CN106032277B - Titanium Si-Al molecular sieve and its preparation method and application and a kind of method of cyclic ketones oxidation - Google Patents
Titanium Si-Al molecular sieve and its preparation method and application and a kind of method of cyclic ketones oxidation Download PDFInfo
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Abstract
The present invention relates to molecular sieve arts, mainly provide a kind of titanium Si-Al molecular sieve and its preparation method and application, which contains aluminium element, titanium elements, element silicon and oxygen element, and Kong Rong is in 0.3cm3/ g or more, total specific surface area is in 200m2/ g or more, external surface area is in 30m2/ g or more, and it is 10 55% that external surface area, which accounts for the ratio of total specific surface area,；The titanium Si-Al molecular sieve is in 25 DEG C, P/P0=0.10 and adsorption time be 1h under conditions of the benzene adsorbance that measures be at least 65mg/g molecular sieves, N2The lower micropore size with 0.9 2.0nm ranges of Static Adsorption test is distributed.The present invention also provides a kind of methods of cyclic ketones oxidation.The present invention higher with the titanium Si-Al molecular sieve of special physical chemical characteristics structure its benzene adsorbance and the advantage being distributed with the micropore size of 0.9 2.0nm ranges, such as the reaction that ring molecule, particularly cyclic ketones molecule are participated in or generated is used it for, better catalytic effect can be obtained.
Description
Technical field
The present invention relates to a kind of titanium Si-Al molecular sieves and a kind of preparation method of titanium Si-Al molecular sieve, the present invention also to relate to
And the method for the application and a kind of oxidation of cyclic ketones of titanium Si-Al molecular sieve.
Background technology
Titanium Sieve Molecular Sieve is the molecular sieve that skeleton is made of silicon, titanium, oxygen element, in petroleum refining and petrochemical industry
It has a extensive future.Wherein, TS-1 molecular sieves are that transition metal element titanium is introduced into the framework of molecular sieve with ZSM-5 structures
It is formed by a kind of novel titanosilicate with superior catalytic selective oxidation performance.
TS-1 not only catalysed oxidns with titanium, but also with the shape-selective effect of ZSM-5 molecular sieve and excellent
Stability successfully realizes commercial Application in the technique that cyclohexanone catalytic ammoxidation prepares cyclohexanone oxime.However, usually existing
Operation a period of time rear catalyst catalytic performance can be deteriorated, and deactivation phenomenom occurs in catalyst.Inactivation be divided into for it is temporary inactivation and
Permanent inactivation.The catalyst of temporary inactivation can be allowed to recovered part or all activity by regeneration, and permanently inactivate
It then can not be by regenerating activity recovery (activity after regeneration is less than the 50% of initial activity).Titanium Sieve Molecular Sieve is lost under alkaline environment
After permanent deactivation occurs for especially oximes catalyst TS-1 living, it can not recycle at present, the main side using accumulation landfill
Formula processing.In this way, occupying valuable land resource and inventory space, it is badly in need of the recycling skill of the oximes catalyst of inactivation
Art is developed.
Invention content
The purpose of the present invention is to provide a kind of titanium Si-Al molecular sieve with special physical chemical characteristics and preparation method thereof and
Using.
Inventor passes through the Titanium Sieve Molecular Sieve such as amidoxime to being inactivated under the Titanium Sieve Molecular Sieve especially alkaline environment of inactivation
Change the physico-chemical property after catalyst generation permanent deactivation to be characterized, it is found that its crystalline framework keeps completely, to be subject to substantially
It utilizes.By a large amount of research, it has furthermore been found that in the preparation process of Titanium Sieve Molecular Sieve, the titanium of inactivation may be used in inventor
Silicalite molecular sieve catalyst (is especially the cyclohexanone oximate of the titanium-silicon molecular sieve catalyst such as inactivation of permanent deactivation under alkaline condition
Catalyst is as primary raw material), it (is handled successively in conjunction with the steps such as heat treatment and roasting using acid, alkali by specific preparation process
Suddenly), the excellent molecular sieve of catalytic oxidation performance can be retrieved, and the molecular sieve prepared has special physical chemical characteristics.
To realize foregoing purpose, the first aspect of the present invention, the present invention provides a kind of titanium Si-Al molecular sieve, the titanium sial
Molecular sieve contains aluminium element, titanium elements, element silicon and oxygen element, and Kong Rong is in 0.3cm3/ g or more, total specific surface area is in 200m2/
G or more, external surface area is in 30m2/ g or more, and it is 10-55% that external surface area, which accounts for the ratio of total specific surface area,；The titanium sial point
Son sieve is in 25 DEG C, P/P0=0.10 and adsorption time be 1h under conditions of the benzene adsorbance that measures be at least 65mg/g molecules
Sieve, N2The lower micropore size with 0.9-2.0nm ranges of Static Adsorption test is distributed.
The second aspect of the present invention, the present invention provides a kind of preparation method of titanium Si-Al molecular sieve of the present invention,
This method includes：
(1) agent will be drawn off to be mixed with beating with acid solution, and obtained slurries will be subjected to the first heat treatment, isolated first is solid
Body, wherein described to draw off agent be that reaction unit using Titanium Sieve Molecular Sieve as catalyst draws off agent；
(2) it is carried out at the second heat after mixing first solid, silicon source, titanium source in the presence of aqueous solvent with alkali source
Reason.
The third aspect of the present invention, the present invention provides the application of the titanium Si-Al molecular sieve of the present invention in the oxidation reaction.
According to the fourth aspect of the invention, the present invention provides a kind of method of cyclic ketones oxidation, this method includes：By ring
Ketone, oxidant and catalyst contact, the catalyst contain titanium Si-Al molecular sieve of the present invention.
The titanium Si-Al molecular sieve with special physical chemical characteristics structure of the present invention, benzene adsorbance is higher and has 0.9-
The advantage of the micropore size distribution of 2.0nm ranges, such as use it for ring molecule, particularly the participation of cyclic ketone molecule or generate
Reaction, better catalytic effect can be obtained.I.e. since material its benzene adsorbance of the present invention is higher and has 0.9-2.0nm
The micropore size of range is distributed, and is conducive to the diffusion of reactants and products molecule in catalysis is reacted, to ring molecule, particularly
The catalytic oxidation that cyclic ketone participates in is particularly advantageous.
The specific characteristic structure with the present invention can be prepared in the method for preparing titanium Si-Al molecular sieve of the present invention
Titanium Si-Al molecular sieve, such as benzene adsorbance is higher and there is the micropore size of 0.9-2.0nm ranges to be distributed.And the side of the present invention
Method makes the titanium-silicon molecular sieve catalyst of inactivation be utilized, and turns waste into wealth.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
As previously mentioned, the present invention provides a kind of titanium Si-Al molecular sieve, which contains aluminium element, titanium member
Element, element silicon and oxygen element, Kong Rong is in 0.3cm3/ g or more, total specific surface area is in 200m2/ g or more, external surface area is in 30m2/
G or more, and it is 10-55% that external surface area, which accounts for the ratio of total specific surface area,；The titanium Si-Al molecular sieve is in 25 DEG C, P/P0=0.10
And adsorption time be 1h under conditions of the benzene adsorbance that measures be at least 65mg/g molecular sieves, N2Have under Static Adsorption test
The micropore size of 0.9-2.0nm ranges is distributed.
