CN106276948B - A kind of Ti-beta molecular sieve and its synthetic method and application - Google Patents
A kind of Ti-beta molecular sieve and its synthetic method and application Download PDFInfo
- Publication number
- CN106276948B CN106276948B CN201510280601.7A CN201510280601A CN106276948B CN 106276948 B CN106276948 B CN 106276948B CN 201510280601 A CN201510280601 A CN 201510280601A CN 106276948 B CN106276948 B CN 106276948B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sodium
- crystallization
- beta
- crystal seed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of Ti-beta molecular sieve and its synthetic method and applications, its synthetic method obtains the reaction mixture of certain mol ratio the following steps are included: silicon source, titanium source, crystal seed, alkali metal compound mineralizer, structure directing agent, water and optional alkali source are uniformly mixed by (1)；Wherein, the crystal seed is total silicon beta molecular sieve；(2) reaction mixture for obtaining step (1) obtains crystallization product in the closed container of pressure resistance crystallization 0.1-20 days at 90-230 DEG C of temperature and self-generated pressure；(3) crystallization product that recycling step (2) obtains.The technical program is prepared for few skeleton defect, particle size uniformity, the good Ti-beta molecular sieve of catalytic performance in macromolecular reaction by the way that crystal seed and alkali metal compound mineralizer is added under alkaline condition.
Description
Technical field
The present invention relates to a kind of Ti-beta molecular sieve and its synthetic method and applications.
Background technique
Titanium Sieve Molecular Sieve refers to a kind of hetero-atom molecular-sieve containing four-coordination framework titania.Since Enichem company first
Since announcing the titanium-silicon molecular sieve TS-1 with MFI structure in nineteen eighty-three, people successively develop a series of with different skeletons
The Titanium Sieve Molecular Sieve of structure.For example, the Ti-ZSM-12 of Ti-beta, MTW structure of TS-2, BEA structure of MEL structure and
The Ti-MCM-22 etc. of MWW structure.
The stacking fault symbiosis that beta-molecular sieve is made of the polymorph that three kinds of structures are different but are closely related.It has three
Twelve-ring cellular structure is tieed up, wherein the duct in [100] and [010] direction is all straight hole road, aperture may each be about 0.66 ×
0.67nm；[001] it is about 0.55 that the duct in direction, which is by the aperture that the straight hole road of [100] and [010] both direction intersects to form,
The sinusoidal duct of × 0.55nm.Since with biggish twelve-ring duct, the hetero atoms such as Ti are introduced into beta-molecular sieve also to open up
Open up application of the Titanium Sieve Molecular Sieve in macromolecular oxide and reactant.
M.Camblor etc. (Chem Commun, 1992,8:589-590) is first with white carbon black, tetraethyl titanate, aluminum nitrate
It is raw material with tetraethyl ammonium hydroxide, by Al2O3:400[xTi,(1-x)Si]O2:6000H2O:108(TEA)2O (x=0.008~
0.048) material proportion is prepared for Ti- beta-molecular sieve of the silica alumina ratio less than 150, but [Ti, the Al]-β of silica alumina ratio greater than 200 is then
It is difficult to synthesize.
Although [Ti, the Al]-β of direct hydrothermal synthesis method preparation has certain macromolecular oxidation activity, due to
The alkali silicon of crystallization system is relatively high, and the yield of Ti- β and the utilization rate of template are lower；Framework aluminum and largely inside and outside hydroxyl
In the presence of then make the hydrophily of Ti- β compared with strong, the selectivity of oxidation product is lower.Therefore, people further pass through addition crystal seed or make
It is explored with the study on the synthesis that new template agent, mineralizer have carried out Ti- β.
After the aluminium in gel all consumption, Ti- β may continue to grow, M.Camblor etc. (Chem Commun,
1996,11:1339-1140.) Ti- β further is prepared for by crystal seed of the beta-molecular sieve of dealuminzation.Ti- β can be improved in the addition of crystal seed
Yield, and the quantity of crystal seed and granular size can influence the crystallization rate of Ti- β.With the preparation of direct hydrothermal synthesis method
[Ti, Al]-β is compared, and the Ti- β of this method preparation has preferably activity and oxidation product selectivity.
EP0659685A1 for template, passes through hydrothermal synthesis with bis- (N- benzyl-N methyl) piperidines of 4,4 '-trimethylenes-
It is prepared for no aluminium Ti- β, the effectively progress of EPOXIDATION OF ALKENES CATALYZED BY can be combined simultaneously with organic peroxide.
J.Van der Wall etc. (Stud Surf Sci Catal, 1997,105:1093-1100.) uses bis- (hexamethylenes
Ylmethyl) dimethyl hydrogen amine-oxide synthesized and has been uniformly distributed in framework of molecular sieve without aluminium Ti- β, Ti, have no non-skeleton Ti species
In the presence of.Therefore, in chain olefin and the epoxidation reaction of macromolecular alkene, Ti- β has preferable activity.Although this method
Ti can be prepared to be uniformly distributed and have preferable active Ti- beta-molecular sieve, but its synthesis condition is more harsh: crystallization temperature is small
When 408K, crystallization rate is excessively slow, needs longer crystallization time that can just synthesize Ti- β；But when crystallization temperature is greater than 423K,
Ti- β can not then be made by crystallization.
