CN107879355A - Modified with noble metals HTS and its preparation method and application and a kind of method of alkene direct oxidation - Google Patents
Modified with noble metals HTS and its preparation method and application and a kind of method of alkene direct oxidation Download PDFInfo
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Abstract
The present invention relates to catalysis material field, specifically provides a kind of modified with noble metals HTS and its preparation method and application, and the molecular sieve contains precious metal element, titanium elements, element silicon and oxygen element, wherein, the pore volume of the molecular sieve is in 0.25cm3/ more than g, total specific surface area is in 250m2/ more than g, the ratio that external surface area accounts for total specific surface area are 8 50%, N2The lower micropore size with 0.8 2nm scopes of Static Adsorption test is distributed, the N of the HTS‑116/N‑112It is worth for 0.01 0.2.The invention provides a kind of method of alkene direct oxidation, this method includes：Using methanol as solvent, alkene, oxygen-containing gas and catalyst are contacted, the catalyst contains molecular sieve of the present invention.Its benzene adsorbance with the modified with noble metals HTS of special physical chemical characteristicses structure of the present invention is higher, uses it for ring molecule, the reaction that olefin hydrocarbon molecules are participated in or generated, can obtain more preferable catalytic effect.
Description
Technical field
The present invention relates to a kind of modified with noble metals HTS and its preparation method and application, relate more specifically to one kind
The method that modified with noble metals HTS is prepared using the titanium-silicon molecular sieve catalyst of inactivation, the invention further relates to a kind of alkene
The method of direct oxidation.
Background technology
HTS is the new hetero-atom molecular-sieve that last century early eighties start exploitation.Synthesize at present
There are the TS-1 of MFI type structure, the TS-2 of MEL type structures, and Ti-MWW with larger pore structure etc..This molecular sieve analog is to being permitted
More organic oxidizing reactions, for example, the epoxidation of alkene, arene hydroxylation, cyclohexanone oximate, alcohol the reaction such as oxidation have it is excellent
Selective oxidation performance and higher catalytic activity, before they have good application as redox-type molecular sieve catalyst
Scape.
TS-1 molecular sieves are that transition metal titanium is introduced to one formed in the framework of molecular sieve with ZSM-5 structures
Novel titanosilicate of the kind with superior catalytic selective oxidation performance.TS-1 not only has the catalysed oxidn of titanium, and
And also there is the shape-selective effect of ZSM-5 molecular sieve and excellent stability.Because TS-1 molecular sieves are in the oxidation reaction of organic matter
In, free of contamination low concentration hydrogen peroxide can be used to avoid oxidizing process complex process as oxidant and pollute environment
Problem, there is conventional oxidation system unrivaled energy-conservation, economy and advantages of environment protection, and there is good selecting response
Property, therefore there is great prospects for commercial application.However, can be generally deteriorated in operation a period of time rear catalyst catalytic performance,
There is deactivation phenomenom in catalyst.The reason for causing catalyst inactivation be probably impurity due to being introduced during synthesis of molecular sieve or
Byproduct of reaction is gathered in plug-hole etc. in catalyst micropore.
The content of the invention
Modified with noble metals HTS with special physical chemical characteristicses is prepared it is an object of the invention to provide a kind of
Method.
To realize object defined above, the first aspect of the present invention, the invention provides a kind of modified with noble metals HTS,
The molecular sieve contains precious metal element, titanium elements, element silicon and oxygen element, wherein, the pore volume of the molecular sieve is in 0.25cm3/g
More than, total specific surface area is in 250m2/ more than g, the ratio that external surface area accounts for total specific surface area are 8-50%, N2Static Adsorption is tested
The micropore size with 0.8-2nm scopes is distributed down, the N of the HTS-116/N-112It is worth for 0.01-0.2.
The second aspect of the present invention, the invention provides a kind of preparation method of modified with noble metals HTS, the party
Method includes：(1) by noble metal source, ammonia source, alternatively water mixing contact obtains mixture；(2) by the mixture, titanium silicon molecule
Sieve, alternatively water mix laggard water-filling heat treatment.
The third aspect of the present invention, the invention provides the molecular sieve of the present invention answering in catalytic hydrocarbon direct oxidation reaction
With.
According to the fourth aspect of the invention, the invention provides a kind of method of alkene direct oxidation, this method to include：With
Methanol is solvent, and alkene, oxygen-containing gas and catalyst are contacted, and the catalyst contains molecular sieve of the present invention and Ben Fa
The molecular sieve that bright described preparation method is prepared.
Its benzene adsorbance with the modified with noble metals HTS of special physical chemical characteristicses structure of the present invention is higher, will
It is used for ring molecule, olefin hydrocarbon molecules participate in or the reaction of generation, can obtain more preferable catalytic effect.I.e. due to the present invention's
The special physico-chemical structure of material, be advantageous to reactant and product molecule (such as aromatic compound), alkene point in catalytic reaction
The diffusion of son, the catalytic oxidation participated in aromatic hydrocarbon compound, ring class hydrocarbon compound equimolecular and olefin hydrocarbon molecules are special
It is not favourable.
The method for preparing modified with noble metals HTS of the present invention, the special spy with the present invention can be prepared
Levy the modified with noble metals HTS of structure.And the method for the present invention causes the titanium-silicon molecular sieve catalyst of inactivation to obtain profit
With turning waste into wealth.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
As it was previously stated, the invention provides a kind of modified with noble metals HTS, the molecular sieve contain precious metal element,
Titanium elements, element silicon and oxygen element, wherein, the pore volume of the molecular sieve is in 0.25cm3/ more than g, total specific surface area is in 250m2/g
More than, the ratio that external surface area accounts for total specific surface area is 8-50%, N2The lower micropore with 0.8-2nm scopes of Static Adsorption test
Pore-size distribution, the N of the HTS-116/N-112It is worth for 0.01-0.2.
In the present invention, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses X
Ray fluorescence spectrometry determines.
In the present invention, total specific surface area of molecular sieve refers to BET specific surface area, and external surface area refers to molecular sieve
Outer surface surface area, can be also simply referred to as external surface area, can be measured according to ASTMD4222-98 standard methods.
In the present invention, the pore volume of molecular sieve and aperture refer to pore volume and bore dia in molecular sieve respectively, and this is this area
Known to technical staff, do not repeat herein.
According to the modified with noble metals HTS of the present invention, the pore volume of preferably described molecular sieve is 0.3-0.8cm3/ g,
Preferably 0.31-0.42cm3/g；Total specific surface area is 250-650m2/ g, preferably 300-420m2/g；External surface area is 30-
150m2/ g, preferably 35-80m2/g；The ratio that external surface area accounts for total specific surface area is 10-35%, preferably 12-30%；With/
Or
The molecular sieve is in 25 DEG C, P/P0=0.1 and adsorption time be 1h under conditions of the benzene adsorbance that measures for extremely
Few 80mg/g molecular sieves, preferably at least 100mg/g molecular sieves, more preferably 100-130mg/g molecular sieves；And/or
The micropore size of 0.8-2nm scopes accounts for ratio >=2% of total micropore size abundance, preferably >=5%；And/or institute
Noble metal is stated as the one or more in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, preferably one in Pd, Ag, Au and Pt
Kind is a variety of.
