CN109019627A - The preparation method of Titanium Sieve Molecular Sieve and preparation method thereof and propylene glycol - Google Patents
The preparation method of Titanium Sieve Molecular Sieve and preparation method thereof and propylene glycol Download PDFInfo
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Abstract
The present invention relates to Titanium Sieve Molecular Sieve fields, and in particular, to the preparation method of a kind of Titanium Sieve Molecular Sieve and preparation method thereof and propylene glycol.This method comprises: (1) mixes alkali source template and titanium source；(2) mixture that step (1) obtains is mixed with inorganic silicon source, and gained mixture is successively subjected to the first crystallization and the second crystallization；(3) product of second crystallization is directly roasted.The suitable Titanium Sieve Molecular Sieve of particle size can be made with higher yield and higher relative crystallinity in the preparation method of Titanium Sieve Molecular Sieve of the invention, and the Titanium Sieve Molecular Sieve is when preparing the catalyst of propylene glycol as low-carbon alcohols and propylene oxide progress etherification reaction, it can be improved the selectivity of 1,2-PD -1- monoalky lether in etherification product (namely 1- alkoxy -2- propyl alcohol).
Description
Technical field
The present invention relates to Titanium Sieve Molecular Sieve fields, and in particular, to a kind of Titanium Sieve Molecular Sieve and preparation method thereof and the third two
The preparation method of alcohol ether.
Background technique
Titanium-silicon molecular sieve TS-1 is introduced transition metal element titanium formed in the framework of molecular sieve with ZSM-5 structure
A kind of novel titanosilicate with superior catalytic selective oxidation performance.TS-1 not only has the catalysed oxidn of titanium,
But also shape-selective effect and excellent stability with ZSM-5 molecular sieve.Since TS-1 molecular sieve is anti-in the oxidation of organic matter
Ying Zhong can be used free of contamination low concentration hydrogen peroxide as oxidant, avoid oxidation process complex process and pollution environment
The problem of, there is the unrivaled energy conservation of conventional oxidation system, economy and advantages of environment protection, and there is good reaction choosing
Selecting property, therefore there is great prospects for commercial application.
The method of modifying of TS-1 is in 1981 by first public (USP 4410501).This method is that first modified one kind contains
There is the reaction mixture of silicon source, titanium source, organic base and/or basic anhydride, by this reaction mixture in 130- in autoclave
200 DEG C hydrothermal crystallizing 6-30 days, then separate, wash, dry, roast and product.Thangaraj et al. thinks the above method
In the TS-1 molecular sieve synthesized into skeleton effective titanium content it is seldom, then they disclosed in 1992 it is a kind of can be effective
The method (Zeolites, 1992, Vol.12:943) for increasing the synthesis TS-1 of Ti content in skeleton, it is said that this method can be by molecule
The Si/Ti ratio of sieve drops to 20 from 39.Wherein, this method is to be added to suitable tetrapropylammonium hydroxide (TPAOH) aqueous solution
Then stirring and dissolving certain time in ethyl silicate solution is slowly added to the aqueous isopropanol of butyl titanate with vigorous stirring
Obtaining clear liquid mixture (must be slowly added dropwise to prevent that tetrabutyl titanate hydrolysis is too fast and form white TiO2Precipitating),
After stirring 15min, it is slow added into suitable TPAOH aqueous solution, is turned after reaction mixture is then removed alcohol 3-6h in 75-80 DEG C
Move in autoclave the hydrothermal crystallizing 3-6d at 170 DEG C, it is dry after TS-1, wherein a mole group for reaction mixture becomes
SiO2: (0.01~0.10) TiO2: 0.36TPAOH:35H2O。
However, in the method for existing preparation Titanium Sieve Molecular Sieve, due to Ti itself to lead brilliant ability weak so that preparing titanium
The crystallization time of si molecular sieves is longer, while yield is relatively low.And when applying in catalytic oxidation, there are Titanium Sieve Molecular Sieve
The problems such as big activity of crystal grain is low, and the small separation of crystal grain is difficult.In recent years, although the technology of preparation Titanium Sieve Molecular Sieve is by certain
It improves, but effect is not also very ideal.