M.Sasidharan etc. (Phys Chem Chem Phys, 2011,13,16282-16294.) is then contained by investigating
F-In system, double quaternary ammonium base [R of several different structures3N+–(CH2)x–N+R3](OH)2The property of (x=1~6) in Ti- β synthesis
Energy and law discovery, the length and property of the bridge alkyl chain of double quaternary ammonium bases have a significant impact the synthesis of Ti- β with physico-chemical property.
T.Blasco etc. (Chem Commun, 1996,20:2367-2368.) is using white carbon black as silicon source, tetraethyl hydroxide
Ammonium is template, contains F near neutral-It has been synthesized in system without aluminium Ti- β.Under alkaline condition, direct hydrothermal synthesis legal system
Standby Ti- β is compared, the exoskeletal defect of molecular sieve of this method preparation, and its hydrophobicity, thermal stability and catalytic activity are all more excellent.
But when PH is about 7, when the upper limit of Ti contained by unit cell is that 2.3, Ti content is more than this value, there is anatase generation.
In short, adding crystal seed or can all prepare the Ti- β with certain oxidation activity using new template agent and HF mineralizer
Molecular sieve.But when the beta-molecular sieve of dealuminzation being used to be crystal seed, the crystallization time of molecular sieve is long, and the defect of crystallization product is more, and dealuminzation
Process is more difficult to control, and dealumination treatment can not completely remove aluminium, and the presence of aluminium can then increase the acidity of molecular sieve, reduces oxygen
Change the selectivity of product；Structure is complicated for new template agent, and synthesis is difficult；When neutrallty condition synthesizes, the dosage of mineralizer HF is big, malicious
Property it is big, and under neutrallty condition Ti- β synthesis cycle is long, particle is big, its selective oxidation activity can be reduced.
Summary of the invention
The object of the present invention is to provide a kind of Ti-beta molecular sieve and its synthetic method and application, wherein this method be with
Total silicon beta molecular sieve is crystal seed, using the compound containing alkali metal ion as mineralizer, and synthesis particle under alkaline condition
Size is smaller and the active higher Ti-beta molecular sieve of selective oxidation.
To achieve the goals above, the present invention provides a kind of method for synthesizing Ti-beta molecular sieve, comprising the following steps:
(1) silicon source, titanium source, crystal seed, alkali metal compound mineralizer, structure directing agent, water and optional alkali source are mixed
It closes uniformly, obtaining mol ratio is OH-: SiO2: TiO2: B:A:R:H2O=(0.15-3): 1:(0.001-0.1): (0.01-2):
(0.011-5): (0.2-5): the reaction mixture of (3-90)；Wherein, the crystal seed is total silicon beta molecular sieve；B represents anti-
The molal quantity of the silica in mixture in crystal seed is answered, A represents mole of alkali metal compound mineralizer in reaction mixture
Number, R represent the molal quantity of structure directing agent in reaction mixture；
(2) reaction mixture for obtaining step (1) is in the closed container of pressure resistance in 90-230 DEG C of temperature and spontaneous
Crystallization 0.1-20 days under pressure, obtain crystallization product；
(3) crystallization product that recycling step (2) obtains.
On the other hand, the invention also includes the Ti-beta molecular sieves obtained by above-mentioned preparation method.
In another aspect, the present invention also provides a kind of method that 1- octene catalysis epoxidation prepares octylene oxide, this method
Including 1- octene is reacted in the presence of a catalyst with oxidant, which is characterized in that the catalyst contains the above method
The Ti-beta molecular sieve being prepared.
The present invention provides a kind of method for synthesizing Ti-beta molecular sieve, this method is under alkaline condition, brilliant by being added
Kind and alkali metal compound mineralizer are prepared for the Ti-beta molecular sieve that skeleton defect is few, particle size is small, which exists
There is good catalytic performance in macromolecular oxidation reaction.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the Ti-beta molecular sieve obtained according to the method (embodiment 1) for synthesizing Ti-beta molecular sieve in the present invention
X-ray diffraction (XRD) crystalline phase figure.
Fig. 2 is the Ti-beta molecular sieve obtained according to the method (embodiment 1) for synthesizing Ti-beta molecular sieve in the present invention
Scanning electron microscope (SEM) shape appearance figure.
Fig. 3 is the crystal phase of the X-ray diffraction (XRD) of the Ti-beta molecular sieve obtained according to method described in comparative example 1
Figure.
Fig. 4 is the scanning electron microscope (SEM) of the Ti-beta molecular sieve obtained according to method described in comparative example 1
Shape appearance figure.
Fig. 5 is the scanning electron microscope (SEM) of the Ti-beta molecular sieve obtained according to method described in comparative example 2
Shape appearance figure.
Fig. 6 is the scanning electron microscope (SEM) of the Ti-beta molecular sieve obtained according to method described in comparative example 3
Shape appearance figure
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of method for synthesizing Ti-beta molecular sieve, comprising the following steps:
(1) silicon source, titanium source, crystal seed, alkali metal compound mineralizer, structure directing agent, water and optional alkali source are mixed
It closes uniformly, obtaining mol ratio is OH-: SiO2: TiO2: B:A:R:H2O=(0.15-3): 1:(0.001-0.1): (0.01-2):
(0.011-5): (0.2-5): the reaction mixture of (3-90)；Wherein, the crystal seed is total silicon beta molecular sieve；B represents anti-
The molal quantity of the silica in mixture in crystal seed is answered, A represents mole of alkali metal compound mineralizer in reaction mixture
Number, R represent the molal quantity of structure directing agent in reaction mixture；
(2) reaction mixture for obtaining step (1) is in the closed container of pressure resistance in 90-230 DEG C of temperature and spontaneous
Crystallization 0.1-20 days under pressure, obtain crystallization product；
(3) crystallization product that recycling step (2) obtains.