According to the foregoing modified with noble metals HTS of the present invention, the micropore hole of the modified with noble metals HTS
Except there is typical micro porous molecular sieve in the range of 0.4-0.7nm, (such as the aperture of MFI topological structures molecular sieve is attached in 0.55nm in footpath
Specific to closely) outside pore-size distribution, it is also distributed in the range of 0.8-2nm.Special instruction is needed exist for, if in 0.8-
Micropore size distribution accounts for the ratio of total micropore size abundance in the range of 2nm<When 1%, then the pore size distribution of this partial pore is ignored
Disregard, that is, think there is no micropore distribution in the range of 0.8-2nm, this is known to those skilled in the art.Therefore, institute of the present invention
State in N2The lower micropore size with 0.8-2nm scopes of Static Adsorption test refers to the micropore size in the range of 0.8-2nm
Distribution accounts for the ratio of total micropore size abundance>1%.
, according to the invention it is preferred to the micropore size distribution in the range of 0.4-0.7nm accounts for the ratio of total micropore size abundance
Example≤95%, the micropore size distribution in the range of 0.8-2nm account for ratio >=5% of total micropore size abundance；It is furthermore preferred that
The ratio that micropore size distribution in the range of 0.8-2nm accounts for total micropore size abundance is 8-20%.In the present invention, micropore hole
The method of testing in footpath is well known to those skilled in the art, and such as uses N2The methods of Static Adsorption, tests.
The micropore size of 0.8-2nm scopes accounts for the ratio of total micropore size abundance and is calculated as follows in the present invention：
[quantity of the micropore size of 0.8-2nm scopes/(quantity of the micropore size of 0.8-2nm scopes)+(in the range of 0.4-0.7nm
The quantity of micropore size)] × 100%.
According to the molecular sieve of the present invention, preferably element silicon：Titanium elements：The mol ratio of precious metal element is 100：(0.1-
10)：(0.01-5), more preferably element silicon：Titanium elements：The mol ratio of precious metal element is 100：(0.1-5)：(0.02-2), enters
The preferred element silicon of one step：Titanium elements：The mol ratio of precious metal element is 100：(1-4)：(0.5-2).
According to the modified with noble metals HTS of the present invention, it is preferable that the surface silicon titanium ratio and the body phase silicon titanium
The ratio of ratio is more than 1, preferably more than 1.2；It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be
1.2-5；It is further preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5.In the present invention, institute
State mol ratio of the silicon titanium than referring to silica and titanium oxide.
A preferred embodiment of the invention, the N of the HTS-116/N-112It is worth for 0.02-0.15, it is excellent
Elect 0.02-0.1 as.
In the present invention, N-116Refer to29Si is rotated in magic angle solid state nmr, and the place of relative chemical shifts -116 absorbs peak intensity
Degree, N-112Refer to29Si is rotated in magic angle solid state nmr, the place of relative chemical shifts -112 absorption peak strength, N-116/N-112It is worth table
Show the ratio of the place of relative chemical shifts -116 absorption peak strength and the place of relative chemical shifts -112 absorption peak strength.The present invention's29It is enterprising in the type NMRs of Varian Infinity plus 400 that Si MAS NMR rotate magic angle solid core mass analysis
OK,29Si rotation MAS speed is 4kHz, is designated as methyl-monosilane outside.
A preferred embodiment of the invention, the micropore size of 0.8-2nm scopes account for total micropore size abundance
Ratio be 6-20%, preferably 8-15%；And/or
Element silicon：Titanium elements：The mol ratio of precious metal element is 100：(0.2-5)：(0.05-2), preferably 100：
(0.5-4)：(0.05-1)；And/or
The surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5, preferably 1.5-4.5；And/or
The U of the HTS480/U330It is worth for 0.5-5, preferably 0.6-2.5；And/or
The I of the HTS960/I550It is worth for 0.5-0.9, preferably 0.55-0.85.
In the present invention, U480Refer in ultraviolet-visible spectrum, 480nm vicinity absorption peak strength, U330Refer to purple
In outside-visible spectrum, 330nm vicinity absorption peak strength, U480/U330Value represents 480nm vicinity absorption peak strengths and 330nm
The ratio of vicinity absorption peak strength, in the HTS ultraviolet-visible spectrum without noble metal of routine, typically exist
480nm vicinity absorbs without obvious, therefore the U of conventional HTS480/U330For 0.The ultraviolet-visible spectrum point of the present invention
Analysis is carried out on Japanese JASCO companies UV550 UV detectors, molecular sieve solid ultraviolet-visible spectrum test process
Scanning wavelength scope 190nm~800nm.
The foregoing modified with noble metals HTS of the present invention has a special physical chemical characteristicses structure, and benzene adsorbance is higher；
Surface silicon titanium than not less than body phase silicon titanium ratio and with 0.8-2nm scopes micropore size be distributed etc. advantage, the present invention to foregoing
The preparation method of modified with noble metals HTS is without particular/special requirement, as long as the noble metal with said structure can be prepared
Modifying titanium-silicon molecular sieve, according to a kind of preferred embodiment of the present invention, before the method preparation comprised the following steps
Modified with noble metals HTS is stated, this method includes：
(1) by noble metal source, ammonia source, alternatively water mixing contact obtains mixture；
(2) by the mixture, alternatively HTS, the laggard water-filling heat treatment of water mixing.
In accordance with the present invention it is preferred that non-aqueous content of material is 0.01-50 weight % in the first mixture in step (1), it is excellent
Elect 0.02-25 weight %, more preferably 0.05-10 weight %, most preferably 0.1-5 weight % as；And/or
The condition of mixing contact includes in step (1)：Temperature be room temperature to 80 DEG C, time 0.1-24h, preferably room temperature are extremely
60 DEG C, time 0.5-12h；It is possible thereby to improve the performance of molecular sieve.
In the present invention, the material that non-aqueous content of material (solutes content) refers to than water accounts for the weight hundred of total mixture
Divide ratio, i.e., non-water substance/(non-water substance+water) * 100 weight %.
In accordance with the present invention it is preferred that solid content is 10-70 weight %, preferably 40-60 weight % after being mixed in step (2).
In the present invention, solid content refers to the content of solid matter in slurries.
In accordance with the present invention it is preferred that the weight of ammonia source and noble metal source ratio is (5-10000)：100, preferably (10-
5000)：100.
In accordance with the present invention it is preferred that the weight of HTS and noble metal source ratio is 100：(0.1-15), it is preferably
100：(0.2-10).
In accordance with the present invention it is preferred that the ammonia source is in the organic solution of ammonia, liquefied ammonia, ammoniacal liquor, a hydration ammonia and ammonia
It is one or more.The organic solution of ammonia is, for example, the alcoholic solution of ammonia.
With the method for the invention it is preferred to the noble metal source is the oxide of noble metal, the halide of noble metal, your gold
The carbonate of category, the nitrate of noble metal, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, the hydroxide of noble metal
With the one or more in the complex compound of noble metal, the noble metal is one in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au
Kind is a variety of；It is preferred that the noble metal is Pd, Ag, Au and/or Pt, by taking palladium as an example, the noble metal source is selected from palladium oxide, carbonic acid
Palladium, palladium bichloride, palladium nitrate, ammonium nitrate palladium, sal-ammoniac palladium, acid chloride, palladium dydroxide, the complex compound of palladium, palladium and levulinic
One or more in ketone palladium.