Propylene glycol monoether is important organic chemicals, such as propylene glycol monomethyl ether, also known as propylene glycol monomethyl ether, including two kinds same
Enantiomers: 1- methoxy-2-propanol (MME-1 namely 1,2-PD -1- monomethyl ether) and 2- methoxy-1-propanol (MME-
2 namely 1,2-PD -2- monomethyl ether).Propylene glycol monomethyl ether has faint ether taste, but does not have strong and stimulating smell, makes its purposes
It is more safe extensively.In addition to for the solvent of a variety of high-grade paints, it may also be used for conduct in chemical intermediate, brake formula of liquid
The numerous areas such as viscosity modifier and organic synthesis.
Summary of the invention
The purpose of the invention is to provide a kind of high income, relative crystallinity is high and the suitable titanium silicon of particle size point
The preparation method of son sieve and the preparation method of Titanium Sieve Molecular Sieve obtained by this method and propylene glycol.
To achieve the goals above, first aspect present invention provides a kind of preparation method of Titanium Sieve Molecular Sieve, this method packet
It includes:
(1) alkali source template and titanium source are mixed；
(2) mixture that step (1) obtains is mixed with inorganic silicon source, and gained mixture is successively subjected to the first crystallization
With the second crystallization；
(3) product of second crystallization is directly roasted；
Wherein, the temperature of first crystallization is 10-50 DEG C higher than the temperature of the second crystallization,
The condition of first crystallization includes: that temperature is 80-150 DEG C, time 4-10h；
The condition of second crystallization includes: that temperature is 140-200 DEG C, time 6-24h.
Second aspect of the present invention provides Titanium Sieve Molecular Sieve made from the above method.
Third aspect present invention provides a kind of preparation method of propylene glycol monomethyl ether, this method comprises: in above-mentioned titanium silicon point
Low-carbon alcohols and propylene oxide are carried out etherification reaction as in the presence of catalyst by son sieve.
The preparation method of Titanium Sieve Molecular Sieve of the invention can be obtained with higher yield and higher relative crystallinity
The suitable Titanium Sieve Molecular Sieve of particle size, is omitted the solid-liquid separation steps such as the filtering of conventional manufacturing process, so that entire molecular sieve
The basic non-wastewater discharge of preparation process.And the Titanium Sieve Molecular Sieve is carrying out etherification reaction preparation third as low-carbon alcohols and propylene oxide
When the catalyst of glycol ethers, 1,2-PD -1- monoalky lether in etherification product (namely 1- alkoxy -2- propyl alcohol) can be improved
Selectivity.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of preparation method of Titanium Sieve Molecular Sieve, this method comprises:
(1) alkali source template and titanium source are mixed；
(2) mixture that step (1) obtains is mixed with inorganic silicon source, and gained mixture is successively subjected to the first crystallization
With the second crystallization；
(3) product of second crystallization is directly roasted；
Wherein, the temperature of first crystallization is 10-50 DEG C higher than the temperature of the second crystallization,
The condition of first crystallization includes: that temperature is 80-150 DEG C, time 4-10h；
The condition of second crystallization includes: that temperature is 140-200 DEG C, time 6-24h.
According to the present invention, the preparation method of above-mentioned Titanium Sieve Molecular Sieve, first by by titanium source in the presence of alkali source template
It is hydrolyzed, is then mixed again with inorganic silicon source, can be used to subsequent hydrothermal crystallizing processing, doing so not only can be improved instead
The solid content to feed intake in kettle is answered, improves the capacity utilization of crystallization apparatus, and surprisingly, titanium silicon molecule of the invention
The preparation method of sieve can obtain the relatively high Titanium Sieve Molecular Sieve of crystallinity, and such titanium silicon molecule with higher yield
Sifter device has higher catalytic activity, can be improved 1 in etherification product when being catalyzed low-carbon alcohols and propylene oxide carries out etherification reaction,
The selectivity of 2- propylene glycol -1- monoalky lether (namely 1- alkoxy -2- propyl alcohol).
According to the present invention, the titanium source is introduced in the aqueous solution of the alkali source template and is carried out, example in step (1)
Such as concentration of the aqueous solution of the alkali source template can be 5-30 weight %.
According to the present invention, the titanium source can be the chemical combination containing titanium used by this field routinely preparation Titanium Sieve Molecular Sieve
Object, such as the titanium source are one of inorganic titanium salt and organic titanate or a variety of.Wherein, the inorganic titanium salt can be various
Hydrolyzable inorganic titanium salt, preferably TiCl4、Ti(SO4)2And TiOCl2One of or it is a variety of.Wherein, organic metatitanic acid
Ester is preferably formula R1 4TiO4Compound represented, wherein R1Alkyl selected from C2-C4, and 4 R1It can be identical or different.It is more excellent
Selection of land, the organic titanate are selected from as one of isopropyl titanate, metatitanic acid n-propyl, butyl titanate and tetraethyl titanate
Or it is a variety of.
