CN104944441B - Method for synthesizing titanium-silicon molecular sieve - Google Patents
Method for synthesizing titanium-silicon molecular sieve Download PDFInfo
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Abstract
The invention relates to a method for synthesizing a titanium-silicon molecular sieve, which is characterized by comprising the following steps: dissolving a titanium source in an alkali source template, adding an inorganic silicon source to obtain a mixture, and adding compensation water to obtain a mixture of the silicon source, titanium source, alkali source template and water in a mole ratio of 100:(0.5-5):(5-20):(200-1000), wherein the inorganic silicon source is metered on the basis of SiO2, the titanium source is metered on the basis of TiO2, and the alkali source template is metered on the basis of OH- or N; and sequentially carrying out Stage (1), Stage (2) and Stage (3) in a sealed reaction kettle, wherein in the Stage (1), crystallizing at 80-120 DEG C for 6-72 hours; in the Stage (2), cooling to not higher than 70 DEG C, and keeping for at least 0.5 hour; and in the Stage (3), heating to 120-200 DEG C, carrying out secondary crystallization for 6-96 hours and recovering the product. The solid content in the material in the reaction kettle after synthesis is greater than 20%; and the method enhances the volume utilization ratio of the reaction kettle and other pressure devices, lowers the preparation cost, and enhances the yield and relative crystallinity of the obtained molecular sieve.
Description
Technical field
The present invention relates to a kind of method of synthesis of titanium silicon molecular sieve.
Background technology
HTS is important catalysis oxidation material, such as have MFI crystal structures titanium-silicon molecular sieve TS-1 be by
One kind that transition metal titanium is introduced formed in the framework of molecular sieve with ZSM-5 structures has superior catalytic selectivity oxygen
Change the novel titanosilicate of performance.TS-1 not only has the catalysed oxidn of titanium, but also selecting with ZSM-5 molecular sieve
Shape is acted on and excellent stability.Because TS-1 molecular sieves are in the oxidation reaction of organic matter, free of contamination low concentration can be used
Hydrogen peroxide is used as oxidant, it is to avoid the problem of oxidizing process complex process and pollution environment, with conventional oxidation system without
Analogous energy-conservation, economy and advantages of environment protection, and with good reaction selectivity.
The synthetic method of TS-1 is by Taramasso et al.（USP4410501）It is first public.The method is first to prepare one kind
Reactant mixture containing silicon source, titanium source, organic base and/or basic anhydride, then by this reactant mixture in autoclave in
130~200 DEG C of 6~30d of hydrothermal crystallizing, are then peeled off, wash, dry, are calcined and obtain product.On Thangaraj et al. thinks
Effective titanium content in the TS-1 molecular sieves that the method for stating synthesizes into skeleton is little, and then they disclosed one kind in 1992
The method of the synthesis TS-1 of Ti content in skeleton can be effectively increased（Zeolites, 1992, Vol.12：943）, it is said that the method energy
The Si/Ti ratios of molecular sieve are dropped to 20 from 39, methods described is by appropriate TPAOH（TPAOH）The aqueous solution is added
The stirring and dissolving certain hour in ethyl silicate solution, the isopropanol that butyl titanate is then slowly added to vigorous stirring is molten
The liquid mixture that liquid is clarified（Must be slowly added dropwise and white TiO is formed to prevent tetrabutyl titanate hydrolysis too fast2It is heavy
Form sediment）, stirring 15min after, be slow added into the appropriate TPAOH aqueous solution, then by reactant mixture in 75~80 DEG C except alcohol 3~
Be transferred to after 6h in autoclave in 3~6d of hydrothermal crystallizing at 170 DEG C, after drying TS-1, wherein, mole group of reactant mixture
As SiO2：（0.01~0.10）TiO2：0.36TPAOH：35H2O。
In the existing technology for preparing HTS（Such as USP4410501, and Zeolites, 1992, Vol.12：
943）In, because the Ti brilliant abilities of leading in itself are weak so that the crystallization time for preparing HTS is more long, while yield also compared with
It is low.In the last few years, although preparing the technology of HTS by certain improvement（Such as CN101134575A, CN1247771A）,
But effect is not also very good.