In the present invention, total specific surface area of titanium Si-Al molecular sieve refers to the total specific surface areas of BET, and what external surface area referred to
It is the surface area of the outer surface of titanium Si-Al molecular sieve, can be also simply referred to as external surface area, it can be according to ASTM D4222-98 standards
Method measures.
In the present invention, the Kong Rong of titanium Si-Al molecular sieve and aperture respectively refer to the pore volume in molecular sieve and hole interior diameter, this
It is well known to those skilled in the art, does not repeat herein.
Titanium Si-Al molecular sieve according to the present invention, the Kong Rongwei 0.3-0.7cm of the preferably described titanium Si-Al molecular sieve3/ g, it is excellent
It is selected as 0.31-0.41cm3/g；Total specific surface area is 200-450m2/ g, preferably 270-410m2/g；External surface area is 30-
150m2/ g, preferably 40-120m2/ g, further preferably 40-70m2/g；The ratio that external surface area accounts for total specific surface area is 10-
35%, preferably 13-30%, more preferably 17-25%；The titanium Si-Al molecular sieve is in 25 DEG C, P/P0=0.10 and absorption when
Between be 1h under conditions of the benzene adsorbance that measures be at least 75mg/g molecular sieves, more preferably 80-110mg/g molecular sieves；0.9-
The micropore size of 2.0nm ranges accounts for ratio >=5% of total micropore size abundance.
Aforementioned titanium Si-Al molecular sieve according to the present invention, the micropore size of the titanium Si-Al molecular sieve is in addition in 0.4-
There is typical micro porous molecular sieve (such as the aperture of MFI topological structures molecular sieve is near 0.55nm) specific within the scope of 0.7nm
Outside pore-size distribution, it is also distributed within the scope of 0.9-2.0nm.It is necessary to be noted that in poromerics field, if
Micropore size distribution accounts for the ratio of total micropore size abundance within the scope of 0.9-2.0nm<When 1%, then the hole of this partial pore is divided
Cloth generally can be ignored, that is, think within the scope of 0.9-2.0nm without micropore be distributed, this by those skilled in the art public affairs
Know.Therefore, of the present invention in N2The lower micropore size with 0.9-2.0nm ranges of Static Adsorption test refers in 0.9-
Micropore size distribution within the scope of 2.0nm accounts for the ratio of total micropore size abundance>1% the case where.
, according to the invention it is preferred to which the micropore size distribution within the scope of 0.4-0.7nm accounts for the ratio of total micropore size abundance
Example≤95%, the micropore size distribution within the scope of 0.9-2.0nm account for ratio >=5% of total micropore size abundance；More preferably
, the micropore size distribution within the scope of 0.4-0.7nm accounts for ratio≤90% of total micropore size abundance, in 0.9-2.0nm
Micropore size distribution in range accounts for ratio >=10% of total micropore size abundance.In the present invention, the test side of micropore size
Method is well known to those skilled in the art, and such as uses N2The methods of Static Adsorption is tested.
Therefore, the micropore size of titanium Si-Al molecular sieve according to the present invention, preferably 0.9-2.0nm ranges accounts for total micropore size
Ratio >=10% of abundance, the micropore size distribution of more preferable 0.9-2.0nm ranges account for the ratio of total micropore size abundance
12-25%.
The micropore size of 0.9-2.0nm ranges accounts for the ratio of total micropore size abundance and counts as follows in the present invention
It calculates：[the quantity of the micropore size of 0.9-2.0nm ranges/(quantity of the micropore size of 0.9-2.0nm ranges)+(0.4-0.7nm
The quantity of micropore size in range)] × 100%.
Titanium Si-Al molecular sieve according to the present invention, preferably element silicon：Titanium elements：The molar ratio of aluminium element is 100：(0.1-
10)：(0.1-8), more preferable element silicon：Titanium elements：The molar ratio of aluminium element is 100：(0.2-5)：(0.2-7.5), further
It is preferred that element silicon：Titanium elements：The molar ratio of aluminium element is 100：(1-4)：(0.5-5.5).
The aforementioned titanium Si-Al molecular sieve of the present invention is higher with benzene adsorbance and with the micropore size of 0.9-2.0nm ranges
Distribution etc. advantages, the present invention to the preparation method of aforementioned titanium Si-Al molecular sieve without particular/special requirement, as long as can be prepared has
The titanium Si-Al molecular sieve of above structure, according to a preferred embodiment of the present invention, the present invention use and draw off agent system
Standby aforementioned titanium Si-Al molecular sieve.
Therefore, as previously mentioned, the present invention provides a kind of preparation method of titanium Si-Al molecular sieve of the present invention, the party
Method includes：
(1) agent will be drawn off to be mixed with beating with acid solution, and obtained slurries will be subjected to the first heat treatment, isolated first is solid
Body, wherein described to draw off agent be that reaction unit using Titanium Sieve Molecular Sieve as catalyst activity component draws off agent；
(2) it is carried out at the second heat after mixing first solid, silicon source, titanium source in the presence of aqueous solvent with alkali source
Reason.
In the present invention, the reaction unit using Titanium Sieve Molecular Sieve as catalyst activity component draw off agent can be from
It is various using Titanium Sieve Molecular Sieve as the device of catalyst activity component in draw off draw off agent, such as can be from titanium silicon point
Son sieve draws off agent as what is drawn off in the oxidation reaction apparatus of catalyst activity component.The oxidation reaction can be various oxidations
Reaction, such as the agent that draws off using Titanium Sieve Molecular Sieve as the reaction unit of catalyst activity component can be Ammoximation reaction
Device draw off agent, hydroxylating device one or more in agent, the tool that draws off drawing off for agent and epoxidation reaction device
Body can be cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draw off agent and epoxidation of propylene is anti-
Answer drawing off for device one or more in agent, it is preferably described that draw off agent be that the catalyst of inactivation is reacted under alkaline environment, therefore,
Preferably described to draw off agent be that cyclohexanone oxamidinating reaction unit draws off agent (such as the Titanium Sieve Molecular Sieve TS- of inactivation for of the invention
1, powdery, grain size is in 100-500nm).
In the present invention, it is described draw off agent refer to using solvent wash or roast 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 to catalyst under identical reaction conditions
Average activity within 1h.Such as in the reaction of practical 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 activity) when fresh.Preferably, the activity for drawing off agent can be the titanium silicon molecule
Sieve when fresh active 50% hereinafter, the activity for further preferably drawing off agent can be the Titanium Sieve Molecular Sieve when fresh
Active 10-40%.The activity of fresh dose of the Titanium Sieve Molecular Sieve is generally 90% or more, and usually 95% or more.
