CN106915753A - Modified with noble metals HTS and its preparation method and application and a kind of method of alkene direct oxidation - Google Patents
Modified with noble metals HTS and its preparation method and application and a kind of method of alkene direct oxidation Download PDFInfo
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- CN106915753A CN106915753A CN201510983129.3A CN201510983129A CN106915753A CN 106915753 A CN106915753 A CN 106915753A CN 201510983129 A CN201510983129 A CN 201510983129A CN 106915753 A CN106915753 A CN 106915753A
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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 art, mainly there is provided a kind of modified with noble metals HTS and its preparation method and application, the molecular sieve includes：Precious metal element, titanium elements, element silicon and oxygen element, the pore volume of the molecular sieve is in 0.3cm3/ more than g, total specific surface area is in 200m2/ more than g, external surface area is in 30m2/ more than g, and external surface area account for total specific surface area ratio be 7-55%；The molecular sieve is in 25 DEG C, P/P0=0.10 and adsorption time be that the benzene adsorbance measured under conditions of 1 hour is at least 75mg/g molecular sieves, N2The lower micropore size with 0.9-1.5nm scopes of Static Adsorption test is distributed；The surface silicon titanium ratio of the molecular sieve is not less than body phase silicon titanium ratio.Present invention also offers a kind of method of alkene direct oxidation.Its benzene adsorbance of modified with noble metals HTS with special physical chemical characteristicses structure of the invention it is higher and with 0.9-1.5nm scopes micropore size distribution advantage, the reaction that ring molecule, olefin hydrocarbon molecules are participated in or generated for example is used it for, more preferable catalytic effect can be obtained.
Description
Technical field
The present invention relates to a kind of modified with noble metals HTS and its preparation method and application, more specifically to one
The method for preparing modified with noble metals HTS using the titanium-silicon molecular sieve catalyst of inactivation is planted, the invention further relates to a kind of alkene
The method of hydrocarbon direct oxidation.
Background technology
HTS, is molecular sieve that skeleton is made up of silicon, titanium, oxygen element, in petroleum refining and petrochemical industry
Have a extensive future.Wherein, TS-1 molecular sieves are that transition metal titanium is introduced into the framework of molecular sieve with ZSM-5 structures
A kind of novel titanosilicate with superior catalytic selective oxidation performance for being formed.
TS-1 not only catalysed oxidns with titanium, but also the shape-selective effect with ZSM-5 molecular sieve and excellent
Stability, commercial Application is successfully realized in cyclohexanone catalytic ammoxidation prepares the technique of cyclohexanone oxime.However, generally 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
Then cannot be by regenerating activity recovery (activity after regeneration is less than the 50% of initial activity).HTS loses under alkaline environment
After particularly oximes catalyst TS-1 living occurs permanent deactivation, cannot recycle at present, it is main using the side for piling up landfill
Formula treatment.So, the land resource and inventory space of preciousness are occupied, is badly in need of the recycling skill of the oximes catalyst of inactivation
Art is developed.
Although hydrogen peroxide (H2O2) it is generally acknowledged Green Oxidant, its oxidized byproduct only has water.But due to H2O2Pole is not
Stabilization, heat, light, rough surface, heavy metal and other impurity can be decomposed, and with corrosivity, in packaging, storage, transport
Take special safety measure.Therefore, by H2O2Apply on the spot, or by H2O2Production technology with use H2O2Downstream process is mutually tied
Close, just can more effectively utilize this chemical products.Using H2And O2H can be directly 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.Because Pt, Pd, Au etc. are H2And O2Synthesis H2O2Active principle, there are many document patent reports to be loaded
The in-situ preparation H on titanium silicalite material2O2For the research of organic matter selective oxidation reaction.Such as, Meiers R. etc.
(J.Catal., 1998,176：Propylene gas-phase epoxidation is studied by catalyst of Pt-Pd/TS-1 376-386)；
US6867312B1 and US6884898B1 etc. has also carried out the research of this respect.Noble-metal-supported is former on titanium silicalite material
Position generation H2O2Although method mild condition, selectivity good (can reach more than 95%) for organic matter selective oxidation, bear
The titanium silicalite material catalyst activity of supported noble metal is relatively low, and stability is poor.
The content of the invention
Agent noble metal modified titanium of the preparation with special physical chemical characteristicses is drawn off it is an object of the invention to provide a kind of use
The method of si molecular sieves.
Inventor by inactivate HTS particularly alkaline environment under inactivate HTS such as amidoxime
Change the physico-chemical property after catalyst generation permanent deactivation to be characterized, it is found that its crystalline framework keeps complete substantially, can be subject to
Utilize.Inventor is by substantial amounts of research it has furthermore been found that in the preparation process of HTS, can use the titanium of inactivation
Silicalite molecular sieve catalyst (the cyclohexanone oximate of the titanium-silicon molecular sieve catalyst of permanent deactivation such as inactivation particularly under alkalescence condition
Catalyst is used as primary raw material), (combine heat treatment and roasting etc. using acid, alkali etc. successively treatment by specific preparation process
Step), the excellent molecular sieve of catalytic oxidation performance can be retrieved, and the molecular sieve prepared has special materialization special
Levy.
To realize object defined above, the first aspect of the present invention, the invention provides a kind of modified with noble metals HTS,
The molecular sieve includes：Precious metal element, titanium elements, element silicon and oxygen element, wherein, the pore volume of the molecular sieve is in 0.3cm3/g
More than, total specific surface area is in 200m2/ more than g, external surface area is in 30m2/ more than g, and external surface area accounts for the ratio of total specific surface area
It is 7-55%；The molecular sieve is in 25 DEG C, P/P0=0.10 and adsorption time be the benzene adsorbance measured under conditions of 1 hour
It is at least 75mg/g molecular sieves, N2The lower micropore size with 0.9-1.5nm scopes of Static Adsorption test is distributed；The noble metal
One or more in for Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au；The surface silicon titanium ratio of the molecular sieve is not less than body phase
Silicon titanium ratio, the silicon titanium than refer to silica and titanium oxide mol ratio.
The second aspect of the present invention, the invention provides a kind of preparation method of molecular sieve of the present invention, the method
Including：
(1) agent will be drawn off and will mix mashing with acid solution, the slurries that will be obtained will carry out the first heat treatment, isolated first will consolidate
Body, wherein, described to draw off agent be the agent that draws off using HTS as the reaction unit of catalyst, 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
Treatment.
The third aspect of the present invention, the invention provides molecular sieve of the invention answering in catalytic hydrocarbon direct oxidation reaction
With.