The content of the invention
The present inventor has found by substantial amounts of research, in the preparation process of HTS, if first by titanium source
Be dissolved in the alkali source template aqueous solution, after titanium source hydrolysis after add silica gel and at once by mixture in sealed reactor substep water
Thermal crystallisation, by parameters such as the conditions of the proportioning of control material and crystallization, the solid of material in reactor contains after can causing synthesis
Amount is more than 20%.The capacity utilization of crystallization apparatus is so not only improved, and surprisingly, so synthesizes the titanium for obtaining
Si molecular sieves, its catalytic oxidation activity is high, and its yield and relative crystallinity are higher.Based on this, the present invention is formed.
The purpose of the present invention is on the basis of existing technology, there is provided a kind of method of synthesis of titanium silicon molecular sieve.
The method of the synthesis of titanium silicon molecular sieve that the present invention is provided, it is characterised in that first titanium source is dissolved in alkali source template,
Inorganic silicon source is added thereto again obtains mixture, optional supplement water, it is silicon source to obtain a mole composition：Titanium source：Alkali source template
Agent：Water=100：（0.5~5）：（5~20）：（200~1000）Mixture, wherein, described inorganic silicon source is with SiO2Meter,
Titanium source is with TiO2Meter, alkali source template is with OH-Or N meters, mixture is sequentially then experienced into the stage in sealed reactor（1）80
~120 DEG C of 6~72h of crystallization, stage（2）After being cooled to not higher than 70 DEG C and residence time at least 0.5h, and the stage（3）Heat up again
Second 6~96h of crystallization and recovery product are carried out in 120~200 DEG C.
The method of the synthesis of titanium silicon molecular sieve that the present invention is provided, be one kind during synthesis of titanium silicon molecular sieve using inorganic
Silicon source is constituted as whole silicon sources, and control material, while the method for multistep variable temperature crystallization step is effectively combined, with following
Advantage：
（1）It is whole silicon with relatively inexpensive silica gel or Ludox without organo-silicon ester hydrolysis time without organo-silicon ester
Source.
（2）The solid content of material in reactor is more than 20% after synthesis, increases substantially combined coefficient and benefit.
（3）In phenol hydroxylation reaction probe reaction, the HTS that the inventive method synthesis is obtained shows to urge
The characteristics of changing oxidation activity high and hydroquinones selectively high.
（4）Especially it was unexpected that the relative crystallinity and yield of the HTS sample that the preferred process of the present invention is obtained
Improve, and crystal grain average radial length is more than or equal to 0.3 μm.
Specific embodiment
The method of the synthesis of titanium silicon molecular sieve that the present invention is provided, it is characterised in that first titanium source is dissolved in alkali source template,
Inorganic silicon source is added thereto again obtains mixture, optional supplement water, it is silicon source to obtain a mole composition：Titanium source：Alkali source template
Agent：Water=100：（0.5~5）：（5~20）：（200~1000）Mixture, wherein, described inorganic silicon source is with SiO2Meter,
Titanium source is with TiO2Meter, alkali source template is with OH-Or N meters, mixture is sequentially then experienced into the stage in sealed reactor（1）80
~120 DEG C of 6~72h of crystallization, stage（2）After being cooled to not higher than 70 DEG C and residence time at least 0.5h, and the stage（3）Heat up again
Second 6~96h of crystallization and recovery product are carried out in 120~200 DEG C.
In the method that the present invention is provided, described alkali source template can be generally to make during synthesis of titanium silicon molecular sieve
Various templates, for example：The alkali source template can be quaternary ammonium base, aliphatic amine and aliphatic hydramine in one kind or
It is various.The quaternary ammonium base can be various organic level Four ammonium alkali, and the aliphatic amine can be various NH3At least one of hydrogen
By aliphatic alkyl（Such as alkyl）The compound formed after substitution, the aliphatic hydramine can be various NH3In at least one
Individual hydrogen is by the aliphatic group of hydroxyl（Such as alkyl）The compound formed after substitution.
Specifically, the alkaline template can be the aliphatic amine that the quaternary ammonium base that represents selected from formula I, formula II are represented
One or more in the aliphatic hydramine represented with general formula III.
In Formulas I, R1、R2、R3And R4Respectively C1~C4Alkyl, including C1~C4Straight chained alkyl and C3~C4Side chain
Alkyl, for example：R1、R2、R3And R4Each can for methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or
The tert-butyl group.
