diameter is unevenly distributed in figure, is in ball
Shape, crystallite dimension is less than 0.5 μm.
Comparative example 4
This comparative example provides a kind of preparation method of little crystal grain Beta zeolite, specifically includes the following steps:
Taking the tetraethyl ammonium hydroxide solution of the 25wt% of 18.60g, (0.031568mol is equivalent to the 0.19 of silochrom
Times) 7.95g deionized water (0.441667mol is equivalent to 2.71 times of silochrom) is added, 0.533g sodium aluminate is added
(the Al of 0.00235239mol2O3, it is equivalent to 0.014 times of silochrom), 0.16g sodium hydroxide (0.00400029mol, phase
When in 0.025 times of silochrom), 0.495g potassium hydroxide (0.00749866mol is equivalent to 0.046 times of silochrom),
It stirs 5-10min and forms homogeneous solution, be then slowly added to silochrom 10g (0.163062mol) and at the uniform velocity stir 3h.
The crystal seed of Beta zeolite prepared by embodiment 1 is added, dosage 0.2g is sufficiently stirred.
Above-mentioned raw material preparation liquid is transferred in reaction kettle and is placed in crystallization 48h in 140 DEG C of baking ovens.
Product after crystallization is subjected to conventional suction filtration or centrifuge separation, being washed with deionized to product leacheate pH is 7-8,
The dry 12h in 100 DEG C of baking oven later, is finally warming up to after 550 DEG C with the rate of 2 DEG C/min in Muffle furnace and continues to roast
6h obtains Beta zeolite powder；
Obtained Beta zeolite powder is put into conical flask, the NH4Cl solution of 1mol/L, In is added in 1:20 in mass ratio
3h is stirred under 90 DEG C of water bath conditions carries out ion exchange, sample is separated, washed, dried, roast, repeat ammonium exchange once,
Obtain final Beta zeolite.
Figure 12 is the scanning electron microscope (SEM) photograph for the Beta zeolite being prepared, and shows that sample particle diameter is uniform in figure, is in spherical, crystal grain
Size is about 0.3-0.5 μm.
Pass through the comparison of embodiment 2, embodiment 5 and comparative example 1-4, it is found that obtain big crystal grain Beta zeolite
Synthesis, the introducing of crystal seed is necessary, meanwhile, there are specific silicon source and silicon source for silicon-aluminum sol-gel configuration step
It is required that: silicon source, using K ion is introduced, changes the depolymerization and polycondensation state of silicate ion in alkaline solution, obtains specific
Silicate ion state；Silicon source obtains specific hydrolysate under the action of alkaline organic formwork agent；Silicon source and silicon source mixing
Afterwards, under the auxiliary of crystal seed, promote the growth of crystal.
Application examples 1
BET test is done to embodiment 2, embodiment 5 and comparative example 1Beta zeolite；It the results are shown in Table 1.
Wherein, specific surface and Kong Rong are obtained by the method that nitrogen adsorption is desorbed, and by detection device, (nitrogen adsorption is desorbed data
Analyzer) it provides.
The specific surface and Kong Rong of 1 sample of table
Table 1 is as the result is shown: compared with conventional Beta zeolite, embodiment 2, embodiment 5 have lower mesopore volume.
NH is done to embodiment 2, embodiment 5 and comparative example 13- TPD and levulic acid are esterified reaction test；It the results are shown in Table 2.
Wherein, peak position and acid amount are obtained by the method that ammonia gas absorption is desorbed, and list data is (multi-functional dynamic by detection device
State adsorption instrument) processing after provide.Reaction condition are as follows: ethyl alcohol: levulic acid=19.8:5.0g；Catalyst: 0.5g；Reaction temperature:
70℃；Reaction time: 1h；TOF value is the result that the acidimeter based on zeolite strong acid is calculated.
The Acidity and levulic acid of 2 sample of table are esterified reactivity
As seen from the results in Table 2, big crystal grain Beta zeolite synthesized compared with traditional Beta zeolite has good acidity
Matter, and there is good catalytic reaction activity and stability in levulic acid esterification reaction.
The above result shows that Beta zeolite provided by the invention is big crystal grain Beta zeolite, activity is high, and stability is good, In
There is excellent performance in levulic acid esterification reaction.
Claims (10)
1. a kind of preparation method of Beta zeolite, the preparation method the following steps are included:
Micropore organic formwork agent, water are mixed, silicon source is added after stirring, stirs to clarify, obtains silicon source solution；
Sodium hydroxide and/or ammonium hydroxide is added in Xiang Shuizhong, and the halide of potassium hydroxide or potassium is added, adds silicon source, stirs, obtains
Silicon source solution；
Silicon source solution and silicon source solution are mixed, the crystal seed of Beta zeolite is added in stirring, carries out crystallization；
Crystallization product is separated, washed, dried, roast, ammonium ion exchange is then carried out, obtains Beta zeolite.
