CN107879357A - A kind of HTS and its synthetic method and application and a kind of method of cyclic ketones oxidation - Google Patents
A kind of HTS and its synthetic method and application and a kind of method of cyclic ketones oxidation Download PDFInfo
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Abstract
The present invention relates to catalysis material field, specifically provides a kind of HTS and its preparation method and application, and the HTS is made up of noble metal, silicon, titanium and oxygen element, the I of the HTS960/I550It is worth for 0.5 0.9, the U of the HTS480/U330It is worth for 0.5 5, the N of the HTS‑117/N‑114It is worth for 0.01 0.25.The invention provides a kind of method of cyclic ketones oxidation, this method includes：Cyclic ketones, oxidant and catalyst are contacted, the catalyst contains HTS of the present invention.The HTS of the present invention, compared with prior art, in the oxidation reaction, not only improve the diffusion of reactant and product, make oxidation activity give full play to and selectivity raising, such as use it for ring molecule, the reaction that particularly cyclic ketone molecule is participated in or generated, more preferable catalytic effect can be obtained；Be advantageous to the filtering and separation of post catalyst reaction again, be easy to industrial applications.
Description
Technical field
The present invention relates to a kind of HTS and its synthetic method and application, and a kind of method of cyclic ketones oxidation.
Background technology
HTS is important catalysis oxidation material, such as have MFI crystal structures titanium-silicon molecular sieve TS-1 be by
One kind formed in framework of molecular sieve of the transition metal titanium introducing with ZSM-5 structures is with superior catalytic selectivity oxygen
Change the novel titanosilicate of performance.TS-1 not only has the catalysed oxidn of titanium, but also selecting with ZSM-5 molecular sieve
Shape acts on and excellent stability.Because TS-1 molecular sieves are in the oxidation reaction of organic matter, free of contamination low concentration can be used
Hydrogen peroxide is as oxidant, the problem of avoiding oxidizing process complex process and pollution environment, have conventional oxidation system without
Analogous energy-conservation, economy and advantages of environment protection, and there is good reaction selectivity, therefore should with greatly industry
Use prospect.
TS-1 preparation method is first public by Taramasso et al. (USP 4410501).This method is first to prepare one kind
Reactant mixture containing silicon source, titanium source, organic base and/or basic anhydride, then by this reactant mixture in autoclave in
130~200 DEG C of 6~30d of hydrothermal crystallizing, then separate, wash, dry, be calcined and obtain product.On Thangaraj et al. thinks
Effective titanium content in the TS-1 molecular sieves that the method for stating is prepared into skeleton is seldom, and then they disclosed one kind in 1992
Can be effectively increased Ti content in skeleton prepare TS-1 method (Zeolites, 1992, Vol.12：943), it is said that this method energy
The Si/Ti ratios of molecular sieve are dropped to 20 from 39, methods described is by appropriate TPAOH (TPAOH) aqueous solution addition
The stirring and dissolving certain time into ethyl silicate solution, the isopropanol for being then slowly added to butyl titanate with vigorous stirring are molten
The liquid mixture that liquid is clarified (must be slowly added dropwise to prevent tetrabutyl titanate hydrolysis too fast and form white TiO2It is heavy
Form sediment), stir 15min after, be slow added into the appropriate TPAOH aqueous solution, then by reactant mixture in 75~80 DEG C except alcohol 3~
3~6d of hydrothermal crystallizing at 170 DEG C is transferred in autoclave after 6h, TS-1 is obtained after drying, wherein, mole group of reactant mixture
As SiO2：(0.01~0.10) TiO2：0.36TPAOH：35H2O。
HTS is prepared existing technology (such as GB 2071071A, USP 4410501, and Zeolites,
1992, Vol.12：943) in, because the brilliant ability of Ti leading in itself is weak so that it is longer to prepare the crystallization time of HTS, together
When yield it is relatively low.In the last few years, although prepare the technology of HTS by it is certain improve (such as CN101134575A,
CN1247771A), but effect is not also very good.
The content of the invention
It is an object of the present invention to the deficiency existing for existing process for preparing titanium-silicon molecular sieve, there is provided one kind has spy
Other physical chemical characteristicses structure and the high HTS of catalytic oxidation activity and its synthetic method and application.
To realize object defined above, according to the first aspect of the invention, the invention provides a kind of HTS, the titanium silicon
Molecular sieve is made up of noble metal, silicon, titanium and oxygen element, the I of the HTS960/I550It is worth for 0.5-0.9, the titanium silicon
The U of molecular sieve480/U330It is worth for 0.5-5, the N of the HTS-117/N-114It is worth for 0.01-0.25.
According to the second aspect of the invention, the invention provides a kind of synthesis side of HTS of the present invention
Method, this method include：(1) by noble metal source, ammonia source, alternatively water mixing contact obtains the first mixture；
(2) in the presence of template, by titanium source, first mixture, alternatively water is mixed to get the second mixture；
(3) by second mixture, inorganic silicon source, alternatively water is mixed to get the 3rd mixture；
(4) the 3rd mixture is subjected to hydrothermal crystallizing, recovery obtains HTS.
According to the third aspect of the invention we, obtained titanium silicon molecule is synthesized the invention provides the method according to the present invention
Sieve.
According to the fourth aspect of the invention, the invention provides HTS of the present invention in the oxidation reaction
Using.
