CN106915753B - Modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of alkene direct oxidation - Google Patents
Modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of alkene direct oxidation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The present invention relates to molecular sieve arts, mainly provide a kind of modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application, which includes: precious metal element, titanium elements, element silicon and oxygen element, and the Kong Rong of the molecular sieve 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 the ratio of the total specific surface area of external surface area Zhan is 7-55%；The molecular sieve is in 25 DEG C, P/P0=0.10 and adsorption time be 1 hour under conditions of the benzene adsorbance that measures be at least 75mg/g molecular sieve, N2The lower micropore size with 0.9-1.5nm range of Static Adsorption test is distributed；The urface silicon titanium of the molecular sieve is not less than body phase silicon titanium ratio.The present invention also provides a kind of methods of alkene direct oxidation.The advantage that the micropore size higher and with 0.9-1.5nm range with the modified with noble metals Titanium Sieve Molecular Sieve of special physical chemical characteristics structure its benzene adsorbance of the invention is distributed, such as it is used for ring molecule, the reaction that olefin hydrocarbon molecules are participated in or generated, better catalytic effect can be obtained.
Description
Technical field
The present invention relates to a kind of modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application, more specifically to one
The method that kind prepares modified with noble metals Titanium Sieve Molecular Sieve using the titanium-silicon molecular sieve catalyst of inactivation, the invention further relates to a kind of alkene
The method of hydrocarbon direct oxidation.
Background technique
Titanium Sieve Molecular Sieve is skeleton molecular sieve as composed by silicon, titanium, oxygen element, in petroleum refining and petrochemical industry
It has a extensive future.Wherein, TS-1 molecular sieve is to be introduced into transition metal element titanium in the framework of molecular sieve with ZSM-5 structure
It is formed by a kind of novel titanosilicate with superior catalytic selective oxidation performance.
TS-1 not only has a catalysed oxidn of titanium, but also the shape-selective effect with ZSM-5 molecular sieve and excellent
Stability successfully realizes industrial 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 again be divided into 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
Can not then regeneration activity recovery be passed through (activity after regeneration is lower than the 50% of initial activity).Titanium Sieve Molecular Sieve is lost under alkaline environment
It after permanent deactivation occurs for especially ammonia deuteration catalyst TS-1 living, 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 ammonia deuteration catalyst of inactivation
Art exploitation.
Although hydrogen peroxide (H2O2) it is generally acknowledged Green Oxidant, oxidized byproduct only has water.But due to H2O2Pole is not
Stablize, heat, light, rough surface, heavy metal and other impurity can decompose, and have corrosivity, in packaging, storage, transport
Take special safety measure.Therefore, by H2O2It applies on the spot, or by H2O2Production technology with use H2O2Downstream process is mutually tied
It closes, just can more effectively utilize this chemical products.Utilize H2And O2H can directly be synthesized2O2, and atom utilization reaches
100%, and then people want to utilize H2And O2Carry out fabricated in situ H2O2Organic Ingredients is reoxidized to solve directly to utilize H2O2Cost
And safety problem.Since Pt, Pd, Au etc. are H2And O2Synthesize H2O2Active principle, loaded there are many document patent report
The in-situ preparation H on titanium silicalite material2O2Research for organic matter selective oxidation reaction.Such as, Meiers R. etc.
(J.Catal., 1998,176:376-386) studies propylene gas-phase epoxidation using Pt-Pd/TS-1 as catalyst；
US6867312B1 and US6884898B1 etc. has also carried out the research of this respect.Noble-metal-supported is former on titanium silicalite material
Position generates H2O2Although method mild condition, selectivity good (can reach 95% or more) for organic matter selective oxidation, bear
The titanium silicalite material catalyst activity of supported noble metal is lower, and stability is poor.
Summary of the invention
The purpose of the present invention is to provide a kind of noble metal modified titaniums for having special physical chemical characteristics using agent preparation is drawn off
The method of si molecular sieves.
Inventor passes through to the Titanium Sieve Molecular Sieve such as amidoxime inactivated under the Titanium Sieve Molecular Sieve especially alkaline environment of inactivation
Physico-chemical property after changing catalyst generation permanent deactivation is characterized, it is found that its crystalline framework keeps completely, to be subject to substantially
It utilizes.Inventor, it has furthermore been found that in the preparation process of Titanium Sieve Molecular Sieve, can use the titanium of inactivation by a large amount of research
Silicalite molecular sieve catalyst (the cyclohexanone oximate of the titanium-silicon molecular sieve catalyst of permanent deactivation such as inactivation especially under alkaline condition
Catalyst is as primary raw material), it (is successively handled using acid, alkali etc. in conjunction with heat treatment and roasting etc. by specific preparation step
Step), the excellent molecular sieve of catalytic oxidation performance can be retrieved, and the molecular sieve prepared has special materialization special
Sign.
To realize foregoing purpose, the first aspect of the present invention, the present invention provides a kind of modified with noble metals Titanium Sieve Molecular Sieve,
The molecular sieve includes: precious metal element, titanium elements, element silicon and oxygen element, wherein the Kong Rong of the molecular sieve is in 0.3cm3/g
More than, total specific surface area is in 200m2/ g or more, external surface area is in 30m2/ g or more, and the ratio of the total specific surface area of external surface area Zhan
For 7-55%；The molecular sieve is in 25 DEG C, P/P0=0.10 and adsorption time be the benzene adsorbance that measures under conditions of 1 hour
It is at least 75mg/g molecular sieve, N2The lower micropore size with 0.9-1.5nm range of Static Adsorption test is distributed；The noble metal
For one of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au or a variety of；The urface silicon titanium of the molecular sieve is not less than body phase
Silicon titanium ratio, molar ratio of the silicon titanium than referring to silica and titanium oxide.
The second aspect of the present invention, the present invention provides a kind of preparation method of molecular sieve of the present invention, this method
Include:
(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, and the acid solution contained
Oxide and nitric acid；
(2) the second heat is carried out after mixing first solid, titanium source, noble metal source in the presence of aqueous solvent with alkali source
Processing.