R5(NH2)n（Formula II）
In Formula II, n is 1 or 2 integer.When n is 1, R5It is C1~C6Alkyl, including C1~C6Straight chained alkyl and C3~
C6Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, new
Amyl group, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5It is C1~C6Alkylidene, including C1~C6Straight-chain alkyl-sub and C3
~C6Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.
(HOR6)mNH(3-m) （Formula III）
In formula III, m R6It is identical or different, respectively C1~C4Alkylidene, including C1~C4Straight-chain alkyl-sub and C3
~C4Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.
The alkali source template is specifically as follows but is not limited to：TMAH, tetraethyl ammonium hydroxide, tetrapropyl
Ammonium hydroxide（Various isomers including TPAOH, such as four n-propyl ammonium hydroxide and tetra isopropyl hydroxide
Ammonium）, TBAH（Various isomers including TBAH, such as 4-n-butyl ammonium hydroxide and four isobutyls
Base ammonium hydroxide）, ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine and three second
One or more in hydramine.Preferably, the template is tetraethyl ammonium hydroxide, TPAOH and tetrabutylammonium hydrogen
Amine-oxides, it is highly preferred that described alkali source template is TPAOH.
Described titanium source is inorganic titanium salt or organic titanate, preferably organic titanate.Described inorganic titanium salt can be with
It is TiCl4、Ti(SO4)2Or TiOCl2；Its formula of described organic titanate is R7 4TiO4, wherein R7It is with 1~6 carbon
The alkyl of atom, preferred R7It is with 2~4 alkyl of carbon atom.
In the method that the present invention is provided, without organo-silicon ester, without organo-silicon ester hydrolysis time, with relatively inexpensive silica gel or
Ludox is whole silicon sources, is not only reduction of cost, and it is surprising that when we are with identical reaction condition, only
It is with identical SiO to change part2When the tetraethyl orthosilicate TEOS of content replaces silica gel, crystallization product is spawn,
It is amorphous powder after roasting, XRD crystalline phases figure is without obvious diffraction maximum（Reference can be made to embodiment 1 and comparative example 6）.What the present invention was provided
In method, described inorganic silicon source refers mainly to silica gel or Ludox, can be the silicon that various forms and various production methods are obtained
Glue or Ludox, preferably silica gel.The silica gel of various models forms different microcellular structures because of its manufacture method difference, such as silica gel
Size according to its aperture is divided into：Macro porous silica gel, silochrom, Type B silica gel, the Kiselgel A present invention are to described silica gel
The aperture of grain, specific surface area and pore volume（Pore volume）Etc. no particular/special requirement, the silica gel can be with commercially available or according to existing method
Prepare.In the methods of the invention, it is general to require SiO in wherein silica gel in order to obtain superior technique effect2Quality percentage contain
Amount is that mass fraction is more than 90%, preferably greater than 95%, more preferably greater than 99%；SiO in Ludox2Mass fraction be more than 10%,
Preferably greater than 15%, more preferably greater than 20%.
In the method for the present invention, in described mixture, a mole composition is silicon source：Titanium source：Alkali source template：Water=100：
（0.5~5）：（5~20）：（200~1000）；It is preferred that a mole composition is silicon source：Titanium source：Alkali source template：Water=100：（1~
4）：（6~15）：（300~800）.
One of the method for the present invention preferred embodiment in, the crystallization of mixture experience multiple stages：（1）Prior to 80
~120 DEG C of 6~72h of crystallization,（2）After being cooled to not higher than 70 DEG C and residence time at least 0.5h, and（3）Heat up again in 120~
200 DEG C of 6~96h of crystallization.Wherein, by room temperature to described stage（1）The heating rate of crystallization temperature is 0.1~20 DEG C/min,
By the stage（1）Temperature is to the stage（2）The rate of temperature fall of temperature is 1~50 DEG C/min, by the stage（2）Temperature is to the stage（3）Temperature
Heating rate be 1~50 DEG C/min.Preferably, it is described by room temperature to stage（1）The heating rate of crystallization temperature be 0.1~
10 DEG C/min, by the stage（1）Temperature is to the stage（2）The rate of temperature fall of temperature is 2~20 DEG C/min, by the stage（2）Temperature is to rank
Section（3）The heating rate of temperature is 2~40 DEG C/min.