It is described to draw off the inactivation after agent derive from industrial deactivator or be reacted in the lab in the present invention
Catalyst.
Certainly, from the angle for preparing effect, method of the invention can also use fresh molecular sieve such as Titanium Sieve Molecular Sieve
It is only improper for cost control angularly as raw material, method provided by the invention, mainly with the titaniferous silicon of inactivation point
The catalyst of son sieve is turned waste into wealth, as raw material to save cost.
In the present invention, the agent that draws off of each device is respectively measured 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, and as of the invention draws off
Agent.As previously mentioned, in the case of preferred, the activity for drawing off agent is less than active the 50% of fresh catalyst.
In the present invention, by cyclohexanone oxamidinating reaction unit draw off agent for, the activity measures by the following method：
Take TS-1 molecular sieves (by " and Zeolites, 1992, Vol.12：Prepared by the method described in 943~950 ", TiO2
Mass percentage be 2.1%) be placed in slurry bed reactors of the 100mL with continuous feed and membrane separation device, stirring
The mixture of the hydrogen peroxide of water and 30wt% is added under state with the speed of 5.7mL/h, and (volume ratio of water and hydrogen peroxide is
10：9), with the mixture of the speed of 10.5mL/h addition cyclohexanone and the tert-butyl alcohol, (volume ratio of cyclohexanone and the tert-butyl alcohol is 1：
2.5) 36wt% ammonium hydroxide, is added with the speed of 5.7mL/h, above-mentioned three strands of materials stream is while being added, while with corresponding speed
Continuous discharge, reaction temperature maintain 80 DEG C, after stable reaction every 1h to product sampling gas chromatography to the group of liquid phase
At being analyzed, the conversion ratio of cyclohexanone is calculated using following formula and as the activity of Titanium Sieve Molecular Sieve.Cyclohexanone
Conversion ratio=[(mole of the unreacted cyclohexanone of mole-of the cyclohexanone of addition)/mole for the cyclohexanone being added]
× 100%.Wherein, using the result of 1h as initial activity.
With the method for the invention it is preferred to which step (2) carries out as follows：Silicon source and alkali source are existed in aqueous solvent
Under be mixed to get mixed solution, carried out after the mixed solution is mixed with first solid and titanium source it is described second heat at
Reason.The micropore size distribution that 0.9-2.0nm ranges can so be further increased accounts for the ratio of total micropore size abundance, and energy
Enough improve the activity of titanium Si-Al molecular sieve.
With the method for the invention it is preferred to which the mashing carries out at normal temperatures and pressures.
According to the method for the present invention, in the case of no specified otherwise, heat treatment is usually in the case of sealing spontaneous
It is carried out under pressure.
With the method for the invention it is preferred to the temperature of the first heat treatment is 10-200 DEG C, and more preferably 50-180 DEG C, into one
Preferably 60-180 DEG C of step.
According to the method for the present invention, the time of first heat treatment can according to needing be determined, for the present invention,
It is preferred that the time of the first heat treatment is 0.5-36h, preferably 1-24h, more preferably 1-12h.
With the method for the invention it is preferred to the temperature of the second heat treatment is 100-200 DEG C, more preferably 120-180 DEG C, into
One step is preferably 140-170 DEG C.
With the method for the invention it is preferred to which the time of second heat treatment can be according to needing to be determined, for this
The time of invention, the preferably second heat treatment is 0.5-24h, preferably 2-24h, more preferably 6-24h.
With the method for the invention it is preferred to which the method for the present invention further includes：Before it will draw off agent and be mixed with beating with acid solution,
First draws off agent by described and roast.
In the present invention, optional wider range of the condition of the roasting, for the condition packet of the preferably roasting of the invention
It includes：The temperature of roasting is 300-800 DEG C, preferably 550-600 DEG C；The time of roasting be 2-12h, preferably 2-4h, roasting
Atmosphere includes air atmosphere；The condition of the more preferable roasting includes：0.5- is roasted in nitrogen atmosphere at 350-600 DEG C first
Then 6h roasts 0.5-12h at 350-600 DEG C in air atmosphere.
With the method for the invention it is preferred to the concentration of the acid solution>0.1mol/L, more preferably >=1mol/L, further
It is preferred that 2-15mol/L.In the present invention, the primary solvent of the acid solution is water, also can be according to needing that other solvents aids are added.
Titanium Si-Al molecular sieve its Kong Rong, specific surface area, benzene adsorbance and the micropore pore size distribution etc. in 0.9-2.0nm being so prepared
Feature become apparent from.
With the method for the invention it is preferred to which the mass ratio for drawing off agent, titanium source, silicon source, acid, alkali source and water is 100：(0.1-
10)：(0.1-10)：(0.005-50)：(0.5-50)：(20-1000) preferably draws off agent, titanium source, silicon source, acid, alkali source and water
Mass ratio is 100：(0.5-10.0)：(0.5-10.0)：(1-15)：(1-20)：(100-800) draws off agent with SiO2Meter, acid with
H+Meter, alkali source is with N or OH-Meter, the mass ratio for more preferably drawing off agent and acid is 100：(10-15).
In the present invention, the Titanium Sieve Molecular Sieve can be the common Titanium Sieve Molecular Sieve with various topological structures, such as：
The Titanium Sieve Molecular Sieve can be selected from Titanium Sieve Molecular Sieve (such as TS- of the Titanium Sieve Molecular Sieve (such as TS-1) of MFI structure, MEL structures
2), the Titanium Sieve Molecular Sieve (such as Ti-Beta) of BEA structures, the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structures, hexagonal structure
The titanium silicon of Titanium Sieve Molecular Sieve (such as Ti-MCM-41, Ti-SBA-15), the Titanium Sieve Molecular Sieve (such as Ti-MOR) of MOR structures, TUN structures
The Titanium Sieve Molecular Sieve (such as Ti-ZSM-48) of molecular sieve (such as Ti-TUN) and other structures.
Preferably, the Titanium Sieve Molecular Sieve is selected from Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve and BEA of MEL structures of MFI structure
The Titanium Sieve Molecular Sieve of structure.It is highly preferred that the Titanium Sieve Molecular Sieve is the Titanium Sieve Molecular Sieve of MFI structure, such as TS-1 molecular sieves.
According to the method for the present invention, optional wider range of the type of the acid can be organic acid and/or inorganic
Acid, preferably inorganic acid；Wherein, inorganic acid can be one or more in HCl, sulfuric acid, perchloric acid, nitric acid and phosphoric acid, excellent
It is selected as phosphoric acid；The organic acid can be the organic carboxyl acid of C1-C10, preferably formic acid, acetic acid, propionic acid, aphthenic acids Peracetic acid
With it is one or more in Perpropionic Acid.