According to the fourth aspect of the invention, the invention provides a kind of method of alkene direct oxidation, the method includes：With
Methyl alcohol is solvent, and by the contact of alkene, oxygen-containing gas and catalyst, the catalyst contains molecular sieve of the present invention and Ben Fa
The molecular sieve that bright described preparation method is prepared.
Its benzene adsorbance of modified with noble metals HTS with special physical chemical characteristicses structure of the invention is higher, table
Face silicon titanium is for example used it for than being not less than the advantage that body phase silicon titanium ratio and micropore size with 0.9-1.5nm scopes are distributed
The reaction that ring molecule, olefin hydrocarbon molecules are participated in or generated, can obtain more preferable catalytic effect.I.e. due to material of the invention its
Benzene adsorbance is higher, surface silicon titanium than be not less than body phase silicon titanium ratio and with 0.9-1.5nm scopes micropore size distribution, urging
Change in reacting and be conducive to reactant and product molecule (such as aromatic compound), the diffusion of olefin hydrocarbon molecules, to aromatic hydrocarbon chemical combination
The catalytic oxidation that thing, ring class hydrocarbon compound equimolecular and olefin hydrocarbon molecules are participated in is particularly advantageous.
The method for preparing modified with noble metals HTS of the invention, can prepare with special spy of the invention
The modified with noble metals HTS of structure is levied, such as benzene adsorbance is higher, surface silicon titanium ratio is not less than body phase silicon titanium ratio and tool
The micropore size for having 0.9-1.5nm scopes is distributed.And the method for the present invention causes that the titanium-silicon molecular sieve catalyst of inactivation is obtained
Utilize, turn waste into wealth.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
As it was previously stated, the invention provides a kind of modified with noble metals HTS, the molecular sieve includes：Noble metal unit
Element, titanium elements, element silicon and oxygen element, wherein, the pore volume of the molecular sieve is in 0.3cm3/ more than g, total specific surface area exists
200m2/ more than g, external surface area is in 30m2/ more than g, and external surface area account for total specific surface area ratio be 7-55%；The molecule
Sieve is in 25 DEG C, P/P0=0.10 and adsorption time be that the benzene adsorbance measured under conditions of 1 hour is at least 75mg/g molecules
Sieve, N2The lower micropore size with 0.9-1.5nm scopes of Static Adsorption test is distributed；The noble metal be Ru, Rh, Pd, Re,
One or more in Os, Ir, Pt, Ag and Au；The surface silicon titanium ratio of the molecular sieve is not less than body phase silicon titanium ratio, the silicon titanium
Than the mol ratio for referring to silica and titanium oxide.
In the present invention, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses X
Ray fluorescence spectrometry is determined.
In the present invention, total specific surface area of molecular sieve refers to BET specific surface area, and external surface area refers to molecular sieve
Outer surface surface area, can be also simply referred to as external surface area, can be measured according to ASTMD4222-98 standard methods.
In the present invention, the pore volume of molecular sieve and aperture refer to pore volume and bore dia in molecular sieve respectively, and this is this area
Known to technical staff, do not repeat herein.
Modified with noble metals HTS of the invention, the pore volume of preferably described molecular sieve is 0.3-0.5cm3/ 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 that external surface area accounts for total specific surface area is 10-35%, preferably 10-15%；It is described
Molecular sieve is in 25 DEG C, P/P0=0.10 and adsorption time be that the benzene adsorbance that measures be that at least 100mg/g divides under conditions of 1h
Son sieve, preferably 100-130mg/g molecular sieves；The micropore size of 0.9-1.5nm scopes accounts for the ratio of total micropore size abundance
>=5%；It is preferred that the noble metal is one or more in Pd, Ag, Au and Pt.
Foregoing modified with noble metals HTS of the invention, the micropore hole of the modified with noble metals HTS
Except there is typical micro porous molecular sieve in the range of 0.4-0.7nm, (aperture of such as MFI topological structures molecular sieve is attached in 0.55nm in footpath
Outside pore-size distribution specific to closely), it is also distributed in the range of 0.9-1.5nm.Special instruction is needed exist for, if in 0.9-
Micropore size distribution accounts for the ratio of total micropore size abundance in the range of 1.5nm<When 1%, then the pore size distribution of this partial pore is neglected
Slightly disregard, that is, think there is no micropore to be distributed in the range of 0.9-1.5nm, 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 scopes of Static Adsorption test refers in the range of 0.9-1.5nm
Micropore size distribution accounts for the ratio of total micropore size abundance>1%.
, according to the invention it is preferred to the micropore size distribution in the range of 0.4-0.7nm accounts for the ratio of total micropore size abundance
Example≤95%, the micropore size distribution in the range of 0.9-1.5nm accounts for ratio >=5% of total micropore size abundance；More preferably
, the ratio that the micropore size distribution in the range of 0.9-1.5nm accounts for total micropore size abundance is 8-20%.In the present invention,
The method of testing of micropore size is well known to those skilled in the art, and such as uses N2The methods such as Static Adsorption are tested.
The micropore size of 0.9-1.5nm scopes accounts for the ratio of total micropore size abundance and counts as follows in the present invention
Calculate：[the quantity of the micropore size of 0.9-1.5nm scopes/(quantity of the micropore size of 0.9-1.5nm scopes)+(0.4-0.7nm
In the range of micropore size quantity)] × 100%.
Molecular sieve of the invention, preferably element silicon：Titanium elements：The mol ratio of precious metal element is 100：(0.1-
10)：(0.01-5), more preferably element silicon：Titanium elements：The mol ratio of precious metal element is 100：(0.2-5)：(0.2-2.5), enters
The preferred element silicon of one step：Titanium elements：The mol ratio of precious metal element is 100：(1-4)：(0.5-2.5).
Modified with noble metals HTS of the invention, it is preferable that the surface silicon titanium ratio and the body phase silicon titanium
The ratio of ratio is more than 1.2；It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5；Further
Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5.
Foregoing modified with noble metals HTS of the invention has benzene adsorbance higher；Surface silicon titanium ratio is not less than body phase
The advantage such as silicon titanium ratio and the distribution of the micropore size with 0.9-1.5nm scopes, the present invention is to foregoing noble metal modified titanium silicon molecule
The preparation method of sieve is without particular/special requirement, as long as the modified with noble metals HTS with said structure can be prepared i.e.
Can, preferred embodiment, present invention use draws off agent and prepares foregoing noble metal modified titanium silicon molecule one kind of the invention
Sieve.