It is preferred according the present invention, that the mol ratio of reaction mixture obtained in the step (1) is OH-:
SiO2: TiO2: B:A:R:H2O=(0.35-2): 1:(0.01-0.06): (0.02-1.5): (0.015-2): (0.25-2.5):
(5-50)；Further preferred mol ratio is OH-: SiO2: TiO2: B:A:R:H2O=(0.5-1.5): 1:(0.02-0.05):
(0.04-1): (0.02-1.5): (0.5-2): (8-80).
According to the present invention, the silicon source in the step (1) can be synthesis Ti- well-known to those skilled in the art
Silicon source commonly used by beta molecular sieve, the present invention are not particularly limited it, such as the silicon source can be estersil (organic silicic acid
Ester), solid silicone, at least one of white carbon black and silica solution；In order to avoid trivalents such as the hetero atom in silicon source such as boron or aluminium
For hetero atom on the issuable influence of the crystallization of Ti-beta molecular sieve, silicon source described in step (1) is preferably that silica contains
Measure at least one of estersil, solid silicone and white carbon black high and that impurity content is few；Further preferably estersil, wherein institute
The general formula for the estersil said are as follows:
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as: R1、R2、R3And R4It respectively can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or tertiary fourth
Base, wherein it is preferred that R1、R2、R3And R4It is methyl or ethyl.
According to the present invention, titanium source used in the step (1) can be those skilled in the art and synthesize Ti-beta points
Titanium source commonly used by son sieve, the present invention is not particularly limited it, such as the titanium source can be titanium tetrachloride, titanium sulfate, nitre
At least one of sour titanium, tetraethyl titanate, metatitanic acid orthocarbonate and butyl titanate；Preferably butyl titanate.
According to the present invention, it is common when structure directing agent used in the step (1) can be to synthesize Ti- beta-molecular sieve
Structure directing agent, the present invention is not particularly limited it, such as the structure directing agent can be quaternary ammonium base class, quaternary ammonium salt
At least one of with fatty amines, wherein described quaternary ammonium base can be quaternary ammonium base, and described quaternary ammonium salt can be
Organic quaternary ammonium salt, described aliphatic amine can be NH3In at least one hydrogen by aliphatic alkyl (such as alkyl) replace after
The compound of formation.
Specifically, the structure directing agent can be the quaternary ammonium of the quaternary ammonium base, general formula III expression that indicate selected from general formula II
At least one of the aliphatic amine that salt and general formulae IV indicate.
In Formula II, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as: R1、R2、R3And R4Can respectively be each independently methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group or tert-butyl.
In formula III, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as: R1、R2、R3And R4Can respectively be each independently methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group or tert-butyl；X represents halide anion or acid ion, such as can be F-、Cl-、Br-、I-Or HSO4 -。
R5(NH2)n(formula IV)
In formula IV, n is an integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, new penta
Base, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.
Preferably, structure directing agent described in step (1) is tetraethyl ammonium hydroxide, tetraethyl ammonium fluoride, tetraethyl chlorine
Change at least one of ammonium, tetraethylammonium bromide, tetraethyl ammonium iodide, diethylamine and triethylamine；Further, the structure is led
It can be tetraethyl ammonium hydroxide to agent.
According to the present invention, mineralizer described in step (1) can be commonly containing the compound of alkali metal ion, such as
It can be sodium chloride, sodium fluoride, sodium bromide, sodium iodide, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium sulphate, sodium sulfite, chlorine
Change potassium, potassium fluoride, potassium bromide, potassium iodide, potassium hydroxide, potassium carbonate, saleratus, potassium sulfate, potassium sulfite, lithium chloride, fluorine
Change at least one of lithium, lithium bromide, lithium iodide, lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium sulfate and lithium sulfite；It is preferred that
Mineralizer be the compound containing sodium ion；Further preferably sodium fluoride and sodium hydroxide.
According to the present invention, crystal seed total silicon beta molecular sieve described in step (1) can be known to those skilled in the art
Total silicon beta molecular sieve such as can be the total silicon beta of conventional hydrothermal crystallization method synthesis, be also possible to other methods synthesis
Total silicon beta molecular sieve；Preferred crystal seed total silicon beta molecular sieve is that the crystal form that hydrothermal crystallization method synthesizes is complete, ties in the present invention
The high total silicon beta molecular sieve of brilliant degree；Further preferably sheet total silicon of the length and width no more than 1um, thickness no more than 200nm
Beta molecular sieve.
According to the present invention, the OH in the reaction mixture in the step (1)-Either being led from the structure
To OH present in agent, the silicon source or the mineralizer-, it is also possible in the alkali source additionally incorporated
OH-；Term " optional alkali source ", refers to and works as OH present in the structure directing agent being added or the silicon source-Amount it is full
When the mol ratio of the foot reaction mixture requires, it is not required to that alkali source is still further added；And work as OH-Amount be not able to satisfy it is described anti-
When the mol ratio of mixture being answered to require, the alkali source is still further added.The used alkali source can be art technology
Known to personnel when synthesis Ti-beta molecular sieve commonly used by any alkali source, the present invention is not particularly limited it, such as
The alkali source can be at least one in sodium hydroxide, ammonium hydroxide, lithium hydroxide, rubidium hydroxide, sodium carbonate, sodium bicarbonate and lithium carbonate
Kind；Preferably, alkali source used in step (1) is sodium hydroxide and ammonium hydroxide.