The third aspect of the present invention, the present invention provides molecular sieve of the invention answering in catalytic hydrocarbon direct oxidation reaction
With.
According to the fourth aspect of the invention, the present invention provides a kind of methods of alkene direct oxidation, this method comprises: 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 the bright preparation method is prepared.
Of the invention has its benzene adsorbance of the modified with noble metals Titanium Sieve Molecular Sieve of special physical chemical characteristics structure higher, table
Face silicon titanium is than such as being used for not less than body phase silicon titanium ratio and advantage that the micropore size with 0.9-1.5nm range is distributed
The reaction that ring molecule, olefin hydrocarbon molecules are participated in or generated, can obtain better catalytic effect.I.e. due to material of the invention its
Benzene adsorbance is higher, and urface silicon titanium is not less than body phase silicon titanium ratio and the micropore size with 0.9-1.5nm range is distributed, and is urging
Change and is conducive to reactants and products molecule (such as aromatic compound) in reaction, the diffusion of olefin hydrocarbon molecules, to aromatic hydrocarbon chemical combination
The catalytic oxidation that the molecules such as object, ring class hydrocarbon compound and olefin hydrocarbon molecules participate in is particularly advantageous.
The method for preparing modified with noble metals Titanium Sieve Molecular Sieve of the invention can be prepared with special spy of the invention
The modified with noble metals Titanium Sieve Molecular Sieve of sign structure, such as benzene adsorbance are higher, and urface silicon titanium is not less than body phase silicon titanium ratio and tool
There is the micropore size of 0.9-1.5nm range to be distributed.And method of the invention obtains the titanium-silicon molecular sieve catalyst of inactivation
It utilizes, turns waste into wealth.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
As previously mentioned, the molecular sieve includes: noble metal member the present invention provides a kind of modified with noble metals Titanium Sieve Molecular Sieve
Element, titanium elements, element silicon and oxygen element, wherein the Kong Rong of the molecular sieve is in 0.3cm3/ g or more, total specific surface area exist
200m2/ g or more, external surface area is in 30m2/ g or more, and the ratio of the total specific surface area of external surface area Zhan is 7-55%；The molecule
Sieve is in 25 DEG C, P/P0=0.10 and adsorption time be 1 hour under conditions of the benzene adsorbance that measures be at least 75mg/g molecule
Sieve, N2The lower micropore size with 0.9-1.5nm range of Static Adsorption test is distributed；The noble metal be Ru, Rh, Pd, Re,
One of Os, Ir, Pt, Ag and Au or a variety of；The urface silicon titanium of the molecular sieve is not less than body phase silicon titanium ratio, the silicon titanium
Than the molar ratio for referring to silica and titanium oxide.
In the present invention, the urface silicon titanium is measured using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses X
Ray fluorescence spectrometry measurement.
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 method.
In the present invention, the Kong Rong of molecular sieve and aperture respectively refer to pore volume and bore dia in molecular sieve, this is this field
Known to technical staff, do not repeat herein.
Modified with noble metals Titanium Sieve Molecular Sieve according to the present invention, the Kong Rongwei 0.3-0.5cm of the preferably described molecular sieve3/ g,
Preferably 0.31-0.42cm3/g；Total specific surface area is 200-450m2/ g, preferably 300-420m2/g；External surface area is 30-
150m2/ g, preferably 35-80m2/g；The ratio of the total specific surface area of external surface area Zhan is 10-35%, preferably 10-15%；It is described
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 100mg/g points
Son sieve, preferably 100-130mg/g molecular sieve；The ratio of the total micropore size abundance of the micropore size Zhan of 0.9-1.5nm range
>=5%；It is preferred that the noble metal is one of Pd, Ag, Au and Pt or a variety of.
Aforementioned modified with noble metals Titanium Sieve Molecular Sieve according to the present invention, the micropore hole of the modified with noble metals Titanium Sieve Molecular Sieve
(such as the aperture of MFI topological structure molecular sieve is attached in 0.55nm in addition to there is typical micro porous molecular sieve within the scope of 0.4-0.7nm for diameter
Outside pore-size distribution specific to closely), it is also distributed within the scope of 0.9-1.5nm.It is necessary to be noted that if in 0.9-
Within the scope of 1.5nm micropore size distribution the total micropore size abundance of Zhan ratio < 1% when, then the pore size distribution of this partial pore is neglected
Slightly disregard, that is, thinks to be distributed within the scope of 0.9-1.5nm without micropore, this is known to those skilled in the art.Therefore, this hair
It is bright described in N2The lower micropore size with 0.9-1.5nm range of Static Adsorption test refers within the scope of 0.9-1.5nm
Ratio > 1% of the micropore size distribution total micropore size abundance of Zhan.
, according to the invention it is preferred to the ratio of the micropore size distribution total micropore size abundance of Zhan within the scope of 0.4-0.7nm
Example≤95%, ratio >=5% of the micropore size distribution total micropore size abundance of Zhan within the scope of 0.9-1.5nm；More preferably
, the ratio of the micropore size distribution total micropore size abundance of Zhan within the scope of 0.9-1.5nm is 8-20%.In the present invention,
The test method of micropore size is well known to those skilled in the art, and such as uses N2The test of the methods of Static Adsorption.
The ratio of the total micropore size abundance of the micropore size Zhan of 0.9-1.5nm range is counted as follows in the present invention
It calculates: [the quantity of the micropore size of 0.9-1.5nm range/(quantity of the micropore size of 0.9-1.5nm range)+(0.4-0.7nm
The quantity of micropore size in range)] × 100%.
Molecular sieve according to the present invention, preferably element silicon: titanium elements: the molar ratio of precious metal element is 100:(0.1-
10): (0.01-5), more preferable element silicon: titanium elements: the molar ratio of precious metal element is 100:(0.2-5): (0.2-2.5), into
The preferred element silicon of one step: titanium elements: the molar ratio of precious metal element is 100:(1-4): (0.5-2.5).