According to the fifth aspect of the invention, the invention provides a kind of method of cyclic ketones oxidation, this method to include：By ring
Ketone, oxidant and catalyst contact, the catalyst contain HTS of the present invention.
The HTS of the present invention, compared with prior art, in the oxidation reaction, not only improve reactant and product
Diffusion, make oxidation activity give full play to and selectivity raising, such as use it for ring molecule, particularly cyclic ketone molecule
The reaction for participating in or generating, can obtain more preferable catalytic effect；Be advantageous to the filtering and separation of post catalyst reaction again, be easy to
Industrial applications.
The method of the present invention is simple without particular/special requirement, preparation technology to raw material.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In the present invention, I960Refer in FFIR, 960cm-1Locate absorption peak strength, I550Refer to Fu
In vertical leaf transformation infrared spectrum, 550cm-1Locate absorption peak strength, I960/I550Value represents 960cm-1Locate absorption peak strength and 550cm-1Locate the ratio of absorption peak strength.The Fourier turn infrared of the present invention is in the type fourier infrareds of Nicolet 8210
Carried out on spectrometer, KBr tablettings (molecular sieve quality content is 10%), infrared photometer resolution ratio is 2cm-1, test scope
400cm-1~4000cm-1, scanning accumulative frequency 20 times.
In the present invention, U480Refer in ultraviolet-visible spectrum, 480nm vicinity absorption peak strength, U330Refer to purple
In outside-visible spectrum, 330nm vicinity absorption peak strength, U480/U330Value represents 480nm vicinity absorption peak strengths and 330nm
The ratio of vicinity absorption peak strength, in the HTS ultraviolet-visible spectrum without noble metal of routine, typically exist
480nm vicinity absorbs without obvious, therefore the U of conventional HTS480/U330For 0.The ultraviolet-visible spectrum point of the present invention
Analysis is carried out on Japanese JASCO companies UV550 UV detectors, molecular sieve solid ultraviolet-visible spectrum test process
Scanning wavelength scope 190nm~800nm.
In the present invention, N-117Refer to29Si is rotated in magic angle solid state nmr, the vicinity of relative chemical shifts -117 absworption peak
Intensity, N-114Refer to29Si is rotated in magic angle solid state nmr, the vicinity of relative chemical shifts -114 absorption peak strength, N-117/
N-114Value represents the vicinity absorption peak strength of relative chemical shifts -117 and the vicinity of relative chemical shifts -114 absorption peak strength
Ratio.The present invention's29Si MAS NMR rotate magic angle solid core mass analysis in the types of Varian Infinity plus 400
Carried out on NMR,29Si rotation MAS speed is 4kHz, is designated as methyl-monosilane outside.
According to the present invention, bullion content 0.01-10 mass % and/or Ti content are 0.01-10 mass %, preferably your gold
It is 0.05-5 mass % to belong to content 0.02-5 mass % and/or Ti content.
, according to the invention it is preferred to the I of the HTS960/I550It is worth for 0.55-0.85, preferably 0.65-0.8；
And/or the U of the HTS480/U330It is worth for 0.6-2.5, preferably 0.6-2；And/or the HTS
N-117/N-114It is worth for 0.02-0.15, preferably 0.02-0.08.
, according to the invention it is preferred to the particle diameter of HTS is 0.2-5 μm, more preferably 0.3-3 μm.
, according to the invention it is preferred to the pore volume of the HTS is in 0.15cm3/ more than g, preferably in 0.5cm3/ below g,
More preferably 0.25-0.45cm3/g。
, according to the invention it is preferred to total specific surface area of the HTS is in 300m2/ more than g, more preferably in 350m2/g
More than.
, according to the invention it is preferred to the ratio that the external surface area of the HTS accounts for total specific surface area is 5-30%, more
Preferably 8-25%.
, according to the invention it is preferred to the particle diameter of HTS is 0.3-5 μm, more preferably 0.3-3 μm.
In the present invention, total specific surface area of HTS refers to BET specific surface area, and external surface area refers to titanium
The surface area of the outer surface of si molecular sieves, external surface area is can be also simply referred to as, can be surveyed according to ASTM D4222-98 standard methods
.
In the present invention, the pore volume of HTS and aperture refer to pore volume and bore dia in molecular sieve respectively, and this is this
Known to art personnel, do not repeat herein.
, according to the invention it is preferred to the surface silicon titanium ratio of the HTS is not less than body phase silicon titanium ratio, the silicon titanium ratio
Refer to the mol ratio of silica and titanium oxide, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, the body phase silicon
Titanium ratio uses x-ray fluorescence spectrometry；Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2
More than；It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5；It is further preferred that the table
Face silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5.
In the present invention, as long as there is the HTS preceding feature purpose of the present invention, its synthesis side can be achieved
Method can be with a variety of, as long as can synthesize to obtain the HTS with preceding feature, for the present invention, preferably described titanium
Si molecular sieves synthesize as follows, and this method includes：
(1) by noble metal source, ammonia source, alternatively water mixing contact obtains the first mixture；
(2) in the presence of template, by titanium source, first mixture, alternatively water is mixed to get the second mixture；
(3) by second mixture, inorganic silicon source, alternatively water is mixed to get the 3rd mixture；
(4) the 3rd mixture is subjected to hydrothermal crystallizing, recovery obtains HTS.
, according to the invention it is preferred to non-aqueous content of material is 0.01-50 weight % in the first mixture in step (1), preferably
For 0.02-25 weight %, more preferably 0.05-10 weight %, most preferably 0.1-5 weight %.