One of the method for the present invention preferred embodiment in, the described stage（1）Crystallization temperature be less than the stage
（3）Crystallization temperature, difference can so obtain more preferable effect at 10 DEG C~50 DEG C, preferably 20 DEG C~40 DEG C.For example from specific
The Data Comparison of the embodiment 1,7 and 8 of implementation method can be seen that（It is shown in Table 1）：In the case that the difference of crystallization temperature is 30 DEG C
（Embodiment 1）, the yield of sample, crystallite dimension, relative crystallinity and phenol hydroxylation performance are superior to crystallization temperature and do not have
The situation of difference（Embodiment 7）And the situation that crystallization temperature difference is 60 DEG C（Embodiment 8）, wherein sample yield raising 2~5
Percentage point, particle size increases by 0.1~0.2 μm, and relative crystallinity increases by 1~2 percentage point, in phenol hydroxylation performance pair
Than in, phenol conversion increases by 2.5~6.6 percentage points, and hydroquinones selectively increases by 6~11 percentage points.
The method of the present invention another preferred embodiment in, the stage（1）Crystallization time be less than the stage（3）Crystalline substance
Change time, difference can so obtain more preferable effect in 5~24h, preferably 6~12h.For example, from the reality of specific embodiment
The Data Comparison for applying example 1,9 can be seen that（It is shown in Table 1）：In the case that the time difference of crystallization is 6h（Embodiment 1）, the receipts of sample
Rate, crystallite dimension, relative crystallinity and phenol hydroxylation performance are superior to the indistinguishable situation of crystallization time（Embodiment
9）, wherein 4 percentage points of sample yield raising, 0.1 μm of particle size increase, relative crystallinity increases by 4 percentage points, in phenol
In hydroxylating performance comparison, phenol conversion increases by 5.9 percentage points, and hydroquinones selectively increases by 8 percentage points.
The method of the present invention another preferred embodiment in, in the stage（2）Temperature not higher than 70 DEG C and to stop
It is at least 0.5h, such as 0.5~5h to stay the time；Preferably, temperature be not higher than 50 DEG C and residence time be at least 0.5h, example
Such as 0.5~5h；It is highly preferred that temperature be not higher than 30 DEG C and residence time be at least 1h, such as 1~8h, can so obtain
More preferable effect, such as Data Comparison from the embodiment 1,10 and 11 of specific embodiment can be seen that（It is shown in Table 1）：Stage
（2）Temperature be 2h for 30 DEG C and residence time in the case of（Embodiment 1）, the yield of sample, crystallite dimension, relative crystallization
Degree and phenol hydroxylation performance are superior to the stage（2）Temperature for 80 DEG C of residence times be 2h（Embodiment 10）Or temperature is 30
DEG C residence time is the situation of 0.2h（Comparative example 2）, wherein, sample yield improves 2~7 percentage points, and particle size increases by 0.2
μm, relative crystallinity increases by 2~4 percentage points, and in phenol hydroxylation performance comparison, phenol conversion increases by 2~2.7 hundred
Branch, hydroquinones selectively increases by 2~3 percentage points.
In the method for the present invention, the process of described recovery product, by those skilled in the art is familiar with, has no herein
Special requirement, generally refer to crystallization product filtering, washing, the process for drying and being calcined.More it is beneficial that excellent in the present invention
In the method for choosing, filtering and washing step can be saved, need to be only dried and calcination stepses.So that building-up process does not have
Discharge of wastewater, environmental pressure is small.Drying therein and calcination stepses do not have particular/special requirement, and usually, described drying can be in room
Being carried out at a temperature of temperature~200 DEG C, described roasting can carry out 2 in 300~800 DEG C, such as 550 DEG C in air atmosphere~
12h。
Below by embodiment, the invention will be further described, but and is not so limited present disclosure.
It is raw materials used to be commercially available, wherein silica gel in comparative example and embodiment（Bead）It is Qingdao silica gel factory product, SiO2
Mass fraction be more than 95%, Kiselgel A A basic parameters are as follows：Average pore size 2.6nm, specific surface 680m2/ g, pore volume
0.38ml/g；Silica gel B gross parameters：Average pore size 5.3nm, specific surface 550m2/ g, pore volume is 0.71ml/g；Reagent is equal
It is commercially available AR, is all from Chemical Reagent Co., Ltd., Sinopharm Group's product.
