CN106904632B - A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol - Google Patents

A kind of HTS and its synthetic method and application and a kind of method for hydroxylation of phenol Download PDF

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CN106904632B
CN106904632B CN201510977713.8A CN201510977713A CN106904632B CN 106904632 B CN106904632 B CN 106904632B CN 201510977713 A CN201510977713 A CN 201510977713A CN 106904632 B CN106904632 B CN 106904632B
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titanium
molecular sieve
crystallization
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sieve
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CN106904632A (en
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史春风
朱斌
林民
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • 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
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/08—Dihydroxy benzenes; Alkylated derivatives thereof

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Abstract

The present invention relates to molecular sieve arts, specifically provide a kind of HTS and its synthetic method and application, this method comprises: (1) is hydrolyzed organic silicon source, titanium source, noble metal source and alkaline template to obtain mixture A, the mixture A is subjected to the first crystallization；(2) material after the first crystallization is mixed to get mixture B with Titanium Sieve Molecular Sieve original powder, the mixture B is subjected to the second crystallization, the dosage of Titanium Sieve Molecular Sieve original powder makes the solid content of mixture B be 30-80 weight %.The present invention also provides a kind of method for hydroxylation of phenol.The relative crystallinity for the Titanium Sieve Molecular Sieve that the method according to the invention is prepared is higher, and urface silicon titanium is high, particle size is more uniform, and height is measured on Ti, and Kong Rong and external surface area are big.

Description

A kind of HTS and its synthetic method and application and a kind of phenol hydroxylation Method
Technical field
It is synthesized the present invention relates to a kind of synthetic method of Titanium Sieve Molecular Sieve and by the synthetic method of Titanium Sieve Molecular Sieve The application in the oxidation reaction of Titanium Sieve Molecular Sieve and Titanium Sieve Molecular Sieve of the invention and a kind of method for hydroxylation of phenol.
Background technique
Titanium-silicon molecular sieve TS-1 is introduced transition metal element titanium formed in the framework of molecular sieve with ZSM-5 structure A kind of novel titanosilicate with superior catalytic selective oxidation performance.TS-1 not only has the catalysed oxidn of titanium, But also shape-selective effect and excellent stability with ZSM-5 molecular sieve.Since TS-1 molecular sieve is anti-in the oxidation of organic matter Ying Zhong can be used free of contamination low concentration hydrogen peroxide as oxidant, avoid oxidation process complex process and pollution environment The problem of, there is the unrivaled energy conservation of conventional oxidation system, economy and advantages of environment protection, and there is good reaction choosing Selecting property, therefore there is great prospects for commercial application.
The synthetic method of TS-1 is in 1981 by first public (USP4410501).This method is first to synthesize one kind to contain silicon Source, titanium source, organic base and/or basic anhydride reaction mixture, by this reaction mixture in 130-200 DEG C in autoclave It hydrothermal crystallizing 6-30 days, then separates, washes, dries, roast and obtains product.During plastic, the mixing of estersil and titanium esters The control of solution hydrolysising condition is very harsh, because the hydrolysis rate of the two mismatches, the latter is higher than the former, and the speed of organic base is added Degree will slightly generate the polymer of irreversible titanium fastly, and the polymer of these titaniums is difficult to enter skeleton in crystallization process, and more It being entrained in molecular sieve in the form of extra-framework titanium, this partial-titanium may not only block duct, but also hydrogen peroxide can be catalytically decomposed, Waste raw material.
Hereafter, researcher has carried out many trials to the synthetic method of Titanium Sieve Molecular Sieve and has improved and optimizated, but existing production Method still has that solid content is low, the production cycle is long, titanium is unevenly distributed, prepares the problems such as poor repeatability more；Especially titanium silicon molecule For sieve when applying in catalytic oxidation, the generally existing big activity of Titanium Sieve Molecular Sieve crystal grain is low, and crystal grain is small is separated by filtration difficulty The problems such as.
Summary of the invention
The purpose of the present invention is to provide a kind of synthetic methods of new Titanium Sieve Molecular Sieve, and synthesize to obtain by this method Titanium Sieve Molecular Sieve.
The present inventor has been surprisingly found that in the course of the research, first will be organic in the preparation process of Titanium Sieve Molecular Sieve The mixture that silicon source, titanium source, noble metal source are hydrolyzed with alkaline template, and hydrolysis obtained carries out Crystallizing treatment, then Titanium Sieve Molecular Sieve original powder is added in material after crystallization to solid content 30-80 weight %, mixture is then subjected to crystalline substance again Change processing, the relative crystallinity and particle diameter distribution and the parameters such as hole and specific surface area of Titanium Sieve Molecular Sieve so obtained are further Improve.Based on this discovery, the present invention is completed.
In order to realize foregoing purpose, according to the first aspect of the invention, the present invention provides a kind of conjunctions of Titanium Sieve Molecular Sieve At method, this method comprises:
(1) it is hydrolyzed organic silicon source, titanium source, noble metal source and alkaline template to obtain mixture A, by the mixing Object A carries out the first crystallization；
(2) by after the first crystallization material and Titanium Sieve Molecular Sieve original powder be mixed to get mixture B, by the mixture B into The second crystallization of row, wherein the dosage of Titanium Sieve Molecular Sieve original powder makes the solid content of mixture B be 30-80 weight %.
According to the second aspect of the invention, the present invention provides the Titanium Sieve Molecular Sieve synthesized by preceding method.
According to the third aspect of the invention we, the present invention provides the Titanium Sieve Molecular Sieve synthesized by method of the invention to exist Application in oxidation reaction.
According to the fourth aspect of the invention, the present invention provides a kind of method for hydroxylation of phenol, this method comprises: in benzene Under the conditions of phenolic hydroxyl group, phenol, hydrogen peroxide are contacted with catalyst, the catalyst contains titanium silicon molecule of the present invention Sieve.
The relative crystallinity for the Titanium Sieve Molecular Sieve that the method according to the invention is prepared is higher, and particle size is more uniform. And it was unexpected that bigger, surface silicon is measured on Ti using method of the invention compared with molecular screen primary powder method is not routinely added For titanium than high, Kong Rong and external surface area are bigger.
Synthetic method provided by the invention is able to suppress the decomposition of organic base template, and organic base template therein can With recycling (such as embodiment 5), cost is reduced, mitigates environmental pollution.
When the molecular sieve prepared using method of the invention is in phenol hydroxylation reaction, phenol conversion and to benzene two Sample resulting result of the selectivity of phenol obviously higher than the method preparation by comparative example.
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 synthetic methods of Titanium Sieve Molecular Sieve, this method comprises:
(1) it is hydrolyzed organic silicon source, titanium source, noble metal source and alkaline template to obtain mixture A, by the mixing Object A carries out the first crystallization；
(2) by after the first crystallization material and Titanium Sieve Molecular Sieve original powder be mixed to get mixture B, by the mixture B into The second crystallization of row, wherein the dosage of Titanium Sieve Molecular Sieve original powder makes the solid content of mixture B be 30-80 weight %.
Synthetic method according to the present invention, solid content principle refer to that the quality of solid matter in reaction kettle accounts for material in reactor The percentage composition of gross mass, it is general using by the total weight of total material metage, that is, material in reactor in reaction kettle, then will The solid matters such as the molecular sieve in reaction kettle are weighed after filtering is drawn off dry (temperature is less than 200 DEG C), are counted The percent data for the total weight that the solid matters weight such as the molecular sieve after calculating drying account for material in reactor is denoted as in reaction kettle The solid content of material.In the specific implementation process, it is not necessary to directly specifically go measurement solid content, but can first laboratory according to The volume ratio of solid and liquid after centrifugation, providing respective volume, working curve can than the working curve with solid content, and then whereby Intuitively provide the solid content of material in embodiment each time.It is preferred that the dosage of Titanium Sieve Molecular Sieve original powder makes mixture B's Solid content is 50-60 weight %.Thus the Titanium Sieve Molecular Sieve Ti being prepared is more evenly distributed, and relative crystallinity is higher, particle Size also more evenly, and higher for phenol conversion in oxidation reaction such as phenol hydroxylation reaction and hydroquinone choosing Selecting property is higher.
Synthetic method according to the present invention, the preferably temperature of the second crystallization are 20-100 DEG C higher than the temperature of the first crystallization, more It is preferred that 50-70 DEG C high.Thus the Titanium Sieve Molecular Sieve Ti being prepared is more evenly distributed, and urface silicon titanium is higher, relative crystallinity Higher, particle size is also more evenly, and higher for phenol conversion in oxidation reaction such as phenol hydroxylation reaction and to benzene The selectivity of diphenol is higher.
According to the method for the present invention, the hydrolysis carries out in the presence of aqueous solvent, and the type of the aqueous solvent can be with For the conventional selection of this field, various aqueous solvents may be incorporated for realizing the present invention, as long as the wherein water in aqueous solvent It is able to satisfy the condition that organic silicon source generates Titanium Sieve Molecular Sieve in crystallization process.The solvent is preferably water, can also foundation Need to be added other cosolvents, to this present invention without specific requirement, this is not described in detail here.It should be noted that containing water-soluble Agent can arise directly from the solvent portion of other material solutions, such as can be directed to the molten of alkaline template aqueous solution Agent part；It can also directly add, if the solvent portion of other aqueous solution of raw material can satisfy the requirement that feeds intake of aqueous solvent, Addition aqueous solvent is no longer needed to, if not satisfied, then needing that aqueous solvent additionally is added.
The purpose of the present invention can be realized according to preceding solution in synthetic method according to the present invention, for the present invention, It is preferred that the condition of the first crystallization includes: to carry out crystallization in confined conditions, temperature is 70-130 DEG C, preferably 80-120 DEG C.
The time of synthetic method according to the present invention, the first crystallization can be adjusted according to specific crystallization temperature etc., For the present invention, the preferably time of the first crystallization is 12-96h, more preferably 60-80h.
In the present invention, to the pressure of the first crystallization without particular/special requirement, crystallization can be carried out at autogenous pressures.
The purpose of the present invention can be realized according to preceding solution in synthetic method according to the present invention, for the present invention, It is preferred that the condition of the second crystallization includes: to carry out crystallization in confined conditions, temperature is 140-180 DEG C, preferably 150-170 DEG C.
The time of synthetic method according to the present invention, the second crystallization can be adjusted according to specific crystallization temperature etc., For the present invention, the preferably time of the second crystallization is 6-24h.
In the present invention, to the pressure of the second crystallization without particular/special requirement, crystallization can be carried out at autogenous pressures.
Synthetic method according to the present invention, preferably this method further include: by the Titanium Sieve Molecular Sieve obtained after the second crystallization with Processing is modified containing the contact of the modification liquid of nitric acid and at least one peroxide.
With the method for the invention it is preferred to which this method further includes, the solid product after modification is dried.
Synthetic method according to the present invention, preferably in the modification, as raw material Titanium Sieve Molecular Sieve with it is described The molar ratio of peroxide be 1:0.01-5, preferably 1:0.05-3, more preferably 1:0.1-2, the peroxide with it is described The molar ratio of nitric acid be 1:0.01-50, preferably 1:0.1-20, more preferably 1:0.2-10, further preferably 1:0.5-5, Particularly preferably 1:0.6-3.5, the Titanium Sieve Molecular Sieve is in terms of silica.
Synthetic method according to the present invention, in the preferably described modification liquid, the concentration of the peroxide and nitric acid is respectively 0.1-50 weight %, preferably 0.5-25 weight %, more preferably 5-15 weight %.
Synthetic method according to the present invention, preferably in the modification, as raw material Titanium Sieve Molecular Sieve with it is described Modification liquid 10-350 DEG C, preferably 20-300 DEG C, it is 50-250 DEG C more preferable, it is further preferred 60-200 DEG C at a temperature of connect Touching, the contact carry out in the container that pressure is 0-5MPa, and the pressure is gauge pressure, and the duration of the contact is 1-10 Hour, preferably 3-5 hours.
Synthetic method according to the present invention, the preferably described peroxide are selected from hydrogen peroxide, tert-butyl hydroperoxide, peroxide Change hydrogen isopropylbenzene, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
Synthetic method according to the present invention, preferably in the modification, as raw material Titanium Sieve Molecular Sieve with it is described The exposure level of modification liquid makes, using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, and modified titanium The peak area of absorption peak of the si molecular sieves between 230-310nm reduces by 2% or more, preferably reduction 2-30%, more preferably reduces 2.5-15%, further preferably reduction 3-10%, still more preferably reduction 3-6%；The Kong Rong of modified Titanium Sieve Molecular Sieve subtracts Few 1% or more, preferably reduction 1-20%, more preferably reduction 1.5-10%, further preferably reduction 2-5%, the Kong Rong use Static determination of nitrogen adsorption.
Synthetic method according to the present invention, the condition of preferably the first crystallization include: to carry out crystallization, temperature in confined conditions It is 70-130 DEG C, time 12-96h；
Second crystallization successively undergoes stage (1), stage (2) and stage (3) in confined conditions, and the stage, (1) was in 80-150 DEG C, preferably 110-140 DEG C, more preferably 120-140 DEG C, further preferably 130-140 DEG C crystallization 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, and preferably 1-5 hours, the stage (3) rose Temperature to 120-200 DEG C, preferably 140-180 DEG C, it is 160-170 DEG C more preferable, then crystallization 6-96 hours, preferably 12-20 hours.
Synthetic method according to the present invention, preferably stage (1) and stage (3) meet one or both of the following conditions:
Condition 1: the crystallization temperature in stage (1) is lower than the crystallization temperature of stage (3), it is preferable that the crystallization temperature in stage (1) Crystallization temperature than the stage (3) is 10-50 DEG C low, 20-40 DEG C preferably low；
Condition 2: the crystallization time in stage (1) is less than the crystallization time of stage (3), it is preferable that the crystallization time in stage (1) Crystallization time than the stage (3) 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 crystallization device that body uses is selected, and is not particularly limited.In general, raising the temperature to stage (1) crystalline substance Change 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 rank The rate of temperature fall of section (1) temperature to stage (2) temperature can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 5- 10℃/min.It can be 1-50 DEG C/min, preferably 2-40 by the heating rate of stage (2) temperature to stage (3) crystallization temperature DEG C/min, more preferably 5-20 DEG C/min.
Synthetic method according to the present invention, the percent hydrolysis of organic silicon source is 10-100% in preferred mixture A, further excellent It is selected as 50-90%, more preferably 60-80%.Thus the Titanium Sieve Molecular Sieve Ti being prepared is more evenly distributed, and relative crystallinity is more Height, particle size are also more evenly, and higher for phenol conversion in oxidation reaction such as phenol hydroxylation reaction and to benzene two The selectivity of phenol is higher.
Synthetic method according to the present invention, in preferred steps (1), with SiO2The organic silicon source of meter, with TiO2The titanium source of meter, Noble metal source, with NH3The alkaline template of meter and the dosage molar ratio of water are 100:(0.005-10): (0.1-10): (0.005- 40): (200-10000), preferably 100:(0.05-5): (0.5-2.0): (0.05-20): (500-5000).
According to the method for the present invention, the organic silicon source can be capable of forming two under the conditions of hydrolysis-condensation reaction to be various The silicon-containing compound of silica.Specifically, the organic silicon source can for one of silicon-containing compound shown in the Formulas I or It is a variety of,
In Formulas I, R1、R2、R3And R4Respectively C1~C4Alkyl, including C1~C4Straight chained alkyl and C3~C4Branch Alkyl, such as: R1、R2、R3And R4Respectively can for methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or Tert-butyl.
Specifically, the organic silicon source can be positive quanmethyl silicate, tetraethyl orthosilicate, four n-propyl of positive silicic acid and just One of four N-butyl of silicic acid is a variety of.Use in a specific embodiment of the present invention is tetraethyl orthosilicate.
According to the method for the present invention, the titanium source can be the conventional selection of this field, for the present invention, the preferably described titanium Source is selected from inorganic titanium salt and/or organic titanate, preferably organic titanate.
In the present invention, the inorganic titanium salt is selected from various hydrolyzable titanium salts, such as can be selected from TiX4、TiOX2Or Ti (SO4)2Contain titanium salt etc. various forms of, X is halogen in formula, preferably chlorine, wherein the preferred inorganic titanium salt is selected from TiCl4、 Ti(SO4)2And TiOCl2One of or it is a variety of.
In the present invention, it is M that the organic titanate, which preferably has structural formula,4TiO4Organic titanate, wherein M is preferred For the alkyl with 1-4 carbon atom, and 4 M can be identical or different, and it is metatitanic acid isopropyl that the preferably described organic titanate, which is selected from, One of ester, metatitanic acid n-propyl, butyl titanate and tetraethyl titanate are a variety of, use in a specific embodiment of the present invention It is butyl titanate as example, but the range being not intended to limit the present invention.
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.
According to the method for the present invention, optional wider range of the type of the alkaline template, can be aliphatic amine One of compound, aliphatic alcohol amine compounds and quaternary ammonium alkali cpd are 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.
It should be noted that when such as quaternary ammonium base of the organic base using strong basicity is as alkaline template, due to its alkalinity It is relatively strong, it can satisfy the requirement in Titanium Sieve Molecular Sieve synthesis process to mixture alkalinity, therefore, quaternary ammonium base is closed in Titanium Sieve Molecular Sieve Alkali source is used as at template is not only used as in the process.
When using other alkaline templates, the alkalinity of the mixture obtained after mixing is not able to satisfy Titanium Sieve Molecular Sieve conjunction When at requirement to mixture alkalinity in the process, those skilled in the art can according to need by way of adding alkali source and adjust The alkalinity of whole mixture.Optional wider range of the type of the alkali source, preferably inorganic alkali source.Wherein, inorganic alkali source can be with It is the alkaline matter of alkali or alkaline earth metal for ammonium hydroxide or cation, such as can is sodium hydroxide, potassium hydroxide, hydroxide One of calcium, sodium carbonate and potassium carbonate are a variety of.
In the present invention, advantage of the invention is illustratively illustrated as template using tetrapropylammonium hydroxide.
With the method for the invention it is preferred to when step (2) mixes the material after the first crystallization with Titanium Sieve Molecular Sieve original powder, Material after first crystallization cools (no particular/special requirement, crystallizing kettle can be opened by being down to room temperature) after referring to the first crystallization Afterwards without material obtained from other any processing.
With the method for the invention it is preferred to this method further include: be filtered, washed the second crystallization products therefrom and consolidated Body, by obtained solid it is dry or not dry after roast.
In the present invention, optional wider range of the condition of the drying is specifically referred to prior art progress.For this Invention, the condition of the preferably described drying include: that temperature is room temperature to 200 DEG C, more preferably 80-120 DEG C；Time is 1-24h, excellent It is selected as 2-10h.
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 450-550 DEG C；The time of roasting is 2-12h, preferably 2-4h；More preferably The condition of the roasting includes: to roast 0.5-6h in nitrogen atmosphere at 350-600 DEG C first, then at 350-600 DEG C in sky 0.5-12h is roasted in gas atmosphere.
According to the method for the present invention, the type of the Titanium Sieve Molecular Sieve original powder can be containing template without particular/special requirement Titanium Sieve Molecular Sieve original powder may be the Titanium Sieve Molecular Sieve original powder without template, such as can for synthesis after by stripper plate Agent step or Titanium Sieve Molecular Sieve without Template removal step, for the present invention, mould in the preferably described Titanium Sieve Molecular Sieve original powder The content of plate agent is lower than 0.1 weight %, that is, passes through the Titanium Sieve Molecular Sieve original powder of Template removal.
Synthetic method provided by the invention, has an advantage that
1, high solids content synthesizes, and improves production efficiency；
2, the Titanium Sieve Molecular Sieve relative crystallinity that synthesis obtains improves, and urface silicon titanium is high, and Ti content is high, Kong Rong and outer ratio Surface area increases；
3, the particle diameter distribution etc. for the Titanium Sieve Molecular Sieve crystal grain that synthesis obtains also is improved, and the general integrated distribution of partial size exists 150nm-350nm, it can be seen that, method of the invention is optimized and adjusts to the nucleation and growth course of poromerics, So that crystal grain is more uniform；
4, synthetic method provided by the invention is able to suppress the decomposition of organic base template, organic base template therein It can be recycled, reduce cost, mitigate environmental pollution；
5, when the molecular sieve prepared using method of the invention is in phenol hydroxylation reaction, phenol conversion and to benzene Sample resulting result of the selectivity of diphenol obviously higher than the method preparation by comparative example.
The present invention provides a kind of Titanium Sieve Molecular Sieve that synthetic method according to the invention synthesizes.
The urface silicon titanium of Titanium Sieve Molecular Sieve according to the present invention, the Titanium Sieve Molecular Sieve is not less than body phase silicon titanium ratio, institute Molar ratio of the silicon titanium than referring to silica and titanium oxide is stated, the urface silicon titanium is measured using X-ray photoelectron spectroscopy, institute Body phase silicon titanium ratio is stated using x-ray fluorescence spectrometry；Preferably, the ratio of the urface silicon titanium and the body phase silicon titanium ratio Value is 1.2 or more；It is highly preferred that the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5；Further preferably The ratio of ground, the urface silicon titanium and the body phase silicon titanium ratio is 1.5-4.5.
Titanium Sieve Molecular Sieve according to the present invention has higher catalytic activity.Specifically, it is prepared by method of the invention Titanium Sieve Molecular Sieve shows higher catalytic activity and hydroquinone selection when being used as the catalyst of phenol hydroxylation reaction Property.Advantage of the invention is illustrated as example using phenol hydroxylation reaction in a specific embodiment of the present invention, but of the invention Titanium Sieve Molecular Sieve is not limited only to have advantage for phenol hydroxylation reaction, equally has good effect for other oxidation reactions Fruit.
The present invention provides the application of Titanium Sieve Molecular Sieve of the invention in the oxidation reaction.
The present invention provides a kind of method for hydroxylation of phenol, this method comprises: under the conditions of phenol hydroxylation, by benzene Phenol, hydrogen peroxide are contacted with catalyst, and the catalyst contains Titanium Sieve Molecular Sieve of the present invention.
According to the method for the present invention, preferably described to urge as long as the catalyst contains Titanium Sieve Molecular Sieve of the invention The content of Titanium Sieve Molecular Sieve is 50 weight % or more in agent, and more preferable content is 60-100 weight %.Of the invention specific The content for used in embodiment being Titanium Sieve Molecular Sieve is the catalyst of 100 weight %, but this is not intended to limit the present invention Range.Catalyst composition when content herein is referred to without carrier.
When the catalyst is formed body, the catalyst further includes carrier, wherein carrier can be Al2O3、ZnO、 MgO、SiO2, CaO and TiO2, rare earth oxide RE2O3(RE La, Ce, Y or Nd etc.).
In the present invention, in the catalyst, in addition to including Titanium Sieve Molecular Sieve, also other it commonly can also to be used for phenol Hydroxylated catalyst.
According to a preferred embodiment of the present invention, the preferably described catalyst is Titanium Sieve Molecular Sieve, the phenol hydroxyl Base condition includes: that temperature is 30-120 DEG C, and preferably 50-90 DEG C, the temperature used in an embodiment of the present invention is 80 DEG C, benzene The molar ratio of phenol and hydrogen peroxide is (1-10): 1, more preferable (2-5): 1, the weight ratio of Titanium Sieve Molecular Sieve and phenol is (0.001-0.5): 1, preferably (0.01-0.08): 1, more preferably (0.04-0.06): 1.In this way, can get better phenol Conversion ratio and hydroquinone selectivity.
It is necessary to be noted that those skilled in the art, under close high phenol conversion, merely By the change of method for preparing catalyst, it is more difficult (especially improving 5 percentage points or more) to improve hydroquinone selectivity.And this The inventor of invention is but found surprisingly that, uses Titanium Sieve Molecular Sieve of the present invention for catalyst, relative to conventional titanium silicon point Sub- sieve catalyst can effectively improve hydroquinone selectivity (improving 5 percentage points or more).
The present invention is further illustrated for embodiment below, but the content being not intended to limit the present invention.Implement All reagents used are commercially available chemically pure reagent in example and comparative example.
In embodiment and comparative example, using water as aqueous solvent, in mixed process, the contained water energy if other feed intake Enough requirements that feeds intake met to water, then without adding water, if not satisfied, water is then added as needed.
The measurement of X-ray diffraction (XRD) crystalline phase figure of embodiment and comparative example sample is penetrated in Siemens D5005 type X- It is carried out on line diffractometer, wherein with sample and authentic specimen in 2 θ be spreading out for the five fingers diffractive features peak between 22.5 ° -25.0 ° The crystallinity for penetrating the ratio of the sum of intensity (peak height) to indicate sample relative to authentic specimen, wherein the sample with comparative example 1 is Authentic specimen, crystallinity are calculated as 100%；Relative crystallinity data and grain size distribution data of each sample etc. are shown in Table 1.Its In, crystal grain (particle) size distribution data is the percentage that crystal grain quantity of the sample between 150nm-350nm accounts for total crystal grain quantity Number (uses PHILIPS company, Holland XL 30ESEM type scanning electron microscope SEM, observes sample particle size and carry out crystal grain Size distribution statistics, wherein acceleration voltage is 20kV).The infrared spectrum of each sample passes through 8210 type fourier infrared of Nicolet Spectrometer obtains.
In the present invention, external surface area, Kong Rong are measured using BET method.
The surface Si/Ti (molar ratio) of embodiment and comparative example sample by X-ray photoelectron spectroscopic analysis (XPS) than being surveyed Amount and calculating obtain.Body phase Si/Ti (molar ratio) is obtained than being measured and being calculated by x-ray fluorescence analysis (XRF).Surface Silicon titanium ratio/body phase silicon titanium ratio data are shown in Table 1.
In the present invention, organic silicon source amount of hydrolysis is measured by gas chromatography.Gas-chromatography used is Agilent 6890N is equipped with the capillary column (30m*320 μm * 25 μm) of thermal conductivity detector (TCD) TCD and HP-5.Wherein, injector temperature 180 DEG C, column temperature is 150 DEG C, uses nitrogen as carrier gas, and the flow velocity of carrier gas is 25mL/min.Method particularly includes: it takes a certain amount of mixed Object is closed from gas chromatograph injection port sample introduction, detect and quantified by external standard method using TCD after flowing through chromatographic column.It adopts Organic silicon source percent hydrolysis is calculated with following formula:
XOrganic silicon source[(m ° of %=Organic silicon source-mOrganic silicon source)/m°Organic silicon source] × 100%
In formula, XOrganic silicon sourceIndicate the percent hydrolysis of organic silicon source；m°Organic silicon sourceIndicate the quality for the organic silicon source being added；mOrganic silicon sourceTable Show the quality of unhydrolysed organic silicon source.
Comparative example 1
Method described in this comparative example reference literature (Zeolites, volume 1992,12,943-950 pages) prepares TS-1 points Son sieve, for illustrating the process according to conventional hydrothermal crystallization method synthesis of titanium silicon molecular sieve.
22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of tetrapropylammonium hydroxide, and are added by (20 DEG C) at room temperature 59.8 grams of distilled water hydrolyze 1.0 hours at normal pressure and 60 DEG C after being stirred, obtain the hydrating solution of tetraethyl orthosilicate, It is slowly added into the solution as composed by 1.1 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring, gained is mixed It closes object to stir 3 hours at 75 DEG C, obtains clear colloid.This colloid is put into stainless steel sealing reaction kettle, at 170 DEG C At a temperature of constant temperature place 3 days, obtain the mixture of crystallization product；It by the filtering of this mixture, is washed with water, and in 110 DEG C of dryings 60 minutes, obtain TS-1 original powder.This TS-1 original powder is roasted 3 hours in 550 DEG C of temperature in air atmosphere, obtains TS-1 molecular sieve B1。
Through detecting, the XRD crystal phase of gained molecular sieve B1 is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ The five fingers diffractive features peak shows that molecular sieve B1 has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Near There is the unexistent characteristic absorption peak of silica zeolite in place, shows that titanium has entered sample skeleton.
Embodiment 1
Titanium Sieve Molecular Sieve is prepared according to the method for comparative example 1, the difference is that titanium silicon is added after crystallization condition difference and crystallization Molecular sieve.Detailed process is as follows:
(20 DEG C) at room temperature, by 22.5 grams of tetraethyl orthosilicates and 7.0 grams of tetrapropylammonium hydroxide and 0.2 gram of palladium chloride Mixing, and 59.8 grams of distilled water are added, it is hydrolyzed 1.0 hours at normal pressure and 60 DEG C after being stirred, obtains tetraethyl orthosilicate Hydrating solution, be slowly added into vigorous stirring as 1.1 grams of butyl titanates with it is molten composed by 5.0 grams of anhydrous isopropyl alcohols Liquid stirs gained mixture 3 hours at 75 DEG C, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).It will This colloid is put into stainless steel sealing reaction kettle, places 3 days in 110 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product, unload Titanium Sieve Molecular Sieve original powder (B1) is added after pressure to 50 weight % of solid content, then by slurry in closed reactor in 160 DEG C and It is handled for 24 hours under self-generated pressure；It by the filtering of this mixture, is washed with water, and 60 minutes dry in 110 DEG C, in 550 DEG C of temperature in sky It is roasted 3 hours in gas atmosphere, obtains TS-1 molecular sieve-4 A 1.
Through detecting, the XRD crystal phase of gained molecular sieve-4 A 1 is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ The five fingers diffractive features peak shows that molecular sieve-4 A 1 has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Near There is the unexistent characteristic absorption peak of silica zeolite in place, shows that titanium has entered sample skeleton.
Comparative example 2
At a temperature of 20 DEG C, first the tetrapropylammonium hydroxide solution that concentration is 10 weight % is mixed with butyl titanate It closes, is subsequently added into tetraethyl orthosilicate, form mixture.With SiO in mixture2The tetraethyl orthosilicate of meter, with TiO2The titanium of meter Sour four butyl esters, with NH3The tetrapropylammonium hydroxide of meter and the molar ratio of water are 100:5:10:800.By gained mixture at 75 DEG C Lower stirring 3 hours, obtains clear colloid.This colloid is put into stainless steel sealing reaction kettle, in 120 DEG C of at a temperature of constant temperature It places 3 days, obtains the mixture of crystallization product, by the filtering of gained crystallization product, be washed with water, and dry 120 points in 110 DEG C Then clock roasts 3 hours in 550 DEG C of temperature in air atmosphere, obtain molecular sieve B2.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve B2 It is almost the same.
Embodiment 2
At a temperature of 20 DEG C, first the tetrapropylammonium hydroxide solution that concentration is 10 weight % is mixed with butyl titanate It closes, is subsequently added into tetraethyl orthosilicate and palladium chloride, form mixture.With SiO in mixture2The tetraethyl orthosilicate of meter, with TiO2The butyl titanate of meter, palladium chloride, with NH3The tetrapropylammonium hydroxide of meter and the molar ratio of water are 100:5:2:10:800. Gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).By this Colloid is put into stainless steel sealing reaction kettle, places 3 days in 120 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product, release Titanium Sieve Molecular Sieve original powder (B1) is added afterwards to 60 weight % of solid content, then by slurry in closed reactor in 170 DEG C of temperature Degree and self-generated pressure under crystallization 12 hours, by gained crystallization product filtering, be washed with water, and in 110 DEG C dry 120 minutes, so It is roasted in air atmosphere 3 hours in 550 DEG C of temperature afterwards, obtains molecular sieve-4 A 2.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 2 It is almost the same.
Embodiment 3
At a temperature of 20 DEG C, first the tetrapropylammonium hydroxide solution that concentration is 25 weight % is mixed with butyl titanate It closes, is subsequently added into tetraethyl orthosilicate and palladium chloride, form mixture.With SiO in mixture2The tetraethyl orthosilicate of meter, with TiO2The butyl titanate of meter, palladium chloride, with NH3The tetrapropylammonium hydroxide of meter and the molar ratio of water are 100:2:1:15: 1500.Gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid (percent hydrolysis of organic silicon source is 100%). This colloid is put into stainless steel sealing reaction kettle, is placed 3 days in 100 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product, Titanium Sieve Molecular Sieve original powder (B1) is added after release to 30 weight % of solid content, then by slurry in closed reactor in 170 DEG C Temperature and self-generated pressure under crystallization 6 hours, by gained crystallization product filtering, be washed with water, and in 110 DEG C dry 120 minutes, Then it is roasted in air atmosphere 3 hours in 550 DEG C of temperature, obtains molecular sieve-4 A 3.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 3 It is almost the same.
Embodiment 4
Using the method synthesis of molecular sieve of embodiment 1, the difference is that, Titanium Sieve Molecular Sieve original powder (B1) is added after release to admittedly 70 weight % of content obtains molecular sieve-4 A 4.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 4 It is almost the same.
Embodiment 5
Using the method synthesis of molecular sieve of embodiment 1, the difference is that, tetrapropylammonium hydroxide used is that embodiment 1 is returned What receipts obtained, obtain molecular sieve-4 A 5.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 5 It is almost the same.
Embodiment 6
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, Titanium Sieve Molecular Sieve original powder (B1) is added after release to admittedly 55 weight % of content obtains molecular sieve-4 A 6.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 6 It is almost the same.
Embodiment 7
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, the temperature of the second crystallization is 190 DEG C, obtains molecular sieve A7。
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 7 It is almost the same.
Embodiment 8
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, hydrolysising condition is adjusted, so that the colloid that hydrolysis obtains The percent hydrolysis of middle organic silicon source is 60%, obtains molecular sieve-4 A 8.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 8 It is almost the same.
Embodiment 9
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, hydrolysising condition is adjusted, so that the colloid that hydrolysis obtains The percent hydrolysis of middle organic silicon source is 80%, obtains molecular sieve-4 A 9.
The SPECTROSCOPIC CHARACTERIZATION of X-ray diffraction and the Fourier infrared spectrum characterization and 1 sample A1 of embodiment of gained molecular sieve-4 A 9 It is almost the same.
Embodiment 10
Using the method synthesis of molecular sieve of embodiment 3, the difference is that, hydrolysising condition is adjusted, so that the colloid that hydrolysis obtains The percent hydrolysis of middle organic silicon source is 40%, obtains molecular sieve-4 A 10.
X-ray diffraction and the Fourier infrared spectrum characterization of gained molecular sieve-4 A 10 and the spectroscopy of 1 sample A1 of embodiment are special It levies almost the same.
Embodiment 11
By TS-1 molecular sieve-4 A 1 that embodiment 1 obtains and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide be The aqueous solution mixing of (mass concentration of hydrogen peroxide is 7.5%) stirs obtained mixture in closed container at 70 DEG C 5h is reacted, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dried extremely at 120 DEG C Constant weight obtains modified Titanium Sieve Molecular Sieve A11.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide Molar ratio be 1:0.1.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 1 sample of embodiment through X-ray diffraction.With Titanium Sieve Molecular Sieve A1 It compares, the peak area of the absorption peak in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve A11 of obtained modification between 230-310nm subtracts Few 3.4%, held by the hole of static determination of nitrogen adsorption and reduces 2.7%.
Embodiment 12
By TS-1 molecular sieve-4 A 2 that embodiment 2 obtains and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide be The aqueous solution mixing of (mass concentration of hydrogen peroxide is 5%), obtained mixture is anti-in 120 DEG C of stirrings in closed container 4h is answered, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C Weight, obtains modified Titanium Sieve Molecular Sieve A12.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide Molar ratio is 1:0.4.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 1 sample of embodiment through X-ray diffraction.With raw material Titanium Sieve Molecular Sieve A2 is compared, the peak area of the absorption peak in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve A12 of obtained modification between 230-310nm 4.1% is reduced, is held by the hole of static determination of nitrogen adsorption and reduces 3.3%.
Embodiment 13
By TS-1 molecular sieve-4 A 3 that embodiment 3 obtains and contain HNO3(HNO3Mass concentration 15%) and hydrogen peroxide be The aqueous solution mixing of (mass concentration of hydrogen peroxide is 8%), obtained mixture is anti-in 150 DEG C of stirrings in closed container 3h is answered, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C Weight, obtains modified Titanium Sieve Molecular Sieve A13.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide Molar ratio is 1:2.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 1 sample of embodiment through X-ray diffraction.With raw material Titanium Sieve Molecular Sieve A3 It compares, the peak area of the absorption peak in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve A13 of obtained modification between 230-310nm subtracts Few 4.5%, held by the hole of static determination of nitrogen adsorption and reduces 4.4%.
Embodiment 14
It prepares according to the method for embodiment 1, unlike, specifically carry out as follows:
(20 DEG C) at room temperature, by 22.5 grams of tetraethyl orthosilicates and 7.0 grams of tetrapropylammonium hydroxide and 0.2 gram of palladium chloride Mixing, and 59.8 grams of distilled water are added, it is hydrolyzed 1.0 hours at normal pressure and 60 DEG C after being stirred, obtains tetraethyl orthosilicate Hydrating solution, be slowly added into vigorous stirring as 1.1 grams of butyl titanates with it is molten composed by 5.0 grams of anhydrous isopropyl alcohols Liquid stirs gained mixture 3 hours at 75 DEG C, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).It will This colloid is put into stainless steel sealing reaction kettle, places 3 days in 110 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product, unload Titanium Sieve Molecular Sieve original powder (B1) is added after pressure to 50 weight % of solid content, then passes through slurry at 140 DEG C in closed reactor First stage crystallization 6h is gone through, after mixture is then cooled to 30 DEG C of experience second stage stop 2h, is continued in sealing reaction kettle In at a temperature of 170 DEG C undergo phase III crystallization 12h (wherein, by room temperature to the heating of first stage crystallization temperature Rate is 2 DEG C/min, is 5 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature, by second The heating rate of phase process temperature to phase III crystallization temperature is 10 DEG C/min)；By crystallization product filtering, it is washed with water, And it is 60 minutes dry in 110 DEG C, it is roasted in air atmosphere 3 hours in 550 DEG C of temperature, obtains TS-1 molecular sieve-4 A 14.Sample warp X-ray diffraction is similar with the SPECTROSCOPIC CHARACTERIZATION of 1 sample of embodiment.
Embodiment 15
It is prepared according to the method for embodiment 2, unlike, specifically carry out as follows:
At a temperature of 20 DEG C, first the tetrapropylammonium hydroxide solution that concentration is 10 weight % is mixed with butyl titanate It closes, is subsequently added into tetraethyl orthosilicate and palladium chloride, form mixture.With SiO in mixture2The tetraethyl orthosilicate of meter, with TiO2The butyl titanate of meter, palladium chloride, with NH3The tetrapropylammonium hydroxide of meter and the molar ratio of water are 100:5:2:10:800. Gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid (percent hydrolysis of organic silicon source is 100%).By this Colloid is put into stainless steel sealing reaction kettle, places 3 days in 120 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product, release Titanium Sieve Molecular Sieve original powder (B1) is added afterwards to 60 weight % of solid content, then undergoes slurry at 130 DEG C in closed reactor First stage crystallization 8h continues in sealing reaction kettle after mixture is then cooled to 50 DEG C of experience second stage stop 5h Undergo phase III crystallization 16h (wherein, by the heating speed of room temperature to first stage crystallization temperature at a temperature of 170 DEG C Rate is 1 DEG C/min, is 10 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature, by second-order The heating rate of section treatment temperature to phase III crystallization temperature is 20 DEG C/min), by the filtering of gained crystallization product, it is washed with water It washs, and is dried 120 minutes in 110 DEG C, then roasted in air atmosphere 3 hours in 550 DEG C of temperature, obtain molecular sieve-4 A 15.It should Sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 1 sample of embodiment through X-ray diffraction.
Embodiment 16
It is prepared according to the method for embodiment 3, unlike, specifically carry out as follows:
At a temperature of 20 DEG C, first the tetrapropylammonium hydroxide solution that concentration is 25 weight % is mixed with butyl titanate It closes, is subsequently added into tetraethyl orthosilicate and palladium chloride, form mixture.With SiO in mixture2The tetraethyl orthosilicate of meter, with TiO2The butyl titanate of meter, palladium chloride, with NH3The tetrapropylammonium hydroxide of meter and the molar ratio of water are 100:2:1:15: 1500.Gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid (percent hydrolysis of organic silicon source is 100%). This colloid is put into stainless steel sealing reaction kettle, is placed 3 days in 100 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product, Titanium Sieve Molecular Sieve original powder (B1) is added after release to 30 weight % of solid content, then by slurry in closed reactor at 140 DEG C First stage crystallization 6h is undergone, after mixture is then cooled to 40 DEG C of experience second stage stop 1h, continues to react in sealing Undergo phase III crystallization 12h (wherein, by room temperature to the liter of first stage crystallization temperature at a temperature of 160 DEG C in kettle Warm rate is 5 DEG C/min, is 5 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature, by the The heating rate of two-stage treatment temperature to phase III crystallization temperature is 5 DEG C/min), by the filtering of gained crystallization product, use water Washing, and dried 120 minutes in 110 DEG C, it is then roasted in air atmosphere 3 hours in 550 DEG C of temperature, obtains molecular sieve-4 A 16. The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 1 sample of embodiment through X-ray diffraction.
Embodiment 17
Titanium Sieve Molecular Sieve A17 is prepared according to the method for embodiment 14, unlike, the crystallization temperature of phase III is also 140℃。
Embodiment 18
Titanium Sieve Molecular Sieve A18 is prepared according to the method for embodiment 14, unlike, the crystallization temperature of first stage is 110 ℃。
Embodiment 19
Titanium Sieve Molecular Sieve A19 is prepared according to the method for embodiment 14, unlike, the crystallization time of first stage is 12h, Second stage is to be cooled to 70 DEG C of stop 2h.
Embodiment 20
By Titanium Sieve Molecular Sieve A14 that embodiment 14 obtains and contain HNO3(HNO3Mass concentration 10%) and peroxidating be The aqueous solution mixing of hydrogen (mass concentration of hydrogen peroxide is 7.5%), obtained mixture is stirred in closed container at 70 DEG C Reaction 5h is mixed, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, by obtained solid matter in 120 DEG C of dryings To constant weight, modified Titanium Sieve Molecular Sieve A20 is obtained.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and peroxidating The molar ratio of hydrogen is 1:0.1.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of 1 sample of embodiment through X-ray diffraction.With Titanium Sieve Molecular Sieve A14 is compared, the peak face of the absorption peak in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve A20 of obtained modification between 230-310nm Product reduces 5.8%, is held by the hole of static determination of nitrogen adsorption and reduces 4.3%.
Test case
This test case is for illustrating what the method for the molecular sieve that the method provided through the invention obtains and comparative example obtained Molecular sieve is used for the reaction effect of phenol hydroxylation reaction.
By sample prepared by above-described embodiment 1-20 and comparative example 1-2 according to sample: phenol: acetone=1:20:16 Weight ratio is uniformly mixed in a three-necked flask with condenser pipe, 80 DEG C is warming up to, then according to benzene under stirring Phenol: the hydrogen peroxide that concentration is 27.5 weight % is added in hydrogen peroxide=3:1 molar ratio, reacts 3 hours at this temperature, institute It obtains product and measures each product distribution using HP-5 capillary column (30m × 0.25mm) on Agilent6890N chromatograph, as a result It is shown in Table 1.
Wherein:
Wherein, the molal quantity of the phenol of reaction is participated in the total mole number of the molal quantity of benzenediol and the molal quantity of benzoquinones Meter, the benzenediol includes catechol, resorcinol and hydroquinone.
Table 1
From the results shown in Table 1, the relative crystallinity for the Titanium Sieve Molecular Sieve that the method according to the invention is prepared It is higher, and particle size is more uniform, and urface silicon titanium is high, and Kong Rong and external surface area are larger.In addition, using side of the invention When the molecular sieve of method preparation is in phenol hydroxylation reaction, the selectivity of phenol conversion and hydroquinone obviously higher than by The resulting result of sample of the method preparation of comparative example.In addition, organic base template follows in synthetic method provided by the invention Ring uses, still can obtain higher relative crystallinity and more uniform particle size and higher phenol conversion and The selectivity of hydroquinone also significantly reduces consumption of raw materials in this way while improving combined coefficient, mitigates environmental pollution.
By the result of the embodiment of the present invention 11-20 it is found that being modified using method of the invention and crystallization, can make Obtained Titanium Sieve Molecular Sieve physico-chemical property and catalytic activity is greatly improved.
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 (43)

1. a kind of synthetic method of Titanium Sieve Molecular Sieve, which is characterized in that this method comprises:
(1) it is hydrolyzed organic silicon source, titanium source, noble metal source and alkaline template to obtain mixture A, by the mixture A Carry out the first crystallization；
(2) by after the first crystallization material and Titanium Sieve Molecular Sieve original powder be mixed to get mixture B, the mixture B is carried out the Two crystallization, wherein the dosage of Titanium Sieve Molecular Sieve original powder makes the solid content of mixture B be 30-80 weight %；
Wherein, the temperature of the second crystallization is 20-100 DEG C higher than the temperature of the first crystallization.
2. synthetic method according to claim 1, wherein the dosage of Titanium Sieve Molecular Sieve original powder contains consolidating for mixture B Amount is 50-60 weight %.
3. synthetic method according to claim 1, wherein the temperature of the second crystallization is 50-70 higher than the temperature of the first crystallization ℃。
4. synthetic method described in any one of -3 according to claim 1, wherein
The condition of first crystallization includes: to carry out crystallization in confined conditions, and temperature is 70-130 DEG C, time 12-96h；
The condition of second crystallization includes: to carry out crystallization in confined conditions, and temperature is 140-180 DEG C, time 6-24h.
5. synthetic method according to claim 1, wherein this method further include: by the titanium silicon obtained after the second crystallization point Son sieve is contacted with the modification liquid containing nitric acid and at least one peroxide is modified processing.
6. synthetic method according to claim 5, wherein the Titanium Sieve Molecular Sieve in the modification, as raw material It is 1:0.01-5 with the molar ratio of the peroxide, the molar ratio of the peroxide and the nitric acid is 1:0.01-50, institute Titanium Sieve Molecular Sieve is stated in terms of silica.
7. synthetic method according to claim 6, wherein the Titanium Sieve Molecular Sieve in the modification, as raw material It is 1:0.05-3 with the molar ratio of the peroxide, the molar ratio of the peroxide and the nitric acid is 1:0.1-20, institute Titanium Sieve Molecular Sieve is stated in terms of silica.
8. synthetic method according to claim 7, wherein the Titanium Sieve Molecular Sieve in the modification, as raw material It is 1:0.1-2 with the molar ratio of the peroxide, the molar ratio of the peroxide and the nitric acid is 1:0.2-10, described Titanium Sieve Molecular Sieve is in terms of silica.
9. synthetic method according to claim 8, wherein in the modification, the peroxide and the nitre The molar ratio of acid is 1:0.5-5.
10. synthetic method according to claim 9, wherein in the modification, the peroxide and the nitre The molar ratio of acid is 1:0.6-3.5.
11. synthetic method according to claim 5, wherein in the modification liquid, the concentration of the peroxide and nitric acid Respectively 0.1-50 weight %.
12. synthetic method according to claim 11, wherein in the modification liquid, the peroxide and nitric acid it is dense Degree is respectively 0.5-25 weight %.
13. synthetic method according to claim 12, wherein in the modification liquid, the peroxide and nitric acid it is dense Degree is respectively 5-15 weight %.
14. synthetic method according to claim 5, wherein the Titanium Sieve Molecular Sieve in the modification, as raw material With the modification liquid 10-350 DEG C at a temperature of contacted, it is described contact pressure be 0-5MPa container in carry out, institute Stating pressure is gauge pressure, and the duration of the contact is 1-10 hours.
15. synthetic method according to claim 14, wherein the titanium silicon molecule in the modification, as raw material Sieve and the modification liquid 20-300 DEG C at a temperature of contacted, duration of the contact is 3-5 hours.
16. synthetic method according to claim 15, wherein the titanium silicon molecule in the modification, as raw material Sieve with the modification liquid 50-250 DEG C at a temperature of contacted.
17. synthetic method according to claim 16, wherein the titanium silicon molecule in the modification, as raw material Sieve with the modification liquid 60-200 DEG C at a temperature of contacted.
18. synthetic method according to claim 5, wherein the peroxide is selected from hydrogen peroxide, tert-butyl hydroperoxide Hydrogen, cumyl hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
19. the synthetic method according to any one of claim 5-18, wherein in the modification, as original The Titanium Sieve Molecular Sieve of material and the exposure level of the modification liquid make, using on the basis of the Titanium Sieve Molecular Sieve as raw material, it is ultraviolet- In visible spectrum, the peak area of absorption peak of the modified Titanium Sieve Molecular Sieve between 230-310nm reduces by 2% or more；Modified The hole of Titanium Sieve Molecular Sieve, which holds, reduces 1% or more, and the Kong Rong is using static determination of nitrogen adsorption.
20. synthetic method according to claim 19, wherein the titanium silicon molecule in the modification, as raw material It sieves and makes with the exposure level of the modification liquid, using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, The peak area of absorption peak of the modified Titanium Sieve Molecular Sieve between 230-310nm reduces 2-30%；Modified Titanium Sieve Molecular Sieve Hole, which holds, reduces 1-20%, and the Kong Rong is using static determination of nitrogen adsorption.
21. synthetic method according to claim 20, wherein the titanium silicon molecule in the modification, as raw material It sieves and makes with the exposure level of the modification liquid, using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, The peak area of absorption peak of the modified Titanium Sieve Molecular Sieve between 230-310nm reduces 2.5-15%；Modified Titanium Sieve Molecular Sieve Hole hold and reduce 1.5-10%, the Kong Rong is using static determination of nitrogen adsorption.
22. synthetic method according to claim 21, wherein the titanium silicon molecule in the modification, as raw material It sieves and makes with the exposure level of the modification liquid, using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, The peak area of absorption peak of the modified Titanium Sieve Molecular Sieve between 230-310nm reduces 3-10%；Modified Titanium Sieve Molecular Sieve Hole, which holds, reduces 2-5%, and the Kong Rong is using static determination of nitrogen adsorption.
23. synthetic method according to claim 22, wherein the titanium silicon molecule in the modification, as raw material It sieves and makes with the exposure level of the modification liquid, using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, The peak area of absorption peak of the modified Titanium Sieve Molecular Sieve between 230-310nm reduces 3-6%.
24. synthetic method described in any one of -3 according to claim 1, wherein
The condition of first crystallization includes: to carry out crystallization in confined conditions, and temperature is 70-130 DEG C, time 12-96h；
Second crystallization successively undergoes stage (1), stage (2) and stage (3) in confined conditions, and the stage, (1) was in 80-150 DEG C of crystalline substance Change 6-72 hours, the stage (2) is cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, and the stage (3) is warming up to 120- 200 DEG C, then crystallization 6-96 hours.
25. synthetic method according to claim 24, wherein
In second crystallization, the stage (1) 110-140 DEG C crystallization 6-8 hours, the stage (2) is cooled to not higher than 70 DEG C and when stopping Between be at least 1-5 hours, the stage (3) is warming up to 140-180 DEG C, then crystallization 12-20 hours.
26. synthetic method according to claim 25, wherein
In second crystallization, the stage (1) is warming up to 160-170 DEG C in 120-140 DEG C of progress crystallization, stage (3).
27. synthetic method according to claim 26, wherein
In second crystallization, the stage (1) is in 130-140 DEG C of progress crystallization.
28. synthetic method according to claim 24, wherein stage (1) and stage (3) meet one of the following conditions Or both:
Condition 1: the crystallization temperature in stage (1) is lower than the crystallization temperature of stage (3)；
Condition 2: the crystallization time in stage (1) is less than the crystallization time of stage (3)；
Stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.
29. synthetic method according to claim 28, wherein
Condition 1: the crystallization temperature in stage (1) is 10-50 DEG C lower than the crystallization temperature in stage (3)；
Condition 2: the crystallization time in stage (1) is 5-24 hours shorter than the crystallization time in stage (3).
30. synthetic method according to claim 29, wherein
Condition 1: the crystallization temperature in stage (1) is 20-40 DEG C lower than the crystallization temperature in stage (3)；
Condition 2: the crystallization time in stage (1) is 6-12 hours shorter than the crystallization time in stage (3).
31. synthetic method described in any one of -3 according to claim 1, wherein the percent hydrolysis of organic silicon source in mixture A For 10-100%.
32. synthetic method according to claim 31, wherein the percent hydrolysis of organic silicon source is 50-90% in mixture A.
33. synthetic method according to claim 32, wherein the percent hydrolysis of organic silicon source is 60-80% in mixture A.
34. synthetic method described in any one of -3 according to claim 1, wherein in step (1), with SiO2The organosilicon of meter Source, with TiO2The titanium source of meter, noble metal source, with NH3The alkaline template of meter and the dosage molar ratio of water are 100:(0.005- 10): (0.1-10): (0.005-40): (200-10000).
35. synthetic method described in any one of -3 according to claim 1, wherein in step (1), the organic silicon source is One of silicon-containing compound shown in the Formulas I is a variety of, and the titanium source is selected from inorganic titanium salt and/or organic titanate, institute It states alkaline template and is selected from one of quaternary ammonium base, aliphatic amine and aliphatic hydramine or a variety of；
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl；
The noble metal source is the nitric acid of the oxide of noble metal, the halide of noble metal, the carbonate of noble metal, noble metal One of salt, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, the hydroxide of noble metal and complex compound of noble metal Or it is a variety of, the noble metal is one of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au or a variety of.
36. the Titanium Sieve Molecular Sieve that synthetic method described in any one of claim 1-35 synthesizes.
37. Titanium Sieve Molecular Sieve according to claim 36, wherein the urface silicon titanium of the Titanium Sieve Molecular Sieve is not less than body Phase silicon titanium ratio, molar ratio of the silicon titanium than referring to silica and titanium oxide, the urface silicon titanium use x-ray photoelectron energy Spectrometry measurement, the body phase silicon titanium ratio use x-ray fluorescence spectrometry.
38. the Titanium Sieve Molecular Sieve according to claim 37, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio Value is 1.2 or more.
39. the Titanium Sieve Molecular Sieve according to claim 38, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio Value is 1.2-5.
40. Titanium Sieve Molecular Sieve according to claim 39, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio Value is 1.5-4.5.
41. the application of Titanium Sieve Molecular Sieve in the oxidation reaction described in any one of claim 36-40.
42. a kind of method for hydroxylation of phenol, this method comprises: by phenol, hydrogen peroxide and being urged under the conditions of phenol hydroxylation Agent contact, which is characterized in that the catalyst contains Titanium Sieve Molecular Sieve described in any one of claim 36-40.
43. according to the method for claim 42, wherein the catalyst is the Titanium Sieve Molecular Sieve, the phenol hydroxyl Base condition includes: that temperature is 30-120 DEG C, and the molar ratio of phenol and hydrogen peroxide is (1-10): 1, Titanium Sieve Molecular Sieve and phenol Weight ratio be (0.001-0.5): 1.
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