2. preparation method according to claim 1, wherein the micropore organic formwork agent is tetraethyl ammonium hydroxide or four
Ethyl phosphonium bromide ammonium.
3. preparation method according to claim 2, wherein with SiO in silicon source2, Al in silicon source2O3With micropore organic formwork
The molar ratio computing of tetraethylammonium cation in agent:
When using tetraethyl ammonium hydroxide as micropore organic formwork agent, tetraethyl ammonium hydroxide, water, silicon source, silicon source, sodium ion and
The molar ratio of potassium ion is (0.15-0.55): (2.25-4.25): (0.014-0.017): 1:(0.01-0.04): (0.04-
0.08)；
When using tetraethylammonium bromide as micropore organic formwork agent, tetraethylammonium bromide, water, silicon source, silicon source, ammonium hydroxide, sodium ion
Molar ratio with potassium ion is (0.15-0.55): (17-26): (0.02-0.1): 1:(0.6-0.8): (0.15-0.25):
(0.07-0.14)。
4. preparation method according to claim 1, wherein the crystal seed of the Beta zeolite is prepared by following steps
It arrives:
Micropore organic formwork agent, water are mixed, silicon source is added after stirring, stirs to clarify, obtains silicon source solution；
Sodium hydroxide is added in Xiang Shuizhong, and silicon source is added, and stirring obtains silicon source solution；
Silicon source solution and silicon source solution are mixed, stirring carries out crystallization；
Crystallization product is separated, washed, dried, roast, the crystal seed of Beta zeolite is obtained.
5. preparation method according to claim 1, wherein the crystal seed of the Beta zeolite and the mass ratio of silicon source are
(0.02-0.15): 1.
6. preparation method according to claim 1, wherein the temperature of the crystallization is 130 DEG C -150 DEG C, the time of crystallization
For -80h for 24 hours.
7. preparation method according to claim 1, wherein the ammonium ion exchange follows the steps below:
With the mass ratio of 1:20-40, the NH of 0.5mol/L-1.5mol/L is added into the crystallization product after roasting4Cl solution, In
2h-4h is stirred under 80 DEG C of -100 DEG C of water bath conditions and carries out ion exchange, is separated, washed, dried, roasts, and repeats ammonium exchange one
It is secondary；
Preferably, washing to solution ph is 7-8；
Preferably, dry temperature is 60 DEG C -100 DEG C, and the dry time is 8h-12h；
Preferably, roasting is constant temperature calcining 4h-6h after being warming up to 500 DEG C -600 DEG C with the rate of 1 DEG C/min-4 DEG C/min.
8. preparation method according to claim 1, wherein source of aluminium is sodium aluminate or boehmite；Preferably, institute
Stating silicon source is silochrom or white carbon black.
9. a kind of Beta zeolite is prepared by the preparation method of the described in any item Beta zeolites of claim 1-8
's；
The partial size of the Beta zeolite is 0.6 μm -1.1 μm.
10. the application of Beta zeolite as claimed in claim 9, the Beta zeolite is for being catalyzed levulic acid esterification reaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114713279A (en) * | 2021-01-06 | 2022-07-08 | 中国石油天然气股份有限公司 | Light gasoline olefin-reduction-modification catalyst and preparation method thereof, and light gasoline olefin-reduction-modification method |
| CN114931971A (en) * | 2022-04-26 | 2022-08-23 | 榆林学院 | Nickel nanocluster supported intercrystalline mesoporous zeolite catalyst and preparation method and application thereof |
| CN115385353A (en) * | 2022-09-14 | 2022-11-25 | 青岛惠城环保科技集团股份有限公司 | Method for preparing Beta molecular sieve by using green low-template agent |
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| US5164170A (en) * | 1991-06-14 | 1992-11-17 | Mobil Oil Corporation | Synthesis of zeolite Beta |
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| US5164170A (en) * | 1991-06-14 | 1992-11-17 | Mobil Oil Corporation | Synthesis of zeolite Beta |
| CN108275698A (en) * | 2018-03-19 | 2018-07-13 | 中国石油大学(北京) | A kind of Beta/ZSM-12 symbiosis zeolite molecular sieve and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114713279A (en) * | 2021-01-06 | 2022-07-08 | 中国石油天然气股份有限公司 | Light gasoline olefin-reduction-modification catalyst and preparation method thereof, and light gasoline olefin-reduction-modification method |
| CN114931971A (en) * | 2022-04-26 | 2022-08-23 | 榆林学院 | Nickel nanocluster supported intercrystalline mesoporous zeolite catalyst and preparation method and application thereof |
| CN114931971B (en) * | 2022-04-26 | 2023-11-14 | 榆林学院 | Nickel nanocluster loaded intergranular mesoporous zeolite catalyst and preparation method and application thereof |
| CN115385353A (en) * | 2022-09-14 | 2022-11-25 | 青岛惠城环保科技集团股份有限公司 | Method for preparing Beta molecular sieve by using green low-template agent |
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