Therefore, as it was previously stated, the invention provides a kind of preparation of modified with noble metals HTS of the present invention
Method, the method includes：
(1) agent will be drawn off and will mix mashing with acid solution, the slurries that will be obtained will carry out the first heat treatment, isolated first will consolidate
Body, wherein, described to draw off agent be the agent that draws off using HTS as the reaction unit of catalyst, 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
Treatment.
In the present invention, the agent that draws off using HTS as the reaction unit of catalyst can be to be used from various
HTS draws off agent as what is drawn off in the device of catalyst, for example, can be from using HTS 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 and unloaded as draw off the draw off agent, hydroxylating device that agent can be Ammoximation reaction device of the reaction unit of catalyst
Go out one or more drawn off in agent of agent and epoxidation reaction device, be specifically as follows unloading for cyclohexanone oxamidinating reaction unit
Go out agent, one or more drawn off in agent that draws off agent and propylene ring oxidation reaction device of phenol hydroxylation reaction unit, it is excellent
Agent is drawn off described in choosing to react the catalyst of inactivation under alkaline environment, therefore, agent is drawn off for hexamethylene for the present invention is preferably described
Ketone oxamidinating reaction unit draws off agent (such as the titanium-silicon molecular sieve TS-1 of inactivation, powdery, particle diameter is in 100-500nm).
In the present invention, it is described draw off agent refer to using solvent wash or roasting etc. conventional regeneration processes cannot be allowed to activity it is extensive
(initial activity refers to catalyst under identical reaction conditions to arrive the catalyst of the inactivation in the case of initial activity 50% again
Average activity within 1h.Such as in the reaction of actual cyclohexanone oximeization, the initial activity of general catalyst to reach 95% with
On).
The activity for drawing off agent is different according to its source.Usually, the activity for drawing off agent can be the titanium silicon molecule
Sieve the 5-95% of the activity (that is, fresh dose of activity) when fresh.Preferably, the activity for drawing off agent can be the titanium silicon molecule
Active less than 50% when fresh is sieved, the activity for further preferably drawing off agent can be the HTS when fresh
The 10-40% of activity.The activity of fresh dose of the HTS is generally more than 90%, and usually more than 95%.
It is described to draw off agent and carry out from industrial deactivator or in the lab reacted inactivation in the present invention
Catalyst.
Certainly, from the angle for preparing effect, the method for the present invention can also use fresh HTS as raw material,
Simply will not be suitable from for cost control angularly, the present invention provide method, mainly using inactivate HTS as
Raw material, turns waste into wealth, so as to save cost.
In the present invention, the agent that draws off of each device is each determined using the reaction of each device, as long as ensureing, in phase
In same device, under identical reaction condition, the activity of the activity less than fresh catalyst of agent is drawn off, it is as of the invention to draw off
Agent.As it was previously stated, in the case of preferred, drawing off active 50% of the activity less than fresh catalyst of agent.
In the present invention, by cyclohexanone oxamidinating reaction unit draw off agent as a example by, the activity is determined by the following method：
TS-1 molecular sieves are taken (by " Zeolites, 1992, Vol.12：Prepared by the method described in 943~950 ", TiO2
Weight/mass percentage composition 2.1%) to be placed in slurry bed reactors of the 100mL with continuous feed and membrane separation device, in stirring
(water is with the volume ratio of hydrogen peroxide to add the mixture of the hydrogen peroxide of water and 30wt% under state with the speed of 5.7mL/h
10：9), with the mixture of the speed addition cyclohexanone of 10.5mL/h and the tert-butyl alcohol, (volume ratio of cyclohexanone and the tert-butyl alcohol is 1：
2.5) 36wt% ammoniacal liquor, is added with the speed of 5.7mL/h, above-mentioned three strands of material stream is addition simultaneously, while with corresponding speed
Continuous discharge, reaction temperature maintains 80 DEG C, after stable reaction every 1 hour to product sampling gas chromatography to liquid phase
Composition is analyzed, and the conversion ratio of cyclohexanone is calculated and as the activity of HTS using below equation.Cyclohexanone
Conversion ratio=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/add cyclohexanone mole
Amount] × 100%.Wherein, using the result of 1h as initial activity.
With the method for the invention it is preferred to, step (2) is carried out as follows：By noble metal source with alkali source containing water-soluble
Mixed solution is mixed to get in the presence of agent, described second is carried out after the mixed solution, titanium source are mixed with first solid
Heat treatment.
With the method for the invention it is preferred to the mashing is carried out at normal temperatures and pressures.
The method according to the invention, in the case of specified otherwise, heat treatment is usually spontaneous in the case of sealing
Carried out under pressure.
A preferred embodiment of the invention, the temperature of the preferably first heat treatment is 10-200 DEG C, more preferably
50-180 DEG C, more preferably 60-180 DEG C；First heat treatment time be 0.5-36h, preferably 1-24h, more preferably
1-12h；
Second heat treatment experience stage (1), stage (2) and stage (3) successively, 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 process 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, more preferably 160-170 DEG C, reprocess 6-96 hours, preferably 12-20 hours.
A preferred embodiment of the invention, preferably stage (1) and stage (3) meet one of following condition
Or both：
Condition 1：Temperature of the temperature in stage (1) less than the stage (3), it is preferable that the temperature in stage (1) is than the stage (3)
Temperature is low 10-50 DEG C, preferably low 20-40 DEG C；
Condition 2：Time of the time in stage (1) less than the stage (3), it is preferable that the time in stage (1) is than the stage (3)
Time is short 5-24 hours, preferably short 6-12 hours.
A preferred embodiment of the invention, the stage (2) is cooled to not higher than 50 DEG C, preferably 30-50 DEG C, and
Residence time is at least 1 hour, preferably 1-5h.
The method according to the invention, the heating rate and rate of temperature fall that temperature is adjusted to each phase temperature can be according to tools
The type of the reactor that body is used is selected, and is not particularly limited.In general, temperature is increased into stage (1) temperature
Heating rate can be 0.1-20 DEG C/min, preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By stage (1) temperature
Rate of temperature fall to stage (2) temperature can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 5-10 DEG C/min.
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
It is 5-20 DEG C/min.
With the method for the invention it is preferred to the method for the present invention also includes：Before it will draw off agent and mix mashing with acid solution,
First draw off described agent and be calcined.