According to the present invention, common water when water used in the step (1) can be synthesis of molecular sieve, in order to avoid
Heteroatomic introducing, the present invention in preferably deionized water.
According to the present invention, the silicon source in the step (1), titanium source, crystal seed, alkali metal ionic compounds mineralizer, structure
Directed agents, water and optional alkali source can be conventionally uniformly mixed, that is, be worth the reaction mixture.
A kind of preferred embodiment of the invention are as follows: in step (1), can first by silicon source, titanium source, structure directing agent,
Water and optional alkali source after mixing, add crystal seed and alkali metal compound mine within the temperature range of 30-90 DEG C
Agent obtains reaction mixture after mixing；Wherein, the crystal seed is total silicon beta molecular sieve.
According to the present invention, crystallization condition is preferred in the step (2) are as follows: crystallization temperature is 110-190 DEG C, and crystallization time is
0.5-15 days.
According to the present invention, the crystallization in the step (2) can be in a static condition or under the conditions of dynamic agitation into
Row；It is uniformly mixed for guarantee crystallization system and obtains uniform crystallization product, crystallization process is optimized under the conditions of dynamic agitation
It carries out；It advanced optimizes to carry out dynamic crystallization under the mixing speed of 100-800r/min.
According to the present invention, the recovery method in the step (3) can be conventional absorption method, such as can be by step (2)
Obtained crystallization product obtains dry crystallization product after filtration, washing and drying；Dry temperature can be 60-180 DEG C,
The dry time can be 0.5-24 hours, further preferably are as follows: dry temperature can be 90-130 DEG C, and the dry time can
Think 2-12 hours.
According to the present invention, which can also include the following steps (4): by step (3) recycling crystallization product into
Row calcination process, to remove the structure directing agent in molecular sieve pore passage.
According to the present invention, the condition of calcination process described in the step (4) may is that maturing temperature is 400-800
DEG C, calcining time is 1-16 hours.
On the other hand, the invention also includes the Ti-beta molecular sieves obtained by above-mentioned preparation method.
In another aspect, the present invention also provides a kind of method that 1- octene catalysis epoxidation prepares octylene oxide, this method
Including reacting 1- octene in the presence of a catalyst with oxidant, prepared according to the method described above wherein the catalyst contains
Obtained Ti-beta molecular sieve；The oxidant such as can be able to be organic peroxy to commonly use oxidant in chemical industry
Object, in the present invention it is preferable to use oxidant be tert-butyl hydroperoxide.The reaction can under conventional reaction condition into
Row, as reaction condition can be with are as follows: the molar ratio of oxidant and 1- octene is 0.25-2, pressure 0.1-5MPa, and reaction temperature is
40-150 DEG C, reaction time 1-120h, the amount of catalyst is the 0.01%-40% of reactant total weight.In the present invention, when
When reaction condition is following: Ti-beta molecular sieve amount is 0.6g, and 1- octene amount is 0.1mol, tert-butyl hydroperoxide and 1- octene
Molar ratio be 1:1, normal pressure, reaction temperature be 100 DEG C, the reaction time be 4 hours, Ti-beta molecular sieve is in the reaction condition
Under show preferable catalytic performance.
It below will the present invention will be described in detail by specific embodiment.In following embodiment and comparative example, X is penetrated
The crystalline phase figure of line diffraction (XRD) is to measure to obtain with Philips Panalytical X'pert, test condition are as follows: Cu target, K α
Radiation, Ni filter plate, super detector, tube voltage 30KV, tube current 40mA；The shape appearance figure of scanning electron microscope (SEM) is
It is measured with the S4800 of Hitachi company, acceleration voltage 20KV, environmental scanning.
29The phenogram of Si NMR is measured with Varian INOVA300 type nuclear magnetic resonance chemical analyser, test condition are as follows: altogether
Vibration frequency spectrum is 59.588MHz, magic angle rotating speed 3kHz.29Q4 signal in Si NMR refers to Si- in molecular sieve (O-Si)4Structure
Generated formant, i.e. silicon atom be connected by silicon oxygen bond with four silicon atoms composed by structure generate formant；
Q3 signal refers to HO-Si- in molecular sieve (O-Si)3Formant caused by structure, i.e. silicon atom pass through silicon oxygen bond and three silicon
The formant that atom is connected and the composed structure that is connected with a hydroxyl generates.29The characterization result explanation of Si NMR, according to
The Ti-beta molecular sieve of method synthesis of the invention has strong Q4 signal, and almost without the signal of Q3, this illustrates prepared by this method
Ti-beta molecular sieve almost without skeleton defect, there is high-crystallinity.It is right29Si NMR formant spectrogram carries out swarming fitting
Each peak area is calculated using integration method afterwards, the ratio between Q4 and Q3 peak area are Q4/Q3 value.