In method provided by the invention, the titanium source can be organic titanium source (such as organic titanate) and/or inorganic titanium
Source (such as inorganic titanium salt).Wherein, inorganic ti sources can be TiCl4、Ti(SO4)2、TiOCl2, titanium hydroxide, titanium oxide, nitric acid
One or more in titanium salt and phosphoric acid titanium salt etc., organic titanium source can be fatty alcohol titanium and one kind or more in organic titanate
Kind.The titanium source is preferably organic titanium source, further preferably organic titanate.The organic titanate preferably has structure
Formula is M4TiO4Organic titanate, wherein M is preferably the alkyl with 1-4 carbon atom, and 4 M can be identical or different,
It is preferred that the organic titanate is selected from for one kind in isopropyl titanate, metatitanic acid n-propyl, butyl titanate and tetraethyl titanate
Or it is a variety of.The specific example of the titanium source can be but be not limited to：TiOCl2、Titanium tetrachloride, titanium sulfate, metatitanic acid orthocarbonate (including
The various isomers of metatitanic acid orthocarbonate, such as four n-propyl of tetraisopropyl titanate and metatitanic acid), butyl titanate is (butyl titanate
Various isomers, such as tetra-n-butyl titanate) and tetraethyl titanate in it is one or more.
According to the method for the present invention, optional wider range of the type of the alkali source can be organic base source and/or nothing
Machine alkali source, wherein inorganic alkali source can be ammonia or the alkali that cation is alkali 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
It closes one or more in object, aliphatic alcohol amine compounds 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 (preferably alkyl) substitution of at least one hydrogen, the aliphatic hydramine can be each
Kind NH3At least one of the compound that is formed after aliphatic alkyl (preferably alkyl) substitution of hydroxyl of 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 indicates
Aliphatic amine, the aliphatic hydramine can be as formula IV indicate 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 respectively methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle
Butyl.
R9(NH2)n(formula III)
In formula III, n is an integer of 1 or 2.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, tertiary butyl, n-pentyl, new
Amyl, 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 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
Amine compounds are one or more in monoethanolamine, diethanol amine and triethanolamine.
According to a preferred embodiment of the present invention, obtained titanium Si-Al molecular sieve is synthesized in order to further increase
Duct order, the preferably described alkali source be sodium hydroxide, ammonium hydroxide, ethylenediamine, n-butylamine, butanediamine, hexamethylene diamine, monoethanolamine,
It is one or more in diethanol amine, triethanolamine, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide.
Wherein, when containing ammonium hydroxide in the alkali source, the molar ratio of alkali source is to include 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 pH of more preferable aqueous slkali>9.
According to the method for the present invention, source of aluminium is to be capable of providing the substance of aluminium, and preferably source of aluminium is Aluminum sol, aluminium
One or more in salt, aluminium hydroxide and aluminium oxide, Aluminum sol preferred content in terms of aluminium oxide is 10-50 weight %.
In the present invention, the aluminium salt can be inorganic aluminate and/or organic aluminium salt, and the organic aluminium salt is preferably C1-C10
Organic aluminium salt, the inorganic aluminate for example can be aluminum sulfate, sodium metaaluminate, aluminium chloride and aluminum nitrate in one kind or more
Kind.
It is described to draw off agent and molar concentration in the more preferable embodiment of the present invention>The acid solution of 0.1mol/L
The process for being mixed with beating processing is carried out under acid solution counterflow condition, and the titanium Si-Al molecular sieve obtained with this condition has more
Apparent distinctive physical chemical characteristics.
, according to the invention it is preferred to which the method for the present invention further includes the step of the recovery product from the material that step (2) is heat-treated
Suddenly, the step of recovery product is conventional method, is familiar with by those skilled in the art, herein and is had no special requirements, usually
Refer to the process that product is filtered, washed, dries and roasts.Wherein, described drying process can be in the temperature between -200 DEG C of room temperature
Lower progress, described roasting process can between 300-800 DEG C first in nitrogen atmosphere after 0.5-6h in air atmosphere 3-12h
It carries out.
Since the benzene adsorbance of material of the present invention is higher and there is the micropore size of 0.9-2.0nm ranges to be distributed, it is being catalyzed
It is special to be conducive to the catalytic oxidation that reactants and products molecule especially participates in ring molecule, particularly cyclic ketone in reaction
Favorably.
The present invention also provides the application of the titanium Si-Al molecular sieve of the present invention in the oxidation reaction.In the oxidation reaction, example
Such as in cyclic ketones oxidation reaction, the selectivity and catalytic activity of target product such as carboxylic acid significantly improve.
According to the fourth aspect of the invention, the present invention provides a kind of method of cyclic ketones oxidation, this method includes：By ring
Ketone, oxidant and catalyst contact, the catalyst contain titanium Si-Al molecular sieve of the present invention.
According to the method for the present invention, the condition of the contact can be the conventional selection of this field, for the present invention, preferably
The condition of contact includes：Temperature is 40-150 DEG C, preferably 40-120 DEG C；Pressure is 0.1-3.0MPa, preferably 0.1-
2.5MPa；Time is 0.1-24h, and the molar ratio of cyclic ketones and oxidant is 1：1-20, preferably 1：2-15.
With the method for the invention it is preferred to which the mass ratio of cyclic ketones and catalyst is 0.5-150：1.
With the method for the invention it is preferred to which the contact carries out in the presence of solvent, wherein preferred solvent and catalyst
Mass ratio is 1-200：1, preferably 2-150:1；The more preferable solvent is in water, alcohol, linear chain or branched chain ketone, acid and nitrile
One or more, the preferably described solvent is water, the alcohol of C1-C5, the linear chain or branched chain ketone of C2-C6, the nitrile of C2-C8 and C2-C5
It is one or more in acid.
According to the method for the present invention, the solvent is preferably selected from water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, different
One or more in butanol, acetone, butanone, acetonitrile, propionitrile, benzene acetonitrile, acetic acid and propionic acid, the more preferable solvent is selected from second
One or more in nitrile, acetone, methanol, acetic acid and water, the more preferable solvent is acetonitrile and/or acetone.
According to the method for the present invention, charging order is also required without special, and cyclic ketones can first be added, oxygen can also first be added
Agent or solvent.
With the method for the invention it is preferred to which the oxidant is hydrogen peroxide, tert-butyl hydroperoxide, peroxidating isopropyl
It is one or more in benzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid, the cyclic ketones be cyclohexanone, cyclopentanone and
It is one or more in methyl cyclohexanone.
According to the method for the present invention, after haptoreaction, the side of common distillation or rectifying may be used in the material after reaction
Method, after isolating target product, unreacted cyclic ketones raw material etc. does not have to separating-purifying, directly backs within reaction unit relaying
Continuous reaction.
Below by embodiment, the invention will be further described, but the content being not intended to limit the present invention.