In the present invention, optional wider range of the condition of the roasting, for the condition bag of the preferably roasting of the invention
Include：The temperature of roasting is 300-800 DEG C, preferably 550-600 DEG C；The time of roasting be 2-12h, preferably 2-4h, roasting
Atmosphere includes air atmosphere；The condition of more preferably described roasting includes：0.5- is calcined in nitrogen atmosphere at 350-600 DEG C first
6h, is then calcined 0.5-12h at 350-600 DEG C in air atmosphere.
In the present invention, the primary solvent of the acid solution is water, also can be according to needing to add other solvents aids.
With the method for the invention it is preferred to the concentration of peroxide and nitric acid is respectively described in the acid solution>
0.1mol/L, more preferably >=1mol/L, more preferably further preferred 2-15mol/L, 2-6mol/L.It is thus prepared obtain point
Son sieve its pore volume, specific surface area, surface silicon titanium than with body phase silicon titanium than, 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 the peroxide is selected from hydrogen peroxide, TBHP, hydrogen peroxide
One or more in isopropylbenzene, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
With the method for the invention it is preferred to 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 is
100：(0.5-10.0)：(0.5-2.0)：(1-20)：(100-800).
With the method for the invention it is preferred to it is 100 to draw off agent with the mass ratio of acid：(0.005-50), preferably draw off agent with
The mass ratio of acid is 100：(1-15), in terms of nitric acid, it is 100 more preferably to draw off agent with the mass ratio of acid for acid：(10-15).
In the present invention, the HTS can be the common HTS with various topological structures, for example：
The HTS can be selected from HTS (such as TS-1), HTS (such as TS- of MEL structures of MFI structure
2), HTS (such as Ti-Beta), the HTS (such as Ti-MCM-22) of MWW structures, the hexagonal structure of BEA structures
HTS (such as Ti-MCM-41, Ti-SBA-15), the HTS (such as Ti-MOR) of MOR structures, the titanium silicon of TUN structures
The HTS (such as Ti-ZSM-48) of molecular sieve (such as Ti-TUN) and other structures.
Preferably, the HTS is selected from HTS, the HTS and BEA of MEL structures of MFI structure
The HTS of structure.It is highly preferred that HTS of the HTS for MFI structure, such as TS-1 molecular sieves.
The method according to the invention, the titanium source can be the conventional selection of this area, for the present invention, 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, for example, can be selected from TiX4、TiOX2Or Ti
(SO4)2Etc. various forms of containing titanium salt, X is halogen in formula, preferably chlorine, wherein, preferably described inorganic titanium salt is selected from TiCl4、
Ti(SO4)2And TiOCl2In one or more.
In the present invention, it is M that the organic titanate is preferably with structural formula4TiO4Organic titanate, wherein, M is preferred
It is that, with the 1-4 alkyl of carbon atom, and 4 M can be with identical or different, it is metatitanic acid isopropyl that preferably described organic titanate is selected from
One or more in ester, metatitanic acid n-propyl, butyl titanate and tetraethyl titanate.
What is used in a particular embodiment of the present invention is titanium sulfate, butyl titanate as example, but is not therefore limited
The scope of the present invention processed.
The method according to the invention, optional wider range of the species of the alkali source, it can be organic base source and/or nothing
Machine alkali source, wherein, inorganic alkali source can be the alkali that ammonia or cation are alkali metal or alkaline-earth metal, such as can for NaOH,
Potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide etc., organic alkali source can be urea, aliphatic amination
One or more in compound, aliphatic alcohol amines and quaternary ammonium alkali cpd.
In the present invention, the quaternary ammonium base can be various organic level Four ammonium alkali, and the aliphatic amine can be various NH3In
At least one hydrogen by aliphatic alkyl (preferably alkyl) replace after formed compound, the aliphatic hydramine can be each
Plant NH3At least one of hydrogen by hydroxyl aliphatic alkyl (preferably alkyl) substitution after formed compound.
Specifically, the quaternary ammonium base can be the quaternary ammonium base as shown in Formula II, and the aliphatic amine can be represented for formula III
Aliphatic amine, the aliphatic hydramine can be the aliphatic hydramine represented such as formula IV：
In Formula II, R5、R6、R7And R8Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, for example：R5、R6、R7And R8Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle
Butyl.
R9(NH2)n(formula III)
In formula III, n is 1 or 2 integer.When n is 1, R9It is C1~C6Alkyl, including C1~C6Straight chained alkyl and C3-
C6Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, new
Amyl group, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R9It is C1-C6Alkylidene, including C1~C6Straight-chain alkyl-sub and C3
~C6Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.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
Amines is one or more in MEA, diethanol amine and triethanolamine.
It is of the invention it is a kind of preferred embodiment, preferably described alkali source is NaOH, ammoniacal liquor, ethylenediamine, just
Butylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine, triethanolamine, tetraethyl ammonium hydroxide and TPAOH
In one or more.
Wherein, when ammoniacal liquor is contained in the alkali source, the mol ratio of alkali source is with including molecular forms NH3With ionic species NH4 +The ammonia meter of presence.
With the method for the invention it is preferred to the alkali source is provided in the form of aqueous slkali, the more preferably pH of aqueous slkali>9.
With the method for the invention it is preferred to oxide, the halide of noble metal, your gold of the noble metal source for noble metal
The carbonate of category, the nitrate of noble metal, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, the hydroxide of noble metal
With one or more in the complex compound of noble metal, the noble metal is in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au
Plant or various；It is preferred that the noble metal is Pd, Ag, Au and/or Pt, by taking palladium as an example, the noble metal source is selected from palladium oxide, carbonic acid
Palladium, palladium bichloride, palladium nitrate, ammonium nitrate palladium, sal-ammoniac palladium, acid chloride, palladium dydroxide, the complex compound of palladium, palladium and levulinic
One or more in ketone palladium.
Using palladium bichloride, palladium acetylacetonate, acetic acid platinum, property illustrates of the invention as an example in an embodiment of the present invention
Advantage.
In one of the invention more preferably implementation method, it is described draw off agent mix with acid solution mashing treatment process be
Carried out under acid solution counterflow condition, the molecular sieve for obtaining with this understanding has more obvious distinctive physical chemical characteristicses.
, according to the invention it is preferred to the method for the present invention also includes the step of the recovery product from the material of step (2) heat treatment
Suddenly, the step of recovery product is conventional method, by those skilled in the art is familiar, herein and is had no special requirements, usually
The process for refer to product filtering, washing, drying and being calcined.Wherein, described drying process can be in the temperature between -200 DEG C of room temperature
Under carry out, described roasting process can between 300-800 DEG C first in nitrogen atmosphere after 0.5-6 hours in air atmosphere 3-
Carry out within 12 hours.