Embodiment 1
Under agitation, by ethyl orthosilicate, butyl titanate, total silicon beta-molecular sieve crystal seed, tetraethyl ammonium hydroxide and
Deionized water mixes at 60 DEG C, and obtaining mol ratio is SiO2:TiO2: crystal seed: structure directing agent: H2O=1:0.03:0.8:
The alkaline mixed solution of 1.3:20, then press mineralizer: SiO2It is molten to be added to above-mentioned mixing by=0.8 mol ratio for sodium fluoride
OH is uniformly mixing to obtain in liquid-:SiO2About 1.3 Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 135 DEG C,
Constant temperature 10 days at autogenous pressures obtain the mixture of crystallization product；This mixture is filtered, after being washed with water several times；110
At a temperature of DEG C after dry 6h 550 DEG C at a temperature of carry out calcination process, calcining time 5h obtains Ti- beta-molecular sieve.It should
The XRD spectra of molecular sieve is as shown in Figure 1, the shape appearance figure of scanning electron microscope (SEM) is as shown in Figure 2.
Embodiment 2
Under agitation, by methyl orthosilicate, metatitanic acid orthocarbonate, total silicon beta-molecular sieve crystal seed, diethylamine and deionized water
And additional alkali source ammonium hydroxide mixes at 40 DEG C, obtaining mol ratio is SiO2:TiO2: crystal seed: structure directing agent: H2O=1:
The alkaline mixed solution of 0.01:0.02:0.25:5, then press mineralizer: SiO2=0.015 mol ratio, by sodium hydroxide plus
Enter and is uniformly mixing to obtain OH into above-mentioned mixed solution-:SiO2=0.35 Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 110 DEG C,
Constant temperature 15 days at autogenous pressures obtain the mixture of crystallization product；This mixture is filtered, after being washed with water several times；90
At a temperature of DEG C after dry 12h 450 DEG C at a temperature of carry out calcination process, calcining time 10h obtains Ti- beta-molecular sieve.
Embodiment 3
Under agitation, by silica gel, tetraethyl titanate, total silicon beta-molecular sieve crystal seed, tetraethyl ammonium fluoride and deionized water
And additional alkali source sodium hydroxide mixes at 80 DEG C, obtaining mol ratio is SiO2:TiO2: crystal seed: structure directing agent: H2O=
1:0.06:1.5:2.5:50 alkaline mixed solution, then press mineralizer: SiO2Sodium bromide is added to by=2 mol ratio
It states and is uniformly mixing to obtain OH in mixed solution-:SiO2=2 Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 190 DEG C,
Constant temperature 0.5 day at autogenous pressures obtains the mixture of crystallization product；This mixture is filtered, after being washed with water several times；?
At a temperature of 130 DEG C after dry 2h 600 DEG C at a temperature of carry out calcination process, calcining time 3h obtains Ti- beta-molecular sieve.
Embodiment 4
Under agitation, by positive silicic acid propyl ester, titanium tetrachloride, total silicon beta-molecular sieve crystal seed, tetraethylammonium bromide and go from
Sub- water and additional alkali source lithium hydroxide mix at 30 DEG C, and obtaining mol ratio is SiO2:TiO2: crystal seed: structure directing agent:
H2The alkaline mixed solution of O=1:0.005:0.01:0.2:3, then press mineralizer: SiO2=0.011 mol ratio, by carbonic acid
Sodium, which is add to the above mixed solution, is uniformly mixing to obtain OH-:SiO2=0.15 Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 90 DEG C,
Constant temperature 20 days under self-generated pressure, obtain the mixture of crystallization product；This mixture is filtered, after being washed with water several times；At 60 DEG C
At a temperature of it is dry for 24 hours after 800 DEG C at a temperature of carry out calcination process, calcining time 1h obtains Ti- beta-molecular sieve.
Embodiment 5
Under agitation, by white carbon black, titanium sulfate, total silicon beta-molecular sieve crystal seed, etamon chloride and deionized water with
And additional alkali source potassium hydroxide mixes at 90 DEG C, obtaining mol ratio is about SiO2:TiO2: crystal seed: structure directing agent: H2O=
The alkaline mixed solution of 1:0.1:2:4.5:90, then press mineralizer: SiO2Sodium sulphate is added to by=4.5 mol ratio
It states and is uniformly mixing to obtain OH in mixed solution-:SiO2=3 Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 230 DEG C,
Constant temperature 0.1 day at autogenous pressures obtains the mixture of crystallization product；This mixture is filtered, after being washed with water several times；?
At a temperature of 180 DEG C after dry 0.5h 400 DEG C at a temperature of carry out calcination process, calcining time 16h obtains Ti- beta molecule
Sieve.
Embodiment 6
Under agitation, by ethyl orthosilicate, butyl titanate, total silicon beta-molecular sieve crystal seed, tetraethyl ammonium hydroxide and
Deionized water mixes at 60 DEG C, and obtaining mol ratio is OH-:SiO2:TiO2: crystal seed: structure directing agent: H2O=1:0.03:
The alkaline mixed solution of 0.8:1.3:20, then press mineralizer: SiO2Potassium bromide is added to above-mentioned mixed by=0.8 mol ratio
It closes in solution and is uniformly mixing to obtain OH-:SiO2=1.3 Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 135 DEG C,
Constant temperature 10 days at autogenous pressures obtain the mixture of crystallization product；This mixture is filtered, after being washed with water several times；110
At a temperature of DEG C after dry 6h 550 DEG C at a temperature of carry out calcination process, calcining time 5h obtains Ti- beta-molecular sieve.