In comparative example and embodiment, agents useful for same is commercially available analytical reagents.
Wherein, oxidants hydrogen peroxide is provided by the hydrogen peroxide solution of a concentration of 30 weight %.
The agent that draws off of following embodiment and comparative example obtains as follows, and measures Titanium Sieve Molecular Sieve using following methods
The activity of (including Titanium Sieve Molecular Sieve draws off agent and fresh dose of Titanium Sieve Molecular Sieve).
Take TS-1 molecular sieves (by " and Zeolites, 1992, Vol.12：Prepared by the method described in 943~950 ", TiO2
Mass percentage be 2.1%) be placed in 100mL band continuous feed and membrane separation device slurry bed reactor in, stirring shape
With the mixture of the speed of 5.7mL/h addition water and the hydrogen peroxide of 30wt%, (volume ratio of water and hydrogen peroxide is 10 under state：
9), with the mixture of the speed of 10.5mL/h addition cyclohexanone and the tert-butyl alcohol, (volume ratio of cyclohexanone and the tert-butyl alcohol is 1：2.5),
36wt% ammonium hydroxide is added with the speed of 5.7mL/h, above-mentioned three strands of materials stream is while being added, while continuously going out with corresponding speed
Material, reaction temperature maintain 80 DEG C, are carried out to the composition of liquid phase with gas chromatography to product sampling every 1h after stable reaction
Analysis calculates the conversion ratio of cyclohexanone and as the activity of Titanium Sieve Molecular Sieve using following formula.The conversion ratio of cyclohexanone
=[(mole of the unreacted cyclohexanone of mole-of the cyclohexanone of addition)/mole for the cyclohexanone being added] ×
100%.
The yclohexanone conversion ratio for being for the first time 1h measurement is its initial activity, value 99.5%.Through after a period of time
After yclohexanone conversion ratio drops to 50% by initial 99.5%, roasting regeneration mode is used again after isolating catalyst by about 168h
Raw (4h is roasted in air atmosphere at 570 DEG C) then proceedes in cyclohexanone oxamidinating reaction, this step to be repeated
Suddenly, until the activity after regeneration is less than the 50% of initial activity, the oximes catalyst sample at this moment inactivated is as the present invention's
Agent is drawn off, obtains drawing off agent SH-1 (activity is 50%), SH-2 (activity is 40%), SH-3 (activity successively according to preceding method
For 25%), SH-4 (activity is 10%).
In each embodiment and comparative example, X-ray diffraction (XRD) 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 are 22.5 ° -25.0 ° with sample and authentic specimen
The ratio of the sum of intensity (peak height) indicates crystallinity of the sample relative to authentic specimen, here on the basis of 1 sample of comparative example
Sample, crystallinity are calculated as 100%, and the relative crystallinity data of each sample are shown in Table 1.The benzene adsorbance of sample, Kong Rong, aperture point
Cloth, total specific surface area and external surface area measure on Micromeritics companies ASAP2405 static state n2 absorption apparatus, specific number
According to being shown in Table 1.Mole composition of the elements such as aluminium, titanium and the silicon of sample is in Rigaku Electric Co., Ltd 3271E type x-ray fluorescence
It is measured on spectrometer, specific data are shown in Table 2.
In comparative example and embodiment：
Comparative example 1
This comparative example illustrates the conventional Titanium Sieve Molecular Sieve sample for being prepared for silicon source hydrothermal crystallizing using estersil and not containing aluminium
Process.
Tetraethyl orthosilicate, isopropyl titanate are mixed with tetrapropylammonium hydroxide, and appropriate distilled water is added and is stirred,
Mole group becomes tetraethyl orthosilicate among reaction system：Isopropyl titanate：Tetrapropylammonium hydroxide：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, it then will mixing
Liquid is put into stainless steel sealing reaction kettle, and constant temperature places 3d at a temperature of 170 DEG C, obtains the mixture of crystallization product；This is mixed
It closes object filtering, be washed with water, and in 110 DEG C of dry 60min, obtain molecular screen primary powder, and in 550 DEG C of roasting temperature 3h, obtain
The Titanium Sieve Molecular Sieve of hydro-thermal direct crystallization, XRD crystalline phases are MFI structure.
Comparative example 2
This comparative example illustrates the conventional mistake for preparing the Titanium Sieve Molecular Sieve sample containing aluminium for silicon source hydrothermal crystallizing using estersil
Journey.
Tetraethyl orthosilicate, aluminium isopropoxide, isopropyl titanate are mixed with tetrapropylammonium hydroxide, and appropriate distilled water is added
It is stirred, mole group becomes tetraethyl orthosilicate among reaction system：Isopropyl titanate：Aluminium isopropoxide：Tetrapropylammonium hydroxide：
Water=100：5：2：10：200, wherein tetraethyl orthosilicate is with SiO2Meter；1.0h is hydrolyzed at normal pressure and 60 DEG C, then at 75 DEG C
3h is stirred, mixed liquor, which is then put into stainless steel, seals reaction kettle, and constant temperature places 3d at a temperature of 170 DEG C, obtains crystallization production
The mixture of object；It by the filtering of this mixture, is washed with water, and in 110 DEG C of dry 60min, obtains molecular screen primary powder, and in 550
DEG C roasting temperature 3h, obtains the titanium Si-Al molecular sieve of hydro-thermal direct crystallization, and XRD crystalline phase figures are unanimously tied for MFI with comparative example 1
Structure.
Comparative example 3
This comparative example illustrates the process of the Titanium Sieve Molecular Sieve sample dip loading aluminium prepared using comparative example 1.
Titanium Sieve Molecular Sieve prepared by comparative example 1 is mixed with sodium metaaluminate aqueous solution, wherein Titanium Sieve Molecular Sieve and meta-aluminic acid
The mass ratio of sodium and 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 Titanium Sieve Molecular Sieve of aluminium must be loaded, XRD crystalline phases are
MFI structure.
Comparative example 4
This comparative example illustrates to utilize the process for drawing off agent SH-2 sample dip loading aluminium.
Agent SH-2 will be drawn off to mix with sodium metaaluminate aqueous solution, wherein drawing off agent and sodium metaaluminate and the mass ratio of water
It is 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 Titanium Sieve Molecular Sieve of aluminium must be loaded, XRD crystalline phases are MFI structure.
Comparative example 5
This comparative example illustrates to utilize the process for drawing off agent SH-3 dip loading aluminium.
SH-3 is mixed with sodium metaaluminate aqueous solution, wherein Titanium Sieve Molecular Sieve and the mass ratio of sodium metaaluminate and water is
10:1:50, stir 12h at normal pressure and 40 DEG C, then by the filtering of this mixture, be washed with water, and in 110 DEG C of dry 60min,
And in 550 DEG C of roasting temperature 3h, the Titanium Sieve Molecular Sieve of aluminium must be loaded, XRD crystalline phases are MFI structure.