Palladium bichloride, palladium acetylacetonate, acetic acid platinum are used in an embodiment of the present invention as the exemplary illustration present invention's
Advantage.
, according to the invention it is preferred to which hydro-thermal process is carried out in confined conditions, stage (1), stage (2) and stage are undergone successively
(3), the stage (1) at 80-150 DEG C, preferably at 110-140 DEG C, more preferably at 120-140 DEG C, further preferably at 130-140 DEG C
Handle 6-72 hours, preferably 6-8 hours, the stage (2) is cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, preferably
For 1-5 hours, the stage (3) is warming up to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160-170 DEG C, and reprocessing 6-96 is small
When, preferred 12-20 hours.
A preferred embodiment of the invention, preferably stage (1) and stage (3) meet one of following condition
Or both：
Condition 1：The temperature in stage (1) is less than the temperature in stage (3), it is preferable that the temperature in stage (1) is than the stage (3)
Temperature is low 10-50 DEG C, preferably low 20-40 DEG C；
Condition 2：The time in stage (1) is less than the time in stage (3), it is preferable that the time in stage (1) is than the stage (3)
Time short 5-24 hours, preferably short 6-12 hours.
A preferred embodiment of the invention, stage (2) are cooled to not higher than 50 DEG C, preferably 30-50 DEG C, and
Residence time is at least 1 hour, preferably 1-5h.
The method according to the invention, temperature is adjusted can be according to tool to the heating rate of each phase temperature and rate of temperature fall
The type for the reactor that body uses is selected, and is not particularly limited.In general, temperature is increased to stage (1) temperature
Heating rate can be 0.1-20 DEG C/min, preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By stage (1) temperature
Rate of temperature fall to stage (2) temperature can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 5-10 DEG C/min.
Can be 1-50 DEG C/min by the heating rate of stage (2) temperature to stage (3) temperature, preferably 2-40 DEG C/min, more preferably
For 5-20 DEG C/min.
In the present invention, the HTS can be the common HTS with various topological structures, such as：
The HTS can be selected from HTS (such as TS-1), HTS (such as TS- of MEL structures of MFI structure
2), the HTS (such as Ti-Beta) of BEA structures, the HTS (such as Ti-MCM-22) of MWW structures, hexagonal structure
HTS (such as Ti-MCM-41, Ti-SBA-15), the HTS (such as Ti-MOR) of MOR structures, the titanium silicon of TUN structures
The HTS (such as Ti-ZSM-48) of molecular sieve (such as Ti-TUN) and other structures.
Preferably, the HTS is selected from HTS, the HTS and BEA of MEL structures of MFI structure
The HTS of structure.It is highly preferred that the HTS is the HTS of MFI structure, such as TS-1 molecular sieves.
In the present invention, the HTS can be that fresh titanium si molecular sieves can also be regenerative agent, in order to effectively sharp
With resource, in the present invention, preferably described HTS be regenerative agent, preferably regeneration the step of include：(i) agent and acid will be drawn off
Property peroxide mix in the presence of the aqueous solvent after carry out the first contact, obtain the first mixture；
(ii) carry out second after first mixture is mixed with alkali source in the presence of aqueous solvent to contact, second is connect
Touch obtained the second mixture to be filtered, wash to obtain solid, the solid is dried, wherein, it is described to draw off agent and be
Agent is drawn off using HTS as the reaction unit of catalyst.
In the present invention, the agent that draws off using HTS as the reaction unit of catalyst can be from various uses
HTS is as the agent that draws off drawn off in the device of catalyst, such as can be to be used as catalyst from using HTS
What is drawn off in oxidation reaction apparatus draws off agent.The oxidation reaction can be various oxidation reactions, such as described with titanium silicon molecule
Sieve as the reaction unit of catalyst draw off agent can for Ammoximation reaction device draw off agent, hydroxylating device unloads
Go out the one or more drawn off in agent of agent and epoxidation reaction device, be specifically as follows unloading for cyclohexanone oxamidinating reaction unit
Go out agent, the one or more drawn off in agent for drawing off agent and propylene ring oxidation reaction device of phenol hydroxylation reaction unit, it is excellent
Agent is drawn off described in choosing to react the catalyst of inactivation under alkaline environment, therefore, preferably described to draw off agent be hexamethylene for of the invention
Ketone oxamidinating reaction unit draws off agent (such as the titanium-silicon molecular sieve TS-1 of inactivation, powdery, particle diameter is in 100-500nm).
In the present invention, it is described draw off agent refer to using solvent wash or be calcined etc. conventional regeneration processes can not be allowed to activity it is extensive
Arriving the catalyst of the inactivation in the case of initial activity 50% again, (initial activity refers under identical reaction conditions, catalyst
Average activity within 1h.Such as in the reaction of actual cyclohexanone oximeization, the initial activity of general catalyst to reach 95% with
On).
The activity for drawing off agent is different according to its source.Usually, the activity for drawing off agent can be the titanium silicon molecule
Sieve the 5-95% of the activity (that is, fresh dose of activity) when fresh.Preferably, the activity for drawing off agent can be the titanium silicon molecule
Active less than 50% when fresh is sieved, the activity for further preferably drawing off agent can be the HTS when fresh
The 10-40% of activity.The activity of fresh dose of the HTS is generally more than 90%, and usually more than 95%.
It is described to draw off agent and derive from industrial deactivator or carry out reacted inactivation in the lab in the present invention
Catalyst.
In the present invention, the agent that draws off of each device is each determined using the reaction of each device, as long as ensureing, in phase
In same device, under identical reaction condition, the activity for drawing off agent is less than the activity of fresh catalyst, is drawing off for the present invention
Agent.As it was previously stated, in the case of preferable, the activity for drawing off agent is less than active 50% of fresh catalyst.
In the present invention, by cyclohexanone oxamidinating reaction unit draw off agent exemplified by, the activity determines by the following method：
Take TS-1 molecular sieves (by " and Zeolites, 1992, Vol.12：Prepared by the method described in 943~950 ", TiO2
Weight/mass percentage composition 2.1%) to be placed in slurry bed reactors of the 100mL with continuous feed and membrane separation device, stirring
Under state using 5.7mL/h speed add water and 30wt% hydrogen peroxide mixture (volume ratio of water and hydrogen peroxide as
10：9), using the mixture of 10.5mL/h speed addition cyclohexanone and the tert-butyl alcohol, (volume ratio of cyclohexanone and the tert-butyl alcohol is 1：
2.5) 36wt% ammoniacal liquor, is added with 5.7mL/h speed, above-mentioned three bursts of material flows are to add simultaneously, while with corresponding speed
Continuous discharge, reaction temperature maintain 80 DEG C, after stable reaction every 1 hour to product sampling gas chromatography to liquid phase
Composition is analyzed, and the conversion ratio of cyclohexanone is calculated and as the activity of HTS using below equation.Cyclohexanone
Mole of cyclohexanone that adds of conversion ratio=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/
Amount] × 100%.Wherein, initial activity is used as using 1h result.
In the present invention, optional wider range of the temperature of first contact, for the present invention, in order to further improve point
The catalytic performance of son sieve, the temperature of preferably described first contact are preferably room temperature to 100 DEG C, more preferably below 100 DEG C
50-100 DEG C, particularly preferably 40-90 DEG C.