Embodiment 7
Under agitation, it by ethyl orthosilicate, titanium tetrachloride, total silicon beta-molecular sieve crystal seed, tetraethyl ammonium hydroxide and goes
Ionized water mixes at 60 DEG C, and obtaining mol ratio is SiO2:TiO2: crystal seed: structure directing agent: H2O=1.3:1:0.03:
The alkaline mixed solution of 0.8:1.3:20, then press mineralizer: SiO2Sodium fluoride is added to above-mentioned mixed by=0.8 mol ratio
It closes in solution and is uniformly mixing to obtain OH-:SiO2About 1.3 Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 135 DEG C,
Constant temperature 10 days at autogenous pressures obtain the mixture of crystallization product；This mixture is filtered, after being washed with water several times；110
At a temperature of DEG C after dry 6h 550 DEG C at a temperature of carry out calcination process, calcining time 5h obtains Ti- beta-molecular sieve.
Embodiment 8
Under agitation, by silica solution, Titanium Nitrate, total silicon beta-molecular sieve crystal seed, triethylamine and deionized water and exogenously added alkali
Source sodium hydroxide mixes at 60 DEG C, and obtaining mol ratio is SiO2:TiO2: crystal seed: structure directing agent: H2O=1:0.04:
The alkaline mixed solution of 0.5:0.8:15, then press mineralizer: SiO2Potassium bromide is added to above-mentioned mixing by=4 mol ratio
OH is uniformly mixing to obtain in solution-:SiO2=1 Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 150 DEG C,
Constant temperature 10 days at autogenous pressures obtain the mixture of crystallization product；This mixture is filtered, after being washed with water several times；100
At a temperature of DEG C after dry 8h 500 DEG C at a temperature of carry out calcination process, calcining time 7h obtains Ti- beta-molecular sieve.
Comparative example 1
This comparative example illustrates technical solution not according to the invention, but use the prior art (Chem Commun, 1996,
20:2367-2368.) described in conventional method synthesize Ti- beta-molecular sieve in neutral conditions.Detailed process is as follows:
Under agitation, by ethyl orthosilicate, butyl titanate, tetraethyl ammonium hydroxide and deionized water at 60 DEG C
Mixing, obtains SiO2:TiO2: structure directing agent: H2The alkaline mixed solution of O=1:0.03:1.3:20, then hydrofluoric acid is added
And crystallization system is adjusted to neutrality to obtain Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 135 DEG C,
Constant temperature 10 days at autogenous pressures obtain the mixture of crystallization product；This mixture is filtered, after being washed with water several times；110
At a temperature of DEG C after dry 6h 550 DEG C at a temperature of carry out calcination process, calcining time 5h obtains Ti- beta-molecular sieve.It should
The XRD spectra of molecular sieve is as shown in figure 3, the shape appearance figure of scanning electron microscope (SEM) is as shown in Figure 4.
Comparative example 2
According to synthetic method similar to Example 1, difference is: total silicon beta-molecular sieve crystalline substance is not added in this comparative example
Kind, specific implementation process is as follows:
Under agitation, by ethyl orthosilicate, butyl titanate, tetraethyl ammonium hydroxide and deionized water at 60 DEG C
Mixing, obtaining mol ratio is OH-:SiO2:TiO2: structure directing agent: H2The alkalinity mixing of O=1.3:1:0.03:1.3:20 is molten
Liquid, then press mineralizer: SiO2=0.8 mol ratio, sodium fluoride is add to the above mixed solution and is uniformly mixing to obtain Ti-
Beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 135 DEG C,
Constant temperature 10 days at autogenous pressures obtain the mixture of crystallization product；This mixture is filtered, after being washed with water several times；110
At a temperature of DEG C after dry 6h 550 DEG C at a temperature of carry out calcination process, calcining time 5h obtains Ti- beta-molecular sieve.It should
The XRD spectra of molecular sieve is similar with Fig. 1, and the shape appearance figure of scanning electron microscope (SEM) is as shown in Figure 5.
Comparative example 3
According to synthetic method similar to Example 1, difference is: with total silicon β points of dealuminzation preparation in this comparative example
Son sieve is crystal seed, and specific implementation process is as follows:
Under stirring condition, processing 8h is carried out to beta-molecular sieve containing aluminium using the nitric acid that 80 DEG C of concentration are 0.1mol/L；It crosses
Filter, 110 DEG C of dry 6h, 550 DEG C of roasting 3h obtain the beta-molecular sieve of dealuminzation.
Under agitation, total silicon beta-molecular sieve crystal seed, the tetraethyl prepared by ethyl orthosilicate, butyl titanate, dealuminzation
Ammonium hydroxide and deionized water mix at 60 DEG C, and obtaining mol ratio is SiO2:TiO2: crystal seed: structure directing agent: H2O=1:
The alkaline mixed solution of 0.03:0.8:1.3:20, then press mineralizer: SiO2Sodium fluoride is added to by=0.8 mol ratio
It states and is uniformly mixing to obtain OH in mixed solution-:SiO2About 1.3 Ti- beta-molecular sieve presoma.
After the colloid to be transferred to the closed reactor of pressure resistance, under agitation, crystallization system is warming up to 135 DEG C,
Constant temperature 10 days at autogenous pressures obtain the mixture of crystallization product；This mixture is filtered, after being washed with water several times；110
At a temperature of DEG C after dry 6h 550 DEG C at a temperature of carry out calcination process, calcining time 5h obtains Ti- beta-molecular sieve.It should
The XRD spectra of molecular sieve is similar with Fig. 1, and the shape appearance figure of scanning electron microscope (SEM) is as shown in Figure 6.