According to the present invention, the alkali source template can be used to prepare various alkali used by Titanium Sieve Molecular Sieve for this field
The template of property, for example, one of quaternary amine alkaloid compound, fat amine compound and alcamine compound or a variety of.
Wherein, the quaternary amine alkaloid compound can be the various quaternary amine alkalis of this field, and the quaternary amine alkaloid compound can
By formulaIt is represented, each R in the formula2It is each independently the alkyl of C1-C4, such as can be with
It is each independently methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or tert-butyl.Preferably, described
Quaternary amine alkaloid compound is one of tetrapropylammonium hydroxide, tetraethyl ammonium hydroxide and tetrabutylammonium hydroxide or a variety of.
Wherein, the fat amine compound can be the various fatty amines of this field, can be primary amine, secondary amine or uncle
Amine can be monoamine, diamines, tertiary amine or more amine.Preferably, the fat amine compound is formula R3-NH2Shown in
Monoamine and formula NH2-R9-NH2Shown in one of diamines or a variety of, wherein R9For C2-C6 alkyl or alkylidene (optionally
Depending on), preferably methyl (methylene), ethyl (ethylidene), n-propyl (sub- n-propyl), normal-butyl (sub- normal-butyl), positive penta
Base (sub- n-pentyl) or n-hexyl (sub- n-hexyl).It is highly preferred that the fat amine compound is ethamine, n-butylamine, fourth two
One of amine and hexamethylene diamine are a variety of.
Wherein, the alcamine compound can be the various hydramine of this field, can be monoalkyl hydramine, dialkyl group alcohol
Amine or trialkylalcohol amine, it is preferable that the alcamine compound is formula HO-R4-N(R5)2Shown in monoalkyl hydramine, formula HO-
R4-N(R5)-R4Dialkyl group hydramine and formula HO-R shown in-OH4-N(-R4-OH)-R4One of trialkylalcohol amine shown in-OH
It is or a variety of, wherein each R4Each independently represent the alkylidene of C1-C4, each R5Each independently represent the alkane of H and C1-C4
Base, wherein the alkylidene of C1-C4 and the alkyl of C1-C4 are as described above, and details are not described herein.Preferably, the alcamines
Conjunction object is one of monoethanolamine, diethanol amine and triethanolamine or a variety of.
According to the present invention, the temperature of the hydrolysis for example can be 10-30 DEG C.The time of hydrolysis can be according to required titanium source
Hydrolysis situation is controlled, and there is no particular limitation to this by the present invention.
According to the present invention, it in step (2), after hydrolysate is mixed with inorganic silicon source, can be used to carry out hydrothermal crystallizing.
Wherein, the inorganic silicon source is preferably silica gel and/or silica solution.Wherein, silica gel is mainly provided in the form of solid silica,
Its SiO2Content it is higher, generally 90 weight % or more, preferably 95 weight % or more, more preferably 99 weight % or more.
And silica solution is provided in the form of the aqueous solution of silica, wherein the content of silica for example can be 10 weight %,
Preferably 15 weight % or more, more preferably 20 weight % or more.
In the case of, according to the invention it is preferred to, with SiO2Meter the inorganic silicon source, with TiO2Meter the titanium source and with OH-
The molar ratio of the dosage of the alkali source template of meter is 100:0.5-5:5-20, preferably 100:1-4:6-15.
Wherein, the dosage of water is also optimized in the present invention, it is preferable that in mixture obtained in step (2), with
SiO2The inorganic silicon source of meter and the molar ratio of water are 100:200-1200, preferably 100:300-1000.It is possible thereby to just
In with the obtained higher Titanium Sieve Molecular Sieve of catalytic activity of higher yield.The water can be the water directly provided, or can be
It is provided by the aqueous solution of alkali source template, can also partially come from silica solution.
In a preferred embodiment of the invention, with SiO2Meter the inorganic silicon source, with TiO2The titanium of meter
Source, with OH-The molar ratio of the dosage of the alkali source template and water of meter be 100:0.5-5:5-20:200-1200, preferably 100:
1-4:6-15:300-1000, more preferably 100:1-4:8-15:400-800.