In the present invention, the optional scope of the time of first contact is very wide, can specifically be selected according to needs, pin
To the present invention, in order to further improve the performance of molecular sieve, time of preferably described first contact in more than 0.5h, is preferably
0.5-72h, more preferably 1-12h.
In the present invention, optional wider range of the temperature of second contact, for the present invention, in order to further improve point
The performance of son sieve, the temperature of preferably described second contact is below 200 DEG C, preferably 50-180 DEG C.
In the present invention, the optional scope of the time of second contact is very wide, can specifically be selected according to needs, pin
To the present invention, in order to further improve the performance of molecular sieve, the time of the preferably second contact is in more than 0.1h, preferably 0.2-
12h。
With the method for the invention it is preferred to the method for the present invention also includes：Mixed agent will be drawn off with acidic peroxide
Before mashing, first draw off agent by described and be calcined.
In the present invention, optional wider range of the condition of the roasting, for the condition bag of the preferably roasting of the invention
Include：The temperature of roasting is 300-800 DEG C, preferably 550-600 DEG C；The time of roasting is 2-12h, preferably 2-4h, roasting
Atmosphere includes air atmosphere；The condition of more preferably described roasting includes：0.5- is calcined in nitrogen atmosphere at 350-600 DEG C first
6h, 0.5-12h is then calcined in air atmosphere at 350-600 DEG C.
In the present invention, the primary solvent of the acidic peroxide solution is water, also can be according to needing to add other solvents
Auxiliary agent.
With the method for the invention it is preferred to step (i) draws off agent to step (ii)：Acidic peroxide：The quality of alkali source
Than for 100：(100-1000)：(100-500), preferably draws off agent：Acidic peroxide：The mass ratio of alkali source is 100：(400-
800)：(300-400).
With the method for the invention it is preferred to the mixed solid content of step (i) is 5-50 weight %, preferably 40-50 weights
Measure %.
With the method for the invention it is preferred to step (ii) mixed solid content is 2-50 weight %, preferably 20-30 weights
Measure %.
With the method for the invention it is preferred to the acidic peroxide is selected from hydrogen peroxide, TBHP, peroxide
Change the one or more in hydrogen isopropylbenzene, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
, according to the invention it is preferred to aqueous solvent described in step (i) is water.
A preferred embodiment of the invention, aqueous solvent described in step (ii) are the mixture of water and alcohol,
The weight of water and alcohol ratio is 1:0.1-0.5, preferred alcohols are the one or more in methanol, ethanol, the tert-butyl alcohol and isopropanol.
The method according to the invention, optional wider range of the species of the alkali source, it can be organic base source and/or nothing
Machine alkali source, wherein, the alkali that inorganic alkali source can be ammonia or cation is alkali metal or alkaline-earth metal, such as can be sodium hydroxide,
Potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide etc., organic alkali source can be urea, aliphatic amination
One or more in compound, aliphatic alcohol amines and quaternary ammonium alkali cpd.
In the present invention, the quaternary ammonium base can be various organic level Four ammonium alkali, and the aliphatic amine can be various NH3In
The compound that is formed after aliphatic alkyl (be preferably alkyl) substitution of at least one hydrogen, the aliphatic hydramine can be each
Kind NH3In the compound that is formed after aliphatic alkyl (the be preferably alkyl) substitution of hydroxyl of at least one hydrogen.
Specifically, the quaternary ammonium base can be the quaternary ammonium base as shown in Formula II, and the aliphatic amine can be that formula III represents
Aliphatic amine, the aliphatic hydramine can be as formula IV represent aliphatic hydramine：
In Formula II, R5、R6、R7And R8Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as：R5、R6、R7And R8Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle
Butyl.
R9(NH2)n(formula III)
In formula III, n is 1 or 2 integer.When n is 1, R9For 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, R9For 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.More preferably
Aliphatic amine compound is the one or more in ethamine, n-butylamine, butanediamine and hexamethylene diamine
(HOR10)mNH(3-m)(formula IV)
In formula IV, m R10It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3-C4
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.It is further preferred that the aliphatic alcohol
Amines is the one or more in MEA, diethanol amine and triethanolamine.
According to a kind of preferred embodiment of the present invention, preferably described alkali source is sodium hydroxide, ammoniacal liquor, ethylenediamine, just
Butylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine, triethanolamine, tetraethyl ammonium hydroxide and TPAOH
In one or more.
Wherein, when containing ammoniacal liquor in the alkali source, the mol ratio of alkali source is with including molecular forms NH3With ionic species NH4 +Existing ammonia meter.
With the method for the invention it is preferred to the alkali source is provided in the form of aqueous slkali, the more preferably pH of aqueous slkali>9.
Wherein, described drying process can be carried out at a temperature of between -200 DEG C of room temperature, and described roasting process can be
First 3-12 hours are carried out in air atmosphere after 0.5-6 hours in nitrogen atmosphere between 300-800 DEG C.
The benzene adsorbance of the molecular screen material obtained due to molecular screen material of the present invention and the inventive method is higher, surface silicon
Titanium than not less than body phase silicon titanium ratio and with 0.9-1.5nm scopes micropore size be distributed, be advantageous to react in catalytic reaction
The catalysis oxidation that thing and product molecule especially participate in aromatic hydrocarbon compound, ring class hydrocarbon compound, olefin(e) compound equimolecular
React particularly advantageous.
Present invention also offers the molecular sieve of the present invention and the obtained molecular sieve of the inventive method in the direct oxygen of catalytic hydrocarbon
Change the application in reaction.In the oxidation reaction, such as in preparing epoxypropane by epoxidation of propene (PO) reaction, reaction product
PO selectivity and catalytic activity significantly improves.
According to the fourth aspect of the invention, the invention provides a kind of method of alkene direct oxidation, this method to include：With
Methanol is solvent, and alkene, oxygen-containing gas and catalyst are contacted, and the catalyst contains molecular sieve of the present invention and Ben Fa
The molecular sieve that bright described preparation method is prepared.
The method according to the invention, the condition of the contact can be the conventional selection of this area, for the present invention, preferably
The condition of contact includes：Temperature is 0-80 DEG C, pressure 0.1-5.0MPa, time 0.1-24h, and alkene air speed is 0.1-100h-1,
Alkene air speed namely olefin gas air speed, i.e., pass through the amount of the volume of the alkene of unit catalyst in the unit interval.
The mol ratio 0.1-10 of oxygen and alkene more preferably in oxygen-containing gas:1.
Optional wider range of the species of alkene, such as can be propylene.
The method according to the invention, in the oxygen-containing gas in addition to containing oxygen, the gas such as hydrogen, nitrogen can also be contained
Body, also contain hydrogen and nitrogen in preferably described oxygen-containing gas, the preferably mol ratio of oxygen, hydrogen and nitrogen is 0.1-10：
0.1-10：0.5-100.That is, the mol ratio of preferred alkenes, oxygen, hydrogen and nitrogen is 1：0.1-10：0.1-10：0.5-100.
According to a kind of preferred embodiment of the present invention, 0.05-2g (such as 0.5g) catalyst is added to containing 1-
It is 1 according to mol ratio in the reaction vessel of 500ml (such as 80ml) methanol：0.1-10：0.1-10：0.5-100 (such as 1:1:1:7)
The diluent gas such as alkene, oxygen, hydrogen and nitrogen are passed through, at temperature 0-80 DEG C (such as 60 DEG C), pressure 0.1-5.0MPa is (such as
1.0MPa), alkene air speed is 0.1-100h-1(such as 10h-1) under conditions of, carry out alkene direct oxidation reaction, reaction time
0.1-24h (such as 2h).