The XRD characterization figure and SEM phenogram of embodiment 2-8 is similar with the characterization result of embodiment 1, therefore does not list one by one；
The Ti-beta molecular sieve of embodiment 1-8 and comparative example 1-3 passes through29Q4/Q3 value that Si NMR is characterized and in 1- octene oxygen
The catalytic result changed in reaction is as shown in table 1, and reaction condition includes: that Ti- beta-molecular sieve amount is 0.6g, and 1- octene amount is 0.1mol,
Tert-butyl hydroperoxide and 1- octene molar ratio=1:1, reaction temperature are 100 DEG C, reaction time 4h.By using gas phase color
The composition for the liquid phase mixture that spectrometry measurement reaction obtains, is quantified by correcting normalization method, wherein and reaction-ure conversion-age=
Amount × 100% of (amount-residual reactant amount of the reactant of addition)/addition reactant；Target product selectivity=conversion
At amount × 100% of amount/conversion reactant of reactant consumed by target product.
Table 1
| Q4/Q3 | 1- octene conversion (%) | Octylene oxide selectivity (%) | |
| Embodiment 1 | 47 | 44.8 | 98.9 |
| Embodiment 2 | 40 | 33.3 | 98.8 |
| Embodiment 3 | 44 | 40.3 | 98.2 |
| Embodiment 4 | 30 | 30.6 | 97.1 |
| Embodiment 5 | 39 | 34.5 | 97.5 |
| Embodiment 6 | 41 | 38.9 | 97.9 |
| Embodiment 7 | 35 | 32.4 | 98.0 |
| Embodiment 8 | 27 | 27.8 | 96.4 |
| Comparative example 1 | 38 | 12.9 | 99.2 |
| Comparative example 2 | 41 | 40.8 | 98.8 |
| Comparative example 3 | 12 | 27.1 | 28.5 |
As can be seen that technical solution of the present invention can be under alkaline condition by adding from data in table and characterization result
Enter total silicon beta molecular sieve as crystal seed and alkali metal compound mineralizer, can prepare that skeleton defect is less, particle size
Uniform Ti-beta molecular sieve, and the molecular sieve has good catalytic performance in 1- octene oxidation reaction.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention
Monotropic type, these 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 (12)
1. a kind of method for synthesizing Ti-beta molecular sieve, comprising the following steps:
(1) silicon source, titanium source, crystal seed, alkali metal compound mineralizer, structure directing agent, water and optional alkali source are mixed equal
Even, obtaining mol ratio is OH-: SiO2: TiO2: B:A:R:H2O=(0.5-1.5): 1:(0.02-0.05): (0.04-1):
(0.02-1.5): (0.5-2): the reaction mixture of (8-50)；Wherein, the crystal seed is total silicon beta molecular sieve；B represents anti-
The molal quantity of the silica in mixture in crystal seed is answered, A represents mole of alkali metal compound mineralizer in reaction mixture
Number, R represent the molal quantity of structure directing agent in reaction mixture；
(2) temperature and self-generated pressure of the reaction mixture for obtaining step (1) in the closed container of pressure resistance at 90-230 DEG C
Lower crystallization 0.1-20 days, obtain crystallization product；
(3) crystallization product that recycling step (2) obtains；
Structure directing agent described in step (1) is tetraethyl ammonium hydroxide, tetraethyl ammonium fluoride, etamon chloride, tetrem
Base ammonium bromide, tetraethyl ammonium iodide, diethylamine or triethylamine.
2. according to the method described in claim 1, wherein, silicon source described in step (1) is estersil, solid silicone, white carbon black
Or silica solution.
3. according to the method described in claim 1, wherein, titanium source described in step (1) is titanium tetrachloride, titanium sulfate, nitric acid
Titanium, tetraethyl titanate, metatitanic acid orthocarbonate or butyl titanate.
4. according to the method described in claim 1, wherein, alkali metal compound mineralizer described in step (1) is sodium chloride, fluorine
Change sodium, sodium bromide, sodium iodide, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium sulphate or sodium sulfite.
5. according to the method described in claim 1, wherein, alkali metal compound mineralizer described in step (1) is selected from fluorine
Change sodium or sodium hydroxide.
6. according to the method described in claim 1, wherein, alkali source described in step (1) is sodium hydroxide, ammonium hydroxide, hydroxide
Lithium, rubidium hydroxide, sodium carbonate, sodium bicarbonate or lithium carbonate.
7. crystallization temperature described in step (2) is 110-190 DEG C according to the method described in claim 1, wherein, when crystallization
Between be 0.5-15 days.
8. according to the method described in claim 1, wherein, this method further includes step (4): the crystallization of step (3) recycling is produced
Object carries out calcination process.
9. according to the method described in claim 8, wherein, the condition of calcination process described in step (4) is: maturing temperature is
400-800 DEG C, calcining time is 1-16 hours.
10. a kind of Ti-beta molecular sieve, the method as described in any one of claim 1-9 is prepared.
11. a kind of method that 1- octene catalysis epoxidation prepares octylene oxide, this method include urging 1- octene and oxidant
It is reacted in the presence of agent, which is characterized in that the catalyst contains Ti-beta molecular sieve described in claim 10.
