CN106966407A - A kind of method of the synthesizing small-grain TS 1 in eutectic solvent - Google Patents
A kind of method of the synthesizing small-grain TS 1 in eutectic solvent Download PDFInfo
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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Abstract
The invention discloses a kind of method of the synthesizing small-grain TS 1 in eutectic solvent, comprise the following steps：A is mixed it with urea, ethylene glycol or glycerine based on Choline Chloride, and eutectic solvent is made at 70 100 DEG C；Eutectic solvent made from titanium source, silicon source, alkali source and step a is placed in there-necked flask by b, is stirred at room temperature, is obtained reactant mixture；The obtained reactant mixtures of step b are placed in static crystallization at 170 200 DEG C by c, and then cooling obtains the products of little crystal grain TS 1.The present invention uses eutectic solvent, and the solvent is good to dissolution of raw material performance, is conducive to the scattered of raw material；Without vapour pressure during crystallization, and be conducive to the generation of the molecular sieves of little crystal grain TS 1；Reaction mother liquor is non-toxic, biodegradable, more environmentally friendly.This method also has technique simple, it is easy to operate, the advantages of synthesis cycle is shorter, can meet the current growing market demand.
Description
Technical field
The present invention relates to a kind of synthetic method of TS-1 molecular sieves, concretely relate to one kind and closed in eutectic solvent
Into little crystal grain TS-1 method, belong to catalyst carrier preparation field.
Background technology
Catalytic chemistry is a not only ancient but also practical subject, and catalyst is used as a kind of indispensable chemical industry medicine
Product, are widely used in the every field of chemical industry.Porous catalyst material (molecular sieve) is due to its Hole bottom cavity blast and activity
Controllability, developing environmentally friendly technique, promoting have huge potentiality in environment sustainable development.Particularly in recent years,
The use of molecular sieve catalyst has greatly facilitated the development of the industries such as petrochemical industry, fine chemistry industry and environmental protection.Classical zeolite
Molecular sieve refers to silicon aluminate crystal, later, and the hetero atoms such as titanium, vanadium, cerium, cobalt are introduced into molecular sieve and form hetero atom boiling by people
Stone molecular sieve.Titanium atom is incorporated into the HTS that molecular sieve obtains can make it obtain special catalytic selective oxidation
Energy.The titanium-silicon molecular sieve TS-1 that nineteen eighty-three Taramasso etc. is reported first, with H2O2To have in the oxidation reaction of oxidant
Special catalytic performance, reaction condition is gentle, and reaction selectivity is high, and byproduct is water, and environmental sound, atom utilization is high.
In recent years, TS-1/H can be applied2O2The reaction of oxidation system has：Phenol hydroxylation system is adjacent, hydroquinones, ammoxidation of cyclohexanone
Preparing cyclohexanone oxime, epoxidation of propylene expoxy propane, styrene oxidation producing benzaldehyde, phenylacetaldehyde etc..Numerous oxidation systems into
Work(exploitation imply that TS-1 molecular sieves have a wide range of applications value in the industry.Therefore, inexpensive, safe and environment-friendly TS-1
Zeolite synthesis method is always the emphasis of researcher (including manufacturing enterprise) concern.
Patent CN 201310564398.7 discloses a kind of method for preparing TS-1 molecular sieves, although the synthetic method is not
Using template, pollution can be reduced to a certain extent, but building-up process is relatively complicated, raw material dosage is more, and yield is relatively low.
Patent CN 201310368674.2 discloses a kind of preparation method of TS-1 HTSs, and this method is at 55 DEG C
Environment in synthesized, and crystallization time is longer, and condition is complex.
Patent CN 97104636.0 discloses a kind of process using silica gel as Material synthesis titanium-silicon molecular sieve TS-1,
This method whole process is carried out in autoclave, and condition is more harsh, and crystallization time is longer, and the synthesis of molecular sieve cycle is longer.
Patent CN 201610052270.6 discloses a kind of hydrothermal synthesis method of TS-1 molecular sieves, and program cost is low
It is honest and clean, but building-up process is longer, temperature is higher, and process is complex.
TS-1 molecular sieves in aqueous systems, under conditions of highly basic is present, are synthesized by the self-generated pressure of water mostly.This is to anti-
Equipment is answered to propose certain pressure-resistant, corrosion-resistant requirement.Meanwhile, most synthetic methods are to add the bar of organic formwork agent
Carried out under part, its crystallization time does not refer to the reaction mother liquor recycling containing organic solvent from a few houres by several days yet
Problem.
The content of the invention
Based on above-mentioned technical problem, the present invention provides a kind of method of the synthesizing small-grain TS-1 in eutectic solvent.
The adopted technical solution is that：
A kind of method of the synthesizing small-grain TS-1 in eutectic solvent, comprises the following steps：
A is mixed with urea (urea), ethylene glycol (ETA) or glycerine (GLY) by it based on Choline Chloride (ChCl)
Close, eutectic solvent is made at 70-100 DEG C；
Eutectic solvent made from titanium source, silicon source, alkali source and step a is placed in there-necked flask by b, is stirred at room temperature, and obtains anti-
Answer mixture；
The obtained reactant mixtures of step b are placed in static crystallization at 170-200 DEG C by c, and then cooling obtains little crystal grain TS-
1 product.
In step a：The mol ratio of Choline Chloride and urea, ethylene glycol or glycerine is preferably 1: 2；Solvent mixing temperature is more
Plus preferably 80 DEG C.
In step b：Titanium source is preferably the one or more in titanium dioxide, butyl titanate, ammonium hexa-fluorotitanate；Silicon source is preferred
For the one or more in tetraethyl orthosilicate, Ludox, waterglass；Alkali source (i.e. template) is preferably TPAOH
(TPAOH)。
In above-mentioned steps, silicon source is with SiO2Meter, titanium source is with TiO2Meter, titanium source, silicon source, alkali source and eutectic solvent system
The mol ratio of standby raw material (Choline Chloride and urea/ethylene glycol/glycerin) is 1TiO2:(14~60) SiO2:13.8 tetrapropyl hydrogen
Amine-oxides (TPAOH):206.8 urea (urea)/ethylene glycol (ETA)/glycerine (GLY):103.4 Choline Chlorides (ChCl).
In step b：The mixing time is preferably 1-3 hours, more preferably 1.5 hours.
In step c：Static crystallization temperature is more preferably 180 DEG C, and the static crystallization time is preferably 24-72 hours, more
It is preferred that 48 hours.
In step c：Static crystallization is carried out preferably in closed container, without autoclave.
The method have the benefit that：
The present invention uses eutectic solvent, and the solvent is good to dissolution of raw material performance, is conducive to the scattered of raw material；During crystallization without
Vapour pressure, and be conducive to the generation of little crystal grain TS-1 molecular sieves；Reaction mother liquor is non-toxic, biodegradable, more environmentally friendly.The party
Method also has technique simple, it is easy to operate, the advantages of synthesis cycle is shorter, can meet the current growing market demand.
Object TS-1 molecular sieves of the present invention can be with H2O2A kind of oxidation system is formed, the system can be applied to phenolic hydroxy
In the reaction such as change, cyclohexanone oxamidinating, epoxidation of propylene, styrene oxidation, with reaction condition is gentle, reaction selectivity is high,
Environmentally friendly (byproduct is water), the advantages of atom utilization is high.
Brief description of the drawings
Fig. 1 is the gained TS-1 of embodiment 1 X-ray diffraction (XRD) figure；
Fig. 2 is the gained TS-1 of embodiment 1 ESEM (SEM) figure；
Fig. 3 is the gained TS-1 of embodiment 1 FFIR (FTIR) figure.
Embodiment
The present invention, which is solved, must use autoclave to cause asking for certain potential safety hazard in existing preparation method
There is provided the synthesizing small-grain TS- in without the high eutectic solvent system of vapour pressure, nontoxicity, biodegradable, solubility for topic
1 method.This method replaces water from the eutectic solvent based on urea, using inorganic and organic compound as titanium source and silicon
Source, under the template action of TPAOH, has obtained that crystal grain is small, crystallinity is high in certain temperature crystallization certain time
TS-1 molecular sieves.Than hydrothermal synthesis method, self-generated pressure is not present in this method, therefore without using autoclave, it is only necessary to
Want closed container；Remaining reaction mother liquor is non-toxic after crystallization, biodegradable, effectively reduces environmental pollution；In synthesis
Titanium source is no longer only limitted to butyl titanate, and inorganic ti sources are included into raw material range, has widened the range of choice of titanium source and silicon source, can
Cost is reduced to a certain extent；Building-up process is simple and easy to apply, and gained TS-1 sieve particles are tiny, crystallinity is high.
With reference to specific embodiment, the invention will be further described.
Embodiment 1
According to 1TiO2:14SiO2:13.8TPAOH:206.8urea:103.4ChCl ratio carries out the conjunction of TS-1 molecular sieves
Into.11.10 kilograms of urea and 12.9 kilograms of Choline Chlorides are added in there-necked flask, are heated to after molten condition being down to room in 80 DEG C
Temperature.0.30 kilogram of butyl titanate, 10.00L TPAOHs, 10.00L tetraethyl orthosilicates are added into there-necked flask.Room temperature
Stir after 1.5h, mixed solution is transferred in sealed polytetrafluoroethylcontainer container, in 180 DEG C of crystallization 48h.Produced after cooling
Thing, sample is obtained by the product through centrifugation, washing, dry and roasting.The XRD of the sample as shown in figure 1, through with TS-1 molecules
Sieve standard sample crystalline phase figure compares, it was demonstrated that synthesized product is TS-1 molecular sieves.The SEM figures of the sample are as shown in Fig. 2 through analysis
Gained molecular sieve particle diameter is 0.3 μm.The FTIR spectrograms of the sample are as shown in Figure 3.Composed through corresponding to TS-1 zeolites samples
Figure compares, it was demonstrated that Ti has been successfully entered skeleton in gained sample, that is, successfully synthesizes TS-1 molecular sieves.
Embodiment 2
According to 1TiO2:14SiO2:13.8TPAOH:206.8urea:103.4ChCl ratio carries out the conjunction of TS-1 molecular sieves
Into.11.10 kilograms of urea and 12.9 kilograms of Choline Chlorides are added in there-necked flask, are heated to after molten condition being down to room in 80 DEG C
Temperature.0.30 kilogram of butyl titanate, 10.00L TPAOHs, 3.83 kilograms of Ludox are added into there-necked flask.Room temperature is stirred
Mix after 1.5h, mixed solution is transferred in sealed polytetrafluoroethylcontainer container, in 180 DEG C of crystallization 72h.Produced after cooling
Thing, sample is obtained by the product through centrifugation, washing, dry and roasting.Through analysis, gained molecular sieve particle diameter is 0.5 μm.
Embodiment 3
According to 1TiO2:14SiO2:13.8TPAOH:206.8urea:103.4ChCl ratio carries out the conjunction of TS-1 molecular sieves
Into.11.10 kilograms of urea and 12.9 kilograms of Choline Chlorides are added in there-necked flask, are heated to after molten condition being down to room in 80 DEG C
Temperature.0.30 kilogram of butyl titanate, 10.00L TPAOHs, 2.94 kilograms of waterglass are added into there-necked flask.Room temperature is stirred
Mix after 1.5h, mixed solution is transferred in sealed polytetrafluoroethylcontainer container, in 180 DEG C of crystallization 72h.Produced after cooling
Thing, sample is obtained by the product through centrifugation, washing, dry and roasting.Through analysis, gained molecular sieve particle diameter is 0.4 μm.
Embodiment 4
According to 1TiO2:14SiO2:13.8TPAOH:206.8urea:103.4ChCl ratio carries out the conjunction of TS-1 molecular sieves
Into.11.10 kilograms of urea and 12.9 kilograms of Choline Chlorides are added in there-necked flask, are heated to after molten condition being down to room in 80 DEG C
Temperature.0.18 kilogram of ammonium titanium fluoride, 10.00L TPAOHs, 2.94 kilograms of waterglass are added into there-necked flask.Room temperature is stirred
Mix after 1.5h, mixed solution is transferred in sealed polytetrafluoroethylcontainer container, in 180 DEG C of crystallization 72h.Produced after cooling
Thing, sample is obtained by the product through centrifugation, washing, dry and roasting.Through analysis, gained molecular sieve particle diameter is 0.5 μm.
Embodiment 5
According to 1TiO2:14SiO2:13.8TPAOH:206.8urea:103.4ChCl ratio carries out the conjunction of TS-1 molecular sieves
Into.11.10 kilograms of urea and 12.9 kilograms of Choline Chlorides are added in there-necked flask, are heated to after molten condition being down to room in 80 DEG C
Temperature.0.074 kilogram of titanium oxide, 10.00L TPAOHs, 3.83 kilograms of Ludox are added into there-necked flask.It is stirred at room temperature
After 1.5h, mixed solution is transferred in sealed polytetrafluoroethylcontainer container, in 190 DEG C of crystallization 48h.Product is obtained after cooling,
The product is obtained into sample through centrifugation, washing, dry and roasting.Through analysis, gained molecular sieve particle diameter is 0.5 μm.
Embodiment 6
According to 1TiO2:14SiO2:13.8TPAOH:206.8urea:103.4ChCl ratio carries out the conjunction of TS-1 molecular sieves
Into.11.10 kilograms of urea and 12.9 kilograms of Choline Chlorides are added in there-necked flask, are heated to after molten condition being down to room in 80 DEG C
Temperature.0.09 kilogram of ammonium titanium fluoride, 10.00L TPAOHs, 2.94 kilograms of waterglass are added into there-necked flask.Room temperature is stirred
Mix after 1.5h, mixed solution is transferred in sealed polytetrafluoroethylcontainer container, in 180 DEG C of crystallization 72h.Produced after cooling
Thing, sample is obtained by the product through centrifugation, washing, dry and roasting.Through analysis, gained molecular sieve particle diameter is 0.5 μm.