In comparative example and each embodiment, the X-ray diffraction of sample（XRD）Crystalline phase figure is penetrated in Siemens D5005 types X
It is measured on line diffractometer, the diffraction at the five fingers diffractive features peak between with sample and authentic specimen being 22.5 °~25.0 ° in 2 θ
Intensity（Peak height）The ratio of sum represents crystallinity of the sample relative to authentic specimen, here on the basis of the sample of comparative example 1
Sample, its crystallinity is calculated as 100%, and the relative crystallinity data of each sample are shown in Table 1.
The fourier infrared of sample（FT-IR）Spectrogram is measured on Nicolet8210 type Fourier infrared spectrographs.
The crystallite dimension of sample is in Dutch FEI Co. Tecnai G2F20S-TWIN type transmission electron microscopes（TEM）On
Obtain, the crystallite dimension of each sample（The average radial length of particle）Data are shown in Table 1.
The yield of sample refers to the percentage of the product quality and theoretical calculation product quality for actually obtaining, and data are shown in Table 1.
The Ti content of sample in terms of titanium dioxide, using Rigaku Electric Co., Ltd 3271E type X-ray fluorescence spectras
Instrument is determined, and the Ti content data of each sample are shown in Table 1.
The interior molecular sieve amount for generating of reactor accounts for total reactor after the solid content of material in reactor refers to synthesis after synthesis
The weight/mass percentage composition of interior material is general to be drawn off doing by steps such as filterings using by the molecular sieve in reactor after reaction
Weighed after dry, the percent data that the dried molecular sieve of calculating accounts for the gross weight of material in reactor after reacting is designated as closing
Into the solid content of rear material in reactor.The solid content data of the material in reactor of each comparative example and embodiment building-up process are detailed
See each comparative example and embodiment.
Comparative example 1
This comparative example is by " Zeolites, 1992, Vol.12：943~950 " the method synthesis TS-1 molecules described in
Sieve the process of sample.It is specific as follows：22.5g tetraethyl orthosilicates are mixed with 7.0g TPAOHs, and adds 59.8g
Distilled water, is well mixed after 1h is hydrolyzed at normal pressure and 60 DEG C, obtains the hydrating solution of tetraethyl orthosilicate, with vigorous stirring
The solution being made up of 1.1g butyl titanates and 5.0g anhydrous isopropyl alcohols is slowly added into, gained mixture is stirred at 75 DEG C
3h is mixed, clear colloid is obtained.This colloid is put into stainless steel sealed reactor, constant temperature places 3d at a temperature of 170 DEG C,
Obtain the mixture of crystallization product（The solid content of material in reactor about 14% after synthesis）；By the filtering of this mixture, wash with water
Wash, and 60min is dried in 110 DEG C, obtain TS-1 original powder.By this TS-1 original powder in 3h is calcined at 550 DEG C, TS-1 molecular sieves are obtained,
Its XRD crystalline phase is MFI structure, and fourier infrared spectrogram is in 960cm-1Nearby there is the unexistent INFRARED ABSORPTION of silica zeolite
Peak, shows that titanium has been enter into framework of molecular sieve.
Embodiment 1
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel A is subsequently adding in it
In obtain mixture, the mixture material mole composition be silicon source：Titanium source：Alkali source template：Water=100：4：12：400, silicon source
With SiO2Meter, titanium source are with TiO2Meter, alkali source template are with OH-Meter, then by mixture in sealed reactor in 140 DEG C of experience the
One stage crystallization 6h, then by mixture be cooled to 30 DEG C experience second stage stop 2h after continue in sealed reactor in
170 DEG C of temperature experience phase III crystallization 12h（It is 2 wherein by the heating rate of room temperature to described first paragraph treatment temperature
DEG C/min, by first paragraph treatment temperature to second segment treatment temperature rate of temperature fall be 5 DEG C/min, by second segment treatment temperature to
The 3rd section of heating rate for the treatment of temperature is 10 DEG C/min）, by gained crystallization product（The solid content of material in reactor after synthesis
About 85%）Without filtering and washing step after taking-up, 2h directly is dried in 110 DEG C, 3h is then calcined at 550 DEG C, obtain molecule
Sieve.