According to the present invention, the present inventor surprisingly it has been found that, after the processing of step (1) and (2) gained mixing
Object, then cooperate specific two crystallization of the present invention that can obtain with yield highland relative crystallinity is high and the suitable height of particle size is urged
Change active Titanium Sieve Molecular Sieve.Wherein, the temperature of first crystallization is 10-50 DEG C higher than the temperature of the second crystallization, preferably high 20-
40℃。
According to the present invention, the condition for the first crystallization that the present invention uses includes: temperature for 80-150 DEG C, time 4-10h,
The condition of the second crystallization used includes: temperature for 140-200 DEG C, time 6-24h.By control the first crystallization temperature and
Second crystallization temperature meets above-mentioned relation, and further controls the condition of first crystallization and the second crystallization in above range
It is interior, the resulting mixture crystallization of step (2) can be made to obtain the crystallization product of excellent structural, it is then high after subsequent roasting
The Titanium Sieve Molecular Sieve that the relative crystallinity for being made to yield of the invention is high, particle size is suitable, catalytic activity is high.
Under preferable case, the condition of first crystallization includes: that temperature is 100-140 DEG C, time 5-8h.More preferably
Ground, the condition of first crystallization include: that temperature is 120-140 DEG C, time 6-8h.
Under preferable case, the condition of second crystallization includes: that temperature is 150-180 DEG C, time 8-20h.More preferably
Ground, the condition of second crystallization include: that temperature is 160-180 DEG C, time 8-16h.
According to the present invention, crystallization process of the invention can more efficiently obtain Titanium Sieve Molecular Sieve of the invention, described
Material solid content after second crystallization in reaction kettle can achieve 25 weight % or more, preferably reach 30 weight % or more, more excellent
It is selected as 35-60 weight %.
In the case of, according to the invention it is preferred to, the condition of the roasting includes: that temperature is 300-800 DEG C, time 2-12h.
It is highly preferred that it is 400-700 DEG C that the condition of the roasting, which includes: temperature, time 2-10h.It is further preferred that the roasting
The condition of burning includes: that temperature is 500-600 DEG C, time 2-5h.
Wherein, can also be dry by the solid phase of separation of solid and liquid before the roasting, such as the dry 60- at 100-150 DEG C
200min。
Above-mentioned preparation method of the invention can with 88% or more yield be made Titanium Sieve Molecular Sieve, preferably yield be 90% with
On, more preferably 95% or more, it might even be possible to reach 98% or more.
Second aspect of the present invention provides Titanium Sieve Molecular Sieve prepared by the above method.
The above method through the invention can in high yield, expeditiously be made higher relative crystallinity and particle ruler is made
Very little suitable Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve are preparing propylene glycol as low-carbon alcohols and propylene oxide progress etherification reaction
Catalyst when, can be improved the selection of 1,2-PD -1- monoalky lether in etherification product (namely 1- alkoxy -2- propyl alcohol)
Property.
Third aspect present invention provides a kind of preparation method of propylene glycol, this method comprises: in above-mentioned titanium silicon molecule
Low-carbon alcohols and propylene oxide are carried out etherification reaction as in the presence of catalyst by sieve.
Wherein, the low-carbon alcohols can be the alcohol of C1-C6, such as in methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol
It is one or more.Such as using methanol, in resulting etherification product, 1- methoxy-2-propanol (MME- may be contained
1), double methyl ethers of 2- methoxy-1-propanol (MME-2), 1,2-PD etc., and use Titanium Sieve Molecular Sieve of the invention as catalysis
When agent, it will make moderate progress to the selectivity of MME-1.The etherificate of low-carbon alcohols is given in the embodiment of the present invention by taking methanol as an example
Response situation is detailed in each embodiment.
According to the method for the present invention, optional wider range of the condition of the etherification reaction, oxygen etherificate commonly used in the art
Reaction condition may be incorporated for the present invention, and for the present invention, the preferably molar ratio of propylene oxide and low-carbon alcohols is 1:0.1-10.
Wherein, the mass ratio of propylene oxide and catalyst is preferably 1-100:1.
Wherein it is preferred to it is 20-120 DEG C, pressure 0.1-2MPa that the condition of the etherification reaction, which includes: temperature, the time
For 0.2-24h.It is highly preferred that it is 40-100 DEG C, pressure 0.1-1MPa that the condition of the etherification reaction, which includes: temperature, reaction
Time is 1-8h.
