CN107879355B - 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 PDF

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CN107879355B
CN107879355B CN201610873325.XA CN201610873325A CN107879355B CN 107879355 B CN107879355 B CN 107879355B CN 201610873325 A CN201610873325 A CN 201610873325A CN 107879355 B CN107879355 B CN 107879355B
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molecular sieve
titanium
sieve
stage
ratio
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CN107879355A (en
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史春风
林民
朱斌
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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China Petrochemical Corp
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    • 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
    • C01B39/085—Group IVB- metallosilicates
    • 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
    • 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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    • 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
    • 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
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • 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
    • C01P2006/12—Surface area
    • 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
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Abstract

The present invention relates to catalysis material field, a kind of modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application is specifically provided, which contains precious metal element, titanium elements, element silicon and oxygen element, wherein the Kong Rong of the molecular sieve is in 0.25cm3/ g or more, total specific surface area is in 250m2The ratio of the total specific surface area of/g or more, external surface area Zhan is 8-50%, N2The lower micropore size with 0.8-2nm range of Static Adsorption test is distributed, the N of the Titanium Sieve Molecular Sieve‑116/N‑112Value is 0.01-0.2.The present invention provides a kind of methods of alkene direct oxidation, this method comprises: contacting alkene, oxygen-containing gas and catalyst using methanol as solvent, the catalyst contains molecular sieve of the present invention.Of the invention has its benzene adsorbance of the modified with noble metals Titanium Sieve Molecular Sieve of special physical chemical characteristics structure higher, is used for ring molecule, the reaction that olefin hydrocarbon molecules are participated in or generated, can obtain better catalytic effect.

Description

Modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application and a kind of alkene are straight The method for connecing oxidation
Technical field
The present invention relates to a kind of modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application, relate more specifically to one kind The method for preparing 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 direct oxidation.
Background technique
Titanium Sieve Molecular Sieve is the novel hetero-atom molecular-sieve that last century early eighties start exploitation.Synthesize at present There are the TS-1 of MFI type structure, the TS-2, and the Ti-MWW with larger pore structure etc. of MEL type structure.This molecular sieve analog is to perhaps More organic oxidizing reactions, for example, the epoxidation of alkene, arene hydroxylation, cyclohexanone oximate, alcohol the reactions such as oxidation have it is excellent Selective oxidation performance and higher catalytic activity, they as redox-type molecular sieve catalyst have good application before Scape.
TS-1 molecular sieve is introduced transition metal element titanium one formed in the framework of molecular sieve with ZSM-5 structure Kind has the novel titanosilicate of superior catalytic selective oxidation performance.TS-1 not only has the catalysed oxidn of titanium, and And also with the shape-selective effect and excellent stability of ZSM-5 molecular sieve.Since TS-1 molecular sieve is in the oxidation reaction of organic matter In, free of contamination low concentration hydrogen peroxide can be used as oxidant, avoid oxidation process complex process and pollute environment Problem has the unrivaled energy conservation of conventional oxidation system, economy and advantages of environment protection, and has good selecting response Property, therefore there is great prospects for commercial application.However, usually catalyst catalytic performance can be deteriorated after running for a period of time, There is deactivation phenomenom in catalyst.The reason of leading to catalyst inactivation may be impurity due to introducing during synthesis of molecular sieve or Byproduct of reaction is gathered in plug-hole etc. in catalyst micropore.
Summary of the invention
Modified with noble metals Titanium Sieve Molecular Sieve with special physical chemical characteristics is prepared the purpose of the present invention is to provide a kind of Method.
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 contains precious metal element, titanium elements, element silicon and oxygen element, wherein the Kong Rong of the molecular sieve is in 0.25cm3/g More than, total specific surface area is in 250m2The ratio of the total specific surface area of/g or more, external surface area Zhan is 8-50%, N2Static Adsorption test The micropore size with 0.8-2nm range is distributed down, the N of the Titanium Sieve Molecular Sieve-116/N-112Value is 0.01-0.2.
The second aspect of the present invention, the present invention provides a kind of preparation method of modified with noble metals Titanium Sieve Molecular Sieve, the party Method include: (1) by noble metal source, ammonia source, optionally water is mixed to obtain mixture；(2) by the mixture, titanium silicon molecule Sieve, optionally water carry out hydro-thermal process after mixing.
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, will The reaction that it is used for ring molecule, olefin hydrocarbon molecules are participated in or generated, can obtain better catalytic effect.I.e. due to of the invention The special physico-chemical structure of material is conducive to reactants and products molecule (such as aromatic compound), alkene point in catalysis reaction The diffusion of son, the catalytic oxidation participated in the molecules such as aromatic hydrocarbon compound, ring class hydrocarbon compound and olefin hydrocarbon molecules are special It is not 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 Levy the modified with noble metals Titanium Sieve Molecular Sieve of structure.And method of the invention makes the titanium-silicon molecular sieve catalyst of inactivation obtain benefit With turning 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 present invention provides a kind of modified with noble metals Titanium Sieve Molecular Sieve, the molecular sieve contain precious metal element, Titanium elements, element silicon and oxygen element, wherein the Kong Rong of the molecular sieve is in 0.25cm3/ g or more, total specific surface area is in 250m2/g More than, the ratio of the total specific surface area of external surface area Zhan is 8-50%, N2The lower micropore with 0.8-2nm range of Static Adsorption test Pore-size distribution, the N of the Titanium Sieve Molecular Sieve-116/N-112Value is 0.01-0.2.
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 0.3-0.8cm of the preferably described molecular sieve3/ g, Preferably 0.31-0.42cm3/g；Total specific surface area is 250-650m2/ g, preferably 300-420m2/g；External surface area is 30- 150m2/ g, preferably 35-80m2/g；The ratio of the total specific surface area of external surface area Zhan is 10-35%, preferably 12-30%；With/ Or
The molecular sieve is in 25 DEG C, P/P0=0.1 and adsorption time be 1h under conditions of the benzene adsorbance that measures be extremely Few 80mg/g molecular sieve, preferably at least 100mg/g molecular sieve, more preferably 100-130mg/g molecular sieve；And/or
Ratio >=2% of the total micropore size abundance of the micropore size Zhan of 0.8-2nm range, preferably >=5%；And/or institute Stating noble metal is one of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au or a variety of, one preferably in Pd, Ag, Au and Pt Kind is 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 0.8-2nm.It is necessary to be noted that if in 0.8- Within the scope of 2nm micropore size distribution the total micropore size abundance of Zhan ratio < 1% when, then the pore size distribution of this partial pore is ignored Disregard, that is, thinks to be distributed within the scope of 0.8-2nm without micropore, this is known to those skilled in the art.Therefore, institute of the present invention State in N2The lower micropore size with 0.8-2nm range of Static Adsorption test refers to the micropore size within the scope of 0.8-2nm It is distributed ratio > 1% of the 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 0.8-2nm；It is furthermore preferred that The ratio of the micropore size distribution total micropore size abundance of Zhan within the scope of 0.8-2nm is 8-20%.In the present invention, micropore hole The test method of diameter 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 0.8-2nm range is calculated as follows in the present invention: [quantity of the micropore size of 0.8-2nm range/(quantity of the micropore size of 0.8-2nm range)+(within the scope of 0.4-0.7nm The quantity of micropore size)] × 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:(0.1-5): (0.02-2), into The preferred element silicon of one step: titanium elements: the molar ratio of precious metal element is 100:(1-4): (0.5-2).
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 or more, preferably 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；It is further preferred that the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.5-4.5.In the present invention, institute State molar ratio of the silicon titanium than referring to silica and titanium oxide.
A preferred embodiment of the invention, the N of the Titanium Sieve Molecular Sieve-116/N-112Value is 0.02-0.15, excellent It is selected as 0.02-0.1.
In the present invention, N-116It refers to29Si rotates in the solid state nmr of magic angle, and -116 place of relative chemical shifts absorbs peak intensity Degree, N-112It refers to29Si rotates in the solid state nmr of magic angle, -112 place's absorption peak strength of relative chemical shifts, N-116/N-112It is worth table Show the ratio of -116 place's absorption peak strength of relative chemical shifts Yu -112 place's absorption peak strength of relative chemical shifts.Of the invention29It is enterprising in 400 type Nuclear Magnetic Resonance of Varian Infinity plus that Si MAS NMR rotates magic angle solid state nmr spectrum analysis Row,29It is 4kHz that Si, which rotates MAS speed, is designated as methyl-monosilane outside.
A preferred embodiment of the invention, the total micropore size abundance of the micropore size Zhan of 0.8-2nm range Ratio be 6-20%, preferably 8-15%；And/or
Element silicon: titanium elements: the molar ratio of precious metal element is 100:(0.2-5): (0.05-2), preferably 100: (0.5-4): (0.05-1)；And/or
The ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5, preferably 1.5-4.5；And/or
The U of the Titanium Sieve Molecular Sieve480/U330Value is 0.5-5, preferably 0.6-2.5；And/or
The I of the Titanium Sieve Molecular Sieve960/I550Value is 0.5-0.9, preferably 0.55-0.85.
In the present invention, U480It refers in ultraviolet-visible spectrum, the vicinity 480nm absorption peak strength, U330Refer to purple In outside-visible spectrum, the vicinity 330nm absorption peak strength, U480/U330Value indicates the vicinity 480nm absorption peak strength and 330nm The ratio of vicinity absorption peak strength generally exists in conventional Titanium Sieve Molecular Sieve ultraviolet-visible spectrum without precious metal The vicinity 480nm is absorbed without obvious, therefore the U of conventional Titanium Sieve Molecular Sieve480/U330It is 0.Ultraviolet-visible spectrum of the invention point Analysis carries out on Japanese JASCO company UV550 UV detector, molecular sieve solid ultraviolet-visible spectrum test process Scanning wavelength range 190nm~800nm.
Aforementioned modified with noble metals Titanium Sieve Molecular Sieve of the invention has special physical chemical characteristics structure, and benzene adsorbance is higher； The advantages such as micropore size distribution of the urface silicon titanium not less than body phase silicon titanium ratio and with 0.8-2nm range, the present invention is to aforementioned The preparation method of modified with noble metals Titanium Sieve Molecular Sieve is without particular/special requirement, as long as the noble metal with above structure can be prepared Modifying titanium-silicon molecular sieve, according to a preferred embodiment of the present invention, before the method preparation included the following steps Modified with noble metals Titanium Sieve Molecular Sieve is stated, this method comprises:
(1) by noble metal source, ammonia source, optionally water is mixed to obtain mixture；
(2) by the mixture, Titanium Sieve Molecular Sieve, optionally water mix after carry out hydro-thermal process.
In accordance with the present invention it is preferred that non-aqueous content of material is 0.01-50 weight % in the first mixture in step (1), it is excellent It is selected as 0.02-25 weight %, further preferably 0.05-10 weight %, most preferably 0.1-5 weight %；And/or
The condition being mixed in step (1) includes: that temperature is room temperature to 80 DEG C, and time 0.1-24h, preferably room temperature are extremely 60 DEG C, time 0.5-12h；It is possible thereby to improve the performance of molecular sieve.
In the present invention, non-aqueous content of material (solutes content) refers to that substance than water accounts for the weight hundred of total mixture Divide ratio, i.e., non-water substance/(non-water substance+water) * 100 weight %.
In accordance with the present invention it is preferred that solid content is 10-70 weight %, preferably 40-60 weight % after mixing in step (2).
In the present invention, solid content refers to the content of solid matter in slurries.
In accordance with the present invention it is preferred that the weight ratio of ammonia source and noble metal source is (5-10000): 100, preferably (10- 5000): 100.
In accordance with the present invention it is preferred that Titanium Sieve Molecular Sieve and the weight ratio of noble metal source are 100:(0.1-15), preferably 100:(0.2-10).
In accordance with the present invention it is preferred that the ammonia source is in the organic solution of ammonia, liquefied ammonia, ammonium hydroxide, a hydration ammonia and ammonia It is one or more.The organic solution of ammonia is, for example, the alcoholic solution of ammonia.
With the method for the invention it is preferred to 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.
, according to the invention it is preferred to which hydro-thermal process carries out in confined conditions, stage (1), stage (2) and stage are successively undergone (3), the stage (1) at 80-150 DEG C, preferably at 110-140 DEG C, more preferably at 120-140 DEG C, further preferably at 130-140 DEG C Processing 6-72 hours, preferably 6-8 hours, the stage (2) was cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, preferably Be 1-5 hours, the stage (3) be warming up to 120-200 DEG C, preferably 140-180 DEG C, it is 160-170 DEG C more preferable, reprocessing 6-96 it is small When, 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.
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.
In the present invention, the Titanium Sieve Molecular Sieve can may be regenerative agent for fresh titanium si molecular sieves, in order to effectively sharp The step of with resource, in the present invention, the preferably described Titanium Sieve Molecular Sieve is regenerative agent, is preferably regenerated includes: that (i) will draw off agent and acid Property peroxide mixed in the presence of aqueous solvent after carry out first contact, obtain the first mixture；
(ii) second is carried out after mixing first mixture in the presence of aqueous solvent with alkali source to contact, and second is connect It touches obtained the second mixture to be filtered, wash and obtain solid, the solid is dried, wherein is described to draw off agent and be Agent is drawn off using Titanium Sieve Molecular Sieve as the reaction unit of catalyst.
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.
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.
In the present invention, optional wider range of the temperature of first contact, for the present invention, in order to further increase point The catalytic performance of son sieve, the temperature of preferably described first contact is at 100 DEG C hereinafter, being preferably room temperature to 100 DEG C, more preferably 50-100 DEG C, particularly preferably 40-90 DEG C.
In the present invention, the optional range of the time of first contact is very wide, specifically can be according to being selected, needle To the present invention, in order to further increase the performance of molecular sieve, the time of preferably described first contact in 0.5h or more, preferably 0.5-72h, more preferably 1-12h.
In the present invention, optional wider range of the temperature of second contact, for the present invention, in order to further increase point The performance of son sieve, the temperature of preferably described second contact is at 200 DEG C hereinafter, preferably 50-180 DEG C.
In the present invention, the optional range of the time of second contact is very wide, specifically can be according to being selected, needle To the present invention, in order to further increase the performance of molecular sieve, the time of the preferably second contact is in 0.1h or more, preferably 0.2- 12h。
With the method for the invention it is preferred to method of the invention further include: mixed agent will be drawn off with acidic peroxide Before mashing, 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 acidic peroxide solution is water, can also be according to needing to be added other solvents Auxiliary agent.
With the method for the invention it is preferred to which step (i) draws off agent to step (ii): acidic peroxide: the quality of alkali source Than preferably drawing off agent for 100:(100-1000): (100-500): acidic peroxide: the mass ratio of alkali source is 100:(400- 800): (300-400).
With the method for the invention it is preferred to which the mixed solid content of step (i) is 5-50 weight %, preferably 40-50 weight Measure %.
With the method for the invention it is preferred to which step (ii) mixed solid content is 2-50 weight %, preferably 20-30 weight Measure %.
With the method for the invention it is preferred to which the acidic peroxide is selected from hydrogen peroxide, tert-butyl hydroperoxide, peroxide Change one of hydrogen isopropylbenzene, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid or a variety of.
, according to the invention it is preferred to which aqueous solvent described in step (i) is water.
A preferred embodiment of the invention, aqueous solvent described in step (ii) are the mixture of water and alcohol, The weight ratio of water and alcohol is 1:0.1-0.5, and preferred alcohols are one of methanol, ethyl alcohol, the tert-butyl alcohol and isopropanol or a variety of.
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.
Wherein, described drying process can carry out at a temperature of between -200 DEG C of room temperature, and described roasting process can be It carries out within first 3-12 hours in air atmosphere after 0.5-6 hours in nitrogen atmosphere between 300-800 DEG C.
The benzene adsorbance of the molecular screen material obtained due to molecular screen material of the present invention and the 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 Siemens D5005 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.
(1) it under the conditions of normal pressure, 80 DEG C, is contacted after aqueous hydrogen peroxide solution is mixed with deactivated titanium silicon molecular sieve (SH-2) 2.5h obtains the first mixture, wherein the weight ratio of deactivated titanium silicon molecular sieve (SH-2) and hydrogen peroxide is 1:8, mixed Solid content is 50 weight %；
(2) under 80 DEG C and normal pressure, 1h is contacted after the first mixture is mixed with ammonia spirit again, wherein deactivated titanium silicon The weight ratio of molecular sieve and ammonia is 1:3, and mixed solid content is 30 weight %；Then by after products therefrom filtration washing in It is dried 120 minutes at 150 DEG C, obtains regeneration titanium-silicon molecular sieve catalyst A；
(3) it is mixed noble metal source palladium chloride and ammonium hydroxide (concentration is 20 weight %) to obtain mixture；Noble metal source: Ammonia source (weight ratio)=2:20, solutes content are 1 weight %, and the condition being mixed includes: 30 DEG C, normal pressure, 4h；
(4) hydro-thermal process is carried out after mixing mixture with regeneration titanium-silicon molecular sieve catalyst A；Hydrothermal treatment step is such as Under:
In 140 DEG C of experience first stage 6h in sealing reaction kettle, mixture is then cooled to 30 DEG C of experience second-orders 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, it is 10 DEG C/min by the heating rate of second stage treatment temperature to phase III temperature), in hydrothermal treatment process: Noble metal source: Titanium Sieve Molecular Sieve (weight ratio)=2:200, solid content are 40 weight %；
(5) products therefrom filtered, be washed with water, and in 110 DEG C of drying 120min, then in 550 DEG C of roasting temperatures 3h obtains molecular sieve, and 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.
Comparative example 8
(1) it under the conditions of normal pressure, 80 DEG C, is contacted after aqueous hydrogen peroxide solution is mixed with deactivated titanium silicon molecular sieve (SH-2) 2.5h obtains the first mixture, wherein the weight ratio of deactivated titanium silicon molecular sieve (SH-2) and hydrogen peroxide is 1:8, mixed Solid content is 50 weight %；
(2) under 80 DEG C and normal pressure, 1h is contacted after the first mixture is mixed with ammonia spirit again, wherein deactivated titanium silicon The weight ratio of molecular sieve and ammonia is 1:3, and mixed solid content is 30 weight %；Then by after products therefrom filtration washing in It is dried 120 minutes at 150 DEG C, obtains regeneration titanium-silicon molecular sieve catalyst A；
(3) noble metal source palladium chloride is mixed with ammonium hydroxide (concentration is 20 weight %) with regeneration titanium-silicon molecular sieve catalyst A Contact obtains mixture and then carries out hydro-thermal process；Hydrothermal treatment step is as follows:
In 140 DEG C of experience first stage 6h in sealing reaction kettle, mixture is then cooled to 30 DEG C of experience second-orders 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, it is 10 DEG C/min by the heating rate of second stage treatment temperature to phase III temperature), in hydrothermal treatment process: Noble metal source: ammonia source (weight ratio)=2:20, noble metal source: Titanium Sieve Molecular Sieve (weight ratio)=2:200, solid content are 40 weights Measure %；
(4) products therefrom filtered, be washed with water, and in 110 DEG C of drying 120min, then in 550 DEG C of roasting temperatures 3h obtains molecular sieve, and XRD crystalline phase figure and comparative example 1 are consistent, and what is illustrated is the Titanium Sieve Molecular Sieve with MFI structure.
Embodiment 2
This example demonstrates that method provided by the invention and product.
(1) it under 60 DEG C, condition of normal pressure, is contacted after aqueous hydrogen peroxide solution is mixed with deactivated titanium silicon molecular sieve (SH-3) 2.5h obtains the first mixture, wherein the weight ratio of deactivated titanium silicon molecular sieve (SH-3) and hydrogen peroxide is 1:6, mixed Solid content is 40 weight %；
(2) under 60 DEG C and normal pressure, 1h is contacted after the first mixture is mixed with ammonia spirit again, wherein deactivated titanium silicon The weight ratio of molecular sieve and ammonia is 1:3, and mixed solid content is 20 weight %；Then by after products therefrom filtration washing in It is dried 120 minutes at 150 DEG C, obtains regeneration titanium-silicon molecular sieve catalyst B；
(3) it is mixed noble metal source palladium acetylacetonate and ammonium hydroxide (concentration is 20 weight %) to obtain mixture；Your gold Category source: ammonia source (weight ratio)=2:10, solutes content are 2 weight %, and the condition being mixed includes: 40 DEG C, normal pressure, 3h；
(4) hydro-thermal process is carried out after mixing mixture with regeneration titanium-silicon molecular sieve catalyst B；Hydrothermal treatment step is such as Under: in 130 DEG C of experience first stage 8h in sealing reaction kettle, mixture is then cooled to 50 DEG C of experience second stage and is stopped After 5h, continue seal reaction kettle in 170 DEG C at a temperature of undergo phase III 16h (wherein, by room temperature to the first rank The heating rate of Duan Wendu is 1 DEG C/min, is 10 DEG C/min by the rate of temperature fall of first stage temperature to second stage temperature, by The heating rate of second stage temperature to phase III temperature is 20 DEG C/min), wherein in hydrothermal treatment process: noble metal source: Titanium Sieve Molecular Sieve (weight ratio)=2:100, solid content are 50 weight %.
(5) then recovery product according to the method for embodiment 1, obtains Titanium Sieve Molecular Sieve, XRD crystalline phase figure and comparative example 1 Unanimously.
Embodiment 3
This example demonstrates that method provided by the invention and product.
(1) it under 40 DEG C, condition of normal pressure, is contacted after aqueous hydrogen peroxide solution is mixed with deactivated titanium silicon molecular sieve (SH-4) 2.5h obtains the first mixture, wherein the weight ratio of deactivated titanium silicon molecular sieve (SH-3) and hydrogen peroxide is 1:4, mixed Solid content is 45 weight %；
(2) under 60 DEG C and normal pressure, 1h is contacted after the first mixture is mixed with ammonia spirit again, wherein deactivated titanium silicon The weight ratio of molecular sieve and ammonia is 1:10, and mixed solid content is 25 weight %；Then by after products therefrom filtration washing in It is dried 120 minutes at 150 DEG C, obtains regeneration titanium-silicon molecular sieve catalyst C；
(3) it is mixed noble metal source acetic acid platinum and ammonium hydroxide (concentration is 10 weight %) to obtain mixture；Noble metal source: Ammonia source (weight ratio)=2:30, solutes content are 5 weight %, and the condition being mixed includes: 50 DEG C, normal pressure, 5h；
(4) hydro-thermal process is carried out after mixing mixture with regeneration titanium-silicon molecular sieve catalyst C；Hydrothermal treatment step is such as Under: in 140 DEG C of experience first stage 6h in sealing reaction kettle, mixture is then cooled to 40 DEG C of experience second stage and is stopped After 1h, continue seal reaction kettle in 160 DEG C at a temperature of undergo phase III 12h (wherein, by room temperature to the first rank The heating rate of Duan Wendu is 5 DEG C/min, is 5 DEG C/min by the rate of temperature fall of first stage temperature to second stage temperature, by The heating rate of second stage temperature to phase III temperature is 5 DEG C/min), in hydrothermal treatment process: noble metal source: titanium silicon point Son sieve (weight ratio)=2:150, solid content are 60 weight %.
(5) then recovery product, acquisition molecular sieve, XRD crystalline phase figure and comparative example 1 are consistent according to the method for embodiment 1.
Embodiment 4
This example demonstrates that method provided by the invention and product.
Molecular sieve is prepared according to the method for embodiment 3, unlike, ammonia spirit replaces with the alcohol water of ammonia in step (2) Mixture, wherein the weight ratio of water and methanol is 1:0.3.The XRD crystalline 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, unlike, using is fresh Titanium Sieve Molecular Sieve as raw material generation (fresh Titanium Sieve Molecular Sieve is used to be prepared according to the method for comparative example 1), gained sample are used for regeneration titanium-silicon molecular sieve catalyst C XRD crystalline phase figure and comparative example 1 it is 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 Acidic peroxide processing, alkali process regenerative process；Wherein, the condition of roasting includes: to roast in air atmosphere at 570 DEG C 4h is burnt, the XRD crystalline phase figure and comparative example 1 of gained sample 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 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 9
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 10
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
Wherein, A indicates the ratio of the total specific surface area of external surface area Zhan.
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, 0.8-2.0nm pore-size distribution, urface silicon titanium and body phase silicon titanium ratio value, benzene adsorbance, N-116/N-112、U480/U330、I960/I550 Etc. data fully meet whole features of product of the present invention.Opposite, either comparative example 1 is that silicon source is prepared not using estersil Titanium Sieve Molecular Sieve containing noble metal, comparative example 2 utilize the Titanium Sieve Molecular Sieve containing noble metal that estersil is silicon source preparation, comparison The Titanium Sieve Molecular Sieve containing noble metal that example 3 is prepared using the Titanium Sieve Molecular Sieve carried noble metal prepared such as comparative example 1, still Comparative example 4-6 utilization draws off the titanium silicalite material that agent carried noble metal obtains and comparative example 7 draws off acid treated your gold of load of agent Belong to obtained titanium silicalite material, relative crystallinity, Kong Rong, total specific surface area, external surface area, 0.9-1.5nm pore-size distribution, benzene Adsorbance, N-116/N-112、U480/U330、I960/I550Etc. data be unable to satisfy whole features of product of the present invention.
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 at 40 DEG C of temperature, pressure 1.0MPa, alkene air speed is 20h-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 (25)

1. a kind of modified with noble metals Titanium Sieve Molecular Sieve, which is characterized in that the molecular sieve contains precious metal element, titanium elements, silicon member Element and oxygen element, wherein the Kong Rong of the molecular sieve is in 0.25cm3/ g or more, total specific surface area is in 250m2/ g or more, outer surface The ratio of the product total specific surface area of Zhan is 8-50%, N2The lower micropore size with 0.8-2nm range of Static Adsorption test is distributed, institute State the N of Titanium Sieve Molecular Sieve-116/N-112Value is 0.01-0.2；
The ratio of urface silicon titanium and body phase silicon titanium ratio is 1 or more in the molecular sieve, and the silicon titanium ratio refers to silica and oxygen Change the molar ratio of titanium, the urface silicon titanium is measured using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses X-ray Fluorescence spectrum method for measuring.
2. molecular sieve according to claim 1, wherein
The Kong Rongwei 0.3-0.8cm of the molecular sieve3/ g, total specific surface area are 250-650m2/ g, external surface area 30-150m2/ The ratio of the total specific surface area of g, external surface area Zhan is 10-35%；And/or
The molecular sieve is in 25 DEG C, P/P0=0.1 and adsorption time be 1 hour under conditions of the benzene adsorbance that measures be at least 80mg/g molecular sieve；And/or
Ratio >=2% of the total micropore size abundance of the micropore size Zhan of 0.8-2nm range in the molecular sieve；And/or
The noble metal is one of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au or a variety of；And/or
Element silicon in the molecular sieve: titanium elements: the molar ratio of precious metal element is 100:(0.1-10): (0.01-5)；And/or
The N of the Titanium Sieve Molecular Sieve-116/N-112Value is 0.02-0.15.
3. molecular sieve according to claim 2, wherein the ratio of the total specific surface area of external surface area Zhan of the molecular sieve is 12-30%；And/or
The molecular sieve is in 25 DEG C, P/P0=0.1 and adsorption time be 1 hour under conditions of the benzene adsorbance that measures be at least 100mg/g molecular sieve；And/or
Ratio >=5% of the total micropore size abundance of the micropore size Zhan of 0.8-2nm range in the molecular sieve；And/or
The noble metal is one of Pd, Ag, Au and Pt or a variety of；And/or
Element silicon in the molecular sieve: titanium elements: the molar ratio of precious metal element is 100:(0.1-5): (0.02-2)；And/or
The ratio of urface silicon titanium and the body phase silicon titanium ratio is 1.2 or more in the molecular sieve；And/or
The N of the Titanium Sieve Molecular Sieve-116/N-112Value is 0.02-0.1.
4. molecular sieve described in any one of -3 according to claim 1, wherein
The ratio of the total micropore size abundance of the micropore size Zhan of 0.8-2nm range is 6-20%；And/or
Element silicon: titanium elements: the molar ratio of precious metal element is 100:(0.2-5): (0.05-2)；And/or
The ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5；And/or
The U of the Titanium Sieve Molecular Sieve480/U330Value is 0.5-5；And/or
The I of the Titanium Sieve Molecular Sieve960/I550Value is 0.5-0.9.
5. molecular sieve according to claim 4, wherein
The ratio of the total micropore size abundance of the micropore size Zhan of 0.8-2nm range is 8-15%；And/or
Element silicon: titanium elements: the molar ratio of precious metal element is 100:(0.5-4): (0.05-1)；And/or
The ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.5-4.5；And/or
The U of the Titanium Sieve Molecular Sieve480/U330Value is 0.6-2.5；And/or
The I of the Titanium Sieve Molecular Sieve960/I550Value is 0.55-0.85.
6. the preparation method of molecular sieve described in a kind of any one of claim 1-5, this method comprises:
(1) by noble metal source, ammonia source, optionally water is mixed to obtain mixture；
(2) by the mixture, Titanium Sieve Molecular Sieve, optionally water mix after carry out hydro-thermal process；
Wherein, the heat treatment carries out in confined conditions, successively undergoes stage (1), stage (2) and stage (3), stage (1) It is handled 6-72 hours at 80-150 DEG C, the stage (2) is cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, the stage (3) it is warming up to 120-200 DEG C, is reprocessed 6-96 hours；
The Titanium Sieve Molecular Sieve is regenerative agent, and the step of regeneration includes:
(i) progress first after agent mixes in the presence of aqueous solvent with acidic peroxide will be drawn off to contact, obtain the first mixing Object；
(ii) second is carried out after mixing first mixture in the presence of aqueous solvent with alkali source to contact, and second is contacted To the second mixture be filtered, wash and obtain solid, the solid is dried；
It is wherein, described that draw off agent be that reaction unit using Titanium Sieve Molecular Sieve as catalyst draws off agent.
7. preparation method according to claim 6, wherein
Non-aqueous content of material is 0.01-50 weight % in the first mixture in step (1)；And/or
The condition being mixed in step (1) includes: that temperature is room temperature to 80 DEG C, time 0.1-24h；And/or
Solid content is 10-70 weight % after mixing in step (2)；And/or
The weight ratio of ammonia source and noble metal source is (5-10000): 100；And/or
Titanium Sieve Molecular Sieve and the weight ratio of noble metal source are 100:(0.1-15)；And/or
The ammonia source is one of organic solution of ammonia, liquefied ammonia, ammonium hydroxide, a hydration ammonia and ammonia or a variety of；And/or
The noble metal source is the carboxylic acid of the oxide of noble metal, the halide of noble metal, the carbonate of noble metal, noble metal Salt, the nitrate of noble metal, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, noble metal hydroxide and noble metal One of complex compound or a variety of；And/or
The noble metal is one of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au or a variety of.
8. preparation method according to claim 7, wherein non-aqueous content of material is in the first mixture in step (1) 0.02-25 weight %；And/or
The condition being mixed in step (1) includes: room temperature to 60 DEG C, time 0.5-12h；And/or
Solid content is 40-60 weight % after mixing in step (2)；And/or
The weight ratio of ammonia source and noble metal source is (10-5000): 100；And/or
Titanium Sieve Molecular Sieve and the weight ratio of noble metal source are 100:(0.2-10).
9. preparation method according to claim 8, wherein non-aqueous content of material is in the first mixture in step (1) 0.05-10 weight %.
10. preparation method according to claim 9, wherein non-aqueous content of material is in the first mixture in step (1) 0.1-5 weight %.
11. the preparation method according to any one of claim 6-10, wherein
Hydro-thermal process carries out in confined conditions, successively stage (1) is undergone to handle 6-8 hours at 110-140 DEG C, the stage (2) It is cooled to not higher than 70 DEG C and the residence time is 1-5 hours, the stage (3) is warming up to 140-180 DEG C, reprocesses 12-20 hours.
12. preparation method according to claim 11, wherein the stage (1) is handled at 120-140 DEG C, stage (3) heating To 160-170 DEG C.
13. preparation method according to claim 12, wherein the stage (1) is handled at 130-140 DEG C.
14. preparation method according to claim 11, 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.
15. preparation method according to claim 14, wherein
In condition 1, the temperature in stage (1) is 10-50 DEG C lower than the temperature in stage (3)；
In condition 2, the time in stage (1) is 5-24 hours shorter than the time in stage (3).
16. preparation method according to claim 15, wherein
In condition 1, the temperature in stage (1) is 20-40 DEG C lower than the temperature in stage (3)；
In condition 2, the time in stage (1) is 6-12 hours shorter than the time in stage (3).
17. the preparation method according to any one of claim 6-10, wherein described using Titanium Sieve Molecular Sieve as catalysis The agent that draws off of the reaction unit of agent draws off agent for Ammoximation reaction device.
18. preparation method according to claim 17, wherein
It is 50-100 DEG C that the condition of first contact, which includes: temperature, time 0.5-72h；
It is 50-180 DEG C that the condition of second contact, which includes: temperature, time 0.2-12h.
19. preparation method according to claim 17, wherein
Step (i) draws off agent to step (ii): acidic peroxide: the mass ratio of alkali source is 100:(100-1000): (100- 500)；
The mixed solid content of step (i) is 5-50 weight %；
Step (ii) mixed solid content is 2-50 weight %.
20. preparation method according to claim 19, wherein
The mixed solid content of step (i) is 40-50 weight %；
Step (ii) mixed solid content is 20-30 weight %.
21. preparation method according to claim 17, wherein
Aqueous solvent described in step (i) is water；
Aqueous solvent described in step (ii) is the mixture of water and alcohol, and the weight ratio of water and alcohol is 1:0.1-0.5, and alcohol is first One of alcohol, ethyl alcohol, the tert-butyl alcohol and isopropanol are a variety of；
The alkali source is one of ammonia, aliphatic amine, aliphatic hydramine and quaternary ammonium base or a variety of；
The acidic peroxide be selected from hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide, One of cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid are a variety of.
22. preparation method according to claim 17, wherein the Titanium Sieve Molecular Sieve is MFI structure, described to draw off agent Activity is active 50% or less of Titanium Sieve Molecular Sieve when fresh.
23. application of the molecular sieve described in any one of claim 1-5 in catalytic hydrocarbon direct oxidation reaction.
24. 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 1-5.
25. according to the method for claim 24, 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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