The benzene adsorbance of the molecular screen material obtained due to molecular screen material of the present invention and the inventive method is higher, surface silicon
Titanium than be not less than body phase silicon titanium ratio and with 0.9-1.5nm scopes micropore size distribution, be conducive in catalytic reaction reaction
The catalysis oxidation that thing and product molecule are especially participated in aromatic hydrocarbon compound, ring class hydrocarbon compound, olefin(e) compound equimolecular
Reaction is particularly advantageous.
The molecular sieve obtained present invention also offers molecular sieve of the invention and the inventive method is in the direct oxygen of catalytic hydrocarbon
Change the application in reaction.In the oxidation reaction, for example in the reaction of preparing epoxypropane by epoxidation of propene (PO), product
The selectivity and catalysis activity of PO are significantly improved.
According to the fourth aspect of the invention, the invention provides a kind of method of alkene direct oxidation, the method includes：With
Methyl alcohol is solvent, and by the contact of alkene, oxygen-containing gas and catalyst, the catalyst contains molecular sieve of the present invention and Ben Fa
The molecular sieve that bright described preparation method is prepared.
The method according to the invention, the condition of the contact can be the conventional selection of this area, for the present invention, preferably
The condition of contact includes：Temperature is 0-80 DEG C, and pressure is 0.1-5.0MPa, and time 0.1-24h, alkene air speed is 0.1-100h-1,
Alkene air speed namely in olefin gas air speed, i.e. unit interval by the amount of the volume of the alkene of unit catalyst.
The mol ratio 0.1-10 of oxygen and alkene more preferably in oxygen-containing gas:1.
Optional wider range of the species of alkene, for example, can be propylene.
The method according to the invention, in the oxygen-containing gas in addition to containing oxygen, can also contain the gas such as hydrogen, nitrogen
Body, also contains hydrogen and nitrogen in preferably described oxygen-containing gas, the preferably mol ratio of oxygen, hydrogen and nitrogen is 0.1-10：
0.1-10：0.5-100.That is, the mol ratio of preferred alkenes, oxygen, hydrogen and nitrogen is 1：0.1-10：0.1-10：0.5-100.
0.05-2g (such as 0.5g) catalyst preferred embodiment, is added to and contains 1- by one kind of the invention
It is 1 according to mol ratio in the reaction vessel of 500ml (such as 80ml) methyl alcohol：0.1-10：0.1-10：0.5-100 (such as 1:1:1:7)
The diluent gas such as alkene, oxygen, hydrogen and nitrogen are passed through, in 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 and is not so limited present disclosure.
In comparative example and embodiment, agents useful for same is commercially available chemically pure reagent.
The agent that draws off of following examples and comparative example is obtained as follows, and determines HTS using following methods
The activity of (including HTS draws off agent, and fresh dose of HTS).
TS-1 molecular sieves are taken (by " Zeolites, 1992, Vol.12：Prepared by the method described in 943~950 ", TiO2
Weight/mass percentage composition for 2.1%) be placed in 100mL band continuous feed and membrane separation device slurry bed reactor in, stirring shape
With the mixture of the hydrogen peroxide of the speed addition water and 30wt% of 5.7mL/h, (water is 10 with the volume ratio of hydrogen peroxide under state：
9), with the mixture of the speed addition cyclohexanone of 10.5mL/h and the tert-butyl alcohol, (volume ratio of cyclohexanone and the tert-butyl alcohol is 1：2.5),
36wt% ammoniacal liquor is added with the speed of 5.7mL/h, above-mentioned three strands of material stream is addition simultaneously, while continuously going out with corresponding speed
Material, reaction temperature maintains 80 DEG C, product sampling gas chromatography is entered to the composition of liquid phase every 1 hour after stable reaction
Row analysis, the conversion ratio of cyclohexanone is calculated and as the activity of HTS using below equation.The conversion of cyclohexanone
Rate=[mole of the cyclohexanone of (mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/addition] ×
100%.
It is for the first time that the cyclohexanone conversion ratio that 1h is determined is its initial activity, its value is 99.5%.Through after a while
About 168 hours, after cyclohexanone conversion ratio drops to 50% by initial 99.5%, roasting regeneration mode is used after isolating catalyst
Regeneration (is calcined 4 hours) at 570 DEG C in air atmosphere, in then proceeding to be reacted for cyclohexanone oxamidinating, is repeated
The step for, until the activity after regeneration is less than the 50% of initial activity, the oximes catalyst sample at this moment inactivating is used as this
That invents draws off agent, obtains drawing off agent SH-1 (activity is 50%), SH-2 (activity is 40%), SH-3 successively according to preceding method
(activity is 25%), SH-4 (activity is 10%).
In each embodiment and comparative example, X-ray diffraction (XRD) the crystalline phase figure of sample is penetrated in SiemensD5005 types X-
It is measured on line diffractometer, the diffraction at the five fingers diffractive features peak between with sample and authentic specimen being 22.5 ° -25.0 ° in 2 θ
The ratio of intensity (peak height) sum represents crystallinity of the sample relative to authentic specimen, here on the basis of the sample of comparative example 1
Sample, its crystallinity is calculated as 100%, and the relative crystallinity data of each sample are shown in Table 1.The benzene adsorbance of sample, pore volume, aperture point
Cloth, total specific surface area and external surface area are determined on Micromeritics companies ASAP2405 static state n2 absorption apparatus, specific number
According to being shown in Table 1.The elements such as the noble metal and silicon of sample are constituted in Rigaku Electric Co., Ltd 3271E type X-ray fluorescence spectras
Determined on instrument, specific data are shown in Table 2.
In the present invention, surface silicon titanium is than the ESCALab250 type x-ray photoelectrons using Thermo Scientific companies
Energy disperse spectroscopy is determined, and body phase silicon titanium ratio is determined using Rigaku Electric Co., Ltd 3271E types Xray fluorescence spectrometer.
Comparative example 1
The conventional HTS sample for not containing noble metal for the preparation of silicon source hydrothermal crystallizing using estersil of this comparative example explanation
The process of product.