According to the method for the present invention, after etherification reaction, the material after reaction can be using the side of common distillation or rectifying
Method, after isolating target product, unreacted raw material etc. does not have to separating-purifying, directly backs in reaction unit and continues instead
It answers.
Using Titanium Sieve Molecular Sieve of the invention as catalyst in the case where, above-mentioned reaction can obtain higher 1- alcoxyl
The selectivity of base -2- propyl alcohol.It is reacted with methanol with propylene oxide and prepares propylene glycol monomethyl ether MME-1 (1- methoxy-2-propanol)
For, for example, the epoxypropane conversion rate that this method can obtain is 70% or more, more preferably 80% or more (for example, 82-
90%)；The MME-1 that this method can obtain selectively is 40% or more, more preferably 45% or more (for example, 50-60%).
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example:
SiO in silica gel2Content be 99 weight %.
X-ray diffraction (XRD) crystalline phase figure of sample is measured on Siemens D5005 type x-ray diffractometer, with
Sample and authentic specimen are in the ratio that 2 θ are the sum of diffracted intensity (peak height) at the five fingers diffractive features peak between 22.5 °~25.0 °
Indicate crystallinity of the sample relative to authentic specimen, here using 1 sample of embodiment as benchmark sample, crystallinity is calculated as
100%, the relative crystallinity data of each sample are shown in Table 1.
Fourier infrared (FT-IR) spectrogram of sample is surveyed on 8210 type Fourier infrared spectrograph of Nicolet
It is fixed.
The crystallite dimension of sample is in Dutch FEI Co. Tecnai G2On F20S-TWIN type transmission electron microscope (TEM)
It obtains, crystallite dimension (the average radial length of particle) data of each sample are shown in Table 1.
The yield of each sample refers to the percentage of the product quality and theoretical calculation quality actually obtained, and data are shown in Table 1.
The present invention is further illustrated for embodiment below, but the content being not intended to limit the present invention.Implement
All reagents used are commercially available chemically pure reagent in example and comparative example.
In embodiment and comparative example, unless otherwise specified, reaction is carried out in the universal autoclave of 250mL,
Used reagent is commercially available analytical reagents.
In the present invention, using the analysis respectively formed in gas-chromatography carry out system, quantified by correcting normalization method,
It can refer to prior art progress, calculate the evaluation indexes such as the conversion ratio of reactant and the selectivity of product on this basis.
Epoxypropane conversion rate %=(propylene oxide molal quantity/addition propylene oxide total mole number of conversion) ×
100%.
MME-1 selectivity %=(molal quantity of MME-1 in product/converted propylene oxide molal quantity) × 100%.
Embodiment 1
The present embodiment is for illustrating Titanium Sieve Molecular Sieve and preparation method thereof of the invention.
(1) titanium source butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution (concentration is 15 weight %)
In；
(2) silica gel is added into above-mentioned solution and obtains mixture, in the mixture, with SiO2The silica gel of meter, with TiO2Meter
Titanium source, with OH-The molar ratio of the dosage of the alkali source template and water of meter is 100:4:12:400.Mixture is reacted in sealing again
The first crystallization and the second crystallization are successively carried out in kettle, wherein the condition of the first crystallization includes: that temperature is 140 DEG C, time 6h；
The condition of second crystallization includes: that temperature is 170 DEG C, time 12h；
(3) gained crystallization product (about 47 weight % of the solid content of material in reactor) is directly roasted into 3h at 550 DEG C,
Obtain molecular sieve S1.The sample yield, sieve particle size and relative crystallinity are as shown in table 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Embodiment 2
The present embodiment is for illustrating Titanium Sieve Molecular Sieve and preparation method thereof of the invention.
(1) titanium source butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution (concentration is 20 weight %)
In；
(2) silica gel is added into hydrolysate and obtains mixture, in the mixture, with SiO2The silica gel of meter, with TiO2Meter
Titanium source, with OH-The molar ratio of the dosage of the alkali source template and water of meter is 100:2:10:600.Mixture is reacted in sealing again
The first crystallization and the second crystallization are successively carried out in kettle, wherein the condition of the first crystallization includes: that temperature is 140 DEG C, time 6h；
The condition of second crystallization includes: that temperature is 170 DEG C, time 16h；
(3) gained crystallization product (about 36 weight % of the solid content of material in reactor) is directly roasted into 3h at 550 DEG C,
Obtain molecular sieve S2.The sample yield, sieve particle size and relative crystallinity are as shown in table 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Embodiment 3
The present embodiment is for illustrating Titanium Sieve Molecular Sieve and preparation method thereof of the invention.