Modified with noble metals Titanium Sieve Molecular Sieve according to the present invention, it is preferable that the urface silicon titanium and the body phase silicon titanium
The ratio of ratio is 1.2 or more；It is highly preferred that the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5；Further
Preferably, the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.5-4.5.
Aforementioned modified with noble metals Titanium Sieve Molecular Sieve of the invention has benzene adsorbance higher；Urface silicon titanium is not less than body phase
The advantages such as silicon titanium ratio and the micropore size distribution with 0.9-1.5nm range, the present invention is to aforementioned noble metal modified titanium silicon molecule
The preparation method of sieve is without particular/special requirement, as long as the modified with noble metals Titanium Sieve Molecular Sieve with above structure can be prepared i.e.
Can, according to a preferred embodiment of the present invention, present invention use draws off agent and prepares aforementioned noble metal modified titanium silicon molecule
Sieve.
Therefore, as previously mentioned, the present invention provides a kind of preparations of modified with noble metals Titanium Sieve Molecular Sieve of the present invention
Method, this method comprises:
(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, and the acid solution contained
Oxide and nitric acid；
(2) the second heat is carried out after mixing first solid, titanium source, noble metal source in the presence of aqueous solvent with alkali source
Processing.
In the present invention, the agent that draws off of the reaction unit using Titanium Sieve Molecular Sieve as catalyst can be from various uses
Titanium Sieve Molecular Sieve is as the agent that draws off drawn off in the device of catalyst, such as can be from using Titanium Sieve Molecular Sieve as catalyst
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 catalyst reaction unit draw off agent can be Ammoximation reaction device draw off agent, hydroxylating device unloads
Agent and epoxidation reaction device draw off one of agent or a variety of out, are specifically as follows unloading for cyclohexanone oxamidinating reaction unit
Out agent, phenol hydroxylation reaction unit draw off agent and propylene ring oxidation reaction device draw off one of agent or a variety of, it is excellent
It is the catalyst that inactivation is reacted under alkaline environment that agent is drawn off described in choosing, therefore, draws off agent for the present invention is preferably described as hexamethylene
Ketone oxamidinating reaction unit draws off agent (such as the titanium-silicon molecular sieve TS-1 of inactivation, powdery, partial 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 where initial activity 50% again, (initial activity refers under identical reaction conditions, catalyst
Average activity within 1h.Such as practical cyclohexanone oximeization reaction in, the initial activity of general catalyst to reach 95% with
On).
The activity for drawing off agent is different according to its source.Generally, 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
Active 50% when fresh is sieved 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.
In the present invention, it is described draw off agent can inactivation from industrial deactivator or after being reacted in the lab
Catalyst.
Certainly, from the angle of preparation effect, method of the invention can also using fresh Titanium Sieve Molecular Sieve as raw material,
Only will not be suitable for cost control angularly, method provided by the invention, mainly using the Titanium Sieve Molecular Sieve of inactivation as
Raw material is turned waste into wealth, 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 guaranteeing, in phase
In same device, under identical reaction condition, the activity for drawing off agent is lower than the activity of fresh catalyst, and as of the invention draws off
Agent.As previously mentioned, the activity for drawing off agent is lower than active the 50% of fresh catalyst in preferred situation.
In the present invention, by cyclohexanone oxamidinating reaction unit draw off agent for, it is described activity by the following method measure:
Take TS-1 molecular sieve (by " Zeolites, the preparation of method described in 1992, Vol.12:943~950 ", TiO2
Mass percentage be 2.1%) be placed in slurry bed reactor of the 100mL with continuous feed and membrane separation device, stirring
With the speed of 5.7mL/h the mixture of water and the hydrogen peroxide of 30wt% being added under state, (volume ratio of water and hydrogen peroxide is
10:9), with the speed of 10.5mL/h be added cyclohexanone and the tert-butyl alcohol mixture (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 1 hour to product sampling gas chromatography to liquid phase
Composition is analyzed, and the conversion ratio of cyclohexanone and the activity as Titanium Sieve Molecular Sieve are calculated using the following equation.Cyclohexanone
Mole of cyclohexanone that is added of conversion ratio=[(mole of the unreacted cyclohexanone of the mole-of the cyclohexanone of addition)/
Amount] × 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: by noble metal source and alkali source containing water-soluble
It is mixed to get mixed solution in the presence of agent, carries out described second after the mixed solution, titanium source are mixed with first solid
Heat treatment.
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 where no specified otherwise, heat treatment is usually in the case where sealing spontaneous
It is carried out under pressure.
A preferred embodiment of the invention, the temperature of the preferably first heat treatment are 10-200 DEG C, more preferably
50-180 DEG C, further preferably 60-180 DEG C；First heat treatment time be 0.5-36h, preferably 1-24h, more preferably
1-12h；
Stage (1), stage (2) and stage (3) are successively undergone in second heat treatment, the stage (1) 80-150 DEG C, preferably exist
110-140 DEG C, more preferably 120-140 DEG C, further preferably 130-140 DEG C processing 6-72 hours, preferably 6-8 hours, rank
Section (2) is cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, and preferably 1-5 hours, the stage (3) was warming up to 120-
200 DEG C, preferably 140-180 DEG C, 160-170 DEG C more preferable, reprocessing 6-96 hours, preferably 12-20 hours.
A preferred embodiment of the invention, preferably stage (1) and stage (3) meet one of the following conditions
Or both:
Condition 1: the temperature in stage (1) is lower than the temperature of stage (3), it is preferable that the temperature in stage (1) is than the stage (3)
Temperature is 10-50 DEG C low, 20-40 DEG C preferably low；
Condition 2: the time in stage (1) is less than the time of stage (3), it is preferable that the time in stage (1) is than the stage (3)
Time is 5-24 hours short, preferably 6-12 hours short.
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.
According to the method for the present 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, raising the temperature 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
To stage (2) temperature rate of temperature fall can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 5-10 DEG C/min.
By stage (2) temperature to stage (3) temperature heating rate can be 1-50 DEG C/min, preferably 2-40 DEG C/min, more preferably
For 5-20 DEG C/min.