The XRD crystalline phase figures of gained sample are consistent with comparative example, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；
In fourier infrared spectrogram, in 960cm-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Embodiment 2
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel B is subsequently adding in it
In obtain mixture, the mixture material mole composition be silicon source：Titanium source：Alkali source template：Water=100：2：10：600, silicon source
With SiO2Meter, titanium source are with TiO2Meter, alkali source template are with OH-Meter, then by mixture in sealed reactor in 140 DEG C of experience the
One stage crystallization 6h, then by mixture be cooled to 50 DEG C experience second stage treatment 5h after continue in sealed reactor in
170 DEG C of temperature experience phase III crystallization 16h（It is 1 wherein by the heating rate of room temperature to described first paragraph treatment temperature
DEG C/min, it is 10 DEG C/min by the rate of temperature fall of first paragraph treatment temperature to second segment treatment temperature, by second segment treatment temperature
It is 20 DEG C/min to the 3rd section of heating rate for the treatment of temperature；The solid content of material in reactor about 71% after synthesis）, then press
Method according to embodiment 1 reclaims crystallization product, obtains molecular sieve.
The XRD crystalline phase figures of gained sample are consistent with comparative example, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；
In 960cm in fourier infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Embodiment 3
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel A is subsequently adding in it
In obtain mixture, the mixture material mole composition be silicon source：Titanium source：Alkali source template：Water=100：1：15：800, silicon source
With SiO2Meter, titanium source are with TiO2Meter, alkali source template are with OH-Meter, then by mixture in sealed reactor in 140 DEG C of experience the
One stage crystallization 6h, then by mixture be cooled to 40 DEG C experience second stage treatment 1h after continue in sealed reactor in
160 DEG C of temperature experience phase III crystallization 12h（It is 5 wherein by the heating rate of room temperature to described first paragraph treatment temperature
DEG C/min, by first paragraph treatment temperature to second segment treatment temperature rate of temperature fall be 5 DEG C/min, by second segment treatment temperature to
The 3rd section of heating rate for the treatment of temperature is 5 DEG C/min；The solid content of material in reactor about 63% after synthesis）, then according to reality
The method for applying example 1 reclaims crystallization product, obtains molecular sieve.
The XRD crystalline phase figures of gained sample are consistent with comparative example, illustrate that what is obtained is the TS-1 molecular sieves of MFI structure；Fourier
In 960cm in leaf infrared spectrum-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Embodiment 4
First tetraethyl titanate is dissolved in the alkali source template hexamethylene diamine aqueous solution, silica gel B is subsequently adding in wherein being mixed
Compound, the mixture material mole composition is silicon source：Titanium source：Alkali source template：Water=100：5：18：1000, silicon source is with SiO2
Meter, titanium source are with TiO2Meter, alkali source template experience first stage crystalline substance in sealed reactor in terms of N, then by mixture at 140 DEG C
Change 6h, continue in sealed reactor in 150 DEG C of temperature after mixture then is cooled into 60 DEG C of experience second stage treatment 2h
Degree experience phase III crystallization 12h（It is 1 DEG C/min wherein by the heating rate of room temperature to described first paragraph treatment temperature, by
The rate of temperature fall of first paragraph treatment temperature to second segment treatment temperature is 15 DEG C/min, by second segment treatment temperature to the 3rd section
The heating rate for managing temperature is 20 DEG C/min；The solid content of material in reactor about 27% after synthesis）, by gained crystallization product mistake
Filter, wash with water, and 2h is dried in 110 DEG C, then in 550 DEG C of roasting temperature 3h, obtain molecular sieve.
The XRD crystalline phase figures of gained sample are consistent with comparative example, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；
In 960cm in fourier infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Embodiment 5
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel A is subsequently adding in it
In obtain mixture, the mixture material mole composition be silicon source：Titanium source：Alkali source template：Water=100：3：12：500, silicon source
With SiO2Meter, titanium source are with TiO2Meter, alkali source template are with OH-Meter, then by mixture in sealed reactor in 140 DEG C of experience the
One stage crystallization 6h, then by mixture be cooled to 30 DEG C experience second stage treatment 0.5h after continue in sealed reactor in
170 DEG C of temperature experience phase III crystallization 8h（It is 2 wherein by the heating rate of room temperature to described first paragraph treatment temperature
DEG C/min, it is 10 DEG C/min by the rate of temperature fall of first paragraph treatment temperature to second segment treatment temperature, by second segment treatment temperature
It is 20 DEG C/min to the 3rd section of heating rate for the treatment of temperature；The solid content of material in reactor about 80% after synthesis）, by gained
Crystallization product is filtered, washed with water, and dries 2h in 110 DEG C, then in 550 DEG C of roasting temperature 3h, obtains molecular sieve.