Below by embodiment, the invention will be further described, but and is not so limited present disclosure.
In comparative example and embodiment, agents useful for same is commercially available chemically pure reagent.
The agent that draws off of following examples and comparative example obtains as follows, and using following methods measure HTS
The activity of (including HTS draws off agent, and fresh dose of HTS).
Take TS-1 molecular sieves (by " and Zeolites, 1992, Vol.12：Prepared by the method described in 943~950 ", TiO2
Weight/mass percentage composition for 2.1%) be placed in 100mL band continuous feed and membrane separation device slurry bed reactor in, stirring shape
Using the mixture of 5.7mL/h speed addition water and 30wt% hydrogen peroxide, (volume ratio of water and hydrogen peroxide is 10 under state：
9), using the mixture of 10.5mL/h speed addition cyclohexanone and the tert-butyl alcohol, (volume ratio of cyclohexanone and the tert-butyl alcohol is 1：2.5),
36wt% ammoniacal liquor is added with 5.7mL/h speed, above-mentioned three bursts of material flows are continuously gone out to add simultaneously with corresponding speed
Material, reaction temperature maintain 80 DEG C, product sampling gas chromatography are entered to the composition of liquid phase every 1 hour after stable reaction
Row analysis, the conversion ratio of cyclohexanone is calculated and as the activity of HTS using below equation.The conversion of cyclohexanone
Rate=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/mole of the cyclohexanone added] ×
100%.
The cyclohexanone conversion ratio for being for the first time 1h measure is its initial activity, and its value is 99.5%.Through after a while
About 168 hours, after cyclohexanone conversion ratio drops to 50% by initial 99.5%, roasting regeneration mode is used after isolating catalyst
Regenerate (being calcined 4 hours in air atmosphere at 570 DEG C), then proceed to be used in cyclohexanone oxamidinating reaction, be repeated
The step for, until the activity after regeneration is less than the 50% of initial activity, the oximes catalyst sample at this moment inactivated is used as this
Invention draws off agent, obtains drawing off agent SH-1 (activity is 50%), SH-2 (activity is 40%), SH-3 successively according to preceding method
(activity is 25%), SH-4 (activity is 10%).
In each embodiment and comparative example, X-ray diffraction (XRD) the crystalline phase figure of sample is penetrated in Siemens D5005 types X-
It is measured on line diffractometer, the diffraction at the five fingers diffractive features peak between 2 θ is 22.5 ° -25.0 ° using sample and authentic specimen
The ratio of intensity (peak height) sum represents crystallinity of the sample relative to authentic specimen, here on the basis of the sample of comparative example 1
Sample, its crystallinity are calculated as 100%, and the relative crystallinity data of each sample are shown in Table 1.The benzene adsorbance of sample, pore volume, aperture point
Cloth, total specific surface area and external surface area determine on Micromeritics companies ASAP2405 static state n2 absorption apparatus, specific number
According to being shown in Table 1.The elements such as the noble metal and silicon of sample are formed in Rigaku Electric Co., Ltd 3271E type X-ray fluorescence spectras
Determined on instrument, specific data are shown in Table 2.
In the present invention, surface silicon titanium is than the ESCALab250 type x-ray photoelectrons using Thermo Scientific companies
Energy disperse spectroscopy is determined, and body phase silicon titanium ratio is determined using Rigaku Electric Co., Ltd 3271E types Xray fluorescence spectrometer.
Comparative example 1
This comparative example illustrates the conventional HTS sample for being prepared using estersil for silicon source hydrothermal crystallizing and not containing noble metal
The process of product.
Tetraethyl orthosilicate, isopropyl titanate are mixed with TPAOH, and adds appropriate distilled water and is stirred,
A mole composition is tetraethyl orthosilicate among reaction system：Isopropyl titanate：TPAOH：Water=100：5：10：200,
Wherein tetraethyl orthosilicate is with SiO2Meter；1.0h is hydrolyzed at normal pressure and 60 DEG C, then 3h is stirred at 75 DEG C, then by mixed liquor
Stainless steel sealing reactor is put into, constant temperature places 3d at a temperature of 170 DEG C, obtains the mixture of crystallization product；This is mixed
Thing filtering, it is washed with water, and in 110 DEG C of dry 60min, obtains molecular screen primary powder, and in 550 DEG C of roasting temperature 3h, obtain water
The HTS of hot direct crystallization, its XRD crystalline phase are MFI structure.
Comparative example 2
This comparative example illustrates that routine prepares the HTS sample containing noble metal using estersil for silicon source hydrothermal crystallizing
Process.
Tetraethyl orthosilicate, palladium bichloride, isopropyl titanate are mixed with TPAOH, and adds appropriate distilled water and stirs
Mixing is mixed, a mole composition is tetraethyl orthosilicate among reaction system：Isopropyl titanate：Palladium bichloride：TPAOH：Water=
100：5：2：10：200, wherein tetraethyl orthosilicate is with SiO2Meter；1.0h is hydrolyzed at normal pressure and 60 DEG C, then is stirred at 75 DEG C
3h, mixed liquor is then put into stainless steel sealing reactor, constant temperature places 3d at a temperature of 170 DEG C, obtains crystallization product
Mixture；By the filtering of this mixture, it is washed with water, and in 110 DEG C of dry 60min, obtains molecular screen primary powder, and in 550 DEG C of temperature
The lower roasting 3h of degree, obtains the HTS of hydro-thermal direct crystallization, its XRD crystalline phases figure and comparative example 1 are unanimously MFI structure.
Comparative example 3
This comparative example illustrates the process of the HTS sample dip loading noble metal prepared using comparative example 1.
HTS prepared by comparative example 1 is mixed with palladium chloride aqueous solution, wherein HTS and palladium bichloride with
And the mass ratio of water is 10:2:25,6h is stirred at normal pressure and 60 DEG C, then this mixture is filtered, is washed with water, and in
110 DEG C of dry 60min, and in 550 DEG C of roasting temperature 3h, the HTS of noble metal must be loaded with, its XRD crystalline phase is
MFI structure.
Comparative example 4
This comparative example illustrates to utilize the process for drawing off agent SH-2 sample dip loading noble metals.
Agent SH-2 will be drawn off to mix with palladium chloride aqueous solution, wherein HTS and palladium bichloride and the mass ratio of water
For 10:0.5:10,12h is stirred at normal pressure and 40 DEG C, then this mixture is filtered, is washed with water, and in 110 DEG C of dryings
60min, and in 550 DEG C of roasting temperature 3h, the HTS of noble metal must be loaded with, its XRD crystalline phase is MFI structure.
Comparative example 5
This comparative example illustrates to utilize the process for drawing off agent SH-3 dip loading noble metals.
SH-3 is mixed with palladium chloride aqueous solution, wherein HTS and the mass ratio of palladium bichloride and water are 10:
1:50,12h is stirred at normal pressure and 40 DEG C, then this mixture is filtered, is washed with water, and in 110 DEG C of dry 60min, and
In 550 DEG C of roasting temperature 3h, the HTS of noble metal must be loaded with, its XRD crystalline phase is MFI structure.