With the method for the invention it is preferred to method of the invention further include: 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
Include: 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: that 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.
In the present invention, the primary solvent of the acid solution is water, can also be according to needing to be added other solvents aids.
With the method for the invention it is preferred to the concentration of peroxide described in the acid solution and nitric acid be respectively >
0.1mol/L, more preferably >=1mol/L, further preferred 2-15mol/L, more preferably 2-6mol/L.Point being so prepared
Son sieves its Kong Rong, specific surface area, urface silicon titanium and body phase silicon titanium ratio, benzene adsorbance and the micropore pore size distribution in 0.9-1.5nm
Deng feature become apparent from.
With the method for the invention it is preferred to which the peroxide is selected from hydrogen peroxide, tert-butyl hydroperoxide, hydrogen peroxide
One of isopropylbenzene, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid are a variety of.
With the method for the invention it is preferred to which the mass ratio for drawing off agent, titanium source, noble metal source, alkali source and water is 100:(0.1-
10): (0.1-10): (0.5-50): (20-1000), the mass ratio for preferably drawing off agent, titanium source, noble metal source, alkali source and water are
100:(0.5-10.0): (0.5-2.0): (1-20): (100-800).
With the method for the invention it is preferred to draw off agent and acid mass ratio be 100:(0.005-50), preferably draw off agent with
The mass ratio of acid is 100:(1-15), for acid in terms of nitric acid, 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 structure
2), the Titanium Sieve Molecular Sieve (such as Ti-Beta) of BEA structure, the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structure, 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 structure, TUN structure
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 structure 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 sieve.
According to the method for the present invention, the titanium source can be the conventional selection of this field, for the present invention, the preferably described titanium
Source is selected from inorganic titanium salt and/or organic titanate.
In the present invention, the inorganic titanium salt is selected from various hydrolyzable titanium salts, such as can be selected from TiX4、TiOX2Or Ti
(SO4)2Contain titanium salt etc. various forms of, X is halogen in formula, preferably chlorine, wherein the preferred inorganic titanium salt is selected from TiCl4、
Ti(SO4)2And TiOCl2One of or it is a variety of.
In the present invention, it is M that the organic titanate, which preferably has structural formula,4TiO4Organic titanate, wherein M is preferred
For the alkyl with 1-4 carbon atom, and 4 M can be identical or different, and it is metatitanic acid isopropyl that the preferably described organic titanate, which is selected from,
One of ester, metatitanic acid n-propyl, butyl titanate and tetraethyl titanate are a variety of.
Using in a specific embodiment of the present invention is titanium sulfate, butyl titanate as example, but is not therefore limited
The scope of the present invention processed.
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 cation is the alkali of alkali or alkaline earth metal, such as can for sodium hydroxide,
Potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide etc., organic alkali source can be urea, aliphatic amination
Close one of object, aliphatic alcohol amine compounds and quaternary ammonium alkali cpd or a variety of.
In the present invention, the quaternary ammonium base can be various organic level Four ammonium alkali, and the aliphatic amine can be various NH3In
At least one hydrogen replaced by aliphatic alkyl (preferably alkyl) after the compound that is formed, the aliphatic hydramine can be each
Kind NH3In at least one hydrogen replaced by the aliphatic alkyl (preferably alkyl) of hydroxyl after the compound that is formed.
Specifically, the quaternary ammonium base can be the quaternary ammonium base as shown in Formula II, and the aliphatic amine can indicate for formula III
Aliphatic amine, the aliphatic hydramine can for 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 R8It respectively can be 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, tert-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 of ethamine, n-butylamine, butanediamine and hexamethylene diamine or a variety of
(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 of monoethanolamine, diethanol amine and triethanolamine or a variety of.
According to a preferred embodiment of the present invention, the preferably described alkali source is sodium hydroxide, ammonium hydroxide, ethylenediamine, just
Butylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanol amine, triethanolamine, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide
One of or it is a variety of.
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, pH > 9 of more preferable aqueous slkali.
With the method for the invention it is preferred to which 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, noble metal hydroxide
With one of the complex compound of noble metal or a variety of, 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 chloride, palladium nitrate, ammonium nitrate palladium, sal-ammoniac palladium, acid chloride, palladium dydroxide, the complex compound of palladium, palladium acetate and levulinic
One of ketone palladium is a variety of.
Use palladium chloride, palladium acetylacetonate, acetic acid platinum of the invention as exemplary illustration in an embodiment of the present invention
Advantage.
It is described to draw off the process that agent is mixed with beating processing with acid solution and be in of the invention one more preferable embodiment
It is carried out under acid solution counterflow condition, the molecular sieve obtained with this condition has more obvious distinctive physical chemical characteristics.
, according to the invention it is preferred to which method of the invention further includes the step of the recovery product from the material that step (2) are 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 0.5-6 hours in air atmosphere 3-
It carries out within 12 hours.
The benzene adsorbance of the molecular screen material obtained due to molecular screen material of the present invention and the method for the present invention is higher, surface silicon
Titanium is than being not less than body phase silicon titanium ratio and the micropore size with 0.9-1.5nm range is distributed, and is conducive to react in catalysis reaction
The catalysis oxidation that object and product molecule especially participate in the molecules such as aromatic hydrocarbon compound, ring class hydrocarbon compound, olefin(e) compound
React particularly advantageous.
The molecular sieve obtained the present invention also provides molecular sieve of the invention and the method for the present invention is in the direct oxygen of catalytic hydrocarbon
Change the application in reaction.In the oxidation reaction, such as in the reaction of preparing epoxypropane by epoxidation of propene (PO), reaction product
The selectivity and catalytic activity of PO significantly improves.
According to the fourth aspect of the invention, the present invention provides a kind of methods of alkene direct oxidation, this method comprises: 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 the bright preparation method is prepared.
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: that 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 pass through the amount of the volume of the alkene of unit catalyst that is, in the unit time.
The molar ratio 0.1-10:1 of oxygen and alkene in more preferable oxygen-containing gas.