The XRD crystalline phase figures of gained sample are consistent with comparative example, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；
In 960cm in fourier infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Embodiment 6
First titanium source butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel B is subsequently adding
In mixture is wherein obtained, the mixture material mole composition is silicon source：Titanium source：Alkali source template：Water=100：2：12：300,
Silicon source is with SiO2Meter, titanium source are with TiO2Meter, alkali source template are with OH-Meter, then mixture is passed through in sealed reactor at 140 DEG C
First stage crystallization 6h is gone through, is continued in sealed reactor after mixture then is cooled into 50 DEG C of experience second stage treatment 4h
Phase III crystallization 12h is experienced in 180 DEG C of temperature（Wherein it is to the heating rate of described first paragraph treatment temperature by room temperature
2 DEG C/min, be 5 DEG C/min by the rate of temperature fall of first paragraph treatment temperature to second segment treatment temperature, by second segment treatment temperature
It is 5 DEG C/min to the 3rd section of heating rate for the treatment of temperature；The solid content of material in reactor about 92% after synthesis）, finally according to
The method of embodiment 1 reclaims crystallization product, obtains molecular sieve.
The XRD crystalline phase figures of gained sample are consistent with comparative example, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；
In 960cm in fourier infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Embodiment 7
Method according to embodiment 1 prepares HTS, the difference is that the crystallization temperature of phase III is also 140 DEG C
（The solid content of material in reactor about 84% after synthesis）.The XRD crystalline phase figures of gained sample are consistent with comparative example, illustrate what is obtained
It is the TS-1 molecular sieves with MFI structure；In 960cm in fourier infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into
Framework of molecular sieve.
Embodiment 8
Method according to embodiment 1 prepares HTS, the difference is that the crystallization temperature of first stage is changed into 110 DEG C
（The solid content of material in reactor about 88% after synthesis）.Its XRD crystalline phase figures are consistent with comparative example, and illustrate to obtain is have
The TS-1 molecular sieves of MFI structure；In 960cm in fourier infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into molecular sieve
Skeleton.
Embodiment 9
Method according to embodiment 1 prepares HTS, the difference is that the crystallization time of first stage is 12h（Synthesis
The solid content of material in reactor about 83% afterwards）.Its XRD crystalline phase figures are consistent with comparative example, and illustrate to obtain is with MFI knots
The TS-1 molecular sieves of structure；In 960cm in fourier infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Embodiment 10
Method according to embodiment 1 prepares HTS, the difference is that second stage is to be cooled to 70 DEG C of stop 2h.It
XRD crystalline phases figure it is consistent with comparative example 1, illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier infrared spectrogram
In 960cm-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Comparative example 2
Method according to embodiment 1 prepares HTS, the difference is that second stage is to be cooled to 30 DEG C of stop 0.2h.
Its XRD crystalline phases figure is consistent with comparative example 1, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；Fourier infrared spectrogram
In in 960cm-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Comparative example 3
Method according to embodiment 1 prepares HTS, the difference is that without second stage.Its XRD crystalline phase figures
Consistent with comparative example 1, illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier infrared spectrogram-1It is attached
Closely there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Comparative example 4
Method according to embodiment 2 prepares HTS, the difference is that without second stage.Its XRD crystalline phase figures
Consistent with comparative example 1, illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier infrared spectrogram-1It is attached
Closely there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Comparative example 5
Method according to comparative example 1 prepares HTS, the difference is that utilizing identical SiO2The silica gel of content replaces just
Tetraethyl orthosilicate.Its XRD crystalline phases figure is consistent with comparative example 1, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；Fu
In 960cm in vertical leaf infrared spectrum-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve.