According to the present invention, mixing the condition of contact includes：Temperature is that room temperature to 80 DEG C and/or time are 0.1-24h, preferably
Room temperature is to 60 DEG C and/or time 0.5-12h.It is possible thereby to further improve the performance of HTS.
In the present invention, the material that non-aqueous content of material (solutes content) refers to than water accounts for the weight hundred of total mixture
Divide ratio, i.e., non-water substance/(non-water substance+water) * 100 weight %.
, according to the invention it is preferred to the weight of ammonia source and noble metal source ratio is (5-50000)：100, it is preferably (10-
10000)：100, more preferably (50-5000)：100, be most preferably (100-2000)：100.It is possible thereby to further carry
The performance of high HTS.
, according to the invention it is preferred to inorganic silicon source：Titanium source：Noble metal source：Template：Mol ratio=100 of water：(0.5-5)：
(0.1-5)：(5-50)：(200-5000)；Preferably 100：(1-4)：(0.2-4)：(6-25)：(300-800), wherein, it is inorganic
Silicon source is with SiO2Meter, titanium source are with TiO2Meter, noble metal source are in terms of precious metal element, and template is with N or OH-Meter.
, according to the invention it is preferred to which hydrothermal crystallizing is carried out in confined conditions, stage (1), stage (2) and stage are undergone successively
(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
Handle 6-72 hours, preferably 6-8 hours, the stage (2) is cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, preferably
For 1-5 hours, the stage (3) is warming up to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160-170 DEG C, and reprocessing 6-96 is small
When, preferred 12-20 hours.
A preferred embodiment of the invention, preferably stage (1) and stage (3) meet one of following condition
Or both：
Condition 1：The temperature in stage (1) is less than the temperature in stage (3), it is preferable that the temperature in stage (1) is than the stage (3)
Temperature is low 10-50 DEG C, preferably low 20-40 DEG C；
Condition 2：The time in stage (1) is less than the time in stage (3), it is preferable that the time in stage (1) is than the stage (3)
Time short 5-24 hours, preferably short 6-12 hours.
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.
The method according to the 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, temperature is increased 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
Rate of temperature fall to stage (2) temperature can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 5-10 DEG C/min.
Can be 1-50 DEG C/min by the heating rate of stage (2) temperature to stage (3) temperature, preferably 2-40 DEG C/min, more preferably
For 5-20 DEG C/min.
The method according to the invention, optional wider range of the species of the inorganic silicon source are preferably described for the present invention
Inorganic silicon source is the one or more in silicate, Ludox and silica gel, and heretofore described silica gel or Ludox can be each
The silica gel or Ludox that the kind various production methods of form obtain, silicate is, for example, sodium metasilicate.
According to the present invention, optional wider range of the species of the template specifically can be according to the titanium of required preparation
Si molecular sieves type is determined, for example, in quaternary amine alkali cpd, aliphatic amine compound and aliphatic alcohol amines
It is one or more.
In the present invention, the quaternary ammonium base can be various organic level Four ammonium alkali, and the aliphatic amine can be various NH3In
The compound that is formed after aliphatic alkyl (be preferably alkyl) substitution of at least one hydrogen, the aliphatic hydramine can be each
Kind NH3In the compound that is formed after aliphatic alkyl (the be preferably alkyl) substitution of hydroxyl of at least one hydrogen.
Specifically, the quaternary ammonium base can be quaternary ammonium base shown in formula I, and the aliphatic amine can be what Formula II represented
Aliphatic amine, the aliphatic hydramine can be the aliphatic hydramine represented such as formula III：
In Formulas I, R5、R6、R7And R8Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as：R5、R6、R7And R8Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle
Butyl.
R9(NH2)n(Formula II)
In Formula II, n is 1 or 2 integer.When n is 1, R9For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, new penta
Base, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R9For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.It is more preferably fatty
Race's amines is the one or more in ethamine, n-butylamine, butanediamine and hexamethylene diamine
(HOR10)mNH(3-m)(formula III)
In formula III, m R10It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3-
C4Branched 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 compound is the one or more in MEA, diethanol amine and triethanolamine.
The template used in a particular embodiment of the present invention is TPAOH, hexamethylene diamine or n-butylamine.
, according to the invention it is preferred to the ammonia source is the one or more in the organic solution of ammonia, liquefied ammonia and ammoniacal liquor and ammonia；
One or more preferably in ammonia, liquefied ammonia and ammoniacal liquor, further preferred ammoniacal liquor.
In the present invention, the titanium source can be inorganic ti sources and/or organic titanium source.
A preferred embodiment of the invention, the titanium source are inorganic titanium salt and/or organic titanate.
In the present invention, the inorganic titanium salt is selected from various hydrolyzable titanium salts, such as can be selected from TiX4、TiOX2Or Ti
(SO4)2Containing titanium salt etc. various forms of, X is halogen in formula, preferably chlorine, wherein, preferably described inorganic titanium salt is selected from TiCl4、
Ti(SO4)2And TiOCl2In one or more.
In the present invention, it is M that the organic titanate, which preferably has structural formula,4TiO4Organic titanate, wherein, M is preferred
For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom, and 4 M can be with identical or different, preferably
The one kind or more of the organic titanate in for isopropyl titanate, metatitanic acid n-propyl, butyl titanate and tetraethyl titanate
Kind, what is used in a particular embodiment of the present invention is butyl titanate as example, but and is not so limited model of the invention
Enclose.
A preferred embodiment of the invention, preferably described noble metal source are oxide, the noble metal of noble metal
Halide, the carbonate of noble metal, the nitrate of noble metal, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, your gold
One or more in the hydroxide of category and the complex compound of noble metal, the noble metal be Ru, Rh, Pd, Re, Os, Ir, Pt,
One or more in Ag and Au.
With the method for the invention it is preferred to this method also includes：By obtained HTS and containing nitric acid and at least
A kind of modification liquid contact of peroxide is modified processing.
With the method for the invention it is preferred to which this method also includes, the solid product after modification is dried.
According to the present invention synthetic method, preferably in the modification, as raw material HTS with it is described
The mol ratio of peroxide is 1：0.01-5, preferably 1：0.05-3, more preferably 1：0.1-2, the peroxide with it is described
The mol ratio of nitric acid is 1：0.01-50, preferably 1：0.1-20, more preferably 1：0.2-10, more preferably 1：0.5-5,
Particularly preferably 1：0.6-3.5, the HTS is in terms of silica.
With the method for the invention it is preferred in the 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 %.
With the method for the invention it is preferred in the modification, HTS and the modification as raw material
Liquid 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, it is further preferred 60-200 DEG C at a temperature of contacted,
The contact is carried out in the container that pressure is 0-5MPa, and the pressure is gauge pressure, and the duration of the contact is small for 1-10
When, preferably 3-5 hours.
With the method for the invention it is preferred to the peroxide is selected from hydrogen peroxide, TBHP, hydrogen peroxide
Isopropylbenzene, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.
With the method for the invention it is preferred in the modification, HTS and the modification as raw material
The exposure level of liquid causes, using on the basis of the HTS as raw material, in ultraviolet-visible spectrum, and modified titanium silicon point
The peak area of absworption peak of the son sieve between 230-310nm reduces by more than 2%, preferably reduces 2-30%, more preferably reduces 2.5-
15%, 3-10% is further preferably reduced, still more preferably reduces 3-6%；The pore volume of modified HTS reduces 1%
More than, 1-20% is preferably reduced, more preferably reduces 1.5-10%, further preferably reduces 2-5%, the pore volume uses static nitrogen
Determination of adsorption method.
With the method for the invention it is preferred in the modification, HTS and the modification as raw material
The exposure level of liquid causes, using on the basis of the HTS as raw material, in ultraviolet-visible spectrum, and modified titanium silicon point
The peak area of absworption peak of the son sieve between 230-310nm reduces by more than 2%, preferably reduces 2-30%, more preferably reduces 2.5-
15%, 3-10% is further preferably reduced, still more preferably reduces 3-6%；The pore volume of modified HTS reduces 1%
More than, 1-20% is preferably reduced, more preferably reduces 1.5-10%, further preferably reduces 2-5%, the pore volume uses static nitrogen
Determination of adsorption method.
The method according to the invention, the process of described recovery product are well known to those skilled in the art, and are had no especially
Part, generally include processes such as product filtering or natural subsidence, washing, drying, roastings.
The invention provides the HTS obtained according to the method described in the present invention.
The invention provides the application of HTS of the present invention in the oxidation reaction.
Present invention also offers a kind of method of cyclic ketones oxidation, this method includes：Cyclic ketones, oxidant and catalyst are connect
Touch, the catalyst contains HTS of the present invention.
The method according to the invention, the condition of the contact can be the conventional selection of this area, for the present invention, preferably
The condition of contact includes：Temperature is 40-150 DEG C, preferably 40-120 DEG C；Pressure is 0.1-3.0MPa, preferably 0.1-
2.5MPa；Time is 0.1-24h, and the mol ratio of cyclic ketones and oxidant is 1：1-20, preferably 1：2-15.
With the method for the invention it is preferred to the mass ratio of cyclic ketones and catalyst is 0.5-150：1.
With the method for the invention it is preferred to the contact is carried out in the presence of solvent, wherein, preferred solvent and catalyst
Mass ratio is 1-200：1, preferably 2-150:1；More preferably described solvent is in water, alcohol, straight or branched ketone, acid and nitrile
One or more, preferably described solvent are water, C1-C5 alcohol, C2-C6 straight or branched ketone, C2-C8 nitrile and C2-C5
One or more in acid.
The method according to the invention, the solvent are preferably selected from water, methanol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, different
One or more in butanol, acetone, butanone, acetonitrile, propionitrile, benzene acetonitrile, acetic acid and propionic acid, more preferably described solvent are selected from second
One or more in nitrile, acetone, methanol, acetic acid and water.
The method according to the invention, charging order also requires without special, can first add cyclic ketones, can also first add oxygen
Agent or solvent.
With the method for the invention it is preferred to the oxidant is hydrogen peroxide, TBHP, peroxidating isopropyl
One or more in benzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid, the cyclic ketones be cyclohexanone, cyclopentanone and
One or more in methyl cyclohexanone.
The method according to the invention, after haptoreaction, reacted material can use the side of common distillation or rectifying
Method, after isolating target product, unreacted cyclic ketones raw material etc. does not have to separating-purifying, directly backs within reaction unit relaying
Continuous reaction.
Following embodiment will be further described to the present invention, but and be not so limited the present invention.
In each embodiment and comparative example, X-ray diffraction (XRD) the crystalline phase figure of sample is penetrated in Siemens D5005 types X-
It is measured on line diffractometer, the diffraction at the five fingers diffractive features peak between 2 θ is 22.5 ° -25.0 ° using sample and authentic specimen
The ratio of intensity (peak height) sum represents crystallinity of the sample relative to authentic specimen, here on the basis of the sample of comparative example 1
Sample, its crystallinity are calculated as 100%, and the relative crystallinity data of each sample are shown in Table 1.The benzene adsorbance of sample, pore volume, aperture point
Cloth, total specific surface area and external surface area determine on Micromeritics companies ASAP2405 static state n2 absorption apparatus.Sample
The elements such as noble metal, titanium and silicon composition determines on Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometers.
Comparative example 1
This comparative example explanation with reference to Zeolites, prepared by 1992, the Vol.12 method described in the 943-950 pages
TS-1 sieve samples.
22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOHs, and add 59.8 grams of distilled water, mixing
Uniformly after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C, the hydrating solution of tetraethyl orthosilicate is obtained, with vigorous stirring slowly
The solution being made up of 1.1 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols is added, gained mixture is stirred 3 at 75 DEG C
Hour, obtain clear colloid.This colloid is put into stainless steel cauldron, constant temperature is placed 3 days at a temperature of 170 DEG C, is obtained
To the mixture of crystallization product；It is 6-8 to filter, be washed with water to pH this mixture, and is dried 60 minutes in 110 DEG C, is obtained
TS-1 original powder.By this TS-1 originals powder in 550 DEG C of roasting temperatures 3 hours, TS-1 molecular sieves DB-1 is obtained.
Particle diameter, pore volume, total specific surface area, external surface area, the external surface area of its crystal grain account for total specific surface area ratio,
Relative crystallinity and I960/I550Table 1 is listed in etc. data.
Comparative example 2
(1) by noble metal source palladium bichloride, ammoniacal liquor (concentration is 20 weight %), butyl titanate, TPAOH, silicon
Glue mixes laggard water-filling thermal crystallisation；Silicon source：Titanium source：Noble metal source：Template：Water (mol)=100：2：1：15：1000；Your gold
Category source：Ammonia source (weight ratio)=2:20；
Hydrothermal crystallizing：First stage 6h is undergone in 140 DEG C in reactor is sealed, mixture is then cooled to 30 DEG C of warps
After going through second stage stop 2h, continue to undergo phase III 12h at a temperature of 170 DEG C in reactor is sealed (wherein, by room
The heating rate that temperature is warming up to first stage temperature is 2 DEG C/min, the drop by first stage temperature to second stage treatment temperature
Warm speed is 5 DEG C/min, is 10 DEG C/min by the heating rate of second stage treatment temperature to phase III temperature)；
(4) most afterwards through being cooled to room temperature and pressure release, by product in reactor is filtered, washing, dry and 550 DEG C at be calcined
5 hours, obtain HTS sample DB-2.
Embodiment 1
(1) noble metal source palladium bichloride is mixed into contact with ammoniacal liquor (concentration is 20 weight %) and obtains mixture；Noble metal source：
Ammonia source (weight ratio)=2:20, solutes content is 1 weight %, and mixing the condition of contact includes：30 DEG C, normal pressure, 4h；
(2) and then by mixture with butyl titanate, TPAOH mix；
(3) and then silica gel is added, mixes laggard water-filling thermal crystallisation；Silicon source：Titanium source：Noble metal source：Template：Water (mol)
=100：2：1：15：1000；
Hydrothermal crystallizing：First stage 6h is undergone in 140 DEG C in reactor is sealed, mixture is then cooled to 30 DEG C of warps
After going through second stage stop 2h, continue to undergo phase III 12h at a temperature of 170 DEG C in reactor is sealed (wherein, by room
The heating rate that temperature is warming up to first stage temperature is 2 DEG C/min, the drop by first stage temperature to second stage treatment temperature
Warm speed is 5 DEG C/min, is 10 DEG C/min by the heating rate of second stage treatment temperature to phase III temperature)；
(4) most afterwards through being cooled to room temperature and pressure release, by product in reactor is filtered, washing, dry and 550 DEG C at be calcined
5 hours, obtain HTS sample A.
Through characterizing：The crystal structure types of sample A HTS are MFI.It is its particle diameter, pore volume, total specific surface area, outer
Surface area accounts for ratio, relative crystallinity and the I of total specific surface area960/I550Table 1 is listed in etc. data.
Embodiment 2
(1) noble metal source palladium acetylacetonate is mixed into contact with ammoniacal liquor (concentration is 20 weight %) and obtains mixture；Your gold
Category source：Ammonia source (weight ratio)=2:10, solutes content is 2 weight %, and mixing the condition of contact includes：40 DEG C, normal pressure, 3h；
(2) and then by mixture with isopropyl titanate, n-butylamine mix；
(3) and then Ludox (solid content is 40 weight %) is added, mixes laggard water-filling thermal crystallisation；Silicon source：Titanium source：Your gold
Category source：Template：Water (mol)=100：3：2：35：3000；
Hydrothermal crystallizing：First stage 8h is undergone in 130 DEG C in reactor is sealed, mixture is then cooled to 50 DEG C of warps
After going through second stage stop 5h, continue to undergo phase III 16h at a temperature of 170 DEG C in reactor is sealed (wherein, by room
The heating rate that temperature is warming up to first stage temperature is 1 DEG C/min, by the cooling speed of first stage temperature to second stage temperature
Rate is 10 DEG C/min, is 20 DEG C/min by the heating rate of second stage temperature to phase III temperature)；
(4) most afterwards through being cooled to room temperature and pressure release, by product in reactor is filtered, washing, dry and 550 DEG C at be calcined
5 hours, obtain HTS sample B.
Through characterizing：The crystal structure types of sample B HTS are MFI.It is its particle diameter, pore volume, total specific surface area, outer
Surface area accounts for ratio, relative crystallinity and the I of total specific surface area960/I550Table 1 is listed in etc. data.
Embodiment 3
(1) noble metal source acetic acid platinum is mixed into contact with ammoniacal liquor (concentration is 10 weight %) and obtains mixture；Noble metal source：
Ammonia source (weight ratio)=2:10, solutes content is 5 weight %, and mixing the condition of contact includes：50 DEG C, normal pressure, 5h；
(2) and then by mixture with tetraethyl titanate, hexamethylene diamine mix；
(3) and then Ludox (solid content is 40 weight %) is added, mixes laggard water-filling thermal crystallisation；Silicon source：Titanium source：Your gold
Category source：Template：Water (mol)=100：4：3：25：2000；
Hydrothermal crystallizing：First stage 6h is undergone in 140 DEG C in reactor is sealed, mixture is then cooled to 40 DEG C of warps
After going through second stage stop 1h, continue to undergo phase III 12h at a temperature of 160 DEG C in reactor is sealed (wherein, by room
The heating rate that temperature is warming up to first stage temperature is 5 DEG C/min, by the cooling speed of first stage temperature to second stage temperature
Rate is 5 DEG C/min, is 5 DEG C/min by the heating rate of second stage temperature to phase III temperature)；
(4) most afterwards through being cooled to room temperature and pressure release, by product in reactor is filtered, washing, dry and 550 DEG C at be calcined
5 hours, obtain HTS sample C.
Through characterizing：The crystal structure types of sample C HTS are MFI.It is its particle diameter, pore volume, total specific surface area, outer
Surface area accounts for ratio, relative crystallinity and the I of total specific surface area960/I550Table 1 is listed in etc. data.
Embodiment 4
By HTS A that embodiment 1 obtains and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide for
The aqueous solution mixing of (mass concentration of hydrogen peroxide is 7.5%), obtained mixture is stirred in closed container at 70 DEG C
5h is reacted, the temperature of obtained reactant mixture is filtered after being down to room temperature, and obtained solid matter is dried extremely at 120 DEG C
Constant weight, obtain modified HTS D.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS and hydrogen peroxide
Mol ratio is 1：0.1.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of the sample of embodiment 1 through X-ray diffraction.With HTS A phases
Than the peak area of the absworption peak in the HTS D of obtained modification UV-Vis spectrum between 230-310nm is reduced
3.2%, reduce 2.8% by the pore volume of static determination of nitrogen adsorption.
Embodiment 5
By HTS B that embodiment 2 obtains and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide for
The aqueous solution mixing of (mass concentration of hydrogen peroxide is 5%), obtained mixture is stirred instead in closed container at 120 DEG C
4h is answered, the temperature of obtained reactant mixture is filtered after being down to room temperature, and obtained solid matter is dried to perseverance at 120 DEG C
Weight, obtains modified HTS E.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS and hydrogen peroxide rub
You are than being 1：0.4.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of the sample of embodiment 2 through X-ray diffraction.With raw material HTS B phases
Than the peak area of the absworption peak in the HTS E of obtained modification UV-Vis spectrum between 230-310nm is reduced
4.4%, reduce 3.5% by the pore volume of static determination of nitrogen adsorption.
Embodiment 6
By HTS C that embodiment 3 obtains and contain HNO3(HNO3Mass concentration 15%) and hydrogen peroxide for
The aqueous solution mixing of (mass concentration of hydrogen peroxide is 8%), obtained mixture is stirred instead in closed container at 150 DEG C
3h is answered, the temperature of obtained reactant mixture is filtered after being down to room temperature, and obtained solid matter is dried to perseverance at 120 DEG C
Weight, obtains modified HTS F.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS and hydrogen peroxide rub
You are than being 1：2.The sample is similar with the SPECTROSCOPIC CHARACTERIZATION of the sample of embodiment 3 through X-ray diffraction.With raw material HTS C phases
Than the peak area of the absworption peak in the HTS F of obtained modification UV-Vis spectrum between 230-310nm is reduced
4.7%, reduce 3.8% by the pore volume of static determination of nitrogen adsorption.
Embodiment 7
Identical with the raw material type and proportioning of embodiment 1, difference is the condition of hydro-thermal process.
By mixture be placed in stainless steel sealing reactor in, by room temperature with 15 DEG C/min heating rates by kettle temperature lifted to
190 DEG C and hydro-thermal process 6 hours, then kettle temperature is reduced to by 170 DEG C and herein temperature with 10 DEG C/min cooling rates at this temperature
The lower hydro-thermal process of degree 48 hours.
Through characterizing：The crystal structure types for obtaining HTS sample G are MFI, are observed and found by transmission electron microscope, and it is brilliant
Body particle is made up of single crystal grain substantially.Particle diameter, pore volume, total specific surface area, external surface area, the external surface area of its crystal grain account for
Ratio, relative crystallinity and the I of total specific surface area960/I550Data are listed in table 1.
Embodiment 8
Identical with the raw material type and proportioning of embodiment 1, difference is hydrothermal conditions.
Mixture is placed in stainless steel sealing reactor, lifted kettle temperature to 100 with 2 DEG C/min heating rates by room temperature
DEG C and hydro-thermal process 24 hours at this temperature；Then kettle temperature is raised to 170 DEG C and in this temperature with 10 DEG C/min heating rates
Lower hydro-thermal process 48 hours.
Through characterizing：The crystal structure types for obtaining HTS sample H are MFI, are observed and found by transmission electron microscope, and it is brilliant
Body particle is made up of the crystal grain that particle diameter is 3-80nm.
Particle diameter, pore volume, total specific surface area, external surface area, the external surface area of its crystal grain account for total specific surface area ratio,
Relative crystallinity and I960/I550Data are listed in table 1.
Embodiment 9
Method according to embodiment 1 prepares molecular sieve, unlike, the crystallization temperature of first stage is 110 DEG C.Then press
According to the method recovery product of embodiment 1, molecular sieve containing noble metal is obtained, its XRD crystalline phases figure is consistent with comparative example 1.
Embodiment 10
Method according to embodiment 1 prepares molecular sieve, unlike, the crystallization time of first stage is 12h, second stage
It is to be cooled to 70 DEG C of stop 2h.Then according to the method recovery product of embodiment 1, molecular sieve containing noble metal, its XRD crystalline phase are obtained
Figure is consistent with comparative example 1.
Table 1
As can be seen from Table 1：Sample prepared by the inventive method, has special physico-chemical structure.So that it is used for
In oxidation reaction, its catalytic oxidation activity, the selectivity of reaction product significantly improve compared with prior art, while have preferably
Stability of catalytic activity.
Testing example
Catalyst molecule sieve, cyclohexanone, hydrogen peroxide source and solvent methanol prepared by comparative example and embodiment is according to ring
Hexanone is 1 with the mol ratio of hydrogen peroxide and solvent methanol：2：5, wherein solvent methanol quality is 20g, solvent methanol and catalysis
The mass ratio of agent is 30：1, in temperature it is to carry out reaction 3h under 45 DEG C of pressure are 0.8MPa in closed reactor.It the results are shown in Table
2。
Table 2
| Sample source | Cyclic ketones conversion ratio, % | Carboxylic acid selectivity, % | Oxidant utilization, % |
| Embodiment 1 | 79.5 | 78.4 | 82.9 |
| Embodiment 2 | 76.8 | 70.3 | 73.8 |
| Embodiment 3 | 74.3 | 74.8 | 78.3 |
| Embodiment 4 | 84.1 | 89.7 | 83.2 |
| Embodiment 5 | 83.6 | 92.1 | 83.6 |
| Embodiment 6 | 87.6 | 89.6 | 83.1 |
| Embodiment 7 | 60.5 | 55.6 | 45.1 |
| Embodiment 8 | 60.7 | 53.7 | 44.9 |
| Embodiment 9 | 70.0 | 68.4 | 64.7 |
| Embodiment 10 | 71.2 | 65.3 | 63.2 |
| Comparative example 1 | 55.1 | 50.8 | 40.9 |
| Comparative example 2 | 55.3 | 50.2 | 41.3 |
From the results shown in Table 2：The catalyst Ti-si molecular sieves of the present invention are used for cyclic ketones oxidation reaction, carboxylic acid choosing
Selecting property is high, and the effective rate of utilization of oxidant is high.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (17)
1. a kind of HTS, it is characterised in that the HTS is made up of noble metal, silicon, titanium and oxygen element, the titanium
The I of si molecular sieves960/I550It is worth for 0.5-0.9, U480/U330It is worth for 0.5-5, N-117/N-114It is worth for 0.01-0.25.
2. HTS according to claim 1, wherein,
Bullion content 0.01-10 mass %, Ti content are 0.01-10 mass %, I960/I550It is worth for 0.55-0.85, U480/
U330It is worth for 0.6-2.5, N-117/N-114It is worth for 0.02-0.15；
It is preferred that bullion content 0.02-5 mass %, Ti content is 0.05-5 mass %, I960/I550It is worth for 0.65-0.8, U480/
U330It is worth for 0.6-2, N-117/N-114It is worth for 0.02-0.08.
3. HTS according to claim 1 or 2, wherein,
The particle diameter of the HTS is 0.2-5 μm, and pore volume is in 0.15cm3/ more than g, total specific surface area is in 300m2/ more than g, outside
The ratio that surface area accounts for total specific surface area is 5-30%；
It is preferred that the particle diameter of the HTS is 0.3-3 μm, pore volume 0.25-0.45cm3/ g, total specific surface area is in 350m2/ g with
On, the ratio that external surface area accounts for total specific surface area is 8-25%.
4. according to the HTS described in claim 1 or 2 or 3, wherein,
The surface silicon titanium ratio of the HTS is not less than body phase silicon titanium ratio, and the silicon titanium is than referring to silica and titanium oxide
Mol ratio, the surface silicon titanium ratio are determined using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses XRF light
Spectrometry determines；
Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be more than 1.2；
It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5；
It is further preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5.
A kind of 5. synthetic method of the HTS in claim 1-4 described in any one, it is characterised in that this method bag
Include：
(1) by noble metal source, ammonia source, alternatively water mixing contact obtains the first mixture；
(2) in the presence of template, by titanium source, first mixture, alternatively water is mixed to get the second mixture；
(3) by second mixture, inorganic silicon source, alternatively water is mixed to get the 3rd mixture；
(4) the 3rd mixture is subjected to hydrothermal crystallizing, recovery obtains HTS.
6. synthetic method according to claim 5, wherein,
Non-aqueous content of material is 0.01-50 weight % in the first mixture in step (1), preferably 0.02-25 weight %, enters one
Step is preferably 0.05-10 weight %, most preferably 0.1-5 weight %；And/or
The condition of mixing contact includes in step (1)：Temperature be room temperature to 80 DEG C, time 0.1-24h, preferably room temperature to 60
DEG C, time 0.5-12h.
7. the synthetic method according to claim 5 or 6, wherein,
The weight of ammonia source and noble metal source ratio is (5-50000)：100, be preferably (10-10000)：100, more preferably
(50-5000)：100, be most preferably (100-2000)：100；And/or
Inorganic silicon source：Titanium source：Noble metal source：Template：Mol ratio=100 of water：(0.5-5)：(0.1-5)：(5-50)：
(200-5000)；Preferably 100：(1-4)：(0.2-4)：(6-25)：(300-800), wherein, inorganic silicon source is with SiO2Meter, titanium
Source is with TiO2Meter, noble metal source are in terms of precious metal element, and template is with N or OH-Meter.
8. the synthetic method according to claim 5 or 6, wherein,
Hydrothermal crystallizing is carried out in confined conditions, undergoes stage (1), stage (2) and stage (3) successively, 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 handle 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 1-5 hours, and the stage (3) rises
Temperature reprocesses 6-96 hours, preferably 12-20 hours to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160-170 DEG C.
9. synthetic method according to claim 8, wherein, stage (1) and stage (3) meet one of following condition or
Both：
Condition 1：The temperature in stage (1) is less than the temperature in stage (3), it is preferable that temperature of the temperature in stage (1) than stage (3)
It is low 10-50 DEG C, preferably low 20-40 DEG C；
Condition 2：The time in stage (1) is less than the time in stage (3), it is preferable that time of the time in stage (1) than stage (3)
Short 5-24 hours, preferably short 6-12 hours；
Stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.
10. the synthetic method according to claim 5 or 6, wherein,
The ammonia source is the one or more in the organic solution of ammonia, liquefied ammonia, ammoniacal liquor and ammonia；Preferably ammonia, liquefied ammonia and ammonia
One or more in water, further preferred ammoniacal liquor；And/or
The template is the one or more in quaternary amine alkali cpd, aliphatic amine compound and aliphatic alcohol amines；
And/or
The inorganic silicon source is the one or more in silicate, Ludox and silica gel；And/or
The titanium source is inorganic titanium salt and/or organic titanate；And/or
The noble metal source is the oxide of noble metal, the halide of noble metal, the carbonate of noble metal, the nitric acid of noble metal
One kind in salt, the ammonium salt of noble metal, the chlorination ammonia salt of noble metal, the hydroxide of noble metal and the complex compound of noble metal
Or it is a variety of, the noble metal is the one or more in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au.
11. the synthetic method according to claim 5 or 6, wherein, this method also includes：By obtained HTS with
Processing is modified containing the contact of the modification liquid of nitric acid and at least one peroxide, in the modification, as raw material
The mol ratio of HTS and the peroxide be 1：(0.01-5), preferably 1：(0.05-3), more preferably 1：
The mol ratio of (0.1-2), the peroxide and the nitric acid is 1：(0.01-50), preferably 1：(0.1-20), more preferably
1：(0.2-10), more preferably 1：(0.5-5), particularly preferably 1：(0.6-3.5), the HTS is with titanium dioxide
Silicon meter.
12. synthetic method according to claim 11, wherein, in the modification liquid, the peroxide and nitric acid it is dense
Degree is respectively 0.1-50 weight %, more preferably preferably 0.5-25 weight %, 5-15 weight %；Wherein, the peroxide
Selected from hydrogen peroxide, TBHP, cumyl hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, peroxide second
Acid and Perpropionic Acid.
13. synthetic method according to claim 11, wherein, in the modification, the titanium silicon molecule as raw material
Sieve is with the modification liquid in 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, further preferred 60-200 DEG C of temperature
Under contacted, the contact is carried out in the container that pressure is 0-5MPa, and the pressure is gauge pressure, the contact it is lasting when
Between be 1-10 hours, preferably 3-5 hours.
14. synthetic method according to claim 11, wherein, in the modification, the titanium silicon molecule as raw material
Sieve and cause with the exposure level of the modification liquid, using on the basis of the HTS as raw material, in ultraviolet-visible spectrum,
The peak area of absworption peak of the modified HTS between 230-310nm reduces by more than 2%, preferably reduces 2-30%, more
It is preferred that reducing 2.5-15%, 3-10% is further preferably reduced, still more preferably reduces 3-6%；Modified HTS
Pore volume reduce more than 1%, preferably reduce 1-20%, more preferably reduce 1.5-10%, further preferably reduce 2-5%, it is described
Pore volume uses static determination of nitrogen adsorption.
15. the HTS that the method in claim 5-14 described in any one obtains.
16. the application of HTS in the oxidation reaction in claim 1-4 and claim 15 described in any one.
17. a kind of method of cyclic ketones oxidation, this method include：Cyclic ketones, oxidant and catalyst are contacted, it is characterised in that institute
State catalyst and contain HTS in claim 1-4 and claim 15 described in any one.
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| CN112744837B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin |
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