Embodiment 7
According to 1TiO2:14SiO2:13.8TPAOH:206.8urea:103.4ChCl ratio carries out the conjunction of TS-1 molecular sieves
Into.11.10 kilograms of urea and 12.9 kilograms of Choline Chlorides are added in there-necked flask, are heated to after molten condition being down to room in 80 DEG C
Temperature.0.15 kilogram of butyl titanate, 10.00L TPAOHs, 20.00L tetraethyl orthosilicates are added into there-necked flask.Room temperature
Stir after 1.5h, mixed solution is transferred in sealed polytetrafluoroethylcontainer container, in 180 DEG C of crystallization 72h.Produced after cooling
Thing, sample is obtained by the product through centrifugation, washing, dry and roasting.Through analysis, gained molecular sieve particle diameter is 0.6 μm.
Embodiment 8
According to 1TiO2:14SiO2:13.8TPAOH:206.8ETA:103.4ChCl ratio carries out the conjunction of TS-1 molecular sieves
Into.11.42 kilograms of ethylene glycol and 12.9 kilograms of Choline Chlorides are added in there-necked flask, are heated to being down to after molten condition in 80 DEG C
Room temperature.0.30 kilogram of butyl titanate, 10.00L TPAOHs, 10.00L tetraethyl orthosilicates are added into there-necked flask.Room
After temperature stirring 1.5h, mixed solution is transferred in sealed polytetrafluoroethylcontainer container, in 190 DEG C of crystallization 72h.Obtained after cooling
Product, sample is obtained by the product through centrifugation, washing, dry and roasting.Through analysis, gained molecular sieve particle diameter is 0.7 μm.
Embodiment 9
According to 1TiO2:14SiO2:13.8TPAOH:206.8GLY:103.4ChCl ratio carries out the conjunction of TS-1 molecular sieves
Into.16.95 kilograms of glycerine and 12.9 kilograms of Choline Chlorides are added in there-necked flask, are heated to being down to after molten condition in 80 DEG C
Room temperature.0.30 kilogram of butyl titanate, 10.00L TPAOHs, 10.00L tetraethyl orthosilicates are added into there-necked flask.Room
After temperature stirring 1.5h, mixed solution is transferred in sealed polytetrafluoroethylcontainer container, in 180 DEG C of crystallization 48h.Obtained after cooling
Product, sample is obtained by the product through centrifugation, washing, dry and roasting.Through analysis, gained molecular sieve particle diameter is 0.5 μm.
Claims (7)
1. a kind of method of the synthesizing small-grain TS-1 in eutectic solvent, it is characterised in that comprise the following steps：
A is mixed it with urea, ethylene glycol or glycerine based on Choline Chloride, eutectic is made at 70-100 DEG C molten
Agent；
Eutectic solvent made from titanium source, silicon source, alkali source and step a is placed in there-necked flask by b, is stirred at room temperature, and obtains reaction mixed
Compound；
The obtained reactant mixtures of step b are placed in static crystallization at 170-200 DEG C by c, and then cooling obtains little crystal grain TS-1 productions
Thing.
2. a kind of synthesizing small-grain TS-1 in eutectic solvent according to claim 1 method, it is characterised in that step
In rapid a：The mol ratio of Choline Chloride and urea, ethylene glycol or glycerine is 1: 2.
3. a kind of synthesizing small-grain TS-1 in eutectic solvent according to claim 1 method, it is characterised in that step
In rapid b：Titanium source is the one or more in titanium dioxide, butyl titanate, ammonium hexa-fluorotitanate；Silicon source is tetraethyl orthosilicate, silicon is molten
One or more in glue, waterglass；Alkali source is TPAOH.
4. a kind of synthesizing small-grain TS-1 in eutectic solvent according to claim 3 method, it is characterised in that：Silicon
Source is with SiO2Meter, titanium source is with TiO2Meter, titanium source, silicon source, the mol ratio of alkali source and eutectic solvent preparing raw material are 1TiO2:
(14~60) SiO2:13.8 TPAOHs:206.8 urea/ethylene glycol/glycerin:103.4 Choline Chloride.
5. a kind of synthesizing small-grain TS-1 in eutectic solvent according to claim 1 method, it is characterised in that step
In rapid b：The mixing time is 1-3 hours.
6. a kind of synthesizing small-grain TS-1 in eutectic solvent according to claim 1 method, it is characterised in that step
In rapid c：The static crystallization time is 24-72 hours.
7. a kind of synthesizing small-grain TS-1 in eutectic solvent according to claim 1 method, it is characterised in that step
In rapid c：Crystallization is carried out in closed container.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112919442A (en) * | 2021-01-25 | 2021-06-08 | 中南大学 | Preparation method of sodium ion battery positive electrode material sodium vanadium fluorophosphate |
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Application publication date: 20170721 |