Tetraethyl orthosilicate, isopropyl titanate are mixed with TPAOH, and add appropriate distilled water stirring mixing,
A mole composition is tetraethyl orthosilicate among reaction system：Isopropyl titanate：TPAOH：Water=100：5：10：200,
Wherein tetraethyl orthosilicate is with SiO2Meter；In hydrolyzing 1.0h at normal pressure and 60 DEG C, then 3h is stirred at 75 DEG C, then by mixed liquor
Stainless steel sealed reactor is put into, constant temperature places 3d at a temperature of 170 DEG C, obtains the mixture of crystallization product；This is mixed
Thing is filtered, washed with water, and dries 60min in 110 DEG C, obtains molecular screen primary powder, and in 550 DEG C of roasting temperature 3h, obtain water
The HTS of hot direct crystallization, its XRD crystalline phase is MFI structure.
Comparative example 2
It is that silicon source hydrothermal crystallizing prepares the HTS sample containing noble metal using estersil that the explanation of this comparative example is conventional
Process.
Tetraethyl orthosilicate, palladium bichloride, isopropyl titanate are mixed with TPAOH, and adds appropriate distilled water to stir
Mixing is mixed, a mole composition is tetraethyl orthosilicate among reaction system：Isopropyl titanate：Palladium bichloride：TPAOH：Water=
100：5：2：10：200, wherein tetraethyl orthosilicate is with SiO2Meter；In hydrolyzing 1.0h at normal pressure and 60 DEG C, then stirred at 75 DEG C
3h, is then put into stainless steel sealed reactor by mixed liquor, and constant temperature places 3d at a temperature of 170 DEG C, obtains crystallization product
Mixture；By the filtering of this mixture, wash with water, and 60min is dried in 110 DEG C, obtain molecular screen primary powder, and in 550 DEG C of temperature
The lower roasting 3h of degree, obtains the HTS of hydro-thermal direct crystallization, and it is MFI structure that its XRD crystalline phases figure is consistent with comparative example 1.
Comparative example 3
The process of the HTS sample dip loading noble metal that the explanation of this comparative example is prepared using comparative example 1.
HTS prepared by comparative example 1 is mixed with palladium chloride aqueous solution, wherein HTS and palladium bichloride with
And the mass ratio of water is 10:2:25, in 6h is stirred at normal pressure and 60 DEG C, then this mixture is filtered, is washed with water, and in
110 DEG C dry 60min, and in 550 DEG C of roasting temperature 3h, must be loaded with the HTS of noble metal, and its XRD crystalline phase is
MFI structure.
Comparative example 4
The explanation of this comparative example is using the process for drawing off agent SH-2 sample dip loading noble metals.
Agent SH-2 will be drawn off to mix with palladium chloride aqueous solution, wherein HTS and palladium bichloride and the mass ratio of water
It is 10:0.5:10, in 12h is stirred at normal pressure and 40 DEG C, then this mixture is filtered, is washed with water, and in 110 DEG C of dryings
60min, and in 550 DEG C of roasting temperature 3h, the HTS of noble metal must be loaded with, its XRD crystalline phase is MFI structure.
Comparative example 5
The explanation of this comparative example is using the process for drawing off agent SH-3 dip loading noble metals.
SH-3 is mixed with palladium chloride aqueous solution, wherein HTS and the mass ratio of palladium bichloride and water is 10:
1:50, in 12h is stirred at normal pressure and 40 DEG C, then this mixture is filtered, is washed with water, and 60min is dried in 110 DEG C, and
In 550 DEG C of roasting temperature 3h, the HTS of noble metal must be loaded with, its XRD crystalline phase is MFI structure.
Comparative example 6
The explanation of this comparative example is using the process for drawing off agent SH-4 dip loading noble metals.
SH-4 is mixed with palladium chloride aqueous solution, wherein HTS and the mass ratio of palladium bichloride and water is 10:
2:20, in 3h is stirred at normal pressure and 50 DEG C, then this mixture is filtered, is washed with water, and 60min is dried in 110 DEG C, and in
550 DEG C of roasting temperature 3h, must be loaded with the titanium silicalite material of noble metal, and its XRD crystalline phase is MFI structure.
Embodiment 1
This example demonstrates that the method and product of present invention offer.
In normal temperature (20 DEG C, remaining comparative example is identical with embodiment) normal pressure (0.1MPa, remaining comparative example and embodiment phase
Under together), the cyclohexanone oximate catalyst SH-2 and acid solution (aqueous solution containing nitric acid and hydrogen peroxide, nitric acid that will first inactivate
Concentration with hydrogen peroxide is 4mol/L) mixing mashing, mixed serum is then mixed treatment 12h at 80 DEG C；Gu
Liquid will mixing after mixing solid, noble metal source palladium bichloride, titanium source titanium sulfate with sodium hydrate aqueous solution (pH is 12) after separating
Liquid is put into stainless steel sealed reactor, and first stage 6h is experienced at 140 DEG C, and mixture then is cooled into 30 DEG C of experience second-orders
After section stops 2h, continue to experience phase III 12h (wherein, by room temperature extremely at a temperature of 170 DEG C in sealed reactor
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, 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
Thing is filtered, washed with water, and dries 120min in 110 DEG C, then in 550 DEG C of roasting temperature 3h, obtains molecular sieve, its XRD
Crystalline phase figure is consistent with comparative example 1, and illustrate to obtain is the HTS with MFI structure.
Comparative example 7
The explanation utilization of this comparative example draws off the process of dip loading noble metal after agent SH-2 acid treatments.
At normal temperatures and pressures, first the combined of the cyclohexanone oximate catalyst SH-2 for inactivating and 1mol/L is beaten
Slurry, mixed serum is then mixed treatment 12h at 80 DEG C；The SH-2 of acid treatment is obtained after separation of solid and liquid, then by it
Mix with palladium chloride aqueous solution, wherein HTS and the mass ratio of palladium bichloride and water is 10:2:20, in normal pressure and 50
3h is stirred at DEG C, then this mixture is filtered, is washed with water, and 60min is dried in 110 DEG C, and in 550 DEG C of roasting temperatures
3h, must be loaded with the titanium silicalite material of noble metal, and its XRD crystalline phase is MFI structure.
Embodiment 2
This example demonstrates that the method and product of present invention offer.