(1) titanium source butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution (concentration is 15 weight %)
In；
(2) silica gel is added into hydrolysate and obtains mixture, in the mixture, with SiO2The silica gel of meter, with TiO2Meter
Titanium source, with OH-The molar ratio of the dosage of the alkali source template and water of meter is 100:1:15:800.Mixture is reacted in sealing again
The first crystallization and the second crystallization are successively carried out in kettle, wherein the condition of the first crystallization includes: that temperature is 140 DEG C, time 6h；
The condition of second crystallization includes: that temperature is 160 DEG C, time 12h；
(3) gained crystallization product (about 36 weight % of the solid content of material in reactor) is directly roasted into 3h at 550 DEG C,
Obtain molecular sieve S3.The sample yield, sieve particle size and relative crystallinity are as shown in table 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Embodiment 4
The present embodiment is for illustrating Titanium Sieve Molecular Sieve and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, with SiO in mixture obtained in step (2)2The silica gel of meter,
With TiO2The titanium source of meter, with OH-The molar ratio of the dosage of the alkali source template and water of meter is 100:2:12:300.And second is brilliant
The condition of change includes: that temperature is 180 DEG C, time 12h；To which step (3) resulting crystallization product makes material in reactor
About 53 weight % of solid content；It is final to obtain molecular sieve S4.The sample yield, sieve particle size and relative crystallinity such as table
Shown in 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Embodiment 5
The present embodiment is for illustrating Titanium Sieve Molecular Sieve and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, the temperature of the second crystallization is 150 DEG C；It is final to obtain molecular sieve
S5.The sample yield, sieve particle size and relative crystallinity are as shown in table 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Embodiment 6
The present embodiment is for illustrating Titanium Sieve Molecular Sieve and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, the content of water is higher in mixture obtained in step (2), i.e.,
With SiO2The silica gel of meter, with TiO2The titanium source of meter, with OH-The molar ratio of the dosage of the alkali source template and water of meter is 100:4:12:
1000.To which step (3) resulting crystallization product makes the about 26 weight % of solid content of material in reactor；It is final to obtain molecule
Sieve S6.The sample yield, sieve particle size and relative crystallinity are as shown in table 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Comparative example 1
22.5g tetraethyl orthosilicate is mixed with 7.0g tetrapropylammonium hydroxide, and 59.8g distilled water is added, mixing is equal
Hydrolyze 1h at normal pressure and 60 DEG C after even, obtain the hydrating solution of tetraethyl orthosilicate, be slowly added into vigorous stirring by
Solution composed by 1.1g butyl titanate and 5.0g anhydrous isopropyl alcohol, stirs 3h at 75 DEG C for gained mixture, obtains clear
Clear transparent colloid.This colloid is put into stainless steel sealing reaction kettle, 3d is placed in 170 DEG C of at a temperature of constant temperature, obtains crystallization production
The mixture (about 14 weight % of the solid content of material in reactor after synthesis) of object；By the filtering of this mixture, it is washed with water, and in
110 DEG C of dry 60min, then roast 3h at 550 DEG C, obtain molecular sieve DS1.The sample yield, sieve particle size and phase
It is as shown in table 1 to crystallinity.
Its XRD crystal phase is MFI structure, and fourier infrared spectrogram is in 960cm-1It is unexistent red nearby to there is silica zeolite
Outer absorption peak shows that titanium has entered framework of molecular sieve.
Comparative example 2
According to method described in embodiment 1, the difference is that, the temperature of the second crystallization is 140 DEG C, thus obtained by step (3)
Crystallization product make the about 84 weight % of solid content of material in reactor；It is final to obtain molecular sieve DS2.The sample yield divides
Son sieve particle size and relative crystallinity are as shown in table 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Comparative example 3
According to method described in embodiment 1, the difference is that, the temperature of the first crystallization is 110 DEG C, thus obtained by step (3)
Crystallization product make the about 88 weight % of solid content of material in reactor；It is final to obtain molecular sieve DS3.The sample yield divides
Son sieve particle size and relative crystallinity are as shown in table 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Comparative example 4
According to method described in embodiment 1, the difference is that, the time of the first crystallization is 12h, so that step (3) is resulting
Crystallization product makes the about 83 weight % of solid content of material in reactor；It is final to obtain molecular sieve DS4.The sample yield, molecule
It sieves particle size and relative crystallinity is as shown in table 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Comparative example 5
According to method described in embodiment 1, the difference is that, it is replaced using the identical organic silicon source ethyl orthosilicate of silicon mole
For inorganic silicon source；It is final to obtain molecular sieve DS5.The sample yield, sieve particle size and relative crystallinity are as shown in table 1.