Comparative example 6
This comparative example illustrates to utilize the process for drawing off agent SH-4 dip loading aluminium.
SH-4 is mixed with sodium metaaluminate aqueous solution, wherein Titanium Sieve Molecular Sieve and the mass ratio of sodium metaaluminate and water is
10:2:20, stir 3h at normal pressure and 50 DEG C, then by the filtering of this mixture, be 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 aluminium must be loaded, XRD crystalline phases are MFI structure.
Embodiment 1
This example demonstrates that method provided by the invention and product.
In room temperature (20 DEG C, remaining comparative example is identical with embodiment) normal pressure (0.1MPa, remaining comparative example and embodiment phase
Under together), first the combined of cyclohexanone oximate the catalyst SH-2 and 1mol/L of inactivation are beaten, then by mixing slurry
Processing 12h is mixed in liquid at 80 DEG C；By solid, silicon source aluminum sulfate, titanium source titanium sulfate and sodium hydroxide water after separation of solid and liquid
Mixed liquor is put into stainless steel after solution (pH 12) mixing and seals reaction kettle, handles 12h at 170 DEG C, wherein quality of material
Group is as the cyclohexanone oximate catalyst inactivated：Titanium source：Silicon source：Acid：Alkali：Water=100：1：1：10：5：250, the hexamethylene of inactivation
Ketoxime catalyst is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.It by products therefrom filtering, is washed with water, and in 110 DEG C of drying
120min obtains molecular sieve, XRD crystalline phase figures are consistent with comparative example 1, illustrate then in 550 DEG C of roasting temperature 3h
It is the titanium Si-Al molecular sieve with MFI structure.
Comparative example 7
This comparative example illustrates to utilize the process for drawing off dip loading aluminium after agent SH-2 acid is handled.
At normal temperatures and pressures, first the combined of cyclohexanone oximate the catalyst SH-2 and 1mol/L of inactivation are beaten
Processing 12h is then mixed in mixed serum by slurry at 80 DEG C；The SH-2 that acid processing is obtained after separation of solid and liquid, then by it
It is mixed with aluminum sulfate aqueous solution, wherein Titanium Sieve Molecular Sieve and the mass ratio of aluminum sulfate and water are 10:2:20, in normal pressure and 50
3h is stirred at DEG C, and 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, must load the titanium silicalite material of aluminium, and XRD crystalline phases are MFI structure.
Embodiment 2
This example demonstrates that method provided by the invention and product.
At normal temperatures and pressures, first the cyclohexanone oximate catalyst SH-3 of inactivation is mixed with the hydrochloric acid solution of 5mol/L and is beaten
Processing 1h is then mixed in mixed serum by slurry at 60 DEG C；By solid, silicon source Aluminum sol (content 20 after separation of solid and liquid
Weight %), titanium source butyl titanate mixed liquor is put into stainless steel after being mixed with tetrapropylammonium hydroxide solution (pH 10)
Reaction kettle is sealed, 12h is handled at 150 DEG C, wherein quality of material group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Aluminium
Source：Acid：Alkali：Water=100：2：0.5：15：15：200, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali with
OH-Meter.Then according to the method recovery product of embodiment 1, titanium Si-Al molecular sieve, XRD crystalline phase figures and comparative example 1 one are obtained
It causes.
Embodiment 3
This example demonstrates that method provided by the invention and product.
At normal temperatures and pressures, the cyclohexanone oximate catalyst SH-4 of inactivation is mixed with the aqueous solution of nitric acid of 8mol/L and is beaten
Processing 2h is then mixed in mixed serum by slurry at 100 DEG C；By solid, silicon source aluminium hydroxide, titanium source four after separation of solid and liquid
Mixed liquor is put into stainless steel after being mixed with ethylenediamine solution (pH 11) and seals reaction kettle, the hydro-thermal at 140 DEG C by titanium chloride
Handle 18h, wherein quality of material group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Silicon source：Acid：Alkali：Water=100：5：
2：10：5：150, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is in terms of N.Then according to the side of embodiment 1
Method recovery product, obtains molecular sieve, and XRD crystalline phase figures are consistent with comparative example 1.
Embodiment 4
This example demonstrates that method provided by the invention and product.
At normal temperatures and pressures, first the cyclohexanone oximate catalyst SH-1 of inactivation is mixed with the aqueous sulfuric acid of 5mol/L and is beaten
Processing 1h is then mixed in mixed serum by slurry at 120 DEG C；By solid, silicon source aluminium chloride, titanium source metatitanic acid after separation of solid and liquid
Mixed liquor is put into stainless steel after being mixed with n-butylamine aqueous solution (pH 12.0) and seals reaction kettle by tetra-isopropyl, at 170 DEG C
Handle 12h, wherein quality of material group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Silicon source：Acid：Alkali：Water=100：1：
1：2：2：50, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is in terms of N.By products therefrom filtering, it is washed with water
It washs, and 120min is dried in 110 DEG C, then in 550 DEG C of roasting temperature 3h, obtain molecular sieve, XRD crystalline phase figures and comparative example
1 is consistent.
Embodiment 5
This example demonstrates that method provided by the invention and product.
At normal temperatures and pressures, first the cyclohexanone oximate catalyst SH-2 of inactivation is mixed with the high chloro acid solution of 2mol/L
Processing 5h is then mixed in mixed serum by mashing at 70 DEG C；By solid, silicon source aluminium oxide, titanium source titanium after separation of solid and liquid
Mixed liquor is put into stainless steel after being mixed with ammonium hydroxide (pH 11) and seals reaction kettle by sour tetra-ethyl ester, and 12h is handled at 170 DEG C,
Middle quality of material group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Silicon source：Acid：Alkali：Water=100：0.5：1：5：20：
100, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is in terms of N.By products therefrom filtering, it is washed with water, and
120min is dried in 110 DEG C, then in 550 DEG C of roasting temperature 3h, obtains molecular sieve, XRD crystalline phase figures and comparative example 1 one
It causes.
Embodiment 6
This example demonstrates that method provided by the invention and product.
At normal temperatures and pressures, first the cyclohexanone oximate catalyst SH-2 of inactivation is mixed with the acetic acid aqueous solution of 12mol/L
Processing 6h is then mixed in mixed serum by mashing at 160 DEG C；By solid, silicon source aluminium chloride, titanium source after separation of solid and liquid
TiOCl2Mixed liquor is put into stainless steel after being mixed with diethanol amine aqueous solution (pH 11) and seals reaction kettle, at 170 DEG C
Reason is for 24 hours, wherein quality of material group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Silicon source：Acid：Alkali：Water=100：6：
0.2：12：18：500, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is in terms of N.Then according to embodiment 1
Method recovery product, obtain molecular sieve, XRD crystalline phase figures and comparative example 1 are consistent.
Embodiment 7
This example demonstrates that method provided by the invention and product.
At normal temperatures and pressures, first the cyclohexanone oximate catalyst SH-2 of inactivation is mixed with the aqueous sulfuric acid of 0.5mol/L
Processing 4h is then mixed in mixed serum by mashing at 130 DEG C；By solid, silicon source aluminum phosphate, titanium source titanium after separation of solid and liquid
Mixed liquor is put into stainless steel after being mixed with tetraethyl ammonium hydroxide aqueous solution (pH 11) and seals reaction kettle by sour four butyl esters,
12h is handled at 170 DEG C, wherein quality of material group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Silicon source：Acid：Alkali：Water=
100：1：1：1：1：800, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.Then according to implementation
The method recovery product of example 1, obtains molecular sieve, and XRD crystalline phase figures are consistent with comparative example 1.
Embodiment 8
This example demonstrates that method provided by the invention and product.
At normal temperatures and pressures, first the cyclohexanone oximate catalyst SH-2 of inactivation is mixed with the phosphate aqueous solution of 15mol/L
Processing 3h is then mixed in mixed serum by mashing at 180 DEG C；By solid, silicon source aluminum nitrate, titanium source sulphur after separation of solid and liquid
Mixed liquor is put into stainless steel after being mixed with sodium hydrate aqueous solution (pH 14) and seals reaction kettle by sour titanium, is handled at 150 DEG C
6h, wherein quality of material group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Silicon source：Acid：Alkali：Water=100：10：1：10：
15：600, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.Then according to the method for embodiment 1
Recovery product, obtains molecular sieve, and XRD crystalline phase figures are consistent with comparative example 1.
Embodiment 9
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 8, the difference is that in quality of material composition, the cyclohexanone oximate of inactivation is urged
Agent：Acid=100：5, the XRD crystalline phase figures of gained sample are consistent with comparative example 1.
Embodiment 10
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 8, the difference is that in quality of material composition, the cyclohexanone oximate of inactivation is urged
Agent：Acid=100：100, the XRD crystalline phase figures of gained sample are consistent with comparative example 1.
Embodiment 11
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 8, the difference is that a concentration of 0.2mol/L of phosphate aqueous solution, gained sample
The XRD crystalline phase figures of product are consistent with comparative example 1.
Embodiment 12
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 8, unlike, agent SH-2 will be drawn off and roast then progress subsequently
Mashing, heat treatment process, wherein the condition of roasting includes：4h, the XRD of gained sample are roasted at 570 DEG C in air atmosphere
Crystalline phase figure is consistent with comparative example 1.
Embodiment 13
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 8, the difference is that mixed serum closed static processing 3h at 180 DEG C,
The XRD crystalline phase figures of gained sample are consistent with comparative example 1.
Embodiment 14
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 2, the difference is that substituting HCl with phosphoric acid.The XRD crystalline phase figures of gained sample
It is consistent with comparative example 1.
Embodiment 15
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 2, unlike, agent SH-3 will be drawn off and roast then progress subsequently
Mashing, heat treatment process, wherein the condition of roasting includes：4h, the XRD of gained sample are roasted at 570 DEG C in air atmosphere
Crystalline phase figure is consistent with comparative example 1, and the XRD crystalline phase figures of gained sample are consistent with comparative example 1.
Embodiment 16
Molecular sieve is prepared according to the method for embodiment 2, unlike, the agent that draws off used is SH-1, remaining condition is homogeneous
Together, the XRD crystalline phase figures Yu comparative example 1 of gained sample are consistent.
Embodiment 17
Molecular sieve is prepared according to the method for embodiment 2, unlike, raw material addition sequence changes：
At normal temperatures and pressures, first the cyclohexanone oximate catalyst SH-3 of inactivation is mixed with the hydrochloric acid solution of 5mol/L and is beaten
Processing 1h is then mixed in mixed serum by slurry at 60 DEG C；Solid is obtained after separation of solid and liquid, by silicon source Aluminum sol (content
For 20 weight %) with tetrapropylammonium hydroxide solution (pH 10) be mixed to get mixed solution, by the mixed solution and institute
State solid and titanium source butyl titanate mixing after by mixed liquor be put into stainless steel seal reaction kettle, handle 12h at 150 DEG C,
Middle quality of material group becomes the cyclohexanone oximate catalyst of inactivation：Titanium source：Silicon source：Acid：Alkali：Water=100：2：0.5：15：15：
200, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.Then it is returned according to the method for embodiment 1
Product is received, titanium Si-Al molecular sieve is obtained, XRD crystalline phase figures are consistent with comparative example 1.
Table 1
From the results shown in Table 1：
Its large pore volume of the titanium Si-Al molecular sieve of preferred process of the present invention preparation is in 0.3cm3/ g, benzene adsorbance are more than 65mg/
G, total specific surface area are 200-450m2/ g, wherein external surface area 30-150m2/ g, and external surface area accounts for the ratio of total specific surface area
Example is between 10%-35%；The preferred process of the present invention prepare Titanium Sieve Molecular Sieve its accounted in the micropore size of 0.9-2.0nm ranges
Always the ratio of micropore size abundance is>5%.
It can also be seen that from the result of table 1：
Titanium Sieve Molecular Sieve its relative crystallinity prepared by the preferred process of the present invention, Kong Rong, total specific surface area, Extra specific surface area
The data such as product, 0.9-2.0nm pore-size distributions, benzene adsorbance fully meet whole features of product of the present invention.Opposite, either
Comparative example 1 is containing for silicon source preparation using estersil using the Titanium Sieve Molecular Sieve without containing aluminium that estersil is silicon source preparation, comparative example 2
The titanium silicon containing aluminium for thering is the Titanium Sieve Molecular Sieve that the Titanium Sieve Molecular Sieve of aluminium, comparative example 3 are prepared using comparative example 1 to load aluminium and preparing
Molecular sieve or comparative example 4-6 using draw off titanium silicalite material that agent load aluminium obtains and comparative example 7 to draw off agent acid treated negative
Carry the obtained titanium silicalite material of aluminium, relative crystallinity, Kong Rong, total specific surface area, external surface area, 0.9-2.0nm pore-size distributions,
The data such as benzene adsorbance cannot be satisfied whole features of product of the present invention.Only have as its hole of the molecular sieve of comparative example 1 holds
0.264cm3/ g, external surface area 24m2/ g, and external surface area accounts for the ratio of total specific surface area 5% or so.
Testing example
Catalyst molecule sieve, cyclohexanone, hydrogen peroxide source and solvent methanol prepared by comparative example and embodiment is according to ring
Hexanone is 1 with the molar ratio of hydrogen peroxide and solvent methanol：2：5, wherein solvent methanol quality is 20g, solvent methanol and catalysis
The mass ratio of agent is 20：1, it is to carry out reaction 2h under 60 DEG C of pressure are 1.5MPa in temperature.