Comparative example 6
This comparative example illustrates to utilize the process for drawing off agent SH-4 dip loading noble metals.
SH-4 is mixed with palladium chloride aqueous solution, wherein HTS and the mass ratio of palladium bichloride and water are 10:
2:20,3h is stirred at normal pressure and 50 DEG C, then this mixture is filtered, is washed with water, and in 110 DEG C of dry 60min, and in
550 DEG C of roasting temperature 3h, the titanium silicalite material of noble metal must be loaded with, its XRD crystalline phase is MFI structure.
Embodiment 1
This example demonstrates that method provided by the invention and product.
(1) under the conditions of normal pressure, 80 DEG C, contacted after aqueous hydrogen peroxide solution is mixed with deactivated titanium silicon molecular sieve (SH-2)
2.5h obtains the first mixture, wherein, the weight ratio of deactivated titanium silicon molecular sieve (SH-2) and hydrogen peroxide is 1:8, it is mixed
Solid content is 50 weight %；
(2) under 80 DEG C and normal pressure, 1h is contacted after the first mixture is mixed with ammonia spirit again, wherein, deactivated titanium silicon
The weight of molecular sieve and ammonia ratio is 1:3, mixed solid content is 30 weight %；Then by products therefrom filtration washing after
Dried 120 minutes at 150 DEG C, obtain regenerating titanium-silicon molecular sieve catalyst A；
(3) noble metal source palladium bichloride is mixed into contact with ammoniacal liquor (concentration is 20 weight %) and obtains mixture；Noble metal source：
Ammonia source (weight ratio)=2:20, solutes content is 1 weight %, and mixing the condition of contact includes：30 DEG C, normal pressure, 4h；
(4) mixture is mixed into laggard water-filling with regeneration titanium-silicon molecular sieve catalyst A to be heat-treated；Hydrothermal treatment step is such as
Under：
First stage 6h is undergone in 140 DEG C in reactor is sealed, mixture is then cooled to 30 DEG C of experience second-orders
After section stops 2h, continue to undergo phase III 12h (wherein, by room temperature extremely at a temperature of 170 DEG C in reactor is sealed
The heating rate of first stage temperature is 2 DEG C/min, is 5 by the rate of temperature fall of first stage temperature to second stage treatment temperature
DEG C/min, and it is 10 DEG C/min by the heating rate of second stage treatment temperature to phase III temperature), in hydrothermal treatment process：
Noble metal source：HTS (weight ratio)=2:200, solid content is 40 weight %；
(5) products therefrom is filtered, be washed with water, and 120min is dried in 110 DEG C, then in 550 DEG C of roasting temperatures
3h, molecular sieve is obtained, its XRD crystalline phases figure is consistent with comparative example 1, and illustrate to obtain is the HTS with MFI structure.
Comparative example 7
This comparative example illustrates to utilize the process for drawing off dip loading noble metal after agent SH-2 acid treatments.
At normal temperatures and pressures, first cyclohexanone oximate the catalyst SH-2 and 1mol/L of inactivation combined are beaten
Slurry, mixed serum is then mixed to processing 12h at 80 DEG C；The SH-2 of acid treatment is obtained after separation of solid and liquid, then by it
Mixed with palladium chloride aqueous solution, wherein HTS and the mass ratio of palladium bichloride and water are 10:2:20, in normal pressure and 50
3h is stirred at DEG C, then this mixture is filtered, is washed with water, and in 110 DEG C of dry 60min, and in 550 DEG C of roasting temperatures
3h, the titanium silicalite material of noble metal must be loaded with, its XRD crystalline phase is MFI structure.
Comparative example 8
(1) under the conditions of normal pressure, 80 DEG C, contacted after aqueous hydrogen peroxide solution is mixed with deactivated titanium silicon molecular sieve (SH-2)
2.5h obtains the first mixture, wherein, the weight ratio of deactivated titanium silicon molecular sieve (SH-2) and hydrogen peroxide is 1:8, it is mixed
Solid content is 50 weight %；
(2) under 80 DEG C and normal pressure, 1h is contacted after the first mixture is mixed with ammonia spirit again, wherein, deactivated titanium silicon
The weight of molecular sieve and ammonia ratio is 1:3, mixed solid content is 30 weight %；Then by products therefrom filtration washing after
Dried 120 minutes at 150 DEG C, obtain regenerating titanium-silicon molecular sieve catalyst A；
(3) noble metal source palladium bichloride is mixed with ammoniacal liquor (concentration is 20 weight %) with regeneration titanium-silicon molecular sieve catalyst A
Contact obtains mixture and then carries out hydro-thermal process；Hydrothermal treatment step is as follows：
First stage 6h is undergone in 140 DEG C in reactor is sealed, mixture is then cooled to 30 DEG C of experience second-orders
After section stops 2h, continue to undergo phase III 12h (wherein, by room temperature extremely at a temperature of 170 DEG C in reactor is sealed
The heating rate of first stage temperature is 2 DEG C/min, is 5 by the rate of temperature fall of first stage temperature to second stage treatment temperature
DEG C/min, and it is 10 DEG C/min by the heating rate of second stage treatment temperature to phase III temperature), in hydrothermal treatment process：
Noble metal source：Ammonia source (weight ratio)=2:20, noble metal source：HTS (weight ratio)=2:200, solid content is 40 weights
Measure %；
(4) products therefrom is filtered, be washed with water, and 120min is dried in 110 DEG C, then in 550 DEG C of roasting temperatures
3h, molecular sieve is obtained, its XRD crystalline phases figure is consistent with comparative example 1, and illustrate to obtain is the HTS with MFI structure.
Embodiment 2
This example demonstrates that method provided by the invention and product.
(1) under 60 DEG C, condition of normal pressure, contacted after aqueous hydrogen peroxide solution is mixed with deactivated titanium silicon molecular sieve (SH-3)
2.5h obtains the first mixture, wherein, the weight ratio of deactivated titanium silicon molecular sieve (SH-3) and hydrogen peroxide is 1:6, it is mixed
Solid content is 40 weight %；
(2) under 60 DEG C and normal pressure, 1h is contacted after the first mixture is mixed with ammonia spirit again, wherein, deactivated titanium silicon
The weight of molecular sieve and ammonia ratio is 1:3, mixed solid content is 20 weight %；Then by products therefrom filtration washing after
Dried 120 minutes at 150 DEG C, obtain regenerating titanium-silicon molecular sieve catalyst B；
(3) noble metal source palladium acetylacetonate is mixed into contact with ammoniacal liquor (concentration is 20 weight %) and obtains mixture；Your gold
Category source：Ammonia source (weight ratio)=2:10, solutes content is 2 weight %, and mixing the condition of contact includes：40 DEG C, normal pressure, 3h；
(4) mixture is mixed into laggard water-filling with regeneration titanium-silicon molecular sieve catalyst B to be heat-treated；Hydrothermal treatment step is such as
Under：First stage 8h is undergone in 130 DEG C in reactor is sealed, mixture then is cooled into 50 DEG C of experience second stage stops
After 5h, continue to undergo phase III 16h at a temperature of 170 DEG C in reactor is sealed (wherein, by room temperature to the first rank
Duan Wendu heating rate is 1 DEG C/min, is 10 DEG C/min by the rate of temperature fall of first stage temperature to second stage temperature, by
The heating rate of second stage temperature to phase III temperature is 20 DEG C/min), wherein, in hydrothermal treatment process：Noble metal source：
HTS (weight ratio)=2:100, solid content is 50 weight %.