At normal temperatures and pressures, the cyclohexanone oximate catalyst SH-3 for inactivating (is first contained into nitric acid and peroxidating with acid solution
The concentration of the aqueous solution of hydrogen, nitric acid and ethylbenzene hydroperoxide is respectively 2mol/L, 6mol/L) mixing mashing, then by mixing slurry
Liquid mixes treatment 1h 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 sealed reactor after the TPAOH aqueous solution (pH is 10) mixing, in 130 DEG C of experience the
One stage 8h, after mixture then is cooled into 50 DEG C of experience second stage stop 5h, continues in sealed reactor in 170 DEG C
At a temperature of to experience phase III 16h (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 the liter of second stage temperature to phase III temperature
Warm speed is 20 DEG C/min), wherein, quality of material composition is the cyclohexanone oximate catalyst of inactivation：Titanium source：Noble metal source：Acid：
Alkali：Water=100：2：0.5：15：15：200.Then according to the method recovery product of embodiment 1, HTS, its XRD are obtained
Crystalline phase figure is consistent with comparative example 1.
Embodiment 3
This example demonstrates that the method and product of present invention offer.
At normal temperatures and pressures, the cyclohexanone oximate catalyst SH-4 for inactivating (is first contained into nitric acid and peroxidating with acid solution
The concentration of the aqueous solution of hydrogen, nitric acid and TBHP is respectively 6mol/L, 2mol/L) mixing mashing, then will mixing
Slurries mix treatment 3h 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 is put into stainless steel sealed reactor after changing sodium water solution (pH is 14) mixing, first stage 6h is experienced at 140 DEG C, connect
After mixture is cooled into 40 DEG C of experience second stage stop 1h, continuation is passed through in sealed reactor at a temperature of 160 DEG C
It (is wherein, 5 DEG C/min by the heating rate of room temperature to first stage temperature, by first stage temperature to go through phase III 12h
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 composition is the cyclohexanone oximate catalyst of inactivation：Titanium source：Noble metal source：Acid：Alkali：Water=
100：10：2：10：15：600.Then according to the method recovery product of embodiment 1, molecular sieve, its XRD crystalline phases figure and contrast are obtained
Example 1 is consistent.
Embodiment 4
This example demonstrates that the method and product of present invention offer.
Method according to embodiment 3 prepares molecular sieve, the difference is that in quality of material composition, the cyclohexanone oximate of inactivation is urged
Agent：Acid=100：5, the XRD crystalline phases figure of gained sample is consistent with comparative example 1.
Embodiment 5
This example demonstrates that the method and product of present invention offer.
Method according to embodiment 3 prepares molecular sieve, the difference is that in quality of material composition, the cyclohexanone oximate of inactivation is urged
Agent：Acid=100：100, the XRD crystalline phases figure of gained sample is consistent with comparative example 1.
Embodiment 6
This example demonstrates that the method and product of present invention offer.
Method according to embodiment 2 prepares molecular sieve, unlike, will draw off agent SH-3 be calcined and then carries out follow-up
Mashing, heat treatment process, wherein, the condition of roasting includes：4h, the XRD of gained sample are calcined at 570 DEG C in air atmosphere
Crystalline phase figure is consistent with comparative example 1, and the XRD crystalline phases figure of gained sample is consistent with comparative example 1.
Embodiment 7
Method according to embodiment 2 prepares molecular sieve, unlike, what is used draws off agent for SH-1, and remaining condition is homogeneous
Together, the XRD crystalline phases figure of gained sample is consistent with comparative example 1.
Embodiment 8
Method according to embodiment 2 prepares molecular sieve, unlike, raw material addition sequence changes：
At normal temperatures and pressures, first the cyclohexanone oximate catalyst SH-3 for inactivating is mixed with the hydrochloric acid solution of 5mol/L and is beaten
Slurry, mixed serum is then mixed treatment 1h at 60 DEG C, solid is obtained after separation of solid and liquid, by noble metal source acetylacetone,2,4-pentanedione
Palladium is mixed to get mixed liquor with the TPAOH aqueous solution (pH is 10), after solid, butyl titanate, mixed liquor are mixed
Stainless steel sealed reactor is put into, 12h is processed at 150 DEG C, wherein quality of material composition is the cyclohexanone oximate catalysis of inactivation
Agent：Titanium source：Noble metal source：Acid：Alkali：Water=100：2：0.5：15：15：200.Then according to the method recovery product of embodiment 1,
Molecular sieve containing noble metal is obtained, its XRD crystalline phases figure is consistent with comparative example 1.
Embodiment 9
Method according to embodiment 1 prepares molecular sieve, unlike, the crystallization temperature of phase III is also 140 DEG C.Then
According to the method recovery product of embodiment 1, molecular sieve containing noble metal is obtained, its XRD crystalline phases figure is consistent with comparative example 1.
Embodiment 10
Method according to embodiment 1 prepares molecular sieve, unlike, the crystallization temperature of first stage is 110 DEG C.Then press
According to the method recovery product of embodiment 1, molecular sieve containing noble metal is obtained, its XRD crystalline phases figure is consistent with comparative example 1.
Embodiment 11
Method according to embodiment 1 prepares molecular sieve, unlike, the crystallization time of first stage is 12h, second stage
It is to be cooled to 70 DEG C of stop 2h.Then according to the method recovery product of embodiment 1, molecular sieve containing noble metal, its XRD crystalline phase are obtained
Figure is consistent with comparative example 1.
Table 1
From the results shown in Table 1：Its pore volume of molecular sieve prepared by the preferred process of the present invention is more than 0.3cm3/ g, benzene is inhaled
Attached amount is more than 75mg/g, and total specific surface area is 200-450m2/ g, wherein, external surface area is 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 prepare molecular sieve its in 0.9-1.5nm scopes
The ratio that micropore size accounts for total micropore size abundance is>5%.
Be can also be seen that from the result of table 1：
Molecular sieve its relative crystallinity prepared by the preferred process of the present invention, pore volume, total specific surface area, external surface area,
The data such as 0.9-1.5nm pore-size distributions, surface silicon titanium ratio and body phase silicon titanium ratio, benzene adsorbance fully meet product of the present invention
Whole features.It is relative, either comparative example 1 using estersil be silicon source prepare do not contain the HTS of noble metal, right
The titanium that ratio 2 is prepared using the HTS containing noble metal, comparative example 3 that estersil is silicon source preparation using such as comparative example 1
Si molecular sieves carried noble metal and the HTS containing noble metal for preparing, or comparative example 4-6 is using drawing off agent load
The titanium silicalite material and comparative example 7 that noble metal is obtained draw off the titanium silicalite material that the acid treated carried noble metal of agent is obtained, and its is relative
The data such as crystallinity, pore volume, total specific surface area, external surface area, 0.9-1.5nm pore-size distributions, benzene adsorbance cannot meet this
Whole features of invention product.Such as the molecular sieve of comparative example 1, its pore volume only has 0.264cm3/ g, external surface area 24m2/ g, and appearance
Area accounts for the ratio of total specific surface area 5% or so.
Testing example
0.5g catalyst is added in the closed tank reactor containing 50ml methyl alcohol, is 1 then according to mol ratio:1:
1:7 ratio is passed through propylene, oxygen, hydrogen and nitrogen (diluent gas), in temperature 50 C, pressure 1.5MPa, and 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 equation below：
Propylene conversion=(participating in the amount of the material of amount/total propylene for adding of the material of the propylene of reaction) * 100%；
PO selectivity=(amount of the material of the amount/gross product of the material of the PO of reaction generation) * 100%.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
Claims (16)
1. a kind of modified with noble metals HTS, it is characterised in that the molecular sieve includes：Precious metal element, titanium elements, silicon unit
Element and oxygen element, wherein, the pore volume of the molecular sieve is in 0.3cm3/ more than g, total specific surface area is in 200m2/ more than g, outer surface
Product is in 30m2/ more than g, and external surface area account for total specific surface area ratio be 7-55%；The molecular sieve is in 25 DEG C, P/P0=
0.10 and adsorption time be that the benzene adsorbance measured under conditions of 1 hour is at least 75mg/g molecular sieves, N2Static Adsorption is surveyed
The lower micropore size with 0.9-1.5nm scopes of examination is distributed；The noble metal is in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au
One or more；The surface silicon titanium ratio of the molecular sieve is not less than body phase silicon titanium ratio, and the silicon titanium ratio refers to silica and oxygen
Change the mol ratio of titanium.
2. molecular sieve according to claim 1, wherein, the pore volume of the molecular sieve is 0.3-0.5cm3/ g, total specific surface area
It is 200-450m2/ g, external surface area is 30-150m2/ g, the ratio that external surface area accounts for total specific surface area is 10-35%；Described point
Son sieve is in 25 DEG C, P/P0=0.10 and adsorption time be that the benzene adsorbance measured under conditions of 1 hour is at least 100mg/g point
Son sieve；The micropore size of 0.9-1.5nm scopes accounts for ratio >=5% of total micropore size abundance；The noble metal be Pd, Ag,
One or more in Au and Pt, element silicon：Titanium elements：The mol ratio of precious metal element is 100：(0.1-10)：(0.01-5),
The surface silicon titanium than with the body phase silicon titanium than ratio be more than 1.2.
3. molecular sieve according to claim 2, wherein, the micropore size of 0.9-1.5nm scopes accounts for total micropore size distribution
The ratio of amount is 8-20%, element silicon：Titanium elements：The mol ratio of precious metal element is 100：(0.2-5)：(0.2-2.5), it is described
Surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5.
4. molecular sieve according to claim 3, wherein, the surface silicon titanium than with the body phase silicon titanium than ratio be
1.5-4.5。
5. a kind of preparation method of the molecular sieve in claim 1-4 described in any one, the method includes：
(1) agent will be drawn off and will mix mashing with acid solution, the slurries that will be obtained will carry out the first heat treatment, isolated first solid,
Wherein, described to draw off agent be the agent that draws off using HTS as the reaction unit of catalyst, and the acid solution contains peroxide
Compound and nitric acid；
(2) 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.
6. preparation method according to claim 5, wherein, it is described using HTS as the reaction unit of catalyst
Draw off agent and draw off agent for Ammoximation reaction device.
7. the preparation method according to claim 5 or 6, wherein, step (2) is carried 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. the preparation method according to claim 5 or 6, wherein,
The temperature of the first heat treatment is 10-200 DEG C, and the time of the first heat treatment is 0.5-36h；
Stage (1), stage (2) and stage (3) are experienced in second heat treatment successively, and the stage (1) is at 80-150 DEG C, preferably in 110-
140 DEG C, more preferably 120-140 DEG C, further preferably 130-140 DEG C process 6-72 hours, preferably 6-8 hours, stage (2)
Be cooled to not higher than 70 DEG C and the residence time be at least 0.5 hour, preferably 1-5 hours, the stage (3) be warming up to 120-200 DEG C,
It is preferred that 140-180 DEG C, more preferably 160-170 DEG C, reprocess 6-96 hours, preferably 12-20 hours.
9. preparation method according to claim 8, wherein, stage (1) and stage (3) meet one of following condition or
Both：
Condition 1：Temperature of the temperature in stage (1) less than the stage (3), it is preferable that the temperature of the temperature than stage (3) in stage (1)
It is low 10-50 DEG C, it is preferably low 20-40 DEG C；
Condition 2：Time of the time in stage (1) less than the stage (3), it is preferable that the time of the time than stage (3) in stage (1)
It is short 5-24 hours, it is preferably short 6-12 hours；
Stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.
10. the preparation method according to claim 5 or 6, wherein, the method also includes：Mixed with acid solution agent will be drawn off
Before closing mashing, first draw off described agent and be calcined.
11. 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, more preferably >=1mol/L, more preferably
2-15mol/L；The peroxide is selected from hydrogen peroxide, TBHP, cumyl hydroperoxide, ethylbenzene peroxidating
One or more in hydrogen, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
12. preparation method according to claim 5 or 6, wherein, the HTS is MFI structure, described to draw off agent
Activity be active less than 50% of HTS when fresh.
13. preparation method according to claim 5 or 6, wherein,
The alkali source is one or more in ammonia, aliphatic amine, aliphatic hydramine and quaternary ammonium base；
The noble metal source is oxide, the halide of noble metal, the carbonate of noble metal, the nitric acid of noble metal of noble metal
One kind in salt, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, the hydroxide of noble metal and the complex compound of noble metal
Or it is various, the noble metal is one or more in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au；
The titanium source is selected from inorganic titanium salt and/or organic titanate.
Preparation side in molecular sieve and claim 5-13 in 14. claim 1-4 described in any one described in any one
Application of the molecular sieve that method is prepared in catalytic hydrocarbon direct oxidation reaction.
A kind of 15. methods of alkene direct oxidation, the method includes：With methyl alcohol as solvent, by alkene, oxygen-containing gas and catalyst
Contact, it is characterised in that the catalyst contains the molecular sieve and claim 5-13 described in any one in claim 1-4
The molecular sieve that preparation method described in middle any one is prepared.
16. methods according to claim 15, wherein, alkene is propylene, and the condition of contact includes：Temperature is 0-80 DEG C,
Pressure is 0.1-5.0MPa, and time 0.1-24h, alkene air speed is 0.1-100h-1, oxygen in oxygen-containing gas and alkene mole
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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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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