Table 2
From the results shown in Table 2：The catalyst Ti Si-Al molecular sieve of the present invention is used for cyclic ketones oxidation reaction, carboxylic acid
High selectivity, and the effective rate of utilization of oxidant is high.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
Claims (15)
1. a kind of titanium Si-Al molecular sieve, which is characterized in that the titanium Si-Al molecular sieve contains aluminium element, titanium elements, element silicon and oxygen
Element, Kong Rong is in 0.3cm3/ g or more, total specific surface area is in 200m2/ g or more, external surface area is in 30m2/ g or more, and appearance
The ratio that area accounts for total specific surface area is 10-55%；The titanium Si-Al molecular sieve is in 25 DEG C, P/P0=0.10 and adsorption time
Benzene adsorbance to be measured under conditions of 1h is at least 65mg/g molecular sieves, N2Static Adsorption test is lower to have 0.9-2.0nm models
The micropore size distribution enclosed, element silicon：Titanium elements：The molar ratio of aluminium element is 100：(0.1-10)：(0.1-8).
2. titanium Si-Al molecular sieve according to claim 1, wherein the Kong Rongwei 0.3-0.7cm of the titanium Si-Al molecular sieve3/
G, total specific surface area are 200-450m2/ g, external surface area 30-150m2/ g, the ratio that external surface area accounts for total specific surface area are 10-
35%；The titanium Si-Al molecular sieve is in 25 DEG C, P/P0=0.10 and adsorption time be the benzene adsorbance that measures under conditions of 1h
It is at least 75mg/g molecular sieves；The micropore size of 0.9-2.0nm ranges accounts for ratio >=5% of total micropore size abundance.
3. titanium Si-Al molecular sieve according to claim 1, wherein the micropore size of 0.9-2.0nm ranges accounts for total micropore hole
The ratio of diameter abundance is 12-25%.
4. the preparation method of the titanium Si-Al molecular sieve described in a kind of any one of claim 1-3, this method include：
(1) agent will be drawn off to be mixed with beating with acid solution, obtained slurries, which are carried out first, to be heat-treated, isolated first solid,
It is wherein, described that draw off agent be that reaction unit using Titanium Sieve Molecular Sieve as catalyst activity component draws off agent；
(2) the second heat treatment is carried out after mixing first solid, silicon source, titanium source in the presence of aqueous solvent with alkali source；
The concentration of the acid solution>0.1mol/L；Draw off agent：Titanium source：Silicon source：Acid：Alkali source：The mass ratio of water is 100：(0.1-
10)：(0.1-10)：(0.005-50)：(0.5-50)：(20-1000) draws off agent with SiO2Meter, acid is with H+Meter, alkali source with N or
OH-Meter.
5. preparation method according to claim 4, wherein described using Titanium Sieve Molecular Sieve as the anti-of catalyst activity component
The agent that draws off of device is answered to draw off agent for Ammoximation reaction device.
6. preparation method according to claim 4 or 5, wherein step (2) carries out as follows：By silicon source and alkali source
It is mixed to get mixed solution in the presence of aqueous solvent, is carried out after the mixed solution is mixed with first solid and titanium source
Second heat treatment.
7. preparation method according to claim 4 or 5, wherein the temperature of the first heat treatment is 10-200 DEG C；At second heat
The temperature of reason is 100-200 DEG C.
8. preparation method according to claim 4 or 5, wherein the time of the first heat treatment is 0.5-36h；At second heat
The time of reason is 0.5-24h.
9. preparation method according to claim 4 or 5, wherein this method further includes：It is mixed with acid solution agent will be drawn off
Before mashing, first draws off agent by described and roast.
10. preparation method according to claim 4 or 5, wherein the Titanium Sieve Molecular Sieve is MFI structure, described to draw off agent
Activity be the catalyst when fresh active 50% or less.
11. preparation method according to claim 4 or 5, wherein the acid is organic and or inorganic acids；The alkali source
It is one or more in ammonia, aliphatic amine, aliphatic hydramine and quaternary ammonium base；Source of aluminium is Aluminum sol, aluminium salt, aluminium hydroxide
With it is one or more in aluminium oxide；The titanium source is selected from inorganic titanium salt and/or organic titanate.
12. described in any one of titanium Si-Al molecular sieve or claim 4-11 described in any one of claim 1-3
The application of the titanium Si-Al molecular sieve that preparation method is prepared in the oxidation reaction.
13. a kind of method of cyclic ketones oxidation, this method include：Cyclic ketones, oxidant and catalyst are contacted, which is characterized in that institute
State any one of titanium Si-Al molecular sieve or the claim 4-11 that catalyst contains described in any one of claim 1-3 institutes
The titanium Si-Al molecular sieve that the preparation method stated is prepared.
14. according to the method for claim 13, wherein the condition of the contact includes：Temperature is 40-150 DEG C, and pressure is
The molar ratio of 0.1-3.0MPa, time 0.1-24h, cyclic ketones and oxidant is 1：The mass ratio of 1-20, cyclic ketones and catalyst is
0.5-150：1；The oxidant is hydrogen peroxide, tert-butyl hydroperoxide, dicumyl peroxide, cyclohexyl hydroperoxide, mistake
It is one or more in fluoroacetic acid and Perpropionic Acid, the cyclic ketones be cyclohexanone, cyclopentanone and methyl cyclohexanone in one kind or
It is a variety of.
15. the method according to claim 13 or 14, wherein the contact carries out in the presence of solvent, wherein solvent with
The mass ratio of catalyst is 1-200：1, the solvent is one or more in water, alcohol, linear chain or branched chain ketone, acid and nitrile.
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| CN109384656B (en) * | 2017-08-09 | 2021-12-17 | 中国石油化工股份有限公司 | Process for preparing cyclohexanone |
| CN109593033B (en) * | 2017-09-30 | 2022-01-04 | 中国石油化工股份有限公司 | Method for oxidizing cyclohexanone |
| CN109593072B (en) * | 2017-09-30 | 2020-09-22 | 中国石油化工股份有限公司 | Method for oxidizing olefin |
| CN110128313B (en) * | 2018-02-09 | 2021-04-06 | 中国石油化工股份有限公司 | Process for preparing tert-butyl hydroperoxide |
| CN110156571B (en) * | 2018-02-13 | 2022-03-11 | 中国石油化工股份有限公司 | Propylene oxidation process |
| CN110143905B (en) * | 2018-02-13 | 2021-05-14 | 中国石油化工股份有限公司 | Process for preparing peroxypropionic acid |
| CN110317128B (en) * | 2018-03-30 | 2021-09-07 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether |
| CN108706716A (en) * | 2018-06-22 | 2018-10-26 | 浙江海洋大学 | The processing method of itrogenous organic substance in a kind of waste water |
| CN111484031B (en) * | 2019-01-28 | 2023-03-10 | 中国石油化工股份有限公司 | Modified titanium-silicon molecular sieve, preparation method and application thereof, and thioether oxidation method |
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