(5) HTS, its XRD crystalline phases figure and comparative example 1 and then the method recovery product according to embodiment 1, are obtained
Unanimously.
Embodiment 3
This example demonstrates that method provided by the invention and product.
(1) under 40 DEG C, condition of normal pressure, contacted after aqueous hydrogen peroxide solution is mixed with deactivated titanium silicon molecular sieve (SH-4)
2.5h obtains the first mixture, wherein, the weight ratio of deactivated titanium silicon molecular sieve (SH-3) and hydrogen peroxide is 1:4, it is mixed
Solid content is 45 weight %；
(2) under 60 DEG C and normal pressure, 1h is contacted after the first mixture is mixed with ammonia spirit again, wherein, deactivated titanium silicon
The weight of molecular sieve and ammonia ratio is 1:10, mixed solid content is 25 weight %；Then by products therefrom filtration washing after
Dried 120 minutes at 150 DEG C, obtain regenerating titanium-silicon molecular sieve catalyst C；
(3) noble metal source acetic acid platinum is mixed into contact with ammoniacal liquor (concentration is 10 weight %) and obtains mixture；Noble metal source：
Ammonia source (weight ratio)=2:30, solutes content is 5 weight %, and mixing the condition of contact includes：50 DEG C, normal pressure, 5h；
(4) mixture is mixed into laggard water-filling with regeneration titanium-silicon molecular sieve catalyst C to be heat-treated；Hydrothermal treatment step is such as
Under：First stage 6h is undergone in 140 DEG C in reactor is sealed, mixture then is cooled into 40 DEG C of experience second stage stops
After 1h, continue to undergo phase III 12h at a temperature of 160 DEG C in reactor is sealed (wherein, by room temperature to the first rank
Duan Wendu heating rate is 5 DEG C/min, is 5 DEG C/min by the rate of temperature fall of first stage temperature to second stage temperature, by
The heating rate of second stage temperature to phase III temperature is 5 DEG C/min), in hydrothermal treatment process：Noble metal source：Titanium silicon point
Son sieve (weight ratio)=2:150, solid content is 60 weight %.
(5) and then the method recovery product according to embodiment 1, acquisition molecular sieve, its XRD crystalline phases figure are consistent with comparative example 1.
Embodiment 4
This example demonstrates that method provided by the invention and product.
Method according to embodiment 3 prepares molecular sieve, unlike, ammonia spirit replaces with the alcohol water of ammonia in step (2)
Mixture, wherein, the weight ratio of water and methanol is 1:0.3.The XRD crystalline phases figure of gained sample is consistent with comparative example 1.
Embodiment 5
This example demonstrates that method provided by the invention and product.
Method according to embodiment 3 prepares molecular sieve, unlike, what is used is fresh HTS as raw material generation
(fresh HTS uses to be prepared according to the method for comparative example 1), gained sample are used for regeneration titanium-silicon molecular sieve catalyst C
XRD crystalline phases figure it is consistent with comparative example 1.
Embodiment 6
This example demonstrates that method provided by the invention and product.
Method according to embodiment 2 prepares molecular sieve, unlike, agent SH-3 will be drawn off and be calcined and then carry out follow-up
Acidic peroxide processing, the regenerative process of alkali process；Wherein, the condition of roasting includes：Roasted at 570 DEG C in air atmosphere
4h is burnt, the XRD crystalline phases figure of gained sample is consistent with comparative example 1, and the XRD crystalline phases figure of gained sample is consistent with comparative example 1.
Embodiment 7
Method according to embodiment 2 prepares molecular sieve, unlike, the agent that draws off used is SH-1, and remaining condition is homogeneous
Together, the XRD crystalline phases figure of gained sample is consistent with comparative example 1.
Embodiment 8
Method according to embodiment 1 prepares molecular sieve, unlike, the crystallization temperature of phase III is also 140 DEG C.Then
According to the method recovery product of embodiment 1, molecular sieve containing noble metal is obtained, its XRD crystalline phases figure is consistent with comparative example 1.
Embodiment 9
Method according to embodiment 1 prepares molecular sieve, unlike, the crystallization temperature of first stage is 110 DEG C.Then press
According to the method recovery product of embodiment 1, molecular sieve containing noble metal is obtained, its XRD crystalline phases figure is consistent with comparative example 1.
Embodiment 10
Method according to embodiment 1 prepares molecular sieve, unlike, the crystallization time of first stage is 12h, second stage
It is to be cooled to 70 DEG C of stop 2h.Then according to the method recovery product of embodiment 1, molecular sieve containing noble metal, its XRD crystalline phase are obtained
Figure is consistent with comparative example 1.
Table 1
Wherein, A represents that external surface area accounts for the ratio of total specific surface area.
It can also be seen that from the result of table 1：
Molecular sieve its relative crystallinity prepared by the preferred process of the present invention, pore volume, total specific surface area, external surface area,
0.8-2.0nm pore-size distributions, surface silicon titanium ratio and body phase silicon titanium ratio, benzene adsorbance, N-116/N-112、U480/U330、I960/I550
Etc. whole features that data fully meet product of the present invention.Relative, either comparative example 1 is that silicon source is prepared not using estersil
HTS containing noble metal, comparative example 2 utilize HTS containing noble metal of the estersil for silicon source preparation, contrast
The HTS containing noble metal that example 3 is prepared using the HTS carried noble metal prepared such as comparative example 1, still
Comparative example 4-6 is using drawing off titanium silicalite material that agent carried noble metal obtains and comparative example 7 draws off agent is acid treated to load for your gold
Belong to obtained titanium silicalite material, its relative crystallinity, pore volume, total specific surface area, external surface area, 0.9-1.5nm pore-size distributions, benzene
Adsorbance, N-116/N-112、U480/U330、I960/I550Etc. whole features that data can not meet product of the present invention.
Testing example
0.5g catalyst is added in the closed tank reactor containing 50ml methanol, is 1 then according to mol ratio:1:
1:7 ratio is passed through propylene, oxygen, hydrogen and nitrogen (diluent gas), and in 40 DEG C, pressure 1.0MPa of temperature, alkene air speed is
20h-1Under conditions of, carry out alkene direct oxidation reaction.Reaction time 4h propylene conversion and PO selectivity etc. the results are shown in Table
2。
Table 2
Wherein, propylene conversion and PO selectively calculate according to equation below：
Propylene conversion=(amount for participating in the material of the propylene of reaction/amount of the material of the propylene always added) * 100%；
PO selectivity=(amount of the material of amount/gross product of the PO of reaction generation material) * 100%.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
Claims (15)
1. a kind of modified with noble metals HTS, it is characterised in that the molecular sieve contains precious metal element, titanium elements, silicon member
Element and oxygen element, wherein, the pore volume of the molecular sieve is in 0.25cm3/ more than g, total specific surface area is in 250m2/ more than g, outer surface
The ratio that product accounts for total specific surface area is 8-50%, N2The lower micropore size with 0.8-2nm scopes of Static Adsorption test is distributed, institute
State the N of HTS-116/N-112It is worth for 0.01-0.2.