Optional wider range of the type of alkene, such as can be propylene.
According to the method for the present invention, in the oxygen-containing gas other than containing oxygen, the gas such as hydrogen, nitrogen can also be contained
Body also contains hydrogen and nitrogen in the preferably described oxygen-containing gas, and the preferably molar ratio of oxygen, hydrogen and nitrogen is 0.1-10:
0.1-10:0.5-100.That is, preferred alkenes, oxygen, hydrogen and nitrogen molar ratio be 1:0.1-10:0.1-10:0.5-100.
According to a preferred embodiment of the present invention, 0.05-2g (such as 0.5g) catalyst is added to containing 1-
It is 1:0.1-10:0.1-10:0.5-100 (such as 1:1:1:7) according to molar ratio in the reaction vessel of 500ml (such as 80ml) methanol
The diluent gas such as alkene, oxygen, hydrogen and nitrogen are passed through, at 0-80 DEG C of temperature (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 the content being not intended to limit the present invention.
In comparative example and embodiment, agents useful for same is commercially available chemically pure reagent.
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 sieve (by " Zeolites, the preparation of method described in 1992, Vol.12:943~950 ", TiO2
Mass percentage be 2.1%) be placed in 100mL band continuous feed and membrane separation device slurry bed reactor in, stirring shape
Under state with the speed of 5.7mL/h be added water and the hydrogen peroxide of 30wt% mixture (volume ratio of water and hydrogen peroxide is 10:
9) mixture (volume ratio of cyclohexanone and the tert-butyl alcohol is 1:2.5) of cyclohexanone and the tert-butyl alcohol, is added with the speed of 10.5mL/h,
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 maintains 80 DEG C, after stable reaction every 1 hour to product sampling gas chromatography to the composition of liquid phase into
Row analysis, is calculated using the following equation the conversion ratio of cyclohexanone and the activity as Titanium Sieve Molecular Sieve.The conversion of cyclohexanone
Rate=[(mole of the unreacted cyclohexanone of the 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
About 168 hours, after yclohexanone conversion ratio drops to 50% by initial 99.5%, roasting regeneration mode was used after isolating catalyst
It regenerates (being roasted 4 hours in air atmosphere at 570 DEG C), then proceedes to for being repeated in cyclohexanone oxamidinating reaction
The step for, until the activity after regeneration is lower than the 50% of initial activity, the ammonia deuteration catalyst sample at this moment inactivated is as this
Invention draws off agent, successively obtains drawing off agent SH-1 (activity is 50%) according to preceding method, SH-2 (activity is 40%), SH-3
(activity is 25%), SH-4 (activity is 10%).
In each embodiment and comparative example, X-ray diffraction (XRD) crystalline phase figure of sample is penetrated in SiemensD5005 type X-
It is measured on line diffractometer, with sample and authentic specimen in the diffraction that 2 θ are the five fingers diffractive features peak between 22.5 ° -25.0 °
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 company 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 spectra
It is measured on instrument, specific data are shown in Table 2.
In the present invention, urface silicon titanium uses the ESCALab250 type x-ray photoelectron of Thermo Scientific company
Energy disperse spectroscopy measurement, body phase silicon titanium ratio are measured using Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometer.
Comparative example 1
This comparative example illustrates the conventional Titanium Sieve Molecular Sieve sample for not containing noble metal for the preparation of silicon source hydrothermal crystallizing using estersil
The process of product.
Tetraethyl orthosilicate, isopropyl titanate are mixed with tetrapropylammonium hydroxide, and appropriate distilled water is added and is stirred,
A mole composition is tetraethyl orthosilicate: isopropyl titanate: tetrapropylammonium hydroxide: water=100:5:10:200 among reaction system,
Wherein tetraethyl orthosilicate is with SiO2Meter；1.0h is hydrolyzed at normal pressure and 60 DEG C, then stirs 3h at 75 DEG C, then by mixed liquor
It is put into stainless steel sealing reaction kettle, 3d is placed in 170 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product；This is mixed
Object filtering 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 Titanium Sieve Molecular Sieve of hot direct crystallization, XRD crystal phase are MFI structure.
Comparative example 2
This comparative example illustrates that routine prepares the Titanium Sieve Molecular Sieve sample containing noble metal using estersil for silicon source hydrothermal crystallizing
Process.
Tetraethyl orthosilicate, palladium chloride, isopropyl titanate are mixed with tetrapropylammonium hydroxide, and appropriate distilled water is added and stirs
Mixing is mixed, a mole composition is tetraethyl orthosilicate: isopropyl titanate: palladium chloride: tetrapropylammonium hydroxide among reaction system: 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
Then mixed liquor is put into stainless steel sealing reaction kettle by 3h, place 3d in 170 DEG C of at a temperature of constant temperature, obtain crystallization product
Mixture；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 of temperature
Degree is lower to roast 3h, obtains the Titanium Sieve Molecular Sieve of hydro-thermal direct crystallization, and XRD crystalline phase figure and comparative example 1 are unanimously MFI structure.
Comparative example 3
This comparative example illustrates the process of the Titanium Sieve Molecular Sieve sample dip loading noble metal prepared using comparative example 1.
Titanium Sieve Molecular Sieve prepared by comparative example 1 is mixed with palladium chloride aqueous solution, wherein Titanium Sieve Molecular Sieve and palladium chloride with
And the mass ratio of water is 10:2:25, stirs 6h at normal pressure and 60 DEG C, then filters this mixture, 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 noble metal must be loaded, XRD crystal 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 metal.
Agent SH-2 will be drawn off to mix with palladium chloride aqueous solution, wherein the mass ratio of Titanium Sieve Molecular Sieve and palladium chloride and 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 Titanium Sieve Molecular Sieve of noble metal must be loaded, XRD crystal phase is MFI structure.
Comparative example 5
This comparative example illustrates to utilize the process for drawing off agent SH-3 dip loading noble metal.