Its XRD crystalline phase figure shows that the molecular sieve is the TS-1 molecular sieve with MFI structure；In fourier infrared spectrogram,
In 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve in the molecular sieve.
Testing example
Etherification reaction is carried out in the universal autoclave of 250mL.Under normal pressure, respectively first by above-mentioned molecular sieve, methanol
Carry out with propylene oxide according to the weight ratio of 2:25:10 it is uniformly mixed, while after sealing with nitrogen boost to 0.5MPa stop it is logical
Nitrogen, clock reaction 5h after then heating to 80 DEG C.Products therefrom uses FFAP capillary on Agilent6890N chromatograph
Column (30m × 0.25mm) measures each product distribution, the results are shown in Table 1.
Table 1
It can be seen from Table 1 that method of the invention can be obtained with higher yield and higher relative crystallinity
The suitable Titanium Sieve Molecular Sieve of particle size.And etherification reaction preparation the third two of the Titanium Sieve Molecular Sieve between low-carbon alcohols and propylene oxide
When being used as catalyst in the method for alcohol ether, higher epoxypropane conversion rate can be obtained, and obtain the 1- alkoxy -2- of raising
The selectivity of propyl alcohol.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of Titanium Sieve Molecular Sieve, which is characterized in that this method comprises:
(1) alkali source template and titanium source are mixed；
(2) mixture that step (1) obtains is mixed with inorganic silicon source, and gained mixture is successively carried out to the first crystallization and
Two crystallization；
(3) product of second crystallization is directly roasted；
Wherein, the temperature of first crystallization is 10-50 DEG C higher than the temperature of the second crystallization,
The condition of first crystallization includes: that temperature is 80-150 DEG C, time 4-10h；
The condition of second crystallization includes: that temperature is 140-200 DEG C, time 6-24h.
2. according to the method described in claim 1, wherein, with SiO2Meter the inorganic silicon source, with TiO2Meter the titanium source and
With OH-The molar ratio of the dosage of the alkali source template of meter is 100:0.5-5:5-20, preferably 100:1-4:6-15.
3. method according to claim 1 or 2, wherein in mixture obtained in step (2), with SiO2The nothing of meter
Machine silicon source and the molar ratio of water are 100:200-1200, preferably 100:300-1000.
4. method described in any one of -3 according to claim 1, wherein the titanium source is inorganic titanium salt and organic titanate
One of or it is a variety of, it is preferable that the inorganic titanium salt be TiCl4、Ti(SO4)2And TiOCl2One of or it is a variety of, it is described
Organic titanate is formula R1 4TiO4Compound represented, wherein R1Alkyl selected from C2-C4；
The alkali source template is one of quaternary amine alkaloid compound, fat amine compound and alcamine compound or more
Kind；
The inorganic silicon source is silica gel and/or silica solution.
5. method described in any one of -4 according to claim 1, wherein the temperature of first crystallization is than the second crystallization
Temperature is 20-40 DEG C high.
6. method described in any one of -5 according to claim 1, wherein the condition of first crystallization includes: that temperature is
100-140 DEG C, time 5-8h；
Preferably, it is 120-140 DEG C that the condition of first crystallization, which includes: temperature, time 6-8h.
7. method described in any one of -6 according to claim 1, wherein the condition of second crystallization includes: that temperature is
150-180 DEG C, time 8-20h；
Preferably, it is 160-180 DEG C that the condition of second crystallization, which includes: temperature, time 8-16h.
8. method according to any one of claims 1-7, wherein the condition of the roasting includes: that temperature is 300-
800 DEG C, time 2-12h.
9. Titanium Sieve Molecular Sieve made from the method as described in any one of claim 1-8.
10. a kind of preparation method of propylene glycol, this method comprises: in Titanium Sieve Molecular Sieve as claimed in claim 9 as catalysis
In the presence of agent, low-carbon alcohols and propylene oxide are subjected to etherification reaction.
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