Comparative example 6
Method according to embodiment 1 prepares HTS, the difference is that utilizing identical SiO2The positive silicic acid tetrem of content
Ester TEOS replaces silica gel.Product is spawn, is amorphous powder after roasting, and its XRD crystalline phases figure is without obvious diffraction maximum.
Test case
This test case illustrates that the sample that the sieve sample that the inventive method obtains and comparative example method are obtained is used for phenol
The effect of hydroxylating.
By the sample prepared by above-described embodiment and comparative example according to sample：Phenol：Acetone=1：20：16 weight ratio exists
It is well mixed in one there-necked flask with condenser pipe, 80 DEG C is warming up to, then according to phenol under stirring：Peroxidating
Hydrogen=3：1 mol ratio adds the aqueous hydrogen peroxide solution that mass fraction is 30%, and 3h is reacted at this temperature, and products therefrom exists
HP-5 capillary columns are used on Agilent6890N chromatographs（30m×0.25mm）Each product slates are determined, 1 is the results are shown in Table.
Wherein,
Table 1
As can be seen from Table 1：The phenol hydroxylation of sample prepared by the preferred process of the present invention is active apparently higher than comparative example side
Method prepares sample, and hydroquinones selectively also increases.Simultaneously it can be seen that the sample for preparing of the preferred process of the present invention its relative tie
Brilliant degree and yield particularly yield are higher, and crystallite dimension is all higher than being equal to 0.3 μm.
Claims (9)
1. a kind of method of synthesis of titanium silicon molecular sieve, it is characterised in that first titanium source is dissolved in alkali source template, then by inorganic silicon
Source is added thereto and obtains mixture, optional supplement water, and it is silicon source to obtain a mole composition：Titanium source：Alkali source template：Water=100：
（0.5~5）：（5~20）：（200~1000）Mixture, wherein, described inorganic silicon source is with SiO2Meter, titanium source is with TiO2Meter,
Alkali source template is with OH-Or N meters, mixture is sequentially then experienced into the stage in sealed reactor（1）80~120 DEG C of crystallization 6
~72h, stage（2）After being cooled to not higher than 70 DEG C and residence time at least 0.5h, and the stage（3）Heat up again in 120~200 DEG C
Carry out second 6~96h of crystallization and recovery product.
2. according to the method for claim 1 wherein described titanium source is inorganic titanium salt or organic titanate, described alkali source template
Agent is one or more in quaternary ammonium base, aliphatic amine and aliphatic hydramine；Described inorganic silicon source is silica gel or Ludox.
3. according to the method for claim 2, wherein, described inorganic titanium salt is TiCl4、Ti(SO4)2Or TiOCl2；Described
Its formula of organic titanate is R7 4TiO4, wherein R7Selected from 2~4 alkyl of carbon atom.
4. it is silicon source according to the method for claim 1 wherein mixture mole composition：Titanium source：Alkali source template：Water=100：（1
~4）：（6~15）：（300~800）.
5. according to the method for claim 1, it is characterised in that the described stage（1）Crystallization temperature be less than the stage（3）Crystallization temperature
Degree, difference is 10 DEG C~50 DEG C.
6. according to the method for claim 1, it is characterised in that the described stage（1）Crystallization time be less than the stage（3）Crystallization when
Between, difference is 5~24h.
7. according to the method for claim 1, it is characterised in that the described stage（2）It is cooled to not higher than 50 DEG C.
8. according to the method for claim 7, it is characterised in that the described stage（2）Not higher than 30 DEG C are cooled to, and the residence time is extremely
Few 1h.
9. a kind of HTS, it is characterised in that the molecular sieve is prepared according to any one of claim 1~8 methods described.
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| CN107235868B (en) * | 2016-03-29 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of sulfide oxidation method |
| CN107539999B (en) * | 2016-06-27 | 2020-01-10 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method and application thereof, and cyclic ketone oxidation method |
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| CN108794360B (en) * | 2017-04-28 | 2020-05-19 | 中国石油化工股份有限公司 | Production method of sulfone |
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| CN109019627B (en) * | 2017-06-12 | 2020-12-04 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method thereof and preparation method of propylene glycol ether |
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| CN1089273C (en) * | 1998-06-12 | 2002-08-21 | 中国石油化工集团公司 | Process for synthesizing Ti-Si molecular sieve |
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