SH-3 is mixed with palladium chloride aqueous solution, wherein the mass ratio of Titanium Sieve Molecular Sieve and palladium chloride and water is 10:
1:50 stirs 12h at normal pressure and 40 DEG C, then filters this mixture, 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 noble metal must be loaded, XRD crystal phase is MFI structure.
Comparative example 6
This comparative example illustrates to utilize the process for drawing off agent SH-4 dip loading noble metal.
SH-4 is mixed with palladium chloride aqueous solution, wherein the mass ratio of Titanium Sieve Molecular Sieve and palladium chloride and water is 10:
2:20 stirs 3h at normal pressure and 50 DEG C, then filters this mixture, is washed with water, and in 110 DEG C of dry 60min, and in
550 DEG C of roasting temperature 3h, must load the titanium silicalite material of noble metal, and XRD crystal phase is 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 by the cyclohexanone oximate catalyst SH-2 of inactivation and acid solution (aqueous solution containing nitric acid and hydrogen peroxide, nitric acid
Concentration with hydrogen peroxide is 4mol/L) it is mixed with beating, mixed serum is then mixed to processing 12h at 80 DEG C；Gu
It will mixing after mixing solid, noble metal source palladium chloride, titanium source titanium sulfate with sodium hydrate aqueous solution (pH 12) after liquid separation
Liquid is put into stainless steel sealing reaction kettle and mixture is then cooled to 30 DEG C of experience second-orders in 140 DEG C of experience first stage 6h
Section stop 2h after, continue seal reaction kettle in 170 DEG C at a temperature of experience phase III 12h (wherein, extremely by room temperature
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), wherein quality of material group
Cyclohexanone oximate catalyst as inactivation: titanium source: noble metal source: acid: alkali: water=100:1:1:10:5:250.Gained is produced
Object filtering is washed with water, and in 110 DEG C of drying 120min, then in 550 DEG C of roasting temperature 3h, obtains molecular sieve, XRD
Crystalline phase figure and comparative example 1 are consistent, and what is illustrated is the Titanium Sieve Molecular Sieve 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 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 palladium chloride aqueous solution, wherein the mass ratio of Titanium Sieve Molecular Sieve and palladium chloride and water is 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 noble metal, and XRD crystal phase is MFI structure.
Embodiment 2
This example demonstrates that method provided by the invention and product.
At normal temperatures and pressures, the cyclohexanone oximate catalyst SH-3 of inactivation and acid solution (are first contained into nitric acid and peroxidating
The concentration of the aqueous solution of hydrogen, nitric acid and ethylbenzene hydroperoxide is respectively 2mol/L, 6mol/L) it is mixed with beating, then by mixing slurry
Processing 1h is mixed in liquid at 60 DEG C；After separation of solid and liquid by solid, noble metal source palladium acetylacetonate, titanium source butyl titanate with
Mixed liquor is put into stainless steel sealing reaction kettle after tetrapropylammonium hydroxide solution (pH 10) mixing, in 130 DEG C of experience the
One stage 8h continues in sealing reaction kettle after mixture is then cooled to 50 DEG C of experience second stage stop 5h in 170 DEG C
At a temperature of undergo the phase III 16h (to be wherein, 1 DEG C/min by the heating rate of room temperature to first stage temperature, by the
The rate of temperature fall of one phase temperature to second stage temperature is 10 DEG C/min, by second stage temperature to the liter of phase III temperature
Warm rate is 20 DEG C/min), wherein quality of material group becomes the cyclohexanone oximate catalyst of inactivation: titanium source: noble metal source: acid:
Alkali: water=100:2:0.5:15:15:200.Then recovery product according to the method for embodiment 1 obtains Titanium Sieve Molecular Sieve, XRD
Crystalline phase figure and comparative example 1 are consistent.
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 and acid solution (are first contained into nitric acid and peroxidating
The concentration of the aqueous solution of hydrogen, nitric acid and tert-butyl hydroperoxide is respectively 6mol/L, 2mol/L) it is mixed with beating, it then will mixing
Processing 3h is mixed in slurries at 180 DEG C；By solid, noble metal source acetic acid platinum, titanium source titanium sulfate and hydrogen-oxygen after separation of solid and liquid
Mixed liquor stainless steel sealing reaction kettle is put into after change sodium water solution (pH 14) mixing to connect in 140 DEG C of experience first stage 6h
Mixture is cooled to after 40 DEG C of experience second stage stop 1h, continue in sealing reaction kettle in 160 DEG C at a temperature of pass through
Going through phase III 12h (is wherein, 5 DEG C/min by the heating rate of room temperature to first stage temperature, by first stage temperature
Rate of temperature fall to second stage temperature is 5 DEG C/min, is 5 by the heating rate of second stage temperature to phase III temperature
DEG C/min), wherein quality of material group becomes the cyclohexanone oximate catalyst of inactivation: titanium source: noble metal source: acid: alkali: water=
100:10:2:10:15:600.Then recovery product according to the method for embodiment 1 obtains molecular sieve, XRD crystalline phase figure and comparison
Example 1 is consistent.
Embodiment 4
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 3, the difference is that the cyclohexanone oximate of inactivation is urged in quality of material composition
Agent: acid=100:5, the XRD crystalline phase figure and comparative example 1 of gained sample are consistent.
Embodiment 5
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 3, the difference is that the cyclohexanone oximate of inactivation is urged in quality of material composition
Agent: acid=100:100, the XRD crystalline phase figure and comparative example 1 of gained sample are consistent.
Embodiment 6
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 roasted and then carried out subsequent
Mashing, heat treatment process, wherein the condition of roasting includes: to roast 4h at 570 DEG C in air atmosphere, the XRD of gained sample
Crystalline phase figure and comparative example 1 are consistent, and the XRD crystalline phase figure and comparative example 1 of gained sample are consistent.
Embodiment 7
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 figure Yu comparative example 1 of gained sample are consistent.
Embodiment 8
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 at 60 DEG C, solid is obtained after separation of solid and liquid, by noble metal source acetylacetone,2,4-pentanedione by slurry for mixed serum
Palladium and tetrapropylammonium hydroxide solution (pH 10) are mixed to get mixed liquor, after solid, butyl titanate, mixed liquor are mixed
It is put into stainless steel sealing reaction kettle, 12h is handled at 150 DEG C, wherein quality of material group becomes the cyclohexanone oximate catalysis of inactivation
Agent: titanium source: noble metal source: acid: alkali: water=100:2:0.5:15:15:200.Then recovery product according to the method for embodiment 1,
Molecular sieve containing noble metal is obtained, XRD crystalline phase figure and comparative example 1 are consistent.
Embodiment 9
Molecular sieve is prepared according to the method for embodiment 1, unlike, the crystallization temperature of phase III is also 140 DEG C.Then
Recovery product according to the method for embodiment 1, obtains molecular sieve containing noble metal, and XRD crystalline phase figure and comparative example 1 are consistent.
Embodiment 10
Molecular sieve is prepared according to the method for embodiment 1, unlike, the crystallization temperature of first stage is 110 DEG C.Then it presses
According to the method recovery product of embodiment 1, molecular sieve containing noble metal is obtained, XRD crystalline phase figure and comparative example 1 are consistent.
Embodiment 11
Molecular sieve is prepared according to the method for embodiment 1, unlike, the crystallization time of first stage is 12h, second stage
It is to be cooled to 70 DEG C of stop 2h.Then recovery product according to the method for embodiment 1 obtains molecular sieve containing noble metal, XRD crystal phase
Figure is consistent with comparative example 1.
Table 1
From the results shown in Table 1: its Kong Rong of molecular sieve of preferred process of the present invention preparation is greater than 0.3cm3/ g, benzene are inhaled
Attached amount is greater than 75mg/g, and total specific surface area is 200-450m2/ g, wherein external surface area 30-150m2/ g, and external surface area accounts for
The ratio of total specific surface area is between 10%-35%；The preferred process of the present invention preparation molecular sieve its in 0.9-1.5nm range
The ratio of the total micropore size abundance of micropore size Zhan is > 5%.
It can also be seen that from the result of table 1:
Molecular sieve its relative crystallinity of preferred process of the present invention preparation, Kong Rong, total specific surface area, external surface area,
0.9-1.5nm pore-size distribution, urface silicon titanium and body phase silicon titanium ratio value, the data such as benzene adsorbance fully meet product of the present invention
Whole features.Opposite, either comparative example 1 utilizes the Titanium Sieve Molecular Sieve without containing noble metal that estersil is silicon source preparation, right
Ratio 2 utilizes the titanium prepared such as comparative example 1 using the Titanium Sieve Molecular Sieve containing noble metal that estersil is silicon source preparation, comparative example 3
Si molecular sieves carried noble metal and the Titanium Sieve Molecular Sieve containing noble metal or comparative example 4-6 that prepare are using drawing off agent load
The titanium silicalite material and comparative example 7 that noble metal obtains draw off the titanium silicalite material that the acid treated carried noble metal of agent obtains, opposite
The data such as crystallinity, Kong Rong, total specific surface area, external surface area, 0.9-1.5nm pore-size distribution, benzene adsorbance are unable to satisfy this
Whole features of invention product.There was only 0.264cm as its hole of the molecular sieve of comparative example 1 holds3/ g, external surface area 24m2/ g, and appearance
The ratio of the total specific surface area of area Zhan is 5% or so.
Testing example
0.5g catalyst is added in the closed tank reactor containing 50ml methanol, is 1:1 then according to molar ratio:
The ratio of 1:7 is passed through propylene, oxygen, hydrogen and nitrogen (diluent gas), and in temperature 50 C, pressure 1.5MPa, alkene air speed is
10h-1Under conditions of, carry out alkene direct oxidation reaction.Propylene conversion and PO selectivity of reaction time 4h etc. the results are shown in Table
2。
Table 2
Wherein, propylene conversion and PO selectivity are calculated according to following formula:
Propylene conversion=(amount for participating in the substance of the propylene of reaction/amount of the substance for the propylene being always added) * 100%；
PO selectivity=(amount of amount/gross product substance of the substance for the PO that reaction generates) * 100%.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
Claims (28)
1. a kind of modified with noble metals Titanium Sieve Molecular Sieve, which is characterized in that the molecular sieve includes: precious metal element, titanium elements, silicon member
Element and oxygen element, wherein the Kong Rong of the molecular sieve is in 0.3cm3/ g or more, total specific surface area is in 200m2/ g or more, outer surface
Product is in 30m2/ g or more, and the ratio of the total specific surface area of external surface area Zhan is 7-55%；The molecular sieve is in 25 DEG C, P/P0=
0.10 and adsorption time be 1 hour under conditions of the benzene adsorbance that measures be at least 75mg/g molecular sieve, N2Static Adsorption is surveyed
The lower micropore size with 0.9-1.5nm range of examination is distributed, the total micropore size abundance of the micropore size Zhan of 0.9-1.5nm range
Ratio >=5%；The noble metal is one of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au or a variety of；Element silicon: titanium member
Element: the molar ratio of precious metal element is 100:(1-5): the urface silicon titanium of (0.2-2.5), the molecular sieve are not less than body phase silicon
The ratio of titanium ratio, the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5, and the silicon titanium ratio refers to silica and titanium oxide
Molar ratio.
2. molecular sieve according to claim 1, wherein the Kong Rongwei 0.3-0.5cm of the molecular sieve3/ g, total specific surface area
For 200-450m2/ g, external surface area 30-150m2The ratio of the total specific surface area of/g, external surface area Zhan is 10-35%；Described point
Son sieve is in 25 DEG C, P/P0=0.10 and adsorption time be 1 hour under conditions of the benzene adsorbance that measures be at least 100mg/g points
Son sieve；The noble metal is one of Pd, Ag, Au and Pt or a variety of.
3. molecular sieve according to claim 2, wherein the total micropore size distribution of the micropore size Zhan of 0.9-1.5nm range
The ratio of amount is 8-20%.
4. molecular sieve according to claim 1, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is
1.5-4.5。
5. the preparation method of molecular sieve described in a kind of any one of claim 1-4, this method comprises:
(1) agent will be drawn off to be mixed with beating with acid solution, obtained slurries is carried out first and are heat-treated, isolated first solid,
Wherein, described to draw off agent be that reaction unit using Titanium Sieve Molecular Sieve as catalyst draws off agent, and the acid solution contains peroxide
Compound and nitric acid；
(2) it is carried out at the second heat after mixing first solid, titanium source, noble metal source in the presence of aqueous solvent with alkali source
Reason；Stage (1), stage (2) and stage (3) are successively undergone in second heat treatment, the stage (1) 80-150 DEG C processing 6-72 hours,
Stage (2) is cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, and the stage (3) is warming up to 120-200 DEG C, reprocessing
6-96 hours.
6. preparation method according to claim 5, wherein the reaction unit using Titanium Sieve Molecular Sieve as catalyst
It draws off agent and draws off agent for Ammoximation reaction device.
7. preparation method according to claim 5 or 6, wherein step (2) carries out as follows: by noble metal source with
Alkali source is mixed to get mixed solution in the presence of aqueous solvent, after the mixed solution, titanium source are mixed with first solid
Carry out second heat treatment.
8. preparation method according to claim 5 or 6, wherein
The temperature of first heat treatment is 10-200 DEG C, and the time of the first heat treatment is 0.5-36h.
9. preparation method according to claim 5, wherein the temperature of stage (1) processing is 110-140 DEG C.
10. preparation method according to claim 8, wherein the temperature of stage (1) processing is 120-140 DEG C.
11. preparation method according to claim 8, wherein the temperature of stage (1) processing is 130-140 DEG C.
12. the preparation method according to any one of claim 9-11, wherein the time of stage (1) processing is that 6-8 is small
When.
13. preparation method according to claim 5, wherein (2) residence time in stage is 1-5 hours.
14. preparation method according to claim 5, wherein the stage (3) is warming up to 140-180 DEG C, and reprocessing 6-96 is small
When.
15. preparation method according to claim 5, wherein the stage (3) is warming up to 160-170 DEG C, and reprocessing 6-96 is small
When.
16. preparation method according to claim 14 or 15, wherein the time of stage (3) processing is 12-20 hours.
17. preparation method according to claim 5, wherein stage (1) and stage (3) meet one of the following conditions
Or both:
Condition 1: the temperature in stage (1) is lower than the temperature of stage (3)；
Condition 2: the time in stage (1) is less than the time of stage (3)；
Stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.
18. preparation method according to claim 17, wherein
Condition 1: the temperature in stage (1) is 10-50 DEG C lower than the temperature in stage (3)；
Condition 2: the time in stage (1) is 5-24 hours shorter than the time in stage (3).
19. preparation method according to claim 17, wherein
Condition 1: the temperature in stage (1) is 20-40 DEG C lower than the temperature in stage (3)；
Condition 2: the time in stage (1) is 6-12 hours shorter than the time in stage (3).
20. preparation method according to claim 5 or 6, wherein this method further include: mixed agent will be drawn off with acid solution
Before closing mashing, first draws off agent by described and roast.
21. preparation method according to claim 5 or 6, wherein draw off agent: titanium source: noble metal source: acid: alkali source: water
Mass ratio is 100:(0.1-10): (0.1-10): (0.005-50): (0.5-50): (20-1000), acid is in terms of nitric acid；The acid
In solution, the concentration of the peroxide and nitric acid is respectively > 0.1mol/L；The peroxide is selected from hydrogen peroxide, tertiary fourth
In base hydrogen peroxide, cumyl hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid
It is one or more.
22. preparation method according to claim 21, wherein the concentration of the peroxide and nitric acid be respectively >=
1mol/L。
23. preparation method according to claim 21, wherein the concentration of the peroxide and nitric acid is respectively 2-
15mol/L。
24. preparation method according to claim 5 or 6, wherein the Titanium Sieve Molecular Sieve is MFI structure, described to draw off agent
Activity be the Titanium Sieve Molecular Sieve when fresh active 50% or less.
25. preparation method according to claim 5 or 6, wherein
The alkali source is one of ammonia, aliphatic amine, aliphatic hydramine and quaternary ammonium base or a variety of；
The noble metal source is the nitric acid of the oxide of noble metal, the halide of noble metal, the carbonate of noble metal, noble metal
One of salt, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, the hydroxide of noble metal and complex compound of noble metal
Or it is a variety of, the noble metal is one of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au or a variety of；
The titanium source is selected from inorganic titanium salt and/or organic titanate.
26. preparation side described in any one of molecular sieve and claim 5-25 described in any one of claim 1-4
Application of the molecular sieve that method is prepared in catalytic hydrocarbon direct oxidation reaction.
27. a kind of method of alkene direct oxidation, this method comprises: using methanol as solvent, by alkene, oxygen-containing gas and catalyst
Contact, which is characterized in that the catalyst contains molecular sieve described in any one of claim 1-4 and claim 5-25
Any one of described in the molecular sieve that is prepared of preparation method.
28. according to the method for claim 27, wherein alkene is propylene, and the condition of contact includes: that 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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| CN101274765A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Noble metal-contained micropore titanium-silicon material and preparation thereof |
| CN102441430B (en) * | 2010-10-11 | 2013-06-12 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and alkene epoxidation method |
| CN103183355A (en) * | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Precious metal modification method of titanium silicalite molecular sieve |
| CN103896302A (en) * | 2012-12-28 | 2014-07-02 | 中国石油化工股份有限公司 | Silicon molecular sieve and preparation method thereof |
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| CN101274765A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Noble metal-contained micropore titanium-silicon material and preparation thereof |
| CN102441430B (en) * | 2010-10-11 | 2013-06-12 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and alkene epoxidation method |
| WO2012048527A9 (en) * | 2010-10-11 | 2013-08-01 | 中国石油化工股份有限公司 | Catalyst, preparation method therefor, and a method for epoxidating olefin |
| CN103183355A (en) * | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Precious metal modification method of titanium silicalite molecular sieve |
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