2. molecular sieve according to claim 1, wherein,
The pore volume of the molecular sieve is 0.3-0.8cm3/ g, total specific surface area are 250-650m2/ g, external surface area 30-150m2/
G, the ratio that external surface area accounts for total specific surface area are 10-35%, preferably 12-30%；And/or
The molecular sieve is in 25 DEG C, P/P0=0.1 and adsorption time be 1 hour under conditions of the benzene adsorbance that measures be at least
80mg/g molecular sieves, preferably at least 100mg/g molecular sieves；And/or
The micropore size of 0.8-2nm scopes accounts for ratio >=2% of total micropore size abundance in the molecular sieve, preferably >=5%；
And/or
The noble metal is the one or more in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, preferably Pd, Ag, Au and Pt
In one or more；And/or
Element silicon in the molecular sieve：Titanium elements：The mol ratio of precious metal element is 100：(0.1-10)：(0.01-5), preferably
For 100：(0.1-5)：(0.02-2)；And/or
In the molecular sieve surface silicon titanium than with the body phase silicon titanium than ratio be more than 1, preferably more than 1.2, the silicon titanium
Than the mol ratio for referring to silica and titanium oxide, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, the body phase
Silicon titanium ratio uses x-ray fluorescence spectrometry；And/or
The N of the HTS-116/N-112It is worth for 0.02-0.15, preferably 0.02-0.1.
3. molecular sieve according to claim 1 or 2, wherein,
The ratio that the micropore size of 0.8-2nm scopes accounts for total micropore size abundance is 6-20%, preferably 8-15%；And/or
Element silicon：Titanium elements：The mol ratio of precious metal element is 100：(0.2-5)：(0.05-2), preferably 100：(0.5-4)：
(0.05-1)；And/or
The surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5, preferably 1.5-4.5；And/or
The U of the HTS480/U330It is worth for 0.5-5, preferably 0.6-2.5；And/or
The I of the HTS960/I550It is worth for 0.5-0.9, preferably 0.55-0.85.
4. a kind of preparation method of modified with noble metals HTS, this method include：
(1) by noble metal source, ammonia source, alternatively water mixing contact obtains mixture；
(2) by the mixture, alternatively HTS, the laggard water-filling heat treatment of water mixing.
5. preparation method according to claim 4, wherein,
Non-aqueous content of material is 0.01-50 weight % in the first mixture in step (1), preferably 0.02-25 weight %, enters one
Step is preferably 0.05-10 weight %, most preferably 0.1-5 weight %；And/or
The condition of mixing contact includes in step (1)：Temperature be room temperature to 80 DEG C, time 0.1-24h, preferably room temperature to 60
DEG C, time 0.5-12h；And/or
Solid content is 10-70 weight %, preferably 40-60 weight % after being mixed in step (2)；And/or
The weight of ammonia source and noble metal source ratio is (5-10000)：100, preferably (10-5000)：100；And/or
The weight of HTS and noble metal source ratio is 100：(0.1-15), preferably 100：(0.2-10)；And/or
The ammonia source is the one or more in the organic solution of ammonia, liquefied ammonia, ammoniacal liquor, a hydration ammonia and ammonia；And/or
The noble metal source is the oxide of noble metal, the halide of noble metal, the carbonate of noble metal, the carboxylic acid of noble metal
Salt, the nitrate of noble metal, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, the hydroxide and noble metal of noble metal
Complex compound in one or more；And/or
The noble metal is the one or more in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au.
6. the preparation method according to claim 4 or 5, wherein,
Hydro-thermal process is carried out in confined conditions, undergoes stage (1), stage (2) and stage (3) successively, the stage, (1) was in 80-150
DEG C, preferably 110-140 DEG C, more preferably 120-140 DEG C, further preferably 130-140 DEG C handle 6-72 hours, preferably 6-
8 hours, the stage (2) was cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, preferably 1-5 hours, and the stage (3) rises
Temperature reprocesses 6-96 hours, preferably 12-20 hours to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160-170 DEG C.
7. preparation method according to claim 6, wherein, stage (1) and stage (3) meet one of following condition or
Both：
Condition 1：The temperature in stage (1) is less than the temperature in stage (3), it is preferable that temperature of the temperature in stage (1) than stage (3)
It is low 10-50 DEG C, preferably low 20-40 DEG C；
Condition 2：The time in stage (1) is less than the time in stage (3), it is preferable that time of the time in stage (1) than stage (3)
Short 5-24 hours, preferably short 6-12 hours；
Stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.
8. the preparation method according to claim 4 or 5, wherein, the HTS is regenerative agent, the step preferably regenerated
Suddenly include：
(i) progress first after agent mixes with acidic peroxide in the presence of aqueous solvent will be drawn off to contact, obtain the first mixing
Thing；
(ii) carry out second after first mixture is mixed with alkali source in the presence of aqueous solvent to contact, second is contacted
To the second mixture filtered, wash to obtain solid, the solid is dried；
Wherein, it is described to draw off agent to draw off agent using HTS as the reaction unit of catalyst；
Preferably, it is described to draw off agent drawing off as Ammoximation reaction device using HTS as the reaction unit of catalyst
Agent.
9. preparation method according to claim 8, wherein,
The condition of first contact includes：Temperature is 50-100 DEG C, time 0.5-72h；
The condition of second contact includes：Temperature is 50-180 DEG C, time 0.2-12h.
10. preparation method according to claim 8, wherein,
Step (i) draws off agent to step (ii)：Acidic peroxide：The mass ratio of alkali source is 100：(100-1000)：(100-
500)；
The mixed solid content of step (i) is 5-50 weight %, preferably 40-50 weight %；
Step (ii) mixed solid content is 2-50 weight %, preferably 20-30 weight %.
11. preparation method according to claim 8, wherein,
Aqueous solvent described in step (i) is water；
Aqueous solvent described in step (ii) is the mixture of water and alcohol, and the weight ratio of water and alcohol is 1:0.1-0.5, alcohol are first
One or more in alcohol, ethanol, the tert-butyl alcohol and isopropanol；
The alkali source is the one or more in ammonia, aliphatic amine, aliphatic hydramine and quaternary ammonium base；
The acidic peroxide be selected from hydrogen peroxide, TBHP, cumyl hydroperoxide, ethylbenzene hydroperoxide,
One or more in cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
12. preparation method according to claim 8, wherein, the HTS is MFI structure, described to draw off agent
Active less than 50% that activity is the HTS when fresh.
13. the preparation side in the molecular sieve and claim 4-12 in claim 1-3 described in any one described in any one
Application of the molecular sieve that method is prepared in catalytic hydrocarbon direct oxidation reaction.
14. a kind of method of alkene direct oxidation, this method include：Using methanol as solvent, by alkene, oxygen-containing gas and catalyst
Contact, it is characterised in that the catalyst contains the molecular sieve and claim 4-12 in claim 1-3 described in any one
The molecular sieve that preparation method described in middle any one is prepared.
15. according to the method for claim 14, wherein, alkene is propylene, and the condition of contact includes：Temperature is 0-80 DEG C,
Pressure is 0.1-5.0MPa, and time 0.1-24h, alkene air speed is 0.1-100h-1, mole of oxygen and alkene in oxygen-containing gas
Compare 0.1-10:1.
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