12. method according to claim 11, wherein the molar ratio that the condition of the reaction includes: oxidant and 1- octene is
0.25-2, pressure 0.1-5MPa, reaction temperature are 40-150 DEG C, reaction time 1-120h, and the amount of catalyst is reactant
The 0.01%-40% of total weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510280601.7A CN106276948B (en) | 2015-05-27 | 2015-05-27 | A kind of Ti-beta molecular sieve and its synthetic method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510280601.7A CN106276948B (en) | 2015-05-27 | 2015-05-27 | A kind of Ti-beta molecular sieve and its synthetic method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106276948A CN106276948A (en) | 2017-01-04 |
| CN106276948B true CN106276948B (en) | 2019-02-01 |
Family
ID=57635595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510280601.7A Active CN106276948B (en) | 2015-05-27 | 2015-05-27 | A kind of Ti-beta molecular sieve and its synthetic method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106276948B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109850914A (en) * | 2019-04-15 | 2019-06-07 | 福州大学 | A kind of preparation method of the nanoscale without aluminium Ti-Beta molecular sieve |
| CN112742453B (en) * | 2019-10-30 | 2023-07-14 | 中国石油化工股份有限公司 | Preparation method of titanium-containing molecular sieve, catalyst and selective oxidation method |
| CN114229863B (en) * | 2021-11-30 | 2023-01-13 | 中国矿业大学 | Preparation method of Ti-Beta molecular sieve |
| CN115555045B (en) * | 2022-09-19 | 2023-07-28 | 辽宁师范大学 | Preparation method and application of H-beta molecular sieve catalyst co-modified by titanium silicon oxide |
| CN115557840B (en) * | 2022-11-04 | 2023-11-10 | 浙江新化化工股份有限公司 | Preparation method of 2-nitropropane and catalyst used in preparation method |
| CN116161674B (en) * | 2023-03-17 | 2024-09-10 | 大连理工大学 | Hydrothermal preparation method of nano Ti-Beta molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249271A (en) * | 1998-09-25 | 2000-04-05 | 北京燕山石油化工公司研究院 | Process for synthesizing beta-zeolite |
| CN1727281A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve and preparation method |
| CN101279744A (en) * | 2007-04-05 | 2008-10-08 | Ifp公司 | Method for preparing a beta zeolite |
-
2015
- 2015-05-27 CN CN201510280601.7A patent/CN106276948B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249271A (en) * | 1998-09-25 | 2000-04-05 | 北京燕山石油化工公司研究院 | Process for synthesizing beta-zeolite |
| CN1727281A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve and preparation method |
| CN101279744A (en) * | 2007-04-05 | 2008-10-08 | Ifp公司 | Method for preparing a beta zeolite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106276948A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106276948B (en) | A kind of Ti-beta molecular sieve and its synthetic method and application | |
| CN106145149A (en) | A kind of method preparing multi-stage porous HTS | |
| CN104556115B (en) | Titanium silicalite molecular sieve synthesizing method | |
| JP5752090B2 (en) | Titanium-silicon molecular sieve and method for producing the same, and method for producing cyclohexanone oxime using the molecular sieve | |
| CN106145148B (en) | A method of preparing multi-stage porous Titanium Sieve Molecular Sieve | |
| CN110180586A (en) | The alkali metal ion modifying titanium-silicon molecular sieve TS-1 and preparation method thereof reacted for propylene and hydrogen peroxide gas-phase epoxidation | |
| CN104556114B (en) | A kind of method of the micro- mesoporous composite material of synthesis of titanium silicon | |
| CN106145147B (en) | A method of preparing multi-stage porous Titanium Sieve Molecular Sieve | |
| CN105819464A (en) | High yield rapid synthesis method of titanium-silicon molecular sieve TS-1 | |
| CN101786638A (en) | Titanium silicate molecular sieve modification method | |
| CN106145151A (en) | A kind of multi-stage porous HTS and synthetic method thereof | |
| CN106629762B (en) | A method of utilizing the rapid synthesis TS-1 Titanium Sieve Molecular Sieve of zeolite-water thermal crystallisation filtrate | |
| CN111924854B (en) | ECNU-29 titanium aluminosilicate nanosheet and preparation method and application thereof | |
| CN104556104A (en) | Method for synthesizing titanium-silicalite molecular sieve employing organic quaternary ammonium salt template agent | |
| Li et al. | Titanium species in titanium silicalite TS-1 prepared by hydrothermal method | |
| CN102344150A (en) | Synthetic method for mesopore titanium-silicon molecular sieve | |
| CN109502601A (en) | A kind of Titanium Sieve Molecular Sieve and its preparation method and application | |
| CN107032366A (en) | A kind of method for preparing the HTS TS 1 with high skeleton Ti content | |
| CN106268927A (en) | A kind of Ti-beta-molecular sieve obtained by total silicon beta-molecular sieve modification and its preparation method and application | |
| CN107381592A (en) | The method of titanium tin molecular sieve and preparation method thereof and catalysis oxidation cyclohexanone | |
| CN104512904B (en) | A kind of method preparing mesoporous titanium-silicon material | |
| Moliner et al. | Direct synthesis of a titanosilicate molecular sieve containing large and medium pores in its structure | |
| CN110862098B (en) | Method for synthesizing MCM-22 molecular sieve | |
| CN106276954B (en) | A kind of Ti-beta molecular sieves and its preparation method and application | |
| CN106276955B (en) | A kind of Ti-beta molecular sieves and its synthetic method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |